(European Coatings TECH FILES) Et Al. - Sander, Jörg - Anticorrosive Coatings Fundamental and New Concepts-Vincentz Network (2014)

European Coatings Tech Files
The Mission: To fully grasp, understand and successfully apply

the basics of anticorrosion coatings and novel concepts in
corrosion protection – from substrate pretreatment through
raw material selection and the protection mechanism, up to
self-healing, biopolymers and self-repairing polymer films. This
book explains and elaborates in some depth on the key princip-
les of anticorrosion coatings. Jörg Sander et al.
The Audience: Anybody involved in metal surfaces and/or
coatings engineering – suppliers, users, experts and students
alike. All those seeking a better understanding of the mutual
Anticorrosive Coatings
interactions and roles of organic corrosion protection coatings
The Value: This book brings together all the disciplines invol-
Jörg Sander et al. · Anticorrosive Coatings

ved in the creation and use of corrosion protection coatings
Ulrich Poth • Automotive Coatings Formulation

for metals. It presents the latest insights into the quality and
chemistry of surfaces, the proper way to prepare them by
conversion treatment, the function of resins and anticorrosion
pigments in paints, and novel concepts in corrosion protection.
As an added bonus, all the standards and directives mentioned
in the text are grouped together in their own chapter for a
better overview.
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Jörg Sander | Lars Kirmaier | Mircea Manea | Dmitry Shchukin | Ekaterina Skorb
Fundamentals and New Concepts
Jörg Sander et al.: Anticorrosive Coatings

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ISBN 978-3-86630-805-3
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Jörg Sander | Lars Kirmaier | Mircea Manea |

Dmitry Shchukin | Ekaterina Skorb
Fundamentals and New Concepts

ISBN 978-3-86630-805-3

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Foreword
Metals, in particular steel and aluminium, are among the most important construction
materials to be met in everyday life. However, these versatile materials are prone to corro-
sion, resulting in safety impairments, aesthetic failures, and, on the bottom line, economic
damage. A major part of surface engineering of metals therefore is focused on corrosion
protection.
Organic coatings have been used on any substrate for design purposes as well as to preserve
the outward appearance. When applied to metals, corrosion protection becomes their most
important technical feature. Though, in this respect, the primary effect of a coating is to
form a physical barrier, there is no simple rule of “the thicker, the better”. Effective corro-
sion protection provided by an organic coating requires proper preparation of the substrate
surface, expert formulation of treatment and coating chemicals and appropriate application
processes, as well as adaptation to different uses and service environments.
A lot of literature has been published on single aspects of corrosion protective coatings.
However, corrosion protection by organic coatings is a truly cross-functional issue. Whereas,
to the lead author’s opinion, a unified approach to this task is lacking that highlights the
role of all disciplines involved in the creation and use of corrosion protection coatings for
metals.
The intention of this book is to provide this missing synopsis. It features an up-to-date pic-
ture of the quality and chemistry of a substrate surface, its proper preparation by conversion
treatment, the function of resins and anticorrosive pigments in paints, and novel concepts
for corrosion protection. It is addressed to all parties involved in metal surface and coatings
engineering, both the supplier and the user, both the expert as well as the student in any
of the single disciplines. It is intended to contribute to a better understanding of the mutual
roles and responsibilities in corrosion protective organic coatings, and pave the way to a
more durable and sustainable preservation of our valuables and resources.
Velbert, Germany, April 2010

Jörg Sander

ISBN 978-3-86630-805-3

Contents 7
Contents
1 Introduction.........................................................................................13
1.1 Why corrosion-protective coatings....................................................................... 13
1.2 Literature.................................................................................................................... 14
2 Corrosion protection coatings.............................................................15

2.1 Principles of function............................................................................................... 15
2.1.1 Electrochemistry of corrosion inhibition............................................................. 15
2.1.2 Metal oxide formation.............................................................................................. 16
2.1.3 Cathodic protection................................................................................................... 17
2.1.4 Passivation and conversion coating...................................................................... 18
2.2 Design of organic coating systems....................................................................... 19
2.2.1 Diffusion barrier features – humidity uptake and electrolyte permeation.19
2.2.2 Active pigments........................................................................................................ 20
2.3 Function of individual coating layers................................................................... 21
2.4 Literature.................................................................................................................... 22
3 Surface preparation.............................................................................25
3.1 Industrial cleaning................................................................................................... 25
3.1.1 Importance of cleaning process............................................................................. 25
3.1.2 Contaminants............................................................................................................. 25
3.1.3 Surface energy and tension.................................................................................... 26
3.2 Mechanical cleaning................................................................................................ 27
3.3 Chemical cleaning.................................................................................................... 28
3.3.1 Plasma and corona processes................................................................................. 28
3.3.2 Solvent cleaning........................................................................................................ 29
3.3.3 Chemistry of aqueous cleaners.............................................................................. 29
3.3.3.1 Mechanism: alkalinity, saponification and metal dissolution........................ 29
3.3.3.2 Ingredients of aqueous cleaners .......................................................................... 31
3.3.3.2.1 General considerations............................................................................................ 31
3.3.3.2.2 Surfactants................................................................................................................. 32
3.3.4 Physics of aqueous cleaning, bath life and rinsing........................................... 34
3.4 Literature.................................................................................................................... 37
4 Organic coating materials...................................................................39

4.1 Ingredients of organic coating materials............................................................ 40
4.2 Resins.......................................................................................................................... 40
4.2.1 Alkyd resins............................................................................................................... 41
4.2.1.1 Alkyd resins manufacturing process................................................................... 43
4.2.1.2 Decay of alkyd resins . ............................................................................................ 43
4.2.1.3 Composition of alkyd resins................................................................................... 44
4.2.1.4 Curing of alkyd resins............................................................................................. 45
4.2.2 Chlorinated rubber................................................................................................... 46

ISBN 978-3-86630-805-3

8 Contents
4.2.3 Polyvinyl chloride..................................................................................................... 48

4.2.4 Epoxy resins............................................................................................................... 49
4.2.4.1 Raw materials for epoxy resins............................................................................. 50
4.2.4.2 Manufacturing process for epoxy resins............................................................. 50
4.2.4.3 Cross-linking of the epoxy resins......................................................................... 52
4.2.5 Epoxy esters............................................................................................................... 53
4.2.6 Acrylic resins............................................................................................................. 55
4.2.6.1 Manufacturing of acrylic resins............................................................................ 56
4.2.6.2 Thermoplastic and thermosetting acrylic resins............................................... 56
4.2.7 Polyurethanes............................................................................................................ 57
4.2.7.1 Reactivity of isocyanate group............................................................................... 59
4.2.7.2 Waterborne polyurethanes..................................................................................... 60
4.2.7.3 Isocyanate free polyurethanes.............................................................................. 61
4.2.8 Polyaspartics.............................................................................................................. 62
4.2.8.1 Polyurea systems...................................................................................................... 63
4.2.8.2 Polyaspartic systems................................................................................................ 64
4.2.9.1 Nomenclature of the silicon chemistry................................................................ 66
4.2.9.2 Manufacturing of alkyl silicates............................................................................ 68
4.2.9.3 Reactions of alkyl silicates...................................................................................... 69
4.2.10 Polysiloxanes.............................................................................................................. 70
4.2.10.1 Reactions of siloxanes.............................................................................................. 70
4.2.10.2 Manufacturing of siloxanes.................................................................................... 72
4.3 Pigments – Introduction.......................................................................................... 74
4.3.1 Corrosion protection pigments............................................................................... 75
4.3.1.1 Lead and chromate pigments................................................................................. 76
4.3.1.1.1 Lead pigments........................................................................................................... 76
4.3.1.1.2 Chromate pigments.................................................................................................. 76
4.3.1.2 Phosphate based pigments..................................................................................... 79
4.3.1.2.1. Zinc phosphate........................................................................................................... 79
4.3.1.2.2 Modified orthophosphates....................................................................................... 80
4.3.1.2.3 Modified polyphosphates........................................................................................ 82
4.3.1.3 Inorganic/organic synergies.................................................................................. 82
4.3.1.4 Wide spectrum anticorrosives............................................................................... 83
4.3.1.5 Phosphites and phosphides.................................................................................... 84
4.3.1.5.1 Zinc hydroxyphosphite............................................................................................ 84
4.3.1.5.2 Iron phosphide........................................................................................................... 84
4.3.1.6 Borates......................................................................................................................... 85
4.3.1.6.1 Barium metaborate................................................................................................... 85
4.3.1.6.2 Zinc borate.................................................................................................................. 85
4.3.1.6.3 Calcium borosilicate................................................................................................. 85
4.3.1.7 Molybdates................................................................................................................. 85
4.3.1.8 Ion-exchange pigments........................................................................................... 86
4.3.1.9 Zinc cyanamide ........................................................................................................ 86
4.3.1.10 Hybrid anticorrosive inhibitors............................................................................. 86
4.3.2 Barrier pigments....................................................................................................... 87
4.3.2.1 Micaceous iron oxide............................................................................................... 87
4.3.2.2 Aluminium flakes..................................................................................................... 88
4.3.2.3 Zinc flakes.................................................................................................................. 88
4.3.3 Sacrificial pigments.................................................................................................. 88
4.3.3.1 Zinc dust..................................................................................................................... 88
4.3.3.2 Magnesium................................................................................................................. 89

Contents 9
4.3.4 Colouring agent......................................................................................................... 89

4.3.4.1 White pigment, titanium dioxide.......................................................................... 89
4.3.4.2 Red pigments............................................................................................................. 90
4.3.4.3 Yellow pigments........................................................................................................ 90
4.3.4.4 Green pigments......................................................................................................... 90
4.3.4.5 Blue pigments............................................................................................................ 90
4.3.4.6 Black pigments.......................................................................................................... 90
4.4 Extender pigments.................................................................................................... 91
4.4.1 Carbonates.................................................................................................................. 91
4.4.2 Sulphates..................................................................................................................... 91
4.4.3 Silicas........................................................................................................................... 91
4.4.4 Silicates....................................................................................................................... 91
4.4.4.1 Talc............................................................................................................................... 91
4.4.4.2 Kaolin........................................................................................................................... 92
4.4.4.3 Wollastonite................................................................................................................ 92
4.4.4.4 Mica.............................................................................................................................. 92
4.5 Other additives.......................................................................................................... 92
4.6 Solvents....................................................................................................................... 94
4.7 Raw materials for powder coatings....................................................................... 95
4.8 Literature ................................................................................................................... 97
5 Film formation.....................................................................................101
5.1 Physical drying ........................................................................................................ 101
5.2 Chemical curing........................................................................................................ 102
5.2.1 Thermal cross-linking: chemistry, mechanism, imparted properties.......... 102
5.2.2 Radiation curing........................................................................................................ 103
5.2.2.1 Chemical principles and intrinsic properties..................................................... 103
5.2.2.2 Applications................................................................................................................ 107
5.2.2.3 Equipment.................................................................................................................. 108
5.3 Literature.................................................................................................................... 110
6 Mechanism of protection and properties of organic coatings...........111

6.1 Measurement of physical properties and influence.......................................... 111
6.2 Dry film thickness.................................................................................................... 111
6.3 Adhesiveness............................................................................................................. 112
6.3.1 Role of adhesion and factors of influence............................................................ 112
6.3.2 Measurement of adhesion and elasticity............................................................. 113
6.3.2.1 Industrial methods................................................................................................... 113
6.3.2.2 Laboratory methods.................................................................................................. 114
6.4 Permeation through organic coatings.................................................................. 115
6.5 Corrosion protective performance........................................................................ 115
6.5.1 Titanium and zirconium fluoro complex based pretreatments...................... 115
6.5.2 Weldable corrosion protection primer for automotive sheet............................ 118
6.5.3 Thermally curing 2-in-1 primer-pretreatment................................................... 120
6.5.4 Chromous based pretreatments – chromiting................................................... 120
6.5.5 Active pigments, ion exchangers and scavengers............................................. 121
6.5.6 UV-curable primer-pretreatment.......................................................................... 122
6.6 Degradation and ageing.......................................................................................... 122
6.6.1 Weathering................................................................................................................. 122
6.6.2 Electrochemical degradation.................................................................................. 124
6.6.2.1 Cathodic disbonding: oxygen reduction.............................................................. 124

10 Contents
6.6.2.2 Anodic disbonding: filiform corrosion................................................................. 125

6.7 Literature.................................................................................................................... 126
7 Testing of organic coatings..................................................................129

7.1 Performance testing................................................................................................. 129
7.2 Accelerated corrosion tests..................................................................................... 129
7.2.1 Overview..................................................................................................................... 129
7.2.2 Constant climate tests.............................................................................................. 129
7.2.2.1 Salt spray.................................................................................................................... 129
7.2.2.2 Constant climate, humidity.................................................................................... 130
7.2.2.3 Filiform corrosion..................................................................................................... 130
7.2.2.4 Condensation.............................................................................................................. 131
7.2.2.5 Boiling, water soak................................................................................................... 131
7.2.3 Cyclic climate tests................................................................................................... 131
7.2.3.1 Cyclic humidity......................................................................................................... 131
7.2.3.2 Prohesion.................................................................................................................... 131
7.2.3.3 VDA test...................................................................................................................... 131
7.2.3.4 UV test, weathering................................................................................................. 131
7.3 Electrochemical testing........................................................................................... 132
7.3.1. General remarks....................................................................................................... 132
7.3.2. Electrochemical potential........................................................................................ 132
7.3.2.1 Standard potential ................................................................................................... 132
7.3.2.2 Cyclovoltammetry..................................................................................................... 133
7.3.3 Electrochemical impedance spectroscopy.......................................................... 133
7.3.4. Electrochemical techniques with high spatial resolution............................... 134
7.3.4.1 Scanning vibrating electrode................................................................................. 134
7.3.4.2 Height-regulated Scanning Kelvin Probe............................................................ 134
7.3.4.2.1 General technique.................................................................................................... 134
7.3.4.2.2 Blister test................................................................................................................... 135
7.4 Outdoor exposure tests............................................................................................ 136
7.5 Literature.................................................................................................................... 137
8 Chemical conversion treatment..........................................................139

8.1 Substrates................................................................................................................... 139
8.2 Chemicals for pretreatment.................................................................................... 141
8.2.1 General remarks....................................................................................................... 141
8.2.2 Alkaline passivation................................................................................................. 142
8.2.3 Phosphating................................................................................................................ 143
8.2.3.1 Iron phosphating....................................................................................................... 143
8.2.3.2 Zinc phosphating...................................................................................................... 143
8.2.4 Chromating................................................................................................................. 144
8.2.5 Anodising of aluminium......................................................................................... 144
8.2.6 Chromiting................................................................................................................. 145
8.2.7 Chromium-free pretreatment................................................................................. 145
8.2.7.1 Titanium and zirconium fluoro-complex technology........................................ 145
8.2.7.2 Other chromium-free pretreatments.................................................................... 148
8.2.8 Hybrid pretreatment coatings................................................................................ 148
8.2.8.1 Silane/siloxane coatings.......................................................................................... 148
8.2.8.2 Combined thermal processes for primer-pretreatment .................................. 148
8.2.9 Surface preparation of other substrates – copper alloys, white metal,
magnesium, stainless steel..................................................................................... 149

Contents 11
8.2.10 Environmental considerations............................................................................... 149

8.3 Application of pretreatments.................................................................................. 151
8.3.1 Immersion and Spray Treatment .......................................................................... 151
8.3.2 Pretreatment application for coil: spray/squeeze, spray-cell, roll-coating... 152
8.4 Literature.................................................................................................................... 153
9 Organic coatings for maintenance......................................................157

9.1 Surface tolerant coatings......................................................................................... 157
9.1.1 General considerations............................................................................................ 157
9.1.2 Surface tolerant coating materials........................................................................ 157
9.2 Organic coatings on residual rust and old coatings.......................................... 158
9.3 Literature.................................................................................................................... 159
10 New corrosion protection concepts.....................................................161

10.1 Thin films................................................................................................................... 161
10.1.1 Self-assembling monolayers................................................................................... 163
10.1.2 Conducting polymers............................................................................................... 167
10.1.3 Biopolymers................................................................................................................ 175
10.2 Nanomaterials .......................................................................................................... 179
10.2.1 Nanocomposites........................................................................................................ 179
10.2.2 Sol-gel derived ceramic and hybrid coatings .................................................... 182
10.3 Self-healing coatings .............................................................................................. 184
10.3.1 Self-repairing polymer films.................................................................................. 185
10.3.2 Inhibitor release........................................................................................................ 189
10.4 Conclusions................................................................................................................ 194
10.5 Literature.................................................................................................................... 195
11 Standards and guidelines....................................................................201

11.1 General information................................................................................................. 201
11.2 General norms........................................................................................................... 201
11.2.1 Norms on mechanical testing of organically coated metallic work pieces.. 202
11.2.2 Norms on corrosion testing of organically coated metallic work pieces . ... 202
11.3 Selected European legislation on environmental protection........................... 203
11.4 Literature.................................................................................................................... 204
Authors.................................................................................................205
Index.....................................................................................................206

Why corrosion-protective coatings 13
1 Introduction
Jörg Sander
1.1 Why corrosion-protective coatings

Man has used metal since about 6,500 B.C. Dating back to this time long past, copper items
were found in the neolithic settlement of Çatal Höyük (Catalhoyuk) in Anatolia, where their
appearance coincided with the obvious decline in the use of stone tools [1, 2]. While copper
and its alloys served for decoration, everyday objects, cutlery, tools and weapons of their
era, widespread use of metal only started with the establishing of iron making in the second
half of the second millennium B.C. [3].
Iron has dominated history, culture, engineering sciences and industrial manufacture
grace to its properties, combining availability and convenient refining, versatile workability
by casting, forging, rolling and machining, and, last but not least, structural strength and
ductility. From Damascus steel scimitar blades to Stephenson’s Rocket, from the common
passenger car to the Sears Tower Building, from a washing machine to luxury cruise ships –
the applications of iron and steel are innumerable.
However, since the discovery of iron and the invention of its relative, steel, man has also
been confronted with the degeneration and decay of this so very useful material by cor-
rosion. The corrosion of iron and steel is a very fast process that destroys valuable goods
every day and causes a lot of economic damage. The prevention of corrosion therefore is of
paramount importance.
Organic coatings offer a very attractive road to the corrosion protection of metals. Their
purposes and applications span from the temporary protection of surfaces during storage,
transport and onward processing, over the role as protective primers that may provide a
number of additional features like surface structuring, biostatic finish, conductor proper-
ties, (dry) lubrication etc., cosmetic coatings for colour, haptic and gloss design of surfaces,
and finally surface finishes that provide anti-graffiti, anti-fingerprint, or wear resistant
properties. Organic coatings provide a unique combination of aesthetic appearance and pro-
tection against corrosive decay for man’s most important construction material – metal.
A lot of literature has been issued on corrosion prevention, and a lot of scientific and engi-
neering effort as well as public and institutional funding are spent to understand corrosion
and deterioration phenomena and to find ways for their prevention. The protective coating of
metals primarily intended to retard the start of corrosion damage has often been discussed.
In particular, the organic coating of metals has been described in basic reference works
by representatives of the paint industry, in papers by the scientific community, in guides
to surface engineering, and in monographs dealing with single aspects of use. All authors
had their specialist perspectives on metal and metal finishing, for example in steel making,
on passivation and surface treatment, on the vast number of uses and their respective
anticorrosive measures, and the expertise to formulate and apply coatings. However, it has
proven difficult to obtain the big picture that would demonstrate the interdependence and
the interplay of all parties.
The intention and the purpose of the present book is to provide a synopsis on all aspects of
corrosion protection coatings for metal, from the substrate quality and its chemical proper-

ISBN 978-3-86630-805-3

14 Introduction
ties, the importance of proper cleaning and surface preparation by conversion treatment,
the role of paint ingredients, in particular novel resins and anticorrosive pigments, surface
engineering techniques, and the ongoing research for novel trends that will lead the way
into the future of corrosion-protective coatings.
Five authors, each of them with a good record in the industrial and scientific community,
have joined in this work.
1.2 Literature
[1] Zohar, M., Catal Hüyük, Residential Structures, Mortuary Customs, Material Culture, Artistic Expression,
Catal Hoyuk, a Neolithic Town in Anatolia, Net Industries, Kingston ON, Canada 2010 (www.jrank.org/
history/pages/5978/Catal-H%C3%BCy%C3%BCk.html) (28-03-2010; 15:35 h)
[2] Weipert, H., Palästina in vorhellenistischer Zeit (Palestine in Pre-hellenistic Times) in: Hausmann, U. (ed.),
Handbuch der Archäologie (Handbook of Archeology – Middle East) 2, 1st Vol., Beck, Munich 1988, p. 120
[3] Coghlan, H. H., Prehistoric Iron Prior to the Dispersion of the Hittite Empire, Man 41, Royal Anthropological
Institute of Great Britain and Ireland, 1941, pp. 74 ff

Principles of function 15
2 Corrosion protection coatings

Jörg Sander
2.1 Principles of function

2.1.1 Electrochemistry of corrosion inhibition
Corrosion is an electrochemical process that destroys the surface of metals by dissolution
reactions and formation of corrosion products. On a coated metal surface corrosion takes
place at the interface between substrate and coating. Consequently, a coating must provide
sufficient protection to retard an onset and propagation of corrosion reactions. Strategies for
corrosion prevention therefore involve a number of possible measures that either improve
electrochemical stability of metal surface or restrict access of corrosive media to surface
and along metal/coating interface. Common preventive strategies are summarised below,
that have been discussed elsewhere [1, 2].
Corrosion prevention strategies
• Conversion coatings
• Cathodic protection
- Galvanising
- Zinc dust primers
• Sealing of pores
- Multi-layer coatings
• Barrier effect
• Dielectric properties of a coating
• Reduced moisture and gas uptake
• Interception of corrosive agents
- Active anions
- Ion exchange pigments
• Improvement of substrate adhesion
- Adhesive primers
- Silane/siloxane coatings
• Increase of alkalinity
- Cement coatings
The metallic state is defined as a feature of solid matter, where atoms are located, densely
packed, at the sites of a crystal lattice, and one or more of their electrons (bonding electrons)
released to be freely distributed across the entire macroscopic crystal [3]. Therefore, in prin-
ciple all metals are prone to corrosion due to free availability of their electrons at the outer
surfaces of the metal crystal.
One driving force for corrosion is the ease of electrons to be released, or in other terms, of
the metal to be oxidised. This depends on the kind of metal, and is usually characterised
by the metal’s electrochemical potential. The chemical reactions that take place during
atmospheric corrosion can be resolved into a pair of red-ox reactions, shown in Equations
2.1 and 2.2.

ISBN 978-3-86630-805-3

Figure 2.1: (a) Atmospheric corrosion at a punctured coating over a zinc substrate; (b) Formation of a
barrier layer by precipitation of zinc oxide (native oxide barrier)
Equation 2.1 Zn → Zn2+ + 2 e - Anodic reaction

Equation 2.2 1/2 O2+H2 O+2 e -→2 (OH) - Cathodic reaction
The metal serves as the anode, i.e. the source of free electrons which are released upon the
dissolution of metal atoms. These are oxidised to metal cations (e.g. Zn2+) in the first reac-
tion, and the corresponding equivalent amount of electrons (e–) is made available for the
second reaction. In case of atmospheric corrosion, these electrons pass through the inter-
face into the surrounding solution, where they are consumed for the reduction of oxygen.
Figure 2.1 shows a schematic view of this situation [4, 5].
This description, in fact, leads directly to the major strategic principle of any anticorrosive
coating: If either of the reaction branches is slowed down effectively, the onset and develop-
ment of corrosion can be largely retarded. Corrosion inhibition (passivation) hence can be
achieved by the formation of a physical barrier that either insulates electrically, i.e. prevents
the transition of electrons from the metal to surrounding electrolyte, or mechanically, i.e.
blocks the direct access of electrolyte or atmospheric oxygen to the metal surface.
2.1.2 Metal oxide formation

A passivation or conversion coating, therefore, usually involves formation of a dense coating
of metal oxide, in order to display this barrier effect. The metal oxide, most often incorpo-
rating dissolved ions of the substrate metal itself, precipitates on the substrate surface and
forms a physical barrier. This barrier can only be penetrated by oxygen or ions through
diffusion, thereby slowing down the access of these materials to the base metal.
An effect of metal oxide coatings is sometimes also described in terms of a band model.
Many oxides of transition and higher main group metals have semiconductor properties.
For example, zinc oxide (ZnO) displays characteristics of an n-semiconductor, which means
that electrons in the valence band of the oxide can be promoted to the conducting band by
relatively low energy input. The energy gap (i.e. the distance of energy levels between the
valence and conducting bands) is a characteristic feature for each substance. The band
gap of magnesium oxide, MgO, for example, is much wider, which makes the compound an
insulator. Oxides of alloys, like the species MgZn2, display energy gap values between those
observed for oxides of the pure elements. Additionally, defects in the oxide coating result in
a reduction of the energy gap. A better resistance of an oxide coating against corrosion is
obtained with the widening of the energy gap. Though MgZn2 is the prevailing component
in the new Zn-Mg galvanising coatings, the situation in technical Zn-Mg coatings is compli-
cated by the additional presence of aluminium. The effect of the various corrosion products
in this model is also not yet entirely understood [6].

Principles of function 17
One approach for a rationalisation

of this effect is the respective sta-
bility of corrosion products (oxides
and hydroxides) in alkaline condi-
tions, as occur under the regime
of oxygen reduction. MgO and
Mg(OH)2 are insoluble in alkalis,
and therefore form stable barrier
layers. Consequently, zero-corro-
sion current densities are observed
for lower (more negative) electrode
potentials and higher alkalinities,
the more Mg is present in the ove-
rall metallic coating composition
(cf. Figure 2.2) [7]. In coherence, Figure 2.2: Current/potential curves of passive electrodes in
aerated solutions. Passive layers of Zn, MgZn2 and Mg
micrographic and photo elec-
consist of ZnO, a mixed Zn-Mg hydroxide ([Mg/Zn] = 0.2)
tron spectroscopic (XPS) studies and Mg(OH) , respectively Source: Elsevier Ltd. [7]
2
have shown mainly Zn corrosion
products in defective areas with
high dissolution, while areas with a low corrosion aspect were found to be covered by an
MgO/Mg(OH)2 film.
Native oxide coatings of this kind develop on zinc (Zn), aluminium (Al), magnesium (Mg),
or chromium (Cr), sometimes also incorporating carbonate ions from atmospheric carbon
dioxide (cf. Chapter 3.3.3.1).
Most oxides and hydroxides are instable when contacted with chloride containing electro-
lytes. Chloride can replace oxygen in the crystal lattice, so that mixed oxy/hydroxy chlo-
rides are formed that are known as intermediates in the dissolution process which often
leads to local (pitting) corrosion. Hydrotalcite pigments are reported to act as chloride sca-
vengers by virtue of their ion-exchange properties [8]. Calcium compounds are also known
to intercept residual chloride in coatings for polyalkylene packaging foils [9]. A similar effect
can be expected from calcium compounds in organic coatings for metals.
2.1.3 Cathodic protection

The native oxide layer of ferrous materials is too porous to withstand further corrosive
attack. Iron (Fe) and steel are often saved from corrosion by a coating with less noble metals,
e.g. with a Zn layer in galvanising. Further to its less penetrable native oxide barrier, Zn cor-
rodes preferentially on cut edges or scratches, serving as a “sacrificial anode”, thus keeping
the base metal from destruction. This behaviour is driven by the different electrochemical
potentials. While the potential of Fe is Epot = -0.44 V, (cf. Chapter 7.3.2.1, Table 7.2), that of
Zn is lower, i.e. Epot = -0.76 V. Protection is even active at some distance from the border of
the Zn layer, and may be attributed to a local increase in electron density in front of the Zn
border (cf. Chapter 7.3.4.1). This long-range effect is usually called cathodic protection.
Cathodic protection can also be made a function of the primer. Zinc pigmented primers have
been used as anti-corrosion barrier for various artisan and industrial coating applications,
in particular in heavy machinery, architecture and industrial construction, bridge enginee-
ring, water engineering, shipbuilding, etc. For these purposes, primer coats are used with
gauges of 50 µm and more [10–13]. The usefulness of zinc-rich primers is often attributed to
the cathodic protection provided by zinc particles to otherwise unprotected steel surfaces.
Zinc dust primers have also been reported as protective coatings under powder coatings.

As the authors did not observe any influence of the zinc content in various primer formu-
lations, they conclude that the major contributions to the improved performance are made
by the mechanical barrier effect and the adhesion promotion that is brought about by the
extra primer layer [14].
The principle of cathodic protection has also been used in corrosion protection primers
(CPP) that are applied on sheet for car manufacture [15, 16]. By their use, improved corrosion
protection is achieved particularly in critical areas of a car body, like seams, box sections or
flanges, where a pretreatment is geometrically difficult to apply and may therefore be faulty,
or the cathodic electro-dip primer is only insufficiently deposited due to shielding effects.
2.1.4 Passivation and conversion coating

Native oxide layers may serve well as efficient anticorrosive barriers for bare bulk metal,
but from the perspective of technical surfaces, it is often desired to create a more uniform,
controlled passivation layer, to better preserve the surface aspect and features. To this end,
it is necessary to remove the native oxide film (cf. Chapter 3.3.3.1), and replace it by a similar
film under controlled conditions, with improved features, for instance, uniform thickness,
lower porosity, better transparency, or higher electrical resistance.
Chromate containing chemicals have been quite commonly used for the generation of passi-
vating layers, due to the very high oxidative power of the chromate ion in acid systems. This
results in a very fast superficial red-ox reaction (cf. Chapter 8.2.4, Equations 8.8 to 8.10),
forming an insoluble, very dense mixed oxide layer of Cr3+ and the substrate metal, e.g. Zn.
The cathodic branch of this reaction system is also described by Equation 2.3. Its standard
potential is Epot = 1.195 V [17].
Equation 2.3 (CrO4)2-+ 8 H++ 3 e - → Cr3+ + 4 H2 O Cathodic reaction
Underneath a coating, the situation is more complicated. It is important to provide a good
adhesion of the organic coating by means of a conversion pretreatment. A good conversion
pretreatment has to form chemically bonded layers that are insoluble in water under chan-
ging pH conditions. Under a mild atmosphere, the reduction of oxygen tends to result in an
increase of the pH, as hydroxyl (OH–) ions are released in the course of reaction (Equation
2.2). While these ions may be consumed again by ongoing precipitation of oxides, locally
and temporarily high alkalinity may occur.
The long-lasting corrosion resistance provided by chromate passivation is also due to the
so-called self-healing effect. This is usually attributed to residual chromate ions that are
incorporated in the oxide layer. In case of mechanical damage of the passivation layer that
penetrates through the underlying substrate metal these chromate ions are available for
a quick passivation reaction at the newly exposed metallic location. Other “active anions”
that may also serve as strong oxidants for metals, like the oxo-anions ferrate, (per)manga-
nate, molybdate, tungstate, or vanadate, are considered as possible direct replacements for
chromate [18]. For example, Patent WO 0036182 [19] describes a pretreatment for aluminium
and its alloys, based on an alkaline ferrate (VI) solution and additional oxo-anions like
molybdate. The patent is valid in several European states, but no commercial application is
known yet.

Design of organic coating systems 19
2.2 Design of organic coating systems

2.2.1 Diffusion barrier features –
humidity uptake and electrolyte permeation
While cross-linking of a coating renders a macroscopically intact and closed network with
the required mechanical and chemical features, on a molecular scale, any polymer film will
remain penetrable to some extent by gases and electrolytes, due to diffusion and migration.
Increasing the film thickness is one possible measure to improve on this situation. For
instance, in coil coating, primer coatings are normally used at 5 µm dry-film thickness. For
high anticorrosive requirements, e.g. certain appliances and marine architectural applica-
tions, coil primer coats of up to 30 µm are common.
The uptake of water or moisture is considered an important feature of organic coatings, as it
is linked with changes in the density and dielectric properties of the polymer film. Absorp-
tion and incorporation of water molecules will lead to physical swelling (volume expansion)
and results in a softening of the coating surface. Moreover, as water is an electrolyte carrier,
its presence is related with the ease of dissolved ions to penetrate through a coating, where
they may accumulate and, finally, cause degradation of the polymer film and corrosion of
the metal substrate [20].
Water uptake is influenced by chemical and physical properties of the coating, and therefore
it is determined by the molecular design of the polymer. Typical coating resins like epoxies or
polyurethanes display a modest water uptake in humid atmosphere. However, the rate of incor-
poration is strongly accelerated when approaching the dew point. In principle, polar (hydrophi-
lic) polymers will allow better wetting and hence also a higher water absorption [21].
The elasticity of a coating, on the other hand, plays a role in the diffusion transport of mole-
cules through the interstices of the polymer film, which can be interpreted as the relative
mobility of polymer moieties [22]. While this property changes with temperature, usually
showing a jolt from the rigid to the elastic regime at the glass transition temperature (Tg),
it will also be affected when the film is plasticised by incorporation of water [23]. The design
of the polymer therefore includes the task of reconciling disparate features like flexibility
(formability) vs. curing temperature vs. diffusion barrier properties, or water miscibility vs.
chemical resistance vs. adhesion vs. wetting.
Another strategy involves the use of nanoscale particles like titanium dioxide (TiO2) pre-
parations, or natural or synthetic mineral pigments like clays and hydrotalcites. The lat-
ter two contain agglomerates of
nanosized crystalline platelets
that can be separated from the
agglomerate and distributed
in the bulk coating. The idea is
that these platelets can form an
additional barrier to penetrating
media, as they could extend the
diffusion path for any corrosive
ion or media through the coating,
cf. Figure 2.3. The observation of
the expected effect was reported
for oxygen, carbon dioxide and Figure 2.3: Schematic view of the extension of the diffusion
water vapour [24]. path by a nano-platelet filled coating; according to Lewis [1]

2.2.2 Active pigments

Additives are also used to obtain a higher anticorrosive performance. Often active pigments
are incorporated that interfere with penetrating corrosive agents (cf. also Chapter 4.3). Here
again, chromates, in particular strontium chromate, and dichromates have been used, but
due to their toxicity and pollution control requirements, are being replaced by successors
that are free from hexavalent chromium (chromate) or entirely chromium-free, e.g. zinc
phosphates.
Mineral or synthetically generated particles like hydrotalcites or zeolites can also be de-
signed as carriers to host e.g. anticorrosive ions like molybdates or vanadates. Such carrier
concepts are considered to be particularly useful, because they enable retarded release of the
active agents that thus remain available for longer periods, instead of quickly bleeding out
of a coating, depriving it of its properties. The release might even be controlled by the condi-
tions of the surrounding medium, e.g. pH value, temperature or the presence of (corrosive)
counter ions, so that the active ions are only available on demand (cf. Chapter 6.5.5) [25].
Other suitable anticorrosive additives comprise ion-exchange pigments like calcium-modi-
fied silicates that release calcium ions (Ca2+) in the presence of acids [26] thereby reducing
the corrosivity of the electrolyte, and precipitating corrosive ions like chlorides or sulphates.
A number of products are commercially available.
Condensed conductive polymers like polyaniline (PAni) have been around for a number
of years [27]. They have been shown to suppress delamination on steel. The mechanism of
PAni is attributed mainly to an increase of the electrochemical potential of the substrate
(ennoblement) thereby obstructing oxygen reduction [28]. PAni is rendered conductive by
the formation of its protonated salts, and the reverse deprotonation process is triggered by
the potential decrease during the delamination reaction. If counter-anions were suitably
selected as to inhibit corrosion, they might be truly released on demand with the onset of a
corrosion reaction. However, a controversial discussion is going on around this point. It has
been commented that PAni can be useful when added in low amounts, but can be detrimen-
tal to corrosion protection in other conditions [29-31].
2.3 Function of individual coating layers

Industrial organic coating systems consist of a conversion coating and a single- or multi-
layered paint coating. Any coating is designed to combine a set of varying features appro-
priate for the final use [32, 33]. In many cases, two or three-coat paint systems are used that
comprise a primer layer, an optional intermediate coating and a topcoat. In the manufacture
of cars, multi-coat systems are used. An electrocoat paint is applied as primer, followed by
a filler, then the coloured basecoat and finally a clearcoat.
Features provided by an organic coating system on metals can be summarised as follows
(cf. also Figure 2.4)
• Colour, gloss, structure
• Corrosion resistance
• Chemical resistance
• Adhesion
- Substrate adhesion (fingerprints, condensation, etc.)
- Intercoat adhesion
• Elasticity, formability
• Wear and scratch resistance

Function of individual coating layers 21
Figure 2.4: Schematic of a typical multi-coat paint system and functions of individual layers
• Soil and stain resistance

• Heat resistance
• UV resistance
The conversion coating is necessary to obtain the primary adhesion to the substrate and a
sufficient electronic anticorrosive barrier (cf. Chapters 2.1 and 8). Usually, the primer pro-
vides an additional part of the corrosion resistance and flexibility, while the topcoat is used
to give aesthetic appearance (colour, gloss) and mechanical and chemical resistance.
Primers therefore form a physical barrier that prevents access of moisture, water, electro-
lytes and reactive gases (e.g. oxygen) to the metal surface. This is achieved by choice of the
resin chemistry. Resins that are commonly used in primers comprise acrylates, polyesters,
epoxies and polyurethanes. For example, acrylates are used in primers for polyvinyl chlo-
ride (PVC) plastisol coatings. Polyesters usually display good adhesion to the substrate, and
provide good corrosion resistance. Polyurethanes are known for their flexibility that allows
deformation, resistance against mechanical wear, and a low sensitivity towards thermal
stress, particularly by low temperatures in the environment. Chemical resistance is brought
on by cross-linking of single polymer strands, which is also enabled by the suitable formu-
lation of the paint.
Intermediate coatings are used to build up film thickness, and mediate the distribution of
mechanical stress. They often contain platelet pigments, like micaceous iron oxide, in order
to extend the diffusion path for intruding corrosive species (cf. Chapter 2.2.1).
Applications in particulary demanding corrosive environments may require a topcoat con-
taining such a pigmentation which may restrict the obtainable colour and the level of gloss.
It is also important that the topcoat is non-transparent to UV radiation.
2.4 Literature
[1] Lewis, O. D., A Study of the Influence of Nanofiller Additives on the Performance of Waterborne Primer
Coatings, PhD Thesis, Loughborough Univ., Loughborough 2008, p. 78
[2] Vogelsang, J. A., Selbstheilende Beschichtungssysteme – Ein Überblick (Self-Healing Coating Systems…),
Schiff und Hafen (8) 2009, pp. 28 ff
[3] Barrow, G. M., Physikalische Chemie (Physical Chemistry), vol. 3, 3rd ed., Bohmann-Vieweg, Vienna 1977,
pp. 203 ff
[4] Meuthen, B., Jandel, A.-S., Coil Coating, 2nd ed., Vieweg, Wiesbaden 2008, p. 89 ff

[5] Fafilek, G., Kronberger, H., Thermodynamik, metallische Werkstoffe und Korrosion (Thermodynamics,
Metallic Construction Materials and Corrosion), Experimental Exercises Script, Exercise TK, Inst. Chem.
Technologies and Analytics, TU Vienna 2005, p. 6,
www.tuwien.ac.at/echem/education/158076/pcvt_lu_TK_skriptum.pdf (15-03-2010; 18:42 h)
[6] Giza, M., In-situ Spectroscopic and Kelvin Probe Studies of the Modification of Solid Surfaces in Low
Temperature Plasmas, Diss., University of Paderborn, 2008
[7] Hausbrand, R., Stratmann, M., Rohwerder, M., Corrosion of Zinc-Magnesium Coatings: Mechanism of Paint
Delamination, Corr. Sci. 51, 2009, pp. 2107 ff
[8] Mahajanam, S. V. P., Buchheit, R. G., Characterization of Inhibitor Release from Zn-Al-[V10O28]6- Hydrotalcite
Pigments and Corrosion Protection from Hydrotalcite-Pigmented Epoxy Coatings, Corrosion 64, 2008, pp.
230 ff
[9] Crass, G., Janocha, S., Bothe, L. (inv.), Biaxially oriented multilayered polyolefin film which is printable and
of which both sides are sealable, its production and use, European Patent EP 0263963, Hoechst AG 1987
[10] Meyer, K., Schutz von Stahlkonstruktionen, Beispiele aus der Eisenindustrie und dem Bergbau (Protection
of Steel Constructions…), Fette, Seifen, Anstrichmittel 69, 1967, pp. 90 ff
[11] Schröder, T., Erfahrungen mit Schutzbeschichtungen an Stahlwasserbauten der Wasser- und Schiffahrtsver-
waltung im Bereich der Nord- und Ostsee (Experiences with Protective Coatings on Hydraulic Structures…),
Materials and Corrosion 23, 1972, pp. 993 ff
[12] anon., Kanalüberführung Leine (Canal Flyover Leine River), Wasser- und Schifffahrtsverwaltung des Bundes
– Neubauamt Hannover (Federal Waterways and Shipping Administration), Hannover 2009;
www.nba-hannover.wsv.de/baumassnahmen/abgeschlossene_baumassnahmen/neubau_leinequerung.html
(15-03-2010; 18:45 h)
[13] Vogelsang [2] p. 30
[14] Schütz, A., Kaiser, W.-D., Kein Rasten gegen das Rosten (No Resting versus Rusting), FARBE UND LACK 110,
2004, pp. 26 ff
[15] Meuthen, Jandel [4] p. 75 ff
[16] Schinzel, M., Advanced Corrosion Protection of Automotive Body Sheet – A Challenge for Coil Coating, ECCA
Autumn Congress Brussels, Proc., European Coil Coating Association, Brussels 2009
[17] Weast, R. C., Astle, M. J. (ed.), Handbook of Chemistry and Physics, 60th ed., CRC Press, Boca Raton 1981,
p. D-155
[18] Kendig, M. W., Buchheit, R. G., Corrosion Inhibition of Aluminum and Aluminum Alloys by Soluble
Chromates, Chromate Coatings, and Chromate-Free Coatings, Corrosion 59, 2003, pp. 379 ff
[19] Minevski, Z., Eylem, C., Maxey, J. (inv.), Ferrate Conversion Coatings for Metal Substrates, WO 0036182,
Lynntech Inc., 2001
[20] Goldschmidt, A., Streitberger, H.-J., Basics of Coating Technology, 2nd Edition, BASF Coatings AG,
Münster 2007, p. 447
[21] Öchsner, W. P., Bergk, B., Fischer, E., Gaszner, K., Sorptionsisothermen für Wasser in organischen
Beschichtungen und deren Einfluss auf die Beschichtungseigenschaften (Sorption Isotherms for Water in
Organic Coatings…), FARBE UND LACK 111, 2005, pp. 42 ff
[22] Lewis [1] p. 87
[23] Goldschmidt, Streitberger [20] p. 401
[24] Lewis [1] p. 34
[25] Mahajanam, Buchheit [8] p. 231
[26] Vogelsang [2] p. 29
[27] Wessling, B., Corrosion prevention with an organic metal (polyaniline): Surface ennobling, passivation,
corrosion test results, Materials and Corrosion 47, 1996, pp. 439 ff
[28] Holness, R. J., Williams, G, Worsley, D. A., McMurray, H. N., Polyaniline Inhibition of Corrosion-Driven
Organic Coating Cathodic Delamination on Iron, J. Electrochem. Soc. 152, 2005, pp. B73 ff
[29] Rohwerder, M., Intelligent Corrosion Protection by Conducting Polymers, Smart Coatings II, ACS Sympo-
sium Ser. 1002, Am. Chem. Soc. 2009, pp. 274 ff
[30] Meine, D., Korrosionsschutz der Zukunft? (Future Corrosion Protection?), Conf. Report, Europ. Coatings.
Conf., Vincentz Network 2007, FARBE UND LACK 113, 2007, pp. 33 f
[31] Saji, V. S., Thomas, J., Nanomaterials for corrosion control, Current Science 92, 2007, pp. 51 ff
[32] Kittel, H., Streitberger, H.-J. (ed.), Lehrbuch der Lacke und Beschichtungen (Coursebook of Paints and
Coatings), Vol. 6, 2nd ed., Hirzel, Stuttgart 2008, pp. 485 ff
[33] Meuthen, Jandel [4] pp. 51, 79 ff

Industrial cleaning 23
3 Surface preparation
Jörg Sander
3.1 Industrial cleaning

3.1.1 Importance of cleaning process
Anticorrosive metal coatings require a clean and well-prepared metal surface, if a long-
lasting product with an aesthetic appeal and high durability is to be obtained. The efficiency
of the surface preparation determines the endurance of any conversion, anodic, galvanic or
organic coating between weeks and years. Quite often however, the difference between a
clean and a contaminated surface does not become apparent by visual inspection. Thorough
monitoring of the cleaning [1, 2] stage is therefore mandatory in order to ensure that both a
high-class pretreatment and final coating are achieved.
Mechanical cleaning like brushing, grinding, shot or grit-blasting etc. can serve for a basic
level of surface preparation. Much more often, chemical cleaning is a necessity. Several
application methods are available for industrial cleaning operations, like immersion, spra-
ying, or vapour cleaning. Prior to painting, metal surfaces are most efficiently and econo-
mically cleaned by aqueous spray cleaners, but the choice is made according to the size and
shape of the work pieces and the type of contamination.
In many cases, e.g. job-coater facilities, mixed-metal car body manufacture or coil coating,
a mix of different substrates must be cleaned and pretreated. Most industrial cleaners the-
refore must apply on different substrates. Aqueous cleaner solutions are used on steel, gal-
vanised steel, aluminium, but also on die-cast alloys (Al, Zn, Mg), other non-ferrous metals
and – in the automotive and appliance industries – prephosphated sheet.
3.1.2 Contaminants
Industrial cleaning deals with a great variety of soils and contaminants.
Rust, scale, residues, e.g. of old paints, galvanising layers, faulty conversion or anodic
coatings, usually require mechanical precleaning or pickling.
Oils and fats usually originate from the generation process of the unmanufactured or semi-
finished material. They stem from protective oils (temporary corrosion protection, often
containing additional organic inhibitors, e.g. triethanol amine) or metal working fluids
(drilling, cutting, stamping, drawing oils etc.).
Polishing agents like stearic or paraffinic waxes, usually contain additional grinding
compounds like finely dispersed silica, lime, corundum, colloidal clay minerals etc.
Sweat or fingerprints contain fats, fatty acids, proteins etc.
Fines and metal abrasions originate from rolling, grinding and cutting processes, in
particular also from forming (deep-drawing, flanging).
Pigment soil, graphite and carbonised oil often appear after assembly processes (grinding,
joining, welding) or arise from annealing processes e.g. during coil production.

ISBN 978-3-86630-805-3

Figure 3.1: Schematic: Sessile drop showing the interfacial tension acting at the wetting front
The angle q between the tension vectors s for the solid-liquid (s, l) and the liquid-gas (l, g) interfaces is
measured by microscopic inspection.
3.1.3 Surface energy and tension

“Chemical cleanliness” is often mistaken for a water-break-free surface, i.e. the complete
wettability of a metal. While water-break-free rinsing gives a rough indication of the pre-
sence or absence of oils, fats etc., it depends on the surface tension of contaminating sub-
stances (e.g. self-emulsifying oils) and thickness of the water film, and can be affected by
evaporation of water or the presence of surfactants. Native oxide layers may not result in
particularly poor surface cleanliness, but they usually inhibit any further surface reaction
that is necessary to build up a proper conversion coating prior to painting.
Surface tension occurs at any interface between non-miscible phases. It is brought about by
differences of attractive forces that apply to molecules inside vs. between phases. This effect
rules the form of droplets, micelles and foam bubbles, and it determines the adsorption of
gases to solids, as it brings on capillarity phenomena like wetting and spreading of liquids
on a metal surface [3]. The wettability of a solid by a liquid is characterised by the contact
angle q that liquid makes on the solid. The mathematical description is given by Young’s
equation:
Equations
��
(3.1)
Equation 3.1: �o� � � Young’s equation
��
where: Q is the contact angle of a sessile drop on a solid surface, ss represent the tension vectors for
the solid-liquid (s, l), solid-gas (s, g) and the liquid-gas (l, g) interfaces (cf. Figure 3.1).
(3.2) 2 OH- + CO2 →(CO3 )2- + 2 H2 O Carbonation reaction
(3.3)
Table 3.1: ZnO � � OH � � H� O
Contaminants → �Zn�OH��
Oils, fats, waxes Fines, abrasives Pigments
� ��
(3.4)
Rolling, Zn�OH�
casting oils, � �
emulsifiers � OH → �Zn�OH�
Grinding, cutting, tool fines� � Graphite, molybdenum disulphide
Corrosion protective oil Grinding compounds
(3.5) Zn� �OH�� CO� �� OH � → � �Zn�OH�� CO� ��
Drawing, pressing lubricants, Carbonised oil, welding, brazing
soaps residues
(3.6) Zn � � OH � → �Zn�OH�� Anodic reaction
Drilling, cutting fluids
Waxes
(3.7) O� � � H� O � � �� → � �OH�� Cathodic reaction
Sweat, fingerprints
(3.8) H� C � O � �CO� � �CH� �� CH�

|
HC � O � �CO� � �CH� �� CH� � � OH � Triglyceride (fat)
| + alkali
Anticorrosion.indb 24
H C � O � �CO� � �CH � � CH 24.06.2010 14:16:35
Mechanical cleaning 25
The surface tension of liquids is

usually measured by capillarity or
sessile drop methods. For the lat-
ter, the contact angle, i.e. the angle
that is enclosed by the tension vec-
tors for the solid-liquid and liquid-
gas interfaces (cf. Figure 3.1), is
measured by microscopic inspec-
tion. Table 3.2 gives some exem-
plary values [4]. Contact angles
<90° (i.e. cos q > 0) indicate wet-
ting, angles >90° (cos q < 0) repul-
sion situations. Accordingly,
good wetting is obtained when
the interfacial tension between
solid and liquid exceeds the ten-
sion at the solid-gas boundary. If
the following process requires Figure 3.2: Phase diagram for carbon dioxide (CO2)
the surface to be wet by aqueous 0.1 MPa ≈ 1 atmosphere (Illustration according to Kukova [9])
media, the interfacial tension
should exceed 72 mN/m, which is the surface tension of water vs. air [5].
To determine the surface tension of a solid surface, the contact angles of droplets of diffe-
rent liquids with known surface tensions are measured and the resulting overall surface
tensions calculated [6]. A simple method for measuring surface tension uses prefabricated
test inks [7].
3.2 Mechanical cleaning

Mechanical cleaning is necessary when thick scale or rust layers must be removed. For steel
surfaces, this is quite often supported by acid pickling. Mechanical cleaning, however, does
not give sufficiently clean surfaces for subsequent galvanising or conversion coating. Apart
from brushing or grinding, shot or grit-blasting is often used to remove coarse contamina-
tions like rust, scale, carbonised oil or old paint. Grit-blasting uses various abrasive particles
(e.g. sand, slag, corundum, glass or
plastic beads) that are shot at the Table 3.2: Surface tension of liquids at different temperatures
target by pressurised air. For deli- (in mN/m)
cate surfaces, dry ice (solid CO2) Liquid 20 °C 60 °C 100 °C
has become a familiar abrasive H 2O 72.25 66.18 58.85
that is used to remove fats and oils,
C2H5OH 22.3 22.3 19.0
glues, paints and inks, corrosion
C6H 6 28.9 23.7
products etc. Dry ice sublimates,
i.e. evaporates directly from solid (C2H5) 2O 17.0 80.0
state, at a temperature of -78 °C
at atmospheric pressure. Dry ice Hg 480a)
blasting therefore generates less Ag 800b)
waste than other grit-blasting
NaCl 94c)
processes. Figure 3.2 depicts the
phase diagram of carbon dioxide, AgCl 125d)
showing the solid, liquid and a) at 0°C; b) molten at 970°C; c) molten at 1080°C; d) molten at 452°C;
gaseous states [8, 9]. cf. Barrow [4]

In cases when larger engineered constructions have to be cleaned on the site of their erec-
tion, the ultra-high pressure water jet technique has gained importance, to avoid dust and
soil in the vicinity of the construction ground. Water pressures of 1,700 to 2,100 bar are
sufficient to remove non-adhering rust and salt contaminations [10, 11].
Some discussion has been focused on supercritical CO2 (scCO2). The supercritical state is
achieved when a real gas is heated and pressurised beyond its critical temperature and
pressure. For CO2, the respective data are 31.04 °C and 7.38 MPa. Beyond this point, there
is no physical difference between the liquid and gaseous form, and gas obtains fluid and
solvent features that enable its use as an efficient extractant. scCO2 is used for high purity
extraction of natural substances (e.g. decaffeination) and other food processing applica-
tions[12]. Further applications of scCO2 comprise extractions of fragrances [13], synthesis
and polymer production and processing (octene hydroformylation, fluorinated polymer and
polycarbonate production) and powder production. scCO2 has some potential use as fluid for
cleaning of small metallic work pieces that can be handled in an enclosed, high-pressure
cleaning tank[14].
Finally, ultrasonic cleaning [15] employs the conversion of DC voltage into mechanical waves
above the audible frequency range (>20 kHz) by a piezo-electric generator. The vibrations
create local vacua and overpressure in rapid succession (cavitation) which literally blast off
soil from a contaminated surface. Ultrasonic cleaning achieves a high degree of efficiency
at a very fast rate. It has been used on a wide variety of work pieces of different materials
like glass, ceramics, or metal, regardless of dimension and shape.
3.3 Chemical cleaning

3.3.1 Plasma and corona processes
For finer cleaning that achieves a higher degree of cleanliness, plasma [16] treatments
have gained interest. Plasma is generated by ionisation of vapour, and is sometimes
called the fourth aggregate state of matter. Being accelerated against a solid surface,
the energy of the plasma is transferred to this surface and contaminants are chemically
destroyed and removed. Plasma cleaning is now available in atmospheric operations,
saving expensive vacuum technique that used to be necessary. The equipment that is
available nowadays can operate at a speed of several hundreds of mm/min, and plasma
source arrays can span up to two metres width.
Atmospheric zero-potential plasma cleaning is technically used for applications where
composite materials made from plastics, metal, glass and even ceramics are to be tre-
ated. The plasma beam makes no distinction between materials. Plasma cleaning has
proven sufficient for removal of neat oil residues in stamping of painted lids on jam
jars or air conditioning equipment parts in cars and trucks. The treated surfaces are
sufficiently susceptible for labelling adhesives or printing inks. Applications on bare
metal surfaces include a small aluminium coil coating operation and riveting in aircraft
industry, where former solvent cleaning processes could be successfully replaced [17].
Plasma cleaning has been combined with deposition of materials from the gas or plasma
phase, to form thin protective, in particular soil-repellent coatings [18]. High-voltage
corona discharge treatment is commonly used to clean and activate plastics surfaces,
especially of polyalkylenes [19]. It has also been used to clean and deposit thin coatings
on metal [20].

Chemical cleaning 27
3.3.2 Solvent cleaning

Fatty, oily and wax contaminations can be removed by immersion of work pieces into orga-
nic solvents or by degreasing in condensing solvent vapour. Halogenated hydrocarbons
have been used to this end due to their inflammability and solubilising power towards
most fatty contaminations. To remove pigment and soils, solvent cleaning must be sup-
ported by mechanical means, e.g. brushing or ultrasonic treatment. Soil that adheres by
chemisorption, oxides and metal soaps cannot be removed by solvent cleaning [21]. Fur-
thermore, the use of solvents is subject to legal regulation, i.e. the EU Directive 2008/1/
EC [22], commonly referred to as the Integrated Pollution Prevention and Control (IPPC)
Directive. This directive and related regulations, e.g. on emission of volatile organic
compounds (VOCs) [23], restrict emission levels of volatiles and the use of certain solvents
that pose a health hazard, i.e. due to carcinogenity or mutagenity. Hermetically closed
cleaning systems are therefore mandatory.
3.3.3 Chemistry of aqueous cleaners

3.3.3.1 Mechanism: alkalinity, saponification and metal dissolution
In most metal coating lines, aqueous immersion or spray processes are used to clean the
metal surface, and remove oil, solid contaminations and superficial scale. Typical aqueous
cleaners contain alkalis for saponification of fats and oils, and for pickling of the metal
surface, builders (e.g. phosphate, silicate) to disperse solid dirt particles in the solution
after their removal from the surface, and surfactants to quickly wet the metal surface
and to emulsify fatty and oily contaminations in a cleaner bath. Moreover, additives like
defoamers etc. may be present.
The alkalinity of the cleaner is selected according to the degree of ageing and contamination
of the feedstock. The alkalinity will change during the course of reaction, mainly due to
consumption of the alkali by saponification and metal dissolution. However, ageing effects
caused by entrapment of carbon dioxide (carbonation, see Equation 3.2) from the air must
also be considered, as they leave less “free” alkalinity available for the main reaction paths
(cf. Equations 3.3 to 3.8). The alkalinity therefore must be monitored manually or automati-
cally, preferably by titration methods.
Equation 3.2: 2 OH- + CO2 → (CO3)2- + 2 H2O Carbonation reaction
The reactions of the alkaline cleaning process on galvanised surfaces were studied using
an electro-chemical quartz crystal micro-balance (ECQM) array [24]. The principle of this
method is that the oscillation of a piezo-electric quartz wafer is proportional to the wafer’s
thickness. A galvanic-coated quartz wafer will therefore change its oscillating frequency in
response to any chemical reaction that takes place on its galvanised surface.
Dissolution results in reduction of thickness, hence accelerated oscillation, while coating
formation is supposed to cause an increase of the wafer thickness, thereby slowing down
its motion. The sensitivity of the method allows monitoring of thickness changes on the
atomic scale, so that molecular layers can be detected while forming, recording mass and
charge simultaneously and in-situ. The schematic presentation of the experimental set-up of
the ECQM for registration is given in Figure 3.3. Experimental results were obtained with
a zinc-coated, special quartz crystal, that was mounted in a flow cell and then subjected
to cleaner solutions at various flow rates, temperatures etc. Two different reactions can be
identified when this experiment is carried out in different atmospheres, i.e.

Stage A: Dissolution of the native oxide/carbonate/hydrate layer (chemical)

Equation 3.3: ZnO + 2 OH- + H2O → [Zn (OH)4]2-
Equation 3.4: Zn (OH)2 + 2 OH- → [Zn (OH)4]2-
Equation 3.5: Zn5 (OH)6 (CO3)2 + 14 OH- → 5 [Zn (OH)4]2-+ 2 (CO3)2-
Stage B: Dissolution of metallic zinc and zinc hydroxide layer formation

(electrochemical)
Equation 3.6: Zn + 4 OH- → [Zn (OH)4]2- + 2 e - Anodic reaction
Equation 3.7: O2 + 2 H2O + 4 e - → 4 (OH) - Cathodic reaction
In an aerated solution, both electrochemical reactions are possible. However, in the absence
of oxygen, the cathodic reaction is inhibited, so that only chemical dissolution is observed.
While the chemical reaction is
largely unaffected by process con-
ditions, Zn dissolution is also pro-
foundly influenced by aeration,
alkalinity, “age” of the cleaning
solution and kinetic effects. Bath
ageing thus can be interpreted
as the build-up of dissolved zinc
ions and carbon dioxide absorp-
tion from the air. The results are
illustrated in Figures 3.4 and 3.5.
On aluminium surfaces, similar

reactions take place. For this sub-
strate, an acidic rinse is recom-
Figure 3.3: Experimental set-up: electro-chemical quartz mended after alkaline cleaning,
micro-balance (ECQM). Source: [24] to remove compounds of alloying
W.E.: Working electrode; C.E.: Counter electrode elements that are otherwise inso-
Figure 3.4: ECQM simulation: dissolution of zinc surfaces in alkaline cleaner solution with increas
ing age. Source: [24]

Figure 3.5: ECQM simulation: dissolution of zinc surfaces in alkaline cleaner solution with different
aeration. Source: [24]
Equations
luble. As aluminium is amphoteric,
�� which means it is also dissolved in acids, acid cleaning
is common �o� �
(3.1)practice �
whenever Young’s
a low contamination level allows equation
(coil, can).
��
3.3.3.2 Ingredients of aqueous cleaners

(3.2)
3.3.3.2.1 2 OH
General
-
+ CO2 →(CO3 )2- + 2 H2 O
considerations Carbonation reaction
Major functions
(3.3) ZnO � OH � �cleaner
of an�aqueous H� O [25]→comprise �� ability to emulsify liquid contami-
�Zn�OH��its
nations, deflocculate solid soils and prevent their redeposition. These features are ruled by
� ��
Zn�OH�between
(3.4) tension
the interfacial � � � OHsolution and
→ �Zn�OH� ��
soil, thus directly depending on the wetting
power of the solution.
(3.5) Zn� �OH�� CO� �� OH � → � �Zn�OH�� CO� ��
In general, fats, oils and waxes can be saponified, and the soap that is generated acts as a
surfactant and emulsifier.
(3.6) Zn � � OH �Most industrial
→ �Zn�OH� ��
��cleaners
� � �� thereforeAnodic
are alkaline,
reactionin order to bring
on the required saponification reaction (cf. Equation 3.8). Strong alkaline cleaners often
contain (3.7)
caustic soda
O� �(sodium � �� → � �OH�
� H� O �hydroxide), in�case of liquidCathodic
productsreaction
also potassium hydro-
xide due to its higher solubility. To reduce the alkaline attack, carbonate may be present in
the formulation.
(3.8) H� C � O � �CO� � �CH� �� CH�
Equation 3.8: |
HC � O � �CO� � �CH� �� CH� � � OH � Triglyceride (fat)
| + Triglyceride
alkali (fat) + alkali
H� C � O � �CO� � �CH� �� CH�
H� C � OH
|
→ HC � OH � � H� C � �CH� �� CO�
� Glycerol
| Glycerol +(soap)
+ carboxylate carboxylate (soap)
H� C � OH
Especially when used for metal mixes, alkaline cleaners may also contain silicates which
display a high alkalinity themselves, however form a thin silica layer, once the bare metal
(3.9) � � ��r��u� ��ut�on� � �throughput� � ��r�g � out�
is exposed, thereby inhibiting excessive pickling reaction.

