Hydrophobic Surface Sizing of Testliner: March 2019
Hydrophobic Surface Sizing of Testliner: March 2019
Hydrophobic Surface Sizing of Testliner: March 2019
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Misla Lagus
Faculty of Science and Engineering
Åbo Akademi University
2019
M. Lagus: Hydrophobic surface sizing of testliner II
The starch pickup was shown to depend on surface size solids content and base
paper porosity. The strength of the base paper was tied to the porosity, a more
porous base paper was weaker, as expected. Surface sized paper strength depended
on the base paper strength and the starch amount added.
Differences in sizing effect were witnessed both between different SSAs and
between different base papers. Wettability and starch absorption of base paper
affected the sizing effect. SSA particle size, SSA hydrophobicity, and poly
aluminum chloride (PAC) usage also affected the sizing effect.
Keywords: surface sizing, testliner, packaging, surface sizing agent, base paper
properties, hydrophobicity, sizing effect
Acknowledgements
First and foremost I would like to thank my assistant supervisor Kimmo Huhtala for
guiding the work, for listening to my ideas and suggestions, for motivating me to finish
writing the thesis, and most of all for always asking me to aim a little bit higher.
Sheryl Hildén, Kai Dahlskog and Jussi Salonen, thank you for our insightful
conversations and for sharing your industry knowledge.
I would like to thank Mia Ahokas for providing invaluable insight and advice during
the writing process.
Sanna Salonen, thanks for your innovative ideas and advice on laboratory practicalities.
I would like to thank Professor Martti Toivakka and Assistant Professor Mari Nurmi
for trusting me to complete this master’s thesis and for the final touches.
I am also grateful to everyone involved in sending base paper samples from the
participating paper mills and to Business Finland Oy (former TEKES) for providing
funding for the work inside the BIOBIND project.
M. Lagus: Hydrophobic surface sizing of testliner V
Table of contents
Abstract ...................................................................................................................... II
Acknowledgements .................................................................................................. IV
Introduction ................................................................................................................ 1
I LITERATURE REVIEW................................................................ 3
5. Materials............................................................................................................ 27
6. Methods ............................................................................................................. 29
6.1. Laboratory surface sizing method ............................................................ 29
6.1.1. Surface sizing equipment ..................................................................... 29
6.1.2. Experiment layout for testing the method ............................................ 30
6.1.3. Adjusting the laboratory surface sizing parameters ............................. 31
6.1.4. Surface sizing method used for hydrophobicity tests ........................... 32
6.2. Experiment layout for hydrophobization efficiency testing .................... 33
6.3. Paper analysis ........................................................................................... 33
6.3.1. Hydrophobicity ..................................................................................... 33
6.3.2. Structure and porosity .......................................................................... 34
6.3.3. Strength properties ............................................................................... 35
6.3.4. Other paper analyses ............................................................................ 35
6.4. Surface sizing agent (SSA) analysis ........................................................ 36
Conclusions ............................................................................................................... 54
References ................................................................................................................. 56
M. Lagus: Hydrophobic surface sizing of testliner VII
Figure 21. SCT for 40 kg/t starch sized base paper depends on base paper SCT ...... 49
Figure 22. DWR 12% starch correlation with sizing effect ....................................... 50
Figure 23. t(MAX) and sizing effect .......................................................................... 50
Figure 24. Parameter W and sizing effect .................................................................. 51
Figure 25. Sizing effect and SSA particle size, no PAC ............................................ 52
Figure 26. Sizing effect and SSA particle size, with PAC ......................................... 52
Figure 27. Sizing effect and SSA film water contact angle, no PAC ......................... 53
Figure 28. Sizing effect and SSA film water contact angle, with PAC ..................... 53
M. Lagus: Hydrophobic surface sizing of testliner IX
List of abbreviations
Introduction
Surface sizing, or applying starch and surface sizing agent (SSA) to the paper surface,
is an old process. The application on testliners is nevertheless complex because of the
large number of changing parameters in the hydrophobization. Previously, and in some
cases currently, hydrophobization of liners would be achieved through internal sizing,
i.e., adding the sizing agents to the wet end of the paper machine. However, especially
recycled testliner fibers can contain a wide range of paper chemistries that may
complicate the wet end internal sizing process, leading to deposits and costly
shutdowns. Surface sizing allows for a simplification of the wet end, prevention of the
uneconomical application of sizing agents to the inside of the paper is, and precise
fine-tuning of the surface properties (Bajpai, 2015; Zeng, 2013).
The exact mechanisms for hydrophobization in surface sizing are currently not well
understood, and laboratory studies seldom correlate well with practical on-machine
tests. Furthermore, there is no SSA that would provide the same level of
hydrophobization on all testliners. Through a better understanding of the surface sizing
process, wasteful SSA application amounts could be avoided, and SSA’s could be
developed more efficiently. A reliable laboratory method would facilitate SSA
development further and improve performance prediction possibilities.
materials are discussed from a literature point of view. The methods and materials used
in this study are presented in Chapters 5 and 6. The results of the thesis are covered in
Chapters 7 to 10, starting with observed differences in sizing effect and continuing to
the effect of surface sizing method, base paper and SSA parameters on sizing effect.
M. Lagus: Hydrophobic surface sizing of testliner 3
I LITERATURE REVIEW
The surface sizing operation is placed in the middle of the drying section of the paper
machine. A solution of starch, surface sizing agent and potential additives is applied
to the surface of the paper web, using either a pond type size press, metered film press,
or a novel method presented in the following chapter. The three surface size
ingredients and the application method can be varied, comprising the endless
individual configurations of each paper machine. Further, the pickup and efficiency of
the surface size is dependent on concentration (solids content), starch type,
temperature, viscosity, pH, sheet moisture, internal sizing and its development, and
machine speed (Hagiopol, Johnson, 2012).
The pond type size press, or flooded size press, is the older and nowadays less used of
the two most common surface size application methods. The paper web passes
between two rotating cylinders with a pond of surface size between them (Figure 1).
Wet pickup in the pond type size press is usually 30-50% of the paper weight, i.e., 300
to 500 kg/t. Typically, the pond size press is run at approximately 10% solids,
corresponding to 30-50 kg/t dry pickup (Holik, 2013; Maurer, 2009; Gess, Rodriguez,
2005).