Figure 3.6: Schematic: removal of an oil droplet by surfactant action
For wrought and rolled alloyed aluminium (Mg, Mn containing alloys), alkaline cleaners
usually contain complexants to help solubilise these elements. However, an acid rinse is
often necessary to remove alkali-insoluble alloying elements and their oxides and hydro-
xides (e.g. MnO). In alkaline and acidic aqueous cleaner formulations, the task of dispersing
solid contaminants is frequently taken by builder ingredients, i.e. salts. To remove fat, oil,
and often entrapped solid contaminations from the metal surface, the aqueous products
also contain surface-active substances (surfactants). Table 3.3 summarises the common
ingredients of aqueous cleaners.
Table 3.3: Ingredients of industrial cleaners 3.3.3.2.2 Surfactants

Acidic cleaners Alkaline cleaners Neutral cleaners Surfactants act by virtue of their
Phosphoric acid, Alkali hydroxides Surfactants, amphiphilic nature, i.e. they
dihydrogen phos- solubilisers, assemble at the interface of non-
phate (Al also: inhibitors miscible phases, self-aligning
sulphuric acid) according to the polarity of the
Phosphates, two phases and to their own dipo-
carbonates lar character. They can displace
Fluorides, fluoro Silicates oily matter (and any solid that is
complexes entrapped in it) from a metal sur-
Surfactants, Surfactants, face. Figure 3.6 illustrates this
solubilisers solubilisers process.
Complexants, The amphiphilic character of sur-
sequestrants factants is caused by the mole-
Inhibitors cular structure, having a polar
moiety bonded to an unpolar,
often longer hydrocarbon chain. Depending on the type of polar functionality, surfac-
tants are classified as anionic, cationic or non-ionic. Figure 3.7 illustrates examples for
the three surfactant classes.
Important anionic surfactant groups are salts of fatty acids (soaps), sulphuric acid semi-
esters of long-chain fatty alcohols or alkyl benzene sulphonates. Historically, tetrapropylene
benzene sulphonate (TPBS) played a particularly dominant role as a widely used surfactant
in detergents. However, TPBS had to be replaced, as it was particularly poorly degradable
in the environment. Cationic species are e.g. quaternary alkyl group containing ammo-
nium bases. Typical representatives of the non-ionic classes are polyethoxylated alcohols
or esters.

Figure 3.7: Exemplary formulas of surfactants
A lot of interest has been focused on environmental effects of surfactants, since, being sur-
face active substances they interfere with biological reactions which may make them toxic
to aquatic species. In terms of waste water treatment in public sewage works, it is most
important that surfactants will not be harmful towards aerobic bacteria, and neither are
their metabolic successors that are formed by biodegradation reactions. According to OECD
Screening Test specification of 1976, a surfactant is considered to be biodegradable if its
concentration is reduced by at least 80 % during an incubation test with a small amount of
sewage sludge within 19 days or less [26]. This requirement is codified by European law, for
example the German Surfactant Directive (Tensidverordnung, version of June 1986) [27].
For domestic and industrial detergents, it is required for a surfactant to be even “readily bio-
degradable”. Since the OECD method involves detection of anionic and non-ionic surfactants
by their specific reactions with methylene blue or bismuth iodide, which may not be given
by metabolites, more stringent requirements consider the total chemical oxygen demand
(COD), as an appropriate indicator. Surfactants that pass the 60 % reduction level within 28
days are considered as “readily biodegradable” [28]. Other accepted tests are codified by EU
Directives and Regulations, like the Dissolved Organic Carbon Test (DOC), Closed Bottle
Test, or the Modified OECD Screening Test – DOC Analysis, and related ISO norms [29, 30].
By virtue of the surfactants features, the removed dirt particles are also reliably kept away
from the substrate surface. In immersion cleaners, these dirt particles are often distributed
homogeneously, i.e. emulsified in the diluent. On the contrary, in spray cleaners it is desira-
ble to displace liberated oil droplets as fast as possible from the aqueous phase, to allow their
removal from the system by skimming. Both – contradicting – tasks must be performed by
suitably chosen surfactant blends in case of combined spray-dip cleaners.
As further important tasks, the surfactant mix must effectively allow the adjustment of
the substrate surface wettability for subsequent pretreatment processes, and to control
foam formation in case of spray cleaners.
The chemistry of the non-ionic surfactant class is particularly well suited to match the tasks
described above. Molecules of such surfactants comprise an organic water-repellent part,
to which a polar, hydrophilic non-ionic group is affixed. This polar group is usually formed
by polyethylene oxide/polypropylene oxide chains of different length.
Any surfactant blend must match the physico-chemical features required for its intended
use. As a rule, foaming behaviour, emulsifying power, wetting and detergency of a surfac-
tant blend are laboratory tested in combination with the entire builder composition.

Finally, practical trialling is indispensable. Particularly with respect to their foaming cha-
racteristics, many factors that influence cleaning practice cannot be simulated by experiment.
This includes bath volumes, type and array of spray nozzles, deflector sheets, power data and
arrangement of pumps, as well as chemical parameters like water hardness, type and amount
of contamination on work pieces and other sources of drag-in to the cleaning bath.
3.3.4 Physics of aqueous cleaning, bath life and rinsing

The action of cleaners is substantially affected by the availability of sufficient amounts of
cleaner ingredients at any time, at the metal surface as the point of cleaning. As with any
chemical reaction taking place at an interface, the cleaning action is decelerated when there
is no relative motion between the work piece and the solution. The reaction becomes diffu-
sion controlled, i.e. the ingredients are only transported to the point of reaction by random
motion of molecules. At a given temperature, this means that the reaction speed cannot
exceed a maximum value that is specific to the substance.
Apart from heating, acceleration is only possible by inducing relative motion. Whilst with
spray cleaners, the spray jet impacting on the work piece brings on sufficient motion in the
reaction zone (therefore, in principle, spray cleaners can be used at lower concentrations),
with immersion cleaners, extra measures must be taken. Relative motion between work
piece and solution can be induced by moving treated items (rotating, oscillating or pitch
installations), or by bath agitation (stirring, convection, circulation, air or steam injection).
Typical conditions for spray cleaning are cleaner concentrations of 0.5 to 1 %, pressures of 1
to 2 bar and temperatures of 50 to 70 °C that are applied during a period of usually 5 to 60 s.
Following the cleaning stage, excess cleaner solution, soil and reaction products are remo-
ved from the metal surface in a multi-stage rinsing section. The rinse stages are operated
in a counter-flow cascade to achieve a most efficient use of water. The efficiency of the rinse
increases exponentially with the number of rinse baths. The final rinse is often fed with dei-
onised water (DI). A DI rinse is mandatory when a so-called no-rinse pretreatment is used
(cf. Chapter 8), to avoid high electrolyte concentration and contamination by unwanted,
potentially corrosive ions. Usually a maximum acceptable electrolyte concentration is
specified for the last rinse, given in units of electrical conductivity. Recommended values
range between 30 and 100 µS at room temperature. To minimise drag-out, the liquid film is
generally removed in between individual stages, the drip-off supported by blowers, squeeze
rollers etc., depending on the work piece geometry. For instance in coil operations, the
loss of liquid can be reduced to 2 to 5 ml/m2 with properly maintained squeeze rollers. In
immersion processes, drag-out can be reduced by hot water spray nozzles that are mounted
on both tank sides above the bath surface. It is particularly advantageous to operate those
nozzles by valve control, spraying each rack with fresh hot water when emerging from the
bath liquid.
However, a certain drag-out is often desirable to control the contamination level, and
extend the bath service life. Independently, each tank should be equipped with an overflow
sewer.
Increasing energy costs are also influential in cleaning as they are in other fields of the
metal finishing process. Changing the process to aqueous, alkaline low-temperature
cleaners is facilitated by use of optimised and increased surfactant contents, combined
with highly efficient dispersants. Thus, the working temperature can be reduced to 30 °C
under appropriate conditions. However, higher temperatures (50 to 60 °C) still apply when
highly viscous fats and oils, pastes, and aged, hardened soils must be removed. The clea-
ner must never dry upon a work piece, so that long transfer times must be avoided.

Table 3.4: Typical data for drag-out and required dilution (of initial concentration)
(a) Drag-out (b) Required dilution
Shape Drag-out (ml/m²) Process Dilution
Flat, single 100 Cleaning, hot 35 to 100
Flat, strip 10 electrolytic 100 to 200
Corrugated 200 Acidic rinse 100 to 200
Bowl-shaped 1000 Caustic pickle (Al) 500 to 1000
Galvanising 1000 to 100000a)
Pretreatment 2000 to 5000
a) High figures apply for environmentally critical elements like nickel and chromium
The increase of service life of a cleaner bath by overflow operation can be appreciated by
simple model calculations: The result of such a calculation is that a cleaner bath can achieve
substantially longer service life when, at a given set of equipment and operational condi-
Equations
tions, a part of the cleaner solution (overflow) is continually discarded and replenished. The
��
(3.1)
bath life becomes �o� � �when the overflow amount falls below
shorter Young’s equation level. The
the calculated
��
required overflow rate is dependent on the ratio between drag-in and the acceptable maxi-
mum concentration of the contaminant that reduces bath life. In practice, of course, several
contaminants(3.2)must 2beOH
considered
-
+ CO2 →(CO simultaneously.
2-
3 ) + 2 H2 O Carbonation reaction
The principle applies for any type Table 3.5: Rinse water ��
consumption
ZnO � � OH � � H� O
of process (3.3)
where residual drag- Required→rinse �Zn�OH��
water volume (l/h) per litre of initial
out material must be reduced by a �electrolyte drag-in ��
(3.4) Zn�OH�� OH → �Zn�OH��
rinsing operation. Tables 3.4 and Required dilution 10,000 5,000 1,000 200
3.5 show (3.5)
some considerations
Zn� �OH�� CO� �� Rinse OH � tanks
→ � �Zn�OH�� CO� ��
about expected drag-outs, as well
1 10,000 5,000 1,000 200
as required(3.6)dilution
Zn �ratios
� OH � for
→ �Zn�OH�� Anodic reaction
various work piece geometry and 2 100 71 32 14
treatment processes
(3.7) O[31]
� �. Operatio-
� H � O � � � �
→ � �OH�3 �
22 Cathodic17 reaction10 6
nal savings in a cleaning process 4 10 8 6 4
with an overflow system do not
5 6 5 4 3
(3.8)
only substantiate inH�lower � �CO� � �CH� �� CH�
C � O water
demand, but in reduced | down-
time otherwise necessaryHC � �CO�
� Ofor � �CH� �� dumping
discontinuous CH� � �and OH �make-up
Triglyceride (fat)
of the bath. Overflow
| + alkali
operation is therefore a mandatory measure when working with large bath volumes.
H� C � O � �CO� � �CH� �� CH�
The most efficient use of rinse water can be achieved when rinsing is performed via a
counter-flow bath cascade. This principle can be employed regardless of whether immer-
sion or spray technique His� Cused.
� OHWhen a number of similar bath tanks are connected in-
|
line through a pump or overflow system, and fresh water� is fed (preferably via a separate
→ HC � OH � � H� C � �CH� �� CO� Glycerol
spray riser) into the final tank,
|
the concentration of rinsed-off +substances (excess cleaner,
carboxylate (soap)
by-products, contaminants) is
H� C � OHreduced drastically from bath to bath along the line. The
last tank contains virtually fresh water. The fresh water demand is calculated according to
equation 3.9 [32].
Equation 3.9:(3.9) � � ��r��u� ��ut�on� � �throughput� � ��r�g � out�
where: N is the number of rinse tanks employed, the throughput is given in m2 surface area and drag-out
is given in l/m2
1
Figure 3.8: Schematic for a counterflow rinse cascade with additional filter system (efficiency 80 %) for
the reduction of contaminants from a circulated rinse bath; m0 = contaminant mass flow; v1-3 = drag-out
and overflow volumes; c1-3 = local instantaneous concentrations of contaminant in tanks 1 to 3
The required number of tanks depends on the ratio between the amount of substances
dragged in and the counter-flowing water volume (stationary state). A tank number of
three are considered state-of-the-art according to the European Reference Documents on
Best-available Techniques (BREF Standards) [33]. Table 3.5 also shows that the economic
gain with higher numbers of tanks is only small. After some time, the first rinse bath may
obtain a similar composition as the cleaner bath itself, and can be used to replenish the
working bath. Preferably, this first rinse water is continuously deoiled (by demulsification,
skimming, and ultra-filtration) and reused to replenish the main bath, together with an
appropriate builder/surfactant package. Figure 3.8 shows a schematic for a cascade and
bath maintenance layout.

3.4 Literature
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integrated pollution prevention and control (Codified version) (1), Official Journal of the European Union 51,
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compounds due to the use of organic solvents in certain activities and installations, Official Journal of the
European Union 42, 1999, L 85; eur-lex.europa.eu/…

[24] Androsch, F. M., Stellnberger, K.-H., Wolpers, M., Jandel, L., Drescher, D., Sander, J., Seidel, R., Chromate-
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[26] Karsa, D. R., Porter, M. R. (eds.), Biodegradability of surfactants, Blackie, Glasgow 1995, pp. 1946 ff
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on classification, labelling and packaging of substances and mixtures, amending and repealing Directives
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Min. Traffic, Innovation, Technology (ed.), Vienna 2003, pp. 48 ff;
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[32] Fresner [31] p. 54
[33] Bosse, K. (ed.), Entwurf des deutschen Beitrags zu den besten verfügbaren Techniken bei der Behandlung
metallischer und nichtmetallischer Oberflächen mit chemischen und elektrochemischen Verfahren. (Draft
… Best Available Techniques for the Treatment of Metallic … Surfaces with Chemical … Processes), AG
BREF Oberflächentechnik, Umweltbundesamt (Fed. Environment Agency), Berlin 2003, pp. 49 ff;
www.bvt.umweltbundesamt.de/archiv/oberflaechenbehandlungvonmetallen.pdf; (15-03-2010; 19:08)

Organic coating materials 37
4 Organic coating materials

Mircea Manea, Lars Kirmaier, Jörg Sander
Coatings are defined as liquid, paste or powder materials which enable transparent and/or
opaque coverings exhibiting decorative, protective and/or specific technical properties [1].
Paints may be divided in accordance with different principles (Table 4.1) [6–8].
A coating system selection must be in direct accordance with the specific technical, decora-
tive and functional requirement, as well as with specific application conditions, substrate,
and curing. All these requirements are convergent to achieve the target of an optimum
performance [4, 5].
All coatings have in common a range of properties which secure the functional performance
of the coating:
• Ready to use delivery form
• Easy and fairly quick manufacturing
• Good substrate wetting
• Good formation of a closed film
• Proper rheological behaviour
• Workability
• Good final mechanical and chemical properties
• Good storage stability, small degree of syneresis and sedimentation, redispersibility on
stirring
• Fast curing without chalking
• Sufficient diffusion into substrate for good adhesion and surface hardening
• Good and uniform colour retention on the substrate
• Good weather stability
• Low energy consumption
• Environmental compliance
Table 4.1: Coatings with different principles according to the specific technical, decorative and
functional requirement
Function Layer in Purpose Environmental Chemistry Curing
coating compatibility of the film conditions
system forming agent
clear coat primer car paint water borne alkyd paint baking
metallic paint surfacer decorative paint solvent borne acrylic paint oxidative curing
solid paint topcoat industrial paint radiation curing cellulose physical curing
derivatives
wood paint high solids polyurethane radiation curing
powder paint urethane curing

ISBN 978-3-86630-805-3

4.1 Ingredients of organic coating materials

An organic coating is a disperse system comprising a range of materials specifically
chosen to accomplish a certain role in the manufacturing or application process or in the
service of the final product.
An organic coating is a system comprising organic film formers, solvents (in case of liquid
coatings), pigments, fillers and a range of additives.
4.2 Resins
An organic coating must indispensably contain a film forming agent which is capable to
solidify as a result of physical and/or chemical processes. A film forming agent is an oligo-
meric up to a polymeric compound which controls most of the properties and performance
of the coating:
• hardness
• strength
• adhesion
• elongation
• chemical properties
• outdoor resistance, etc.
The word polymer derives from πολυ (“poly”=many) and μéρος (“meros”=part), and defines
a substance built from many molecules, having a large molecular mass. The name polymer
has been introduced by Berzelius in 1833. The repeating parts are structural units (mono-
mers) bound together by chemical covalent bonds.
Pioneering work on cellulose derivatives by Braconnot and later, the modification of natural
rubber brought polymers into daily industrial life. The first synthetic polymer “Bakelite”
was reported by Baekeland in 1907 and the work by Carothers and Staudinger in the 1920s
made significant inroads in rational synthesis of polymers and helped the understanding of
polymer chemistry.
Polymers use different types of monomers or combinations thereof to generate specific
families used in the coating industry and related industries. Referring to polymers, four
different terms are commonly used in the coating industry:
• Resin as defining any kind of polymeric material in its original state.
• Binder as defining the polymer in a paint composition capable of binding by dispersed
pigment/filler materials.
• Vehicle as defining the property of the polymeric material to carry the pigments in
dispersion by a subsequent multistage manufacturing process.
• Organic film former as the polymer is capable to form a closed solid film which is the
backbone of the organic coating.
The term of organic film former is more suitable for the concept of anticorrosion coa-
tings. The meaning is directly referring to the capability of a polymeric coating applied to
metallic substrates to provide a barrier against corrosive species. The polymeric film is not
purely impermeable and due to exterior factors the polymer will decay in time (as further
explained by humidity and UV irradiation) but also due to defects or mechanical damage.
Pigments having lamellar or plate like shapes, provide further stability and protection by
• increased length of the diffusion path for the corrosive species and

Resins 39
• decreased permeability of the organic coating when an orientation of pigments in the

coating parallel to the surface is achieved.
A requirement is that the pigments involved in the coating formulation exhibit a high com-
patibility with the polymer matrix, for example by forming anticorrosive complexes with
the binder.
The choice of binders in anti corrosive formulations is mainly related to the hydrophobic pro-
perties of the binders but also to their light stability. The hydrophobic properties of a binder
are related to the capability of the organic film to repel humidity. Under UV irradiation the
organic film may undergo changes which will yield a hydrophilic surface. Recent studies
explain the behaviour of a superhydrophobic surface to become superhydrophylic by UV
irradiation and back to superhydrophobic by heating [59].
These organic film formers are either natural substances and/or modified natural
substances or intentionally produced by industrial synthesis processes.
The organic film formers derived from natural substances apparently lost some of their
importance. They still are out in the market and their technical relevance is now mostly
related to the concepts of “renewable raw materials” and “neutral carbon balance”.
The organic film formers may be grouped in two categories:
• Higher and high molecular weight polymers which undergo no further chemical reac-
tion in the film forming process but form organic films by physical drying, eventually
releasing solvent emissions
• Low and lower molecular weight polymers which purposely are designed having a
certain chemical functionality and are capable of forming organic films by a chemical
reaction initiated by light, heat, catalyst, etc.
The liquid organic film formers are produced and supplied in a solvent or solvent blends
but the latter group of polymers generally requires less solvent. However the addition and
selection of solvents is made according to the application processing conditions, in order to
achieve a trouble-free film forming process.
4.2.1 Alkyd resins

Alkyds are B-stage polymers that exhibit by far lower molecular weight compared to
thermoplastic polymers. This feature, however, is compensated by the presence of func-
tional groups (such as double bonds, hydroxyl groups, and carboxylic groups) to a large
extent. Alkyd resins have been regarded as backbones containing ester bonds and having
a modification with a fatty acid.
The etymology of the word alkyd is derived from AL-cohol and a-CID later changed to
ALKYD. For the first time alkyds were mentioned in 1929 in the Chemical Abstracts under
the chapter “Resins”. Although a very strong and well established market segment, the
alkyd resin business has been revived due to the interest in new drying chemistry and envi-
ronmental concerns, targeting high solids and waterborne products [16–19]. To a large extent,
alkyd resins are considered as being renewable raw materials in the coating industry due
to their large content of natural oils and polyols.
Alkyd resins undoubtedly represent a large segment in the coating market due to some
reasons listed below:
• well known technologybroad application range
• one-component application

• broard application range

• good price-quality
• large content of renewable raw materials
• long shelf life
• high build per application
• adhesion for multiple substrates
• predictable drying times
• acceptable odour
• less surface preparation
• independence with respect to humidity
Alkyd resins may be categorised according to the oil length as follows:
• very long oil alkyds (oil content higher than 70 %)
• long oil alkyds (oil content higher than 55 %)
• medium long oil alkyds (oil content of 45 to 55 %)
• short oil alkyds (oil content of less than 45 %)
Further classification of alkyd resins is related to the film forming mechanism:
• air drying alkyds
• non-air-drying alkyds
• oven drying alkyds
Alkyds may be modified in order to improve certain properties, like the hydrophobic beha-
viour and the light fastness, as previously discussed. Modifications done on an alkyd binder
backbone are meant to increase water repellency, improve UV resistance by consuming
the double bonds of the oil by vinylation or by cyclisation through different processes. The
stabilisation of the backbone of the alkyd binder may be done by hydrolytically stable phenol
modification or by introduction of silicone moieties.
A classification according to the chemical modification may be considered as:
• vinylated alkyd resins (modified with acrylic monomers employing unsaturation of
the fatty acid)
• phenol modified alkyd resins (modified with phenol-formaldehyde resins employing
unsaturation of the fatty acid)
• urethane modified alkyd resins (modified with urethanes when isocyanates are
employed as difunctional building blocks replacing a diacid)
• silicone modified alkyd resins (modified with siloxanes when siloxanes are employed
as functional building blocks in a transesterification reaction)
• maleic anhydride modified alkyd resins (modified with maleic anhydride employing
unsaturation of the fatty acids by a Diels-Alder reaction)
Properties of the alkyd resins are strongly related to the composition of raw materials,
achieved molecular weight and molecular weight distribution. Other preliminary reactions
of double bonds, e.g. etherification, dehydration and undesired cyclisation through hydroxyl
and carboxyl groups, affect the final properties of the polymer.
An alkyd may be schematically represented by the following formula. The alkyd resin is a
condensation product which is the result of the reaction between functional groups [20, 21]:
a-A-a + b-B-b → a-A-B-b +a-b
In most cases the reactive group a is a carboxyl group and the reactive group b is a hydro-
xyl group in which case the condensation product a-b is water, but some alkyd binders are
urethane modified and in the respective case the a group is an isocyanate group.

Resins 41
The alkyd resins may be considered as polyesters modified by natural oil. The final proper-
ties of the alkyds are a result of the quality and property of the raw materials involved in
the manufacturing process.
The choice of raw materials for alkyd formulation is made with respect to the target
application and final parameters of the alkyd:
• solubility
• viscosity
• drying properties
• compatibility
• coating hardness
• acid number and hydroxyl functionality
• water resistance
• chemical resistance
• choice of ingredients
• commercial production and cost
• availability
• environmental issues
• hazards to health
• hazards to the environment
• processing
• issues imposed by equipment
Hence, the wide latitude of formulations and choices of raw materials, apart from oils, com-
prises polyols, polyacids and hydroxylated acids (mixed functionality). A range of modified
polyols is also available aiming to improve the drying properties of the binders.
4.2.1.1 Alkyd resins manufacturing process

Alkyd resins manufacturing processes are summarised as follows (see Table 4.2):
4.2.1.2 Decay of alkyd resins

The decay of alkyd resins may occur in the polyester backbone by two different mechanisms
but also in the pendent fatty acids chains:
Table 4.2: Manufacturing processes of alkyd resins

Alcoholysis process Fatty acid process Fatty acid/oil process Acidolysis process
two step process one step process one step process two step process
cost and availability of oil no alcoholysis step oil is integrated in the high melting dibasic acids
recommend the process in alkyd synthesis polymer by interchange like isophthalic acid and
esterification (oil at terephthalic acid are used
most 1/3 of total furnish
of fatty acids)
distinct phase in alkyd distinct phase in alkyd
synthesis. Polyacid is synthesis. Polyol is added
added in a second stage in the second stage
reaction between oil and alkyd results in a higher viscosity pro- reaction between oil and
polyol results in redistri- more linear back- ducts due to seedy po- polyacid results in redistri-
buted fatty acid bone lycondensates between buted fatty acid
polyol and polyacids

Figure 4.1: Hydrolytical decay of the polyester backbone
Figure 4.2: Light induced decay of the polyester backbone
• hydrolytical decay of the polyester backbone

• UV initiated decay
• Decay in the pendent fatty acid chain (indoor yellowing of alkyd resins) [4]
4.2.1.3 Composition of alkyd resins

• To a large extent natural oils are the working horses in the alkyd resin composition. The
oil importance is increasing as a result of the impact on the alkyd resin performance and
as well due to the fact that the natural oils are renewable sources of raw materials [21].
• The backbone of the alkyd resin is a result of condensation of polyols and polyacids. In
most cases the backbone is hydroxyl functional, in which case the fatty acid is pendent
on the backbone through an esterification reaction on the exceeding hydroxyl groups.

Resins 43
Figure 4.3: Indoor decay of the pendent fatty acids
It is obvious that alkyds are more stable when using polyols that have no α-hydrogen in
relation to the carbinol group.
 Polyols used in alkyd synthesis may be di-, tri-, tetra-and hexa-hydroxyl functional. In
general the acids used are mono-, di- and sometimes tri-carboxyl functional.
– difunctional alcohols
– trifunctional alcohols
– tetrafunctional alcohols
– hexafunctional alcohols
 Polyacids employed in alkyd manufacturing are given in the following.
Monofunctional acids are used to limit the molecular weight growth or to improve hardness
or other properties. Largely used are: rosin, benzoic acid, t-butyl benzoic acid.
4.2.1.4 Curing of alkyd resins

The fatty acids play an important role in the air drying process, for which the unsaturation
degree and the conjugation of the double bonds on the fatty acid determin the drying speed
[23]
.
• oxidative drying of alkyd resins is described in Figure 4.4
The process continues by a radical polymerisation mechanism employing the autoxidation
of formed radicals and the double bonds of the fatty acids.
• curing of alkyds by condensation
Other drying mechanisms for alkyd resins involve the alkyd resin functionality, hydroxyl
or carboxyl. The mostly employed cross-linking of alkyd resins, if not air drying systems,
uses the hydroxyl functionality in reaction with amino resins, or isocyanates.

Figure 4.4 Oxidative drying of alkyd resins
Figure 4.5: Thermosetting curing of alkyd resins
4.2.2 Chlorinated rubber

Nature is capable of the synthesis of cyclic terpenes. Some plants also join isoprene in a 1,4
polymerisation forming polyisoprene.
Hevea Brasiliensis produces 1,4-cis-polyisoprene which is harvested from the notches cut
in the three. Other natural rubbers in which 1,4-trans-polyisoprene is present, known as
gutta-percha or balata have achieved less technical importance [24–26].
In coatings natural rubber is submitted to chemical modifications to achieve the properties
required for a film forming polymer. The chemical modification of rubber aims to improve

Resins 45
Figure 4.6: Natural rubber
Figure 4.7: Gutta-percha
certain properties such as resistance to oxygen and light. The approach to improve the
oxidation and light stability of the hydrocarbon backbone of the rubber, otherwise hydro-
lytically stable, is to consume the double bonds by addition of halogens or intramolecular
cyclisation, thus conferring enhanced anticorrosion properties of the polymer which by said
modifications offers less attack points in the backbone.
In the presence of catalysts the process is intended to reduce the number of double bonds
by almost 80 %. The process yields the so-called cyclorubber. Cyclorubber has improved
solvent solubility, a reduced number of double bonds and a reduced molecular weight,
along with an increased melting
point of 130 to 140 °C and solu-
bility in aliphatic and aromatic
hydrocarbons. The compatibility
with other film forming polymers
such as alkyds, drying oils, bitu-
minous materials is also impro-
ved. The chemical resistance and
thermal properties are excellent,
as well as a good acceptance for
basic pigments due to the absence
of acidic groups is obtained.
Another approach of using rub-
ber in the coating industry is the
chlorination of the polymer. In a Figure 4.8: Cyclic rubber

Figure 4.9: Chlorinated rubber
synchronous reaction the chlorine is attached to the double bonds followed by dehydrochlo-
rination and addition of chlorine to the newly formed double bonds, see Figure 4.9.
The reaction is of radical type and may be thermally or UV initiated. However, the chlo-
rinated rubber exhibits limited light and heat resistance, undergoing degradation in which
chlorine is released via the same mechanism as explained for polyvinyl chloride.
4.2.3 Polyvinyl chloride

Polyvinyl chloride is the third most polymer produced in the world. The manufacture of polyvi-
nyl chloride largely uses the suspension polymerisation process starting from vinyl chloride.
Polyvinyl chloride obtained in this
way contains 56.7 % of chlorine
and has very poor solubility [24–26].
Improved solubility is achieved
by copolymerisation with other
monomers such as vinyl acetate,
but the most significant employ-
ment of polyvinyl chloride in coa-
tings is as a post chlorinated mate-
rial. The process is performed by
radical chlorination in thermal or
UV conditions to yield a polymer
containing up to 65 % chlorine.
Also, polymers containing up to
Figure 4.10: Copolymer poly(vinyl chloride-co-vinyl acetate) 74 % chlorine are reported, but the

Resins 47
Figure 4.11: Degradation of poly(vinyl chloride)
polymer becomes unstable at a content of about 70 %. The coating industry generally uses
polymers with a chlorine content of 65 % to yield coatings by physical drying for heavy duty
applications exhibiting good water, solvent and fuel, and chemical resistance.
Polyvinyl chloride exhibits good anticorrosion properties; good hydrolytical and chemical
stability, but the main drawback of the polymer is the poor light and heat resistance. There-
fore the formulations always contain a range of stabilisers to overcome the problem.
Polyvinyl copolymers are employed in formulations targeting high adhesion coatings on
hot galvanised substrates and aluminium, road marking paint, primers and high build
anticorrosive paints.
4.2.4 Epoxy resins

Epoxy resins are generally defined as containing a three-mem-
bered functional group named epoxy, epoxide, or oxirane [27–29].
Epoxy polymers present extremely good barrier properties,
good substrate adhesion and very good mechanical proper-
ties. Several factors may be used to achieve different proper-
ties, basically derived from the functionality of the epoxy Figure 4.12: Epoxy group
Figure 4.13: Epoxy resin

Figure 4.14 Williamson etherification reaction
Figure 4.15: Advancement process reaction
binder. The molecular weight of the epoxy resin controls the cross-linking density, hardness
and flexibility and resistance to chemicals. Although epoxy resins present a weakness by
their poor light stability, generally exhibiting strong chalking, discolouration, loss of gloss
and colour, these degradations mainly take place in the surface of the film, leaving the
protective properties of the coatings unaffected.
4.2.4.1 Raw materials for epoxy resins

Commercial epoxy resins contain aromatic, aliphatic or cycloaliphatic backbones derived
from OH functional substrates. The OH functional substrate is submitted to an etherifica-
tion reaction with epichlorohydrine in the presence of stoichiometric quantities of sodium
hydroxide. Among the aromatic glycidylated substrates, the most interesting are 4,4-methy-
lenediphenol, 4,4’-(propane-2,2-diyl) diphenol, 4,4’-sulfonyldiphenol, 4,4’-(propane-2,2-diyl)
bis-(2,6-dibromophenol), phenol and resorcinol.
Some of the aliphatic substrates used for glycidylation are butan-1-ol, 2,2-dimethylpropane-
1,3-diol, (tetrahydrofuran-2,5-diyl)dimethanol and 3,3’-(1,1,3,3-tetramethyldisiloxane-1,3-
diyl) bis-(propan-1-ol).
The wide majority of the epoxy resins are diglycidyl ether of bisphenol A (DGEBA) also
known as bisphenol A diglycidyl ether (BADGE).
The choice of the backbone and the condensation degree in the backbone offer a wide lati-
tude of formulations resulting in a wide range of reactivity and applications.
4.2.4.2 Manufacturing process for epoxy resins

Epoxy resins are produced by direct condensation reaction between components, epichlo-
rohydrine and hydroxyl functional substrate in the presence of basic catalyst at different
equivalent ratios epichlorohydrine/hydroxyl (Williamson reaction).

Resins 49
Figure 4.16: Reaction of epoxy group with amines
Figure 4.17: Reaction of epoxy group with carboxylic groups
Modern processes (advancement processes) for higher molecular weight epoxy resins
involve as starter a low molecular epoxy resin further reacted with a di-hydroxyl functional
substrate.
The relation between functionality and molecular weight for bisphenol A diglycidyl ethers
is given in Table 4.3.
The amount of bisphenol A necessary to target a certain epoxy index Ef for 1000 parts by
weight epoxy resin of initial epoxy index Ei is calculated with the formula:
Bisphenol A = 1000 (Ei - Ef )

8.7 + Ef
Ei refers to the epoxy value of the liquid resin expressed in equivalents per 1000 g using
a charge of 1000 g of resin; and Ef refers to the final epoxy value of the desired solid resin
product.
Table 4.3: Epoxy resins commercial range (BADGE)

Softening point Average n value Molecular weight Epoxy index (equivalent epoxy/100 g)
(orientative values)
9 ºC 0.10 400 0.50 to 0.52
64 to 75 ºC 2.20 850 to 1000 0.18 to 0.22
90 to 105 ºC 5.50 1800 to 2000 0.10 to 0.12
124 to 135 ºC 12 to 14 3600 to 5000 0.05 to 0.55
135 to 145 ºC 15 to 16 5000 to 8000 0.04 to 0.45

Figure 4.18: Reaction of epoxy group with carbonyl derivatives (1), acetals (2), water (3),
carbon dioxide (4), isocyanates (5), halogenated derivatives (6)
Gel permeation chromatography shows that the condensation process from epichlorohy-
drine and bisphenol A in the presence of stoichiometric quantities of sodium hydroxide
yields a number of repeating moieties of 0, 1, 2, 3, etc., while the advancement process yields
only even numbers of repeating moieties.
4.2.4.3 Cross-linking of the epoxy resins

The epoxy group has a very high reactivity being capable to react with almost any kind of
functional group [30–35]. The epoxy group is capable of self polymerisation in acid or basic
catalysis. However the most important cross-linking reactions are the reaction with amines
and the reactions with anhydrides and acids.

Resins 51
Figure 4.19: Epoxidised oil
Other reactions of the glycidyl group:

An important group of epoxy binders are constituted by the epoxidated oils. Vegetable oils
containing double bonds are submitted to partial oxidation to yield epoxy groups. The epoxi-
dated oils find a broad range of applications from covering plasticisers, halogen scavengers,
or cross-linkers in reaction with carboxyl functional esters in high solids applications.
4.2.5 Epoxy esters

Epoxy resins like bisphenol A diglycidyl ether present the advantage that the backbone as
such is an aromatic polyether having pendent hydroxyl groups [4, 5]. The backbone may be
used as a polyol in formulation of ester resins accordingly named epoxy esters. Thus, the
epoxy esters show a similarity to alkyd resins using a polyol of moderate molecular weight
(800 to 1500) represented by an aromatic polyether. Due to the polyepoxy backbone, epoxy
esters exhibit better chemical resistance and mechanical properties than alkyds. In terms
of properties, epoxy esters may be assimilated to medium oil length alkyds, but exhibiting
higher anticorrosion properties. Due to the polyepoxy backbone they present the same draw
backs as epoxy resins, i.e. chalking and yellowing, but as primers in a coating system they
exhibit outstanding properties.
This group of resins imparts a range of properties from both backbone and the modification
with fatty acids. They exhibit good toughness, flexibility, chemical resistance, durability
and adhesion. The resins are easy to formulate, have good air drying or oven drying fea-
tures and find a wide range of applications in automotive industry, heavy-duty, hardware
and metal decorative and UV curing. The coatings using these resins may be applied by all
methods and are very versatile in curing conditions.
The content of fatty acids in the binder formulation allows a similar classification as in the
case of alkyd resins:
Considering 1 equivalent of epoxy resin as in the Table 4.4, the epoxy esters may be:
• short oil using 0.3 to 0.5 equivalents of fatty acids (30 to 40 % oil length)
• medium oil using 0.5 to 0.7 equivalents of fatty acids (40 to 50 % oil length)
• long oil using 0.7 to 0.9 equivalents of fatty acids (50 to 60 % oil length)
Table 4.4: Esterification equivalent for commercial epoxy resins (BADGE)

Epoxy equivalent weight, Theoretical esterification equivalent Softening point, [°C]
[equivalent/g] weight, [equivalent/g]
186 to 192 91 liquid
475 to 700 160 to 175 65 to 78
730 to 975 188 to 198 88 to 105
1600 to 2000 233 115 to 130

Predicted properties for epoxy

esters are as follows depending on
the ratio of epoxy to fatty acids:
The choice of the fatty acid is impor-
tant for the application area:
• linseed oil fatty acids for fast air
drying, flexibility and durability
• dehydrated castor oil fatty acids
for colour retention and chemical
resistance
• safflower oil fatty acids for
colour retention and fast drying
• soybean oil fatty acids for flexi-
bility, chemical resistance
• tall oil fatty acids for fair pro-
perties and low cost
• coconut oil fatty acids for
Figure 4.20: Impact of esterification degree on properties backing and good colour and che-
mical resistance
Modification of epoxy esters has the purpose to improve certain parameters of the binder
and finally the coating. Dimeric fatty acids improve flexibility and water resistance. Rosin
improves hardness and pigment dispersion, benzoic acid improves hardness and mar resi-
stance, adipic acid improves flexibility.
Figure 4.21: Modification of epoxy esters for water transfer

Resins 53
Figure 4.22: Biosynthesis of acrylic acid
Further modification of epoxy esters may be by grafting the fatty acids with vinyl monomers
such as styrene, acrylates or methacrylate by the same procedure as in the case of vinylated
alkyds.
In most cases the manufacturing process involves catalysts such as sodium bicarbonate,
zirconium octoate, or other salts of zinc, calcium or lithium. The process sets in contact the
epoxy resin with the fatty acids at increasing temperature up to 240 to 260 °C. The epoxy
resin is loaded in small portions or as solution in an appropriate solvent which is later remo-
ved, aiming to avoid lumps which deteriorate the quality of the resin and as well make the
filtration process very difficult.
In some cases the epoxy resins may be produced in-situ, prior to the esterification pro-
cess. Bisphenol A glycidyl ether of higher molecular weight is produced by the advance-
ment process starting with a monomeric epoxy resin of equivalent weight of about 0.5
equivalents/100 g to which bisphenol A is added in the presence of a basic catalyst.
The drying process of epoxy esters is similar to that presented for the alkyds. Oven curing
with amino resins improves certain properties and applies to short oil epoxy esters while
the long oil type cures in the presence of metallic drying agents like alkyd type binders.
An important application of epoxy esters relates to electrodeposition. The anodic electrode-
position is presently used in the appliances coating process. The epoxy esters produced for
electrodeposition contain carboxylic groups which are neutralised by amines.
The carboxyl functionalisation of an epoxy ester is generally performed by a Diels-Alder
reaction between the pendent fatty acids and maleic anhydride. Further modification is
performed by opening the ring of the anhydride.
4.2.6 Acrylic resins

Acrylic resins are polymers emerging from acrylic acid or methacrylic acid derivatives.
Generally water clear and exhibiting a great ageing stability, acrylic resins present a great
latitude of formulation due to the versatility of acrylic blocks and their capability of copoly-
merising with other monomers, such as vinyl acetate, styrene, etc [36–44].
Acrylic acid has been first synthesised in 1843. Presently the production of acrylic resins
is estimated to exceed 1 million tonnes per year. Today along with the petrochemical path
to acrylic monomers, bioacrylic monomers are reported from lactic acid and 3-hydroxy
propanoic acid
The nature of the alcohol generating the acrylic ester, as well as the molecular weight of
the polymer strongly influence the physical properties of the acrylic resins. Generally, the
properties only slightly improve for molecular weights above 100,000 or 200,000.

Figure 4.23: Functional acrylates
An important parameter for acrylic resins is the glass transiotion temperature (Tg). Bellow
the Tg, the polymer chains have a fixed position and configuration, while above the Tg, the
polymer backbone has enough energy for rotational motion and torsion oscillations. All
properties such as chemical reactivity, mechanical properties, refractive index, etc. differ
markedly below and above the glass transition region. The Tg of a copolymer may be esti-
mated by the following equation:
where Wi is the weight fraction of component i having the respective Tgi.

Elasticity increase of acrylic polymers may be done by increasing the ratio of ethyl, 2-ethyl-
hexyl or dodecyl acrylate or methacrylate, while the abrasion resistance may be improved
by a small ratio of (<1.5 %) of itaconic acid. The use of methacrylic acid esters helps to adjust
the melting point of the resin as well as viscosity, gloss, and hardness.
4.2.6.1 Manufacturing of acrylic resins

The manufacturing of acrylic resins is performed by radical polymerisation in solution
or emulsion. Sometimes a preferred supply form may be a non-aqueous dispersion. The
catalysts for the polymerisation process are generally peroxides, selected according to the
synthesis temperature, generally not higher than 150 °C.
For solution polymerisation, the choice of solvent is of importance as it may contribute to
chain transfer reactions, reducing the molecular weight of the final binder. The control of
molecular weight is generally performed by the choice of process temperature, amount of
initiator, use of selected solvent and chain transfer agents such as mercaptanes.
In case the acrylic resin is introduced as an emulsion, the polymerisation process is perfor-
med in water in presence of emulsifying agents which secure monomer droplet formation
and polymer stabilisation. Additional initiators are present like red-ox systems or water
soluble peroxides such as potassium persulphate.
4.2.6.2 Thermoplastic and thermosetting acrylic resins

Acrylic resins present very good outdoor stability, especially when the quantity of aromatic
monomer is zero or very low. They present very good gloss retention and colour retention.
Acrylic resins are build on acrylates and methacrylates from saturated alcohols, styrene
and vinyl toluene. In this case acrylic resins are thermoplastic. The film formation process
is based on solvent release at room temperature or forced drying. They may be used as

Resins 55
Figure 4.24: Curing of acetal and oxazoline functionalised acrylic polymers
such or in combination with other resins such as alkyds, nitrocellulose, etc. Thermoplastic
acrylic resins are presented as organic solvent solutions, non-aqueous dispersions or as
water borne emulsions.
Thermosetting acrylic resins are build on the same range of acrylic monomers as thermo-
plastic resins, which control solvent choice, compatibility with other polymers, Tg, viscosity,
etc., but to a certain extent, some acrylic monomers are functional or contain a precursor
bearing a functionality. These functional groups may cover a wide range of cross-linking
reactions providing the coating with the necessary chemical resistance [45, 46].
Hydroxyl functional acrylic resins may cross-link with other
functional binders containing reactive groups prone to react
with hydroxyl groups: etherified methylol groups, such as
amino resins, glycidyl groups, isocyanates, etc.
Other functional acrylic resins may contain reactive groups
as precursors such as cyclic carbonate (Figure 4.33), acetal
groups or oxazoline groups. Figure 4.25: Urethane bond
4.2.7 Polyurethanes
Synthetic resins containing a repeatable group as shown in Figure 4.25 are named polyuretha-
nes. Polyurethanes are reaction products of isocyanate derivatives which are homologues from
the isocyanic acid, in which different hosts (R) are connected to the functional group [47, 48].
The key benefits presented by polyurethanes making them strongly recommendable for the
paint and coating industry are:

• good abrasion resistance

• good chemical resistance
• good adhesion
• good solvent resistance
• good mechanical properties
• good low-temperature impact strength
• good blocking resistance
• excellent film forming properties
• low migration of plasticiser
• high-gloss “wet look”
Figure 4.26: Isocyanate resonance
The special properties of the isocyanate reaction may be summarised as follows:

• one polymer forming chemical reaction
• randomly reacting functional groups
• monomers disappear early in the polymerisation chain
• molecular weight rises slowly and is high at high conversion degree
• molecular weight distribution is very broad until the very end of the reaction when all
oligomers have reacted
• precise stoichiometric ratio is required
• high-purity monomers and solvents are required
Figure 4.27: Isocyanate cyclo-addition reaction

Resins 57
Figure 4.28: Isocyanate dimmers
4.2.7.1 Reactivity of isocyanate group

Isocyanates are highly reactive and undergo addition reactions with a wide range of organic com-
pounds across the double bond of C=N. The cycloaddition of the C=N group to C=O group is also
a possible reaction leading to new product development. The driver of the addition reaction is the
low electron density at the C atom in the functional group. The reactivity of the isocyanate group
is strongly influenced by the host and its electron withdrawing or donating capability [48].
Isocyanates give insertion reactions
• with an acidic C-H group from a 1,3-dicarbonyl derivative generally yielding a carboxya-
mide at room temperature. Higher temperature favours cyclic compounds.
• with electron rich C=C and C=N double bonds, when the isocyanate group attacks the
double bond.
• with a C-O group:
Isocyanates give cycloaddition reactions. These reactions have been deeply explored.
They lead to heterocycles, offering a wide industrial application. Substrates having dou-
ble bonds such as C=C, C=O, C=S, C=N yield a variety of compounds, see Figure 4.27.
The isocyanate group may polymerise to dimers and trimers which are the forms mostly
used in the coating industry as cross-linkers.
Catalysts generally involved in the isocyanate group polymerisation are: 2,4,6-tris-
([dimethylamino]methyl)phenyl or 1,3,5-tris-(2-[dimethylamino]ethyl) pyrimidine-2,4,6-
(1H,3H,5H)-trione.
Isocyanates react with different functionalities in cross-linking reactions yielding different
polymeric networks or new reactive substrates:

Figure 4.29: Isocyanate cross-linking reactions
Macro-polyols are extensively used, that have a different nature depending on the main
backbone. The mostly used types are polyether, polyester and polyacrylic. Depending on
the targeted application area, these polyols may cross-link with aliphatic or aromatic poly-
isocyanates. For higher temperature, blocked isocyanates are used and the coating is one-
component. The cross-linking temperature is higher than the deblocking temperature. In
any case catalysts are used to ensure the complete cross-linking. The isocyanate reaction
with macropolyols is a stoichiometric reaction and therefore the ratio between components
is chosen to be 1:1, or with a little excess of the isocyanate component.
Further it must be observed that the hydrogen bond between the polyurethane chains and
the very important urea groups that are present to a certain extent-, in but small quantities,
give strength to the polyurethane. In this respect the polymeric chain may be considered
as constituted from soft and hard segments.
The isocyanate reactions are almost always assisted by catalysts. In general, metal catalysts
are used, but recent banning of tin catalysts brought into attention a new range of materials.
Metal catalysts such as Zn, Zr are used, but amine catalysts are also quoted: N,N-dimethyl-
cyclohexyl amine, 2,2’-oxy-bis-(N,N-dimethylethane amine)
4.2.7.2 Waterborne polyurethanes

The transfer to water of a polyurethane system may be done by using a hydrophilic mono-
mer, anionic, cationic, non-ionic, as a building block in the polymer backbone or as pendent
group in a polyisocyanate which thus becomes water dispersible.
Two-component waterborne isocyanate systems comprise a hydroxyl functional polymer
which is waterborne and by nature may be polyester polyol, acrylic polyol, polyurethane
polyol, and the hardener which is at least a diisocyanate having a hydrophilic group in order
to be water dispersible.

Resins 59
Figure 4.30: Hydrophilic monomer for polyurethane water transfer (anionic)
The new group of polyurethanes presented as

dispersions in water is generally known as
PUD (polyurethane dispersions) and combines
the benefits of polyurethane coatings with a
one-pack water borne system, virtually solvent
free.
The hydrophilic moieties of
Figure 4.31: Hydrophilic monomer for
• anionic,
polyurethane water transfer (cationic)
• cationic,
• non-ionic type
are incorporated as building blocks in the poly-
mer chain in order to enable the dispersion of
the polymer in water.
4.2.7.3 Isocyanate free polyurethanes

Following the concern of health hazards posed
by the contact with polyisocyanates, a market
request has been noted as the necessity to Figure 4.32: Hydrophilic monomer for
polyurethane water transfer (non-ionic)
produce NCO-free polyurethanes. The so far
Figure 4.33: Isocyanate-free polyurethane

Figure 4.34: Polyaspartic acid
marketed approaches are building on the reaction between a polymer backbone which is
functionalised with
• cyclic carbonate groups and a polymer backbone which is amino functional
• oxaozoline groups and a polymer backbone which is carboxyl functional (Figure 4.24).
Six membered cyclocarbonates are by far more reactive but also more difficult to produce [49, 51].
4.2.8 Polyaspartics
Polyaspartic acid offers a new technology with a broad application range. Polyaspartic acid as
a biodegradable alternative to polyacrylates has been employed successfully as dispersant,
antiscalant and superabsorber. The
advantage of polyaspartic acid is
the synthesis from L-aspartic acid,
a natural amino acid, and as well
the biodegradation into benign
products such as carbon dioxide
and water. The course of synthesis
is shown in Figure 4.34.
However in the coating industry,
the significance of polyaspartics
is different. The concept relates to
the reaction of a polyisocyanate
with a polyaspartic ester which
is an aliphatic diamine [53, 54, 55].
Figure 4.35: Positioning polyurethanes, polyurea and The technology has been prima-
polyaspartics rily employed in solventborne

Resins 61
Figure 4.36: Reaction of the reactive solvent in polyureas
coatings, two-component polyurethanes, where the polyaspartic ester was employed as a

reactive diluent to yield high solids polyurethane coatings. Recent developments are able
to yield formulations with virtually zero VOC, in which the polyaspartic ester is the main
component.
The polyaspartic coatings are characterised by
• increased speed of cure
• increased film build
• good weatherability
• excellent corrosion and chemical resistance
For a better understanding the isocyanate reaction may be summarised as follows:
• Polyurethane: the result of the reaction between an isocyanate and a hydroxyl functional
component
• Polyurea: the result of the reaction between an isocyanate and a polyether amine
• Polyaspartics: the result of the reaction between an isocyanate and an aspartic ester
The chemistries may be combined to match a range of application conditions and requi-
rements. In the polyurethane landscape the name of hybrid generally refers to the com-
bination between a hydroxyl functional prepolymer and an aspartic ester cured with an
isocyanate.
4.2.8.1 Polyurea systems

Polyurea systems combine isocyanate, generally prepolymers from MDI (bis[4-isocyanato-
phenyl]methane) with an isocyanate content of 10 to 20 %, with propylene glycol carbonate.
The polyether amine (from ethylene oxide or propylene oxide) usually has a molecular
weight in the range of 200 to 5000. Further a reactive diluent is employed. In most cases
Figure 4.37: Chain extenders in polyureas

Figure 4.38: Synthesis of aspartic esters
propylene glycol carbonate is used for its high boiling point and easiness of reaction with
an amine to yield a carbamate.
4.2.8.2 Polyaspartic systems

Polyaspartic systems employ esters of aspartic acid with different substituents which
allow a very good control of the reactivity and gel time. They may be regarded as steri-
cally hindered amines which react with isocyanate to form high build weather-resistant
coatings. The intra-molecular hydrogen bond formed between the carbonyl group and
the amino group keeps the viscosity low and pot-life in place. Humidity will disturb this
intra-molecular hydrogen bond and release free hydrogen atoms, capable to react with iso-
cyanate groups. Polyaspartic esters are different from other amine functional polymers in
their reaction with isocyanate groups, the internal hydrogen bond offering longer pot life
in absence of humidity.

Resins 63
Figure 4.39: Supramolecular monodentate and bidentate urea build up in amino isocyanate curing
Polyaspartic systems have been developed in the beginning of the 1990s and have been
mainly used as reactive thinners for the hydroxyl functional binder further used in combi-
nation with an isocyanate. Recently the use of aspartic esters has moved to the use as main
binders in combination with isocyanates as a broadening of two-component polyurethane
coatings. The characteristic of the coatings using aspartic esters present a tolerance for
excessive film thickness and lower sensitivity to climatic conditions, combined with a rapid
cure. The coatings applied in one layer achieve the same performance as in the case of using
primer and topcoat. The synthesis of polyaspartic components is given in Figure 4.38.
The use of amine functional binders is an important approach to corrosion resistant coa-
tings. One of the most interesting results is the fact that the molecules build supramolecular
systems by H-bonding between urea moieties and therefore the strength of the coating
system is so high and so performing [60–62]. The supramolecular system self assembled by
hydrogen bonding is shown in Figure 4.39, and the strength of the coating is higher with
the higher content of bidentate moieties.
4.2.9 Alkyl silicate

The general formula M2OmSiO2nH2O where M is an alkali metal and m and n are the respec-
tive numbers of moles of SiO2 and H2O, per mole of M2O. For the most common form of solu-
ble silicate m has the value of 3.3, the composition of commercial alkali silicates is typically
described by the weight ratio of SiO2 to M2O.
Sodium silicates [1344-09-8] are
the most common; potassium
silicate [1312-76-1] and lithium
silicate [12627-14-4] are manuf-
actured to a limited extent for
special applications. These mate-
rials are usually manufactured as
glasses that dissolve in water to
form viscous, alkaline solutions. Figure 4.40: Synthesis of a silicate

Figure 4.41: Silicate structures
Waterborne alkali silicates in coatings are believed to be harmless to the environment on

the basis that:
• cured systems are silicate based, which is effectively very close to what already exists
in nature
• are non-hazardous substances
• exhibit no significant health risk during application
• have no allergenic potential from silicate binders
• are zero VOC products
• can provide a good economic lifetime of the coating (leading to a lower requirement to
reapply the coating) due to long term stability.
4.2.9.1 Nomenclature of the silicon chemistry

The nomenclature of silicon chemistry is summarised as such in Table 4.5 [57].
Soluble silicates are primarily used as sources of reactive silica, in detergency, in pulp
and paper production, adhesives
Table 4.5: Nomenclature of silicon chemistry and binders, and in other appli-
cations. The understanding of
Nomenclature Designation silicate chemistry by modern
silicon Si the element analytical techniques contributed
silane substituted silicon compound to the development of new mar-
oxysilane silicon based compound with at least on kets. Thus, the sodium silicates
substituent selected from alkoxide, hydro- constitute a versatile, stable, and
xide or arylxoide growing commodity and are ran-
silicate metal salt of a silicon-oxygen anion ked among the top 50 commodity
chemicals.
silica silicon oxygen compound (sand)
siloxane silicon compound with two or four oxygen Dissolution of sodium silicate glass
atoms bonded to a silicon atom undergoes a two-step mechanism
polysiloxane polymeric compound having a silicon- that involves ion exchange and
oxygen backbone network breakdown.
silicone polysiloxane with one or typically two or- Silicon esters are silicon com-
ganic substituents bonded to each silicon pounds that contain an oxygen
atom in the backbone
bridge from silicon to an organic

Resins 65
Figure 4.42: Dissolution by ion exchange
Figure 4.43: Hydrolytically network breakdown
group, such as Si-OR. The earliest reported organic silicon compounds contain four oxygen
bridges and are often named as derivatives of orthosilicic acid, Si(OH)4.
The best known material is tetraethyl orthosilicate Si(OC2H5)4, (CAS 78-10-4). The use of
organosilanes that contain silicon-carbon bonds, Si-C, initiated an organic nomenclature
by which compounds are named as alkoxy derivatives. For example tetraethyl orthosili-
cate Si(OC2H5)4 becomes tetraethoxy silane. Acyloxy silanes, such as tetraacetoxy silane,
Si(OOCCH3)4, are also members of this class. The chemistry and applications of acyloxy
silanes are significantly different from those of the alkoxy silanes.
The tetraalkoxy silanes exhibit excellent thermal stability and liquid behaviour over a broad
temperature range that widens with length and branching of the substituents. The physi-
cal properties of the silane esters, particularly the polymeric esters containing siloxane
Table 4.6: Silanes

Homologue CAS number Formula
tetramethoxysilane [681-84-5] Si(OCH3 ) 4
tetraethoxysilane [78-10-4] Si(OC2H5) 4
tetrapropoxysilane [682-01-9] Si(O-n- C3H7) 4
tetraisopropoxysilane [1992-48-9] Si(O-i-C3H7) 4
tetrabutoxysilane [4766-57-8] Si(O-n- C4H9 ) 4
tetrakis(s-butoxy)silane [5089-76-9] Si(O-sec-C4H9 ) 4
tetrakis(2-ethyl-butoxy)silane [78-13-7] Si(OCH2CH(C2H5) 2) 4
tetrakis(2-ethyl-hexoxy)silane [115-82-2] Si(OCH2CH(C2H5)(C4H9 )) 4
tetrakis(2-methoxy-ethoxy)silane [2157-45-1] Si(OCH2CH2OCH3 ) 4
tetraphenoxysilane [1174-72-7] Si(OC6H5) 4
hexaethoxydisiloxane [2157-42-8] (C2H5O) 3SiOSi(OC2H5) 3
ethylsilicate 40 [18954-71-7] (OSi(OC2H5) 2) 4-5

Figure 4.44: Preparation of ethyl silicate
bonds Si-O-Si, are often likened to the silicone oils. These have low pour points and similar
temperature-viscosity relationships. The alkoxy silanes generally have fruity odours that
become less apparent as molecular weight increases. The alkoxy silanes generally exhibit
very low levels of toxicity, with the exception of tetramethoxy silane, trimethoxy silane,
triethoxysilane, and a few other closely related compounds that can be absorbed into the
corneal tissue, causing eye damage.
4.2.9.2 Manufacturing of alkyl silicates

The principal method of silicon ester production is described by Von Ebelman’s 1846 syn-
thesis
Continuous processes involve pumping the alcohol and chlorosilane together in a mixing
section, introducing the chlorosilane vopour counter-current to liquid alcohol, or introdu-
cing chlorosilane vopour in a two-column reaction distillation scheme in which substoichi-
ometric alcohol is introduced center-column to a chlorosilane. Removing hydrogen chloride
(HCl) and unreacted alcohol in the overhead is followed by a slight excess of the alcohol bee-
ing introduced center-column, to recover the excess overhead and remove product from the
bottom of the column. All processes provide a method for removal of the by-product HCI. The
energy of activation for the reaction of ethanol with silicon tetrachloride in the vopour phase
is 64.9 kJ/mol (15.5 kcal/mol). The initial stages of the esterification processes are endother-
mic because the heat of evopouration of HCl cools the reaction mixture. In the last stages of
esterification, the mixtures are usually heated during the final addition of alcohol.
In batch processes, the alcohol is always added to the chlorosilane. In the batch production of
tetraethoxysilane from silicon tetrachloride, the initial reaction product contains at least 90
wt % tetraethoxysilane with SiO2 content. By distillation the alcohol and high boiling impu-
Figure 4.45: Ethyl silicate synthesis from Si and ethanol

Resins 67
Figure 4.46: Hydrolysis of ethyl silicate
Figure 4.47: Curing of alkyl silicates
rities are removed, and the distilled product, containing at least 98 % tetraethoxy silane,
is called pure ethyl silicate. Partially hydrolysed or polymeric versions, where substantial
portions have an average of 4 to 5 silicon atoms and 40 % SiO2 or have an average of 5 to 8
silicon atoms and a 50 % SiO2 content, are respectively named ethyl silicate 40 and ethyl
silicate 50.
Direct catalysed reactions of alcohols using silicon metal have become an important com-
mercial technology for the production of lower esters. Patents have reported the reactions of
methanol and ethanol with silicon in high boiling solvents, or in contained reaction products
to give high yields of trialkoxy silanes and tetraalkoxy silanes. In the presence of a methoxy
compound, where M is a metal, and under moderate pressure, substantial improvements in
yield can be achieved.
4.2.9.3 Reactions of alkyl silicates

Ethoxy silanes are used in high-temperature, zinc-rich coatings. Methyl- and phenyltrialk-
oxy silanes are used to prepare abrasion-resistant coatings for plastics, especially polycar-
bonate, and dielectric coatings and seals for high voltage electrical components, including
television tubes. Tetraethyl orthosilicate easily converts into silicon dioxide. This reaction
occurs upon the addition of water:

Figure 4.48: Curing of alkyl silicate in the presence of metal (Zn)
This hydrolysis reaction is an example of a sol-gel process with the side product ethanol.
The reaction proceeds via a series of condensation reactions that convert the tetraethyl
orthosilicate molecule into a mineral-like solid, via the formation of Si-O-Si linkages. The
rates of conversion are sensitive to the presence of acids and bases, both having a catalytic
activity. At temperatures over 600 °C, tetraethyl orthosilicate converts to silicon dioxide
and diethylether.
In general, the curing of alkyl silicates goes through a range of reactions in presence of
water and an acid catalyst.
The quantity of water added to the alkyl silicate should not be excessive as this leads to
premature gelling. Water and elevated pH leads to silica precipitation and consequently
reduces the capacity of formation of inorganic polymer with high molecular weight. Acids
may also have negative impact as in excess they slow down the reaction by the repulsion
of protonated hydroxyl groups. The target is the formation of a polymer of metallic silicates
when metal is used in the formulation, such as zinc:
4.2.10 Polysiloxanes
Generically polysiloxanes relate to a group of polymers based on inorganic siloxane and
organic-inorganic siloxane hybrids [56]. Silicon based polymers are inherently temperature
resistant. Resistance against UV irradiation and oxidation also are important properties
that have motivated attempts to use the chemistry for property improvement of both orga-
nic and inorganic systems, including good resistance to certain acids and solvents, high
nonvolatile content and very good weatherability.
The use of silicon based polymers covers a history of more than 50 years. Silicate pri-
mers and waterborne silicate primers cured respectively by heat or by acid catalysis were
commercial in the 1940s and 1950s. A significant progress has been recorded in 1978 by
improving the curing chemistry at ambient temperature through the introduction of trial-
kyl silane. Later on in 1981 the development of binders based on interpenetrating networks
from a polysiloxane network and an epoxy-polyamine network was an important progress
yielding coating systems with good adhesion, flexibility, acid and solvent resistance.
The name siloxane is pointing out the chemical bond Si-O-Si. The reactions of these com-
pounds may be listed as follows [58]. Siloxanes, considered as hybrids between glass and
organic resins, exhibit an inertness beneficially compared to other organic polymers and
may be used to upgrade other binders or as such as they may react with all materials con-
taining hydroxyl groups. They exhibit an excellent weatherability, good colour and gloss
retention and less chalking.
4.2.10.1 Reactions of siloxanes

Reactions of monofunctional siloxanes yield hexaorganosiloxanes.

Resins 69
Figure 4.49: Reaction of monofunctional siloxanes
Difunctional siloxanes yield privileged rings.
Figure 4.50: Reaction of difunctional siloxanes
Trifunctional siloxanes yield randomly cross-linked macromolecules.
Figure 4.51: Reaction of trifunctional siloxanes
Di- and tetra functional siloxanes yield tetrahedral arrangements.

Figure 4.52: Reaction of di- and tetrafunctional siloxanes
For almost all industrial products, R is methyl or phenyl.
4.2.10.2 Manufacturing of siloxanes

The process of employing the siloxane in binder manufacturing follows the scheme as
shown in Figure 4.53:
Polymethyl siloxanes have the lowest carbon content and therefore exhibit a long-term heat
resistance at 180 to 200 °C. As well, these resins exhibit good water repellency and sol-
vent resistance. At temperatures
over 400 °C, the methyl groups are
oxidised and the skeleton of the
newly formed binder is extremely
stable in combination with lamel-
lar pigments.
Polyphenylsiloxanes contain more
than 20 % phenyl groups. The heat
resistance is generally in the range
of 200 to 250 °C. The polyphenyl
siloxanes exhibit better pigmenta-
bility and very good solubility in
aromatic solvents.
Polyesters, medium and long oil
alkyds, and acrylic binders are
reacted with siloxanes in a ratio
Figure 4.53: Manufacturing scheme for siloxanes of generally 70/30 to obtain resins
Figure 4.54: Siloxane modification of a hydroxyl functional polymer

Resins 71
Figure 4.55: Acryl modified polysiloxane
Figure 4.56: Glycidyl modification of a siloxane
with improved properties. This reaction is a transesterification reaction proceeding in sol-

vent at a temperature of about 140 to 180 °C.
A UV curing system comprising ethylenically modified siloxane backbones is extremely
interesting.
Glycidyl functional siloxanes are produced by the following reaction:
Further, the glycidyl group may be functionalised to any other functional group.
A particular case of the siloxane chemistry is room temperature vulcanising (RTV). The
cross-linking of the resins may be performed by:
• addition between the vinyl groups and the Si-H groups
• vinyl polymerisation in the presence of peroxides
• condensation with α,-ω-dihydroxy-polydimethyl siloxanes and silica esters.
The products obtained by this method are castable, brushable, kneadable and exhibit per-
manent flexibility, good electrical insulating properties, good chemical resistance, etc.

Waterborne polysiloxanes are prepared by polymerisation of low molecular weight silo-

xanes in the presence of intermediates of tri or tetra alcoxysilanes and the aid of an emulsi-
fier. Secondary emulsions are prepared from organic solvent solutions transferred to water
followed by the solvent recovery by distillation. However an elegant method is to employ
low molecular weight amino modified silicone resins neutralised by acetic acid to yield
microemulsions. These microemulsions may be produced shortly before use as their curing
process starts in the frame of few hours.
4.3 Pigments – introduction

It is well-known that the incorporation of pigments with
appropriate characteristics has a distinctive influence
on the performance properties of a protective coating
for metal substrates. If the resin is the most important
part of a coatings formulation, the pigment and its
ratio to the whole matrix is second [63].
Only a few metals occur naturally, namely e.g. the

noble gold, silver and platinum. Other metals must be
produced from their ores by smelting which requires
enormous energy. Following the rules of Lenz the same
energy will be released when the metal is reconverted
back to its ore [63].
As a result, corrosion is the natural tendency of metals
to move towards their thermodynamically most sta-
ble form, for example oxides, sulfides or carbonates.
Figure 4.57: Electromotive series of The more energy is required for isolating the metal
metals in sea water by smelting, the higher the readiness of the produced
metal to return to its lower energy state, which means
corrosion. In the electromotive series of metals, the most active metals are those with ready
release of energy, which means a higher affinity to corrode.
Corrosion is often described to be an electrochemical process of oxidation and reduction
reactions. At the anode the metal dissolves as metal ions with release and flow of electrons.
The electrons migrate through the internal phase to the cathode where the primary reaction
is the consumption of the electrons by reaction with the environment (water/oxygen). The
so-formed hydroxyl ions then react with ferrous ions to produce rust [64].
Every given metal shows hetero-

geneities in its composition, deri-
ving from surface contamination
or grain structures which have
an impact on the readiness to cor-
rode. Once being in contact with
an electrolyte like moisture, those
areas have a higher or lower ten-
dency to corrode and will act as
local anodes or cathodes in a gal-
vanic cell.
Electrolytes might be made up of
Figure 4.58: Electrochemical corrosion cell [63] rain, snow and dew and contain

Pigments –introduction 73
water-soluble corrosion stimulators like chlorides and sulphate salts. These inorganic
salts dissociate into their respective ions which provide an excellent pathway for the
transmission of electric currents generated in the corrosion process. Corrosion control by
means of protective coatings has to interfere with the above described electrochemical
mechanism [63].
4.3.1 Corrosion protection pigments

According to accepted standards, the modern meaning of “pigment” is associated with a
substance consisting of small particles that is nearly insoluble in the applied medium and
is used for colouring, protective or magnetic properties [65]. Corrosion protection pigments
need to have certain solubility in order to display a chemical or electrochemical activity.
Nevertheless, if the solubility behaviour of the anticorrosive pigment is not adjusted pro-
perly, it could lead to osmotic effects and resulting blister formation with deterioration of
the anticorrosive properties of the paint film.
Anticorrosive pigments have a strong influence on the performance of protective coatings
in several ways, for example [66]:
• Increase of the durability of the coating system
• Prevention of undercutting in damaged areas and underfilm corrosion
• Decrease of the corrosion velocity
• Cathodic and/or anodic passivation of the metal surface
Inorganic anticorrosive pigments may be classified by the way they work as
• Active pigments (chemically/electrochemically)
• Barrier pigments (physically) or
• Sacrificial pigments (electrochemically/physically)
Often, optimal protection is achieved through a combination of differently active pigments.
Active pigments show a certain controlled solubility which results in either chemical and/or
electrochemical activity. Passivation of the metal substrate can be achieved with pigments
which show a strong oxidising potential such as chromates or nitrites. These are termed to
be active in the cathodic area by consumption of the free electrons which are released when
the metal at the anode passes into solution. This means a limitation of the anodic process.
The pigments that inhibit the corrosion process by stimulating the growth of the adherent
passive layer on the metal surface are said to be active in the anodic area. Moreover, neutra-
lisation of acidic or corrosion stimulating substances like chlorides or sulphates is another
pathway which can be chosen by utilisation of active anticorrosive pigments [67].
Barrier pigments like chemically inert aluminium, glass flakes and micaceous iron oxide
are also said to be able to reduce the water permeability of paint films due to their lamellar
or platelet structure. These pigments are packed in layers within the paint film and thus
increase the diffusion path for water, oxygen and corrosion stimulating ions to the substrate.
They can also improve adhesion between the metal surface and the coating [68].
Sacrificial pigments: An alternative way of protecting ferrous substrates is the utilisation
of metallic pigments like zinc. Zinc-rich primers contain high levels of powdered zinc, in
general more than 90 % on total formula weight is not unusual in order to ensure optimum
contact of the zinc particles with the steel surface. The zinc itself acts as a sacrificial anode
if its electrochemical activity in the electromotive series is higher than that of the metal
which has to be protected. In this case zinc becomes the sacrificial anode and passes into
solution whereas the substrate acts as the cathode. The whole process is therefore termed

cathodic protection mechanism. In practice only zinc dust or flakes are of economic impor-
tance as sacrificial pigments. The electrochemical efficiency of zinc-rich coatings does not
last forever due to corrosion products formed at the particle interfaces. Nevertheless, this
reaction of zinc with the atmosphere might be beneficial in terms of filling pores or pinholes
of the paint film with insoluble zinc compounds (cementation) [69].
Besides possible classification of anticorrosive pigments discussed above, there is one more
class often described as having film-reinforcement and adhesion promoting properties. For
example, micaceous iron oxid (MIO) is said to be able to reinforce the binder matrix. The
ratio of length to thickness and the alignment of the MIO flakes in a coating toughen and
strengthen the film. Coatings formulated with MIO can show greatly improved resistance to
blistering and increased substrate adhesion. For example, MIO is used to promote adhesion
in coatings formulated for galvanised steel [70].
Extender pigments, especially calcium silicate (wollastonite), have also achieved increasing
importance as reinforcers for paint films. Due to its ability to maintain high pH values and
decreased permeability via improved pigment/binder interfaces, wollastonite has found
increasing use in protective coatings.
4.3.1.1 Lead and chromate pigments
4.3.1.1.1 Lead pigments

Lead-based paints have disappeared from consumer sales for residential use because of
toxicity concerns. However, the use of lead tetroxide, or red lead, can be traced back to
ancient Roman times where it was used simply as a red pigment. The Latin name minium
derives from the Minius River in northwest Spain where it was first mined. Chemically,
red lead is lead tetroxide or triplumbic tetroxide Pb3O4. It is a bright red or orange pigment,
virtually insoluble in water. By contrast, its solubility in hydrochloric acid present in the
stomach is responsible for its toxicity [71].
Lead tetroxide is usually produced on industrial scale by calcination of lead (II) oxide in a
stream of air at 450 to 480 °C.
6 PbO + O2 → 2 Pb3O4
Its electrochemical effectiveness derives from the oxidation potential of red lead (reduction
of Pb(IV) to Pb(II)). It is able to form insoluble plumbate complexes with iron and iron oxides.
The ability to form lead soaps with fatty acids present e.g. in linseed oils is said to be respon-
sible for the anticorrosive properties in paint films [72]. Moreover it has been suggested that
the basic content of lead pigments promotes the reinforcement of the paint film itself with
regard to mechanical sustainability, water resistance and adhesion, even on poorly prepared
and rusty surfaces [73].
Among all lead based anticorrosive pigments, red lead gained the most industrial impor-
tance in the past, followed by lead silico chromate, a so-called core pigment type of anti-
corrosive. It is a composite pigment in which the active lead chromate is precipitated on a
core of silica particles. Due to the silica core, this pigment shows considerably lower density
(4.1 g/cm3) compared with red lead (8.8 g/cm3) [73–75]. However environmental and human
health awareness referring to the lead and also chromate content prevented this pigment
from having an economic breakthrough.
4.3.1.1.2 Chromate pigments

There is almost no other group of anticorrosive pigments that has been the focus of so many
detailed investigations than chromates. The wide success of hexavalent chromium (VI)

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pigments in the past is based on

their ability to be effective in both,
the anodic and also in the cathodic
areas of ferrous substrates. The
anticorrosive properties are based
on chemical and electrochemical
reactions. Protective paints should
be accurately formulated at con-
trolled ratios of pigment volume
concentration and critical pig-
ment volume concentration (PVC/
Figure 4.59: Corrosion of iron and inhibitive effects of CPVC), to ensure a controlled rate
chromate pigments [73] of moisture permeability within
the paint film. When this rate is
adjusted to the solubility of the chromate pigment, chromate ions will migrate to the metal
surface to form passive films [76].
The high amount of water soluble chromate which can be reduced at the cathodic areas is
responsible for the passivation of metal. For steel, a layer of mixed oxide, Fe(III) and Cr(III),
was found which is constantly “repaired” due to the high oxidising potential of hexavalent
chromium compounds. Nevertheless, the layers do breakdown in the presence of depas-
sivating or corrosion stimulating ions like chlorides or sulphates. As these ions originate
from outside the paint film, a properly formulated primer paint film which should be more
permeable to water than to salt solutionshould restrict the access of corrosion stimulators
to the metal interface.
Electrochemical passivation and chemical reaction are illustrated in Figure 4.59.
However, if the PVC/CPVC ratio of the formulated primer is chosen so high that the film is
also permeable to ionogenic solutions (e.g. sodium chloride), the passivation process of the
substrate may be prevented [63].
The effectiveness of chromate based pigments is therefore related to the:
• Amount of water-soluble chromate ions
• Ratio of water-soluble chromate to amount of corrosion stimulating ions
• PVC of the primer formulation
• Particle size and distribution
• Dispersibility
• pH stabilising effect of Zn(OH)2 present in zinc containing chromate pigments
As described before, besides the solubility of the chromate within the paint film, the Zn(OH)2
content in zinc containing pigments plays an important role. The chemical effectiveness is
Table 4.7: Solubility of chromates in water at 25 °C [77]
Pigment Formula Grams of CrO3/

1000 ml of H2O
Calcium chromate CaCrO4 17
Zinc potassium chromate 4 ZnO · K 2O · 4 CrO3 · 3 H2O 1.1
Zinc tetrahydroxychromate ZnCrO4 · 4 Zn(OH) 2 0.6
Strontium chromate SrCrO4 0.6
Barium chromate BaCrO4 0.02

Pigments – introduction 77
due to the neutralising and pH stabilising properties towards acidic decomposition products
of the resin itself.
Zinc potassium chromate or zinc yellow
K2CrO4 ·3 ZnCrO4 · Zn(OH)2 · 2H2O
Zinc chromate based pigments are now classified as either confirmed or at least suspected
human carcinogens. Zinc potassium chromate gained major economic importance primarily
due to the broad application latitude and compatibility with resins and extender pigments
in industrial primer paints [69].
Zinc tetrahydroxy chromate ZnCrO4 · 4 Zn(OH)2
Zinc tetrahydroxychromate has been widely used for wash and shop primer applications
based on polyvinyl butyral (PVB) resin systems. The phosphoric acid which is present in
PVB wash primers reacts with zinc hydroxide and chromate to form adhesive complexes on
the metal substrate [69].
Strontium chromate SrCrO4
One of the key areas of application for strontium chromates is in primers for aluminium.
It still maintains commercial importance as it is considered to be one of the most effective
anticorrosive pigments for aircraft and coil coating primers [69].
To summarise the benefits of chromate based anticorrosive pigments [78]:
• Chromates can be stored as conversion coatings and as pigments in paints.
• Soluble chromates are able to refresh scratched areas of a coating. The released chromate
ions are in equilibrium with the chromate in the coating.
• Chromate is soluble and mobile in solution, so it migrates to exposed areas on the metal
surface. Chromate absorbs on the active site of the surface to form a protective monolayer
of a Cr(III) species.
• Inhibition of oxygen reduction at the cathodic area is an important part of the overall
corrosion inhibition mechanism.
Chromate based pigments are toxic substances. Government regulations, concerning both
protection of the environment and protection of human health have already prompted paint
manufacturers and end-users to favour the use of non-chromium pigments [79].
4.3.1.2 Phosphate based pigments
4.3.1.2.1. Zinc phosphate

The use of lead and chromate based pigments has been restricted by increasing aware-
ness for human health protection. Thus, a large amount of detail had been placed upon
zinc phosphate and its protective properties. Due to the very low solubility compared to
chromate based pigments it can be used with a large variety of protective binder systems
which explains the ongoing economic importance in the protective coatings world. [68, 69].
Still, zinc phosphate is one of the most commonly used phosphate anticorrosive pigments
in the market.
Zinc phosphate is produced on industrial scale by reacting zinc oxide with phosphoric acid
in a wet precipitation process. ISO 6745 – Zinc phosphate for paints – Specifications and
methods of test – defines a zinc phosphate to be either a dihydrate type (Zn3(PO4)2 · 2 H2O),
a tetrahydrate ((Zn3(PO4)2 · 4 H2O) or a mixture of di- and tetrahydrate. According to ISO
6745 there may be differences in the protective behaviour depending on the type of zinc
phosphate which is used [80].

Table 4.8 summarises the main

requirements on zinc phosphate
pigments.
Pure zinc phosphate is extre-
mely insoluble in the neutral pH
range. Nevertheless, the secon-
dary phosphate ions formed due
to the very low solubility are
said to be responsible for the
formation of adherent phosphate
inhibitor complexes on the metal
Figure 4.60: Performance of zinc phosphate
substrate. Another theory for the
mechanism of protection, claims
the formation of tribasic iron phosphate films upon the metal surfaces.
It is well-known that the protective behaviour of zinc phosphate correlates strongly
with the pigment structure, particle size distribution and dispersibility of the pigment.
Micronisation improves the anticorrosive properties [76, 81]. Furthermore, investigations
have shown that the inhibitive action predominantly takes place in slightly acidic envi-
ronments of pH 4.
Under moist conditions, the formation of basic complexes by reaction of zinc phosphate with
inorganic ions or with carboxylic groups of the resin, which leads to so-called adhesion by
reaction with metal ions, cross-linking and inhibitor complexes, is being discussed in the
literature [73, 76, 92]. In contrast to chromate based anticorrosives, the formation of inhibitive
layers on the metal surface is somewhat delayed. The complexation reaction does not start
before the permeability of the coating allows enough moisture to penetrate from outside
for the zinc phosphate to hydrolyse. Practical experience has shown that zinc phosphate
is an active anticorrosive pigment with a minor chemical or electrochemical effectiveness
compared to lead and chromate based pigments. The performance of those pigments can
only be achieved in certain protective primer systems [73, 76].
4.3.1.2.2 Modified orthophosphates

As mentioned before, although the low reactivity as well as the low water solubility of zinc
phosphate is advantageous in terms of paint stability, it does also limit the rate at which
the active ions are released to protect the substrate [68]. Phosphates also require oxygen to
be effective. Nevertheless, it is possible to increase the activity by modifying the pigment
with other functional groups, different anions, organic surface treatments or by blending
with other inorganic anticorrosives (taking advantage of synergistic interactions). Decre-
ased particle size, particle size
distribution and particle shape
Table 4.8: Quality requirements of zinc phosphate
have also been found to have
Characteristic Unit Requirement an effect on the performance of
Zinc as Zn % 50.5 to 52.0 anticorrosive pigments. There-
Phosphorous as PO4 % 47.0 to 49.0 fore, the pigment industry has
Conductivity µS cm-1 max. 154
put a major focus on developing
phosphate based pigments with
pH 6.0 to 8.0
improved properties [76, 81].
Density g cm-3 3.0 to 3.6
With basic zinc phosphates, for
Sieve Residue (45 µm) % max. 0.5
example Zn2(OH)PO4 with an
Colour white increased hydroxyl anion con-

centration, it is possible to stabilise the pH value in the coating and also the equilibrium
of the cathodic reaction, resulting in an inhibition of the emission of electrons [83, 84].
Zinc aluminium phosphate is produced by wet precipitation of aluminium phosphate with
zinc oxide. This yields a pigment with higher phosphate ion content than standard zinc
phosphate. Also, the aluminium ions hydrolyse, causing slight acidity which in turn incre-
ases the solubility and phosphate concentration. The improved performance is attributed
to this higher phosphate content, providing greater interaction with the resin’s carboxyl
groups (soap formation) and the metal substrate [83–85].
Basic zinc molybdate phosphates have an improved anticorrosive activity due to the molyb-
date anion as anodic passivator with a passivating capacity which is only slightly less than
that of the chromate anion [68].
The electrochemical activity of the surface treatment is responsible for the efficiency of
organically modified zinc phosphate. Improved resin/pigment bonding and coating/sub-
strate adhesion are discussed [83, 86].
Phosphate/borate combinations are used due to their improved readiness to hydrolyse. Phos-
phate/silicate types of pigments are so called mixed phase or core pigments [73, 86, 82, 92, 93].
All of the mentioned improvements in performance properties were possible by taking
advantage of synergies. Using synergistic values is not a new concept in the coatings indus-
try. The most important argument for taking the synergy pathway might be the increased
water soluble content resulting in a better supply of inhibitive ions combined with other
synergistic properties [67].
Table 4.9: Orthophosphate based anticorrosive pigments

Pigment Modification
Zinc aluminium phosphates with aluminium phosphate [83-85]
Basic zinc phosphates contains basic contents (e.g. zinc hydroxide) [83, 84]
with different organic compounds treated [83, 86]
with zinc molybdate and/or calcium molybdate [73, 86, 88]
with basic zinc borate [73, 86]
with iron phosphate [89]
with calcium phosphate [88]
with potassium phosphate [84]
with barium phosphate [88]
with aluminium phosphate and zinc molybdate [90]
with inorganic compounds treated [86]
Zinc-free phosphates altering the cations e.g. with calcium phosphate and/or magnesium
phosphate [91, 92]
Zinc phosphate silicates with calcium silicate and strontium phosphate [90, 91, 93]
with calcium carbonate [95]
with different organic compounds treated [91, 94]
Zinc-free phosphate silicates variation of the cations, e.g. with calcium phosphate silicate [94]
with strontium phosphate [94]

4.3.1.2.3 Modified polyphosphates

Though the improvement in the performance of standard zinc phosphate by chemical modifi-
cations is remarkable, there are still some special applications, e.g. coil coatings and aircraft
primers, where the effectiveness of chromates could only be approached to a limited extent.
Intensive research in the field of pigments for those special high-performance applications
has led to a new family of anticorrosive pigments based on modified polyphosphates [75].
While orthophosphates are produced by reaction of orthophosphoric acid with basic or
amphoteric compounds, polyphosphates are manufactured by condensation of acidic ortho-
phosphates at high temperatures [67].
• Orthophosphates
• 3 ZnO + 2 H3PO4 → Zn3(PO4)2 + 3 H2O
• Polyphosphates
• Al(H2PO4)3 → AlH2P3O10+ 2 H2O
Recently, new applications have been opened up again by modifying the chemical structure,
resulting in different electrochemical effectiveness. Most of the modified polyphosphates are
conversion products of acidic aluminium tripolyphosphate with compounds based upon zinc,
strontium and calcium [96]. One key property of the polyphosphate grades is the significantly
increased phosphate content. The corrosion protection is attributed to the ability of the tripo-
lyphosphate ion to chelate metal ions (passivation) and to depolymerise into orthophosphate
ions, providing higher phosphate levels than orthophosphate pigments [97]. Aluminium tripo-
lyphosphate has limited solubility in water and is modified with zinc, calcium or strontium
to control both solubility and reactivity.
Also, the development of modified polyphosphates as active pigments was possible by
taking advantage of synergistic inorganic-inorganic interactions within one pigment [86].
4.3.1.3 Inorganic/organic synergies

Synergy is defined as a mutually advantageous conjunction of distinct elements. Intense
research work in the field of new anticorrosive pigment concepts has led to the conclusion
that there is also the possibility to combine the advantages of modified phosphate pigments
with the advantages of organic corrosion inhibitors. This so called “2-way synergy” is
advantageous in terms of providing improved substrate protection in the initial phase of
exposure and thus resulting in improved long-term protection of the application [98].
Table 4.10: Polyphosphate based anticorrosive pigments

Pigment Modification
Zinc aluminium phosphates with aluminium phosphate [86, 96]
partly with calcium silicate [86]
partly with strontium chromate [86 ]
with silicon dioxide [73]
with different organic compounds [86, 96]
Zinc-free aluminium phosphates with strontium phosphate [86]
with calcium silicate [86]
with magnesium phosphate [96]
with inorganic compounds [86]

Pigments –introduction 81
Figure 4.61: Inorganic/organic synergies
Taking advantage of synergies by combining modified phosphate pigments with an organic

corrosion inhibitor leads to improvement of early substrate protection resulting in increased
long-term substrate protection, a reduced tendency of blistering and enhancement of adhe-
sion, especially wet adhesion [90, 91, 98].
The requirements on organic corrosion inhibitors are as follows:
• High activity at low concentration levels (typ. 0.5 to 2 %)
• Sufficient thermal stability
• High activity in the range of pH 5 to 9 (preferably pH 2 to 14)
• Compatibility with a broad variety of resin systems
• Easiness to add in
• Low water-solubility
Of the variety of potentially suitable corrosion inhibitors, the following compound classes
are generally considered to be useful for coating applications [99]:
• Organic acids and their salts
• Organic bases/amines
• Organic compounds with oxidising properties
The efficiency of organic inhibitors is attributed to different mechanisms. On one hand they
are said to interact with either the anodic or cathodic corrosion reactions. On the other hand
these inhibitors are able to form protective layers on the metal substrate by adsorption and
to improve the barrier function of the paint film [73]. A positive influence on the wet adhesion
to the substrate is also being discussed. Nevertheless, to provide early substrate protection
with long-term performance, it is still essential to combine inorganic anticorrosive pig-
ments with organic inhibitors [86].
4.3.1.4 Wide spectrum anticorrosives

Chromate- based pigments have long been utilised as anticorrosives. In general, the utilisa-
tion of chromate anticorrosive pigments has shrunk significantly as compared to previous
decades. While unrivalled in their performance and flexibility in inhibiting corrosion, they
are classified as either confirmed or suspected human carcinogens and as “dangerous for
the environment”. International legislation, political and ethical pressures have accelerated
the search for viable commercial alternatives [100].
Even though one key feature of modified orthophosphate based anticorrosives is their broad
application latitude, it is necessary to select those pigments which are recommended by the

pigment supplier for any particular application. For a long time the pigment industry has put
focus on developing anticorrosives for universal use [86]. The modern wide spectrum anti-
corrosive pigments are well-engineered high-performance products with layered systems
of active inorganics built up over inert cores. Moreover, some of them are post-treated with
organic or organo-metallic sheaths [101]. Table 4.11 summarises typical properties of two
modified wide spectrum anticorrosives. Unlike many of the non-toxic phosphate based
anticorrosives these products perform well in a broad range of different resins and in both
accelerated and natural environments.
4.3.1.5 Phosphites and phosphides
4.3.1.5.1 Zinc hydroxyphosphite

Zinc hydroxyphosphite is produced by reacting zinc hydroxide with phosphorous acid and
a complex promoter. It has the theoretical chemical composition [2 Zn(OH)2 • ZnHPO3 • x
ZnO]. Zinc hydroxyphosphite is a white pigment with basic characteristics and low water
solubility [69, 102]. It is described to form passivating iron phosphite and phosphate layers on
steel substrates. The zinc oxide content helps to inhibit corrosion by forming zinc soaps
in oleoresinous resin systems [68].
Table 4.11: Typical properties of two assorted pigments for universal application [90]
Zinc aluminium molyb- Zinc calcium strontium
Specific data Unit
denum phosphate aluminium phosphate silicate
Zn as ZnO % 62 37
Phosphorous as P2O5 % 27 18
Aluminium as Al2O3 % 2 3
Molybdenum as MoO3 % 1 -
Calcium as CaO % - 14.5
Silicon as SiO2 % - 15.5
Strontium as SrO % - 5
Conductivity µS/cm max. 300 max. 100
pH 7,. 7.5
Specific gravity g/cm 3
3.7 3.5
Oil absorption value g/100 g 18 30
Average particle size microns 3 3
Colour white white
Table 4.12: Typical properties of molybdates

Specific data Unit Calcium zinc Calcium zinc Zinc Zinc phosphate
molybdate phosphate molybdate molybdate
molybdate
calcium calcium
Core material zinc oxide zinc oxide
carbonate carbonate
Colour white white white white
Specific Gravity g/cm 3
3.0 3.0 5.1 4.1
Oil absorption value g/100 g 18 18 11 13.5

4.3.1.5.2 Iron phosphide

Commercially available iron phosphide pigments are grey ferro-alloy pigments which prima-
rily consist of Fe2P with traces of FeP and SiO2. It is mainly used for partial replacement of
zinc dust in organic and inorganic zinc-rich primer systems. These coatings protect steel by
cathodic protection if an electrical path between the pigment particles and the steel substrate
is given. Iron phosphide is highly conductive and therefore able to provide an electrochemical
path between the zinc particles. It is also said to improve the weldability of a coating if up to
40 % of zinc dust is replaced by iron phosphide [104]. Unlike zinc dust or lamellar zinc flakes,
iron phosphide type pigments have not yet gained major commercial importance [64].
4.3.1.6 Borates
4.3.1.6.1 Barium metaborate

Barium metaborate BaO • B2O3 • H2O is the oldest borate and has been available since the
1960s. The alkalinity helps to neutralise acidic ions and decomposition products of the binder.
In order to reduce the high solubility of barium metaborate it is often coated with silica [63].
Silica coated barium metaborate is produced by precipitation of barium sulphide and borax
in the presence of sodium silicate. Inhibition is derived through the alkalinity and the ability
of the metaborate ion to provide anodic passivation. It should be noted that soluble barium is
an acute toxicant [103].
4.3.1.6.2 Zinc borate

Usually zinc borate is used as a flame retardant in plastics and cellulosic fibres. It is known
that the combination with barium metaborate or zinc phosphate exhibits synergistic effects
resulting in improved anticorrosive performance properties [103].
4.3.1.6.3 Calcium borosilicate

Calcium borosilicate is particularly effective in long and medium oil alkyds [103]. It is some-
times termed as a core pigment like phosphate silicates. It takes advantage of the borate
and silicate chemistry, both soluble and basic, which helps to neutralise acid ions but also
to form borate scales on the anode [74].
4.3.1.7 Molybdates
The basic molybdates introduced in the 1970s are anodic inhibitors and are discussed to
form a protective layer of insoluble ferric molybdic oxide, quite similar to that produced
by chromates. The high cost of molybdenum has limited the acceptance of molybdate
pigments. [68, 105]. Many molybdates nowadays are blended with zinc oxide, zinc phosphate
or fillers like calcium carbonate to overcome the price issue. As both zinc oxide and zinc
phosphate are corrosion inhibitors, those blends show good anticorrosive performance
properties in most solvent-borne resins but also in waterborne acrylic paints [103].
Table 4.13: Typical properties of commercial ion-exchange pigments [86, 108]

Specific data Unit 1 2 3
Calcium content % 6 6 6
Oil absorption value g/100 g 60 80 90
Specific gravity g/cm3 1.8 1.8 2.2
pH 9 9 7.5
Average particle size microns 3 5 3

4.3.1.8 Ion-exchange
pigments
Ion-exchange pigments are the
results of calcium ion exchanging
on a microporous silica gel [106]. The
surface area is quite high com-
pared to conventional anticor-
rosive pigments. The surface is
covered with calcium ions which
are responsible for the alkaline
nature of these pigments.
Figure 4.62: Protective behaviour of ion-exchanged pigments Their anticorrosive performance
is attributed to their ability to
adsorb aggressive ions on the silica surface. At the same time, the release and subsequent
migration of the calcium ions lead to the formation of a protective layer on the surface of
the metal substrate [108]. The advantage of this mechanism is that the anticorrosive species
is used only where and when required. The pigment morphology does not change during
the weathering which prevents the paint film from breakdown and formation of cracks.
Due to the very low specific gravity of the silica based pigment there is a high number
of active particles available for a given weight [86, 108]. Therefore these pigments offer a
different type of chemical and physical constitution and protective behaviour than most
other anticorrosive pigments [64].
4.3.1.9 Zinc cyanamide

Zinc cyanamide, Zn(CN)2 is a white to beige powder and is used as non-toxic replacement
for lead cyanamide in mirror back coatings, electrodeposition coatings and primer appli-
cations [109]. It is produced from industrial grade calcium cyanamide and zinc oxide. Until
now this pigment has not reached the economic importance of lead cyanamide.
4.3.1.10 Hybrid anticorrosive inhibitors

Hybrid corrosion inhibitors are described as composite pigments providing the best of
both inorganic and organic worlds in terms of anticorrosion synergy. Due to increasing
regulation of anticorrosive pigments, combined with the requirement for chromate-
like performance properties, there has been a steady growth in the value of non-toxic
additives that are synergistic or multifunctional [110]. It is proven that synergy can
produce positive effects with various corrosion inhibitors [77]. There are several pig-
ments available on the market referred to as hybrid corrosion inhibitors. One example
is an anticorrosive based on an oxyamino salt of magnesium or calcium. It is said that
compositions of oxyaminophosphate salts were found to form stable layers, composed
of magnesia (MgO) on the steel surface to be protected. The layers act as an effective
barrier against corrosion on aluminium (including alloys), and other metals in a wide
range of applications. [111].
US 6,139,610 patent describes a solid phase inorganic/organic hybrid with a selection
of metal cations and different anions like phosphates, polyphosphates, phosphites,
molybdates or silicates. The organic part includes ammonium salts of mercapto- and
thio compounds and corresponding derivatives which form a stable unitary hybrid
with the inorganic portion [119]. There is another pathway of corrosion prevention by
utilisation of hybrid inhibitors.

Early research into the use of elec-

troactive conducting polymers
(ECPs) as corrosion inhibitors
showed that the ECPs can provide
corrosion inhibition to various
substrates. Unfortunately, the
ECPs formed in this manner often
display poor film quality. In order
to facilitate industrial application,
polypyrrole (PPy) coated alu-
minium flakes were developed,
acting as anticorrosive pigments
in a binder system, synthesised Figure 4.63: Barrier effect of lamellar pigments
through a new aqueous chemical
oxidation process [112].
4.3.2 Barrier pigments

Lamellar pigments such as mica and micaceous iron oxide form a barrier of flat and thin
particles which limits the permeability of the paint film. The degree of reducing the per-
meability depends on:
• Film thickness
• Type of binder
• Cross-linking ratio of the binder
• Pigment volume concentrations
• Type of particle and particle shape
The main difference between barrier pigments and active anticorrosive pigments is that
barrier pigments need to be absolutely insoluble and inert to provide their best possible
performance [97].
4.3.2.1 Micaceous iron oxide

Micaceous iron oxide (MIO) is a crystalline form of iron oxide (α-Fe2O3, haematite) that dif-
fers from the more familiar red, yellow, and black forms of iron oxide pigments. The name
derives from mica. Its crystals are very easily fractured into thin flakes giving it a physical
form similar to mica. MIO is normally dark grey to black in colour.
MIO flakes, when applied properly, align themselves parallel to the substrate surface,
producing a shield or barrier of overlapping plates. This alignment enhances protection by
providing barrier protection, ultraviolet (UV) absorption, film reinforcement and increased
intercoat adhesion. Because the flakes are impermeable, a physical barrier is formed that
prevents the access of water, oxygen and corrosion stimulating ions, thus preventing cor-
rosion of the steel and degradation of the binder [115]. MIO reinforces the binder matrix. The
aspect ratio (ratio of length to thicknewss) and the alignment of flakes in a coating toughen
and strengthen the film. Coatings formulated with MIO can show greatly improved resi-
stance to blistering and increased substrate adhesion [116]. The incorporation of MIO might
produce, after weathering, a surface with an excellent physical profile for subsequent coats.
Alternatively, coatings may be formulated with higher levels of MIO to boost the intercoat
adhesion of freshly applied systems [117].
For effective barrier properties PVC of 25 % to 45 % should be used with material of at least
80 % purity [97].

The most popular example of the use of MIO pigments is probably the Eiffel Tower in Paris.
Since its erection in 1889 MIO has been used in maintenance paints on this tower.
Newer studies in protective coatings have shown no major differences in the performance
properties of MIOs with different shapes i.e. granular and more lamellar [118]. Therefore,
recent studies focus on possible alternative protective mechanisms besides the barrier
effect of lamellar shaped iron oxide.
MIOs are specified in ISO 10601 – Micaceous iron oxide pigments for paints – Specifications
and test methods. There are three different grades according to ISO 10601 with different
lamellar particle content [121]:
• Grade 1: thin-flake content >50 %
• Grade 2: thin-flake content 10 to 50 %
• Grade 3: thin-flake content <10 %
4.3.2.2 Aluminium flakes

There are two different types of aluminium pigments available: Leafing and non-leafing.
Leafing aluminium pigments show a tendency to float to the surface of the coating and to
align themselves parallel to the surface of the coating film. It is necessary to overcoat lea-
fing aluminium coatings with a top coat in order to protect the leafing metallic finish from
unwanted corrosion processes and pigment abrasion [120].
Non-leafing pigments have a more random orientation in the coating and are very effective
in barrier coatings. Systems containing non-leafing aluminium pigments perform signi-
ficantly better under mechanical strain, with less abrasion of the metallic pigments and
notably higher chemical resistance against corrosive chemicals compared to coatings based
on leafing aluminium pigments [120].
4.3.2.3 Zinc flakes

Zinc flakes should not be mixed up with zinc dust which is used in zinc-rich primer systems.
The platelet pigments consisting of metallic zinc might offer cathodic corrosion protection
like zinc dust. Nevertheless, this should be difficult in practice since cathodic protection
requires a gap-free electrical contact of the zinc flakes with each other and the metallic
surface. Due to their lamellar structure they provide an additional barrier effect in the coa-
ting film, resulting in a significantly reduced permeability to corrosive agents especially
in powder coatings [120]. Zinc flakes have been successfully proved in combination with
other lamellar pigments (MIOs or aluminium flakes), spherical active particles like zinc
phosphate or even zinc dust.
4.3.3 Sacrificial pigments

4.3.3.1 Zinc dust
In so-called zinc-rich coatings a high level of zinc dust is incorporated as a pigment. Parti-
cles of the less noble zinc in the paint film protect the ferrous substrate by acting as a sacri-
ficial anode which corrodes in favour to the ferrous cathode. The sacrificial anode protects
the ferrous cathode as long as zinc is able to pass into solution. Cathodic protection in this
way is only possible if the zinc particles are in electrical contact with each other and the
metal substrate. The basic requirement for sacrificial protection is for the sacrificial metal
to be more electrochemically reactive than the metal substrate under the conditions of use.
A guide to choosing a metal for sacrificial protection of another is their relative locations in
the electrochemical series in seawater (see Chapter 4.3).

The most favourable loading level

of zinc dust is still under discus-
sion but normally primers have a
content of more than 80 % in the
dried paint film [122, 123].
Zinc is also able to react with
atmospheric components like
oxygen, moisture or carbon dio-
xide to form voluminous insoluble
salts that might fill voids in the
paint film and decrease the ove-
rall permeability. This process is Figure 4.64: Cementation with zinc dust
often termed as cementation [123].
Today, zinc dust coatings are widely used in organic and inorganic matrices for the protec-
tion of structural steel, marine coatings and underwater steel constructions [123]. Zinc dust
is a blue-gray powder of spherical particles, which is produced from zinc metal by evopoura-
tion and condensation under controlled conditions. Usual particle sizes obtained by different
condensation and sieving processes vary from 2 to 8 µm [122].
4.3.3.2 Magnesium
The need for chromium-free methods of protecting aluminium and its alloys from corro-
sion is very urgent, especially with respect to high-strength aerospace alloys [124]. Recen-
tly, a new concept of a magnesium-rich primer which contains magnesium metal powder
for cathodic corrosion protection of aluminium alloys was developed which is quite
analogous to a conventional zinc-rich primer for protection of steel (see Chapter 4.3.3.1).
Magnesium is less noble and consequently more reactive than aluminium in the galvanic
series of metals in seawater. Therefore the pigment should corrode as sacrificial anode
preferentially to the substrate when there is an electrical contact between the magnesium
particles and aluminium. At the time being, there are no aluminium skinned military
aircraft which have authorisation to use completely chromate-free coating systems. Due to
the cathodic protection mechanism, good performance requires no electrically insulating
surface treatment layer be to present when magnesium is used. This effectively elimi-
nates the need for a chromate- or other heavy metal containing conversion coating surface
treatment. Since magnesium is a very active metal, concerns over the flammability of the
pigment powder are alleviated through the presence of a very thin oxide layer present on
the surface of the particles. [125].
4.3.4 Colouring agents

4.3.4.1 White pigment, titanium dioxide
Today, there is only one white prime pigment of economic importance, titanium dioxide. In
protective coatings only the rutile form with a compact crystal structure is used. Never-
theless, even rutile has to be treated with metallic oxides to prevent chalking processes
and provide exterior durability. Rutile is produced by either the sulphate or the chloride
process [126, 127].
It is inert, has moderate oil absorption and specific gravity and is easy to disperse. Since
1999, there has been a new type of anticorrosive pigment on the market based on an inhi-
biting phosphate modified titanium dioxide [128, 129].
4.3.4.2 Red pigments

There are two general types of reds, the inorganic red oxides and high performance organic
reds such as quinacridones. The best performing pigments used for coatings in aggressive
environments are definitely synthetic iron red oxides with good chemical resistance, opacity
and hiding levels and also low oil absorption values [130]. Cadmium reds made of cadmium
selenium sulphide are now being used less because of toxicity concerns. They are also not
resistant to acids and are quite expensive. The inorganic oxides have a lower degree of
chroma than the organics. The high performance organic quinacridone pigments offer excel-
lent chemical resistance, light and heat stability. Like all organic pigments they suffer from
being relatively difficult to disperse, having high oil absorption values and low opacity [77].
4.3.4.3 Yellow pigments

Like the reds, there are two groups of yellows, inorganic and organic. For low-cost rather
impure yellow ferrites are used (hydrated iron oxide). At high temperatures they turn red
due to the loss of water of crystallisation [77].
Chrome yellows (lead chromate and lead sulphate) have a high chroma ranging from pale
orange to greenish, with increasing lead chromate content [131]. They are sensitive to alkaline
vehicles. Cadmium yellows offer excellent light stability but show poor acid resistance.
Bismuth vanadates are excellent chrome-free alternatives with high lightfastness, opacity
and low oil absorption values.
Titanium yellows are very inert pigments with good opacity and low oil absorption. Despite
their high price they are commonly used as inert high temperature pigments in high per-
formance coatings [132].
Like the reds, the organic yellows suffer from low opacity and high oil absorption. High
performance yellows are benzimidazolones with improved heat, weather and chemical
resistance [133].
4.3.4.4 Green pigments

Chromium oxide green is a trivalent chrome product with good opacity which is inert and
suitable for most protective applications.
The most important organic greens are phthalocyanines which offer excellent tinting
strength and chemical resistance but low opacity in mass-tone [134].
4.3.4.5 Blue pigments

The only pigment of importance for the application in high-performance coatings is phtha-
locyanine blue. It is highly valued for its superior properties such as light fastness, tinting
strength, covering power and chemical resistance to alkalis and acids [77].
4.3.4.6 Black pigments

Virtually all black pigments are inorganic, with carbon blacks and iron oxide blacks being
the most common. Carbon blacks are fine pigments which are difficult to disperse. They
offer good hiding power and relatively high oil absorption. Black iron oxide is not as strong a
black as carbon black. All blacks are excellent UV absorbers and therefore impart excellent
durability to the paint film [77].

Extender pigments 89
4.4 Extender pigments

Traditionally, the accurate choice of extender pigments has not received much attention in
the protective coatings world. Today, formulators use them as engineering tools to optimise
and adjust the function of modern coatings.
Extender particles may be described by three different particle shapes: blocky, platy or lamel-
lar, and acicular. Nevertheless, these pigments should better be classified by their chemistries
i.e. carbonates, sulphates, silicates or oxides [77]. They do not only contribute to the aesthetics
of a coating system but may also have a distinct influence on the overall performance.
4.4.1 Carbonates
Today, the only extender of economic importance is calcium carbonate. It is commercially
available in both natural and synthetic forms. Natural calcium carbonate is a low-cost pig-
ment with low oil absorption and specific gravity, which enables cost savings at high loading
levels. Calcium carbonate pigments are designed to improve the rheological and mechanical
properties of a coating. Their alkalinity might be advantageous for in-can corrosion protec-
tion and metal primers in non-acidic environments. On the other hand the alkalinity limits
the utilisation due to the implied sensitivity to acids or acid rain for exterior use [135].
4.4.2 Sulphates
Like calcium carbonate for carbonates, in the case of sulphate extender pigments, barium
sulphate is the only product of economic importance. It is chemically inert, insoluble in
water, which makes this pigment attractive for use in high-performance chemically resi-
stant coatings. Like calcium carbonate, it is available as a natural pigment (barytes) or syn-
thetic as Blanc Fixe. It is easy to disperse and is extremely resistant to water, acids, alkalis
and corrosive gases. Its low oil absorption combined with a dense structure enables good film
build and packing density also in combination with other suitable extender pigments [77].
4.4.3 Silicas
The only oxide type of extender pigment with a refractive index low enough to be classified
as extender is silica. All silicas are chemically inert and have low specific gravities. There
are natural and also synthetic silicas available. Their oil absorption varies, depending on
the amorphous, crystalline or synthetic types. Since the crystalline silicas are limited for
use in coatings due to their hardness, the amorphous and softer types have found their
way into the pigmentation of protective coatings. In primer applications, these pigments
promote intercoat adhesion and might be used as auxiliary fillers in high solid coatings.
The major use of the fluffier, diatomaceous types is as flatting agents. They are also said to
reduce the blistering tendency because of their ability to control the vapour permeability
of the paint film [136].
4.4.4 Silicates
Silicates represent the largest class of extender pigments. They are all inert materials and
should be divided into talcs, clays, micas and miscellaneous materials.
4.4.4.1 Talc
Talc products are perhaps the most broadly functional of the extender pigments. Magne-
sium silicate or talc is the most popular extender in coatings of all types. It is available in

different particle shapes such as fibrous, platy, acicular or nodular. Moreover it is inert and
low in cost. The platy talcs are suitable for protective coatings as their particles overlap and
increase the diffusion path for corrosion stimulators to the metal substrate from outside.
Nodular talcs are said to improve adhesion properties of the paint film. Acicular types might
improve the film strength like the platy talcs. They are all easy to disperse and show good
anti-settling properties in the paint [77].
4.4.4.2 Kaolin
Kaolin or clay is a hydrous alumino-silicate and is one of the most popular extender pig-
ments in today’s coatings industry. It has a platy structure and is said to reinforce the paint
film. Because of its hydrophilic nature it is not widely used as extenders for anticorrosive
coatings. Its popularity derives more from the contribution to optical properties in archi-
tectural finishes [137].
4.4.4.3 Wollastonite
Wollastonite or calcium silicate is available in grades ranging from 10 to 100 micrometers
in particle size. It is an acicular pigment and acts as a reinforcer of the paint film. It shows
low oil absorption and moderate specific gravity. Wollastonite is slightly alkaline and water
soluble and was originally used in latex paints to maintain high pH levels. In the surface
treated form, the extender is widely used in anticorrosive primers, where it is said to con-
tribute to the corrosion resistance and reduction of blistering [138].
4.4.4.4 Mica
Mica has gained some importance in the formulation of anticorrosive coatings. Only the
Muscovite mica is in use, which is a platy pigment with a thickness no more than 1/25th
of the flake diameter. The wet-ground form is preferred for utilisation in protective coating
primers. The particle structure decreases moisture ingress and reduces blistering pro-
blems. Like talc, the platy particles overlap and increase the diffusion path for corrosion
stimulators. In zinc-rich primers mica has sometimes been used for partial replacement of
zinc. The high oil absorption as well as the high specific gravity have a distinct influence
on the critical pigment volume concentration (CPVC) of the coating [77].
4.5 Other additives

Apart from solvent carrier, binder and pigmentation to obtain colouring and corrosion
protection, organic coating chemicals contain a variety of additives [138, 139]. Any of these
additives are chosen for their specific purposes and their amount delicately tuned in a low
percentage, in order to achieve the desired effect without sacrificing the overall perfor-
mance of the coating.
Cross-linking catalysts may be added, like antimony and high-molecular tin compounds
as starter for the cross-linking of blocked isocyanates, in particular in cathodic electro-dip
paints, and boron trifluoride, BF3, to catalyse oxirane ring opening in epoxy polyaddition.
Extender pigments like silicates, carbonates, talc etc. are often added to give extra volume,
however they may also exhibit additional benefits. For instance, the doting of calcium car-
bonate with magnesium (dolomite, [Ca,Mg]CO3) leads to improved acid resistance, kaolin
(aluminium magnesium silicate) adds to the mechanical resistance, baryte and synthetic
“blanc fixe” barium sulphate, BaSO4, improve resistance vs. acids and other chemicals. The
scratch resistance of a coating is supported by addition of nanoparticulate compounds, e.g.
alumina or silica.

Other additives 91
Anti-microbial properties are achieved by addition of general-purpose antibiotics like

isothiazolinone derivatives or formaldehyde generators, or compounds that interfere spe-
cifically with the metabolism of bacteria, like dithiocarbaminates or silver doted zeolites.
Chlorinated phenols, tin and mercury compounds have been banned due to their eco-toxic
behaviour.
Corrosion and weathering resistance can be furthered by addition of polyolefinic waxes,
stearates and polysiloxanes that bring about a controlled hydrophobicity at the substrate/
coating interface, thereby increasing the insensitivity vs. moisture and water uptake.
Micaceous iron oxide is used as diffusion path extender (cf. Chapters 2.3 and 4.3.2.1). In
metallic paints, aluminium flakes are used that are passivated to improve the water resi-
stance of a film. The weathering resistance is also supported by UV absorbers (e.g. the
colourless and stable additives o-hydroxy benzophenone, oxalic dianilide, or 2-[2’-hydro-
xyphenyl] benzotriazole, that undergo mesomeric rearrangement under UV radiation) and
radical quenchers, i.e. so called “hindered amine light stabilisers” (HALS) like 2,2,6,6-tetra-
methyl piperidine N-ethers that form nitroxide radicals under UV radiation in the presence
of oxygen or peroxides as depicted in Equation 4.1 [140].
Equation 4.1:
Lubrication is brought on by solids or paraffinic wax additives. Solid lubricants comprise

graphite, molybdenum disulphide (MoS2) or polytetrafluoro ethylene (PTFE) and other fluo-
rinated hydrocarbons. The latter are unsuited when over-paintability is required; however,
they are preferred as anti-adhesive and filler (extender) in single-coat paints.
Further auxiliary additives are needed for rheology control (bentonites, polyacrylic acid,
modified siloxanes for surface slip control), as matting agents (silica and polyamide waxes),
or plasticisers (phthalic, phosphate, or adipic esters) that reduce the glass transition tem-
perature (Tg, cf. Chapters 2.2.1 and 5.2.1). Long primary alcohols, e.g. 1-dodecanol, help
to prevent boiling blisters, and various surfactants act as wetting agents and spreaders,
dispersants, defoamers, and degassing agents.
Fire resistant, intumescent coatings extend under increased temperature, thereby forming
effective heat insulation. Typically, they contain thermoplastic resins, e.g. copolymers of
vinyl acetate with ethylene or acrylate, ammonium polyphosphate or melamine phosphate
that release ammonia and water at temperatures of 300 and 550 °C, respectively, or liberate
nitrogen, carbon dioxide and water, as extender gases, in the presence of oxygen. Further-
more, polyalcohols, titanium dioxide (TiO2, rutil), china clay (kaolin) and inorganic fibres
may be incorporated.
Flame retardants may contain alkali silicate water glass, antimony trioxide, Sb2O3, or bro-
minated cycloaliphatic hydrocarbons. Chloroparaffins are being replaced by less toxic
materials, as they release hydrogen chloride, HCl, upon excessive heating.
Wash primers are particularly suitable as primer for repair areas. They contain a high-
molecular polyvinyl butyral resin, phenolic resin, phosphoric acid, and zinc chromate or
phosphate [141, 142].

4.6 Solvents
Solvents are important constituents, with a lot of parameters depending on them, like film
integrity, appearance, application, and even the service life of the coating system. Solvents in
general are transient components in coatings and polymer solutions. Other solvents are func-
tional (reactive solvents, plasticisers, etc.) and are not transient, however. They confer particu-
lar properties to the liquid as well to the dry coating and the finished system in service. Two
parameters related to solvents must be observed in order to make a proper solvent choice [9]:
• The solvency (or solvating power) of a solvent must allow to properly dissolve a polymer
and adjust viscosity in different stages of the manufacturing and application process.
The major principle of choice is generally known as “like dissolves like” (Latin: similia
similibus solvuntur).
• The evopouration rate of solvents, when used as a transient component, controls the
drying process and the viscosity of the film throughout its formation.
However the generally accepted definition of solvents emphasises the fact that they are
volatile in specific drying conditions and can dissolve film forming agents without any che-
mical reaction as well giving the guarantee of a processability of coatings from the liquid
phase [10–15].
Beyond coil expansion of the molecules of the film forming agent, the solvents generally
exhibit a lower surface tension promoting substrate wetting. As well the solvents assist the
application process by spray, dipping, rolling, etc. through the rheological properties they
confer to the coatings.
In general, solvents are considered as environmentally incompatible and also hazardous.
Recent legislation limits the level of solvent content and recommends the replacement of
hazardous solvents by more water which is environmentally compatible.
Organic solvents may be categorised as follows [4, 5], shown also in Table 4.14:
• Aliphatic hydrocarbons are solvents with good solvent power for non-polar polymers.
They may consist in mixtures of similar individual components having different boiling
points. Flash point temperatures below 21 °C require stringent manufacturing and
application conditions while solvents with flash points higher than 21 °C are good sol-
Table 4.14: Organic solvents for coatings

Class Example Features
Aliphatic solvent naphtha, cyclohexane solvate binders of low polarity, for polyvinyl ethers,
hydrocarbons neoprene; not suited for epoxies, polyesters, or
polyurethanes
Aromatic xylene, toluene particularly suitable for polyesters, polyacrylates,
hydrocarbons polyvinyl ethers, vinyl acetate mixed polymers
Alcohols n-butanol for aminophenolic resins, and polyvinyl acetates
form hydrogen bonds
Ketones isophorone low ketones: for polar resins
high ketones: for unpolar resins
Esters butyl glycol acetate suited for most resin types, good spreading,
avoid bubbles
Glycol ethers butyl diglycol propyl ether for polar resins, particularly alkyds, improve wetting
and spreading, co-solvents for aqueous paints

Solvents 93
vents for poor polarity polymers such as chlorinated rubber, long oil alkyds, and some
copolymers.
• Cycloaliphatic hydrocarbons are solvents presenting low solvency and generally a low
evopouration rate. They are less used in the coating industry but may significantly influ-
ence film forming properties at low and very low concentrations.
• Terpene hydrocarbons: are mainly used in combination with mineral spirit in air drying
organic film formers.
• Aromatic hydrocarbons are the “working horses” in the coating industry. They cover a
large range of boiling points and volatilities as well as they present a very good solvency
power. Benzene is effectively forbidden, but substituted derivatives are largely used in
coating formulations.
• Chlorinated hydrocarbons present very good solvency but for environmentally and physi-
ological reasons are limited in use. However they are still used at relatively large extent
for surface cleaning of substrates primarily in North America and Asia.
• Alcohols are solvents with high solvency and hydroxyl functionalisation group. They are
utilised in combination with high polarity polymers. The carbon chain length of alcohols
makes them preferably suitable either as a diluent or as a storage stabiliser in combina-
tion with other solvents.
• Esters are very good solvents for all polar polymers. The solvency and volatility of ester
type solvents are mainly related to the length of the alcohol used, considering the fact
that the main acids employed for these type of solvents are acetic acid and propionic acid.
A class of esters that must be mentioned here as making inroads in the coating market
comprises di-basic esters and cyclic carbonates from ethylene and propylene glycol.
• Ketones are strong solvents for polar polymers due to the capability of forming hydrogen
bridge bonds with polar groups of the polymer.
• Glycol ethers present high capability in hydrogen bonding and are significantly used in
water-borne coatings or high-temperature drying coatings.
• Nitrogen containing solvents such as dimethyl formamide and N-methyl pyrrolidone
have limited use in the coatings market but are of significant importance in relation to
polyurethane polymers.
4.7 Raw materials for powder coatings

Powder paints are considered to be particularly environmentally friendly, as they allow the
coating process to be performed without solvents and provide an efficient application. They
are applied onto cleaned and pretreated metal surfaces, by electrostatic methods (e.g. gun
spraying), by thermal fusion in fluidised bed processes or as slurries in water [145]. When
weathering resistance is required, it is common to use preprimed stock, e.g. in automotive
parts (electro-dip paint) or coil and sheet metal for architectural and appliance uses (con-
ventional coil coating primers).
Most powder paints are single-package, reactive systems. Curing in conventional, infrared,
near-infrared (wavelength 0.8 to 1.5 µm) or induction ovens comprises two steps: First flu-
idising and coalescing occur in the temperature range between 80 and 150 °C. The subse-
quent cross-linking is carried out at typical curing temperatures and times of 150 to 200°C
and 20 to 30 min [146]. Coating gauges usually are in the order of 50 to 100 µm, however, also
higher thicknesses can be obtained [147]. By induction preheating up to 260 °C, also substan-
tially shorter curing times in the order of 1 min are possible, enabling the technology to be
used in compact coil and sheet lines [148].
Powder primers and so called hybrid topcoats are usually based on epoxies and blends of
epoxy/acidic polyester, respectively. Admixing of polyester resins improves the resistance

Figure 4.65: Cross-linking agents for epoxy powder paints
against chalking and yellowing when exposed to elevated temperatures [149]. For increased
weathering resistance, polyester or polyurethane powders are used. In particular for clear-
coats in the automotive industry, polyacrylate based powders have become common that
are mixed from glycidyl functional compounds and dicarboxylic acid cross-linkers. They
are also commercialised as finely dispersed aqueous slurries that cure at particularly low
temperatures of about 140 °C. Thermoplastic powders (polyamide, PVC or PVDF based) are
only of minor importance [150].
Epoxies are commonly cured in the presence of di or trifunctional cross-linkers with epoxy
(glycidyl) groups. The use of triglycidyl isocyanurate (TGIC) has been largely discontinued
due to the mutagenicity of this compound. Alternatives include glycidyl esters of hexahydro
phthalic, isophthalic or trimellitic acid (cf. Figure 4.7.1) or β-hydroxy alkyl adipic amides and
blocked isocyanates or uretdiones in the case of urethane cross-linking [151–153].
a) tri-glycidyl isocyanurate (TGIC)
b) di-glycidyl hexahydrophthalate
c) tri-glycidyl trimellitate
d) di-glycidyl isophthalate
Further common additives for powder paints are alumina or silica to control pourability
while handling, applying and recirculating the overspray, and benzoin derivatives to sup-
port degassing during the melting and gelling phase.