M. Lagus: Hydrophobic surface sizing of testliner 4
Figure 1. Pond type size press (Andersson, Ridgway & Gane, 2013)
Surface size is transferred to the paper through wetting and capillary transfer in the
pond, and pressure penetration in the nip. Wetting and capillary transfer are mainly
controlled by the formation and chemical properties of the paper. The formation
includes porosity, basis weight, density, surface smoothness, moisture content, and
temperature. Increased porosity increases the pickup, and a rougher surface raises
pickup when more liquid is metered through the nip. Chemical properties depend on
the raw material and the presence and development of internal sizing. The internal
sizing influences the fiber surface energy, limiting the capillary transfer of surface size,
thus shifting the transfer mechanism towards pressure penetration. Without internal
sizing, the starch pickup is mostly dependent on pore wall wetting. The low solids
content in the pond type size press means that the paper is rewetted considerably, and
the absence of internal sizing may lead to web breaks especially at slower speeds
(Maurer, 2009; Gane, 2001; Holik, 2013; Andersson, Ridgway & Gane, 2013; Gess,
Rodriguez, 2005).
Other than the pickup, the holdout of surface size should be considered. The added
surface sizing agents are designed to make the surface of the paper hydrophobic, a
higher level of holdout is often desired to prevent the wasteful application of SSA to
the middle of the liner. However, surface size starch contributes to the strength of the
paper, and holdout should be optimized for both strength development and
hydrophobization depending on the requirements. The holdout is generally increased
by lower paper porosity and higher molecular weight or viscosity of starch (Maurer,
2009; Gess, Rodriguez, 2005).
Problems and defects in pond size presses can occur because of web detachment from
the rolls and pond instability. Upon leaving the size press nip, the paper web must be
pulled apart from one of the size press rolls. To prevent defects, the starch viscosity,
roll diameter, web tension and web take-off angle should be optimized. At high
machine speeds, high turbulence may occur in the pond causing instability, e.g.
splashing. Stability problems can be alleviated with foils dipped into the pond on each
side, and by using bigger roll diameters (Maurer, 2009; Gane, 2001; Holik, 2013).
Pond size press pigmentation has been studied showing promising results of decreased
drying energy demand, reduction in fluorescent whitening agent (FWA) addition
amount, and better holdout at the surface due to higher solids content. However,
metered size press pigmentation has been found more efficient for fiber reduction
(Wygant, Lucidi & Kendrick, 2009).
The metered film press is the other of the two most common surface size application
methods and is widely used today. It was developed to reduce the splashing and
rewetting problems with the pond-type size press. Instead of passing the paper through
a pond where starch is picked up, a set amount of starch is metered on an applicator
roll and pressed into the paper (Maurer, 2009; Lehtinen et al., 2000). There are two
widely used methods of starch metering which will be presented next.
M. Lagus: Hydrophobic surface sizing of testliner 6
Pond instability and splashing are common problems with the gate roll film press. They
can be controlled by running the metering roll at slow speeds, or by using higher solids
content and higher viscosity starches. The higher solids content, in turn, allows paper
webs of a higher moisture content to be sized without risk of web breakage, reducing
drying energy and time both before and after the film press. These advantages can
enable higher machine speeds, further increasing the machine efficiency (Maurer,
2009).
The method has the same advantages over pond type size presses as the gate roll film
press, i.e., the higher solids content of the starch allows a reduction in drying energy.
Solids contents up to 30% have been studied and shown to be runnable, giving a higher
holdout of starch, resulting in decreased paper porosity, decreased oil absorption,
decreased internal strength of paper, and increased surface strength and bending
stiffness. However, the effect of higher viscosity starch on the SSA efficiency has not
been evaluated (Lipponen, 2005).
Sources of problems with metered film presses are starch viscosity and film splitting
behavior. Low viscosity starch may lead to fluid spraying in the metering. In the film
splits between rolls and between roll and paper, misting and orange peel pattern can
occur. For the roll-paper split, the problem may be prevented by bringing the film-
splitting closer to the roll (Maurer, 2009).
Metered film press pigmentation has been studied with promising results. Fiber
content could be reduced in the final product for savings in fiber price, and the size
press could be used as a precoating device. However, adding pigments to the surface
size adds viscoelastic behavior to the “sizing color”, and the formulations need
optimized rheology and water retention for runnability (Gane, 2001; Wygant,
Kendrick & Walter, 2008).
M. Lagus: Hydrophobic surface sizing of testliner 8
New methods for surface size application that have been introduced are calender water
boxes, spray application, and foam application. In the calender water boxes, the starch
is usually diluted and applied at a low level with lubricants. Surface strength of the
paper is increased, and fiber swelling after coating is limited (Maurer, 2009). Spray
application may become more important in the future, with possible benefits including
higher starch solids contents, no wearing parts and easy control of surface size amount
(Holik, 2013; Valmet, 2017). Adding foaming agents to the surface size and applying
it as a foam keeps the surface size efficiently on the surface of the paper. The
advantages could be lower coat weights needed and higher solids contents, but the
foaming agent may also hinder the performance of the SSA (Sievänen, 2010).
M. Lagus: Hydrophobic surface sizing of testliner 9
2. Surface size
The surface size applied to the paper consists of starch, surface sizing agent (SSA) and
potential additives. The SSA decreases water absorbency, the starch increases the
strength of the paper, and together they improve printability by controlling ink
penetration (Zeng, 2013). In this work, hydrophobization is the focus point. Strength
is, however, a far too important part of the surface sizing result to be ignored, and thus
the following chapter will cover both starch and surface sizing agents, other additives
will be introduced briefly.
2.1. Starch
Figure 3. Amylose and amylopectin chemical structure (modified from Holik, 2013)
M. Lagus: Hydrophobic surface sizing of testliner 10
In the paper machine, starch can be added to the wet end, sprayed on the forming wire,
and added as surface size. It is by weight the third most used material after cellulose
fibers and mineral pigments in papermaking and paper conversion (Maurer, 2009).
Spray starch
Spray starch is sometimes added to the paper web on the forming wire at addition
levels of up to 20% of the dry product. The starch is usually unmodified and uncooked;
it is assumed that cooking and gelling take place throughout the drying process.
Benefits of spray starch include retention where it is sprayed (surface or between
layers), improved bonding between layers, lower manufacturing costs, and increased
strength. However, when making recycled linerboard at high machine speeds the
starch may not have enough time to penetrate into the sheet and gelatinize, causing
plugged wires and accumulation of starch in discharges (Maurer, 2009; Holik, 2013;
Ryu, Lee, 2007).
vessels and loose fibers with hydrogen bonds, increasing the strength of the paper up
to 60%. Stiffness, dimensional stability, and air leak density are also improved. Native
starch is not suitable due to high viscosity and tendency to retrograde; the starch must
be modified or converted either by the supplier or at the paper mill before use (Zeng,
2013; Maurer, 2009; Holik, 2013).