Literature 95
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Physical drying 99
5 Film formation
Jörg Sander
5.1 Physical drying

Conventional coatings comprise macromolecules being suspended in a solvent, or emul-
sified and complexed in water. The solvent or water is also used to control viscosity of the
liquid. Curing of an organic coating therefore involves evaporation of the carrier solvent
before macromolecules can be physically deposited [1].
Polymer binder molecules that are solvated, i.e. disentangled and individually dissolved,
in the liquid paint close up and coalesce during this process of physical drying, thereby
forming a closed film, cf. Figure 5.3, Chapter 5.2.2.1. A film of suitable hardness and mecha-
nical resistance requires the polymer strands to mechanically entwine and form a spatial
structure, to obtain the necessary cohesion. Weak bonding via hydrogen bridge bonds may
occur and help in aligning the individual molecules. However, when dissolution is less than
ideal, polymer knots will persist throughout the paint manufacture and application and the
drying processes, making for failures in the film and cohesion losses. Therefore, the way of
dissolving has an effect on the final film forming result, and the mechanical/technological
features of coatings may be different, despite an identical composition. Moreover, films
formed in this way do not provide chemical fastness, in particular resistance to solvents.
Furthermore, they display thermoplastic behaviour, which means that they soften and even
may become fluid again with increasing temperature.
The film formation in aqueous dispersions, by contrast, is ruled by the reduction of total
surface of particles that were initially dispersed as individuals, resulting in a fused film
that ideally has no interstices between particles. This can be interpreted as a gain of free
surface energy or as the action of attraction forces between dispersion particles. In effect,
the attraction is so strong as to compress the initially spheric particles to a hexagonally
stacked layer of rhombic dodecahedrons, as can be shown by electron micrographs. Again,
hydrogen bridge bonding does increase the cohesive force. When admixed with a solution
of inorganic compounds, the latter can be found along the interfaces of compressed disper-
sion particles. Reactive inorganics, like chromates, react with the particle surfaces, forming
linking bonds that provide a kind of chemical curing. A similar reaction path is known for
the interaction of acidic polyester resin with ammonium zirconyl carbonate [2].
This mechanism requires a viscosity that allows dispersed polymer particles to flow easily.
Any dispersion, therefore, has a minimum film forming temperature (MFFT), below which
the viscosity is too low. When necessary, the MFFT can be decreased by addition of organic
solvents that boil above water. Alternatively, the molecular mass of the film builder might be
reduced which softens the dispersion, however sacrifices film properties like the abrasion
resistance.
The viscosity change during the process of physical drying can be described by Equation
5.1 which illustrates that the logarithm of the viscosity, η, is proportional to the solid content
percentage, % SC, and the square root of the average molecular mass, Mn, of a liquid paint.
Figure 5.1 depicts the situation for physically drying (a) vs. chemically curing (b) coatings

ISBN 978-3-86630-805-3

100 Film formation
Figure 5.1: Schematic: film formation regimes by physical drying vs. chemical curing [1]
in an lg η / 
Mn diagram for a given solids content. Physically drying coatings contain poly-
mer particles with a relatively high molecular mass that have to be derived from monomers
during the paint manufacture. These are also relatively hard, and must be softened by addi-
tion of solvent. Upon evaporation, the viscosity increases again, forming a film according to
the mechanism described above, without a change in molecular weight. This is represented
by a vertical and reversible shift of the polymer state in the diagram.
Equation 5.1 lg η = ∞ % SC · 
Mn
η = viscosity
% SC = solid content percentage
Mn = average molecular mass
5.2 Chemical curing

5.2.1 Thermal cross-linking: chemistry, mechanism, imparted
properties
To obtain coatings with chemical and higher mechanical resistance, the formation of a
molecular network is necessary. It is brought about by reaction of suitable end or side-chain
groups of the polymers that form additional cross-links. The polymer size, obtained by
prereaction from the monomer, is relatively low, and only little solvent is added to adjust
working viscosity. Curing involves evaporating the solvent plus chemical cross-linking,
thereby increasing polymer size (and molecular mass) by magnitudes (cf. Figure 5.1b).
The enlargement of polymers can occur via addition, condensation or polymerisation mecha-
nisms. Polyurethane links form by reaction of isocyanate and hydroxyl (–OH) functions
by way of an addition. As isocyanates are reactive species, that undergo conversion with
many different partners (amino, thiol, carboxylate, ether) and are also water-sensitive, they
are usually blocked to obtain stabilisation. Suitable blocking agents are protic compounds

Chemical curing 101
like malonic acid derivatives, lactones or lactams (cyclic esters or carboxylic amides), e.g.
ε-caprolactam, that provide thermally reversible blocking. Typical de-blocking temperatures
range from 100 to 180 °C [3]. Cross-linking of polyesters and chemically related alkyds (class
of polymers that is synthesised from natural or semi-synthetic oils and fatty acids and poly-
ols, cf. Chapter 4.2.1) is obtained by reaction of the –OH groups with co-resins like polyisocya-
nate, melamines, anhydrides etc. [4], the reaction with the isocyanates yielding polyurethane
resins with their typical features of high durability and temperature insensitivity.
When the polymer growth is predominantly linear, the resulting coating will behave as a
thermoplastic, i.e. soften and eventually liquefy with increasing temperature. Cross-linking
to a three-dimensional network yields duroplastics. These are characterised by the transi-
tion between the amorphous, glassy and the crystalline state at the glass transition tempe-
rature Tg, where a sudden softening and increase in elasticity occurs, however retaining a
residual level of mechanical hardness [5].
Cross-linking paints cure in a temperature/time window that allows relatively low tempe-
ratures and a wide temperature tolerance band between under and over-curing at extended
curing times, while with shorter times, the required temperature increases as well as the
tolerance becomes more sensitive. Under-curing leads to soft, non-resistant coatings, while
over-curing usually results in brittle, cracking films with poor adhesion or even thermal
degradation indicated by discolouration (yellowing). The required temperature is defined
by type of cross-linking, more often also by the temperature where de-blocking occurs. The
curing time for batch operations often is in the range of 10 to 30 min [6]. In fast coil coating
lines, typical curing temperatures are as high as 240 °C, and reaction times of some 30 s are
required to complete solvent or water evaporation, uniform deposition and cross-linking [7, 8].
5.2.2 Radiation curing

5.2.2.1 Chemical principles and intrinsic properties
In recent years, a fair amount of research has been focused around radiation curing
systems [9–12]. Ultraviolet (UV) or electron beam (EB) curable formulations have been in
use for applications like wood painting and preservation, paper and foil printing, or flexi-
ble packaging. The major advantages of this technology are speed of reaction that allows
short installations and facilitates immediate onward processing and “cold curing” that is
much more energy efficient, i.e. offers up to 90 % energy savings, when compared to con-
ventional thermal curing [13], and enables temperature-sensitive substrates to be coated.
UV coatings are known as solvent or waterborne systems with solid contents up to 85 %.
However, also liquid, fully reactable, “100 %” systems are available that utilise “reactive
thinners” to control viscosity. Obviously, prior to curing, water or solvents must be tho-
roughly evaporated from diluted systems by heating (convection, infrared or induction),
sacrificing part of energy gain. Upon UV irradiation, the reaction completes within fractions
of a second.
The technology of radiation curing involves photo-chemistry, which is utilised to form a
cross-linked polymeric film in-situ on the substrate from monomeric or oligomeric precur-
sors. Issues often encountered with radiation cured polymeric films include volume con-
traction (shrinkage) that occurs during the rapid polymerisation, and brittleness due to
over-dense cross-linking. In combination with lack of suitable anchor groups to attach the
forming film to a metal surface, adhesion to metallic substrates used to prove difficult to
achieve in the past. However, radiation curing also offers undisputable benefits, in parti-
cular for the coil coating process, where a flat substrate has to be coated and cured in very

102 Film formation
Figure 5.2: High-energy end of the electromagnetic spectrum
short times. The economic and environmental efficiency of the process has been the driver
to develop and adapt UV and EB curable formulations for the purpose of coating flat metallic
work pieces. The UV technology has been incorporated into the first coil coating lines.
UV is part of the electromagnetic spectrum, more energetic than visible light. Wavelengths
of UV radiation range from approximately 200 to 400 nm cf. Figure 5.2. UV triggered
polymer formation can occur via radical or cationic mechanisms. The radical mechanism
involves generation of a sufficient concentration of radicals to be started, and propagates
through attack of these radicals on unsaturated organic compounds with carbon-carbon
double bonds (C=C) like acrylic acid and its derivatives. A radical UV photo-polymerisation
is described schematically by Equation 5.2.
Equation 5.2

h = Planck’s Constant; ν = frequency of electromagnetic radiation
UV curable coating chemicals

are fundamentally different from
conventional, thermally curing
systems. Figure 5.3 depicts the
systemic differences. Instead of
polymers dispersed in a solvent,
they consist of a mixture of single
organic molecules (monomers or
so-called prepolymers) and photo-
initiator molecules, R–Y, that are
sensitive to UV radiation of suita-
ble energy, E = hν. Being a latent
and stable system when kept in
the dark, the photoinitiator mole-
cules decompose, via an excited
Figure 5.3: Systemic differences between thermal and state [R–Y]*, into reactive radi-
radiation, e.g. UV curing cals when exposed to radiation.

Chemical curing 103
Figure 5.4: Examples of photoinitiators for radical UV photopolymerisation
Common photoinitiators are benzoyl compounds, preferably with hydroxyl groups on the
adjacent carbon atom, e.g. benzoyl phenyl hydroxyethane, which will readily decompose
under UV irradiation by α-cleavage (Figure 5.4a; Norrish Type I reaction) [14]. Other typical
photoinitiators are acyl phosphine oxides (Figure 5.4b) that undergo a cleavage between
the carbonyl and the phosphino group under radiation with a wavelength above 370 nm, or
benzoyl chloro methane (Figure 5.4c). The radical fragments add to the terminal end of the
prepolymer C=C double bond, resulting in an extended radical which in turn reacts with
further prepolymer, so that a polymer chain or network develops. The most likely pathway
to terminate the polymer growth involves reactive, radical ends of the growing network
to combine and form a bond. Other, less desirable, pathways include reactions with other
accessible partners. For example, oxygen interferes with reactive centres in a radical reac-
tion. Therefore nitrogen atmosphere is often preferred for UV curing.
The most common prepolymers for radical UV polymerisation belong to the class of acrylic
or methacrylic acid esters. The ester can be formed with any hydroxyl function containing
compound, cf. Figure 5.5. Useful synthons for ester groups are multi-functional alcohols,
amino alcohols and their ethoxylated or propoxylated derivatives, as these allow onward
reactions on other terminal functional groups. Polar, and in particular protic, terminal
groups enable metal adhesion by virtue of their acidic nature. Examples are acrylated esters
of phosphoric and phosphonic acid (Figure 5.6) [15].

104 Film formation
Multi-functional acrylates allow

cross-linking in two (“rope lad-
der”) or three dimensions (“net-
work”), thereby increasing the
barrier effect of the film that is
formed. Popular synthons are
trimethylol propane triacrylate
and its ethoxylated derivatives.
In principle, acrylate groups can
be bonded to any core molecule
of suitable chemistry, including
polyurethanes, polyesters and
epoxies. The chemical features of
the resulting polymer correspond
to the properties of the prepoly-
Figure 5.5: Acrylic and methacrylic acid derivatives as
mer backbone. Monomeric and
versatile precursors for radical UV polymerisation
polymeric materials with four or
even six terminal acrylate groups
are commercially available. However with higher cross-link density, the film will also
become less flexible. UV cured coatings must be elaborately tailored to balance the chemical
and mechanical features of the film according to the specific needs. To this end, the vast
variety of acrylate precursors with different backbone chemistry that are commercially
available is very useful.
The cationic mechanism proceeds via liberation of protons (H+) and their attack on electron-
rich C=C groups (vinyl, allyl ethers) or cyclic ethers (epoxides, oxetanes). Cationic processes
display benefits as well as disadvantages vs. the radical systems. They are usually less
prone to shrinkage and brittleness, insensitive to oxygen, and allow “dark” and “shadow
cure”, as the initiating acid remains to be active after the irradiation has stopped. However,
cationic processes are sensitive to moisture, and proceed at lower speed.
Dual cure systems combine both reaction pathways by using precursor materials that carry
both reactive groups. Examples for suitable precursor chemistry are oxetane acrylates
(cf. Figure 5.7) or glycidyl methacrylate.
Figure 5.6: Terminal phosphate and phosphonate functionalised acrylates for UV metal coatings

Chemical curing 105
Figure 5.7: Bifunctional monomer for UV dual cure systems
A summary and comparison of the characteristics of the radical and cationic UV coating
technology is given in Table 5.1.
EB curing is brought about by accelerated electrons of high energy (90 to 250 keV or higher)
that are capable of direct attack on C=C double bonds, triggering radical polymerisation.
Therefore, though in principle similarly constituted as the UV curable formulas, EB curable
coating chemicals do not contain photoinitiators. A further benefit is the very fast reaction,
leaving a very low residual free radical activity, hence no uncontrolled side reactions. More-
over, EB is unobstructed by pigmentation. Currently, EB lines are operated in wood coating
(doors, wood fibre board or parquetry) or in printing. The industrial application for metal
painting is a focus of development for the near future.
5.2.2.2 Applications
An interesting option for radiation curing emerges from the combination of pretreatment
and primer functions in one product. Such a process could be incorporated in a coil coating
Table 5.1: Comparison of UV curing systems

UV curing, radical UV curing, cationic
Binder chemistry prepolymers with polyester, polyure- vinyl ethers, epoxides, oxetanes
thane, epoxy backbone and acrylate
functional groups
Photoinitiator alkyl phenones and a-hydroxy pheno- aryl iodonium or sulphonium salts
nes; acyl phospine oxides; thiols
Advantages fast reaction reaction completes without irradiation

(“dark phase”); formation of hydroxyl
groups supports adherence to metals
Limitations shrinkage, brittleness (cross-linking slow reaction

density)
sensitive to oxygen sensitive to moisture
clearcoats and lightly pigmented
lacquers
photoinitiator cleavage products are
usually not food safe

106 Film formation
Figure 5.8: Proposed workflow for a UV curable primer pretreatment
where: (a) installation integrated in a coil coating line;

(b) in-line operation at the exit of a hot-dip galvanising line;
(c) adapted roll-coater and UV lamp array; (d) in-line or off-line topcoat operation
line. Equally, equipment for the application and the curing can be installed and operated, in
particular, with very low floor space demand and no need for thermal combustion of solvent
exhaust, in the exit zone of a coil galvanising line. Figure 5.8 depicts a schematic overview
on the workflow options of such an operation [16, 17].
Developmental products for a combined primer pretreatment have been reported elsewhere,
yielding cross-linked, non-blocking, adherent films of approximately 2 to 3 µm gauge
(specific consumption 3 g/m2) that provide the required capability for forming, as well as
sufficient corrosion resistance in laboratory testing [18].
As another example for the versatility of UV curing, a protective clearcoat for stainless steel
coil and sheet (ferritic and austenitic alloys) has gone commercial for domestic appliance
uses. The coating is transparent and, being applied in very thin films of less than 2 µm, does
not disguise the metallic look. It is claimed to withstand extended exposure to sunlight or
heat without discolouration and to prevent staining from fingerprints and contaminations
with common domestic cleaners and foodstuffs like mustard, lemon juice etc. Brush and
scratch resistance of this coating was also demonstrated by respective tests. Bending and
deep-drawing capability are restricted, due to the required mechanical hardness [19, 20].
UV curable coatings are also discussed to be used as sealants for bare, exposed metal areas,
like freshly cut edges of sheet. For this purpose, the coatings are applied with thicknesses
of 10 to 250 µm [21].
5.2.2.3 Equipment
Common UV lamps are mercury (Hg) vapour lamps that emit a spectrum with a maximum
around 365 nm. When UV absorbers are present (e.g. titanium dioxide, TiO2) in the formu-
lation, the UV lamps may be doted with gallium, indium or iron, to bring about emission
spectra with bands above 400 nm wavelength.

Chemical curing 107
High-pressure UV equipment [22, 23] is available with high energy output as is required for
the fast and wide-web operation of a coil coating line. Typical lamps have power ratings of
120 to 180 W/cm and offer output densities of 2 W/cm2, sufficient for high-speed curing up
to 100 m/min per lamp for clearcoat systems. For an industrial coil coating line, an array of
several lamp rows must be installed that covers the whole width of the strip and provides
sufficient radiation energy for the desired line speed. A range of industrial suppliers offer
total systems including lamps, power supply and amplifiers, reflectors and shutter systems
as well as cooling and air/nitrogen supply. Lamp technology includes electrode plasma
discharge lamps and electrode-less, microwave triggered lamps.
Obviously, for industrial line operation, safety precautions regarding radiation protec-
tion are a prerequisite. When working without inert atmosphere, the exhaust gas must
be delivered outside the plant building to avoid accumulation of ozone in the workplace
atmosphere. However, no gas washer is required, as the ozone self-decomposes. Moreover,
because there is no solvent involved, the process does not demand an incineration system.

108 Film formation
5.3 Literature
[1] Goldschmidt, A., Streitberger, H.-J., Basics of Coating Technology, 2nd Edition, BASF Coatings AG,
Münster 2007, pp. 327 ff
[2] Manea, M., High Solid Binders, Vincentz, Hannover 2008, p. 106
[3] Müller, B., Rath, W. Formulating Adhesives and Sealants, Vincentz, Hannover 2010, pp. 143 ff
[4] Manea, M., [2] pp. 63 ff, 81 ff, 87 ff
[5] Goldschmidt, A., Streitberger, H.-J., [1] pp. 385 ff
[6] Goldschmidt, A., Streitberger, H.-J., [1] p. 592
[9] Manea, M., [2] pp. 50 ff, 125 ff
[10] Kittel, H., Streitberger, H.-J. (ed.), [8] pp. 253 ff, 378 f
[12] Meuthen, B., Jandel, A.-S., [7] pp. 136 f, 300 f
[14] Coxon, J. M., Halton, B., Organic Photochemistry, Cambridge Univ. Press, London 1974, pp. 58 ff
[15] Grundmeier, G., Stratmann, M., Adhesion and De-Adhesion Mechanisms at Polymer/Metal Interfaces:
Mechanistic Understanding Based on In Situ Studies of Buried Interfaces, Annu. Rev. Mater. Res. 35, 2005,
pp. 571 ff, 577
[16] Heylen, M., Franzolin, G., Radiation Curable Coil Coatings: Innovative and Feasible Solutions for the Steel
and Aluminium Industry, ECCA Autumn Congress Brussels, Proc., European Coil Coating Association,
Brussels 2005
[17] Brown, N., Radiation Curing Systems in Coil Coating, ECCA General Meeting Maastricht, Proc., European
Coil Coating Association, Brussels 2006
[18] Sander, J., Koch, M., Picot, P., Réticulation UV – Une nouvelle approche pour le „coil-coating“ (UV Curing
– A New Chemical Approach for Coil Coating), Centre d’Actualisation des Connaissances et de l’Etude des
Matériaux Industriels (Cacemi), Journée spécialisée, Proc., Paris 2002
[19] anon., Edler Touch für Edelstahl – Neue Oberflächenbehandlungen erhalten die elegante Optik des
Edelstahls (Noble Touch for Stainless Steel – New Surface Treatments Preserve the Elegant Aspect…),
Stahlmarkt 04, 2007, pp. 50 f; cit. re. Meuthen, Jandel [7] p. 136
[20] Sander, J., Up To Scratch With Novacoat 1000 UV, Steel & Aluminium Newsletter, Henkel KGaA,
Düsseldorf 2007
[21] Meuthen, B., Jandel, A.-S.,[7] pp. 227 f
[22] Jung, J., Härtung von Druckfarben und Lacken durch UV-Strahlung (Curing of Printing Inks and Paints by
UV Radiation), IST-Metz GmbH, in: Dtsch. Berufsgenossenschaft Energie Textil Elektro Medienerzeugnisse
(Institution for Statutory Accident Insurance and Prevention – Energy Textile Electro Media Products,
Working Committee for UV printing) BG ETEM (ed.), UV Technology – A Practical Guide for all Printing
Processes, BG ETEM, Wiesbaden 2007, pp. 29 ff
[23] Skinner, D., New Development in UV Curing Systems for the Coil Coating Industry, ECCA Autumn Congress
Brussels, Proc., European Coil Coating Association, Brussels 2004

Measurement of physical properties and influence 109
6 Mechanism of protection and

properties of organic coatings
Jörg Sander
6.1 Measurement of physical properties

and influence
Testing of the performance of an organic coating comprises a number of optical, mecha-
nical and corrosion tests. First and foremost, any coating must be properly cured and it
must adhere well on its substrate,
i.e. the primer must stick to the
metal, which is supported by the Table 6.1: Major test methods on the physical features of
correct pretreatment, and any sub- organic coatings
sequent paint layer must adhere Test, feature Norm
on the foregoing coat (intercoat Film thickness, gauge DIN EN 13523-1
adhesion). While there are speci- Colour DIN EN 13523-3
fic tests for individual layers, par-
Hardness, pencil; scratch resistance DIN EN 13523-4
ticularly related to their curing
Buchholz; resistance to cuts DIN EN ISO 2815
and adhesion features, finally the
Impact; cracking resistance to fast DIN EN 13523-5
entire finish has to pass labora-
deformation
tory and application tests. Table
6.1 summarises the major tests Bending; coating elasticity, DIN EN 13523-7
on the physical features of an crack resistance
adhesive tape; substrate adhesion ditto
organic coating [1].
MEK Test; curing (cross-linking) and DIN EN 13523-11
Apart from cosmetic properties adhesion
(colour, gloss) and hardness, espe- Heat resistance; mechanical effect of DIN EN 13523-13
cially the total thickness of a coat- ageing
ing and its adhesive and elastic
Foil adhesion, protective foils DIN EN 13523-17
properties are of interest, as any
failure in these areas may result According to Meuthen, Jandel [1]
in corrosion.
6.2 Dry film thickness

The thickness (gauge) of an organic coating determines the final aspect, barrier perfor-
mance, and mechanical properties of the surface finish. High gauges are beneficial to the
barrier properties, in particular as an obstacle to the diffusion of water and gas, however
usually adversely affect hardness and deformation behaviour. As surface roughness must
be taken into account, and any coating will retract from edges due to the action of surface
tension, local gauges will inadvertently vary. It is, therefore, important to apply a minimum
average coating thickness, in order to ensure sufficient coverage.
Measurement of the dry film thickness [2, 3] is often done by intrusive methods, e.g. by
cutting a wedge-shaped scribe or drilling a conical bore into a coating, or by preparing a

ISBN 978-3-86630-805-3

110 Mechanism of protection and properties of organic coatings
cross-section and measuring the thickness directly under a microscope. On the micrometre
or even smaller scale, electron microscopy or focused ion beam techniques are used. To cope
with the local thickness variation, several single measurements must be performed and
averaged to obtain a statistically reliable result. Another method uses differential weighing
of coated samples before and after paint stripping. The paint can be removed by wiping with
methyl ethyl ketone or immersing in warm dimethyl formamide. All other, non-destructive
methods rely on intrusive tests for calibration.
Ferromagnetic substrates like carbon steel can be inspected by electromagnetic measure-
ment. The magnetic flow is influenced by the thickness of the non-magnetic coating, there-
by resulting in a decrease of response voltage by induction. Eddy current measurements
form the principle of similar techniques for diamagnetic substrates (aluminium, copper,
brass, austenitic stainless steel). Both methods are subject of norm pr DIN EN 13523-1.
Continuous measurement of the dry film thickness is possible by back-scattering of
β-particles (electrons) released from a radioactive krypton-85 source (85Kr). The emission
of secondary electrons is dependent on the thickness (DIN EN ISO 3543). Another method
uses the propagation and reflection of heat at interfaces. The heat is induced by carbon dio-
xide LASER irradiation and monitored by an infrared sensor (DIN EN 15042-2). Due to their
extremely fast response, both methods are preferably used in coil coating.
Coating thicknesses may vary between a few micrometres (corrosion protection primers,
CPP, or backing coats in coil coating) and several hundred micrometres in severe corrosion
protection in water engineering and shipbuilding cf. Chapters 2.1.3 and 6.5.2.
6.3 Adhesiveness
6.3.1 Role of adhesion and factors of influence
Adhesion [4, 5] of an organic coating is its most important property, as any coating that does
not adhere will not serve any purpose. Adhesion of an organic coating must ensure that the
coating will remain in its place despite any intentional deformation (flanging, profiling, ben-
ding), shear or torque force (cutting, drilling, honing, screw fastening) during the manufac-
turing process of a work piece, dynamic load by stretching, compression and torsion or also
accidental deformation (impact, stone chipping) [6] during service life.
Adhesion, however, is also a precondition for a long lasting coated product to serve in a
corrosive environment. In particular for coil coating, where deformations of the sheet metal
are extreme to obtain the final shaped work piece (e.g. appliance equipment housing, car
body parts made from preprimed sheet, or food cans and lids and crown corks [7]), insuffici-
ent adhesion and elasticity may cause weak points prone to corrosion by the appearance of
cracks, even though no immedi-
Table 6.2: Selected chemical bond strengths ate delamination occurs. In addi-
Chemical bond Binding energy tion, mechanical stress can also
(kJ/mol) be induced by volume changes
Al – O 512.1 due to hydrothermal stress (cf.
Chapter 6.6.1).
C–O 1076.5
Fe – O 408.8 The explanation of adhesion is
P–O 596.6 often reduced to describing a
mere mechanical interlocking of a
Zn – O 284.1
coating in the cavities on a rough
According to Weast, Astle [10] substrate surface. However, while

Adhesiveness 111
a certain micro-roughness of the surface is certainly helpful, adhesion is much more the
effect of van-der-Waals attraction forces between the substrate and molecules of the coating.
As these forces apply in the nanometre range, a precondition is the proper wetting of a sur-
face to allow contact (cf. Chapter 3.1.3). Here again, the importance of proper cleaning and
pretreatment of the surface becomes obvious [8]. Adhesive forces include dipole and inductive
attraction with a binding energy level of 5 to 25 kJ/mol, and hydrogen bridge bonds that can
form between protic molecules (hydroxy, mercapto, amino functions) and metallic/oxidic sur-
faces, representing the 50 kJ/mol level. Chemical bonds like metal-to-oxygen bonds are much
stronger, i.e. several 100 kJ/mol, hence desirable as adhesion promoters. Table 6.2 shows the
strengths of a few selected chemical bonds that occur in organic coating of a metal [9, 10].
In terms of the chemical nature of the binder, thermoplastic binders like polyvinyl chloride,
PVC, provide a very good adhesion which, together with their chemical inertness, makes
them suitable for application in the food and beverage can sector. Also polyesters and poly-
urethanes and their hybrids are acknowledged to give good metal adhesion and formability.
For example, they form the standard resin base for coatings in the manufacture of utility
and railway vehicles or aircraft. Epoxies display very good primary adhesion, however
restricted formability due to their inherent brittleness [11, 12].
6.3.2 Measurement of adhesion and elasticity

6.3.2.1 Industrial methods
In the industrial practice [13 – 15], adhesion tests comprise direct assessments of the adhesive
performance or application tests that simulate practical use. The former class are pull-off
or torsion shear tests. These are carried out by gluing a circular or ring punch onto the test
surface with an adhesive selected to provide a stronger bond than adhesion and cohesion
forces expected for the test specimen, then tearing off the punch from the test panel by
perpendicular pulling or by radial twisting. The applied force is measured and the damaged
area inspected for the aspect and pattern of the rupture.
For the latter class of tests, the cross-hatch test is most common, where two perpendicular
sets of cuts are applied on the coated surface, the cuts being regularly spaced by 1 or 2 mm
(coatings below or above 60 µm thickness, respectively), so that a grid of small squares is
formed in the centre area. The adhesion is assessed by fixing an adhesive strip on to the test
grid, pulling it off and inspecting the grid for the number of removed squares. A code Gt 0
to Gt 5 is defined by norm (DIN EN ISO 2409) for the assessment and classification of the
failure. Other tests comprise peel (e.g. ASTM D-1876-08) [16], stone chip and “coin scratch”.
Concerning adhesion of a coating under deformation, industrial tests usually involve stan-
dardised forming. Common tests comprise bending around cylindrical or conical mandrels
or T-bending, i.e. the bending of sheet material back on itself. For the mandrel tests, the
minimum numerical radius is measured that can be applied before the coating flakes
(adhesion) or shows fissures (elasticity). In the T-bend test, the inner radius is expressed in
multiples of the sheet thickness, i.e. a panel bent back on itself has a bending value of 0T,
when one sheet of the same thickness is slit in, a value of 0.5T and so forth (DIN EN 13523-7);
it must be noted that the corresponding American norm (ASTM D-4145-83) sets a different
definition that results in double T values.
The deep drawing capability of coil coated sheet is assessed using the Erichsen dome test
(Erichsen cupping). A cup is slowly formed in the test specimen, using a punch with a
20 mm spherical tip, and the deformation denoted (in millimetres dome height) that can be
applied before paint delamination occurs on flanks or top of the dome. Often the deformation

is combined with a cross-hatch, and the adhesion assessed by taping. Ideally, no delami-
nation occurs until rupture of the metal itself (DIN EN 13523-6). Other deep drawing tests
comprise the drawing of cylindrical or quadrangular cups, simulated food or beverage cans
etc., and inspection for forming failures.
Shock deformation is assessed by ball impact tests etc., using a weight with a small ball tip
that is dropped on the test surface. The test result displays the energy, given as weight by
fall height, sometimes also converted in Joules, [J], that can be applied before paint delami-
nation is observed (DIN EN 13523-5; DIN EN ISO 6272).
Propagation and reflection patterns of heat or sound in thermographic or (ultrasonic) echo
methods that are used for thickness measurements (cf. Chapter 6.2) can be evaluated to
detect adhesion failures. These methods, however, do not give exact numerical values for
adhesion strength [17].
6.3.2.2 Laboratory methods

A very versatile scientific method to obtain topographic and surface force data in a micro-
scopic scale is the atomic force spectroscopy, AFM. AFM is based on the principle that
a cantilever tip is deflected upon approach towards and removal from a surface, due to
van-der-Waals attraction and repulsion forces. By monitoring the cantilever motion, force-
distance diagrams are obtained. Using an oscillating cantilever, a true topographic map
is derived. The method is applicable in gaseous and liquid environment, thus enabling
the study of adhesion phenomena on electrolyte covered metallic or oxidic surfaces. This
Equations
method is so accurate as to allow studies of the effect of electric field and pH changes in the
electrolyte on attraction forces, or single-molecule adhesion investigations [18].
ி
ߪ ൌ ൌ ‫ߝܧ‬
(6.1)6.1:
Equation Hooke´s Law Hooke’s Law
஺
where σ = tension;
F = force;
where σ = tension; F = force; A = cross-section;  = elongation (as fraction l
A = cross-section;
of the
initial
ε =length l); E(as=fraction
elongation modulus ∆l of(material specific)
the initial length l);
E = modulus (material specific)
Elasticity [19] is described by Hooke’s Law (Equation 6.1), that is followed by any real material
like(6.2 a – d)coating only for very small deformations. Above a critical value, it can be
a polymeric
considered that the polymers of a resin are disentangled and stretched, but can rearrange
and obtain a new conformation upon strain relaxation (visco-elastic flow). Upon overstret-
ching, the material will suffer irreversible conformational changes and finally bond brea-
king and rupture.
Duroplastic materials have two regimes of elastic deformation, separated by the glass transi-
tion temperature Tg, and being characterised by two different moduli. Below Tg, the polymer
film is glassy and rigid (high modulus) and displays brittleness. Above Tg, elasticity is much
higher (low modulus). While part of the conformational changes that have occurred at low
temperature may be reverted when the coating is heated above its Tg (cf. Chapter 6.6.1) [20],
fissures and cracks are irreparable once they have occurred. Deformation of a coated work
piece therefore is preferably done at temperatures above Tg.
Elasticity can be measured macroscopically on free polymer films by monitoring the elonga-
tion or torsion versus force and temperature. To obtain visco-elastic data, dynamic mecha-
nical methods are available. On a microscopic scale, the deflection of a stressed material
can be monitored by AFM.

Permeation through organic coatings 113
6.4 Permeation through organic coatings

The role of water uptake in weathering and corrosion processes has already been touched
in Chapter 2.2.1. Any coating acts as a semi-permeable wall to water vapour and liquid,
which will inadvertently penetrate the coating. It will also serve as a carrier for electrolytes
and corrosive gases [21]. To assess water uptake, gravimetric, optical (e.g. attenuated total
reflection infrared spectroscopy, ATR-IR) and electrochemical, in particular capacitance
and electrochemical impedance spectroscopy (EIS, cf. Chapter 7.2.3), methods have been
used [22]. As the dielectric constant of water is substantially higher than for most organic
matter the water uptake results in an increase of the total capacitance. It can be monitored
over time, as well as in its relative extent, and the percentage of water present in the coating
can be calculated [23, 24].
Water uptake has substantial effects on the plastification of a polymer film and on adhesion,
as shown by a comparison of water uptake and peel test results of an epoxy amine adhesive
as an example [25]. ATR-IR inspection confirmed that the water uptake reaches a saturation
level that is dependent on the relative humidity (rH). For the epoxy amine, saturation is
achieved after 48 h. At high humidity (rH = 97 %), the water uptake is almost double the
value observed at low humidity (rH = 82 %). This coincides with a loss of adhesion. Peel
results were reduced by a factor of 3 between low and high humidity regime. The water is
stored in the bulk coating, which is indicated by the absence of a separated water film at the
interface, the saturation level of 2 to 2.5 % water in the coating, and values of the diffusion
coefficient in the order of 2 · 10–9 cm/s, both regardless of whether an intact or a defective
coating was investigated [26].
The rate of water uptake quite normally depends on the chemical nature of the polymeric
backbone. In a comparison, a polyvinyl chloride paint showed very low, an acrylic coil
coating paint a medium, and an automotive acrylic melamine clearcoat system a relatively
high uptake [27].
6.5 Corrosion protective performance

6.5.1 Titanium and zirconium fluoro complex based
pretreatments
In coil coating, chromium-free pretreatment chemicals based on aqueous solutions of tita-
nium (Ti) and/or zirconium (Zr) fluoro complexes (cf. Chapter 8.2.7.1) have been commercial
since more than a decade. They have been reported to provide sufficient corrosion protection
and adhesion to subsequent topcoats. Figure 6.1 shows a façade part clad with coil-coated
V-groove aluminium panels after 10 years service life. The panels, along with sun blinds,
prepared with a chromium-free no-rinse pretreatment and top-coated with high-durable
polyester, are mounted on a south-facing wall, covering an area of about 1,200 m2. The
façade is exposed to sun, wind and rain in an industrial site, and also encountering mecha-
nical damage around loading areas, but does not show any corrosion even at critical points
like punch-holes, bolt and screw joints or dripping edges [28].
Strong correlation and comparability between chromium-free and chromate pretreatments
in various outdoor and accelerated corrosion tests have been shown for a chromium-free
architectural pretreatment for steel, galvanised steel and Galfan substrates. Figure 6.2 dis-
plays some laboratory results, showing the maximum creepage values from the scribe mark
as were reported under commercial polyester coil coating systems in comparison to stan-
dard chromate spray and no-rinse pretreatments. In the same paper, 360 h salt spray results

were shown to correlate well with

3 years outdoor exposure results
from Hook of Holland, compa-
ring 13 coil coated samples with
chromate and chromium-free pre-
treatments that gave a maximum
creepage of 0.5 mm. Fully equi-
valent anticorrosive performance
between the standard chromate
and the chromium-free systems
Figure 6.1: Chromium-free coil coated was confirmed in cyclic corro-
aluminium V-groove sheet Source: Henkel AG & Co.KGaA [28] sion testing including VDA and
prohesion tests (see Figure 6.3).
Moreover, the chromium-free
pretreatment appeared to provide
good process stability in terms
of the distribution of creepage
and T-bend adhesion values (see
Figure 6.4) [29].
A series of experiments using
the height-regulated “scanning
Kelvin Probe” technique (HR-
SKP, cf. Chapter 7.2.4.2) was
carried out to get some insight
in the anticorrosive mecha-
Figure 6.2: Laboratory testing on corrosion resistance nism. The results are shown in
Source: ECCA 1999, [29]
Figure 6.5. Electro-galvanised
panel samples were cleaned
and etched following a standard
laboratory process, covered
with a protective tape across
one end (forming the y-axis),
then, perpendicular to it, along
the x-axis, pretreated on half
of the remaining bare surface.
The entire specimen was then
coated with a model clearcoat.
Upon removal of the protective
tape, the specimen displayed a
treated and an untreated area
adjacent to each other, both
coated with the clearcoat and
having a sharp border to a bare
metal surface.
One part of the bare surface (left
area in the schematic of Figure
Figure 6.3: Creepage values for chromate and chromium-free 6.5) was encased with small
pretreatments (coils from industrial production, 360 h salt stripes of resin, to form a small
spray vs. 3 a outdoor exposure, Hook of Holland, scribe to container which was filled with
zinc substrate) Source: ECCA 1999, [29] 0.5 M sodium chloride solution.

Corrosion protective performance 115
The HR-SKP device was used

to scan the area 10 mm along
the x-axis into the coating. It
monitors the electrical potential
underneath the paint film and its
propagation from the defect with
time, delivering a vivid picture of
the advancing corrosion. It was
shown that the potential above
the untreated zinc surface exhi-
bits the typical Zn/Zn2+ standard
potential (Epot = -0.76 V) and the
difference in potential between
the actively corroding defect
area and the intact clearcoat/ Figure 6.4: Creepage distribution on polyester coated coil
metal interface is around 0.5 V. with chromate and chromium-free pretreatments (coils from
Contrary to this, the potential of industrial production, 360 h salt spray, scribe to zinc
the pretreated area is shifted to substrate) Source: ECCA 1999, [29]
more cathodic values. The poten-
tial step is therefore only around 0.15 V, making the overall corrosion reaction much
less thermodynamically favourable. Consequently, the delamination front remains
stable over a long time, hence indicating almost no propagation of the corrosion. Inde-
pendent results from another source converse with these findings, suggesting the
improvement resulting from band gap widening in a Ti/Zr oxide layer that effectively
suppresses oxygen reduction [31].
Figure 6.5: Electrochemical delamination: Model experiments studying a chromium-free conversion

treatment with the height-regulated “Scanning Kelvin Probe” Source: Elsevier [30]

Figure 6.6: Corrosion risk areas in automotive construction Source: Chemetall GmbH, 2009; [32]
6.5.2 Weldable corrosion protection primer for automotive

sheet
For the manufacture of car bodies, electro-galvanised sheet is one of the substrates that are
used for the outer skin and hang-on parts. Particularly in doors and in the suspension frame,
flanges and boxes form risk areas that are prone to corrosion, due to the poor accessibility
of these areas for the normal pretreatment and painting process (cf. Chapters 2.1.3; 8.2.3.2).
Examples are depicted in Figure 6.6. Using a corrosion protection primer (CPP) for these
parts, the risk of rusting-through is reduced substantially, thus helping to extend warranty
periods. Cost-driving secondary protective measures, like cavity sealing and seam sealing,
virtually become redundant. The principle of these CPP coatings is illustrated in Figure 6.7.
Table 6.3 summarises the features that characterise CPP for the automotive application.
Features of corrosion protection coatings for automotive sheet

• Improved corrosion protection particularly in box section, flanges or seams, helping to
reduce secondary protection measures (wax flooding, seam sealing etc.)
• Suitable for all common welding techniques (spot, stud, projection, LASER, metal-active
gas welding)
• Compatible with common cleaning and phosphating processes in car making
• Compatible with cathodic electro-dip paint in terms of conductivity and resistance to
high pH at the interface
• Improvements in dynamic crash properties and vehicle safety
• Improved friction and wear properties to reduce lubricant in the press shop
• Compatible with common adhesives and sealants in car making
• Available work range in deep drawing substantially widened, reducing the risk of folds
or ruptures
• Combine with chromium-free pretreatment on all galvanised steel and aluminium sub-
strates
Typical CPP are based on polyester, epoxy or polyurethane resin blends. Apart from corro-
sion protection pigments, they also contain high portions of conductive pigments like zinc
dust or graphite. The products of the so-called first generation comprise up to 70 % of Zn
dust. They are applied with dry film gauges of 2.5 to 4.5 µm. Commercial CPP are applied
on electro or hot-dip galvanised coil that is pretreated with chromium-free, Ti/Zr based
processes, as described in the previous chapter [32 – 34].

Figure 6.7: Corrosion protection primers for automotive sheet Source: [33]
Recently issued products are reported to be suitable for multiple substrates, as have become
particularly common in the premium class segments of vehicle manufacturers. Aluminium/
steel couples in the automotive mixed-metal construction form neuralgic points, where
overlapping metal sheet is tightly joined in flanges by adhesive bonding or welding [35].
Figure 6.8 gives an impression of the performance of a modern CPP for car bodies. Test
specimens were prepared to simulate the situation in a car door. As substrates, cold-rolled
steel (CRS), 5 µm electro-galvanised (ZE) and ZE with CPP coatings of the 1st and 2nd genera-
tions at their respective coating gauges, 4.5 and 3.2 µm, were used. Sheet material was trea-
ted according to a standard car paint shop operation, including alkaline cleaning, tri-cation
Zn phosphating and cathodic electro-dip coating. The interior and exterior sheets were
joined by combined hem flanging and spot welding to form “mini doors”, and then subjected
to a cyclic corrosion test according to norm 621-415 of the German Automobile Associa-
Figure 6.8: Corrosion protection primers: Performance in cyclic climate testing acc. to test norm
VDA 621-415 (German Automobile Association) Source: Chemetall GmbH, [36]

tion (VDA) for several weeks. This

test comprises one-week cycles of
consecutive salt spray, humidity
(condensation) and drying phases
(cf. Chapter 7.2.3.3). Samples were
removed from the test in weekly
intervals, the joined areas opened,
inspected and photographed.
Superior corrosion resistance of
20 cycles (weeks) is achieved by
CPP in this test. While CRS and
ZE substrates show severe corro-
sion (red rust) after only 5 weeks,
the CPP coated samples are only
slightly corroded (white rust)
when thinly coated (3 µm), or
even entirely unaffected with the
higher CPP gauge (4.5 µm) [36].
6.5.3 Thermally
Figure 6.9: Anticorrosive and adhesion performance tests on
curing 2-in-1
a thermally curing 2-in-1 primer pretreatment (5 µm) with primer-pretreatment
commercial liquid polyester topcoat (20 µm). (a) T-bend
A
adhesion; (b) neutral salt spray (504 h); (c) outdoor exposure waterborne primer-pre-
Hook of Holland, 1 - 3a; (d) cross-hatch/Erichsen dome test treatment was reported else-
and Reverse impact where [37] that combines a conven-
Source: Henkel AG & Co. KGaA [37]
tional chromium-free pretreat-
ment chemistry and a dispersion
of a thermally drying acrylic resin in a single-package formulation. In the coil coating
process, the product is roll coater applied with a liquid film of around 10 μm thickness, then
dried in a hot air furnace or an infrared dryer with a metal temperature of below 100 °C to
form a 5 µm primer coating. A line speed of up to 160 m/min is reported from industrial
trials. Performance data were provided that match standard industrial requirements for
indoors and outdoors architectural uses when combined with commercial polyester top-
coats. Adhesion was tested using T-bend, impact and cupping tests. The coating passed
0.5T bending without paint delamination, and little cracking on the bent shoulder. Sufficient
ball impact test results were reported, with around 16 J impact energy, as well as Erichsen
cupping to 8 mm dome height, combined with a cross-hatch and 15 minutes immersion in
boiling deionised water. Both tests were passed without flaking. Corrosion testing included
the neutral salt spray test, 360 h QUV-B weathering, and three years outdoor exposure in
Hook of Holland (see Figure 6.9).
6.5.4 Chromous based pretreatments – “chromiting”

The overall anticorrosive performance of pretreatments based on trivalent chromium, Cr
(III), is claimed to be equivalent to that of chromate standard conversion coatings, however
it is very much dependent on the gauge of the chromous oxy-hydroxide layer and its micro-
structure. EIS studies on galvanised specimens that were obtained after increasing immer-
sion times in the bath solution showed that the impedance increased, having a maximum

between 30 and 60 s, of appro-

ximately squared level of the
untreated zinc specimen at the
low-frequency end of spectrum.
In this optimum region, the Bode
plots exhibit three time constants
which are interpreted as the coa-
ting forming three intact layers of
different composition that serve
as effective oxygen barriers [38].
Upon further extension of the
immersion time, cracks appear
in the coating. Neutral salt spray
resistance shows almost no cree-
page on aluminium and hot-dip Figure 6.10: Schematic of a hydrotalcite-vanadate structure
galvanised steel and only little Source: NACE International [42]
creepage from the scribe (< 1 mm)
on cold-rolled steel after 600 h. As reported, also the acetic acid salt spray on aluminium
shows only little creepage. In constant climate and boiling tests or in “acid rain” cyclic humi-
dity testing, no blisters nor delamination are observed. However, no duration is disclosed
for these tests. Ball impact, taping, Erichsen cupping and thorn bending also show good
adhesion and flexibility [39, 40].
6.5.5 Active pigments, ion exchangers and scavengers

The influence of non-chromate active pigments in a model epoxy coating was investigated
by potential measurements and EIS after salt spray and immersion in sodium chloride
solution. Though zinc chromate standard pigmentation showed the best initial data in elec-
trochemical evaluation, the differences diminished over exposure time, due to the solubility
and leaching of the chromate. Zinc phosphate, and in particular zinc phospho-molybdate
and zinc-calcium phospho-molyb-
date proved to be viable non-toxic
alternatives. Water permeability
of free films did not reveal any dif-
ferences between chromate and
its replacement pigments. Ther-
mogravimetric analysis (TGA)
showed the beneficial effect of
all pigments as compared with a
pigment-free model varnish, thus
indicating some stabilising inter-
action [41].
A coprecipitate of zinc and alu-

minium hydroxide and metava-
nadate VO3 - can be synthesised
from alkaline solution. As veri-
Figure 6.11: EIS Bode plots of hydrotalcite-vanadate pigmen-
fied by X-ray diffraction, the ted epoxy coatings subject to salt spray exposure; near-linear
reaction results in a hydrotalcite curves represent the resistance/frequency plot (left ordinate),
structure that consists of layers wave-shaped curves correspond to the phase angle/
of mixed Zn-Al hydroxide spe- frequency plots (right ordinate). Source: NACE International [43]

cies, whose inter-layer spaces are populated by decavanadate anions [V10O28]6– as illustra-
ted in Figure 6.10 [42].
From there the decavanadate can be released slowly by way of ion exchange, resulting in
equilibrium or steady-state concentrations of vanadate much below its solubility. The steady
state is achieved after approximately 900 h of contact with a chloride solution. Simultane-
ously, Zn2+ ions are released. Both ionic species were shown to reduce the current density
on AA 2024 alloy (AlCu4Mg1) in polarisation experiments, i.e. suppress the corrosion. When
admixed to an epoxy coating, and applied on AA 2024, the coating showed a protective beha-
viour. Figure 6.11 represents the resistance (Bode) and phase angle plots vs. the voltage fre-
quency, as taken in repetitive EIS measurements of specimens that were subject to salt spray.
The bell-shaped phase angle curve shows a maximum at high frequencies, which however is
reduced with time, while a second maximum develops at the low-frequency end.
This resembles an additional capacitance that arises from direct electrolyte/metal contact
and the respective double-layer that is formed at the exposed interface. On the other hand,
the Bode plot does not change much with time. This means that despite the access of elec-
trolyte to the metal surface, no effective dissolution takes place, i.e. active inhibition is dis-
played. However, the performance is less pronounced than with strontium chromate [43].
6.5.6 UV-curable primer-pretreatment

UV technology has been adapted to develop a combined 2-in-1 primer-pretreatment as
mentioned in Chapter 5.2.2.2. The liquid, flowable single-package formulation was reported
to be applicable by roll-coater, at coil speeds of 100 m/min. The developmental formulation
was tested in pilot line trials on galvanised steel, Galfan and Galvalume. Based on titanium-
organic compounds with acrylic acid functional groups as corrosion inhibition system, it
renders corrosion protection under commercial polyester topcoats with creepage levels of
below 2 mm from the scribe after 504 h salt spray test. Sufficient adhesion was demons-
trated with T-bend (0.5T without flaking), reverse impact and Erichsen cupping tests. For
adaptation to the industrial use, further improvements are being sought including higher
application speed, enhanced corrosion resistance for harsh industrial/marine environ-
ments and versatility under a variety of liquid or powder topcoats [44, 45].
6.6 Degradation and ageing

6.6.1 Weathering
In service life, a coated work piece is weathered, i.e. it is subject to manifold random ageing
influences: The UV spectral part of sunlight, combined with oxygen, brings on photoche-
mical reactions. Temperature changes and all forms of precipitation result in mechanical
stress by swelling and shrinking or even hydrolytic or thermal decomposition. Chemicals,
like deicing salts, “acid rain” (sulphur dioxide, SO2), volatiles, solvents or fuel, or natural
substances, like tree gum or mould all have their detrimental effect. All these climatic
factors combine with mechanical loads like static or dynamic deformations, thus leading to
a multiple burden.
Degradation by UV radiation, hydrolysis and thermal destruction, in the presence of oxy-
gen, follows different pathways, but basically, all these reactions lead to a reduction in
molecular weight, thus impairing the mechanical and protective properties of the coating.
This becomes apparent first by gloss reduction, fissures and chalking, later by corrosion and
eventually spalling of the entire coating.

Degradation and ageing 121
Generally, oxidation under UV radiation (photo-oxidation) involves the formation of hydro-

peroxides that further decompose to yield shorter carbonyl compounds and other by-products
under chain cleavage. In this way, ethers and esters undergo the formation of hydroper
oxides on the carbon atom that bears the C–O bond. Further decomposition forms the lower
carbonyl compound and, by further oxidation, eventually liberates carbon dioxide, CO2.
Urea resins are oxidised in a similar way to form carbamides and, finally, free urea com-
pounds, CO2 and water. Radiation cleavage of acrylates may occur in the main chain or in
side branches of the polymer. In polyvinyl chloride, PVC, the C–Cl bonds are homolytically
cleaved by the radiation, finally resulting in chain length reduction and the generation of
CO2 and hydrogen chloride. Chain shortening and, on the other hand, after-curing induced
by UV radiation simultaneously reduce elasticity and cohesion [46].
In a comparative study, different automotive clearcoat systems with variations in their
binder (polyacrylate or polyester polyol), hardener, i.e. hexamethylene or isophorone diiso-
cyanates (HDI or IPDI) and stabiliser (with or without HALS additions, cf. Chapter 4.5) were
investigated regarding their weathering resistance. Apparently, the polyacrylate polyol is
much more prone to photo-oxidative degeneration than the polyester system. HDI on its
own appeared to be the more effective cross-linker for the polyester; for the acrylic system,
a blend of HDI with IPDI was preferable. HALS showed a beneficial effect, decelerating the
degradation, however less pronounced for the acrylic urethane [47, 48].
The interdependence between degradation by weathering and susceptibility to corrosion
was shown in a combined study of the EIS data and performance in salt spray tests of
various coatings on galvanised steel after 2,000 h exposure to QUV-A (cf. Chapter 7.2.3.4).
The organic coatings consisted of polyester or polyurethane primer (5 to 15 µm) and dif-
ferent polyester-melamine topcoats (20 µm). In the majority of cases, blistering occurred
on the unscribed surface that was unrevealed without the UV conditioning. The salt spray
resistance correlated with the impedance values measured in the low-frequency range,
indicating the resistivity at the metal/polymer interface. Good performers with regard to
blistering also had a particularly high insulating protection. The performance observed in
the combined exposure roughly coincides with gloss retention results, but does not neces-
sarily reflect the durability classification of the paint systems as obtained only from UV
resistance measurements [49].
Also hydrothermal stress can result in a mechanical damage. For instance, with poly-
ester-urethane and epoxy-polyamine systems, a reduction in cross-link density of more
than 50 % was observed, though the polymer strands themselves did not seem to break
down, as the average molecular weight between cross-links grew by about the same
factor. The degradation of the epoxy system occurred at about the double rate as with the
polyester-polyurethane, and it also suffered a substantial reduction of the glass transition
temperature (Tg). Moreover, when combined with humidity, the degradation of epoxy was
enhanced [50]. Furthermore, esters can be degraded by saponification. Thermal hydrolysis
of urethanes leads to the formation of alcohols and N-substituted carbamic acids, which
further degrade to the lower amine while liberating CO2 [51].
The susceptibility to blistering of coil applied organic coatings on galvanised steel was also
demonstrated by EIS studies after cyclic humidity testing comprising wet and dry cycles
at 25 °C/50 % rH and 50 °C/95 % rH over four weeks. Critical polyurethane and durable
polyester primer were investigated. The polyurethane system showed significant roughing
and a locally dropping potential (about 100 to 120 mV) in the SKP mapping after exposure
to humidity, in accordance with the blisters that were observed visually. EIS revealed the
resistivity in the low frequency end to be reduced by a factor of >10. There was, however,
no indication of corrosive activity going on, so that the resistivity decrease is interpreted

in terms of displacement of the

polymer from the metal surface
by water molecules. The polyester
system was much less critical [52].
Similar results are also reported
for cathodic electro-dip primers
that were subjected to hydrother-
mal ageing in cyclic tests.
EIS after hydrothermal ageing in
cycles between 55 °C/84 % rH and
23 °C/40 % rH again showed the
decrease of the pore resistance
with ongoing exposure. This elec-
Figure 6.12: Reactions at an iron/polymer interface that trical weakening correlates with
result in delamination and creepage higher residual stress in the coa-
ting. The stress increase was by
the factor 2 for two different coatings. Hence, ageing resulted in an irreversible swelling,
thereby generating more interstices and rendering the coating more prone to water uptake
upon immersion [53].
6.6.2 Electrochemical degradation

6.6.2.1 Cathodic disbonding: oxygen reduction
Apart from mechanical forces, the delamination of organic films from a metallic substrate
occurs via two major different pathways, i.e.
• water uptake, swelling and displacement of adsorptively bonded (hydrogen bridge bond)
polymer moieties
• dissolution of metal/polymer valence bonds by chemical (hydrolysis, saponification) or
electrochemical reactions (corrosion)
The latter interaction will lead to a separation of electrical charges at a metal/polymer
interface, either by hydrolysis (e.g. dissolution of metal soaps) or by the corrosion reactions.
Combined HR-SKP (cf. Chapter 7.2.4.2.1) and atomic force microscopy (AFM) confirmed that
the electrochemical delamination process often takes place before the polymer-to-metal
bonds are weakened by swelling and hydrolysis through the ingressing electrolyte.
The ease of electron transfer depends on the conductive properties of the metal surface
which is covered by native oxide (cf. Chapters 2.1.1, 2.1.2). If this oxide is an insulator (e.g.
SiO2, Al2O3, MgO) the transfer will be decelerated. Oxygen reduction, on the other hand,
leads to the generation of anions that may attack both the native oxide (e.g. dissolution of
zinc or aluminium oxides by formation of zincate or aluminate), and saponifiable bonds
between the metal and the polymer.
Cathodic disbonding prevails on conductive surfaces, like that of steel as shown in Figure
6.12. At the delamination front, the potential, as can be measured by SKP, jumps up from a
low, cathodic level, typical for a bare steel surface that is immersed in an electrolyte, to the
anodic value in the region of the intact coating. Here, the reaction is controlled by the con-
ductivity of the iron oxide layer that diminishes with the conversion of Fe from the divalent
to the trivalent state. Ions that ingress from the defect site into the oxide layer reconstitute
the conductivity and accelerate the corrosion again. In effect, the delamination front pro-
pagates with the diffusion of ions along the interface. Other investigations indicate that

Degradation and ageing 123
the potential front propagates in correlation with a pH gradient that represents the active
oxygen reduction, while the eventual delamination may be kinetically retarded when bond-
breaking reactions are slow [54].
Simultaneously, oxygen, during its reduction, may induce the degradation of the polymer
film itself as depicted in Equations 6.2 a to d. These describe a set of reactions that involve
radical intermediate species like oxygen radical anions that have been confirmed to occur
under these conditions. They may abstract hydrogen from C–H bonds, generating free
organic radicals that undergo onward reaction with molecular oxygen, O2. The formation of
organic peroxides 1 that further decompose to form carbonyl compounds 2 (aldehydes and
ketones) and water is therefore a likely reaction path [55].
Equation 6.2

6.6.2.2 Anodic disbonding: filiform corrosion
Underneath paint films that display a high barrier effect towards oxygen and moisture pene-
tration, a corrosion process is observed that advances in threadlike filaments (filiform cor-
rosion, FFC). FFC has been an issue in the European architecture since the early 1980s [56].
In this kind of corrosion reaction, de-adhesion is anodic-driven. While it preferentially
takes place on aluminium or magnesium surfaces that form insulating oxides, it has also
been reported for galvanised steel. FFC does not appear in a condensation climate, i.e. at
dew point. Its maximum occurrence and speed are observed at relative humidity around
rH = 80 %. The mechanism is explained via an aeration gradient that results from retarded
oxygen supply. That means that the oxygen reduction takes place in the tail section of the
corrosion filament, while its front is characterised by active anodic metal dissolution [57, 58].
Several resin systems were investigated in terms of their resistance against FFC. 40 µm
topcoats were applied on AlMg1 architectural aluminium alloy, on top of 1 µm layers of
adhesion promoting organic primers. When using anodic films as pretreatment, the amount
of FFC was found to decrease exponentially with the thickness of anodic films. Hydrother-
mal sealing was found to further improve the performance. This is attributed to the rough-
ness of the surface that is increased by this treatment, thereby improving the mechanical
interlinking of resin and anodic film. As a general trend, duroplastic primers, e.g. based on
hard polyester or cured phenolic resins, appeared to provide a good result in combination
with a topcoat based on aromatic polyester polyol and aliphatic diisocyanate hardener.
However, the authors make a point in that the performance of coatings may be impaired by
cleavage reactions that are caused by the action of hydrochloric acid on ester and urethane
bonds, and therefore results of the accelerated filiform test, when incubated with hydrogen
chloride vapour, may diverge from practice [59]. The same workgroup, however, explicitly

focusing on the comparability of accelerated test and outdoor exposure results in Hook
of Holland (cf. Chapters 7.2.2.3; 7.4) in a later investigation, observed similar rankings for
various pretreatment/paint combinations in both tests. No clear preference could be given
for particular pretreatments or paint systems. Good results, i.e. a filiform corroded area
of less than 0.5 mm2/cm in front of a scribe mark, were likewise obtained with chromate
or chromium phosphate pretreatment, with 5 µm DC anodic films and a chromium-free,
hexafluoro zirconate based pretreatment. Paint systems comprised chromate containing
polyvinylidene difluoride (PVDF), polyester powder and liquid paints, polyester primer/
polyurethane topcoat and epoxy primer/PVDF powder combinations [60].
For rolled aluminium, literature states a particularly critical susceptibility for FFC. Inve-
stigations of this behaviour studied the influence of the rolling and subsequent annealing
processes. It is believed that the particular electrochemical activity in the magnesium (Mg)
containing AA 3005 and 8006 alloys (AlMg0.5Mn; AlFe1.5Mn0.5) is caused by the forma-
tion of a reactive layer just underneath the superficial 1 µm layer of grain-refined structures
that is effected by the rolling itself. The presence of enrichments of the alloying elements in
the surface layer may cause a negative shift of the electrochemical potential.
Lower alloyed aluminium like 1000 series alloys (i.e. <100 ppm Mg) shows a less criti-
cal behaviour. As a solution to prevent FFC on these substrates, the authors recommend
the complete removal of the critical surface layer by caustic pickling and strong alkaline
cleaning, respectively, or by DC anodic treatment [61 – 63]. Also from other sources, reported
laboratory and long-term exposure data indicate that DC anodising with film gauges of 6 µm
appears to be the most robust pretreatment [64, 65].
Chromating and standard chromium-free pretreatments give a good performance against
FFC, with the exception of high-alloyed copper and zinc containing alloys [66]. Driven by
the high operational cost of anodising, the toxicology of chromate and the missing absolute
performance safety of standard chromium-free pretreatments, alternatives are still being
sought, of which the phospho-molybdate technology seems to have some potential [67].
6.7 Literature
[2] Goldschmidt, A., Streitberger, H.-J., Basics of Coating Technology, 2nd edition, BASF Coatings AG,
[3] Meuthen, B., Jandel, A.-S., [1] pp. 180 ff
[5] Meuthen, B., Jandel, A.-S., [1] pp. 51 ff, 74, 94 f
[6] Goldschmidt, A., Streitberger, H.-J., [2] pp. 715 f
Coatings), Vol. 6, 2nd ed., Hirzel, Stuttgart 2008, pp. 101 f, 384, 495
[8] Goldschmidt, A., Streitberger, H.-J., [2]pp. 452, 451 f, 663, 688 f
pp. 335 f
[10] Weast, R. C., Astle, M. J. (ed.), Handbook of Chemistry and Physics, 60th ed., CRC Press, Boca Raton 1981, pp.
F-220 ff
[11] Kittel, H., Streitberger, H.-J. (ed.), [7] p. 495
[12] Meuthen, B., Jandel, A.-S., [1] p. 95
[13] Goldschmidt, A., Streitberger, H.-J., [2] pp. 373 ff, 391 ff
[14] Meuthen, B., Jandel, A.-S., [1] pp. 189 ff
[15] anon., Internationale Qualitätsrichtlinien für die Beschichtung von Bauteilen aus Aluminium (International
Quality Standards for the Coating of Work Pieces ), GSB AL 631, ed. 07/2009, Gütegemeinschaft für die
Beschichtung von Bauteilen (GSB International), Schwäb. Gmünd 2009, pp. 32, 35 ff