Native starch is rarely used in surface sizing because of the high molecular weight and
corresponding high viscosity. It is either converted, modified, or both to control the
viscosity, charge and bonding ability. Starch is usually supplied dry in package or bulk
container to avoid transporting water. Dispersion and conversion are done on-site at
the paper mill. Common conversion methods include enzymatic conversion, thermal
conversion, thermos-chemical conversion and acid hydrolysis. Chemical modification
(usually oxidation, hydroxyethylation or cationization) can be done either at the
supplier or the paper mill (Holik, 2013; Gane, 2001; Maurer, 2009).
Dispersion
Dispersion is carried out by heating the starch during agitation for a set amount of time,
either continuously or in a batch process. The starch granules swell, and the semi-
crystalline structure breaks up, forming a gel-like network. Minimum requirements are
20 minutes at a temperature of 95 ºC, but granular fractions will persist in the starch
suspension. Jet cooking with pressurized steam at higher temperatures (120-140 ºC)
disperses most residues. Excess steam and pressurized release of starch can increase
dispersion efficiency further, lowering the viscosity. Jet cooking is especially popular
with pre-modified starches (Gess, Rodriguez, 2005; Maurer, 2009; Holik, 2013).
Conversion
Conversion lowers the molecular weight and viscosity of the starch to ease the
application. Thermal conversion happens during efficient thermal dispersion or jet
cooking, heat and shear disperse the starch for complete hydration and lower viscosity.
M. Lagus: Hydrophobic surface sizing of testliner 12
Acid hydrolyzed starch is depolymerized with acids, e.g. hydrochloric acid. The
method is inexpensive, but the resulting depolymerized starch has an unstable viscosity
and is sensitive to retrogradation, and therefore temperature and pH control is required
(Maurer, 2009).
2.1.3. Retrogradation
During cooling and storage, the semi-crystalline structure of starch may recover in a
process called retrogradation. Amylose aggregates form particles, while amylopectin
forms a gel where linear parts of the molecules align. The retrogradation of amylose
can start if dilute starch is kept at a temperature of 67-90 ºC, and amylopectin can start
thickening below 55 ºC. Retrogradation is facilitated by starch molecular weights
between 6500 and 160 000, slightly acidic pH (6.5), high amylose content,
destabilizing ions (for example aluminum and calcium), contamination, well-dispersed
starch and hydrolyzed starch (Maurer, 2009).
2.1.4. Modification
Oxidized starch has improved water holding, film formation, film strength, and film
integrity properties compared to native starch, giving the final paper high surface
strength and improved ink holdout. The new bulky carboxyl groups hinder
retrogradation sterically, reducing the gelatinization temperature. In surface sizing,
oxidized starches have been shown to penetrate deep in the paper structure and
decrease opacity (Gess, Rodriguez, 2005; Jonhed, 2006; Lee et al., 2002).
The anionic character of the starch influences the interaction with other papermaking
substances. Broke recycling brings the anionic starch to the wet end, where it prevents
pigment and cellulose agglomeration through efficient dispersion, and reduces
retention. This leads to anionic trash in the effluent water and increased chemical
oxygen demand (COD). To combat the retention problem, slightly oxidized starch, i.e.,
M. Lagus: Hydrophobic surface sizing of testliner 14
bleached starch, has been developed for surface sizing. Bleached starch is produced
with a low degree of oxidation (carboxyl content less than 0,3%) and partial
crosslinking. However, the dispersing properties of anionic starch still worsen
retention and, therefore, the use of anionic starch in surface sizing is generally
declining (Lee et al., 2002; Jonhed, 2006; Gess, Rodriguez, 2005; Maurer, 2009).
Cationic starch
Cationic starch is produced by a nucleophilic substitution reaction with tertiary or
quaternary amines. The reaction with tertiary amines requires acidic pH, but
quaternary amines work across acid to alkaline pH values. Hydroxyethylated cationic
starch is produced for specialty products (Maurer, 2009).
In surface sizing, cationic starch has been found to increase the holdout of the surface
size on the paper surface. The higher holdout, in turn, improves opacity, brightness,
print gloss, and ink print density (Shirazi et al., 2005; Lee et al., 2002).
The primary advantage of cationic starch over anionic and nonionic starch is improved
binding and retention ability. The cationic starch interacts with the anionic fibers
ionically, which produces stronger binding compared to hydrogen bonds. During
broke processing, the cationic starch binds fillers and fines, reducing the suspended
solids and COD of the wastewater significantly. Because of environmental regulations
and discharge limits, the use of cationic starch in surface sizing is rapidly growing (Lee
et al., 2002; Maurer, 2009; Jonhed, 2006).
M. Lagus: Hydrophobic surface sizing of testliner 15
The purpose of sizing is to make paper water resistant to some degree. In general, the
mechanism is to coat the hydrophilic fibers with hydrophobic sizing agents. The sizing
agents can be either amphipathic molecules, having one hydrophilic and one
hydrophobic part, or highly hydrophobic molecules. The sizing agents can be applied
to the paper either in internal sizing, in surface sizing, or in a combination of the two.
In internal sizing, the sizing agent is added to the paper stock at the wet end of the
paper machine, while surface sizing agents are added to the starch at the size press.
The sizing agents can be characterized according to application method (internal or
surface) and functioning principle (reactive or non-reactive). Reactive sizing agents
form a chemical or physical bond with the cellulose fibers during drying, characterized
by a developing hydrophobicity. Non-reactive sizing agents need a high level of
hydrophobicity to make the paper moisture resistant without the bond to the fibers, but
the hydrophobicity effect is instant (Holik, 2013; Hagiopol, Johnson, 2012).
The most important property for internal sizing agents is the retention. Otherwise, the
sizing agent will flow out with the effluents. Reactive internal sizing agents form a
bond with cellulose and are thus readily retained. Cationic non-reactive sizing agents
are attracted to the anionic fibers because of their charge, but anionic or non-ionic non-
reactive internal sizing agents need a retention aid. Other than retention, the
hydrophobic character, molecular weight, molecular orientation, glass-transition
temperature (Tg), paper surface friction and pH compatibility are all essential factors
for the hydrophobization process (Hagiopol, Johnson, 2012).
The three most popular internal sizing agents are all reactive: rosin, AKD (alkyl ketene
dimer) and ASA (alkenyl succinic anhydride) (Figure 4) (Hagiopol, Johnson, 2012).
M. Lagus: Hydrophobic surface sizing of testliner 16
Figure 4. Structure of internal sizing agents. From left to right: fortified rosin, AKD and ASA
(modified from Holik, 2013)
One of the oldest sizing agents, rosin is extracted from resin that occurs naturally in
trees. Extraction is carried out from the black liquor in the pulping process. Rosin
requires an acidic pH to be effective, limiting the use of calcium carbonate pigments
because of dissolution. Rosin is anionic and needs alum (aluminum sulfate, Al2(SO4)3)
to bind to the fibers. Later, rosin sizing agents have been modified, reacted further
(using either the double bond or the carboxyl group), and saponified to produce a range
of rosin-based sizing agents with increased hydrophobicity (e.g., fortified rosin)
(Hagiopol, Johnson, 2012; Zeng, 2013).
AKD and ASA were invented after rosin sizing for alkaline and neutral papermaking.
They quickly became popular because the pH allowed calcium carbonate pigment to
be used. AKD and ASA are highly reactive with cellulose fibers, but also with the
surrounding water, which can quickly “kill” the sizing agent through hydrolysis. AKD
creates sticky by-products in the hydrolysis reaction, lowering machine efficiency. The
reactive sizing agents are nonpolar, and thus need emulsifiers and stabilizers to be
water soluble (Figure 5). Emulsion stability issues are common, especially ASA
hydrolyzes fast and must be dispersed right before use. AKD size needs a high
temperature curing at drying and grade-dependent curing times to impart
hydrophobicity. ASA size is more reactive than AKD and does not require curing, but
elevated stock temperatures and higher pH increase efficiency (Hagiopol, Johnson,
2012; Holik, 2013; Zeng, 2013).
M. Lagus: Hydrophobic surface sizing of testliner 17
There are many other polymeric internal sizing agents, and new ones are being
researched continuously to combat the problems of dispersion stability, retention and
hydrolysis reactions. Common synthesis methods for non-reactive sizing agents are to
add hydrophobic tails or cationic charges to existing polymers. Reactive sizing agents
can be synthesized utilizing cellulose-reactive groups, for example, epoxy groups,
aziridines, carbamoyl chloride groups, succinic anhydride groups, and ketene dimer
groups (Hagiopol, Johnson, 2012; Gess, Rodriguez, 2005).
Surface sizing agents (SSA) are applied with the starch on the surface of paper. Thus,
wasteful application to the inside of the paper sheet is prevented. The paper machine
wet end chemistry is also simplified because of the exclusion of sizing agents. Surface
sizing agents are usually non-reactive, i.e., they do not participate in reactions that alter
their molecular structure when applied to the paper. To be effective, SSAs need a high
degree of hydrophobicity and a high coverage on the paper sheet. The hydrophobicity
needs to be balanced with hydrophilic character to enable the mixing of SSA with
starch, and thus the SSA particles are amphipathic (they contain one hydrophobic and
one hydrophilic part). Stabilizers are used to prevent agglomeration of the amphipathic
particles, and to prevent foaming of the surface size, both of which decrease coverage
on the paper (Hagiopol, Johnson, 2012; Holik, 2013).
M. Lagus: Hydrophobic surface sizing of testliner 18
The two main, widely used groups of polymeric SSA are styrene-maleic anhydride
copolymers (SMA) and styrene-acrylic ester copolymers (SAE) (Figure 6) (Hagiopol,
Johnson, 2012; Holik, 2013).
Figure 6. Structure of SMA (top) and SAE (bottom) (modified from Holik, 2013)
Other than SSA, prevalent additives in the surface size starch are preservatives for the
starch, promoters, defoamers, fillers, and pigments, FWAs, co-binders and other
functional additives, for example, to improve printability (Holik, 2013).
Promoters in surface sizing are usually aluminum compounds, e.g., poly aluminum
chloride (PAC). Promoters can be used with rosin sizing or ASA sizing to fixate the
molecules to the fibers, but SMA SSA hydrophobization performance has also been
reported to increase. Aluminum has a high cationic charge which gives it high affinity
toward the fibers, as well as the anionic sizing agents. Fines and fillers will also be
M. Lagus: Hydrophobic surface sizing of testliner 20
retained with aluminum, preventing SSA particles absorption only in the fillers and
fines (Holik, 2013).
Pigment addition to the size press has been shown to increase paper smoothness,
improve optical properties, increase density and stiffness, and improve printability.
The pigment can be used to replace some of the fiber in the paper, the size press can
act as a precoater, and FWA demand can be reduced (Wygant, Kendrick & Walter,
2008).
When pigments are added, the surface size solids content increases considerably, up
to 60%. A high pigment loading may require additional binders and rheology modifiers
in addition to starch to improve runnability (Maurer, 2009).
Fluorescent whitening agents (FWAs) are usually added at the size press to prevent
wasteful application in the bulk of the paper. The FWAs improve opacity and
whiteness of the paper (Holik, 2013).
M. Lagus: Hydrophobic surface sizing of testliner 21
The following chapter introduces testliners and the paper machines used to produce
liner in general.
3.1. Testliner
Testliners are produced in grammages of around 70-450 g/m2 globally (in Europe 70-
130 g/m2) with maximum machine speeds above 1500 m/min. The speeds have been
increased through improved designs to achieve high annual production for low basis
weight paper grades. The paper machines for liner production usually have one or two
layer gap formers or one to multi-ply Fourdriniers. The multi-layer design enables
production of white top liners or high-performance liners with kraft pulp additions in
the top layer and also works to decrease sheet two-sidedness (Holik, 2013).
Testliner paper grades are entirely based upon recycled, secondary fibers giving a
structure shown in Figure 7. The fibers are usually sourced from old corrugated
containers, but recycled newsprint and graphical paper may also occur. Fibers are
reused on average 3.5 times in Europe. (ERPC, 2016) For each reuse, the fiber
properties deteriorate, thereby making the paper weaker (Holik, 2013).
Recycled secondary fibers are not as absorbent as virgin fibers. Fiber treatment, e.g.,
refining and sorting, is the primary way to increase the absorbency of the paper for
more efficient starch pickup in the paper. Internal sizing will also impact how the
surface size penetrates the paper or stays at the surface (Holik, 2013).
More fines in paper furnish increase the density of the paper and have an impact on
porosity. Fines naturally fill up pores as well as pull fibers closer together decreasing
the thickness of the sheet. Fibrils contain a tenfold surface area compared to flake-like
fines. The presence of fines on the paper surface can be significant for SSA
performance (Sirviö, Nurminen, 2004).