Literature 125
[16] anon., ASTM D1876 - 08 Standard Test Method for Peel Resistance of Adhesives (T-Peel Test), Am. Soc. f.
Testing and Materials (ASTM) Intern., W. Conshohocken PA, USA, 2010;
www.astm.org/Standards/D1876.htm; (28-03-2010; 11:00 h)
[17] Goldschmidt, A., Streitberger, H.-J., Handbuch Lackiertechnik (Handbook Coating Technology), BASF
Coatings AG, Münster 2002, pp. 396 ff
pp. 584 ff
[20] Shi, X., Fernando, B. M. D., Croll, S. G., Concurrent physical aging and degradation of crosslinked coating
systems in accelerated weathering, J. Coat. Technol. Res. 5, 2008, pp. 299 ff
[21] Kittel, H., Streitberger, H.-J. (ed.), [7] p. 390
Coatings, PhD Thesis, Loughborough Univ., Loughborough 2008,, pp. 77 ff
[23] Vlasak, R., Klüppel, I., Grundmeier, G., Combined EIS and FTIR-ATR study of water uptake and diffusion in
polymer films on semiconducting electrodes, Electrochim. Acta 52, 2007, pp. 8075 ff
[24] Lewis, O. D., [22] pp. 88 ff
[25] Posner, R., Giza, G., Vlasak, R., Grundmeier, G., In-situ electrochemical Scanning Kelvin Probe Blister Test
studies of the de-adhesion kinetics at polymer/zinc oxide/zinc-interfaces, Electrochim. Acta 54, 2009, pp.
4837 ff
[26] Vlasak, R., Klüppel, I., Grundmeier, G., [23]
[27] Hardcastle, H. K., Meeks, W. L., Considerations for characterizing moisture effects in coatings weathering
studies, J. Coat. Technol. Res. 5, 2008, pp. 181 ff
[28] Lienkamp, P. (ed.), Sander, J., Körner, T., Kleinschmidt, T., More than 10 years of experience with chrome-
free pre-treatment of aluminium — Perfect protection against corrosion, Press release, Henkel AG & Co.
KGaA, Düsseldorf 2008, cit. Int. Aluminium. J. 84 (11), 2008, p. 36 ff
[29] Androsch, F. M., Stellnberger, K.-H., Wolpers, M., Jandel, L., Drescher, D., Sander, J., Seidel, R., Chromate-
free Coil Coating and One Year of Production Experience, ECCA General Meeting Monte Carlo, Proc.,
European Coil Coating Association, Brussels 1999, Chapter 3
[30] Klimow, G., Fink, N., Grundmeier, G., Electrochemical Studies of the Inhibition of Cathodic Delamination of
Organically Coated Galvanised Steel by Thin Conversion Films, Electrochim. Acta 53, 2007, pp. 1290 ff, 1291
[31] Stoulil, J., Thierry, D., Structure and corrosion properties of Ti-Zr based conversion coatings applied on
hot-dip galvanised steel, NACE Corrosion Congress 2009, Atlanta GA, USA, Proc., NACE International,
Houston TX, USA 2009
[32] Schinzel, M., Advanced Corrosion Protection of Automotive Body Sheet – A Challenge for Coil Coating,
ECCA Autumn Congress Brussels, Proc., European Coil Coating Association, Brussels 2009
[34] Sander, J., Novel Chromium-free Surface Treatments for Coil, ECCA General Meeting Budapest, Proc.,
European Coil Coating Association, Brussels 2001
[35] anon., Corrosion Protection in Light-Weight Construction, APT Aluminium News 5, 2009, p. 4
[36] Schinzel, M., [32]
[37] Sander, J., Novel Surface Treatment of Metal Strip in the Coil Coating Process, Millennium Steel 2009, pp.
146 ff, 148 ff
[38] Chang, Y.-T., Wen, N.-T., Chen, W.-K., Ger, M.-D., Pan, G.-T., Yang, T.-C.-K., The effects of immersion time on
morphology and electrochemical properties of the Cr(III)-based conversion coatings on zinc coated steel
surface, Corr. Sci. 50, 2008, pp. 3494 ff
[39] Pohl, J., Möller, R., New Cr (III)-based pretreatment — A simple, all-purpose, environmentally friendly
process, JOT International Surf. Technol. (1) 2009, pp. 2 ff
[40] Volk, P., Echte Alternative — Chrom(III)-haltige Vorbehandlung für Aluminium (True Alternative — Cr[III]
Containing Pretreatment ...), Metalloberfläche 60, 2006, pp. 24 ff
[41] de Lima-Neto, P., de Araújo, A. P., Araújo, W. S., Correia, A. N., Study of the anticorrosive behaviour of epoxy
binders containing non-toxic inorganic corrosion inhibitor pigments, Prog. Org. Coatings 62, 2008, pp. 344 ff
[42] Mahajanam, S. V. P., Buchheit, R. G., Characterization of Inhibitor Release from Zn-Al-[V10O28]6-Hydrotalcite
Pigments and Corrosion Protection from Hydrotalcite-Pigmented Epoxy Coatings, Corrosion 64, 2008, p. 231
[43] Mahajanam, S. V. P., Buchheit, R. G., [42] p. 238
[44] Sander, J., Koch, M., Picot, P., Réticulation UV – Une nouvelle approche pour le „coil-coating“ (UV Curing
– A New Chemical Approach for Coil Coating), Centre d’Actualisation des Connaissances et de l’Etude des
Matériaux Industriels (Cacemi), Journée spécialisée, Proc., Paris 2002
[45] Sander, J., UV Curable Coil Coating, Symposium Innovative Surface Treatments for Steel and Aluminium
Coil Coating, Neuss, Proc. Henkel AG & Co.KGaA, Düsseldorf 2004

[47] Krüger, S., Wachtendorf, V., Rauth, W., Klimmasch, T., Krüger, P., Screening the weathering stability of
automotive coatings by chemiluminescence, J. Coat. Technol. Res., 5, 2008, pp. 17 ff
[48] Krüger, S., Brademann-Jock, K., Rauth, W., Klimmasch, T., Krüger, P., Analysis of weathering effects in
automotive coatings using thermoluminescence, J. Coat. Technol. Res., 5, 2008, pp. 11 ff
[49] Mallégol, J., Poelman, M., Olivier. M.-G., Influence of UV weathering on corrosion resistance of prepainted
steel, Prog. Org. Coatings 61, 2008, pp. 126 ff
[50] Croll, S. G., Shi, X., Fernando, B. M. D., The interplay of physical aging and degradation during weathering
for two crosslinked coatings, Prog. Org. Coatings 61, 2008, pp. 136 ff
[52] Nazarov, A. Prosek, T., Thierry, D., Application of EIS and SKP methods for the study of the zinc/polymer
interface, Electrochim. Acta 53, 2008, pp. 7531 ff
[53] Olivier, M.-G., Romano, A.-P., Vandermiers, C., Mathieu, X., Poelman, M., Influence of the stress generated
during an ageing cycle on the barrier properties of cataphoretic coatings, Prog. Org. Coatings 63, 2008, pp.
323 ff
[54] Huang, M.-W., Allely, C., Ogle, K., Orazem, M. E., A Mathematical Model for Cathodic Delamination of Coated
Metal Including a Kinetic pH-Porosity Relationship, J. Electrochem. Soc. 155, 2008, pp. C 279 ff
[55] Grundmeier, G., Stratmann, M., [18] pp. 597 ff
[56] Haagen, H., Rihm, K.-H., Filiformkorrosion auf organisch beschichtetem Aluminium (Filiform Corrosion on
Organically Coated Aluminium), FARBE UND LACK 96, 1990, pp. 509 ff
[58] Heinrich, M., Gaszner, K., Schuler, T., Korrosion von beschichtetem Aluminium (Corrosion of Coated
Aluminium), Metalloberfläche 49, 1995, pp. 802 ff
[59] Haagen, H., Gaszner, K., Scheck, K., Vorbehandlungsschichten und Filiformkorrosion bei organisch beschich-
tetem Aluminium (Pretreatment Layers and Filiform Corrosion…), FARBE UND LACK 97, 1991, pp. 306 ff
[60] Heinrich, M., Gaszner, K., Schuler, T., [58] pp. 802 ff , pp. 804 f
[61] Leth-Olsen, H., Nisancioglu, K., Filiform Corrosion of Aluminium Sheet. I. Corrosion Behaviour of Painted
Material, Corr. Sci. 40, 1998, pp. 1179 ff, 1183
[62] Leth-Olsen, H., Afseth, A., Nisancioglu, K., Filiform Corrosion of Aluminium Sheet. II. Electrochemical and
Corrosion Behaviour of Bare Substrates, Corr. Sci. 40, 1998, pp. 1195 ff
[63] Leth-Olsen, H., Nordlien, J. H., Nisancioglu, K., Filiform Corrosion of Aluminium Sheet. III. Microstructure of
Reactive Surfaces, Corr. Sci. 40, 1998, pp. 2051 ff
[64] Pietschmann, J., Gardein, R., Filiform Corrosion and Results of 10 Years Natural Weathering, Galvanotechnik
106, 2008, pp. 1764 ff
[65] Pietschmann, J. E., Pfeifer, H., Filiformkorrosion auf organisch beschichtetem Aluminium, Teil III (Filiform
Corrosion on Organically Coated Aluminium, Pt. III), Aluminium 70, 1994, pp. 82 ff
[66] Rudolf, A., Kaiser, W.-D., Filiformkorrosion – Einfluss der Legierung und der Vorbehandlung (Filiform
Corrosion – Influence of Alloy and Pretreatment), JOT 42, 2002, pp. 98 ff
[67] Rauscher, G., Neue chromfreie Vorbehandungsverfahren für Aluminium (New Chromium-free Pretreatment
Processes ), JOT, 2005, pp. 54 ff

Performance testing 127
7 Testing of organic coatings

Jörg Sander
7.1 Performance testing

In addition to mechanical testing, the assessment of endurance of a coated metallic work
piece requires certain tests that provide information on the anticorrosive performance of
the coating. This information must be available before such a work piece enters the market
place. Therefore, to enable performance forecasts, a number of accelerated corrosion tests
have been designed.
7.2 Accelerated corrosion tests

7.2.1 Overview
A long-term service life is simulated by a number of accelerated corrosion tests [1 – 5], in
order to assess the effect of corrosive stress in a time lapse. Typical corrosion tests comprise
salt spray, boiling and condensation tests, constant and cyclic climate tests. Weathering
includes combined humidity and irradiation tests (visible light and ultraviolet radiation,
UV), that help in assessing resistance of the coating against photochemical degradation
(chalking, discolouration, gloss reduction). Coil and sheet material that is used for appliance
manufacture is tested on its resistance to water soak and detergents, next to tests regarding
the resistance to e.g. domestic cleaners, foodstuffs, dyes and colourants. Coatings for the
canning industry, e.g. for beverage cans and food containers, are often subject to additional
tests regarding their porosity (e.g. copper sedimentation after immersion in acidulated
copper salt solution) and their sterilisability or retortability in pressurised cooker tests.
Table 7.1 gives an overview on accelerated tests related to corrosion.
7.2.2 Constant climate tests

7.2.2.1 Salt spray
The salt spray test provides data on the corrosion resistance of coated work pieces in gene-
ral. The coating is scratched with a defined tool (scribe mark), and subjected to salt fog
from a solution that contains 50 g/l sodium chloride (NaCl). Steel substrates are usually
tested in a neutral salt fog, while aluminium (Al) is subjected to an atmosphere that is
additionally acidulated with acetic acid (pH ≈ 3.2, AASS test). In some cases, e.g. automo-
tive applications like wheels, this is even enhanced by adding copper sulphate (CASS test).
The usual test temperature is 35 °C. Test specimens are removed from the test chamber
after the agreed test time and inspected for blistering and for adhesion loss (creepage)
progressing from the scribe and, when applicable, from cut edges. Typically, 336 to 1,008 h
(2 to 6 weeks) resistance is required for steel substrates, including galvanised steel, with

ISBN 978-3-86630-805-3

only small defects being accepted. The most stringent requirements are made for Al sheet
for aircraft, i.e. a maximum creepage of 1.25 mm (0.05 in) from the scribe is accepted after
3,000 h AASS.
7.2.2.2 Constant climate, humidity

For constant climate testing, coated specimens are scribe-marked and may be bent or
deformed in another way. After storage in a test compartment under constant humidity
and temperature, they are inspected regarding blistering and other apparent visual
changes.
7.2.2.3 Filiform corrosion

The filiform corrosion test is mainly carried out on Al work pieces. It focuses on the
threadlike corrosion pattern that may occur in chloride containing, reduced-humidity
corrosive environments. Scribe marked work pieces are stored over fuming hydrochloric
acid (HCl, 36 %) for an incubation period, then kept under constant atmosphere with con-
trolled humidity and temperature (80 % relative humidity [rH], 40 °C). The specimens are
inspected for the number and length of threads that have developed. Again the aircraft
industry claims the highest performance, i.e. 1,000 h resistance with max. 2 mm thread
length. Steel based materials are tested after incubation in NaCl solution (EN ISO 4623).
Table 7.1: Major test methods on the corrosion performance of organic coatings
Test, feature Norm
Constant climate tests
Salt spray – neutral EN ISO 9227 NSS (DIN 50021), ASTM B117, EN 13523-8
Salt spray – acetic acid EN ISO 9227 AASS
Salt spray – copper acetate EN ISO 9227 CASS
Humidity DIN 50017 KK, pr EN 13523-25
Condensation EN ISO 6270-1 and 2, pr EN 13523-26
Filiform ISO 4623-2, EN ISO 4628-10, EN 3665
Boiling, water soak EN 13523-9
Cyclic climate tests

Humidity/Temperature cycle tests
- Humidity DIN 50017 KFW, pr EN 13523-25
- Tropical test analogous, ambient to 40 °C
- Humidity-freeze test analogous, -5 °C to ambient
Humidity in SO2 atmosphere EN 13523-13 (DIN 50018)
Cyclic salt spray/humidity tests
- Automotive industry VDA 621-415, Renault ECC1 D172028, VW PV1210, Volvo
VCS1027,149, other OEM specifications
- Prohesion test ASTM G85,A5
Cyclic immersion test ISO 15710, EN 3212
Weathering tests Xenon test, VDA 612-430 etc.
Outdoor exposure EN 13523-19
According to Meuthen, Jandel [1]; Kittel [2]; Goldschmidt, Streitberger [4]; LeBozec et. al. [5]

Accelerated corrosion tests 129
7.2.2.4 Condensation
The condensation test is focused on the resistance of coatings under elevated temperature
and permanent humidity. Specimens are stored at 100 % rH and 40 °C, and then checked
for blisters and visible deterioration.
7.2.2.5 Boiling, water soak

Water soak tests usually comprise immersion in deionised water at 40 °C, however may be
extended to boiling. In case of sheet material, it is usual to apply a deformation by bending
or cupping. Test specimens are checked for blisters and other visual changes, as well as
for adhesion (by taping), if applicable, in deformed areas. Test times range from 15 min to
several hours and are subject to agreement.
7.2.3 Cyclic climate tests

7.2.3.1 Cyclic humidity
All tests described above for constant climate conditions can be combined with repetitive
cyclic variations in temperature, humidity, additional chemical or radiation load, etc.
Cyclic humidity and condensation testing may involve temperature cycles between ambi-
ent and 40 °C (tropical test), or freezing and ambient (humidity-freeze test). Humidity
tests are also combined with cyclic exposure to sulphur dioxide containing atmosphere
(SO2, DIN EN 13523-13), to simulate “acid rain” industrial environments.
7.2.3.2 Prohesion
The so-called prohesion test was invented to cope with the issue that results obtained in
the harsh neutral salt spray on galvanised steel do not correspond very well with reality.
Samples are subjected to a cyclic test comprising salt spray with a diluted, slightly acidu-
lated NaCl solution, with intermediate intervals of drying. Though it was first intended for
use on steel substrates, the test is also used for aluminium. Test times are up to 2,016 h
(12 weeks) on Al materials for the aircraft industry [6].
7.2.3.3 VDA test

In particular, the automotive industry has standardised cyclic tests that involve salt spray,
humidity and open-air storage, to obtain a more realistic representation of outdoor results.
A full cycle usually lasts a week, however the order and duration of the individual load and
relief periods vary with the specific standard. Standard 621-415 of the German Automobile
Association (VDA) is generally accepted as a guideline, though there are also internal norms
by individual manufacturers like Daimler, Ford, General Motors, Renault, Volkswagen, or
Volvo. A minimum of 10 cycles (10 weeks) is usually specified as test duration for cathodic
electro-dip primer coats, whereas the full finish must withstand longer periods.
7.2.3.4 UV test, weathering

Irradiation with UV is primarily used to assess the photochemical resistance of the binder
system, however may also give a good account on the overall resistance of the entire coating
against natural weathering, when combined with humidity (VDA 621-430). Xenon lamps or
special UV lamps are common. The latter provide a smaller spectral segment, either UV-A
(spectral maximum at 340 nm, simulating the short wave solar radiation) or UV-B (313 nm,
more energetic, preferred to simulate extremely solarised climate). Performance require-
ments range up to 2,000 h or more.

7.3 Electrochemical testing

7.3.1. General remarks
Apart from phenomenological assessment of the corrosion of coated metals, as is obtainable
by accelerated and outdoor exposure testing, modern corrosion science has developed a lot
of designs for an experimental access to this problem. Though being still far from providing
a true prediction, modern tools are powerful aids in understanding of corrosion and the
delamination mechanisms it induces. As corrosion is predominantly an electrochemical
phenomenon, electrochemical testing plays an important role in these investigations. How-
ever recently, scientists have focused on combining analytical methods, that comprise e.g.
optical (infrared and Raman, in particular surface-enhanced and total-reflection methods),
electron-optical and atomic force methods, to complement the electrochemical tests. Increas-
ingly often, experimental setups are created to enable real-time, in-situ investigations [7].
Selected electrochemical methods will be described hereunder.
7.3.2. Electrochemical potential

7.3.2.1 Standard potential
Electrochemical potentials apply for any kind of chemical reaction involving free flow of
electrons, and therefore being linked with an electric current. Such reactions are com-
monly referred to as red-ox reactions. The voltage measured in a bridge circuit when
no electric current is observed (galvanostatic method) is defined as the electrochemical
potential. By convention, it is given versus a standardised counter electrode, most com-
monly the standard hydrogen electrode, whose potential is set to be 0 V. Electrochemical
potentials expressed in this way are called standard potentials. The more oxidisable the
metal, the lower (more negative) is its electrochemical potential. On the other hand, a high
Table 7.2: Standard electrochemical potentials of selected elements and compounds

Oxidation occurs more readily with lower potential
Description Electrode reaction Standard potential
in aqueous solution E0 at 25 °C (V)
Pt | F2 | F– F2 (g) + 2 e – → 2 F– 2.87
Au | AuCl4 –, Cl – AuCl4 – + 3 e – → Au + 4 Cl – 1.00
Ag | Ag +
Ag + e → Ag
+ –
0.7991
Pt | Fe2+, Fe3+ Fe3+ + e – → Fe2+ 0.771
Pt | H2 | H + 2 H + + 2 e – → H2 0.0000
Pb | Pb 2+
Pb + 2 e → Pb
2+ –
-0.126
Fe | Fe2+ Fe2+ + 2 e – → Fe -0.4402
Zn | Zn 2+
Zn + 2 e → Zn
2+ –
-0.7628
Al | Al3+ Al3+ + 3 e – → Al -1.662
Mg | Mg 2+
Mg + 2 e → Mg
2+ –
-2.363
Pt | MnO2 | MnO4 – MnO4 – + 2 H2O + 3 e – → MnO2 + 4 OH – 0.588
Pt | O2 | OH –
O2 + 2 H2O + 4 e → 4 OH
– –
0.401
Pt | H2 | OH –
2 H2O + 2 e → H2 + 2 OH
– –
-0.8280
According to Barrow [8]

Electrochemical testing 131
(positive) electrochemical poten-

tial of a metal indicates what is
called a noble metal which is resis-
tant to (atmospheric) corrosion.
A selection of standard potentials
is given in Table 7.2 [8].
7.3.2.2 Cyclo-voltammetry
Red-ox systems can be investi-
gated by a dynamic method that
is carried out by scanning the
voltage (E) up and down in the
expected range of the electro-
chemical reaction to occur, and
monitoring the current (i) that
is measured in response. The Figure 7.1: Cyclovoltammograms on galvanised surfaces;
method is commonly referred to (a) native oxide; (b1) freshly cleaned Zn surface – oxidative
as cyclo-voltammetry (CV). Nega- branch, (b2) reductive branch Source: Fink et al. [10]
tive currents indicate a reduction
process, while positive currents
represent an oxidation. The area (E · i) enveloped by a curve over its base line is an indication
of the reaction turnover. Repetition of the voltage sweep results in a set of curves that form a
loop. In case of ideally reversible reactions, the loops are closed and do not alter their shape.
In real systems, reactions are more likely to be irreversible, i.e. products are removed from
the equilibrium, for example by onward reactions, and in consequence, the curves will be
transitory. Figure 7.1 shows a typical set of voltammograms as can be obtained on a technical
zinc (Zn) surface. Curve (a) represents the situation on Zn covered with native oxide which
inhibits the red-ox reactions (cf. also Chapter 7.3.3) hence almost no current is measured over
the voltage sweep. Curve (b) shows the typical loop of metallic, freshly etched Zn that enables
the oxidation (b1) of the metal and the reduction (b2) of its ions to occur [9, 10].
7.3.3 Electrochemical impedance spectroscopy

Electrochemical impedance spectroscopy (EIS) can be used to monitor any electrochemi-
cal activity that occurs at the paint/substrate interface upon corrosion and degradation of
metal-to-paint bonds. In terms of its electrical behaviour, a coating serves as a barrier that
displays both capacitance and resistivity features which can be simulated by an “equivalent
circuit”. In a simplistic model, such a circuit contains a resistor (considering that the ionic
transport through the electrolyte is slower than the free flow of electrons, hence forms a
resistance to an electric current), followed by a loop with a second resistor and a capacitor in
parallel. This latter resistance is attributed to the retardation of any molecule or ion, when it
passes through the pores and interstices of the coating (pore resistance), while the capaci-
tance is interpreted in terms of the dielectric behaviour of the coating that separates metal
and surrounding electrolyte. As soon as electrochemical activity starts at the metal/coating
interface, the situation is getting more complex. For simulation, additional components must
be incorporated into the equivalent circuit, to account for charge transfer, double layer and
similar phenomena, as illustrated for an example in Figure 7.2 [11].
EIS measurements are carried out by applying AC voltage to a coated test specimen, which,
by nature of the mixed resistor/capacitor behaviour of a coating, results in a responding
electric current that alternates with a phase difference. The phase angle usually shows

a maximum coinciding with the

inflection point of a drop in the
impedance level (Bode plots). By
Fourier transformation, the impe-
dance can be separated into real
and imaginary components which
are plotted against each other in a
diagram (Nyquist plot).
A simple, intact coating usually
shows a semi-circle in this plot,
its radius being an indication of
the overall protective power. For
example, a technical galvanised
steel surface displays a large
semi-circle (i.e. higher protection)
Figure 7.2: Schematic: EIS equivalent circuit; R s = resistance when the native oxide layer, that
of solution, Rf = film (pore) resistance, Rct = charge-transfer mainly consists of mixed oxy-
resistance (electron transport through interface); hydroxide of the alloying element
Cf = film capacitance, Cdl = double-layer capacitance; aluminium, is left intact (solvent
according to Lewis [11] cleaning). An alkali-cleaned sur-
face exposes more oxy-hydroxide
of the base metal, zinc, which is more reactive, hence resulting in a smaller semi-circle in
the Nyquist plot [12]. Film degradation that is induced by electrochemical activity is indicated
by shifts and deformations in the plots of repetitive EIS cycles. In particular, in the Nyquist
plot, the appearance of film defects results in the introduction of a second semi-circle
(i.e. a second time constant representing the additional resistor/capacitance circuit loop),
often camouflaged in real spectra by complex enveloping curves.
7.3.4. Electrochemical techniques with high spatial resolution

7.3.4.1 Scanning vibrating electrode
Local corrosion currents at a metal/electrolyte boundary can be detected and mapped with
a high spatial resolution, i.e. on a micrometre scale, by the scanning vibrating electrode
technique (SVET). This technique is capable of making in-situ studies without intrusive
action. Its principle is the measurement of currents induced by ionic species that migrate
in the course of local corrosive reactions. The locations of anodic and cathodic events can
be clearly separated by the method. The lateral resolution is several 10 µm, and current
densities of less than 5 µA/cm2 can be detected.
For example, the method was used to study the protection mechanism on freshly cut expo-
sed edges of hot-dip galvanised steel [13]. In another application of the method, the effect of
the composition of Al alloyed galvanised (Galfan, ZA) layers on the corrosion performance
was assessed [14].
7.3.4.2 Height-regulated Scanning Kelvin Probe
7.3.4.2.1 General technique

The inhibiting effect of conversion pretreatments can be studied by high-resolution height-
regulated “Scanning Kelvin Probe” (HR-SKP) experiments [15 – 18]. The HR-SKP allows the
precise measurement of the local distribution of electrical potentials on a metal surface
underneath an organic coating. Thereby, changes in the oxide structure and the ingression of

Electrochemical testing 133
ions become detectable. The local

resolution in the x- and y-direc-
tion is approximately 15 µm.
With repetitive measurements, it
is thus possible to obtain a view
of how corrosion and delamina-
tion develop and move forward
over time. The height regulation
(z-axis) has a precision of below
200 nm. With the HR-SKP, it is
possible to distinguish between
the weakening of the structures
by moisture (wet delamination),
and red-ox (corrosive) reactions.
Figure 7.3 shows a schematic of
the experimental array of the HR-
Figure 7.3: Schematic view of the height-regulated Scanning
SKP.
Kelvin Probe (HR-SKP)
7.3.4.2.2 Blister test LIA = Lock-in Amplifier; Ref = Reference Electrode with
capillary tip; d = tip distance over sample
Another test for the investigation ∆E = potential difference, Source: Grundmeier et al. [17]
of corrosive delamination mecha-
nisms combines the HR-SKP with
a setup that allows putting an orga-
nic film under electrochemical
and mechanical strain at once. The
coated test specimen is prepared
by drilling a small hole through
the substrate from the underside.
When an electrolyte is pumped in,
delamination will occur, as soon as
the hydraulic force exerted on the
film by electrolyte exceeds adhe-
sion. Consequently, a blister will
form which is monitored with the
HR-SKP, simultaneously giving
electrochemical and topographic
information on the blister growth.
The test is referred to as the Scan- Figure 7.4: Schematic view of the blister test (HR-SKP-BT)
ning Kelvin Probe blister test Source: Posner et al.[19]
(HR-SKP-BT). Figure 7.4 shows a

schematic.
With this setup, cathodic delamination processes can be studied under variation of atmos-
pheric humidity, electrolyte pressure and polarisation conditions. Combination with data
from peel force and attenuated-total-reflection infrared (ATR-IR) spectroscopic inspection
of water uptake renders additional useful information about the incorporation of water by
the bulk coating and along the interface. Thus it is possible to differentiate between red-ox
driven and chemical delamination that is effected by swelling (plastification of the coating,
cf. Chapter 2.2.1), hydrolysis and displacement of adsorbed organic binders by the water
molecules (cf. Chapter 6.6.1).

Figure 7.5: Blister test (HR-SKP-BT) on a Zn / ZnO / epoxy amine interface at 500 mbar electrolyte
pressure and 97 % rel. humidity; (a) SKP potential profiles; (b) film topography Source: Posner et al. [19]
A basic study with electro-galvanised substrate and an epoxy amine adhesive as model coa-
ting showed that the potential inside a blister dropped to the zinc standard potential within
a day, after which point a steady, linear growth of the corroded area was observed. The cor-
rosion progress was in the order of several 10 µm/h. The delamination rate in high relative
humidity (rH = 97 %) was measured two to three times higher than in less humid conditions
(rH = 82 %). Topographically, the corroded area spread faster than the blister, though this
was apparent only at higher hydraulic strain. Therefore obviously, electrochemical break-
down by oxygen reduction occurs before the onset of mechanical delamination. However
it is largely decelerated in low humidity, which is interpreted in terms of the coating not
being sufficiently softened and a fluid water film not being present at the interface, there-
by suppressing ion transport and slowing down oxygen diffusion to the delamination
front [19]. Figure 7.5 shows an exemplary image of potential and topographic profiles of an
HR-SKP-BT experiment.
7.4 Outdoor exposure tests

Despite the necessity of simulation by accelerated corrosion tests, any of them can only
give a clipped and limited description of the complex reality. Therefore, painted objects
are tested in outdoor exposure [20, 21], covering various climates with regard to solarisa-
tion, temperature and humidity. This includes extremes, for example Florida, with its
set of heat, humidity, high salt load, and high UV irradiation, or highly populated and
industrialised areas on the North Sea or North Atlantic coasts, where high salt concen-
tration and atmospheric contamination, e.g. by sulphur dioxide (SO2), prevail.
Several test sites have been installed that are categorised according to their climate
and corrosivity classification according to ISO 12944-2 (e.g. C2 = low; C3 = moderate;

Outdoor exposure tests 135
C5 = very strong). The European Coil Coating Association has set up its own test pro-
gramme EURODES [22], with certified test sites in
• Geleen (Netherlands); continental/industrial; corrosivity class C2 (steel)/C2 (zinc)
• Brest (France); aggressive marine; (C5/C3)
• Hook of Holland (Netherlands); marine/industrial; (C3/C2)
• Lisbon (Portugal); high UV exposure; (C2/C2)
Test panels are placed at defined declinations according to the type of application and its
typical load that shall be investigated, i.e. for the European sites
• 5° South (low pitched roofing)
• 90° North (cladding)
• 45° South (sunshine)
Other European exposure sites include regional facilities, e.g. in Sweden (Bohus Malmön),
Southern France (Hendaye), Great Britain (Sandwich, Kent) or Italy (Fusina, Venice) [23].
Minimum accepted exposure periods in European exposure sites are two to three years.
Due to its very high solarisation and subtropical climate, the Florida test facility is a prefer-
red test site also for European manufacturers and users, to assess the durability of coatings.
Exposure in this site, located near Daytona Beach at 29° northern latitude, is done in 5° and
45° South declination, with durations of up to five years [24, 25].
Outdoor exposure might be combined with salt contamination that is applied by weekly
spraying of NaCl solution onto the test specimens. Corrosion progress is usually accelerated
by a factor of three to four, as compared to natural exposure, i.e. results may be available
within six months rather than years. The automotive industry often uses combined test
programmes that include humidity and salt spray testing, and exposure in the driving
range [26].
7.5 Literature
Quality Standards for the Coating of Work Pieces…), GSB AL 631, ed. 07/2009, Gütegemeinschaft für die
Beschichtung von Bauteilen (GSB International), Schwäb. Gmünd 2009, pp. 35 ff
[4] Goldschmidt, A., Streitberger, H.-J., Basic of Coating Technology, 2nd edition, BASF Coatings AG, Münster
2007, pp. 414 ff
[5] LeBozec, N., Blandin, N., Thierry, D., Accelerated corrosion tests in the automotive industry: A comparison
of the performance towards cosmetic corrosion, Materials and Corrosion 59, 2008, pp. 889 ff
[6] Yasuda, H. K., Reddy, C. M., Yu, Q. S., Deffeyes, J. E., Bierwagen, G. P., He, L., Effect of Scribing Modes on
Corrosion Test Results, Corrosion 57, 2001, p. 30
pp. 571 ff, 577
[8] Barrow, G. M., Physikalische Chemie (Physical Chemistry), vol. 3, 3rd ed., Bohmann-Vieweg, Vienna 1977, p. 213
[9] Klimow, G., Fink, N., Grundmeier, G., Electrochemical Studies of the Inhibition of Cathodic Delamination of
Organically Coated Galvanised Steel by Thin Conversion Films, Electrochim. Acta 53, 2007, pp. 1290 ff,
1291
[10] Fink, N., Wilson, B., Grundmeier, G., Formation of Ultra-Thin Amorphous Conversion Films on Zinc Alloy
Coatings, Part 1: Composition and Reactivity of Native Oxides on ZnAl (0.05 %)-Coatings, Electrochim. Acta
51, 2006, pp. 2956 ff
Coatings, PhD Thesis, Loughborough Univ., Loughborough 2008, p. 81

[12] Fink, N., Wilson, B., Grundmeier, G., [10] p. 2969

[13] Thébault, F., Vuillemin, B., Oltra, R., Ogle, K., Allely, C., Investigation of self-healing mechanism on galvanized
steels cut edges by coupling SVET and numerical modeling, Electrochim. Acta 53, 2008, pp. 5226 ff
[14] Taylor, C. J., Elvins, J., Sullivan, J. H., Worsley, D. A., Corrosion Performance Evaluation of Zn/Al Galvanized
Steels Using the Scanning Vibrating Electrode Technique (SVET), Electrochem. Soc. Transactions 13, 2008,
pp. 95 ff
[16] Grundmeier, G., Schmidt, W., Stratmann, M., Corrosion Protection by Organic Coatings: Electrochemical
Mechanism and Novel Methods of Investigation, Electrochim. Acta 45, 2000, pp. 2515 ff
[17] Grundmeier, G., Wapner, C., Stratmann, M., Applications of a New Height Regulated Scanning Kelvin Probe
for the Study of Polymer/Metal Interfaces in Corrosive Environments, ICEPAM Conf. Oslo, SINTEF,
Trondheim 2004, www.sintef.no/static/mt/norlight/ICEPAM/09-Grundmeier_Max-Planck.pdf;
(15-03-2010; 19:12 h)
[18] Klimow, G., Fink, N., Grundmeier, G., [9] pp. 1290 ff, 1291
[19] Posner, R., Giza, G., Vlasak, R., Grundmeier, G., In-situ electrochemical Scanning Kelvin Probe Blister Test
studies of the de-adhesion kinetics at polymer/zinc oxide/zinc-interfaces, Electrochim. Acta 54, 2009,
pp. 4837 ff
[22] anon., Eurodes Programme, Eurodes: Outdoor Exposure, European Coil Coating Association (ECCA),
Brussels 2009; www.prepaintedmetal.eu/prg/selfware.pl?id_sitemap=190&language=EN;
(15-03-2010; 19:14 h)
[23] Pietschmann, J., Gardein, R., Filiform Corrosion and Results of 10 Years Natural Weathering, Galvanotechnik
106, 2008, pp. 1764 ff
[24] anon., [3] p. 44
[25] anon., Florida Subtropical Exposure Facility, Brochure: Battelle Florida Materials Research Facility, Battelle
Memorial Institute, Columbus OH, USA 2010; www.battelle.org/daytona.aspx; (16-03-2010; 16:31 h)
[26] Goldschmidt, A., Streitberger, H.-J., [4] pp. 429 f

Substrates 137
8 Chemical conversion treatment
8.1 Substrates
Various metallic materials serve as substrates for industrial painting, however, the most
common metal used in construction is steel [1]. Due to its wide distribution on earth and its
useful features, in particular strength and ductility, iron (Fe) has dominated human culture
and economy for three millennia, making this epoch of human history the “iron age”. As
homage to the metal, the Atomium, architectural highlight of the 1958 World Exposition
in Brussels, Belgium, represents a model of an iron crystal, magnified by 165 billion. The
building, originally clad with aluminium sheet, was refurbished in 2006, its outer skin
being made now from stainless steel.
The earth’s lithosphere contains between 4.5 to 5 % iron, i.e. an existence of two quintillion
(1018) tons, mainly as silicates, oxidic and sulfidic ore [2]. Iron is produced in blast furn-
aces, by smelting the ore with coke and lime under an oxygen-depleted atmosphere, and
separating the molten metal from the silicate/carbonate slag. The crude pig iron is then
converted to steel by controlled oxidation. Further alloying and annealing processes are
used to produce a wide range of steels of different quality [3]. Highly alloyed steels display
particular qualities, like stainless steel (alloying elements: chromium, manganese, nickel,
molybdenum) or electro-sheet with high magnetic susceptibility (silicon). However, only
minor amounts of these materials are subject to painting operations. Low-alloyed, carbon
steel, when exposed to the atmosphere, quickly develops a layer of oxide scale, composed of
FeO (wuestite), mixed oxide Fe3O4 (magnetite) and Fe2O3 (haematite), on its surface.
Massive steel parts are manufactured by casting, hot forging, extrusion or hot rolling. Work
pieces made via these hot production cycles often develop a thick scale that requires mecha-
nical cleaning and pickling prior to any coating process (cf. Chapter 3.3).
The choice of steel is made with respect to the intended use. Particular qualities and
strength properties are required for roll profiling, bending, deep-drawing and other metal
working operations. The mechanical and technological specifications of both the base steel
and any metallic coatings are subject to norms [4]. Sheet steel of high surface quality is pro-
duced by cold rolling, further reducing the gauge of hot-rolled feedstock. Cold-rolled steel
sheet is used for indoor applications like furniture, some appliances or lighting. However,
when intended for outdoor use, e.g. car manufacture, façade cladding or roofing, most of
the material is covered with a zinc (Zn) layer by hot-dip or electro-galvanising, in order to
prevent the reddish-brown iron oxide formation (rust).
Zinc coatings serve as a first protective barrier against corrosion. Due to its lower electro-
chemical potential zinc is less noble than iron [5] (cf. also Chapter 2.1), and therefore corrodes
preferentially. However, this corrosion reaction is kinetically retarded by formation of a
dense surface layer of mixed zinc oxide, hydroxide and carbonate (cf. Chapter 3.3.3.1). More-
over, these corrosion products are colourless (white rust). The service life of a zinc coating
is determined by its thickness (or gauge). Under normal weathering conditions, the gauge
loss of the coating has been reported in the order of 0.4 µm/a (2.5 to 3.5 g/[m2a]) [6].

ISBN 978-3-86630-805-3

Table 8.1: Substrates On hot-dip galvanised sheet metal,

Ferrous Non-ferrous a zinc coating is produced in fast,
continuous coil lines, immersing
Steel, stainless steel Wrought aluminium (alloys)
cleaned, annealed steel in a zinc
Metallic-coated steel Cast aluminium (Si, Cu) melt. The zinc melt may contain
- Galvanised, Magnesium aluminium (Al), as well as small
alloy-galvanised zinc amounts of other alloying ele-
- Electro-galvanised, Cast zinc, zinc sheet ments, e.g. silicon (Si), lead or
alloy-galvanised zinc antimony. Specified alloy-galvani-
- Aluminised Others (copper, brass etc.) sed steel sheet is known as “Gal-
- Tinplate fan”, ZA (5 % Al), or “Galvalume”,
AZ (55 % Al, 1.6 % Si). After the
zinc melt, the strip is cooled down
by pressurised air (air knife) in order to control the Zn thickness. Nowadays, a spangle-free,
finely crystalline surface is state of the art. More recently, ternary systems with magnesium
and aluminium, that provide a corrosion resistance superior to ZA coatings [7], have entered
the marketplace.
Electro-galvanised sheet is produced in a continuous coil operation by electro-deposition of
Zn or Zn alloys from an electrolyte solution onto the clean, annealed and temper-rolled steel
strip. The Zn layer gauge can be adjusted by choice of the parameters of the electrolysis.
Tables 8.1 and 8.2 summarise important substrates for industrial painting.
Aluminium [8 – 10] (Al) is the most common metal in the outermost crust of the earth, making
up for 8 % of this so-called “Si-Al” layer. Even less noble than zinc, Al is found almost exclusi-
vely in its oxidised state in silicate and carbonate ore, i.e. clay and bauxite minerals. Bauxite
contains approx. 50 % Al oxides. Being discovered in the early 19th century, elementary Al
took five decades before being produced on an industrial scale. Today’s improved process
involves hot extraction of Al oxide from the mineral with sodium hydroxide solution, from
which Al hydroxide, gibbsite, Al(OH)3, is precipitated upon cooling, and filtered off. Dehy-
dration at 1.100 °C in fluidised bed furnaces renders pure Al oxide, Al2O3. Elemental Al is
derived from the oxide by electrolysis in molten cryolite, Na3(AlF6). The process requires a
high amount of energy, i.e. up to 16 kWh per kilogramme of Al. The recycling of Al scrap
takes much less energy, making the material that is recovered (secondary Al) an important
Table 8.2: Most common substrates for coil coating

Substrates Uses
Base metal Coating Gauge Symbol* Architec- Appliance Transport
[µm] tural
Cold-rolled none indoor
steel (CRS) electro 3 to 7.5 ZE x
galv. (EG)
hot-dip 7 to 30 Z indoor, x x
(HDG) outdoor
Galfan 7 to 30 ZA indoor, x x
outdoor
Galvalume 15 to 30 AZ outdoor
Aluminium indoor, x x
outdoor
* System of symbols cf. Meuthen, Jandel [4]

Substrates 139
source for the aluminium industry. In 2007, the world production was 38 Mt of primary and
9.6 Mt of secondary Al.
Despite its low standard potential, technical aluminium is resistant to corrosion, since
it forms dense surface oxide layers under normal atmospheric conditions. These layers
inhibit ongoing structural corrosion, as long as the metal surface is neutral and no contact
corrosion with more noble metals is possible. Hence, corrosion phenomena on Al surfaces
are prominent with alloys that contain copper or when acidulated conditions apply, i.e. with
the so-called filiform corrosion (cf. Chapter 6.6.2.2). A multiplicity of Al alloys is used for
different technical purposes. Table 8.3 shows typical alloys and their applications [11, 12].
Al alloys for casting [13, 14] often contain high percentages of silicon (Si), copper (Cu) and
magnesium (Mg), plus smaller amounts of additional elements, in order to obtain materials
of particular workability and strength. Typical alloys for dye-casting contain 8 to 12 % Si,
up to 3 % Cu and/or up to 10 % Mg. Upon cleaning and pickling with strong alkalis, these
alloying elements cause dark deposits on the work piece surface, e.g. enrichments of ele-
mentary Si and metasilicate, Na2SiO3, that require hydrofluoric acid (HF) pickling for their
removal. Alternative measures include the depletion of surfaces of cast work pieces in Si, in
order to avoid the highly toxic and hazardous HF.
8.2 Chemicals for pretreatment

8.2.1 General remarks
Adhesion of a coating is highly dependent on the type of substrate and its proper cleaning
and conversion treatment (pretreatment) [15 – 18] by an adjusted process, that also provides
an improved corrosion resistance and durability. The painting operation, therefore, includes
preceding process steps for cleaning and pretreatment. In immediate succession paint is
applied. Especially when a flexible substrate is coated, or the painted goods are subject to
dynamic stress during their service life, or when the entire paint coat is thin (e.g. <35 µm),
the paint coat often comprises a separate primer and a topcoat, sometimes even additional
layers to mediate stress distribution or to add protective features to the coated surface
(scratch resistance, anti-scaling, anti-fouling properties etc.). The primer is applied to
Table 8.3: Aluminium alloys and typical uses

Alloy AAa Key No. Features Uses
Al 99 % min 1xxx Foil, sheet, litho sheet
Cu 2xxx + mechanical Aircraft industry
– corrosion protection
Mn 3xxx + mechanical Food packaging,
~ deep-drawing architecture, radiators
Si 4xxx + casting Engineering, heat exchangers
Mg 5xxx + strength after cold Food packaging, automotive,
forming transport, architecture
Mg, Si 6xxx + strength Automotive, architecture,
transport
Zn 7xxx – corrosion protection Aerospace, radiators
Others 8xxx Foil (Fe), aircraft industry (Li)
a
The Aluminium Association Inc.

enhance corrosion resistance and to render improved adhesion, while the topcoat provides
the required colour, gloss and texture.
The prominent function of pretreatment and primer is to provide corrosion resistance, if
one is to generate a long-lasting product with an aesthetic appeal and high durability in all
environmental conditions. Pretreatment and primer preclude or delay creepage of organic
coating once it is damaged or punctured. After thorough cleaning (cf. Chapter 3), the che-
mically clean, wettable surface is extremely reactive and therefore needs to be rendered
inert immediately, by coating with a thin, non-metallic layer that simultaneously serves as
passivation and adhesion promoter for the subsequent paint coat. The typical specific weight
of these coatings ranges from 50 to 500 mg/m2, gauges of 20 to 100 nm are common.
Most conversion coatings are applied in spray or immersion processes. Alkaline and chro-
mate passivation or phosphate processes have been widely used. These processes require a
fresh water rinse to remove excess chemicals and by-products. Often, post-rinses are used
to enhance the corrosion resistance. Chromate or chromium-free post-rinses are available.
As an example, Table 8.4 summarises prior-art pretreatment technology as it has been
used in the coil coating industry. In particular, hot-dip galvanised (Z) strip is commercially
pretreated either with alkaline passivation or acidic, chromate passivation processes, while
cold-rolled steel (St) is usually treated with iron phosphating solutions; all of these pretreat-
ments, however, commonly are completed by chromate post-rinses.
After any pretreatment, the work piece surface must be completely dry before being processed
to the paint section. Indirectly fired hot-air, infrared or induction dryers are state of the art.
8.2.2 Alkaline passivation

Alkaline passivation [19, 20] has been the predominant pretreatment process for hot-dip gal-
vanised coil. The treatment solution comprises caustic soda, iron (Fe) and cobalt (Co) com-
pounds and solubilising complexants. Optionally nickel ions (Ni) could be present. In the
course of the reaction, a zinc oxide coating is formed that incorporates the Fe and Co (or Ni)
ions in a spinel-type lattice. The alkaline passivation exhibits outstanding adhesion, thus
allowing extreme deformation, however requires a post-rinse to obtain sufficient corrosion
protection. Typical specific coating weights range between 0.2 and 0.4 g/m2. Key reactions
of the film formation are illustrated by Equations 8.1 to 8.3.
Equation 8.1 2 Co(OH)2 + 0.5 O2 → CoO(OH) + H2 O Co oxidation
Equation 8.2 2 CoO(OH) + Zn(OH)2 → Zn(Co2 O4) ↓ + 2 H2 O Zn,Co spinel
Equation 8.3 2 Fe + Co + 8 OH → Co(Fe2 O4) ↓ + 4 H2 O
3+ 2+ -
Co,Fe spinel
Table 8.4: Conventional coil coating pretreatments for architecture, white goods etc.
Process Substratesa Remarks
Alkali passivation Z, ZA, AZ, ZE Chromate post-rinse
Yellow chromate Z, ZA, AZ, ZE, Al Chromate post-rinseb
Green chromate Al Foodgrade
No-rinse process Z, ZA, AZ, ZE, Al, St Chromate containing
Iron phosphate St Chromate post-rinse
a
Abbreviations: Z: Hot-dip galvanised, ZA: Galfan, ZE: Electro-galvanised, AZ: Galvalume (AluZinc),
Al: Aluminium, St: Cold-rolled steel
b
Except aluminium

Chemicals for pretreatment 141
The conversion layer is completed by a post-rinse that contains chromium (III) and chromate
ions. Alkaline passivation is suitable for all galvanised substrates, including the aluminium
alloyed, Galfan and Galvalume, despite earlier publications [21]. More recently, the use of
heavy metals like Cr, Ni, that form toxic compounds, and in their wake, Co, has become a
matter of concern. As a result, chromium-free post-rinses have been introduced. In Europe,
some development efforts on the alkaline passivation process have been directed towards
the replacement of the heavy metals by magnesium (Mg) [22], however these developments
have not taken ground. Instead, the single-stage, no-rinse chromium-free pretreatments
(cf. Chapter 8.2.7) have proliferated.
8.2.3 Phosphating
8.2.3.1 Iron phosphating
The term “phosphating [23]” is used for two different classes of pretreatment, i.e. iron phospha-
ting, and zinc phosphating. Iron phosphating [24, 25] comprises the treatment of steel surfaces
with acidic sodium phosphate solution (dihydrogen phosphate). Iron is dissolved by the attack
of the acid, and a thin, amorphous iron phosphate layer is formed. The thickness of the con-
version coating is increased by the use of oxidants like molybdate, chlorate or organic nitro
compounds that inhibit the formation of hydrogen, thereby accelerating the net reaction.
Equation 8.4 6 Fe + 3 NaClO3 + 18 H+ → 6 Fe3+ + 3 NaCl + 9 H2 O
Equation 8.5 Fe3+ + H2PO4— → FePO4 ↓ + 2 H+
Commercial iron phosphating processes usually contain surfactants, which makes them
suitable for the use as cleaners. The process is often carried out in two stages, with inter-
mediate and final rinsing, where the first active bath is adjusted for the cleaning step, e.g.
by addition of surfactants, and the second active bath is operated at a lower pH value by
addition of phosphoric acid. The process can be operated in immersion or spray lines. The
conversion coating ranges at specific weights between 0.2 and 1 g/m2. Iron phosphating
renders a basic level of corrosion protection. To enhance the performance, the final rinse
may be carried out with a sealant, including chromate chemicals.
8.2.3.2 Zinc phosphating

Zinc phosphating [26 – 28] is state of the art in the pretreatment of car bodies or appliance
housing. It is particularly well suited for the common process of car manufacture. Car bodies
are constructed of a variety of substrates, mostly hot-dip galvanised or electro-galvanised
steel, but also including cold-rolled steel, and aluminium. After cleaning and phospha-
ting, the entire car body is coated with a cathodic electro-dip primer. Zinc phosphate
pretreatments yield crystalline coatings of 0.5 to 4 g/m2 that mainly consist of hopeite,
Zn3(PO4)2 · 4 H2O, but also contain manganese (Mn) and nickel (Ni) doted phosphates,
in order to improve the stability vs. high pH that occurs during the electro-dip painting
(tri-cation phosphate technology). More recent developments use magnesium (Mg) or cal-
cium (Ca) phosphates. Zinc phosphating baths further contain e.g. nitrite or hydroxyl amine
as accelerators. Common Mn and Ni contents in the coating are 4 and 0.5 %, respectively. On
ferrous surfaces, iron containing phosphate crystals, phosphophyllite, Zn2Fe(PO4)2 · 4 H2O,
are deposited. Quality zinc phosphate coatings require a controlled crystal size that can be
effected by application of e.g. titanium phosphate slurries that provide seeding nuclei for
the crystal growth [29]. Usual crystal sizes range from 1 to 3 µm. Smaller crystals enable
thinner, yet denser phosphate coatings for better formability.
Equation 8.6 Zn + 2 H+ → Zn2+ + H2 ↑

Equation 8.7 3 Zn2+ + 6 H2PO4— → Zn3 (PO4)2 ↓ + 4 H3PO4

The application of Al has proliferated due to the low density of this material and the weight
and resulting fuel savings implied by its use. It is often found as construction material for
hang-on parts like hoods, trunk lids and doors, but also in the suspension and axle assem-
bly. As free Al3+ ions would inhibit the precipitation of Zn phosphate, they must be masked
by appropriate measures. Therefore, fluoride containing anions are present in multi-metal
phosphating compositions. While complex fluorides are preferred, e.g. hexafluoro silicic
or hexafluoro titanic acid, some free fluoride is necessary which is preferably supplied by
ammonium hydrogen fluoride [30]. The free fluoride concentration can be measured by a
fluoride ion sensitive electrode.
8.2.4 Chromating
Historically, the unique properties of chromium have been the key factor of both pretreatments
and paints. Chromium, in its oxidation states +VI and +III, serves as an electrochemical couple
that can inhibit most corrosive reactions on a metal surface [31]. Therefore, most pretreatments
have comprised at least one processing step with chromate containing chemicals to obtain
the necessary corrosion resistance of the final product. Typical reactions for the formation of
a chromate conversion layer on a galvanised steel surface are described as depicted in Equa
tions 8.8 to 8.10. The surface reaction is characterised by acidic attack of zinc and subsequent
film formation by partial reduction of chromic acid. Owing to these reactions, the acid is con-
sumed and zinc dissolves. By using an immersion or spray technology and removing solution
from the bath by drag-out and overflow, the composition of the bath would slowly change with
operating time. In practice, it is therefore necessary to correct the pH and the ingredients
of the bath by an appropriately formulated replenisher which is fed continuously or in short
intervals, to maintain the correct composition.
Equation 8.8 Zn + 2 H+ → Zn2+ + 2 [H]
Equation 8.9 2 H+ + 6 [H] + 2 CrO42— → Cr2 O42— + 4 H2 O
Equation 8.10 Zn2+ + Cr2 O42— → Zn (Cr2 O4) ↓
Similar considerations apply for cold-rolled steel or aluminium substrates. Pretreatments
for aluminium have been extensively reviewed, in order to understand the principles that
would help to identify a suitable chemistry for chromate replacement [32].
Equation 8.11 Al + 2 H2 O → AlO(OH) ↓ + 3 [H]
Equation 8.12 CrO42— + 3 [H] + PO43— + 5 H+ → Cr (PO4) ↓ + 4 H2 O
Equations 8.11 and 8.12 depict the situation for a so-called green chromate coating, i.e. the
chromous phosphate layer that precipitates from a phosphoric acid containing chromate
pretreatment solution and is virtually free of chromium (VI) (chromate). Since chromous
(chromium [III] containing) compounds are almost insoluble and non-toxic, such conversion
coatings have been used for decades on Al surfaces, as a replacement for “yellow” chromium
chromate treatments, and in particular as pretreatments in the food-related sector (canning,
i.e. food containers, beverage cans and lids).
8.2.5 Anodising of aluminium

While chromate containing chemicals have been in use for decades, the discussion on
environmental and health risks and according legislative action have driven the coating
industry’s search for „greener“, more environmentally favourable solutions. It is expected
that the implementation of the new chemical policy REACH will further boost the replace-

ment of the chromate processes that are technically proven, but hazardous to human health
and environment (cf. Chapter 8.2.10) [33]. Additional economic factors are also driving the
need for further coating developments.
Anodising offers an approach to chromium-free treatment of aluminium surfaces. It is
often carried out to provide a stand-alone, dense oxide coating that is left uncoloured or is
coloured with inorganic or organic dyes that settle in the pores of the anodic film before
these pores are closed by hydrothermal sealing. However, thin-layer anodising processes
have been adapted to serve as pretreatments prior to organic coating.
The anodising process is carried out by immersing the work pieces in an acidic bath, and
subjecting them to an electrolytic treatment with asymmetric alternating or pulsed direct
current. The aluminium surface is converted to aluminium oxide, Al2O3, at a typical film
building rate of 3 µm/min. The oxide forms a honeycomb structure, with pores in the cen-
tre of the cells. For the normal anodising process, the most commonly used electrolyte is
sulphuric acid, and anodising is extended to allow the formation of a 20 µm layer, which
is subsequently subjected to a hydrothermal sealing treatment in order to close the pores.
Contrary to this, when used as pretreatment prior to painting, anodic films are only thin
(3 to 8 µm), and they are left unsealed. While historically, phosphoric acid was often used as
the electrolyte, to obtain more flexible, less brittle anodic films, today the DC/sulphuric acid
process is preferred, the operational parameters and obtainable quality properties being
subject to industry specification [34].
Particularly for aircraft and military equipment, however, chromate still is the specified
standard in terms of high durability under severe conditions. The required performance
is prescribed in a series of military specifications (Mil Spec). For these uses, anodising is
carried out in chromic acid, hence resulting in a mixed Al, Cr oxide coating [35, 36].
8.2.6 “Chromiting”
The term “chromiting” refers to a class of passivates and pretreatments that have been
developed on the basis of chromous (Cr [III]) chemicals. Typical, highly acidic pretreatment
baths contain chromous nitrate or sulphate, optionally up to 2.5 g/l cobalt (Co), plus certain
complexants [37, 38]. The process is reported to generate dense, nano-scale oxidic coatings
on various substrates like cold-rolled steel, galvanised steel, and aluminium, providing
good corrosion resistance in salt spray testing. The process is aimed at replacing iron and
tri-cation zinc phosphating in multi-metal lines, substantially reducing the sludge level. It is
claimed to be particularly suited as pretreatment prior to coating with polyester and epoxy/
polyester powder paints [39].
8.2.7 Chromium-free pretreatment

8.2.7.1 Titanium and zirconium fluoro-complex technology
In anticipation of a more stringent environmental protection policy, chromium-free pre-
treatment processes for architectural applications have been developed and introduced to
the market since the early 1990s. This applies to the coating of single work pieces (batch
painting) e.g. window frame profiles and façade parts, as well as to the industrial painting
of metal coil (coil coating) that is used for large wall claddings or roofing, but also for garage
doors or sun blinds and roller shutters [40].
Having been introduced in the batch painting process of aluminium extrusion in 1996,
chromium-free technology nowadays is standard in this market in Europe. It has become
the favourite choice whenever a new painting line is designed, or major renovations imple-

mented in existing lines, and has

been awarded approvals from
several European wide operating
quality associations.
For coil coating of aluminium,
another chromium-free process
was introduced in the same
period, comprising the so-called
no-rinse application. Chromium-
free treated aluminium coil stock
has been in use for over 10 years,
for wall cladding and sun blinds.
Figure 8.1: Potential bonding structures of chromium-free The coil material was top-coated
pretreatments with a single-layer, high-durable
polyester paint. For steel and
galvanised steel surfaces, chromium-free products have been in industrial use since 1998.
Table 8.5 represents the alternative, chromium-free pretreatment processes that have
become available in coil coating. Here, the chromium-free no-rinse pretreatment has become
particularly important, as it is a multi-substrate process, and prevents high amounts of
waste water. Strong correlation and comparability between chromium-free and chromate
pretreatments in various outdoor and accelerated corrosion tests have been reported [41].
Commonly, the chromium-free pretreatments are based on aqueous solutions of non-toxic
transition metal complexes and compounds and special water-soluble polymers. The mecha-
nisms of bonding and corrosion resistance are attributed to a metal oxide layer that is formed
in an initial reaction on top of the treated metal surface and then covered by the organic
matrix. Figure 8.1 shows a corresponding schematic. Thermal and calorimetric experiments,
micrographic methods and spectroscopy of the layers are consistent with this picture [42].
Chromium-free conversion coatings have gauges in the order of a few 10 nm, corresponding
to Ti or Zr build-up values between 1 and 30 mg/m2. The key reactions during the formation
of such chromium-free conversion coatings can be sketched as in Equations 8.13 and 8.14:
Equation 8.13 Zn + 2 H+ → Zn2+ + 2 [H]
Equation 8.14 (Ti, Zr) F62— + H3 PO4 + Zn2+ + 3 H2 O
→ Zn (OH)2 · (Ti, Zr) (OH) (PO4) ↓ + 6 HF
A distinctive layer is reported that was analytically characterised using Auger and photo
electron spectroscopy combined with argon sputtering technique. Figure 8.2 shows the
Table 8.5: Chromium-free coil coating pretreatments for architecture, white goods etc.
Process Substrates* Remarks
Alkali passivation Z, ZA, AZ, ZE Chromium-free post-rinse
Chromium-free pretreatment Z, ZA, Al Spray and dip, optionally:
chromium-free post-rinse
No-rinse process Z, ZA, AZ, ZE, Al, St Chromium-free
Iron phosphate St Chromium-free post-rinse
* Abbreviations: Z: Hot-dip galvanised, ZA: Galfan, ZE: Electro-galvanised, AZ: Galvalume (AluZinc),
Al: Aluminium, St: Cold-rolled Steel