Formation
Different wire configurations impact the final paper structure, which further will have
an impact on surface size penetration and performance. For testliners, standard
configurations are the Fourdrinier, the gap former and the hybrid former. The
Fourdrinier is a long planar wire where almost all dewatering happens on the bottom
side, leading to a pronouncedly two-sided paper with higher compaction of fibers on
the wire side, leaving fines and filler at the top. However, shoeboxes can disturb this
two-sidedness with centrifugal force. A gap former wire means that the fiber
suspension is a jet delivered between two wires and the dewatering is equal to both
sides. The paper will have high symmetry with fillers and fines in the middle. However,
pressure pulses can be used to mix the distribution. A hybrid former is a Fourdrinier
wire with a second wire loop on top. The two wires are adjoined after some dewatering
M. Lagus: Hydrophobic surface sizing of testliner 24
has already taken place before the press section (Figure 8). This configuration gives
higher Z-direction symmetry than the Fourdrinier and also increases the drainage
efficiency (Forsström, 2003; Holik, 2013).
Dryers evaporate the rest of the water by heat, and after this, the surface size is usually
applied to the paper web. Coating takes place after surface sizing if it is required, and
finally the paper may be calendered to increase its smoothness (Holik, 2013).
M. Lagus: Hydrophobic surface sizing of testliner 25
The goal of hydrophobic surface sizing is to increase the water repellence of the paper
surface, i.e. to control water interaction with the paper surface. The interaction depends
on the fiber surface chemistry, or interfacial energies (γ), and on the paper
microstructure (Holik, 2013). Paper microstructure is often modelled as a collection of
capillaries, although in reality the situation is far more complex.
Droplet contact angles (θ) indicate whether the paper is easily wettable (θ < 90º,
cos θ > 0) or liquid repellent (θ > 90º, cos θ < 0). The contact angle is a result of
interfacial energies according to the Young’s equation:
𝛾𝑝𝑎𝑝𝑒𝑟−𝑎𝑖𝑟 − 𝛾𝑝𝑎𝑝𝑒𝑟−𝑙𝑖𝑞𝑢𝑖𝑑
cos 𝜃 =
𝛾𝑙𝑖𝑞𝑢𝑖𝑑−𝑎𝑖𝑟
When the interfacial energy between the air and the paper is lower than the interfacial
energy between paper and water, it is energetically favorable for the paper to have an
interface with air rather than with water, and the paper is hydrophobic. The sizing
agent should thus either decrease the surface free energy (𝛾𝑝𝑎𝑝𝑒𝑟−𝑎𝑖𝑟 ) or increase the
interfacial energy (𝛾𝑝𝑎𝑝𝑒𝑟−𝑙𝑖𝑞𝑢𝑖𝑑 ) (Holik, 2013).
The influence of paper microstructure for wetting driven capillary absorption can be
described by the simplified Washburn equation
1
ℎ≈ × cos 𝜃,
𝑟
where r is the radius of the capillaries, h is the water penetration depth into the paper
and θ is the contact angle. According to the simplified Washburn equation, the water
penetrates deeper into the structure the smaller the capillary radius, if the paper is easily
wettable (θ < 90º, cos θ > 0) (Holik, 2013).
M. Lagus: Hydrophobic surface sizing of testliner 26
In surface sizing, especially when carried out by conventional size presses, the starch
is forced into the paper by the nip pressure during application. This pressure
penetration is controlled not by the surface energetics but rather by the driving pressure,
the compressed pore structure of the paper (permeability) and the starch viscosity.
M. Lagus: Hydrophobic surface sizing of testliner 27
II EXPERIMENTAL PART
The objective of this thesis was to determine what properties of the base paper, the
sizing agent, or the sizing process have an impact on the sizing effect, measured as
paper surface hydrophobicity (Cobb 60s). The study consisted of laboratory surface
sizing experiments on different base papers, paper analysis, surface size analysis, and
sizing agent analysis. The existing laboratory scale sizing method was first studied and
optimized to obtain comparable results. Then, a variety of surface sizing agents were
tested on different base papers.
In this section, all relevant materials, equipment, and methods used in this work are
presented.
5. Materials
Eight base paper mill samples were used in the study: five unsized testliners (TL 1,
TL 2, TL 3, TL 4, and TL 5), one testliner with diluted surface size starch (TL + S)
one unsized kraftliner (KL) and one copy paper grade (C). The base papers were
analyzed, and the results are presented in Chapter 9: Effect of base paper properties.
Starch 1 and Starch 2 were part of Roquette’s “Stabilys A” product line of low
viscosity modified potato starches. Starch 2 had a slightly higher viscosity. The
structure of the starches simulates enzymatically converted starch.
Both starches were available in powder form and cooked with a jet cooker at 134 ºC
at a set level of solids content.
45 different surface sizing agents (SSAs) named SSA 1-45 were tested, including
development products and references of different origin. All SSAs were tested on
testliner 1, SSA 30 and SSA 31 were also tested on the other base papers. Most of the
SSAs were tested both with and without the addition of poly aluminum chloride (PAC),
M. Lagus: Hydrophobic surface sizing of testliner 28
denoted SSA X and SSA X + PAC. The surface sizing agents were analyzed, or previous
analysis data was used, to compare performance with SSA properties. The results are
presented in Chapter 10: Effect of SSA properties on sizing effect.
M. Lagus: Hydrophobic surface sizing of testliner 29
6. Methods
Part of the objective of this master’s thesis was to refine an existing laboratory surface
sizing method and eliminate possible variables to obtain repeatable and comparable
results. The aim was to achieve a constant addition level of surface size to the base
paper (35-45 kg/t) and a repeatable hydrophobization effect of sizing agent dosage.
The following section will describe how the surface sizing method was tested, which
parameters were controlled and the final laboratory surface sizing method.
Starch was jet-cooked with variations in cooking speed, slurry solids content and
temperature. The cooked starch’s solids content was measured with a CEM 5
microwave oven. The surface size was prepared by mixing cooked starch with hot
water and surface sizing agent with a laboratory magnetic mixer. Temperature,
agitation time and solids content were controlled. The surface size was analyzed
(solids content, pH, temperature, Brookfield 100 rpm) after preparation. The surface
size was applied to the base papers using a Mathis pond-type size press (Figure 9) with
soft rolls (70 shore D). The laboratory size press has adjustable speed (2-16 m/min),
adjustable pressure (0-100 on a scale, the actual pressure was not known) between the
rolls and the rolls can be heated with hot water before pouring the surface size into the
pond. After surface size was added into the pond, four base paper sheets were run
through the sizing solution and dried. The surface sized paper sheets were dried either
in an oven or with an infrared dryer with variations in temperature and drying time.
M. Lagus: Hydrophobic surface sizing of testliner 30
To achieve a constant sizing pickup and consistent sizing effect in the size press, the
parameters that can influence the process were first defined. Then, the parameters were
set to benchmark values, which enabled testing of the effect of each one with a number
of experiments on the same base paper (testliner with starch, TL + S) by adjusting one
parameter at the time. The benchmark and tested settings are presented in
Table . For the parameter test, a sizing solution of starch and SSA 1, an anionic, widely
used reference surface sizing agent, was used.
Drying conditions
Drying method, temperature and drying time were investigated both with oven and
infrared drying. The moisture content of the sized paper after drying and after
conditioning was measured for some test points. For oven drying, temperatures of 60,
80, 105, 125, 145 and 180 °C were tested with different drying times resulting in
completely dry (moisture content < 1%) and even burnt (t > 105 °C) samples. The
infrared dryer was tested with drying times of 10, 15 and 20 s with the sized paper in
the middle or at the bottom of the infrared dryer rack.
M. Lagus: Hydrophobic surface sizing of testliner 32
Results of the parameter testing can be found in Chapter 8: Effect of surface sizing
method parameters. The surface sizing method used for hydrophobicity tests in this
study is presented in Table 2.
Parameter Value
Paper humidity 6-7%
Size press speed 4 m/s
Size press pressure 5
Starch volume in pond 150 ml
Oven drying time (105 °C) 3 min
Surface size solids base paper dependent
Surface size temperature 60 °C
M. Lagus: Hydrophobic surface sizing of testliner 33
6.3.1. Hydrophobicity
Cobb 60 s tests were performed according to standard ISO 535 (TAPPI T 441) with
an L&W Cobb Sizing Tester. A 10 cm2 area of the paper was exposed to a 1 cm high
water pillar for 45 seconds. The water was poured off and at the full testing time (60 s)
paper was sandwiched between blotting sheets and rolled with a 10 kg roller. Weight
increase was used to calculate water absorption in g/m2. Two tests were made for each
test point and results were averaged.
Contact angles with water of sized papers (and surface sizing agent films) were
measured with Fotocomp DropPrint software. Ten drops of ion-exchanged water were
dropped from a height of 5 mm on the specimen and photographed at 0,5 s. The
obtained photographs were processed and calculated with the software, and contact
angles were averaged.
M. Lagus: Hydrophobic surface sizing of testliner 34
Porosity of the samples was measured with PASCAL 140/440 mercury porosimeter
at Åbo Akademi University. In mercury porosimetry, the pore structure of a sample
can be determined by the pore volume displaced by mercury. A sample is put in a
vacuum chamber and the chamber is filled with mercury while pressure and volume
are monitored. The resulting data can be used to calculate pore volume and pore
diameters of the sample. Thus, results on both the total porosity and the pore size
distribution are obtained.
Gurley air permeability was measured with an L&W air permeance tester. A sample
was put in the testing device where the time required for a volume of air to flow
through the sample is recorded. Results are given in seconds for flow of 1 liter of air.
Porosity and smoothness were measured with a Bendtsen type tester. The Bendtsen
tester measures air leakage both through the sample (porosity) and between the
measuring head on the sample and the sample surface (smoothness). Results are given
in ml/min.
M. Lagus: Hydrophobic surface sizing of testliner 35
Roughness/smoothness was also tested with Parker Print-surf (PPS) equipment. The
PPS measurement is based on the resistance to airflow between the sample surface and
a metal band in contact with the paper. The result is a measure of roughness in
micrometer.
Dynamic water retention (DWR) was used to measure starch pickup or starch
affinity of the paper. Samples of the base papers were used and a 12% solids starch
solution of starch 1 was kept at 60 °C before filling the DWR testing equipment
cylinder. The device lets starch flow past the surface of the paper sample, and DWR
was measured as weight increase of the paper sample in g/m2.
M. Lagus: Hydrophobic surface sizing of testliner 36
The charge of the SSA’s was measured with a CAS Charge analyzer. A sample was
diluted to 0,1% strength, and the device measured the required amount of anionic
(PES-Na) or cationic (poly-DADMAC) titrant to neutralize the sample.
Hydrophobicity was measured with contact angle measurements from films. SSA was
diluted to 25% solids, and a 150 µm wet film was drawn on a glass plate. The film was
dried in a 100 °C oven to mimic the surface sizing method. After drying, the film was
allowed to stabilize overnight in a conditioned room (t 23 °C, RH 50%) before
measuring water contact angles with Fotocomp DropPrint equipment and software.
The particle size of the SSA solutions was measured with a Malvern Zetasizer. A
diluted sample is put into the machine, and light scattering is used to measure the
particle size distribution.
M. Lagus: Hydrophobic surface sizing of testliner 37
In the surface sizing experiments a broad range of sizing effect, measured in Cobb 60 s
of the sized paper, was witnessed on testliner 1 (see Figure 10). Some sizing agents
gave a low Cobb value with a small addition amount, while other SSAs had barely any
effect even at higher addition amounts.
100 Starch 1
80
Cobb 60 s, g/m²
60
40
20
0
0 1 2 3 4 5 6
Amount sizing agent, kg/t dry
Figure 11 and Figure 12 illustrate a significant difference in the sizing effect of SSA 31
and SSA 30 between the different base papers. Testliner 1 seems to respond very well
to sizing, while testliner 4 is most difficult to hydrophobize. The differences in sizing
effect between sizing agents and between different base papers are well known in the
industry. A study by Karademir et al. (Karademir, Ozdemir & Imamoglu, 2007)
investigated the differences in sizing effect for office paper, old corrugated, magazine
paper and newspaper.