Figure 8.2: Depth profile of a chromium-free pretreatment on galvanised steel

Source: European Coil Coating Association 1999; Androsch et al. [41]
depth profile obtained by this method. Zinc, originating from the substrate, is found in all
parts of the layer, albeit in higher concentration close to the interface between metal and pre-
treatment. This also applies to alloying elements of the galvanising layer, like aluminium.
The transition metals (Me 1 and 2), and fluorine (F) that are ingredients of the pretreatment,
are generally distributed throughout the layer. The concentration of carbon (C), indicating
the presence of the organic polymer, increases sharply close to the outer surface.
Chromium-free pretreatments of the kind described above are used for a variety of sub-
strates, such as aluminium, zinc, zinc alloys and cold-rolled steel. In particular for coil
coating application, the chemical solution is adjusted to a no-rinse process, i.e. applied at
an appropriate dilution onto the clean, dry strip surface where it immediately reacts off to
form transparent, uniform layers upon drying at temperatures above 50 °C. Neither che-
micals in excess nor products of side reactions are left, hence no rinsing is required after
pretreatment.
Currently, pretreatment of Zn-Al-Mg substrate is carried out with unaltered pretreatment
processes that have been in use for state-of-the-art galvanised substrates. Adaptations are
Figure 8.3: Atomic force microscopy (AFM) images of bare, zirconium oxide coated and alkali phospha-
ted cold-rolled steel (CRS) Source: Rogers Publishing Ltd.; cf. Fristad [43]

under way to improve on certain features that are impacted by the physics and surface
chemistry of the new substrate that tends to be less flexible and more sensitive to moisture
than ordinary galvanised material. For the substrate composition and properties itself,
there is yet no standard set.
In the European coil coating market, chromium-free pretreatments have only recently
gained some share, despite the technical acceptance they have achieved. Since 1998 they
have grown from 0.3 to approximately 5 % of the pretreatment use.
Another class of chromium-free processes has been introduced recently for which the
absence of phosphates is claimed as an additional environmental benefit [43, 44]. These are
generally described to form thin (20 to 100 nm) amorphous zirconium oxide (ZrO2) films.
“First generation” products of this class are reported to perform at the level of iron (alkali)
phosphate, while a “second generation” development is compared with zinc phosphates,
in particular under cathodic electro-dip primers. The target use for this latter range of
products is the replacement of tri-cation zinc phosphate pretreatments in the automotive
original equipment manufacturers’ (OEM) market.
8.2.7.2 Other chromium-free pretreatments

Apart from the transition metal complex technology, other approaches for chromium-
free pretreatment have been investigated, including cerate, phospho-molybdate [45, 46] and
cobalt amine [47, 48] processes, as well as processes based on so-called self-assembling mole-
cules (SAMs) [49]. The latter are linear hydrocarbon molecules with two terminal functional
groups, preferably phosphonate groups that have a bonding capability to both the metal and
the subsequent paint coat. Owing to their molecular structure, SAMs assemble to form a
monolayer that has a thickness in order of the hydrocarbon chain length, i.e. 1.5 to 2 nm.
Due to their complexity, these processes currently have found only limited applications, e.g.
in the automotive wheel manufacture and in the aircraft industry [50]. Another approach to
Cr-free pretreatments is opened up by the so-called hybrid coatings.
8.2.8 Hybrid pretreatment coatings

As new developments, aqueous pretreatment processes have been introduced that combine
organic and inorganic chemistry, and are therefore referred to as hybrid coatings. Hybrid
coatings are described in greater detail in Chapter 10. However two examples shall also be
outlined in this current context, as they incorporate typical pretreatment features.
8.2.8.1 Silane/siloxane coatings

One class of these coatings employs the formation of silane/polysiloxane layers [51, 52]
from a sol-gel process [53]. Typical representatives of this class of compounds are termi-
nal aminopropyl triethoxy silane (γ-APS), H2N–(CH2)3–Si(OC2H5)3 or bis-(triethoxysilyl)
ethane (BTSE), (C2H5O)3Si– (CH2)2–Si(OC2H5)3. The technology requires a hydrated metal
oxide surface as obtained by alkaline cleaning. The further process involves controlled
hydrolysation of the Si–OC2H5 functions, bonding to the surface via metal–O–Si links, and
polymerisation/cross-linking of the affixed hydroxy-silane moieties to form a polysilo-
xane. Siloxane coatings can also be coupled with the metal surface by plasma or chemical
vapour deposition technology [54, 55]. The functionalised organic groups protrude from the
surface, becoming available for bonding with the subsequent paint coat.
8.2.8.2 Combined thermal processes for primer-pretreatment

The combination of inorganic and organic, polymeric materials can also render coatings
with additional features apart from adherence and passivation, for instance, fingerprint

resistance, lubrication, or priming capability. Such processes allow add-on quality and
changes in the manufacturing chain, like omission of extra lubrication in the press shop or
in-line application of extra coats and varnishes.
In particular for precoated coil, the idea of combining pretreatment and primer functions
in one single stage in the coil coating process has been around for a number of years. By
employing this principle, workflow changes are rendered possible, like doing away with
one of the currently separate treatment steps, or making the respective treatment station
available for other purposes, i.e. multi-layer coatings.
The advantageous impact of a combined primer-pretreatment on the operating economy of
compact coating lines for coils and sheet has been reported very recently [56]. As described
in the literature [57], a primer-pretreatment may incorporate up to five different technology
steps with their related economic and environmental benefits at once. These include low
toxicity by the omission of chromium (particularly Cr VI) compounds, environmental
benefits by the avoidance of organic solvents and by low curing temperatures, a maximi-
sed yield by a high solids/reactables content, the obsoletion of a separate conventional
priming step, as well as the possibility of in-line priming in galvanising installations.
With an aqueous primer-pretreatment and a powder topcoat an entirely solvent-free
coating process becomes feasible.
Embracing both the pretreatment and priming steps, such a combined process is described
that can be integrated at exit of a coil galvanising line. Even cleaning that is normally the
mandatory first stage in a conventional coil coating line can be omitted. For the first time in
the coil coating history, the new primer-pretreatment enables process speeds in galvanising
and coating to be matched. The process is expected to go fully commercial soon.
8.2.9 Surface preparation of other substrates –

copper alloys, white metal, magnesium, stainless steel
For copper and brass, and similar non-ferrous metals, a conversion treatment is usually omit-
ted. Special care must be taken to use mild cleaning conditions in order to avoid uncontrolled
oxide formation and discolouration. Alkalinity, temperature and also duration of cleaning
must be carefully adjusted. Aged surfaces that have already developed a brownish coloura-
tion must be pickled prior to painting. Environmentally friendly solutions comprise sulphuric
acid and stabilised hydrogen peroxide, instead of nitric acid and/or fluorides. For white metal
(tin and its alloys) mild cleaning forms a sufficient preparation of the surface.
Historically, pretreatment of magnesium and its alloys comprised chromating or anodising
procedures that were adapted from aluminium processing. More recent processes also use
chromium-free chemistry that has been derived from pretreatments for aluminium. Free
fluoride usually must be present in order to achieve sufficient etching of the metal surface.
Stainless steel surfaces develop a chromous oxide (Cr2O3) layer that has a very low wetta-
bility. Work pieces made of stainless steel therefore require a strong alkaline cleaning and
subsequent treatment with a nitrate/fluoride etch or a chromium-free, hexafluoro titanate
based pretreatment immediately prior to the painting operation, in order to achieve proper
adhesion.
8.2.10 Environmental considerations

As mentioned in Chapter 8.2.5, the European Union (EU) has issued strict legislation in
order to control and restrict environmental and health hazards related to the use of chemi-

cals. Some of the related laws and directives have their worldwide counterparts, like the End
of Life Vehicles Directive (ELV), the Waste Electrical and Electronic Equipment Directive
(WEEE) and the Regulation on Hazardous Substances (RoHS), which have resulted in an
effective restriction of the use of chromates and other toxic substances in the respective
target markets. On top, the EU has now brought into force a new codex whose acronym,
REACH, stands for registration, evaluation, authorisation and restriction of chemicals [58].
This policy rules the use of all chemical substances that are manufactured in or imported
into the European Union and is governed by the EC Regulation 1907/2006. Under the provi-
sions of this Regulation, all chemicals that are commercially used above certain threshold
volumes require official authorisation and therefore may be subject to assessments of their
exposure risks to health and environment. Chemicals of very high concern, e.g. CMR-
labelled (carcinogenic, mutagenic and toxic to reproduction), and highly toxic substances
like chromium (VI) (chromate) compounds are likely to be phased out wherever possible or
effectively banned.
Waste water that is generated in a chromating operation (treatment baths and rinses) must
be processed via a detoxification of chromate ions, e.g. by reduction with sodium bisulphite
in acidic solution. After neutralisation with lime and precipitation, the concentration of
heavy metals that are present, like chromium (III), but also zinc, aluminium and others
from the substrate, as well as fluoride can be reduced below the required legal limits.
Table 8.6: Safety data regarding labelling (examples)

Chromium-free pretreatment Chromate containing pretreatment
Hazard Symbols: Hazard Symbols:
C Corrosive T Toxic
C Corrosive
N Environmentally harmful
Hazardous substance: Hazardous substance:
Hexafluoro zirconic acid Cr(III) chromate
Cr(VI) oxide
R clauses: R clauses:
R 34: Causes burns R 45: May cause cancer
R 22: Hazardous when swallowed
R 35: Causes severe burns
R 43: Sensibilisation possible upon skin contact
R 50/53: Very toxic for aquatic organisms, may have
long-term harmful effects on waters
S clauses: S clauses:
S 26: Upon eye contact, immediately S 53: Avoid exposition – get special instructions
flush thoroughly with water. Get medical before use
attention S 26: Upon eye contact, immediately flush tho-
S 36/37/39: During work, wear suitable roughly with water. Get medical attention
protective clothing, gloves, eye/face S 36/37/39: During work, wear suitable protective
protection clothing, gloves, eye/face protection
S 45: In case of an accident or when S 45: In case of accident or when feeling unwell, im-
feeling sick, immediately see a doctor mediately see a doctor (if possible, show this label)
(if possible, show this label)
National regulations (Germany): National regulations (Germany):
WGK = 2, water polluting product. WGK = 3, highly water polluting product.
Classification according to Mixing Rule Classification according to Mixing Rule VwVwS
VwVwS May 17th, 1999 May 17th, 1999

Application of pretreatments 149
The detoxification process, however, also builds up a considerable sulphate level. If limits
for direct effluent discarding apply, a further reduction of the sulphate content is necessary,
e.g. by precipitation with calcium aluminate.
Contrasting to this, waste water treatment for chromium-free processes is simplified to a
treatment with lime, to ensure precipitation of the commonly used titanium or zirconium
compounds, along with metal ions that originate from the substrate. In both cases the
sludge that is obtained must be dehydrated and deposited in a landfill site. The cost for
treatment and disposal of a typical chromating process is five to eight times as much as with
a chromium-free process. Also labelling instructions are advantageous for a chromium-free
process, owing to its much lower hazard potential. Table 8.6 gives examples of the respective
safety data of two typical processes.
Solvent-free coating products as described in Chapter 8.2.6.2, moreover, do away with
expensive installations for combustion and thermal destruction of exhausts from curing
ovens, and substantially reduce fuel consumption and VOC and CO2 emissions.
8.3 Application of pretreatments

8.3.1 Immersion and spray treatment
For the application of pretreatments in single work piece operations, immersion or spray
techniques are used as have been described in Chapter 3 for cleaning. A further technique
that has been developed for single work piece operation is “floating” which involves the use
of a low-pressure spray curtain.
Small parts are often processed in rotating drums that are dipped entirely into the active
and subsequent rinse baths. Larger parts are usually processed in baskets or fastened on a
rack and dipped into the treating baths by a crane. Particularly sophisticated and complex
parts like entire car bodies are transported through a series of treatment baths by a conve-
yor system. These conveyors can be combined also with pitch or even rotating installations,
to make sure that all parts of the metal surface, including bowl-shaped and box sections, are
properly contacted by the treating fluid. For example, patent DE 19950892 describes such a
conveyor system for car bodies [59].
Work pieces that have a comparably simple geometry, like flat parts, sheets, rods or profiles,
can be treated in spray application, providing that all parts of the surface are properly covered.
Such work pieces are fixed to a rack or conveyor chain and transported through a series of
spray booths. Most conveniently, the several compartments form a tunnel through which
the work pieces are moved with a uniform speed. By the similar principles that have been
explained for the cleaning operation, spray pretreatment can be used with lower concen-
trations of the active bath, as compared to the immersion technique. However, spray pres-
sures are usually lower than in the cleaning operation, as no turbulent action is required to
remove excess solution and by-products of the pretreatment reactions. In some cases, e.g.
when treating car bodies, immersion and spray techniques are used in combination.
Considerable care must be taken to avoid excess drag-out, as has already been described in
Chapter 3 for the cleaner case. Therefore, the operation in immersion lines or in installations
with separate spray booths must observe suitable drip-off times, optionally supported by a
brief spray with fresh or deionised water. In tunnel systems, the construction of the spray
tunnel must be adapted to avoid transfer or mixing of fluids between adjacent active or
rinse tanks. Concerning the overflow control and the economy of rinses, the same principles
apply as for the cleaner operation.

8.3.2 Pretreatment application for coil: spray/squeeze,

spray-cell, roll-coating
Immersion and spray techniques are used also for the pretreatment of coil. To immerse the
coil into the treatment bath, dip rolls are used. A number of dip rolls can be mounted in a
way that the strip forms several loops in the bath, in order to extend the available treat-
ment time. The speed of the travelling strip is sufficient to bring on the required exchange
of reactands from the surface. Immersion lines have been common for the so-called green
chromating (chromous phosphate) pretreatment of aluminium coil.
For certain treatments for steel and galvanised steel coil, the so-called spray-cell tech-
nique has been in use. Such equipment is constructed as a virtually enclosed compart-
ment that allows a high excess of a concentrated pretreatment solution to be sprayed onto
the coil at the cell entrance, and staying there for a reaction time of several seconds, before
the excess and reaction by-products are removed from the coil surface by a squeeze roller.
Large amounts of by-products generated by this technique, however, result in a fast con-
tamination of the active bath, and consequently in a poor economy, frequent bath dumps
and downtime for remaking, as well as high pollution.
Ordinary spray technique, applying lower concentrations of the chemicals over the whole
distance of the spray compartment has been more convenient and eco-efficient, also
saving operation time by bath life control measures.
The drag-out of chemicals is restricted by squeeze rollers at the exit of every active or
rinse stage. When properly maintained, the wet film can be minimised to a few millilitres
per square metre with these rollers. To avoid damage of their surface, rollers have to
be lifted off the strip automatically when the welded or stitched joint between two coils
passes, and return to their squeeze position immediately after.
Over the last twenty-five years, coil coating pretreatments have been adapted to the pre-
ferred application method for no-rinse technology. As mentioned before, this involves the
application of a precisely controlled amount of pretreatment chemicals to the aluminium,
steel or zinc-coated steel strip surface. This can be brought about by a roll-coater. The
acidic pretreatment chemicals react with the metallic surface, and the following film for-
mation takes place by drying the strip immediately (dry-in-place principle). No reaction
side-products can therefore change the process chemistry and a following water rinse is
not necessary. Consequently, the main advantages are found in the efficiency of chemical
usage and in substantial waste water savings.
Roll-coaters have been constructed in different ways. When adapted to application of

waterborne pretreatment chemicals, they are often also referred to as chemcoaters. In
principle, the liquid is taken from a tray by a first roller and transferred via another roller
(or a set of rollers) onto the surface of the moving coil. While transferring the liquid, the
wet film thickness is controlled by means of the nip distance and pressure, and by the
relative tangential speeds of rollers. Two or three-roller coaters are common, where the
additional roller (metering roll), which is often mounted between the first roller (pick-up
roll) and the final roller (applicator roll), helps in maintaining a uniform wet film across
the coater. Roller surfaces usually are made from high-grade or hard chrome-plated stain-
less steel. For aqueous pretreatment solutions, that display the low viscosity of water, the
pick-up roll may be ground to a certain roughness or even engraved, in order to facilitate
a sufficient amount of chemical to be taken from the reservoir tray. The applicator roll is
clad with a synthetic rubber blanket that has to be acid-proof (i.e. made of neoprene etc.),
due to the chemistry of the pretreatment solution.

Application of pretreatments 151
Apart from the roll-coater technique, also simpler, less expensive equipment has been
used, involving the controlled spreading of a small amount of the pretreatment liquid that
is applied onto the strip a short distance before squeeze rollers, by flooding, low-pressure
spraying or nip-feeding. Ideally, these rollers are motor-driven, in order to avoid aquapla-
ning effects, and better control the resulting wet film.
8.4 Literature
[1] anon., Eisenkristall – Atomium in Brüssel wieder eröffnet (Iron Crystal – Atomium Re-opened in Brussels),
BauNetz Media, Berlin 2006; www.baunetz.de/meldungen/Meldungen_Atomium_in_Bruessel_wieder_
eroeffnet_22792.html; (15-03-2010; 21:31 h)
[2] Sander, J., Über die Reaktivität von Lithium-trimethylferrat (II) gegenüber organischen Substraten (On the
Reactivity of …vs. Organic Substrates), Diss., Münster University, Münster 1986, p. 5
[3] Lehmann, V., Der moderne Hochofenprozess (Modern Blast-Furnace Process), Naturwissenschaften im
Unterricht Chemie, vol. 4, Friedrich-Verlag, Seelze 1993, p. 4
[5] Barrow, G. M., Physikalische Chemie (Physical Chemistry), vol. 3, 3rd ed., Bohmann-Vieweg, Vienna 1977, p. 213
[6] Townsend, H. E. (ed.), Outdoor Atmospheric Corrosion, Am. Soc. f. Testing and Materials (ASTM) Intern.,
W. Conshohocken PA, USA, 2002, p. 219
[7] Prosek, T., Larché, N., Vlot, M., Goodwin, F., Thierry, D., Corrosion Performance of Zn-Al-Mg Coatings in
Open and Confined Zones in Conditions Simulating Automotive Applications, Materials and Corrosion 60,
2009, publ. pend.
[8] Schäfer, J. H., Stoffstrom Aluminium – vom Bauxitabbau bis zum Recycling (Material Flow Aluminium
– From Bauxite Mining to Recycling), Gesamtverband der Aluminiumindustrie GDA, Düsseldorf 2008;
www.aluminium-ressourceneffizienz.de/media/Stoffstrom_Aluminium.pdf; (15-03-2010; 21:35 h)
[9] anon., Aluminium, GDA, Düsseldorf 2009, www.aluinfo.de/index-php/alu-lexikon.html; (15-03-2010; 21:38)
[10] anon., About Aluminium – Production Process, Europ. Aluminium Assoc., Brussels 2009;
www.eaa.net/en/about-alumium/production-process/; (15-03-2010; 21:44 h)
[11] anon., About Aluminium – Alloys, Novelis Painted Products, Novelis Deutschland, Göttingen 2010;
www.novelis-painted.com/about_alumium/alloys/index_eng.html; (15-03-2010; 21:40 h)
[12] Cornell, R., Bhadeshia, H. K. D. H., Aluminium-Silicon Casting Alloys, Univ. of Cambridge Materials Sc. &
Metallurgy, Cambridge, UK 1999; www.msm.cam.ac.uk/phasetrans/abstracts/M7-8.html; (15-03-2010; 21:45 h)
[13] anon., ISO 3522:2007, Aluminium and aluminium alloys - Castings - Chemical composition and mechanical
properties, International Organization for Standardization (ISO), Geneva 2007
[14] Blecher, A., Grasme, D., Hinüber, H., Husmeier, F., Meyer, B. D., Röhricht, G., Sander, J., Beschichten von
Aluminiumguß – Lackieren (Coating of Cast Aluminium – Painting), Worksheet, Dtsch. Forschungsges.
f. Oberflächenbehandlung DFO, Düsseldorf 1992, p. 5
[15] Androsch, F. M., Stellnberger, K.-H., Wolpers, M., Jandel, L., Drescher, D., Sander, J., Seidel, R.,
Chromate-free Coil Coating and One Year of Production Experience, ECCA General Meeting Monte Carlo,
Proc., European Coil Coating Association, Brussels 1999
[16] Schinzel, M., Chrome-free Systems for Coil Coating, ECCA Autumn Congress Brussels, Proc., European Coil
Coating Association, Brussels 2006
[17] Meuthen, B., Jandel, A.-S., [4] pp. 50, 53 ff
[18] Sander, J., Chromatfreie Systeme für Coil Coating – Stand der Erfahrungen (Chromate-Free Systems for Coil
Coating – Status…), Eur. Coil Coating Assoc. – German Group, Workgroup Proc., Solingen 2002, cit. re.
Schinzel [16]
[19] Meuthen, B., Jandel, A.-S., [4] p. 53 f
[20] Sander, J., Mady, R., Korrosionsschutz durch Feuerverzinken – neue Entwicklungen beim Herstellen,
Passivieren und Lackvorbehandeln von schmelztauchverzinktem Bandstahl (Corrosion Protection by
Hot-Dip Galvanising…), Metalloberfläche 43, 1989, p. 329 ff
[21] Ries, C., Metalloberfläche 41, 1987, p. 81, cit. re. Sander, Mady [20]
[22] Riesop, J., Krautbauer, H. (inv.), Alkaline Strip Passivation, Patent Nos. DE 19733972, US 6346295, Henkel
KGaA, 1997 and 2002
[24] Brands, K. D., Krause, M., Mayer, B., Molz, T., Willer, A. (inv.), Iron Phosphatisation Using Substituted
Monocarboxylic Acids, Patent No. EP0760870, Henkel KGaA 1995
[25] Fristad, W. E., Saad, K. I. (inv.), Phosphate conversion coating concentrate, Patent No. US6706123, Henkel
KGaA 2003
[26] Narayanan, T. S. N. S., Surface Pretreatment by Phosphate Conversion Coating – A Review, Rev. Adv. Mater.
Sci. 9, 2005, pp. 130 ff

[27] Satoh, N., Effects of heavy metal additions and crystal modification on the zinc phosphating of electrogalva-
nized steel sheet, Surf. Coatings Techn. 30, 1987, pp. 171 ff
[28] Ogle, K., Tomandl, A., Meddahi, N., Wolpers, M., The alkaline stability of phosphate coatings I: ICP atomic
emission spectroelectrochemistry, Corrosion Sc. 46, 2004, pp. 979 ff
[29] Tegehall, P.-E., Colloidal titanium phosphate, the chemical activator in surface conditioning before zinc
phosphating , Colloids and Surfaces 42, 1989, pp. 155 ff
[30] Sienkowski, M. L. (inv.), Zinc Phosphating Process And Composition With Reduced Pollution Potential,
Patent Publ. No. WO/2001/032953, Henkel Corp. 2001
[31] Androsch, F. M., et al., [15] Chapter 3
[32] Kendig, M. W., Buchheit, R. G., Corrosion Inhibition of Aluminum and Aluminum Alloys by Soluble
Chromates, Chromate Coatings, and Chromate-Free Coatings, Corrosion 59, 2003, p. 379ff
146 ff, 148 ff
Quality Standards for the Coating of Work Pieces…), GSB AL 631, ed. 07/2009, Gütegemeinschaft für die
Beschichtung von Bauteilen (GSB International), Schwäb. Gmünd 2009, pp. 32-35
[35] anon., Anodic Coatings for Aluminum and Aluminum Alloys, Military Spec., Mil-A-8625F(1), Dept. of
Defense, Defense Logistics Agency, Document Automation & Production Service, Philadelphia PA, USA
2003; www.dodssp.daps.dla.mil/...
[36] anon., Inspection Of Aluminum Alloy Parts, Anodizing Process For, Military Spec. Mil-I-8474C Not 2, Dept.
of Defense, Defense Logistics Agency, Document Automation & Production Service, Philadelphia PA, USA
1998; www.dodssp.daps.dla.mil/...
[37] anon., Product Informations, Surtec GmbH, Zwingenberg 2009; www.chromiting.surtec.com;
(15-03-2010; 21:48 h)
[38] Volk, P., Echte Alternative – Chrom(III)-haltige Vorbehandlung für Aluminium (True Alternative – Cr[III]
Containing Pretreatment…), Metalloberfläche 60, 2006, pp. 24 ff
[39] Pohl, J., Möller, R., New Cr (III)-based pretreatment – A simple, all-purpose, environmentally friendly
process, JOT International Surf. Technol. (1) 2009, pp. 2 ff
[40] Lienkamp, P. (ed.), Sander, J., Körner, T., Kleinschmidt, T., More than 10 years of experience with chrome-
free pre-treatment of aluminium – Perfect protection against corrosion, Press release, Henkel AG & Co.
KGaA, Düsseldorf 2008, cit. Int. Aluminium. J. 84 (11), 2008, p. 36 ff
[41] Androsch, F. M., et al., [15] Figures 18 – 19, discussion
146 ff, 148 ff
[43] Fristad, W. E., Phosphate-free Pretreatments for all Substrates, Coatings Magazine (11) 2008, pp. 14 ff
[44] Saji, V. S., Thomas, J., Nanomaterials for corrosion control, Current Science 92, 2007, pp. 51 ff
[45] Rauscher, G., Neue chromfreie Vorbehandungsverfahren für Aluminium (New Chromium-free Pretreatment
Processes…), JOT, 2005, pp. 54 ff
[46] Jatsch, A., Rauscher, G., Verbesserung des Korrosionsschutzes von Aluminium durch neuartige chromfreie
Vorbehandlungsmethoden vor der Lackbeschichtung, (Improvement of the Corrosion Protection of
Aluminium…), Galvanotechnik 101, 2003, pp. 674 f
[47] Schriever, M. P. (inv.), Non-chromated oxide coating for aluminum substrates, Pat. US 5411606, The Boeing
Comp. 1995
[48] Schriever, M. P. (inv.), Non-chromated oxide coating for aluminum substrates, Pat. US 6432225, The Boeing
Comp. 2002
[49] Pfaff, D., SAM bewährt sich in der Praxis (SAM Proves Itself in Practice), JOT 2003, pp. 22 f
[50] Pietschmann, J., Alternativen zur Chromatierung – Individual- statt Universallösung, (Alternatives to
Chromating…), JOT 2007, pp. 42 ff
[51] Van Ooij, W. J., Replacement of Chromates by Silanes – An Overview, ICEPAM Conf. Oslo, SINTEF,
Trondheim 2004, www.sintef.no/static/mt/norlight/ICEPAM/01-van-Ooij_Cincinnati.pdf;
(15-03-2101; 21:50 h)
[52] Franquet, A., van Schaftinghen, T., de Graeve, I., Laha, P., Le Pen, C., Terryn, H., Vereecken, J., Silane
Coating of Metal Substrates, ICEPAM Conf. Oslo, SINTEF, Trondheim 2004, www.sintef.no/static/mt/
norlight/ICEPAM/03-IDeGraeve_Brussels.pdf; (15-03-2010; 21;52 h)
[54] Lebelt, P., Gehrke, J., Hallmeier, K. H., Reuther, H., Dörfel, I., Qualitative und quantitative Analysen dünner
Funktionsschichten für das Kleben durch XPS-, AES-, REM- und TEM-Untersuchungen (Qualitative and
Quantitative Analyses of Thin Functional Coatings…), Galvanotechnik 107, 2009, p. 930 ff
[55] Kaiser, W.-D., Reinhard, G., Tiller, H.-J., Göbel, R. (inv.), Verfahren zur Oberflächenvorbehandlung von
Metallen für die katodische Elektrotauchlackierung (Process for the Surface Pretreatment of Metals for the
Cathodic Electro-Deposition Coating), Patent DE 4012086A1, Inst. Mat. Sc. Appl. Technique GmbH, 1991

Literature 153
[56] Bielefeld, F.W., de Zeeuw, A., How Can the Steel Industry Generate Add-on Business in the Post-finishing
Market?, ECCA Autumn Congress Brussels, Proc., European Coil Coating Association, Brussels 2009
[57] Sander, J., [42] pp. 148 f
concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH), establishing
a European Chemicals Agency, amending Directive 1999/45/EC and repealing Council Regulation (EEC)
No 793/93 and Commission Regulation (EC) No 1488/94 as well as Council Directive 76/769/EEC and Com-
mission Directives 91/155/EEC, 93/67/EEC, 93/105/EC and 2000/21/EC, Official Journal of the European
Union 49, 2006, L 396; eur-lex.europa.eu/…
[59] Krizek, J. (inv.), Vorrichtung zur Behandlung von Gegenständen (Device for the Treatment of Objects),
Patent DE 19950892, Eisenmann GmbH, 1999

Surface tolerant coatings 155
9 Organic coatings for

maintenance
Jörg Sander
9.1 Surface tolerant coatings

9.1.1 General considerations
The term “surface tolerant coating” [1] (STC) is often used when referring to maintenance
and repair coatings in shipbuilding, pipeline construction, offshore construction and other
water engineering. In these fields of application, damaged areas usually have to be repair-
coated on the spot, i.e. they are treated manually rather than in shop processes. STCs hence
require tolerance in various aspects. For example, they must be applicable in environments
where residual moisture by condensation or spray cannot be avoided or where residual old
coatings or rust cannot be entirely stripped. In short, STCs must adhere, cure and perform
under less than ideal conditions. STCs have been applied for decades [1, 2], but the achievable
results are of variable quality and highly dependent on the preparation of the surfaces and
the way of application [3]. The development of standards for testing the surface tolerance of
coatings is a subject of recent publications, with the aim of identifying critical parameters
that can be used to evaluate the coating performance [4].
As a convenient method for surface preparation in an open construction site, ultra-high
pressure water jet cleaning is recommended (cf. Chapter 3.2). This, however, will leave
residues of the foregoing, aged coatings, and rust on the surface, as well as it causes new,
flash rust on the exposed metal, and obviously the water is unlikely to dry off completely.
Regardless of the apparently good adhesion (that must be proven by inspection tests), rust
and old paint may be loosened by the action of overcoating, causing the whole repair attempt
to fail. The compatibility of old and repair paint systems must be assured, in terms of binder
chemistry, curing type, wettability, tension levels and degree of deterioration. Trialling of
the repair coat on a small test area is therefore recommended, following Standard ASTM
D 5064-95.
9.1.2 Surface tolerant coating materials [5, 6]

To cope with residual rust, imperfectly cleaned surfaces, and old, weathered, micro-cracked
coatings, an STC should provide free, low-molecular binder. The binder furthermore must
provide sufficient flexibility to avoid mechanical stress between old and new paint coatings.
The choice and amount of solvent must be suitable for the purpose, i.e. old paints must not be
weakened, and adhering rust must not be dissolved while the STC is applied. Finally, STCs
must be applicable at low temperatures and high humidity. Historically, this scope has been
matched by alkyd paints with red lead (Pb2[PbO4]) pigmentation, although limitations were
found with these systems in terms of water sensitivity and chemical resistance of the long
oil alkyds. Moreover, the lead compound is being phased out due to its toxicity.

ISBN 978-3-86630-805-3

156 Organic coatings for maintenance
Nowadays, the most common coatings in heavy corrosion protection are high-solids, two-
pack epoxies. STCs of this class can be applied in thick layers in single operation (100 to
200 μm dry film thickness), and provide the required initial adherence and resistance in
dew point conditions. Curing is mostly achieved by diisocyanate agents, rendering a high
degree of cross-linking, hence forming high barriers against humidity and oxygen. The
choice of binders allows UV reflection and dissipation of thermal and mechanical strain.
The formulations might involve active (zinc phosphate etc.) and lamellar pigments (e.g. alu-
minium flakes and micaceous iron oxide), and polysiloxanes or fluorinated polymers to add
barrier properties. STCs may also contain zinc particles for cathodic protection.
Another option is the use of moisture-curing polyurethanes as binder base which can be
applied at up to 98 % relative humidity and temperatures even below the freezing point. As
an advantage in handling, moisture-curing polyurethanes are single-pack products.
9.2 Organic coatings on residual rust

and old coatings
While STCs are often applied on surfaces that are contaminated by residual rust, it is obvi-
ous that this is only acceptable as enforced by the conditions of on-site painting. In proper
shop painting processes, corrosion products like rust from larger damage areas must be
removed by mechanical cleaning, e.g. grit or dry ice blasting, and manual sanding (cf. Chap-
ter 3.2), if possible, supported by pickling.
Residual rust and flash rust are often treated with so-called rust converters that are based
on formulations containing phosphoric acid and/or tannic acid derivatives to remove iron
oxide by acid pickle and form stable precipitates of iron phosphate and iron tannate. Tannin
based industrial rust converters have been in use for the preservation of iron and steel for
half a century [7, 8]. However the usefulness of this method as a preparation for subsequent
coating is doubtful. A number of papers show the controversial results and opinions in the
scientific community [9 – 15]. As a conclusion, the active ingredients of rust converters are
suitable to stabilise residual rust particles and flash rust on steel surfaces, however they do
not release the operator from careful abrasive removal of rust, and they by no means provide
reliable performance as conversion coatings.
In artisan coating operations, corrosion protection is often provided by coating of the dama-
ged, thoroughly cleaned and derusted areas with a so-called wash primer (cf. Chapter 4.5).
Wash primers contain phosphoric acid that enables chemical attack and bonding to the
exposed metal surface. The coatings are only thin and do usually not exceed 8 µm, in order
to secure good bonding. State-of-the-art products still contain zinc chromate as active corro-
sion preventive pigment. Accordingly, their use is subject to safety precautions. Admixtures
for spray application are only allowed with very low chromate contents below 0.1 % [16]. Some
wash primers offer a higher filler pigmentation, which makes them suitable for their use as
undercoats with a gauge around 20 µm. So-called reactive undercoats are based on epoxy
or polyurethane chemistry. Zinc filled corrosion protection primers (CPP) are often used for
larger areas (cf. Chapters 2.1.3; 6.5.2) [17].
Repair coats on automobiles are also manually applied and must not exceed 80 °C for curing,
to avoid damage to other car components. Physically drying or reactive paints that cure
under catalytic action have been replaced by 2-component systems with polyacrylates or
polyesters as base component and isocyanates as cross-linkers. Repair paints are available
as solvent-based and waterborne high-solid systems. They cure at room temperature, but
curing can be shortened by local application of elevated temperatures, e.g. by infrared

Organic coatings on residual rust and old coatings 157
lamps. Old paint may be stripped from the damaged area, using paint strippers based on
e.g. benzyl alcohol or formic acid [18]. The damages are ground down to the metal, derusted,
solvent-cleaned and coated with a corrosion protection primer (CPP) [19, 20]. Cleaning can
be done with solvent wiping or by vapour or high pressure spraying with aqueous, mostly
neutral or mild alkaline cleaners. It must be performed very carefully and its efficiency
controlled by wetting tests (cf. Chapters 3.1.3; 3.3.3).
9.3 Literature
[1] Mühlberg, K., Surface-Tolerant Coatings – Some Experiences, J. Prot. Coat. Lin. Prot. Coat. Europe Techno-
logy Publ. 2001, pp. 13 ff, 18
[2] Flick, E. W., Prepaint Specialties and Surface Tolerant Coatings, Noyes Publ., Park Ridge NJ, USA 1991
[3] Boxall, J., Advances in surface-tolerant coatings, Pigment & Resin Technology 19, 1990, pp. 4 ff
[4] Wilds, N., Surface Tolerant Coatings for Offshore Maintenance, NACE Corrosion Congress 2004, New
Orleans LA, USA, Proc., NACE International, Houston TX, USA 2004
[5] Gui, F., Hill, D., Brossia, C. S., A Method for the Evaluation of Wet Surface Tolerant Coatings, NACE
Corrosion Congress 2008, New Orleans LA, USA, Proc., NACE International, Houston TX, USA 2008
[6] Mühlberg, K., [1] pp. 13 ff, 18
[7] Wilds, N., [4] p. 2
[8] Groysman, A., Corrosion for Everybody, Springer, Dordrecht 2010
[9] Rogers, B. A., The Archeologist’s Manual for Conservation, Kluwer Academic, New York 2004, pp. 69 f
[10] Collazo, A., Nóvoa, X. R., Pérez, C., Puga, B., EIS study of the rust converter effectiveness under different
conditions, Electrochimica Acta 53, 2008, pp. 7565 ff
[11] Singh, D. D. N., Yadav, S., Role of tannic acid based rust converter on formation of passive film on zinc rich
coating exposed in simulated concrete pore solution , Surface and Coatings Technology 202, 2008,
pp. 1526 ff
[12] Ocampo, L. M., Margarit, I. C. P., Mattos, O. R., Córdoba-de-Torresi, S. I., Fragata, F. L., Performance of rust
converter based in phosphoric and tannic acids, Corr. Sci. 46, 2004, pp. 1515 ff
[13] Barrero, C. A., Ocampo, L. M., Arroyave, C. E., Possible improvements in the action of some rust converters,
Corr. Sci. 43, 2001, pp. 1003 ff
[14] Matamala, G., Smeltzer, W., Droguett, G., Comparison of steel anticorrosive protection formulated with
natural tannins extracted from acacia and from pine bark, Corr. Sci. 42, 2000, pp. 1351 ff
[15] Favre, M., Landolt, D., Hoffman, K., Stratmann, M., Influence of gallic acid on the phase transformation in
iron oxide layers below organic coatings studied with Moessbauer spectroscopy, Corr. Sci. 40, 1998,
pp. 793 ff
Coatings), Vol. 6, 2nd ed., Hirzel, Stuttgart 2008, pp. 459 f
[17] Goldschmidt, A., Streitberger, H.-J., Basic of Coating Technology, 2nd edition, BASF Coatings AG,
Münster 2007, pp. 739 f
Coatings), Vol. 6, 2nd ed., Hirzel, Stuttgart 2008, p. 318
Münster 2007, pp. 710 f
[20] Kittel, H., Streitberger, H.-J. (ed.), [18] pp. 452 ff

Thin films 159
10 New corrosion protection concepts

Dmitry Shchukin, Ekaterina Skorb
High-value materials in automotive and aerospace industries, for example, require increas
ingly sophisticated eco-friendly coatings for improved performance, self-healing, and
durability. In this respect, recent developments in nanotechnology are most promising [1].
New types of functional nanomaterials could provide the coating not only with enhanced
characteristics like anticorrosion properties or external performance but also with addi-
tional functionalities which can respond on demand to external factors, thus making the
coating “active” on macro and micro-levels. These modifications are important for protec-
tive coating systems, especially in consideration of the banning of carcinogenic Cr(VI),
Cd, and some organic solvents [2].
Standard anticorrosion coatings developed so far passively prevent the interaction of cor-
rosive species with the metal. This approach requires thicker coatings and does not solve
the “cut-edge” problem. The next generation of protective coatings should be much thinner
(thus reducing CO2 emission) and the quantity of raw materials per 1 m2 of the substrate) and
possess self-healing or self-curing effects in scratched (damaged) areas. This will require to
develop components of the coatings that react to the impact of external or internal conditions
(pH, humidity changes, or distortion of the coating integrity, etc.), and, ideally, combine the
self-healing property with other functionalities (e.g. detection, controlled reflection, self-
cleaning). In the following chapter active coating systems based on self-responding thin
films or nanocontainer-based films are described which have received highest attention in
the scientific community in the scientific community in recent years.
10.1 Thin films

Currently, various types of thin films are employed for corrosion protection. There is a
number of new progressive concepts:
Self-assembled monolayers which started to be widely developed in the 1990s of the last
century (see Chapter 10.1.1);
Conducting polymers (see Chapter 10.1.2) on which corrosion specialists have focused
their interest during the last 10 to 15 years,
Biopolymers (see Chapter 10.1.3) which are interesting either as a potential conductive
matrix or as passive protective coatings with simultaneous biocompatibility.
Individual use of these techniques for corrosion protection and combination of thin films
with nanomaterials enabling the formation of nanocomposites is also an area of growth
in today`s corrosion science. Another type of well-known and widely used coatings are
galvanic coatings; however, these are most conservative and only a few reports dedicated
to their modification can be found in literature [3], mostly related to the incorporation of
nanoparticles and polymer microcontainers into the coating (see Chapter 10.2.1). Due to the
metallic structure of the coating matrix, it is difficult to ensure the mechanical integrity

ISBN 978-3-86630-805-3

Figure 10.1: SEM images of aluminium (a) magnesium (b) alloy and stainless steel
(c) after 40 min sonication at 57 W/cm2 Source: Royal Society of Chemistry
of the containers embedded into the coating as well as to incorporate them into the coating
without agglomeration. A lot of effort will be needed in the future to attain active properties
to the galvanic coatings.
Simultaneously, for the majority of metals, there is native passivity which is based on the
spontaneous formation of a thin oxide layer (the passive film), in the specific environment.
This film can slow down corrosion (dissolution) reactions by many orders of magnitude. For
example, the typical aluminium surface is covered by a 3 to 7 nm thick natural oxide film.
However, this thin layer is not sufficient to protect against corrosion agents and does not
yield good adhesion to subsequent layers of the coating [4]. Therefore, the metal surface is
always pretreated before use. The most extensively used surface pretreatment procedures
are based on aggressive chemicals including chromate solutions [5].One of the functions
of the surface pretreatment is to produce a porous oxide layer on the metal surface with
roughness sufficient for mechanical interlocking.
High intensity ultrasonic irradiation has been used for a long time in metal technology
including metal crystallisation, forming and finishing [6]. The application of ultrasound to a
metal melt generally leads to metals with improved grain refinement and homogeneity [7].
For example, the collapse of cavitation bubbles near an aluminium surface yields surface
cleaning (destruction and removal of impurities);
• significant increase of roughness of the interfacial layer and, therefore, adhesion of
further films to the surface
• formation of a thick oxide layer [8].
The SEM images (Figure 10.1a-c) of metal surfaces sonicated at 57 W/cm2 indicate the
formation of highly developed metal surfaces. It should also be noted that the intensity and
duration of ultrasound treatment dramatically influence the development of porous metal
structures. The thickness of the modified layer estimated by TEM analysis of ultramicroto-
med plates is about 200 nm with a foam cell size of ~7 nm.
The scanning vibrating electrode technique (SVET) allows measuring current density maps
over the selected surface of the sample thus monitoring local cathodic and anodic activity in
the corrosion zones [9]. Figure 10.2 shows the monitoring of corrosion activity of a steel plate
with and without ultrasound treatment, immersed into a corrosive solution (0.1 M NaCl) for
12 hours. It is observed that an intensive corrosion process results in the development of
defects throughout the whole surface of the sample, finally leading to the total corruption of
the unmodified steel surface (Figure 10.2a and c). Figure 10.2e shows the time monitoring
of anodic and cathodic activity of a steel plate without ultrasound treatment (curve 1 and
4) immersed into a corrosive solution (0.1 M NaCl) for 12 hours. It can be seen that corro-
sion increases dramatically with time reaching a very high value of anodic activity ~300

Thin films 161
Figure 10.2: Optical microscopy images (a,b) and 3D current density maps obtained by SVET (c,d) of
the scratched steel plates in a corrosion test of unmodified steel (a,c) and steel after ultrasound
treatment (57 W/cm2, 60 min) (b,d). (e) Time monitoring of the anodic (curves 1 and 2) and cathodic
(curves 3 and 4) activity on the steel surface before sonication (curve 1 and 4) and after sonication at
57 W/cm2 (curve 2 and 3). Source: Royal Society of Chemistry
to 400 μA/cm2. The steel samples after high intensity ultrasonic irradiation (Figure 10.2e
curve 2 and 3) exhibit dramatically different behaviour. The increase in corrosion activity
is very low, after 12 hours of immersion in 0.1 M NaCl the anodic activity is ~8 μA/cm2. In
the long run such pretreated metal surfaces are useful for subsequent application of organic
multi-layers for corrosion protection.
10.1.1 Self-assembling monolayers

The 1980s saw an explosion of interest in “self-assembled monolayers” (SAMs)-densely
packed, oriented monolayer films of long-chain surfactants that spontaneously chemisorbed
from solution onto solid surfaces [10]. SAMs make ideal models for the study of fundamental
processes at organic surfaces, such as wetting [11], adsorption [12], adhesion [13], chemical
reactivity [14] and as a result corrosion stability. They also provide a testing ground for the
physical principles that govern the assembly of other supramolecular structures, such as
membranes and micelles. Potential applications of SAMs are in the traditional areas of sur-
face chemistry-adhesion [15], wetting, corrosion [16], and lubrication.
Among different approaches, the self-assembled monolayer technique has recently attracted
much attention in the coating and corrosion protection research area [17]. While self-assem-
bled monolayers on substrates such as glass and gold electrodes have been studied exten-
sively in the last few decades [18], the application of self-assembled monolayer and multi-layer
films on metal and metal alloy substrates such as aluminium, aluminium alloy and steel
and other corroding metals is still relatively new. Simultaneously, they are very promising
due to the formation of a unique corrosion stable layer. The self-assembled monolayers,
often made from amphiphilic hydrocarbon molecules, are expected to function as a barrier
to prevent the permeation of corrosion accelerants such as moisture and electrolytes into
the metal substrate, therefore improving the corrosion resistance of the substrate materials.
Three categories of molecules are commonly used for this purpose:

• fatty acids with carboxylic end groups that form electrostatic interactions with metal
substrates,
• alkyl thiols that link to the steel substrate by iron-sulfur bonding and
• alkyl silanes that react with the metal oxide from the metal and metal alloy sub-
strates.
Maege et al. [19] reported a systematic study and comparison of self-assembled monolayers on
aluminium alloy substrates using amphiphilic molecules including fatty acids, phosphonic
or phosphoric acids, alkyl silanes and alkyl siloxanes. The fatty acids and phosphonic
acids or phosphoric acids tend to bond with Al2O3 from the aluminium substrates through
electrostatic interactions, and the long alkyl chains interact together through van-der-
Waals interactions to form stable monolayer films. For alkyl silanes, a two-dimensional
hydrolysis-condensation reaction occurs between silane and Al2O3 from the aluminium sub-
strate, leading to a polymerised monolayer film. Due to the film formation, the metal alloy
surface becomes much more hydrophobic, and the corrosion resistance of the substrate was
found to increase significantly. Among all these molecules being studied, it was found that
the phosphonic acid monolayer gave the best corrosion protection according to humidity
test. Despite these extensive studies, many issues associated with this research area remain
unclear. For example, the surface chemistry of metal alloys is much more complicated com-
pared to the well-defined and much smoother glass or gold surface. Such a complex surface
chemistry is certain to bring some significant effects on the self-assembling process and
the properties of the resulting thin films. The surface properties of metal alloys are often
affected by the surface cleaning and treatment procedures, and therefore, so is the molecu-
lar self-assembling process on the metal alloy surface.
Four different alkylsilane compounds, which include octadecyltrichlorosilane (C18H37SiCl3),

octadecyltrimethoxysilane (C18H37Si(OMe)3), octyltrimethoxysilane (C8H17Si(OMe)3) and octa-
decyldimethylchlorosilane (C18H37SiMe2Cl), were suggested in a study [20] to compare the
self-assembled thin film formation from alkly silane compounds with different chemical
structures and to access the corrosion resistance of thin film modified Al 2024 substrates. It
is well known that with different chemical structures, the hydrolysis-condensation kinetics of
sol-gel reactions vary from one type of molecule to the other, as do the self-assembled monola-
yer or multi-layer structures and properties. For example, some alkyl-silane compounds tend
to form monolayer films with more closely packed and ordered monolayer films, while others
will result in films with more defective domains. It is hypothesised that films with less defec-
tive domains will result in a better corrosion protection of the aluminium alloy substrate.
It should also be noted that the traditional means of forming an organic monolayer film
is to spread an insoluble compound on an aqueous subphase, compress the film mecha-
nically with a barrier until the molecules are densely packed and oriented approximately
normal to the surface, and then to transfer this monolayer, if desired, to a solid substrate
by “dipping” using the Langmuir-Blodgett method” [21]. Self-assembled monolayers could
be formed by chemisorption providing a convenient technique to modify surfaces (Figure
10.3). The highly ordered and packed monolayer can prevent solution from transferring
to the metal surface so it can effectively protect the metal from corrosion [22]. Monolayers
of alkane thiols, dialkyl disulfides, and other sulphur-containing molecules prepared on
copper and gold by adsorption from solution were described in numerous reports [23]. A few
studies about iron corrosion were reported [24]. It was shown that the 2-mercaptobenzothi-
azole, an N- and S-containing heterocyclic compound, can form monolayers on iron. These
compounds have been widely investigated because they can form hydrophobic complexes
with many metals such as iron, copper, cobalt, nickel, etc. and therefore are used as cor-
rosion inhibitors [25]. Moreover, based upon the spontaneous adsorption and orientation of

Thin films 163
Figure 10.3: (a) Schematic of an n-dodecanethiolate monolayer self-assembled on an atomically flat

gold substrate with van der Waals interactions between neighboring hydrocarbon chains.
(b) STM image of a 250 Å x 250 Å area of an n-decanethiolate self-assembled monolayer. A step edge
along with several film defects can be seen, including domain boundaries (protruding and depressed
ridged lines) and substrate vacancy islands (dark, circular depressions). Tunneling conditions:
Vsample=-1 V, it=10 pA. Source: Elsevier
molecules with a reactive group bonded chemically to the substrate, 2-mercaptobenzothi-

azole can form self-assembled monolayers on metals. During the adsorption process, the
corresponding heat changes could be detected by microcalorimetry. For copper protection
self-assembled monolayers formed from alkanethiols, alkyl thiosulfates, mercaptoalka-
nols and Schiff bases were suggested [26]. The agent inositol hexaphosphate, also known
as phytic acid and its salts have been suggested to be used as environmentally benign
inhibitors [27].
However much sophisticated work has been performed using the layer-by-layer(LbL) tech-
nique. The multicomponent nano-network formed by polyelectrolyte multi-layers using
the LbL technique [28] could offer new opportunities for anticorrosion coatings. The LbL depo-
sition procedure involves the step-wise electrostatic assembly of oppositely charged species
(e.g., polyelectrolytes and inhibitors, or others: proteins, nanoparticles) on the substrate
surface with nanometre scale precision and allows the formation of a coating with multiple
functionality. The coating properties can be controlled by the number of deposition cycles
and the types of polyelectrolytes used. Polyelectrolytes exhibit very good adhesion to the
substrate surface and are able to seal surface defects. The conformation of polyelectrolytes
is mostly dependent on their nature and adsorption conditions and much less dependent
on the substrate and charge density of the substrate surface. Polyelectrolyte coatings are
expected to cover many kinds of surfaces including non-ionic and polar substrates. The
polyelectrolyte multi-layers offer a broad range of applications in the fields of nonlinear
optics, light emission, sensing, separation, bioadhesion, biocatalytic activity, drug delivery
and specific bio-applications based on surface modifications [29].
In the last years, polyelectrolyte multi-layers have attracted great interest in corrosion
protection [30]. Corrosion processes are accompanied by a number of reactions changing the
composition and properties of both metal surface and local neighbouring environment (e.g.,
formation of oxides, diffusion of metal cations into the coating matrix, local changes of pH
and electrochemical potential) [31]. One approach to prevent corrosion propagation on metal
surfaces is the suppression of accompanying physico-chemical reactions. Polyelectrolytes
are macromolecules that carry a relatively large number of functional groups that are either
charged or, under suitable conditions, can become charged. Polyelectrolyte films are able
to change their chemical composition with the pH value since the degree of dissociation of
the polyelectrolytes is influenced by the local pH value. The films can be enriched in one
polymer compared to the other by fabrication in a pH-regime where one of the polymers is
weakly charged while the other is strongly charged. Active species deposited as a compo-

Figure 10.4 : Schematic mechanism of self-healing action of a “smart” polyelectrolyte anticorrosion

coating. Corrosion attack causes pH change of the system stimulating response of the polyelectrolyte
coating: pH buffering, rearrangement of polymer chains and release of corrosion inhibitor. (PE+:
positively charged polyelectrolyte, PE - : negatively charged polyelectrolyte, Inh – corrosion inhibitor)
nent of the polyelectrolyte nano-network or as a dopand can be released on demand. The

sensitivity of the polyelecrolyte film to a variety of physical and chemical conditions (like
shift of the pH value or mechanical impact, etc.) of the surrounding media provides the abi-
lity of regulated release of the inhibitor species entrapped into multi-layers. The schematic
mechanism of a smart self-healing process is shown in Figure 10.4.
The following mechanisms of the response of the polyelectrolyte multi-layer system to cor-
rosion attack can be proposed:
• polyelectrolytes have buffering activity and can stabilise the pH value at the metal sur-
face in corrosive media;
• inhibitors are released from polyelectrolyte multi-layers only after start of the corrosion
process and directly into the rusted area, preventing corrosion propagation;
• polyelectrolytes forming the coating are relatively mobile and have the tendency to seal
and to eliminate the mechanical cracks of the coating.
Thus, the polyelectrolyte nano-network is effective in both suppression of corrosion propa-
gation and healing of first traces of corrosion microdefects. Two issues related to formation
of the polyelectrolyte coatings and their anticorrosion activities must be addressed. The first
Figure 10.5 : Time dependence of the current density changes of the scratched aluminium alloy covered
by the (PEI-PSS)10 coating obtained by scanning vibrating electrode technique: curve above: anodic
current, curve below: cathodic current (scale units: μA cm−2, spatial resolution 150 μm, solution:
0.1 M NaCl) (a); snapshot measured in 3 h of the experiment time (b); photograph of the behaviour of
the scratched surface during the SVET experiments (c). The scratch is highlighted by arrows

Thin films 165
issue is the nature of the alloy surface, polymer adhe-

sion to the surface and coating stability in aggressive
environment. Aggressive solutions as well as tem-
perature changes or UV irradiation could alter the
structural integrity of multi-layer films. The second
issue is related to the anticorrosion activity of the
coating. The sensitivity of the nano-network formed
by different polyelectrolytes to external stimuli gene-
rated by corrosion degradation (changes of pH value,
interruption of coating integrity) is most important Figure 10.6: Scanning electron
and therefore subject to extensive studies. microscopy image of the surface of the
PEI-PAA coating after 12 h immersion
Weak polyelectrolytes are increasingly used in in 0.1M NaCl
multi-layer thin films because greater control over
film properties can be achieved by varying the ionisation of the weakly charged groups
through adjustments of the pH value. Therefore, one expects a different current density
map for the substrates coated with multi-layers composed of a combination of weak and
strong polyelectrolytes (see Figure 10.5). A combination coating of weak polyethylene
imine (PEI) and strong polystyrene sulphonate (PSS) exhibits very high anticorrosion pro-
tection. The scratched aluminium surface is shown in Figure 10.5 (c). The scratch without
any traces of corrosion degradation is highlighted by arrows. No ionic flux can be seen on
the time monitoring measured by using SVET during 12 hours. The control snapshot in
Figure 10.5 (b) exhibits only background noise. The differences between strong and weak
polyelectrolyte pairs are presumed to reflect the relative degree of association of oppo-
sitely charged polyelectrolyte segments. Polymer pairs which form stronger complexes
are expected to better associate in contact with aqueous solutions and would thus be less
sensitive to pH changes in contrast to weak-strong and weak-weak polyelectrolyte pairs.
pH changes following the corrosion process cause ionisation of the functional groups of the
weak polyelectrolytes which results in an increased repulsion between uncompensated
charges. Small counter-ions can penetrate the layer structure to compensate these charges.
The higher ionic concentration inside polyelectrolyte multi-layers as compared to the sur-
rounding solution increases the osmotic pressure resulting in permeation of water into the
polyelectrolyte multi-layers. Thus, the polyelectrolyte multi-layers start to swell and, there-
fore, increase their mobility. Figure 10.6 shows SEM images of the PEI-PAA covered alumi-
nium plates after 12 hours immersion in 0.1 M NaCl. The scratched surface tends to recover
in aqueous solution due to chain rearrangement in the swollen polymer multi-layers.
A corrosion inhibitor incorporated into the protective coating as a component of the LbL film
is responsible for the most effective mechanism of corrosion suppression. Quinolines are envi-
ronmentally friendly corrosion inhibitors attracting more and more attention as an alternative
to the harmful chromates. 8-HQ was found to prevent the adsorption of chloride ions thus
improving the corrosion resistance due to the formation of an insoluble chelate of aluminium
which protects the metal substrate [32]. Both mechanical (scratch) and chemical (changes of
local pH) rupture of the polyelectrolyte network cause the release of the encapsulated inhibitor
in the damaged part of the metal surface only in response to corrosion attack, resulting in
termination of the corrosion process and prolongation of corrosion protection.
10.1.2 Conducting polymers

Electrically conducting polymers have been the subject of continuous research and deve-
lopment due to their potential applications in many technological areas such as rechar-
geable batteries, sensors, electromagnetic interference shielding, electrochromic display

devices, smart windows, mole-

cular devices, energy storage
systems, membrane gas separa-
tion, and so on [33]. Most recently,
several studies have been carried
out or are still in progress, evalua-
ting various conducting polymers
in different configurations regar-
ding their corrosion protection
towards oxidisable metals. Men-
goli et al. were the first to exa-
mine the protective behaviour of
polyaniline (PAni, Figure 10.7) on
stainless steel, and then in 1985,
DeBerry showed that the electro-
Figure 10.7: Chemical structures of selected conductive
chemically synthesised PAni acts
polymers: (a) poly(aniline); (b) poly(pyrrole);
as corrosion protective layer on
(c) poly(ethylene oxide)
stainless steel in 1 M H2SO4. Since
then, many research groups have
systematically investigated the electrochemical synthesis of various conducting polymers
on oxidisable metal surfaces for corrosion protection purposes.
Although only positive results are reported, in most publications on conducting polymers
for corrosion protection, it is generally known from industrial trials of conducting poly-
mer based coatings that the practical performance is usually by far inferior to coatings
that do not contain conducting polymers (also referred to as intrinsically conducting
polymers). This is due to the fact that in most published reports only simple immersion
tests were performed, where there is a good chance for the conducting polymer to passi-
vate small defects [34], while under atmospheric corrosion conditions or the presence of too
large defects this principle does not work out and fast coating break-down is observed [35].
Such a sudden coating break-down is postulated to be an inherent property of all conduc-
ting polymers [36]. However some works show that by preventing formation of over-extended
percolation networks of the conducting polymer in the composite coating this danger can
be averted, making conducting polymers suitable for intelligent corrosion protection [37].
Thus the coatings can be designed to show efficient corrosion-triggered intelligent release
of inhibitor anions [38]. Coatings which follow these design rules generally seem to per-
form well [39] and especially effectively inhibit fast delamination originating from external
defects. However, even without defects in the coating, corrosion at the buried interface bet-
ween the coating and the metal seems to be a serious problem. Williams and McMurray [40]
observed the growth of a 3 µm oxide film within just 140 h at the interface between an iron
sample and a composite coating of PAni dispersed in a non-conducting polymeric matrix.
They explained this fast interfacial corrosion by galvanic coupling between PAni and iron,
i.e. oxidation of the iron fuelled by reduction of the PAni, which in turn is re-oxidised by
environmental oxygen (which is reduced in this process). In other words, the conducting
polymer serves as a mediator between metal and atmospheric oxygen, thereby promoting
corrosion rather than preventing it. When the same coating was applied to zinc, only a com-
paratively thin oxide layer of about 0.5 µm was formed in this case by interfacial corrosion.
Williams et al. explain this difference with the different acidity of the corresponding metal
cations: while the iron(II) (and also aluminium) cation is quite acidic and thus can effec-
tively buffer the pH value inside the coating, for the case of zinc alkalisation of the interface
occurs as a consequence of the accompanying oxygen reduction, as the lower acidity of the
zinc cation does not suffice for buffering the pH value. Hence, PAni stays intact in the case

Thin films 167
of iron or aluminium as substrate

while it loses its conductivity
due to de-protonation caused by
high pH value in the case of zinc
as substrate. They also observed
that the work function measured
on coated iron or aluminium sub-
strates is determined by the work
function of PAni, while the work
function measured on coated zinc
is more or less equivalent to the
Figure 10.8: Potential maps obtained by SKP over an iron/
one of zinc itself.
aluminium couple and an iron/zinc couple, half covered by a
Nazarov and Thierry [41] report a layer of polypyrrole (Conquest) and half uncovered, as
similar observation: polypyrrole indicated in the drawings depicted above the corresponding
(PPy) covered zinc in wet atmos- potential maps. Source: Elsevier
phere showed a low work func-

tion (respectively potential; see
for details about the correlation of potential and work function measured by Scanning
Kelvin Probe [42]), however upon drying the potential went up to the level corresponding
to PPy. They attribute this change to the formation of an ordered water layer at the buried
interface that induces a dipole potential causing the decrease in the potential measured by
Scanning Kelvin Probe. The observation presented in Figure 10.8 shows an Fe/Al couple
and an Fe/Zn couple partly coated with a PPy film. The observation is that while on iron
and aluminium more or less the original potential of the existing film is measured, on
zinc the low potential of metallic zinc is obtained, although on the surface the existing
film still seemed to be in its oxidised state, i.e. the work function on the surface of the film
should be determined by non-reduced PPy.
Problems with anodic corrosion at the interface between metal and composite coating still
exist. In principle the high potential of the conducting polymer should ensure that the metal
in direct contact with it is kept reliably within its passive range. However, in a composite
coating not all parts of the coated metal surface will be in direct contact with the conduc-
ting polymer, but just in its vicinity. Hence, over time the metal surface that is just close
Figure 10.9: Schematic explanation of the different ion exchange behaviour of different conducting
polymer based composite coatings in the delamination case. Left: composite coating with macroscopic
percolation networks of conducting polymer. This causes cation permselective behaviour and hence
prevents anion release. Middle: low density of conducting polymer. Only a few particles of the conduc-
ting polymer are in contact with the metal and are thus electrochemically active. No cation permselecti-
vity is expected here and anion release may be possible, but only to the limited extent permitted by the
small amount of active polymer. Right: if the conducting polymer forms microscopic networks, but not
macroscopic ones, then cation permselectivity is still prevented, while allowing significant anion
release. Source: Elsevier

to the conducting polymer, but not in direct contact with it, might form a weak galvanic
element with the conducting polymer, due to water and ions diffused through the coating
to the interface. The low conductivity at the interface then prevents the full polarisation to
the potential of the conducting polymer and hence the metal may not be kept in its passive
range. On the contrary it may be polarised towards increased corrosion activity. Different
ion exchange behaviour of different conducting polymer based composite coatings is pos-
sible (Figure 10.9).
The conducting polymers could be synthesised from organic solution. The first attempts
to electrodeposition of conducting polymers on active metals as substrates and investiga-
tions of their properties were undertaken in non-aqueous solutions. The most significant
advantage of organic solvents in comparison to water is the better solubility of monomers,
resulting in more concentrated solutions. Thus, formation of the polymer layer is much
faster, and the anodic dissolution of the substrate does not proceed. In 1982, Skotheim and
co-workers were among the first scientists to examine the formation of conducting polymer
layers on active metals as substrates [43]. The purpose of their investigation was to explain
how the substrate material influences the initiation of the polymer deposition. Polypyrrole
(PPy) was chosen as an example of a conducting polymer. The polymer film was deposited
from a monomer solution in acetonitrile with BF4− anion as a counter-ion. Electropolymeri-
sation was performed on the substrates: Pt, Au, Pd, Ag, Ti, Cr, Ni, Al, In and Fe. These metals
were deposited as a thin film (200 to 300 nm) on a silicon support. The PPy layer could not
be grown on Al, In, Ag and Fe because the thin film of these metals dissolved before the
polymerisation potential was reached. On other metals (Ni, Ti and Cr) an oxide layer was for-
med before the polymer deposition and blocked off the metal surface. The authors found that
the polymerisation process generally proceeded similarly on different electrode materials;
however, the PPy film structures were different when grown on various substrates.
The properties of a PPy-toluene sulphonate film electrodeposited on different electrodes

have been investigated by Cheung et al [44]. As support were chosen: platinum, titanium,
aluminium, mild steel and brass. Electropolymerisation was carried out under galvanostatic
control from a solution of the pyrrole monomer in propylene carbonate. Characterisation
of the polymer included elemental analysis, scanning electron microscopy (SEM), Raman
spectroscopy and conductivity measurements. It was found that the potential of pyrrole
oxidation increased when Ti, Fe and Al were used as substrate instead of Pt. The redox
potential of the PPy-toluene sulphonate film depends on the substrate, while the electrical
conductivities of the free-standing polymer films were independent of the substrate nature.
However, morphology of the polymer film was different depending on the kind of metal
support. The SEM features showed existence of the polymer region adjacent to the electrode
surface which distinguished it from a bulk layer.
The PPy film has also been deposited onto Al and Ti surfaces from organic solvents by other
researchers [45]. Chun et al. electrodeposited the PPy film on stainless steel from benzene
solution in diethyl ether and studied the morphology, mechanical properties and conducti-
vity of the film. They found that the PPy film was flexible and could be cut into any shape,
so the film had properties very useful from a practical point of view. The influence of metal
support (Pt, Ni, Ti and stainless steel) on the PPy electrochemical properties has been
studied by Zalewska et al. [46]. The polymer coating was deposited from acetonitrilic as well
as from aqueous solutions. It was found that the properties of the polymer film depend on
the substrate material, especially when electropolymerisation was carried out onto a nickel
electrode. An assumption about the formation of the PPy-Ni composite film has been formu-
lated. The electropolymerisation of PPy on Zn-Pb-Ag (65 % Zn, 10 % Pb and 25 % Ag) alloys
was studied in organic solvents (acetonitrile, nitrobenzene and propylene carbonate) [47]. It

Thin films 169
has been stated that the well adherent and homogeneous polymer layer can be obtained after
pretreatment of the zinc alloy with aqueous solution of Na2S. Bazzaoui et al. [48] synthesi-
sed well adherent PPy film on Zn from acetonitrile, nitrobenzene and propylene carbonate
media in the presence of para-toluene sulphonate counter-ions.
The formation of a PPy layer on iron surface from 1-butyl-3-methyl imidazolium has been
studied by Fenelon and Breslin [49]. Adherent and highly conducting PPy films have been
obtained. Electropolymerisation of acetylene with copper catalyst on Pt and Cu from acetoni-
trile solution was performed [50]. The polyindole film deposited on Fe from acetonitrilic-water
solution containing tetrabutylammonium tetrafluoro-borate has been examined by Sazou
[51]
. It has been found that increasing concentration of H2O in the electrolyte leads to increa
sing concentration of Fe3+ ions in solution due to dissolution of the iron electrode, thereby
inducing a mechanical instability of the polymer film.
Electrodeposition of polymer layers from aqueous solutions is also one of the possibilities.
However the organic solvents have many disadvantages in comparison to water. They are:
• toxic,
• highly flammable and
• more expensive,
so for practical purposes aqueous solutions are preferred. Thus, electrodeposition of con-
ducting polymers onto active metal surfaces from water solutions has become a challenge.
PPy has been chosen as a subject of a great number of studies due to its relatively easy pre-
paration from aqueous solutions. Schirmeisen and Beck [52] studied the formation of a PPy
layer on inert (Pt, Au and glassy carbon) and active (Cu, Ti, Fe and stainless steel) supports
in aqueous and non-aqueous solutions (acetonitrile, methanol) in the presence of various
inorganic ions. They stated that electrodeposition of the PPy coating proceeds in aqueous
solutions only when substrates do not dissolve simultaneously with the polymerisation
process. Thus, it is very important to select anions which promote the passivation of the
metal surface in contact with the electrolyte [53]. In the case of iron, nitrate ion is such an
anion. Excellent and well adhering PPy coatings have been obtained on the Fe surface in
KNO3 solution. Husler and Beck studied the process of electropolymerisation of PPy on Al
and Ti surfaces [54]. Formation of the strongly adhering PPy film on Al from an aqueous
solution is reported [55]. The polymer film was deposited on the aluminium surface after its
passivation in contact with diluted acids: oxalic, nitric and sulphuric. Lacase et al. obtained
well adhering PPy coatings on Al and other active metals (Zn, Cu, Ni and Fe) from aqueous
or aqueous-alcoholic solutions containing salicylate ions without any pretreatment of the
surface [56]. The kinetics of the pyrrole electropolymerisation and morphology of the PPy
layer on stainless steel was studied in an aqueous medium by Su and Iroh [57]. Apart from
the influence of the current density, temperature and pyrrole concentration on the process
of PPy polymerisation the influence of the concentration of the counter-ion benzene sulpho-
nate has also been shown. It was established that smoother and more compact PPy coatings
were formed at lower electrolyte concentration, while the deposit became less dense and
porous when the concentration was higher. When polymerisation was carried out in the
presence of oxalate, anion formation of a thin layer of FeC2O4·2H2O on the steel surface was
shown. This layer caused passivation of steel, which allowed a deposition of the PPy film.
A single-step electropolymerisation of pyrrole on Fe and Steel has been studied [58] in
presence of malate as counter-ion in the electrolyte. The malate counter-ion slows down the
iron dissolution which allows to obtain uniform and well adherent PPy coatings. The authors
found that a PPy layer formed galvanostatically had a cauliflower-like structure and was
thicker than a film synthesised in potentiodynamic mode. Formation of the PPy coating on

steel coated with various types of zinc alloys was examined in the presence of oxalate in
aqueous solution [59]. Satisfactory PPy coatings were obtained on galvanised steel only after
passivation of the electrode surface in a medium-acidic solution containing high pyrrole
concentration. The possibility of the PPy film formation on Zn in aqueous solutions was also
examined [60]. The authors found that the polymer layer could be deposited on Zn only when
the zinc surface was previously passivated by treatment in 0.2 M Na2S solution.
The mechanism of the two-step electropolymerisation process and the influence of the
current density have been discussed. Later the one-step electrosynthesis of PPy on Zn and
mild steel from aqueous solution containing salicylate was proposed [61]. The authors found
that in the presence of salicylate anions a passivation of the substrate surface took place,
allowing to obtain strongly adherent PPy films with current efficiencies close to 100 %.
One important issue in electropolymerisation of conducting polymers on active metal
surfaces is to obtain good adhesion of the polymer film to the metal. This problem has
been carefully studied [62] for deposition of PPy on titanium. The authors employed various
methods of chemical pretreatment of the titanium surface and made a recommendation
how to obtain an extremely adhesive PPy film on the Ti surface. Aluminium and steel (or
iron), as metals widely employed in practice, are the most often examined substrates for
electrodeposition of conducting polymer coatings. Usually the polymer film is deposited on
Al after passivation of its surface by aqueous solutions of acids: oxalic, nitric or sulphuric.
Deposition from an aqueous oxalic acid solution of the PPy layer on the Al surface and modi-
fication of the PPy film by cementation of copper were performed [63]. The high activity of
the PPy layer on Al in the presence of NO3− ions in alkaline solutions is connected with the
fact that this anion limits anodic dissolution of Al [64]. Formation of the combined Al2O3/PPy
layer in aqueous solution containing sulphonate-based anions was examined [65]. Earlier it
has been established that, the PPy film has a tendency to overoxidise when electropolyme-
risation is accompanied by growth of thickness of the Al2O3 layer, so that the conductivity of
the polymer dramatically decreases. To avoid this effect, it has been proposed to use Tiron
(4,5-dihydroxy-1,3-benzenedisulphonic acid di sodium salt) as an electron transfer medi-
ator in order to catalyse formation of the PPy layer by reduction of the polymer deposition
potential by nearly 500 mV [66]. The authors noted that the polymer film obtained on the sur-
face of AA 2024 T3 had high conductivity and good adhesion to the aluminium alloy in the
presence of Tiron. The authors suggest that salicylate may also act as an electron mediator
in the formation of the PPy film.
PPy coatings have also been deposited on zinc and copper surfaces [67]. Prissanaroon et
al. obtained well adherent PPy coatings on an electropolished Cu electrode from aqueous
dodecylbenzene sulphonic acid solution. The authors showed that a thin Cu2O layer was
formed during transfer processes allowing a PPy coating to be formed. Electropolishing of
Cu leads to partial passivation of the Cu surface and prevents copper dissolution while the
electropolymerisation process takes place without hindrance. The redox behaviour of PPy
layers on Cu was similar to the observed when PPy coatings formed on noble metals. The
synthesis of PPy on copper surfaces could also be carried out aqueous electrolyte contai-
ning sodium salicylate. The PPy coatings were uniform and well adherent to Cu surface.
Formation of the thin intermediate layer was observed during oxidation of copper in sodium
salicylate solution. The existence of that layer allows to avoid copper dissolution. Processes
of PPy electropolymerisation on a steel substrate from aqueous solutions of oxalic acid have
also been studied.
Furthermore, the process of PAni layer formation on active metals has been often investiga-
ted. Abalayeva and co-workers studied the formation of the polyaniline film on Ti, Ta, Pb,
Ni, Ti and Al from aqueous solutions containing 0.1 M H2SO4 [68]. In these solutions, the oxide

Thin films 171
film on Ti, Ta and Pb (formed during contact of the metals with air) remained untouched,
but the aluminium oxide dissolved, thereby necessitating a special procedure of passiva-
tion before the electropolymerisation. Such a procedure is recommended in ref. [69] and as
a result PAni layer on the Al surface could be grown. The electrochemical properties of the
PAni film in dependence of the way of electropolymerisation were examined, too. Formation
of the PAni film on the iron surface from an aqueous solution has been investigated. The
electrosynthesis and the degradation of PAni films on iron from oxalic acid electrolyte have
been studied. The characteristics of PAni coatings prepared on stainless steel electrodes
by various methods galvanostatic, potentiostatic and potentiodynamic have been given [70].
Electropolymerisation of aniline on stainless steel, Mg, Ni, Ti, Al and Pb has been studied
in aqueous solutions of Na2ClO4, H2C2O4 and H2SO4 [71].
Some other polymer coatings or their combination with PPy and PAni or doping with
conducting polymers were examined on active metal surfaces. In literature [72] the polymers
employed as anticorrosive additives are PAni emeraldine salt and base, a PAni emeraldine
salt composite with carbon black, a PPy composite with carbon black and poly(3,4-ethyle-
nedioxythiophene) doped with poly(styrene sulphonate). Initially, the structural, thermal
and mechanical properties of the unmodified epoxy paint as well as the modified coatings,
obtained by the addition of 0.3 % of conducting polymers, have been characterised. After
this, controlled accelerated corrosion assays in an aggressive medium were developed
using coated steel panels. Results indicate that the protection against corrosion imparted
by the formulations modified by the addition of poly(3,4-ethylenedioxythiophene) doped
with poly(styrene sulphonate), PAni emeraldine salt and, especially, PAni emeraldine base
is significantly higher than that of unmodified paint. In contrast, the use of a conducting
polymer composite with carbon black reduces the efficacy of the coating. Results indicate
that some conducting polymer compositions should be considered as a suitable alternative
to replace inorganic anticorrosive pigments currently used in paint formulations. Pisarevs-
kaya et al. studied electropolymerisation of the polyparaphenylene films onto the surface of
Au, Pt, glassy carbon, Ni and Ti. Later, Pisarevskaya et al. applied other metals like Cr, Nb,
Ni-Ru, Cu and Ru for the electropolymerisation of the polyparaphenylene from a solution
containing sulphuric acid and benzene as an emulsion [73]. The polymer films were obtained
by the cyclo-voltammetry method, and the main purpose of this work was to elucidate the
influence of substrate morphology on polymer film behaviour. It has been found that the poly-
mer film morphology, as well as its adhesion, strongly depends on the substrate morphology.
The electrochemical and other properties of poly(3-methylthiophene) coating on type 430
stainless steel have been examined by ref. [74]. The effects of the polymer preparation condi-
tions on the behaviour of poly(3-methylthiophene) films have been studied. Smooth and well
adhering coatings were obtained in oxalic acid solutions on an iron oxide passive film. The
electropolymerisation of 3-methylthiophene on the Mo, Ni and Fe surfaces from a lithium
perchlorate solution was also studied [75]. The authors show that cations of the metal-support
electrode may be incorporated into a polymer matrix, and in result, they have an impact on
the electroactivity of the polymer film. Influence of electrosynthesis conditions (tempera-
ture and current density) on the morphology of poly(o-anisidine) coatings deposited from
an aqueous solution on low carbon steel was discussed in ref. [76]. Recently, electrochemical
synthesis of poly(N-methylpyrrole) films on copper electrodes from diluted oxalic acid has
been achieved [77]. The corrosion inhibiting properties of this coating on copper were inve-
stigated in aqueous 0.1 M NaCl solution using potentiodynamic polarisation. They were
observed to be comparable to those of PPy films. A physical barrier effect is the most likely
protection mechanism. Electrosynthesis of the poly(N-methylpyrrole) on steel surfaces was
studied by Su and Iroh and the existence of the interphase Fe(II)-oxalic thin layer has also
been established. The growth rate of poly(o-phenylenediamine) (o-PD) coatings on type 304

stainless steel in diluted phospho-

ric acid and the structure of the
coating were investigated, too [78].
It was found that the growth rate
of the o-PD film on stainless steel
is much lower than the same pro-
cess on a Pt electrode, and under
potentiostatic conditions the
polymer film was obtained only
after prolonged polarisation time.
The electroformation of a poly
(3,4-ethylenedioxythiophene)
layer on a Ni electrode from
an aqueous solution of LiClO4
and sodium dodecylsulphate
Figure 10.10: (a) SEM image of an electrospun PAni/ has been carried out and the
polystyrene (PS) composite film with lotus-leaf-like structure mechanism of the PEDT film
prepared from a 3.72 wt.-% PS:ABSA/DMF solution (inset: growth is analysed [79]. A poly
water droplet); (b) Magnified view of a single sub-micros- (2,5-dimethoxyaniline) coating
phere from c,d) SEM images of PAni/PS composite films on low carbon steel has been
prepared from solutions with different concentrations of PS grown and examined [80]. Soluble
[wt.-%]: (c) 5.26 wt.-%; (d) 7.10 wt.-%. conducting poly(aniline-co-ortho-
Source: American Chemical Society toluidine) copolymer was used
as corrosion inhibitor for carbon
steel [81]. These results show an
increase in inhibition efficiency
as a function of copolymer con-
centration to attain an optimum
(70 %) for a concentration close to
100 ppm. This is due to the hig-
her coverage of the carbon steel
electrode surface as shown by the
Temkin adsorption isotherm. The
potentiodynamic polarisation
studies reveal that this copolymer
acts as a mixed-type inhibitor. As
mentioned above the conducting
polymer coatings may be used as
blends with conventional coatings
Figure 10.11 : Scheme of polypyrrole container formation: (a) (non-conducting polymers, paints)
gas bubble formation, (b-d) polypyrrole film growth, and (e) or as primer coatings. Electrosyn-
separation of polypyrrole containers by ultrasound. The thesis of polybithiophene and
redox reaction may lead to a PPy shell on the bubbles. its bilayers with PAni coatings
Varying O2 content, surfactants, and parameters of the redox on stainless steel in diluted oxa-
scan, one can obtain and manipulate PPy containers and lic acid containing monomer and
electrodes of different roughness. sodium dodecyl sulfate was car-
Source: American Chemical Society
ried out by the potentiodynamic
synthesis technique [82]. Smooth
and adherent films were obtained on the steel surfaces. Tests for corrosion protection of
polymer coated and uncoated substrates were performed in highly aggressive media, revea-
ling that among the protective coatings obtained, polybithiophene as homopolymer and

Thin films 173
PAni/polybithiophene as bilayer exhibited the most effective anticorrosive properties.

Some interesting results were obtained in the area of designing stable, superhydrophobic,
and conductive PAni/polystyrene films for corrosive environments (Figure 10.10) [83].
A PAni/polystyrene composite film with a lotus-leaf-like structure is prepared via a sim-
ple electrospinning method. The film shows stable superhydrophobicity and conductivity,
even in many corrosive solutions, such as acidic or basic solutions over a wide pH range,
and also in oxidising solutions. The special surface composition and morphology are the
two important aspects that induce such unusual properties. The polystyrene content can
strongly influence the morphology of composite films, which thus display different super-
hydrophobicities and conductivities.
How corrosion protection by conducting polymers might work is actually subject of intense
research [84]. The redox activity offered by conducting polymers together with positive
equilibrium potentials relative to those of Fe and Al, as is the potential of chromate, suggest
that the mechanism is likely to involve anodic protection. The most popular mechanism is
the so-called “ennobling” that is based on the assumption that a conducting polymer could
provide anodic galvanic protection keeping the metal passive in small defects, or may act
as oxidiser, improving the oxide layer at the conducting polymer/metal interface. The pos-
sible reaction between the oxidised form of the polymer (conducting polymer (CP)m+) and
the metal (Me) is:
1/n Me + 1/m CPm+ +y/n H2 O → 1/n Mey(n-y)+ + 1/m CP0 + y/n H+
the conducting polymer being oxidised by atmospheric or dissolved oxygen:
m/4 O2 + m/2 H2 O + CP0 → CPm+ + mOH−
In addition, the electrons produced during metal oxidation at the defect can move into the
polymer and thus dislocate the oxygen reduction process from the metal/CP interface to
the CP/solution interface. This alleviates the local pH increase at the former and in turn the
cathodic disbonding of the coating. All of the processes mentioned above may simultaneously
contribute to substrate protection. It was also suggested in our group that conducting poly-
mers scan be used as a reservoir of corrosion inhibitors that could be released as a result of the
reduction of the conducting polymer [85]. PPy microcontainers were successfully prepared by
electrochemical polymerisation of pyrrole on the surface of stainless steel electrodes (Figure
10.11). The size of the nano-containers and thickness of the PPy shell (up to complete filling
of the container with grown polypyrrole) can be varied by changing both the scan speed of
the electrode potential and potential range. The PPy shell of the microcontainers exhibits
very strong barrier properties in acidic media at 2 < pH < 7 and a high permeability at pH > 7,
providing effective encapsulation of low molecular weight species at low pH values.
10.1.3 Biopolymers
Biological polymers (biopolymers) offer a degree of functionality not available in syn-
thetic conducting polymers. Carbohydrate polymers (polysaccharides) are very frequently
produced in nature [86]. Starch, cellulose, and chitin are some of the most abundant natural
polymers on earth. Biopolymers are a renewable resource and have a wide range of uses,
functioning as energy storage, transport, signaling, and structural components. Agricul-
ture-based biopolymers could have an economic advantage over synthetic, petroleum-based
products in the future.
Starch is composed of a mixture of linear and branched polysaccharides (Figure 10.12a).
Amylose is a linear polymer of α(1,4)-linked anhydroglucose units. Amylopectin is a highly
branched polysaccharide composed of linear α(1,4)-anhydroglucose unit chains with branch-

Figure 10.12: structures of polysaccharides: (a) amylose and amylopectin, (b) cellulose, (c) chitin,
(d) pectin, (e) hyaluronic acid, (f) agarose, (g) carrageenan, (h) heparin, (i) pullulan
points being α(1,6)-linkages. While starch is packed into granules in its native state, the
intrinsic properties of starch materials are exhibited when the granular structure is broken
down by mechanical and thermal means. Thermoplastic starch, produced by reactive extru-
sion, can be doped with metal halides [87]. The amount of moisture in the system affects both
the mobility of polymer and ion within the system and the quality of the physical properties
of thermoplastic starch. Starch is naturally insulating and its proton mobility is low [88].
Cellulose is a β(1,4)-linked D-glucan (Figure 10.12b). Cellulose xanthate was dissolved in
water, mixed with polyethylene glycol, and precipitated with ethanol [89]. The electrical con-
ductance of the polyethylene glycol-plasticised cellulose xanthate depended on the presence
of free ions, since the electron conduction was essentially zero. Hydroxyethyl cellulose was
blended with poly(ethylene oxide) to form good films, which is essential for some applica-
tions [90]. Hydroxyethyl cellulose was also grafted with propylene oxide and then blended
with poly(ethylene oxide) (Figure 10.12c) to form crosslinked polyether networks. Cellulose
serves as a flexible substrate for coating initial conducting polymers [91].
Chitosan is the N-deacetylated form of chitin with the repeat unit β(1,4)-linked 2-aceto-
amido-2-deoxy-D-glucose (Figure 10.12c). Because of its functional groups, chitosan has
many potential applications. In recent work, chitosan was plasticised [92] and doped with
sodium perchlorate (NaClO4) [93], sodium iodide (NaI), lithium trifluoromethanesulphonate
(LiCF3SO3) [94], and lithium acetate (LiCH3CO2) [95]. The crystallinity of the material incre-
ased with deacetylation, preventing mobile species from migrating, due to rigid polymer
chains. Such chitosan films could serve as membranes for alkaline polymer electrolyte

Thin films 175
batteries and fuel cells as well as in cor-

rosion protective films. Pore resistance is
a convenient way to represent corrosion
protection. Pore resistance indicates the
level of ionic conductivity from the elec-
trolyte penetration into the coating, i.e.
as pore resistance increases, ionic con-
ductivity decreases. In the case of corro-
sion protection, penetration of corrosives
(salts, moisture, etc.) is undesirable, so the
conductivity imparted by ionic species
(a measurement of the ionic mobility)
within the matrix should be low. Recen-
tly the group of Zhitomirsky [96] has made Figure 10.13 : (a, b) SEM images of laminates of
progress in constructing effective chi- chitosan-hydroxyapatite layers, prepared from 0.5
tosan composite coatings. They use the g/l chitosan solutions containing 1 g/l hydroxyapa-
electrophoretic deposition method for tite, and chitosan-multiwalled carbon nanotubes
the fabrication of chitosan carbon nanolayers prepared from 0.5 g/l chitosan solutions
tube-hydroxyapatite and hydroxyapa- containing 0.1 g/l multiwalled carbon nanotubes,
tite-CaSiO3-chitosan composite coatings arrows show chitosan-multiwalled carbon nano-
(Figure 10.13). tubes layers, deposition voltage 20 V. (c) SEM image
of the cross-section of a CaSiO3-chitosan(C)/
The use of chitosan enabled the co- hydroxyapatite-chitosan(H)/chitosan(Ch) three-
deposition of hydroxyapatite and car- layer coating on a graphite substrate, prepared
bon nanotubes or CaSiO3 particles and from the 0.5 g/l chitosan suspensions containing
offered the advantage of room tempera- 0.3 g/l CaSiO3 (C) or 1 g/l hydroxyapatite (H);
ture processing of composite materials. (d) SEM top view of coating (c) on stainless steel
The thickness of the individual layers substrate. Source: Elsevier
was varied in the range of 0.1 to 20 μm.

Composite chitosan multi-walled carbon nanotube layers were in the range of 0.5 to 10 μm
which was controlled by variation of the deposition voltage in the range of 20 to 50 V and
deposition time in the range of 1 to 10 min. It was shown that biopolymer multi-walled
carbon nanotube layers for hydroxyapatite films can be prepared as monolayer nanocompo-
sites containing multi-walled carbon nanotube layers and hydroxyapatite in a biopolymer
matrix or laminates, containing biopolymer multi-walled carbon nanotube layers
separated by biopolymer-hydroxyapatite layers. The thickness of individual layers can be
varied in the range of 0.2 to 5 μm by variation in deposition time. Obtained films provided
corrosion protection of NiTi shape memory alloys in Ringer’s physiological solution. The
use of poly(itaconic acid)-modified chitosan coatings for mitigating corrosion of aluminium
substrates was reported [97]. The synthetic poly(itaconic acid)-polymer was added to graft it
onto the liner chitosan chains and to crosslink between the chitosan chains. The grafting
and cross-linking reactions were generated by a strong chemical affinity between NH2
groups in chitosan and COOH groups in poly(itaconic acid), leading to the formation of amide
bonds. When this polymer was applied as environmentally benign waterbased coating to
an aluminium substrate by a simple dip-withdrawing method, the following three factors
played an essential role in mitigating the rate of corrosion of the Al:
• firstly, the polymer conformation, containing hydrophobic amide bonds, together with
a minimal amount of hydrophilic unreacted COOH in poly(itaconic acid) and NH2 in
chitosan;
• secondly, the lesser susceptibility of the coating films to moisture due to the enhanced
degree of grafting and cross-linking;

• thirdly, the interactions at the interfaces between the grafted chitosan and the Al sub-
strate, developing the formation of the –COO–Al linkage. The poly(itaconic acid) -grafted
and -cross-linked chitosan polymer coating films generated from the proper proportions
of poly(itaconic acid) to chitosan included all these factors and displayed low ionic conduc-
tivity, thereby imparting a salt-spray resistance of 694 h for coated Al panels.
Pectin and starch were separately grafted with polyorganosiloxane and blended with an
antimicrobial agent [98]. Pectin is a polygalacturonic acid methyl ester with varying degrees
of methylation (Figure 10.12d). The copolymer mixture was then applied to aluminium
substrates and evaluated for resistance to water, microbial attack, and corrosion protection.
Pectin polyorganosiloxane composite was thermally more stable than pectin, was less
susceptible to moisture due to a loss of hydrophilic groups, and imparted greater corrosion
protection. Aluminium coated with pectin alone had a slightly higher pore resistance than
the bare aluminium surface. However, aluminium coated with pectin polyorganosiloxane or
starch polyorganosiloxane showed an increase of at least one order of magnitude over bare
aluminium. In addition, the incorporation of an antimicrobial agent into the graft polymer
played a role in the overall susceptibility of the coating to degradation by water or bacteria.
There is higher corrosion protection due to both favorable interactions of polyorganosiloxane
with aluminium oxide layers on the metal surface and the reduced hydrophilic nature of
the polysaccharide matrix.
Collier et al. [99] coupled the biocompatibility of hyaluronic acid (Figure 10.12e) with
the electroactive properties of PPy for corrosion protection (see Chapter 10.1.2). Hyaluro-
nic acid is a negatively charged glycosaminoglycan and was chosen for its biocompatibi-
lity and known activity in wound healing and tissue regeneration. Hyaluronic acid was
blended with PPy in a single thin layer (PPy hyaluronic acid) or deposited on a layer
of PPy-poly(styrenesulphonate). The PPy hyaluronic acid/PPy poly(styrenesulphonate)
laminate exceeded the biological responses (such as morphology, hyaluronic acid activity,
cell compatibility, nontoxicity, increased vascularisation) of the control sample of PPy-
poly(styrenesulphonate).
Heparin was incorporated into PPy [100]. Heparin is a linear polysaccharide of glucuronic
acid and glucosamine containing sulfates (Figure 10.12h). Heparin is widely known as an
anticoagulant and has specific affinity for thrombin. It was shown that polyelectrolytes
(such as heparin) can be incorporated in initial conducting polymers during synthesis.
Cyclic voltammetry indicated that the heparin-PPy was electroactive upon oxidation/red-
uction in a reversible process. The primary mode of conduction was cation exchange, with
the cations moving in and out of the heparin-PPy matrix to maintain charge balances during
redox reactions. Cation conduction could be attributed to the large anion (i.e. heparin)
immobilised in the PPy matrix. The cation conductivity of heparin-PPy was significantly
higher than that of doped PPy. The heparin retained its biological activity on the surface of
the heparin-PPy blend. In a separate work, heparin and dextran sulphate were blended with
PPy to create hydrophilic polyelectrolytes that were able to store and release proteins [101].
This process could be controlled by varying the potential or the charge.
While currently most biopolymers have not achieved the level of conductance of some syn-
thetic conducting polymers, it is only a matter of time for them to be be engineered and
developed. The information presented here demonstrates the viability of using naturally
occurring polysaccharides for biobased conducting polymers in applications such as anti-
corrosion technology. Other areas could also be affected: batteries, tissue engineering, actu-
ators, electrochromic paper, molecular wires, and biosensors. There are major opportunities
for the development of biotechnology using integrated biological, chemical, and engineering
approaches, with bioreactors, fermentations, and organisms specifically designed to produce

Thin films 177
electroactive biopolymers. Electroactive biopolymers have better biocompatibility and they

are more environmentally friendly than synthetic conducting polymers. Sustainability could
be achieved by tailored biosynthesis of conductive biopolymers, using plants and microbes.
The use of renewable resources to produce nontraditional biobased products will affect the
worldwide dependence on petroleum-based and synthetic products and feed stocks.
10.2 Nanomaterials
New modern technologies require new materials. During the past decade, the movement
towards nanodimensions in many areas of technology raised a huge interest in nano-
structured materials. Many new corrosion protection treatments based on nano-structured
materials were developed over the last decade. These include the synthesis of different
nanocomposites and their individual use, or, for example, in combination with electrically
conducting polymers, nanocrystalline deposits, nanowires, nanotubes, polyelectrolytes
or polymer nanolayers. The addition of nanomaterials, even in small quantities, into con-
ventional coatings improves the properties of the coatings and, whatis more important,
makes these coatings multi-functional thereby, increasing their durability. Despite the fact
that nanocomposite coatings are already employed in maritime, automobile and aerospace
industries, the main drawback is still the costs of the nanomaterials, especially with func-
tionality, added to the coating. Further sustained development of coating components will
provide efficient solutions in the future for new generations of coatings where the “passive”
component will be added to the “active” one.
10.2.1 Nanocomposites
Layered materials such as anionic clays (e.g., layered double hydroxides) [102] and cationic
clays (e.g., montmorillonite) [103] have been widely investigated as additives in organic anti-
corrosion coatings or as polymer-clay nanocomposite corrosion-resistant coatings. Moreo-
ver, zeolites [104] have been explored as corrosion-resistant coating materials. Hydrophobic
layers [105] of surfactant molecules on the surface have recently been proposed as corrosion
inhibitors but suffer from the drawbacks that the layers have limited stability and molecule-
sized defects which allow water to reach the underlying surface. These problems should be
mitigated if the surfactant could be incorporated in an inorganic host matrix, a thin film of
which has been previously strongly bonded to a metal, for example aluminium, surface.
Layered double hydroxides (LDHs) are one such potential inorganic host. They can be
expressed by the general formula
[M2+1-xM3+x(OH)2]A n-x/n · mH2O,

where the cations M2+(Mg2+, Zn2+, Fe2+, Co2+, Cu2+, and others) and
M3+ (Al3+, Cr3+, Fe3+, Ga3+, and others)
occupy the octahedral holes in a brucite-like layer and the anion An- is located in the hydra-
ted interlayer galleries [106]. The ability to vary the composition over a wide range allows
materials with a wide variety of properties of the preparation. The LDHs have been applied as
catalysts and catalyst supports [107], polymer stabilisers [108], and traps for anionic pollutants
[109]
. In addition, they have been considered for the delivery of drugs at cellular level, with
several studies showing their low toxicity and high biocompatibility, together with the
ability to control release of active species under certain circumstances [110]. Therefore, the
nano-structured systems used for drug-delivery purposes are prospective systems for the
incorporation/encapsulation of corrosion inhibitors.

Figure 10.14 : Various types of nanostructured materials which may be produced by electrodeposition
technique. Source: Elsevier
Application of hydrotalcite-like compounds in corrosion science has covered different

aspects. In some studies, LDHs have been produced in-situ, on the top of metallic substrates
as protective films [111].
Hydrotalcite-based conversion films have demonstrated good corrosion protection, and some
research groups have been trying to improve the interaction between these conversion films
and organic coatings [112]. A different perspective is to use these anionic clays as containers
for corrosion inhibitors and incorporate them into the organic coatings. In this case, the
target is two-fold, i.e. not only to release the species that impart active protection but also to
trap corrosive agents (Cl-, SO42-). Regarding this topic, several works by Buchheit et al. [113],
Williams and McMurray [114] and others [115] can be found in the literature. Within the LDH
family, a class of materials with emerging importance is that constituted by the LDHs loaded
with organic anions [116]. Two short studies on these materials are available in the literature.
Williams and McMurray prepared LDHs with different organic species (benzotriazole, ethyl
xanthate, and oxalate) by re-hydration of commercial hydro-talcite [Mg6Al2(OH)16·CO3·4H2O].
The resulting layered systems were inserted into a poly(vinylbutyral) coating, prepared by a
bar cast on top of AA 2024-T3. In another report, Kendig and Hon [117] prepared LDHs inter-
calated with 2,5-dimercapto-1,3,4-thiadiazolate in a similar way and studied the inhibiting
properties of this anion with respect to the oxygen reduction on copper. Another recently
developed possibility [118] is the use of Zn-Al and Mg-Al LDHs loaded with quinaldate and
2-mercaptobenzothiazolate whose anions were synthesised via anion-exchange reaction.
Spectrophotometric measurements demonstrated that the release of organic anions from
these LDHs into the bulk solution is triggered by the presence of chloride anions, evidencing
the anion-exchange nature of this process. The anticorrosion capabilities of LDHs loaded
with organic inhibitors toward the AA2024 aluminium alloy were analysed by electroche-
mical impedance spectroscopy. A significant reduction of the corrosion rate was observed
when the LDH nanopigments are present in the corrosive media. The mechanism by which
the inhibiting anions can be released from the LDHs underlines the versatility of these
environmentally friendly structures and their potential application as nanocontainers in
self-healing coatings (see Chapter 10.3.2).
Simultaneously, conductive polymers discussed in Chapter 10.1.2 could serve both ways,
as blocks in nanocomposite construction i.e. as nanoparticular dispersions (for example
PAni, PPy [119]) in paints at low concentrations to enhance anticorrosion properties; or as
matrix for the incorporation of inorganic materials, for example LDHs (montmorillonite clay,
Fe3O4, ZnO) [120]. In all cases model coatings showed high corrosion protection in laboratory
scale for aluminium and steel.

Nanomaterials 179
Moreover, recent literature on the

electrodeposition of metallic coa-
tings containing nanosized par-
ticles was surveyed. Nanosized
particles, suspended in electro-
lyte by agitation and/or use of
surfactants, can be codeposited
with metal. The inclusion of nano-
sized particles can give
• an increased microhardness
and corrosion resistance,
• modified growth to form a nano-
crystalline metal deposit and
• a shift in the reduction poten-
tial of a metal ion. Figure 10.15 : SEM and SVET study of the aluminium alloy
AA2024 covered by a cerium/aluminium nanonetwork (up)
Many operating parameters
and a dense cerium oxide layer (down)
influence the quantity of incor-
porated particles, including cur-
rent density, bath agitation (or movement of work piece) and electrolyte composition. High
incorporation rates of the dispersed particles have been achieved using
• a high nanoparticle concentration in the electrolyte solution,

• smaller sized nanoparticles;
• a low concentration of electroactive species,
• ultrasonication during deposition and
• pulsed current techniques.
Compositional gradient coatings are possible, with a controlled distribution of particles in

the metal deposit, and the theoretical models used to describe the phenomenon of particle
co-deposition within a metal deposit are critically considered [121]. Figure 10.14 shows the
categories of nano-structured materials along with various electrodeposition manufac-
turing techniques. Readers are directed to a number of earlier reviews [122] for a detailed
background to composite electrodeposition of larger particles which typically have sizes
in the range of 1 to 80 μm.
Formation of cerium/aluminium oxide anticorrosion protective layers on metal surfaces

has been done by ultrasonic irradiation of high intensity [123]. The mechanism of metal surface
modification in the presence of cerium(III) aqueous solution results from two factors, i.e.
activation of the metal surface by localised heating and activation of cerium ions which are
diffused within liquid jets shot at the metal surface with high velocity. The ultrasonically
increased reactivity of cerium and the engineered metal surface resulted in a novel type of
cerium enriched protective layer, a nanonetwork, where cerium and aluminium oxides are
interlaced in a mixed layer strongly connected to the metal surface. The anticorrosion acti-
vity of the novel cerium/aluminium oxide system was demonstrated by using the scanning
vibrating electrode technique (Figure 10.15). At high intensity of sonication (30 min at 57 W/
cm2) a 20 nm cerium/aluminium nanonetwork deposited on the engineered metal surface
can be formed. The cerium/aluminium nanonetwork exhibits very good adhesion to both
metal surface and components of the anticorrosion system (here, silica/zirconia based sol-
gel film). Corrosion resistance of the metal surface covered by the cerium/aluminium nano-
network is significantly enhanced. Release of cerium ions incorporated into the interfacial
layer is observed after mechanical rupture (cracks) of the protective coating.

10.2.2 Sol-gel derived ceramic and hybrid coatings

One of the prospective candidates for the substitution of chromate pretreatments are sol-gel
derived thin films. Sol-gel films have a good adhesion to both metallic substrates and orga-
nic top coats. Sol-gel technology can offer various ways to prepare functional coatings with
different properties. Sol-gel coatings can be prepared using hydrolytic and non-hydrolytic
procedures in organic or aqueous media [124]. The preparation of sol-gel materials can be
controlled by variation of many parameters that influence the processes, and in turn, the
properties of the final coatings. The sol-gel procedure is a method that allows the deposi-
tion of a thin oxide film at temperatures near to room temperature in contrast to traditional
ceramic processing technologies.
The sol-gel process has an excellent potential to be used for the preparation of inorganic or
organically modified protective coatings. Sol-gel processes are mainly based on hydrolysis
and condensation reactions of metal alkoxides (M(OR)n). The resulting oxide materials present
structures varying in range from nanoparticulate sols to continuous polymer gels depending
on the rate of each of the forming reactions and subsequent drying and processing steps. The
close control of parameters of sol-gel reactions leads to the design of new advanced materials
with interesting properties for many applications. Materials with different compositions can be
easily obtained in the form of glasses, fibres, ceramic powders and thin films. Silicon-organic
based sol-gel chemistry is more developed nowadays when compared to other metal-organic
based precursors. The main aspects of sol-gel chemistry and application of sol-gel derived
materials have already been described in detail in a number of reviews and books [125].
The first sol-gel processes were mainly based on simple alkoxide precursors giving access to
ceramic or glass-like inorganic products. However, the low reaction temperature also allows
the introduction of organic groups in inorganic materials leading to a novel class of materi-
als composed of both inorganic and organic moieties [126]. The inorganic component confers
enhanced mechanical properties while the organic component leads to increased flexibility
[127]
and functional compatibility with organic paint systems. The classical approach to join
the properties of different materials led to the development of composite materials, where
two different phases with complementary physical and chemical properties were mixed.
However, the properties of a hybrid composite material do not only depend on properties of
individual components, but also on synergies between them, providing better properties
than any of the two constituents.
Hybrid inorganic-organic sol-gel composites can be prepared in two ways, i.e. the orga-
nic and inorganic groups can be linked by stable chemical bonds, or the organic component
can be merely embedded in an inorganic material [128]. Another important factor is the size
of organic-inorganic domains in the final composite. Improved physical properties can be
achieved by the reduction of the domain size to nanoscale, increasing the interfacial sur-
face area. Further reduction in domain size leads to the formation of molecular composites
[129]
. This may be accomplished by incorporating the polymerisable inorganic group and an
organic constituent in the same molecule when the organic group is bound to oxide-forming
elements in a hydrolytically stable way.
Nanocomposites with a well defined structure can be obtained using preformed nano-
building blocks, such as nanoclusters, nanoparticles or nanolayered materials. The nano-
building blocks strategy confers several benefits providing a monodispersed, well defined
nanostructure of the final hybrid material. The incorporation of an organic component into
the inorganic materials opens a wide range of possibilities for functionalising and tailoring
of final materials. The addition of chromophore molecules or luminescent groups leads to
hybrids with advanced optical properties [130].

Nanomaterials 181
Figure 10.16 : Schematic representation of enhanced compatibility of different paint systems with an
epoxy-functional hybrid sol-gel coating. Source: Royal Society of Chemistry
Another key property, which can be tuned using modification of the organic functionality, is
compatibility and adhesion of thin protective hybrid sol-gel films to organic paint systems
applied on top. Chemical bonding is possible between the sol-gel film and the top coat
conferring enhanced adhesion in comparison to chromate pretreatments where adhesion is
mainly attributed to mechanical interlocking, dispersion forces and hydrogen bonds. Figure
10.16 depicts possible ways to obtain an enhanced chemical compatibility of an epoxy-based
or amino-containing paint system to a sol-gel pretreatment by functionalising the organic
component of the hybrid film with epoxy groups. Other functional groups were used for pre-
treatment functionalisation in the case of poly(urethane) and thioester paint systems [131].
A number of waterbased stable sol-gel systems have been developed. Functional groups
varied from amino, epoxy, vinyl, and allyl groups can be incorporated into the sol-gel network
to interact with organic polymer resins [132]. A strong motivation for the study of inorganic/
organic hybrid coatings, especially when a significant portion of inorganic network compo-
nents is involved, is their potential to ensure an extended service life as compared to tradi-
tional organic-polymer-based coatings. Current waterbased epoxy resins (organic polymer)
tend to degrade within 3 years of weathering exposure, making them imcompatible with
outdoor use as topcoats. Inorganic networks are resistant to degradation by aging under
UV light. A hybrid coating containing significant portions of inorganic network integrated
with the epoxy polymers may last much longer in a UV environment, moreover the healing
of a sol-gel matrix could be achieved under UV [133]. Figure 10.17 illustrates an inorganic/
organic hybrid coating structure: (top) reaction and curing of sol-gel network with colloidal
particles and silanes with functional groups; (centre) reaction and curing of water-reducible
epoxy based organic primer; (bottom) reaction and curing of a hybrid coating system. The
flexible long strands are epoxy resin polymers. The short zigzag strands are amine-based
curing agents.
One more advantage is an increased of a mechanical strength (such as abrasion resistance)
of the coating. A better incorporation of inorganic salt corrosion inhibitors and fillers is
possible in this case, too. The possibility to develop a true single step coating combing
the functions of the conversion coating, primer, and topcoat becomes more realistic based
on sol-gel hybrid systems. The coating surfaces of the hybrids are glossy and have shown
water repellency. The coatings are also thicker than normal primer coatings (2 mm or
thicker) so that various pigments may be incorporated in the system without sacrificing
the performance of the coating. In a sol-gel/epoxy resin hybrid coating, the combination of
weathering stability and structural strength of a sol-gel network with the flexibility and
room temperature cure of an epoxy resin will hopefully be possible. Figure 10.17 shows the
curing process and final structure depicted in a simplified manner.
In the work [134] inorganic sol-gel

pretreatments show good cou-
pling between the metallic sub-
strate and organic coatings. The
high adhesion of sol-gel films to
metals is due to the formation of
strong covalent Si–O–Me bonds.
This generates corrosion stable
metal/sol-gel film interfaces with
noticeable self-repair ability. The
addition of an organic compo-
nent to the sol-gel systems leads
to the formation of thicker and
more flexible films with better
compatibility with organic top-
coats. Hybrid films have gained
interest because they combine
Figure 10.17 : Illustration of inorganic/organic hybrid the properties of organic polymer
coating structure: (top) reaction and curing of sol-gel materials and ceramics. Hybrid
network with colloidal particles and silanes with functional coatings can be prepared over a
groups; (middle) reaction and curing of water-reducible continuous compositional range
epoxy-resin-based organic primer system; (bottom) reaction from almost organic to almost
and curing of a hybrid coating system. Note: FG: functional
inorganic. An advantage of the
groups such as amino, epoxy groups. The spheres are sol-gel
nanoparticles. The flexible long strands are epoxy resin
organically modified composi-
polymers. The short zigzag strands are amine-based curing tes is the possibility to prepare
agents. Source: Elsevier thick, crack-free coatings that
can provide an effective barrier
to corrosive agents. Moreover,
the hybrid films can be reinforced by doping with nanoparticles that improve corrosion
protection properties. This improvement results from the reduced porosity and cracking
potential of such films.
In the long run, sol-gel derived ceramic and hybrid coatings exhibit a high potential as
substitutes for the environmentally unfriendly chromate surface pretreatment methods.
Inorganic sol-gel derived films offer good adhesion between metals and organic paint.
However, they cannot provide adequate corrosion protection due to their high crack-forming
potential. The introduction of an organic component in an inorganic sol-gel system leads
to the formation of thicker, more flexible and functionalised films with enhanced compa-
tibility to different organic topcoats. The incorporation of nanoparticles in the hybrid sol-
gel systems increases the corrosion protection properties due to lower porosity and lower
cracking potential along with the enhancement of mechanical properties. Furthermore, the
incorporation of inorganic nanoparticles can be a way to insert corrosion inhibitors, pre-
paring inhibitor nanoreservoirs for ‘‘self-repairing’’ pretreatments with controlled release
properties (see Chapter 10.3.2).
10.3 Self-healing coatings

Protective systems should not only react adequately on external impacts, but also respond
to changes in their internal structure, and combine different damage prevention and repair
mechanisms in the same system. Metallic or composite joints bonded by adhesives contai-
ning these types of intelligent release systems also exhibit improved durability against

Self-healing coatings 183
environmental degradation. The

multi-level self-healing concept
is based on gradual active feed-
back of the protective systems
to the environmental conditions.
The protection could be provided
by incorporation of nanotraps
(inorganic nanoparticles able to
absorb aggressive/corrosive spe-
cies if their level exceeds a criti-
cal value, see also Chapter 10.2.1). Figure 10.18 : Schematic presentation of the protection.
Moreover it could be based on Source (a) the Nature Publishing Group and (b) the American
the use of water displacing com- Chemical Society
pounds, which are released from
nanocontainers as soon as the first microdefects appear in the polymer matrix. Further
growth of the defects triggers the release of polymerisable precursors entrapped in other
nanocapsules (Figure 10.18a). Then a new thin polymer film is formed, to cover the damaged
area and repair the layer, preventing crack propagation. The encapsulation of organic and
inorganic corrosion inhibitors in 50 to 500 nm containers suppresses corrosion and delami-
nation processes occurring in open defects or at cut edges (Figure 10.18b).
In general the term ‘‘self-healing’’ in material science means self-recovery of the initial
properties of the material after destructive action of the external environment. The same
definition can be applied to functional coatings. However, a partial recovery of the main
functionality of the material can also be considered as a self-healing ability. Thus, in the
case of corrosion protective coatings, the term ‘‘self-healing’’ can be interpreted in different
ways [135]. The classical understanding of self-healing is based on the complete recovery of
the functionalities of the coating due to a real healing of the defect based on the recovery of
the coating integrity. However, the main function of anticorrosion coatings is the protection
of an underlying metallic substrate against an environment-induced corrosion attack. Thus,
it is not obligatory to recuperate all the properties of the film in this case. The hindering of
the corrosion activity in the defect by any mechanisms employed by the coating itself can
already be considered as self-healing, because the corrosion protective system recovers its
main function, namely the corrosion protection, after being damaged.
The development of an active healing mechanism for the polymer coatings and adhe-
sives becomes an urgent issue for the respective industrial applications. Recently, several
attempts were made in this field using different protection/healing mechanisms for pro-
tective coatings and adhesives. Therefore an active protection based on “self-healing” of
defects in coatings is necessary to provide a long-term effect. A multi-level self-healing
approach as described combines – within one system – several damage prevention and
repair mechanisms, which are activated depending on type and intensity of the environ-
mental impact (pH, irradiation, potential change, etc.).
10.3.1 Self-repairing polymer films

The development of new materials with stimuli-responsive physical properties is a rapidly
expanding area of research [136]. Notable recent developments in this field include self-hea-
ling polymers [137] which, when fractured, can regain the physical properties of the original
polymer either autonomically [138], or in response to an external stimulus such as heat [139]
or pressure [140]. Healable polymeric systems may for example contain encapsulated mono-
mers and polymerisation catalysts, or latent functionalities which are able to participate in

thermally-reversible [141], covalent bond-forming reactions [142], It has also been shown that
non-covalent interactions, specifically hydrogen bonds [143], may be used to effect healing
within a supramolecular polymer blend (albeit in the presence of a plasticising solvent).
In the latter system, it is proposed that fracturing propagates via dissociation of the weak
supramolecular interactions rather than by scission of covalent bonds, so that re-assembly
of the supramolecular network restores the original physical properties of the material.
Thus, due to the self-healing ability of polymers, protective coatings doped with organi-
cally modified hollow glass microspheres exhibited an enhanced resistance to erosive
wear contributing to more intense corrosive wear [144]. The large specific surface area
of glass microspheres coated with a specially developed polymer finish, ensures robust
and tight binding between capsules and epoxide matrix. Polydispersity as well as shape
irregularity enable effective filling of structural voids in the epoxide plastic, reducing the
coating porosity and improving its mechanical properties. Sometimes the active agent
(inhibitor, sealant etc.) to be encapsulated is either only water-soluble or has an essentially
high solubility in aqueous media for incorporation into the waterborne polymeric coating.
In this case, micro- or nanocapsules with aqueous cores and charged polymeric shells
which are dispersible in aqueous solutions have to be synthesised. An interesting possible
route for preparing such a container via w/oil (w/o)/w-emulsion and solvent evaporation
was shown in [145].
Two types of polystyrene microcapsules with aqueous interior and sizes of 6 and 26 mm,
respectively, were formed depending on the chemistry of the stabilising surfactants and
their concentrations. The electrodeposition of microcapsules on a metallic coating carried
out in the next step was only satisfactory when their size was essentially smaller than the
coating thickness (60 mm), stabilising their integrity. A similar way to produce a composite
metal coating with organic liquid-containing microcapsules by electroplating of metal sub-
strate was chosen in order to achieve the sustained release of a liquid lubricant, lowering
the friction between repeatedly contacting surfaces (self-lubricating coating) [146]. Microcap-
sules with liquid organo-silica resin as the core and polyvinyl alcohol as the shell material
were prepared via o/w emulsification using an alkyl polyoxyethylene polyether type sur-
factant as a stabiliser. Subsequent electroplating from the mixture of electrolyte solution
and capsule dispersion completes the formation of the composite capsule-contained metal
coating. When the samples were subjected to a scratch or wear test, surface wetting in the
immediate vicinity of the damaged site was observed, confirming the release of liquid from
the broken microcapsules and the ability of the coating to provide self-lubrication.
For effective performance of self-healing composite coatings, the ability to recover cracks
generated during service of a polymer is essential and may be attained by incorporation of
microcontainers with encapsulated liquid sealant. Urea-formaldehyde microcapsules filled
with drying linseed oil were used for the healing of cracks in an epoxy coating [147]. Micro-
capsules were synthesised by in-situ polymerisation in an o/w-emulsion. Initially fully
water-compatible urea and formaldehyde react in a continuous aqueous medium to form
poly(urea-formaldehyde). As the molecular weight of this polymer increases, the fraction
of polar groups gradually decreases until the polymer molecules become hydrophobic and
are deposited on the surface of o/w emulsion droplets. The obtained microcapsules hereby
obtained were then incorporated into an epoxy coating. Since the outer shell surface of
the microcapsules was very rough, a good binding with the coating matrix was provided.
Upon cracking of the coating the encapsulated linseed oil is released and fills the crack in
the matrix. Finally, oxidation of linseed oil by atmospheric oxygen led to the formation of a
continuous film inside the crack. Superior corrosion resistance of such a self-healing coa-
ting was demonstrated by comparative exposure of two specimens in a salt-spray cabinet.