M. Lagus: Hydrophobic surface sizing of testliner 38
140
120 TL 4
100 TL 2
KL
Cobb 60 s, g/m²
80
C TL 3
60
TL + S
40
TL 5
20
TL 1
0
0 1 2 3 4 5 6 7
Sizing agent amount, kg/t dry
Figure 11. Sizing effect of SSA 31 on the different base papers (TL = testliner, KL = kraftliner,
C = copy paper)
160
140
120
Cobb 60 s, g/m²
TL 5
100
TL + S
TL 3
80
60
TL 2
40
20 TL 1 TL 4 KL
C
0
0 1 2 3 4 5 6
Sizing agent amount, kg/t dry
Before actual experiments on the sizing effect of SSAs could be made, the laboratory
surface sizing method was studied. The following chapter details effects witnessed
on surface size pickup and sizing effect when adjusting the surface sizing method
parameters.
been reported in the literature (Maurer, 2009; Shirazi et al., 2005). Figure 13 shows
the effect on testliner + starch base paper sized with 18% solids surface size. It was
decided to use as low pressure as possible which could still be monitored to prevent
surface size solids content from becoming too high while achieving the goal of 40 kg/t
starch pickup; this was determined to be “5” on the pressure lever.
60
50
Starch pickup, kg/t
40
30
20
0 10 20 30 40 50
Size press pressure lever position
Figure 13. Size press pressure and 18% starch pickup (base paper TL + S)
Drying conditions
IR drying and oven drying above 105 °C burned the sized sheets, causing them to
appear overly hydrophobic. The IR dryer was deemed too unpredictable and powerful
to produce even, consistent drying results. Oven temperature and time did not affect
pickup, except when drying continued during conditioning and pickup seemed too high.
The drying method was left as it was, 3 min in a 105 °C oven.
M. Lagus: Hydrophobic surface sizing of testliner 41
70
60 TL 1 y = -3,9022x + 90,158
R² = 0,9157
Pickup starch 12%, kg/t
TL 5
50
TL 2
40 C
TL 4
30 TL + S
20 KL
TL 3
10
0
7 9 11 13 15 17 19 21
Solids content for 40 kg/t, %
Figure 14. Correlation between size pickup at 12% solids content and solids content required
for 40 kg/t pickup for different base papers.
The holdout of surface size was expected to increase with the higher viscosity starch 2,
as described in the literature (Maurer, 2009; Gess, Rodriguez, 2005; Shirazi et al., 2005;
Jeong et al., 2012). When comparing the pickup of surface size on the different base
papers (Figure 15), the increased holdout may explain the differences observed. The
higher holdout of starch 2 may prevent penetration through the highly porous
testliner 1, thus decreasing pickup. For the dense testliner + starch base paper, starch
holdout may be high irrespective of the starch, and thus the higher viscosity may cause
more starch to stay on the paper surface through the nip passage, increasing pickup.
70
Surface size pickup, kg/t
60
Testliner 3
Testliner 1 Testliner + starch
50
40
30
6 9 12 15 18 21
Surface size solids content, %
Starch 1 LV Starch 2 HV
Figure 15. The effect of starch viscosity on surface size pickup (LV = low viscosity, HV =
high viscosity)
The higher viscosity starch decreased the porosity of the papers, as measured with
Bendtsen air permeability (Figure 16), consistent with results obtained on a pilot scale
paper machine in a doctoral thesis study. (Lipponen, 2005) For base paper testliner +
starch, the difference is negligible, probably because of the already low porosity of the
dilute-starch-containing base paper. No significant differences in Cobb 60 s values
were found.
M. Lagus: Hydrophobic surface sizing of testliner 43
400
200
Testliner 1
0
6 8 10 12 14 16 18 20
Surface size solids content, %
Starch 1 LV Starch 2 HV
In this chapter, the measured base paper properties are presented. Then, the effects of
base paper properties on starch pickup, paper strength and sizing effect are studied.
The results of the basic paper analyses are presented in Table 4. The copy paper is
more porous and less rough than the liners, and the testliner with starch is least porous.
Also between the testliners, differences in bulk, porosity and roughness can be seen,
despite the similar raw material composition. PPS and Bendtsen roughness show that
the other base papers have very rough surfaces, especially the kraftliner, except the
copy paper which is smoother. Ash content is lower for the virgin fiber containing
kraftliner, as expected, and higher for the filled copy paper.
The Hg-porosimetry results (Table 5 and Figure 17) show similarly that the copy
paper is most porous, while the testliner with starch is least porous. The testliners are
equal in porosity, except testliner 4 which is more porous.
Table 5. Hg-porosimetry
Hg-porosimetry TL 1 TL 2 TL 3 TL 4 TL 5 KL TL + C
S
Pore volume mm³/g 530 537 525 605 598 494 395 621
Porosity % 32,0 31,8 33,9 39,3 34,2 28,4 26,1 40,4
250
200
Relative pore volume, mm³/g
150
100
50
0
0,01 0,1 1 10
Pore size diameter, µm
TL 1 TL 2 TL 3 TL 4 TL 5 KL TL + S C
Dynamic water retention measurements with starch (Table 6) show that testliner 1, 2 and 5,
and the copy paper, absorb the highest amounts of 12% starch. The same testliners also have
the lowest t(MAX) values with the ultrasonic dynamic penetration tester, which means that
their surface wetting time is fastest. The W roughness values are also low for these base papers.
M. Lagus: Hydrophobic surface sizing of testliner 46
DWR TL 1 TL 2 TL 3 TL 4 TL 5 KL TL + C
S
DWR starch 12% g/m² 68 82 47 62 72 52 50 69
Ultrasonic dynamic penetration tester, water
I(5s) % 12,86 10,29 50,48 4,63 10,71 70,83 22,76 32,32
t(50%) s 0,59 1,19 5,04 1,57 0,58 9,80 2,77 3,50
t95 s 0,23 0,35 1,26 0,43 0,15 1,24 0,75 1,00
tMAX s 0,13 0,16 0,52 0,21 0,08 0,45 0,32 0,47
W 0,20 0,28 2,03 0,51 0,01 0,90 0,44 1,19
A 30 21,70 24,30 26,90 26,80 24,90 24,10 26,90 25,70
Starch pickup, and therefore solids content for 40 kg/t surface size, varies significantly
between the base papers (Table 7). For all base papers studied, DWR with 12% starch
correlated with 12% starch pickup (Figure 18), except a high starch pickup for
testliner 1. DWR measurements with starch could therefore in many cases be used to
predict starch pickup of the base paper.