When scratched, the sample coated by film containing

capsules remained free from corrosion after up to 72 h
of exposure. In contrast, the control specimen suffered
from corrosion after 48 h.
Significant progress in the preparation of protective
composite coatings with incorporated organic micro-
and nanocontainers was achieved in the past decade
in the group of S. R. White [148]. In the most well-known
paper, published in 2001, they showed the first wor-
king prototype of polymeric coatings with the ability to Figure 10.19 : SEM image of the
‘‘autonomically heal cracks’’ in the structural polymers. fracture plane of a self-healing
The proposed self-healing coating contained microcap- material with a ruptured urea-form-
sules (50 to 200 mm) with poly(urea-formaldehyde) aldehyde microcapsule in a thermo-
shells filled by the healing agent – dicyclopentadiene setting matrix. Source: Elsevier
monomer. These capsules were then mixed with epoxy

resin and Ru-based Grubbs’ catalyst in order to prepare a self-healing epoxy specimen. A
developing crack ruptures the embedded microcapsules and releases healing agent into the
crack channel due to capillary forces (see Figure 10.19).
Polymerisation of the healing agent was triggered by bonding the crack faces. Healing
efficiency was about 60 % (see Figure 10.20). The proposed self-repairing approach had,
however, some essential drawbacks for application of the protective self-healing coatings:
• The concentration of Grubbs’ catalyst has to be quite high increasing the price of the
coating, especially in the case of large surfaces to be protected;
• The relatively large size of capsules (50 to 200 mm) inhibits their application to coatings
with thickness less than 0.5 mm because of integrity failure.
On the other hand, lowering the microcapsule size without reducing the self-healing efficiency
requires much higher concentration in the coating matrix. Samples with smaller microcapsules
must exhibit a very good adhesion to the epoxy matrix to ensure capsule rupture under stress.
Much smaller capsules (nanocapsules) filled by dicyclopentadiene as a self-healing agent
were synthesised very recently
using ultrasonic treatment for the
preparation of initial o/w-emulsi-
ons. Up to 2 % v/v of these cap-
sules can be dispersed in an epoxy
matrix leading to a slight decrease
of tensile strength accompanied by
a significant increase in fracture
toughness. An increase of fracture
toughness up to 59 % was found for
a capsule volume fraction of 0.015.
Because of their size, smaller cap- Figure 10.20 : Self-healing process. (a) Self-healing coating
sules were found to be suitable for containing microencapsulated catalyst and phase-separated
applications in self-healing thin healing agent droplets (small) in a matrix on a metallic
films and coatings. substrate. (b) Damage to the coating layer releases catalyst
and healing agent. (c) Mixing of healing agent and catalyst
A less-expensive and chemically in the damaged region. (d) Damage healed by cross-linked
more stable self-healing compo- polymer, protecting the substrate from the environment. (c,d)
sition was based on the direct SEM images of the scribed region of (e) the control coating
incorporation of phase separated and (f) the self-healing coating after healing (d) Source: Wiley

droplets containing hydroxyl end-functionalised polydimethyl-siloxane and polydietho-

xysiloxane in the coating matrix. Only the catalyst, di-n-butyltin dilaurate or dimethyl
dineodecanoate tin, was embedded in the polymer matrix in the microencapsulated
state, using polyurethane microcapsules of a size up to 450 mm. The advantages of this
self-repairing system were, however, considerably reduced by the large size of the micro-
capsules and poor adhesion of the healing agent (polysiloxanes) and matrix, leading to
the addition of adhesion promoter, and the extreme toxicity of the employed catalyst. The
last point could be especially critical, taking into account the details of preparation of the
polyurethane shell. The reaction between polyurethane and ethylene glycol was done in
an aqueous medium and droplets of o/w-emulsion were stabilised by 15 % solution of gum
arabic. These factors can significantly contribute to the side reaction of polyurea forma-
tion, which is accompanied by the evolvement of CO2 and causes porosity of the capsule
shell. Attempts to use various microencapsulated solvents embedded in a polymer matrix
as a self-healing system were less successful. The encapsulation of five highly efficient
solvents with a high degree of polarity failed, and among the polar solvents used only chlo-
robenzene emerged as a potential candidate for self-healing. Nevertheless, experiments
with poly(ureaformaldehyde) microcapsules (160 mm) filled with chlorobenzene showed
sufficient healing efficiency for the epoxy matrix. The idea of microencapsulation of sol-
vents as active agents for self-healing coatings was further developed by including a reac-
tive epoxy resin component in the capsule core. New, less toxic solvents as compared with
previously used chlorobenzene were employed in the self-healing core mixture. The
use of ultrasonication and a co-stabiliser for the emulsion preparation step yielded much
smaller capsules up to submicrometre size. The resin-solvent capsules of micrometre size
were successfully incorporated in the epoxy matrix and ruptured by a propagating crack.
An epoxy film was then observed to be accumulated on the crack surface evidencing that a
reactive epoxy resin was delivered to the damaged coating site. Almost the same approach
was utilised when a self-repairing coating for corrosion protection of aluminium alloys
was developed using cage-like microcapsules with an oil core and a silica gel shell [149].
Two types of these microcapsules were prepared by interfacial polycondensation on the
surface of Pickering o/w emulsion droplets composed of methyl methacrylate/tetraethyl
orthosilicate mixture stabilised by interfacially-active polystyrene nanoparticles. The
application of polystyrene nanoparticles with two different sulphonation times, 60 and
9 h, yields microcapsules with closed and open state of surface pores, respectively. Closed
microcapsules were then used as a source of self-healing polymer methacrylate and open
highly-porous capsules of smaller size were impregnated with a solution of a polymerisa-
tion initiator. Both types of microcapsules were deposited on a surface of aluminium alloy
AA 2024 and then coated with a sol-gel film. Scratching led to the break-up of capsules
and a monomeric self-healing agent was released, forming a polymeric film. However,
pictures showing microcapsules of both kinds demonstrate a certain, relatively high
porosity. This was also demonstrated for ‘‘closed’’ microcapsules containing a monomeric
sealant, which could open the possibility of spontaneous polymerisation especially when
polymerisation catalyst diffuses from the open microcapsules. Scratch dimensions are
huge compared with the microcapsule size of both types. Therefore, the scratch has to
destroy not only methacrylate-filled microcapsules but also neighbouring catalyst-loaded
containers causing release and immediate polymerisation of methacrylate.
The next promising step is now to proceed to constructing the response in a way that it
will, in turn, affect the stimulus. This feedback loop has to be used to anneal defects, e.g.
to construct a self-repairing coating. It is shown that there are conceptual solutions but
still many technical and economical issues must be solved to arrive at practical solutions.
The stimuli predominantly have been of mechanical and chemical nature but in the future

one may envision more of these,

e.g. friction, biocide. One should,
however, also be aware that feed-
back loops are ubiquitous in nature
and technology, and mostly, they
are not used to remove a stimulus
but to keep it at a defined level,
e.g. concentration, pH value,
potential. Mimicking this, howe-
ver, is a more demanding task
which should be tackled in the Figure 10.21 : IR (upper) and optical (lower) images of
future. On the other hand one self-repairing oxetane-substituted chitosan polyurethane
can envision much potential in networks recorded as a UV exposure time. A1, 0 min; A2,
constructing these more sophi- 15 min; A3, 30 min. (SOM provides details regarding
spectroscopic changes detected by IR imaging.)
sticated regulatory loops, e.g.
Source: Science Publishing Group
maintaining a fixed humidity,
potential or enzyme concentra-
tion. There is a high demand for such feedback active systems in the most urgent areas of
society, energy, health and raw materials, and we look forward to interesting solutions in
these areas in the near or far future.
Also, the development of a new generation of thermosetting polymers that are of consi-
derable technical and commercial importance [150] is extremely interesting (see Figure
10.21). The use of the UV portion of the electromagnetic radiation for repairing mechanical
damages in coatings offers an ambient temperature approach to self-healing . This approach
might avoid the placement of other, often elaborate, network components that is controlled
by the chemistries and morphologies of polymer networks in a number of critical applica-
tions and technologies.
10.3.2 Inhibitor release

The use of different types of micro- and nanocontainers for encapsulation, controlled
delivery and release of active materials has become more and more popular nowadays.
The containers can have an inorganic, organic or composite origin, and can be applied for
encapsulation of drugs, vitamins, quantum dots, bactericides, oils, biopolymers, corrosion
inhibitors, low molecular weight compounds and many other active molecules. For example,
micrometre sized capsules with a layer-by-layer assembled polyelectrolyte shell are used
for the encapsulation and release of drugs, DNA, dendrimers and enzymes [151]; inorganic
halloysite nanotubes were demonstrated to be suitable for loading of ferments and inorganic
nanoparticles [152].
Hydrogels were used for the encapsulation of phospholipids, drugs, as liposome reactors and
plant growth media [153]. Micelles and microemulsions are probably the most investigated
systems for the encapsulation of active biomaterials. There are numerous publications on
this topic and we address several recent reviews to provide better understanding of the
current achievements in the use of micelles and microemulsions for encapsulation [154].
The most interesting feature of containers is their ability to control release/upload. The
controlled release/upload is, in general, dependent on the interaction between the mate-
rial of shell or stopper and the environment surrounding the container. The shell/stopper
of containers should be sensitive to external impact or changes in the local environment;
moreover, it should selectively react only to one or two triggers changing its permeability
while others should leave the shell intact. The permeability of the container shell is

Figure 10.22: Container loading with corrosion inhibitor and modification by polyelectrolyte shell:
(a) scheme; (b) changes of zeta potential during the procedure of polyelectrolyte shell formation;
(c) loading of the interior of SiO2 containers with 2-(benzothiazol-2-ylsulfanyl)-succinic acid under
vacuum; (d) the release of inhibitor from nanocontainers at (a) pH.10.1 and (b) neutral pH. Source: Wiley
determined by balance of electrostatic interactions of surface charges that tend to expand

the surface and, therefore, produce pores in the shell, and hydrophobic interaction contri-
buting to surface energy that tends to reduce the surface [155]. Establishing the equilibrium
between these forces requires work against film elasticity [156]. The following triggers are
utilised for opening/closing of the container shell/stopper:
• local pH changes
• temperature changes
• electromagnetic irradiation
• mechanical pressure (also ultrasonic treatment)
• humidity
• electric (electrochemical) potential
• ionic strength and
• dielectric permeability of the solvent.
The simplest trigger for opening/closing of the container shell is the pH shift in the local
environment. Polyelectrolyte capsules, hydrogels and emulsions with weak acidic or basic
functional groups in the shell are sensitive to it, displaying reversible and/or irreversible
changes of the shell permeability in a wide pH range (e.g. at low pH < 4 or high pH > 9) [157].
The other important triggers are external electromagnetic irradiation and mechanical
impact. For the opening by electromagnetic irradiation, a container shell should have sen-
sitive components, for example, like metal (silver) nanoparticles, for IR [158], dyes for visible
light [159] and semiconductors (TiO2 particles) for UV [160]. The mechanical impact requires
a certain level of rigidity or brittleness of the shell, because the elastic shell can undergo
Figure 10.23 : (a) Scheme of the self-healing effect of anticorrosion coatings and
(b) AFM images of container-loaded SiOx:ZrOx film. Source: Wiley
deformation under pressure instead of rupture [161]; containers with diameters <100 nm
are hardly destroyed with reasonable mechanical force because they tend to escape from
the force direction. On the contrary, ultrasonic treatment can be applied to irreversibly
open containers of any size [162]. Other triggers for capsule opening were demonstrated for
hydrogels (temperature, electric potential, high ionic strength) and polyelectrolyte capsules
(temperature, high ionic strength, dielectric permeability of the solvent) [163] These triggers
are usually involved in feedback active systems of specific functionality (e.g. coatings with
electrochemically reversible permeability) [164].
The strategy of preparation of nanocontainers based on mesoporous oxide core is presented
in [165]. The fabrication of a polyelectrolyte shell around a container can possibly be done by
layer-by-layer assembly (Figure 10.22a) of oppositely charged species, thereby allowing to
prevent the spontaneous release of a loaded corrosion inhibitor. The precision of one adsorbed
layer thickness is about 2 nm. Polyelectrolyte nanocontainers completely repeat the shape
of the templating colloids. The polyelectrolyte shell lends controlled release properties to
the nanocontainers. The opening of the shell can be induced only by changing the surroun-
ding pH value to the acidic or alkali region (which happens when the corrosion starts) [166],
while in neutral pH the polyelectrolyte shell remains intact preventing undesirable leakage
of the entrapped inhibitor. The formation of oppositely charged layers was determined by
zeta-potential measurements (Figure 10.22b). The inhibitor content in the nanocontainers
is equal to 85 mg/g of the initial SiO2 particles (Figure 10.22c). The release kinetics of the
entrapped inhibitor into water at alkaline pH is represented in Figure 10.22d.
As can be seen, the release of the corrosion inhibitor (2-(benzothiazol-2-ylsulfanyl)-
succinic acid) from containers with a polyelectrolyte shell is triggered at pH 10.1, similar
to the pH value in the cathodic zone during the corrosion process of aluminium [167]. Thus,
modification of containers with polyelectrolyte shell is an important issue to achieve con-
trolled release of the encapsulated inhibitor as well as to prevent its undesirable leakage
from the coating [168]. The next step in the anticorrosion self-healing coating formation is the
incorporation of the containers in the coating. It is important to achieve their uniform distri-
bution (Figure 10.23). One of the important characteristics of corrosion is the local change
of the pH value in the corrosive area. Depending on the corrosion mechanism, intermetallic
inclusions, and surface properties of the metal substrate, the local pH shift could occur both
to the acidic and alkaline region [169]. This local pH change influences the polyelectrolyte
shell, in particular, its opening and inhibitor release and, consequently, the healing of the
corrosion area that can be achieved. This effect is self-regulated and an inhibitor release

Figure 10.24 : a) Schematic illustration of the procedure for benzotriazole loading for halloysite
G nanotubes. (b, c) Release of the benzotriazole at different pH values from a) uncovered halloysite G
nanotubes and c) from 1) halloysite G nanotubes modified by PDADMAC/PSS layers, 2) halloysite
G nanotubes modified by PAH/PSS layers, and 3) halloysite G nanotubes modified by PAH/PMA layers
(after 30 min of incubation) a, c). Source: Wiley
takes place just in the region of the pH-change (Figure 10.23a) trigging the self-healing
process. When the pH returns to the initial value, the shell is closed and the release of the
inhibitor stops. The SVET maps have shown that the highest protection was provided by the
container-loaded sol-gel film. The effect of very low corrosion in the case of container-loaded
films could be explained through the additional and very important characteristics of self-
healing. During the corrosion process the pH shifts to the alkaline region. It was shown in
Figure 10.22d that in alkaline pH the release of a loaded inhibitor takes place and, conse-
quently, the inhibitor heals damaged areas, pH returns to neutral, and the polyelectrolyte
shell closes until a new corrosion attack.
The photocatalytic activity inherent in some semiconductors which could be a core of
light sensitive containers (TiO2, TiO2:In2O3 composite, etc.) opens up fresh opportunities
to exert remote control over corrosion protection efficiency under ultraviolet (UV) irra-
diation [170]. The local change in pH at the semiconductor surface under UV irradiation
leads to conformational transitions in the polyelectrolyte shells that switch them into the
opened state. The sensitisation of containers to near-IR LASER irridation can be attained
with the use of metal and semiconductor particles absorbing at long wavelengths. In this
case the container opening will be due to the conformational transitions of thermal nature
occurring in the polyelectrolyte shell under irradiation. These approaches permit to exert
effective remote control over release properties of immobilised nanocontainers and to
ensure rapid release (much faster than in response to the chemical stimuli) of the chemical
species encapsulated within the containers.
Halloysite is an economically viable raw material that can be mined from the correspon-
ding deposit as a raw mineral [171]. As for most natural materials, the size of halloysite parti-
cle varies within 1 to 15 μm of length and 10 to 100 nm of inner diameter depending on the
deposits. Embedding of the corrosion inhibitor (for example, benzotriazole) inside the inner

Figure 10.25 : Images of scratched copper strips painted with oil-based blue paint
(a) containing halloysite nanotubes loaded with benzotriazole and (b) without these tubes, after
exposure to a corrosive environment for 10 days. c) Illustration of stopper formation at halloysite tube
endings by interaction of leaking benzotriazole with Cu(II) ions. Source: American Chemical Society
volume of the halloysite G nanotubes was performed according to the adapted procedure
described by Price et al. [172]. Benzotriazole molecules have good solubility in water, so pure
benzotriazole-filled halloysite can be applied directly in self-healing anticorrosion coatings,
however spontaneous leakage and uncontrolled release of embedded benzotriazole is possi-
ble (Figure 10.24). To attain controlled release properties in the halloysite nanotubes, their
surface could be modified by LbL deposition of polyelectrolyte bilayers [173] (Figure 10.24),
so the openings at the edges became blocked with polyelectrolytes. In this work the use of
different polyelectrolyte composition, was suggested, see [174]: benzotriazole-loaded hallo-
ysite G coated with (poly(diallyl dimethylammonium chloride)/(PDADMAC)/poly(styrene
sulphonate)/(PSS))4 layers, benzotriazole-loaded halloysite G coated with ((poly(allylamine
hydrochloride) (PAH)/PSS)4 layers, and benzotriazole-loaded halloysite G coated with (PAH/
poly(methacrylic acid) (PMA))4 layers. The pH-dependency of benzotriazole release from
halloysite nanocontainers is depicted in Figure 10.24. The increase of the release rate both
at low and high pH value is observed for all polyelectrolyte shells. Controllable release of
benzotriazole from halloysite nanotubes could also be achieved by the formation of metal-
benzotriazole complex caps (stopper) at halloysite tube endings by the interaction of leaking
benzotriazole and metal ions from the bulk solution [175].
This suggested method requires only a short rinsing of benzotriazole-loaded halloysite
nanotubes with an aqueous solution containing metal ions. In Figure 10.25, the formation
of stoppers at halloysite tube openings is demonstrated (using Cu(II) ions). The complex of
copper ions and benzotriazole has been studied thoroughly by various authors and described
in the review by Cease et al. [176]. Benzotriazole forms stable 2D complexes with most of the
transition metals, and Cu(II), Fe(II), Fe(III), and Co(II) salts were used for stopper formation.
Benzotriazole release characteristics were studied in detail, with the formation of stoppers
with Cu(II) ions providing the best release control. The decrease in the benzotriazole release
rate depends on a number of parameters, such as the chemistry and morphology of halloy-
site samples, the concentration and type of the metal ion, and the concentration of benzotri-
azole available at tube openings. One of the important parameters influencing benzotriazole
release rates is the concentrations metal ions that are used for the formation of metal-ben-
zotriazole stoppers. This is an indication that the efficiency of the encapsulation strongly

depends on the concentration of the metal ions used for the formation of stoppers. Another
important factor that influences the benzotriazole release rate is the concentration of benzo-
triazole at the tube endings available for the formation of metal-benzotriazole films. This can
be controlled by washing loaded nanotubes with deionised water after loading them with
benzotriazole and prior to processing them with metal ions. The corrosion inhibition effici-
ency of halloysite nanocontainers for aluminium and copper samples was demonstrated by
monitoring the localised corrosion current density on scratches; it could also be determined
visually by the exposure of a scratched metal sample to a highly corrosive environment
(Figure 10.25) which showed a significant reduction in the metal corrosion rate.
Thus, to gain a solid fundamental knowledge on these “smart” release systems and inherent
prompt feedback effects is an important task. One important concept is to utilise nanoscale
reservoirs allowing a uniform distribution of the inhibitor across the coating. For this reason, the
nano-entrapment of active species is an indispensable issue. Moreover the release of the chemi-
cal agents from the containers can be trigged employing different external stimuli including:
• pH changes due to corrosion reaction and reactions of hydrolysis
• pH changes and changes in the ionic strength resulting from treatment of the coating
with corresponding solutions
• electrochemical switching (when the conducting polymer/polyelectrolyte composite is
used as the host for capsules);
• photocatalytic degradation of capsule shells under irridation at corresponding
wavelength.
• For the construction of containers the following tasks should always be taken into
account:
• entrapment of inhibitors with different nano-containers (polyelectrolyte, nanotubes, etc.)
• tailoring of nanocontainers for specific triggers
• uniform incorporation of nanoreservoirs into coatings
• study of controllable release of active species encapsulated inside nanocontainers by
changing pH, ionic strength, compound modeling agents (chemical and inhibitors
contaminants), electrochemical potential of the coating
• optimisation of corrosion protection and self-healing properties of novel coatings;
• investigation of container-loaded coatings to envisage their important practical applica-
tion for determination and destruction of chemical compounds in water and in air.
10.4 Conclusions
This review comes timely since there have been many developments in recent years to
fabricate new types of nanocomposite coatings and thin films for corrosion protection that
are responsive to environmental stimuli. The future step is to proceed towards a higher
level of intelligence to construct the response in a way that it affects the stimulus in turn.
While conceptual solutions do exist, still many technical and economical issues must be
solved to arrive at a practical level. Predominantly, the stimuli have been of mechanical
and electrochemical nature, but in future one may envision other stimuli, e.g. friction. The
release of active materials (e.g., corrosion inhibitors) only occurs when triggered by envi-
ronmental (corrosion) processes or defects in the coating integrity, which prevents a leakage
of the active component from the coating and increases the coating durability. Moreover,
the active coating might comprise several active functionalities (e.g., antibacterial, anti-
corrosion and antistatic) when several types of nanocomposite materials are incorporated
simultaneously into a coating matrix. This will surely be a matter of intense future research,
which, as a result, may lead to highly sophisticated surfaces. However, one should also be
aware that feedback loops are ubiquitous in nature and technology, and mostly they are not

Literature 193
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composite coatings. However, there is no doubt that nanomaterials in coatings will create
countless new opportunities in research and also in technologies for the fabrication of a new
generation of active composite films.
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General informations 199
11 Standards and guidelines

Jörg Sander
Like every industrial activity, the coating of metallic work pieces is subject to numerous
standards, norms, guidelines and regulations. These have been primarily developed to
ensure a common agreement on reliable quality of operational practice and performance.
However, gaining importance with the awareness of the protection of resources and welfare,
standards are also intended to create a binding framework for sustainable and responsible
manufacturing.
Standards and regulations that are relevant to quality and environment while treating and
coating metals in order to prevent corrosive decay, have been mentioned throughout the
book where appropriate. The following list provides a collection of these norms. It is not
intended to be complete. The reader is referred to standard literature, in particular to the
Handbook of Coating Technology by A. Goldschmidt and H.-J. Streitberger [1], as well as the
book on Coil Coating by B. Meuthen and A.-S. Jandel [2].
11.1 General information

• American Society for Testing and Materials (ASTM) International, W. Conshohocken PA,
USA (www.astm.org)
• Dept. of Defense, Defense Logistics Agency, Document Automation & Production Service,
Philadelphia PA, USA (www.dodssp.daps.dla.mil/...)
• European Aluminium Association (EAA), Brussels (www.eaa.net)
• European Coil Coating Association (ECCA), Brussels (www.prepaintedmetal.eu)
• European Committee for Iron and Steel Standardization (ECISS), Brussels (www.cen.eu/
cen/Sectors/Sectors/Materials/Pages/ECISS.aspx)
• European Committee for Standardization (CEN), Brussels (www.cen.eu)
• Deutsches Institut für Normung (DIN), Berlin (www.din.de)
• Gütegemeinschaft für die Beschichtung von Bauteilen (GSB International), Schwäb.
Gmünd (www.gsb-international.de)
• International Organization for Standardization (ISO), Geneva (www.iso.org)
11.2 General norms

Colour DIN EN 13523-3
Corrosivity classification ISO 12944-2
Designation of intensity, quantity, and size of defects EN ISO 4628
Patch test to assess coating compatibility ASTM 5064-95

ISBN 978-3-86630-805-3

11.2.1 Norms on mechanical testing of organically coated

metallic work pieces
Bending; coating elasticity, crack resistance (T-bend) DIN EN 13523-7
ASTM D-4145-83
Adhesive tape; substrate adhesion ditto, ASTM 3359-95
Coating thickness, magnetic and Eddy current methods DIN EN 13523-1
continuous measurement by β-back-scattering DIN EN ISO 3543
continuous measurement by thermography DIN EN 15042-2
Cross-hatch DIN EN ISO 2409
Erichsen dome test (Erichsen cupping) DIN EN 13523-6
Foil adhesion, protective foils DIN EN 13523-17
Hardness, pencil; scratch resistance DIN EN 13523-4
Buchholz; resistance to cuts DIN EN ISO 2815
Heat resistance; mechanical effect of ageing DIN EN 13523-13
Impact; cracking resistance to fast deformation DIN EN 13523-5
DIN EN ISO 6272
MEK Test; curing (cross-linking) and adhesion DIN EN 13523-11
Peel Tests, T Peel test ASTM D-1876-08
Pull-off Test DIN EN ISO 4624
11.2.2 Norms on corrosion testing of organically coated

metallic work pieces
Constant climate tests
Boiling, water soak EN 13523-9
Condensation EN ISO 6270-1 and 2,
pr EN 13523-26
Filiform EN ISO 4623-2,
EN ISO 4628-10, EN 3665
Humidity DIN 50017 KK,
pr EN 13523-25
Salt spray – neutral EN ISO 9227 NSS
(DIN 50021)
ASTM B117, EN 13523-8
Salt spray – acetic acid EN ISO 9227 AASS
Salt spray – copper acetate EN ISO 9227 CASS
Cyclic climate tests
Cyclic immersion test ISO 15710, EN 3212

General norms 201
Cyclic salt spray/humidity tests

- Automotive industry VDA 621-415
Renault ECC1 D172028
VW PV1210
Volvo VCS1027,149
- Prohesion test ASTM G85,A5
Humidity/temperature cycle tests DIN 50017 KFW
pr EN 13523-25
Humidity in SO2 atmosphere DIN EN 13523-13
(DIN 50018)
Weathering tests VDA 612-430
Outdoor exposure
Outdoor exposure testing EN 13523-19
11.3 Selected European legislation on

environmental protection
ELV
Directive 2000/53/EC, End of Life Vehicles [3]
WEEE
Directive 2002/96/EC, Waste Electrical and Electronic Equipment [4]
COM/2008/0809 final - COD 2008/0240 [5]
COM/2008/0810 final - COD 2008/0241 [6]
RoHS
Directive 2002/95/EC, Restriction of Hazardous Substances [7]
REACH
Regulation (EC) No 1907/2006, Registration, Evaluation, Authorisation and Restriction of
Chemicals [8]
Surfactants, etc.
Regulation (EC) No 1272/2008, Classification, labelling and packaging of substances [9]
Commission Decision 2007/506/EC, Eco-label – Aerobic Biodegradability of Surfactants [10]
Volatile organic compounds, etc.
Directive 2008/1/EC, Integrated pollution prevention and control (IPPC) [11]
Council Directive 1999/13/EC, Volatile Organic Compounds [12]

11.4 Literature
[3] anon., Directive 2000/53/EC of the European Parliament and of the Council of 18 September 2000 on end-of
life vehicles, Official Journal of the European Union, 2000, L 269, pp. 34 ff; eur-lex.europa.eu/…
[4] anon., Directive 2002/96/EC of the European Parliament and of the Council of 27 January 2003 on waste
electrical and electronic equipment (WEEE) - Joint declaration of the European Parliament, the Council and
the Commission relating to Article 9, Official Journal of the European Union, 2003, L 37, pp. 24 ff; eur-lex.
europa.eu/...
[5] anon., COM/2008/0809 final - COD 2008/0240, Proposal for a Directive of the European Parliament and of
the Council on the restriction of the use of certain hazardous substances in electrical and electronic
equipment (recast) {SEC(2008) 2930} {SEC(2008) 2931}; eur-lex.europa.eu/...
[6] anon., COM/2008/0810 final - COD 2008/0241, Proposal for a DIRECTIVE OF THE EUROPEAN PARLIA-
MENT AND OF THE COUNCIL on waste electrical and electronic equipment (WEEE) (Recast){SEC(2008)
2933} {SEC(2008) 2934}; eur-lex.europa.eu/...
[7] anon., Directive 2002/95/EC of the European Parliament and of the Council of 27 January 2003 on the
restriction of the use of certain hazardous substances in electrical and electronic equipment, Official Journal
of the European Union, 2003, L 37, pp. 19 ff; eur-lex.europa.eu/...
concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH), establishing
a European Chemicals Agency, amending Directive 1999/45/EC and repealing Council Regulation (EEC)
No 793/93 and Commission Regulation (EC) No 1488/94 as well as Council Directive 76/769/EEC and Com-
mission Directives 91/155/EEC, 93/67/EEC, 93/105/EC and 2000/21/EC, Official Journal of the European
Union 49, 2006, L 396; eur-lex.europa.eu/…
on classification, labelling and packaging of substances and mixtures, amending and repealing Directives
67/548/EEC and 1999/45/EC, and amending Regulation (EC) No 1907/2006, Chapter 4.1.2.9. Rapid
degradability of organic substances, Official Journal of the European Union L 353, 2008, pp. 1 ff; eur-lex.
europa.eu/…
[10] anon., 2007/506/EC: Commission Decision of 21 June 2007 establishing the ecological criteria for the award
of the Community eco-label to soaps, shampoos and hair conditioners (notified under document number
C(2007) 3127, Appendix “Environmental Criteria”, Part 3.a) Aerobic Biodegradability of Surfactants, Official
Journal of the European Union L 186 , 2007, pp. 36 ff; eur-lex.europa.eu/…
[11] anon., Directive 2008/1/EC of the European Parliament and of the Council of 15 January 2008 concerning
integrated pollution prevention and control (Codified version) (1), Official Journal of the European Union 51,
2008, L 24; eur-lex.europa.eu/…
[12] anon., Council Directive 1999/13/EC of 11 March 1999 on the limitation of emissions of volatile organic
compounds due to the use of organic solvents in certain activities and installations, Official Journal of the
European Union 42, 1999, L 85; eur-lex.europa.eu/…

Authors 203
Authors
Dr. Jörg Sander, born 1958, obtained his Doctor’s degree in chemistry at the University of
Münster, Germany. 1987 he joined the Henkel Group, where he dealt with process chemicals
for the surface technology of metals from both a technical and a commercial perspective for
more than 20 years. Serving the target markets of steel and aluminium strip making and
finishing, the production of beverage cans and the wire and extrusion industry, he managed
teams in the research, product development, sales, and marketing functions. Between 1996
and 2009 he was Official Delegate for the Henkel Group to the European Coil Coating Asso-
ciation (ECCA), where he chaired the Appliance Task Group and related marketing project
teams. Currently, he is working as industry consultant and free scientific writer.
Dr. Lars Kirmaier was born in Berlin in 1970. He studied Chemistry in Oldenburg/Ger-
many and completed his dissertation about highly-reactive silicon intermediates in 1998.
After further education in marketing and management he joined the R&D department of a
leading German paint company and gained hands-on experience in solvent-free and high-
solids polyurethane and epoxy resin applications. He is now with Heubach GmbH since
January 2004 as laboratory manager for anticorrosive pigments. Apart from his research
work he lectures on corrosion and corrosion prevention technology.
Mircea Manea was born in Bucharest, Romania. He graduated from the Polytechnic Insti-
tute of Bucharest 1976 in the field of Chemistry and Technology of Monomers and Polymers.
He occupied several positions in the R&D department for coating binders, and later was
appointed as resin production manager. In 1991 he entered the R&D of Beckers Acroma AB,
Sweden until 1995 and later as laboratory and technical manager for Wedevåg Färg AB, Swe-
den and Wedevåg-Hesse Coatings AB. In 1998, he moved to Perstorp Specialty Chemicals
AB, Sweden as Senior R&D Associate until 2007. He is presently acting as consultant for
the PropanRaya Group, Indonesia and South East Asia. Mircea Manea has been employed as
Associate Professor at the Institute of Chemistry in Bucharest between 1978 and 1987, lectu-
ring in the field of general industrial chemistry. Since 2003 he is member of the EU expert
panel for research activities and growth program (Six and Seventh Framework Program).
Dr. Dmitry G. Shchukin is a group leader at the Max Planck Institute of Colloids and
Interfaces, Potsdam, Germany. He obtained his PhD in Physical chemistry in 2002. He was
an Alexander von Humboldt fellow (2004 to 2005). From 2005 to 2007 he joined the Max
Planck Institute of Colloids and Interfaces. He was awarded the NanoFutur Price of the
German Ministry of Education and Research in 2007. His main scientific interests concern
the fabrication of hollow nanocontainers and the development of feedback active coatings,
interfacial sonochemistry.
Dr. Ekaterina Skorb obtained her PhD in Physical chemistry in 2008. She was LG Chem
fellow (2006) at Belarusian State University and German Academic Exchange Service
(DAAD) until 2008. Currently, she works at Alexander von Humboldt University at the Max
Planck Institute of Colloids and Interfaces. Her main scientific interests concern the new
generation of active anticorrosion and antibacterial coatings with feedback properties as
well as the formation of metal films under ultrasonic excitation in solution.

204 Index
Index
A aqueous dispersions 99
aqueous pretreatment 144, 146, 150
accelerated corrosion test 113, 124, 127, 130, 134, 144 architecture 17, 19, 113, 118, 123, 143
acetic acid 127 aromatic polyester polyol 123
acetic acid salt spray 119 atom 15, 16, 121
acid rain 119, 120, 129 atomic force microscopy, AFM 112, 122
acrylate 21, 121 automobile, automotive 116, 117, 127, 129, 135, 146, 156
acrylic 113
acrylic melamine 113 B
acrylic resin 53, 118
active anion 18 backbone chemistry 104
active pigment 73, 119 backing coat 110
addition of halogens 45 band model 16
adhesion 18, 19, 21, 123, 127, 129, 133, 139, 140, 147, barium metaborate 83
155 barrier effect 16, 18
adhesive bonding 117 barrier pigments 73, 85
advancement processes 49 barrier properties 47
AFM, atomic force microscopy 112 basecoat 20
aged coating 155 basic catalysis 50
aircraft 80, 111, 128, 129, 143, 146 bauxite 138
alcohol 121 bending 110, 129, 137
aldehyde 123 benefits 55
alkali 17, 18, 132, 139, 140 benzyl alcohol 157
alkaline cleaner, alkaline cleaning 117, 124, 146, 147, beverage can 111
157 binder 38, 129, 133, 155, 156
alkaline passivation 140, 141 bioacrylic monomers 53
alkalinity 17, 18, 147 biopolymers 159, 173
alkali silicates 63 bisphenol A 48, 50
alkoxysilanes 66 bis-(triethoxysilyl) ethane, BTSE 146
alkyd 39, 51, 155 black pigments 88
alloy, alloying 16, 18, 120, 123, 124, 132, 137–139, blister 127, 128, 129, 133, 134
141, 145, 147 blocking agents 100
alumina, aluminium oxide 122, 138, 143 blue pigments 88
aluminate 122 Bode plot 120, 132
aluminium, Al 16–18, 113, 117, 119, 123, 124, 127, boiling 119, 127, 129
129, 132, 138, 139, 141–150, 156 box section 18
aluminium flakes 86 brass 147
aluminium hydroxide 119, 138 bridge engineering 17
aluminium tripolyphosphate 80 brittle, brittleness 101, 104, 111, 112, 143
amino 100, 111 brush and scratch resistance 106
aminopropyl triethoxy silane, APS 146
ammonium hydrogen fluoride 142 C
ammonium zirconyl carbonate 99
anion, anionic 59, 120 calcium aluminate 149
annealing 124, 137 calcium borosilicate 83
anodic 123, 124 calcium-modified silicate 20
anodising 124, 143, 147 calcium phosphate 141
anticorrosion properties 159 canning 127, 142
appliance 19, 110, 127, 137, 141 capacitance 113, 120, 131, 132
aqueous cleaner 157 carbamides 121

Index 205
car body 18, 110, 116, 117, 141, 149 conducting polymer, conductive polymer 20, 159, 166
carbonate 17, 89, 137, 138 conductive pigment 116
carbon dioxide 17, 19, 121 constant climate 119, 127, 128, 129
carbon steel 137 continuous processes 66
carbonyl compound 121, 123 conversion coating 16, 20, 21, 118, 140–144, 156
carboxylate 100 copolymerisation 46
carcinogenic 148 copper sulphate 127
car component 156 coprecipitate 119
car manufacture 20, 137, 141 corrosion inhibitor 162, 165, 172, 189, 190
casting 137, 139 corrosion protection primer, CPP 18, 110, 116, 156, 157
cathode, cathodic 18, 115, 122, 132, 133 corrosion resistance 16, 18, 21, 106, 127, 128, 138–144
cathodic electro-dip primer 117, 122 CPP, corrosion protection primer 18, 116–118, 157
cathodic protection 17, 18, 156 creepage 114, 127, 128, 140
cationic 59 cross hatch 111, 112
cationic processes 104 cross-linking 19, 21, 101, 121, 146, 156
cationic UV coating 105 crown cork 110
caustic soda 140 cryolite 138
cavity sealing 116 cupping 118
cementation 74, 87 curing of alkyds by condensation 43
cerate 146 curing of alkyl silicates 68
chalking 120, 127 current 130–132, 143
chemical cross-linking 100 current density 17, 132
chemical resistance 19, 21, 99, 100, 127, 155 cut edge 17, 127, 132
chemical vapour deposition, CVD 146 cutting 110
chlorate 141 cyclic carbonate groups 60
chloride 17, 20, 73, 128 cyclic climate 127, 129
chlorinated rubber 46 cyclic corrosion, cyclic corrosion test 114, 117
chromate, chromating 18, 20, 99, 113, 114, 118, 119, cyclic terpenes 44
124, 140–144, 147-149, 156 cyclisation 40
chromate pigments 74 cycloaddition 57
chromic acid 142, 143 cyclorubber 45
chromiting 143 cyclovoltammetry 131
chromium chromate 142
chromium-free 20, 113, 114, 116, 118, 124, 140–149 D
chromium phosphate 124
chromous 142 decavanadate 120
chromous nitrate 143 decay of alkyd resins 41
chromous oxide 147 decomposition 121
chromous oxy-hydroxide 118 deep-drawing 112, 137
chromous phosphate 142, 150 deformation 120
chromous sulphate 143 degradation 19, 120, 123, 127, 131, 132
cladding 135, 137, 143, 144 deicing salts 120
clay 19, 138 deionised water, DI 129, 149
cleaner, cleaning 111, 139, 141, 147, 149, 157 delamination 20, 112, 115, 118, 122, 130, 133, 134
clearcoat 20, 113, 114, 115 di- and tetrafunctional siloxanes 69
cobalt amine 146 dichromate 20
coil coating 19, 80, 101, 105–107, 110, 113, 118, 140, dielectric 19, 113, 131
143–147, 150 diffusion 16, 19, 21, 122, 134
coin scratch 111 difunctional siloxane 69
cold-rolled steel 117, 119, 137, 140–145 diisocyanate 123, 156
colorant 127 dimethyl formamide 110
complexant 140, 143 discoloration 101, 106, 127, 147
complex fluoride 142 domestic cleaner 127
condensation 40, 118, 123, 127, 129, 155 double bonds 57
conducting band 16 drilling 110

206 Index
dripping edge 113 filler 20, 156

dry ice 156 film forming agent 38
dual cure systems 104 film forming mechanism 40
duroplastic 101, 112, 123 film forming temperature 99
dye 127, 143 final parameters 41
fingerprint resistance 147
E flange, flanging 18, 110
flash rust 155, 156
ε-caprolactam 101 flexibility 19, 21, 155
EB curing 105 Florida test 135
economic 102 fluoride 142, 147, 148
EIS, electrochemical impedance spectroscopy 113, fluorinated polymer 156
118–122, 131, 132 food can 110, 111
elasticity 112, 121 foodstuff 127
electrical resistance, resistivity 18, 131 formic acid 157
electroactive conducting polymers frame profile 143
ECP 85 furniture 137
electrochemical 122, 124
electrochemical corrosion cell 72 G
electrochemical potential 15, 17, 20, 124, 130, 131, 137
electrochemical process 15 Galfan 113, 120, 132, 138, 141
electrodeposition 53 Galvalume 120, 138, 141
electrode potential 17 galvanised steel 113, 120–123, 127, 129, 132, 138,
electro-dip primer 18, 129, 141, 146 142–144, 150
electro-galvanised 114, 116, 117, 134, 138, 141 galvanising 16, 17, 137, 145, 147
electrolyte 16–21, 112, 113, 120, 122, 131–133, 138, 143 garage door 143
electromagnetic spectrum 102 German Automobile Association, VDA 118, 129
electromotive series of metals 72 gibbsite 138
electron 15–17, 21, 122, 130, 131 glass transition temperature, Tg 19, 112
electron beam (EB) 101 gloss 21, 109, 120, 127, 140
electro-sheet 137 graphite 116
ELV, End of Life Vehicles Directive 148 green chromate 142, 150
energy saving 101 green pigments 88
environmental efficiency 102
epichlorohydrine 48, 50 H
epoxidated oils 51
epoxy amine 113, 134 haematite 137
epoxy, epoxies 19, 21, 47, 111, 116, 119–121, 124, 156 halloysite 187, 190
epoxy-polyamine 121 hang-on part 116
epoxy/polyester 143 hardness 99
equivalent circuit 131 heavy machinery 17
Erichsen 111, 119, 120 hem flanging 117
ester 121, 123 hexafluoro silicic acid 142
ether 100, 121 hexafluoro titanate 147
ethoxysilanes 67 hexafluoro titanic acid 142
EU Directive 148 hexafluoro zirconate 124
European Coil Coating Association, ECCA 135 honing 110
extender pigments 89 hopeite 141
hot-dip galvanised steel 116, 119, 132, 138, 140, 141
F humidity 127–129, 133–135, 155, 156
hybrid anticorrosive inhibitors 84
façade 113 hydrocarbon 146
fatty acid chain, decay 42 hydrochloric acid, hydrogen chloride 121, 123, 128
ferrate 18 hydrofluoric acid 139
filiform corrosion, FFC 123, 124, 128, 129 hydrogen bridge bond 99, 111, 122

Index 207
hydrogen peroxide 147 malonic acid 101

hydrolysis 68, 120–122 mandrel 111
hydrolytical decay 42 manganate 18
hydroperoxide 121 manufacturing 53
hydrotalcite 17, 19, 20, 119 manufacturing of acrylic resins 54
hydrothermal sealing 123 manufacturing processes 41
hydrothermal stress 110, 121 marine 19
hydroxide 17 mechanical cleaning 137, 156
hydroxy chloride 17 mechanical hardness 101
hydroxyl amine 141 mechanical resistance 21, 99
hydroxy silane 146 medium oil 51
mercapto 111
I metal/coating interface 15, 131
metallic state 15
immersion 127, 129, 140–142, 149, 150 metal soap 122
impact, impact test 110, 112, 118–120 metal working 137
induction 140 metasilicate 139
insertion 57 metavanadate 119
intercoat adhesion 109 methyl ethyl ketone 110
interstice 19, 99, 131 mica 90
intramolecular cyclisation 45 micaceous iron oxide 21, 73, 85, 156
ion exchange 120 microcapsules 184, 185
ion exchange pigments 84 Mil Spec 143
IR, infrared 118, 130, 140, 156 mixed-metal construction 117
iron, Fe 17, 137, 140, 141, 156 modification of epoxy esters 52
iron oxide 122, 137, 156 modified orthophosphates 78, 81
iron phosphate, iron phosphating 140–143, 146, 156 modified polyphosphates 80
iron phosphide 83 moisture 104
iron tannate 156 molybdate 18, 20, 83, 141
isocyanate 100, 156 monofunctional siloxanes 68
isocyanate reaction 56 mould 120
isocyanic acid 55 multi-functional acrylates 104
mutagenic 148
K
kaolin 90 N
ketone 123
nano 19, 143
nanocomposites 177, 180
L nanocontainers 159, 173, 178, 183–192
lactams 101 nanomaterials 177
lactones 101 native oxide 17, 18, 122, 132
layer-by-layer, LBL 163 natural rubber 44
layered double hydroxides 177 NCO free polyurethanes 59
lead pigments 74 nitrate 147
lighting 137 nitric acid 147
lime 137, 148, 149 nitrite 141
lithium silicates 63 nitro compound 141
long oil 51 noble metal 131, 139
lubrication 147 non-ferrous metal 147
non-ionic type 59
M non-resistant coatings 101
no-rinse 113, 141, 144, 150
magnesium phosphate 141 Norrish Type I reaction 103
magnetite 137 N-substituted carbamic acid 121
maleic anhydride modified alkyd resins 40 Nyquist plot 132

208 Index
O polyether amine 61
polymer 19, 21, 38, 99, 112, 122, 123, 144, 145
offshore 155 polyols 43
organically modified zinc phosphate 79 polyphosphates 80
organic corrosion inhibitors 80 polypyrrole 167, 168
organic film former 38 polysiloxane 68, 146, 156
organic inhibitors 81 polyurea 61
organosilanes 65 polyurethane 19, 21, 61, 111, 116, 121, 124, 156
orthophosphates 80 polyvinyl chloride, PVC 21, 111, 113, 121
outdoor exposure 124, 134 polyvinylidene difluoride, PVDF 124
oxazoline groups 60 post-rinse 140, 141
oxidation 72, 121 potassium silicate 63
oxidative drying 43 powder paint, powder coating 17, 124, 143
oxide 122, 123 preprimed 110
oxidic ore 137 pretreatment 18, 109, 111–118, 123, 124, 132, 139–151
oxy chloride 17 primer 17–21, 109, 121, 123, 124, 139, 140, 147
oxygen, O, oxygen reduction 16–21, 103, 120–123, primer-pretreatment 118, 120, 147
134, 137, 156 profiling 110
oxy-hydroxide 132 prohesion 114, 129
protic 111
P protic compounds 100
punch-hole 113
paint stripper 157 PVC, polyvinyl chloride 21, 111
PAni, polyaniline 20 PVDF, polyvinylidene difluoride 124
passivation 16, 73
peel test 111, 113
Q
permanganate 18
phase angle plot 120 QUV-A 121
phenolic resin 123 QUV-B 118
phenol modified alkyd resins 40
phospho-molybdate 124, 146
R
phosphonate 146
phosphophyllite 141 radiation curing systems 101
phosphoric acid 141–143, 156 radical 123
photochemical 120 radical anion 123
photochemical resistance 127, 129 railway vehicles 111
photo-chemistry 101 Raman 130
photo electron spectroscopy, XPS 17, 144 raw materials 41
photoinitiator 102 REACH, registration, evaluation, authorisation and
pickling 124, 137, 139, 156 restriction of chemicals 142, 148
pipeline construction 155 red lead 74, 155
pitting 17 red-ox 15, 18, 130, 131, 133
plasma discharge lamps 107 red pigments 88
plasma vapour deposition, PVD 146 reduction 72
plastisol 21 relative humidity 113
polyacids 43 repair coating 155
polyacrylate 156 resin 38
polyalkylene 17 retortability 127
polyaniline, PAni 20, 170 rinsing 141, 145
polyaspartics 61, 63 RoHS, Regulation on Hazardous Substances 148
polyelectrolyte multilayers 163–165 roll-coater 118, 150, 151
polyepoxy backbone 51 roller shutter 143
polyester 21, 41, 111, 113, 116–124, 143, 144, 156 rolling 124, 137
polyester-melamine 121 roll profiling 137
polyester-urethane 121 roofing 135, 137, 143

Index 209
rust 137, 155, 156 steel 17, 20, 113, 117, 122, 127–129, 135, 137, 138,
rust converter 156 140–145, 150, 156
stone chipping 110, 111
S strontium chromate 20, 77, 120
substrate 15–21, 109, 116, 118, 122, 127, 129, 131, 133,
sacrificial anode 17 134, 137–149
sacrificial pigments 73, 86 substrate adhesion 47
salt spray 118–121, 127–129, 135, 143 sulfidic ore 137
SAM, self-assembling molecule, self-assembled sulphate 73, 89
monolayers 146, 159, 161, 163 sulphur dioxide 120, 129, 134
sanding 156 sulphuric acid 143, 147
saponification 121, 122 sun blinds 113
Scanning Kelvin Probe, SKP 114, 132, 133 supramolecular system 63
scanning vibrating electrode technique, SVET 132, surface tolerant coating 155
160, 179 surfactant 141
scratch resistance 139 swelling 19, 120, 122, 133
screw fastening 110 synergy 79, 80, 84
scribe 124, 127, 128 synthesis of polyaspartics 63
sealants 106
seam 18 T
seam sealing 116
self-healing 18, 159, 164, 178, 183–192 talc 89
self-polymerisation 50 tannic acid, tannin 156
semiconductor 16 T-bend 111, 114, 118, 120
shear test 111 temperature-sensitive substrates 101
shipbuilding 17, 110, 155 temperature, thermal resistance 129
short oil 51 tetraalkoxysilanes 65
shot-blasting, grit-blasting 156 tetraethyl orthosilicate 65, 67
shrinkage 101, 104 thermal decomposition, thermal destruction 120
silane 146 thermogravimetric analysis, TGA 119
silicas 89 thermoplastic 99
silicate 89, 137, 138 thermoplastic acrylic resins 55
silicone modified alkyd resins 40 thermosetting acrylic resins 55
siloxane 68, 70, 146 thiol 100
SKP, Scanning Kelvin Probe 114, 115, 121, 122, titanium dioxide 19, 87
132–134 titanium fluoro complex 113
slag 137 titanium phosphate 141
sodium bisulphite 148 topcoat 20, 21, 118, 121–124, 139, 140, 147
sodium chloride 114, 119, 127 toxic to reproduction 148
sodium dihydrogen phosphate 141 tree gum 120
sodium hydroxide 138 tri-cation phosphating 117, 141, 146
sodium silicates 63 trifunctional siloxanes 69
solarisation 134, 135 trigger 183, 187, 188, 189, 192
solar radiation 129 trivalent chromium 141, 142, 148
sol-gel 162, 179–182 tropical test 129
solvent 99, 100–102, 106, 107, 120, 147, 149, 155–157 tungstate 18
solvent cleaning 132, 157
spinel 140 U
spot welding 117
spray, spraying 140–142, 149, 150, 156, 157 ultra-high pressure water jet 155
spray-cell 150 ultrasound 160, 179, 193
spray pretreatment 113 ultraviolet, UV 21, 101, 120, 121, 127, 129, 134, 135, 156
stainless steel 137, 147, 150 under-curing 101
standard hydrogen electrode 130 urea 121
standard potential 115 urethane 121, 123

210 Index
urethane modified alkyd resins 40 wheel 127, 146

utility vehicles 111 white metal 147
UV equipment 107 wide spectrum anticorrosives 81
UV lamps 106 Williamson reaction 48
UV initiated decay 42 wollastonite 74, 90
UV photopolymerisation 102 wuestite 137
UV polymerisation 103
UV resistance 121 X
V XPS, photo electron spectroscopy 17
valence band 16 Y
vanadate 18, 20, 120
van-der-Waals force 111, 112 yellowing 101
VDA, German Automobile Association 114, 118, 129 yellow pigments 88
vehicle 38
V-groove panel 113 Z
vinylated alkyd resins 40
zeolite 20
vinylation 40
zinc aluminium phosphate 79
viscosity 99, 150
zinc, Zn 17, 18, 115, 116, 119, 124, 131, 132, 134, 135,
VOC, volatile organic compound 149
137, 138, 142, 145, 148, 150, 156
voltage 130, 131
zincate 122
zinc borate 83
W
zinc calcium phospho-molybdate 119
wash primer 156 zinc carbonate 137
waste water 144, 148, 149, 150 zinc chromate 119, 156
water 18–21, 99, 100, 101, 113, 121, 133, 134, 140, 144, zinc cyanamide 84
150, 155 zinc dust 74, 83, 86
waterborne 118, 150, 156 zinc flakes 86
waterborne alkali silicates 64 zinc hydroxide 119, 137
waterborne polysiloxanes 72 zinc hydroxyphosphite 82
water engineering 17, 110, 155 zinc oxide 16, 122, 137, 140
water resistance 127, 129, 155, 156 zinc phosphate, zinc phosphating 20, 77, 78, 119, 141,
water uptake 19, 113, 122, 133 143, 146, 156
weathering 118, 127, 137 zinc phosphating 141, 143
weathering resistance 129 zinc phospho-molybdate 79, 119
WEEE, Waste Electrical and Electronic Equipment zinc potassium chromate 77
Directive 148 zinc-rich primer 73, 83
welding 117 zinc tetrahydroxy chromate 77
wettability 147, 155 zirconium fluoro complex 113
wetting 19, 157 zirconium oxide 146

Buyers´ Guide 211
BUYERS´ GUIDE
Raw Materials Diamino resins

HUNTSMAN Advanced Materials
Tel. +41 61 299 1111
Binders [email protected]
www.huntsman.com/advanced_materials
Acrylic resins, modified
Evonik Röhm GmbH Dispersions
Visit our website:
www.evonik.com/degalan HUNTSMAN Advanced Materials
[email protected] Tel. +41 61 299 1111
[email protected]
Acrylic resins, multifunctional
Evonik Röhm GmbH Epoxy hardeners
Visit our website:
www.evonik.com/degalan CRODA Coatings & Polymers
[email protected] P.O. Box 2
2800 AA Gouda, NL
[email protected]
Acrylic resins, unspecified www.crodacoatingsandpolymers.com
DOW COATING MATERIALS
Kronberger Hang 4 HUNTSMAN Advanced Materials
D-65824 Schwalbach Tel. +41 61 299 1111
Tel. +49 6196 5660 [email protected]
Alkyd resins, Monomers
Epoxy phenolic resins
CRODA Coatings & Polymers
P.O. Box 2 HUNTSMAN Advanced Materials
2800 AA Gouda, NL Tel. +41 61 299 1111
[email protected] [email protected]
www.crodacoatingsandpolymers.com www.huntsman.com/advanced_materials
Amide resins Epoxy resins for powder coatings

HUNTSMAN Advanced Materials HUNTSMAN Advanced Materials
Tel. +41 61 299 1111 Tel. +41 61 299 1111
www.huntsman.com/advanced_materials www.huntsman.com/advanced_materials
Amino epoxy resins Epoxy resins, liquid

Tel. +41 61 299 1111 Tel. +41 61 299 1111
Amino resins Epoxy resins, modified

Tel. +41 61 299 1111 Tel. +41 61 299 1111

212 Buyers´ Guide
Epoxy resins, OH-functional Novolak resins

Tel. +41 61 299 1111 Tel. +41 61 299 1111
Epoxy resins, UV-curing Phenolic resins for powder coatings

Tel. +41 61 299 1111 Tel. +41 61 299 1111
Epoxy resins, water-based Phenolic resins, unspecified

Tel. +41 61 299 1111 Tel. +41 61 299 1111
Epoxy resins, unspecified Polyacrylates, non-crosslinking

DOW COATING MATERIALS Evonik Röhm GmbH
Kronberger Hang 4 Visit our website:
D-65824 Schwalbach www.evonik.com/degalan
Tel. +49 6196 5660 [email protected]
Tel. +41 61 299 1111 Polyacrylates, unspecified
[email protected]
www.huntsman.com/advanced_materials Evonik Röhm GmbH
Visit our website:
www.evonik.com/degalan
Epoxy resins, Monomers [email protected]
Tel. +41 61 299 1111
[email protected]
Polyamide resins, thermoplastic
www.huntsman.com/advanced_materials HUNTSMAN Advanced Materials
Tel. +41 61 299 1111
Fatty acids, saturated [email protected]
P.O. Box 2
2800 AA Gouda, NL
Polyamide resins, unspecified
[email protected] HUNTSMAN Advanced Materials
www.crodacoatingsandpolymers.com Tel. +41 61 299 1111
[email protected]
Fatty acids, unsaturated www.huntsman.com/advanced_materials
CRODA Coatings & Polymers Polyamines

P.O. Box 2
2800 AA Gouda, NL HUNTSMAN Advanced Materials
[email protected] Tel. +41 61 299 1111
www.crodacoatingsandpolymers.com [email protected]
Fatty acids, unspecified
Polyaminoamides
P.O. Box 2 HUNTSMAN Advanced Materials
2800 AA Gouda, NL Tel. +41 61 299 1111
www.crodacoatingsandpolymers.com www.huntsman.com/advanced_materials
Glycerin esters Polyesters, OH-functional

CRODA Coatings & Polymers CRODA Coatings & Polymers
P.O. Box 2 P.O. Box 2
2800 AA Gouda, NL 2800 AA Gouda, NL
www.crodacoatingsandpolymers.com www.crodacoatingsandpolymers.com

Buyers´ Guide 213
Printing ink resins Yellow pigments, inorganic

Evonik Röhm GmbH
Visit our website: Bismuth vanadate/
www.evonik.com/degalan molybdate pigments
[email protected]
Heubach GmbH
HUNTSMAN Advanced Materials Tel. +49 5326 52-0, Fax -213
Tel. +41 61 299 1111 [email protected]
[email protected] www.heubachcolor.de
Resins, UV-curing Chrome titanium yellow

Heubach GmbH
Triglycidyl isocyanurate (TGIC) Nickel titanium yellow

Heubach GmbH
Binders, unspecified Coloured pigments, organic

Evonik Röhm GmbH Blue pigments, organic
Visit our website:
www.evonik.com/degalan Indanthrene blue
[email protected]
Heubach GmbH
Red and orange pigments, organic
Colourants and Pigments Diketo pyrrolo pyrrole
pigments (DPP)
Coloured pigments, inorganic
Heubach GmbH
Blue pigments, inorganic Tel. +49 5326 52-0, Fax -213
[email protected]
www.heubachcolor.de
Cobalt blue
Heubach GmbH Isoindoline/Isoindolinone yellow
Tel. +49 5326 52-0, Fax -213
[email protected] pigments
www.heubachcolor.de Heubach GmbH
Tel. +49 5326 52-0, Fax -213
Green pigments, inorganic [email protected]
www.heubachcolor.de
Cobalt green (spinel green)

Functional pigments
Heubach GmbH
Tel. +49 5326 52-0, Fax -213 Anticorrosive pigments
[email protected]
www.heubachcolor.de Phosphate pigments
Heubach GmbH
Tel. +49 5326 52-0, Fax -213
[email protected]
www.heubachcolor.de

214 Buyers´ Guide
Anticorrosive pigments, Silica flour

unspecified SIBELCO N.V.
Quellinstraat 49, BE-2018 Antwerp
ECKART GmbH
www.sibelco.com
Guentersthal 4
[email protected]
91235 Hartenstein, Germany
T.+32 32236611,F. +32 32236735
[email protected]
www.eckart.net
Heubach GmbH
Silica sand
Tel. +49 5326 52-0, Fax -213 SIBELCO N.V.
[email protected] Quellinstraat 49, BE-2018 Antwerp
www.heubachcolor.de www.sibelco.com
[email protected]
T.+32 32236611,F. +32 32236735
Functional pigments,
unspecified Siliceous chalk
ECKART GmbH
HOFFMANN MINERAL GmbH
Guentersthal 4
Münchener Str. 75
91235 Hartenstein, Germany
86633 Neuburg, Germany
[email protected]
Phone: +49 8431 53-0
www.eckart.net
www.hoffmann-mineral.com
[email protected]
Fillers Fillers, unspecified

Cristobalite HOFFMANN MINERAL GmbH
Münchener Str. 75
SIBELCO N.V. 86633 Neuburg, Germany
Quellinstraat 49, BE-2018 Antwerp Phone: +49 8431 53-0
www.sibelco.com www.hoffmann-mineral.com
T.+32 32236611,F. +32 32236735
Feldspar Solvents
SIBELCO N.V.
Quellinstraat 49, BE-2018 Antwerp Solvents, unspecified
www.sibelco.com
[email protected]
Kronberger Hang 4
T.+32 32236611,F. +32 32236735
D-65824 Schwalbach
Tel. +49 6196 5660
Kaolin
SIBELCO N.V.
Quellinstraat 49, BE-2018 Antwerp Additives
www.sibelco.com
[email protected] Adhesion promoters
T.+32 32236611,F. +32 32236735
Tel. +41 61 299 1111
Silica [email protected]
Crosslinking additives
Tel. +41 61 299 1111
[email protected]
Emulsifying additives
P.O. Box 2
2800 AA Gouda, NL
[email protected]
www.crodacoatingsandpolymers.com

Buyers´ Guide 215
Surfactants
P.O. Box 2
2800 AA Gouda, NL
[email protected]
www.crodacoatingsandpolymers.com
Additives, unspecified
Kronberger Hang 4
D-65824 Schwalbach
Tel. +49 6196 5660
Laboratory and
Production
Testing and Measuring

Equipment
Salt spray testers
TQC GmbH
[email protected]
www.tqc.eu
Tel. +49 2103 25326-0
Testing and measuring systems,

unspecified
TQC GmbH
[email protected]
www.tqc.eu
Tel. +49 2103 25326-0

The Mission: To fully grasp, understand and successfully apply
the basics of anticorrosion coatings and novel concepts in
corrosion protection – from substrate pretreatment through
raw material selection and the protection mechanism, up to
self-healing, biopolymers and self-repairing polymer films. This
book explains and elaborates in some depth on the key princip-
les of anticorrosion coatings. Jörg Sander et al.
The Audience: Anybody involved in metal surfaces and/or
coatings engineering – suppliers, users, experts and students
alike. All those seeking a better understanding of the mutual
interactions and roles of organic corrosion protection coatings
The Value: This book brings together all the disciplines invol-
Jörg Sander et al. · Anticorrosive Coatings

ved in the creation and use of corrosion protection coatings
Ulrich Poth • Automotive Coatings Formulation

for metals. It presents the latest insights into the quality and
chemistry of surfaces, the proper way to prepare them by
conversion treatment, the function of resins and anticorrosion
pigments in paints, and novel concepts in corrosion protection.
As an added bonus, all the standards and directives mentioned
in the text are grouped together in their own chapter for a
better overview.
eBook
ISBN 978-3-86630-805-3

(European Coatings TECH FILES) Et Al. - Sander, Jörg - Anticorrosive Coatings Fundamental and New Concepts-Vincentz Network (2014)

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What is the book about?

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What audiences is the book aimed at?

What audiences is the book aimed at?

European Coatings Tech Files

The Mission: To fully grasp, understand and successfully apply

Jörg Sander et al. · Anticorrosive Coatings

Ulrich Poth • Automotive Coatings Formulation

Fundamentals and New Concepts

Jörg Sander et al.: Anticorrosive Coatings

Anticorrosion.indb 1 24.06.2010 14:16:28

Bibliographische Information der Deutschen Bibliothek

© 2010 Vincentz Network GmbH & Co. KG, Hanover

Please ask for our book catalogue

Layout: Vincentz Network, Hannover, Germany

Anticorrosion.indb 2 24.06.2010 14:16:28

Jörg Sander | Lars Kirmaier | Mircea Manea |

Fundamentals and New Concepts

Jörg Sander et al.: Anticorrosive Coatings

Anticorrosion.indb 3 24.06.2010 14:16:28

Continous Direct coatings industry.

Polymerisation Evonik Röhm GmbH

Process for future trends Germany

Anticorrosion.indb 4 24.06.2010 14:16:28

Velbert, Germany, April 2010

Jörg Sander et al.: Anticorrosive Coatings

Anticorrosion.indb 5 24.06.2010 14:16:28

2 Corrosion protection coatings.............................................................15

4 Organic coating materials...................................................................39

Jörg Sander et al.: Anticorrosive Coatings

Anticorrosion.indb 7 24.06.2010 14:16:31

4.2.3 Polyvinyl chloride..................................................................................................... 48

Anticorrosion.indb 8 24.06.2010 14:16:31

4.3.4 Colouring agent......................................................................................................... 89

6 Mechanism of protection and properties of organic coatings...........111

Anticorrosion.indb 9 24.06.2010 14:16:31

6.6.2.2 Anodic disbonding: filiform corrosion................................................................. 125

7 Testing of organic coatings..................................................................129

8 Chemical conversion treatment..........................................................139

Anticorrosion.indb 10 24.06.2010 14:16:31

8.2.10 Environmental considerations............................................................................... 149

9 Organic coatings for maintenance......................................................157

10 New corrosion protection concepts.....................................................161

11 Standards and guidelines....................................................................201

Anticorrosion.indb 11 24.06.2010 14:16:31

1.1 Why corrosion-protective coatings

Jörg Sander et al.: Anticorrosive Coatings

Anticorrosion.indb 13 24.06.2010 14:16:33

Anticorrosion.indb 14 24.06.2010 14:16:33

2 Corrosion protection coatings

2.1 Principles of function

Jörg Sander et al.: Anticorrosive Coatings

Anticorrosion.indb 15 24.06.2010 14:16:33

Equation 2.1 Zn → Zn2+ + 2 e - Anodic reaction

2.1.2 Metal oxide formation

Anticorrosion.indb 16 24.06.2010 14:16:33

One approach for a rationalisation

2.1.3 Cathodic protection

Anticorrosion.indb 17 24.06.2010 14:16:34

(3.8) H� C � O � �CO� � �CH� �� CH�

Equation 3.9:(3.9) � � ��r��u� ��ut�on� � �throughput� � ��r�g � out