Starch pickup TL 1 TL 2 TL 3 TL 4 TL 5 KL TL + C
S
Pickup starch 12% kg/t 60 40 16 25 40 19 20 33
Solids for 40 kg/t % 9 12 20 17 12 17 17 16
M. Lagus: Hydrophobic surface sizing of testliner 47
70
60 TL 1
40 TL 2
TL 5
30
C
20 TL 4
10 y = 0,9004x - 24,865
TL 3 KL
TL + S
0
40 45 50 55 60 65 70 75 80 85
DWR starch 12%, g/m2
Figure 18. DWR with 12% starch correlation to 12% starch pickup
1,8
1,7
1,6
SCT CD, kN/m
1,5
1,4
1,3
1,2
y = 0,0087x + 1,0848
1,1
1
0 20 40 60 80
Starch amount applied, kg/t
Z-direction TL 1 TL 2 TL 3 TL 4 TL 5 KL TL + C
strength S
base paper kPa 638 527 791 420 569 495 850 634
with starch 40 kg/t kPa 750 580
SCT, cd
base paper kN/m 1,1 1,5 1,8 1,7 1,5 2,0 2,1 1,2
with starch 40 kg/t kN/m 1,5 2,0 2,2 2,6 1,9 2,4 2,3 1,6
increase kN/m 0,4 0,5 0,4 0,9 0,4 0,4 0,2 0,4
increase % 36 33 22 53 27 20 10 33
Base paper and surface sized paper strength is presented in Table 8. The kraftliner and
the testliner with starch have the highest SCT strengths, and the testliner with starch
also has the highest Z-direction strength. This is to be expected because of the higher
strength and increased bonding potential of virgin fibers compared to recycled fibers,
and because the added starch serves to glue together the base paper.
900
800
Z-direction strength, kPa
TL + S
700 TL 3
C
600 TL 1
TL 5
500
TL 2
400
KL
TL 4
300
0 10 20 30 40 50 60
Gurley air permeability, s
For the liners, Z-direction strength correlates with porosity measured by air
permeability (Figure 20). The copy paper has higher Z-direction strength with higher
porosity, probably because of the different raw material and production process. SCT
strength of sized paper correlates with SCT strength of base paper (Figure 21), which
M. Lagus: Hydrophobic surface sizing of testliner 49
means that liner can be strengthened by either adding more starch or strengthening the
base paper.
1,5
KL
TL + S
TL 4
1 TL 3
C TL 5 TL 2
TL 1
0,5
1,4 1,6 1,8 2 2,2 2,4 2,6 2,8
SCT CD with 40 kg/t starch, kN/m
Figure 21. SCT for 40 kg/t starch sized base paper depends on base paper SCT
The sizing effect, measured in Cobb 60 s, of SSA 30 and SSA 31 on different base
papers is presented in Table 9. Testliner 1 and testliner 5 had the highest sizing effect
with both sizing agents, while testliner 3, testliner with starch and copy paper had the
lowest sizing effect.
90
80
60 KL TL 1
TL 1
50
KL TL 2
40
TL 4
30 TL 3
TL 4 TL 2
20
TL 3
10 TL + S
C
TL + S C
0
40 45 50 55 60 65 70 75 80 85 90
DWR 12% starch, g/m²
SSA 30 SSA 31
Both testliner 1 and testliner 5 have high DWR values with starch 12% (Figure 22),
however, so does the copy paper and testliner 2 despite having a lower sizing effect.
When comparing only the testliners, a higher DWR value seems to indicate better
sizing effect.
160
TL 5
140
Cobb improvement 3kg/t, g/m²
TL 5
120
100
TL 4
80 KL
TL 1
TL 1
60
TL 2 KL
40
TL 2
20 TL 4
TL + S TL 3
TL + S C TL 3
0
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7
t(MAX), s
SSA 30 SSA 31
Figure 23 shows that the t(MAX) parameter in ultrasonic dynamic penetration testing
does correlate with the sizing effect. The t(MAX) parameter signifies the time point
when the surface of the paper is wetted, and could thus indicate whether the paper
surface is already hydrophobic or not. The base paper usually contains trace amounts
of internal sizing agents to control surface size pickup and prevent web breaks, which
could explain the differences in t(MAX). Fiber refining processes, and recycled fiber
prior sizing could also cause differences in the paper surface chemistry.
160 TL 5
140 TL 5 TL 1
3 kg/t SSA Cobb 60s improvement, g/m2
120 TL 1
100
80 KL
60
TL 4 KL
40
TL 2
TL 4
20 TL 3
TL + S
TL 2 TL + S C TL 3
0
0 0,5 1 1,5 2
Ultrasonic dynamic penetration tester, W
SSA 30 SSA 31
Particle size
A smaller particle size of the sizing agent was found to give better sizing effect, and
PAC addition aids the sizing further (Figure 25 and Figure 26). Smaller SSA particles
should logically cover more of the paper surface because the number of particles is
higher for the same weight of SSA and therefore the specific surface area is higher.
120
TL 1 4 kg/t SSA Cobb 60s, g/m²
100
80
60
40
20
0
0 50 100 150 200 250 300
SSA particle size z-average, nm
100
90
TL 1 4 kg/t SSA Cobb 60s, g/m²
80
70
60
50
40
30
20
10
0
0 50 100 150 200 250 300
SSA particle size z-average, nm
Figure 26. Sizing effect and SSA particle size, with PAC
M. Lagus: Hydrophobic surface sizing of testliner 53
120
TL 1 4 kg/t SSA Cobb 60s, g/m²
100
80
60
40
20
0
0 20 40 60 80 100 120
SSA film water contact angle, °
Figure 27. Sizing effect and SSA film water contact angle, no PAC
100
90
TL 1 4 kg/t SSA Cobb 60s, g/m²
80
70
60
50
40
30
20
10
0
0 20 40 60 80 100 120
SSA film water contact angle, °
Figure 28. Sizing effect and SSA film water contact angle, with PAC
M. Lagus: Hydrophobic surface sizing of testliner 54
Conclusions
In this study, eight different base papers were analyzed, and 45 different surface sizing
agents (SSA’s) were tested. The goal was to optimize a laboratory scale method for
studying surface sizing and to increase the understanding of the mechanisms that
control hydrophobization of paper by surface sizing.
Differences in base paper properties were found to impact the starch pickup, paper
strength, and sizing efficiency. For SSA’s both the particle size and the particle
hydrophobicity was found to influence the sizing effect.
A range of sizing effects with the same dosage of different SSA’s was witnessed on
testliner 1. Some SSAs gave a low Cobb value with a small addition amount, while
others did not respond to even higher dosages. Differences were also witnessed
between base papers; the same SSA worked well with some base papers while others
were more difficult to make hydrophobic.
The surface sizing method was optimized for 40 kg/t starch pickup for all the base
papers. Nip pressure and surface size solids content affected the starch pickup. Nip
pressure was set to a minimum and solids content was adjusted for each base paper.
The starch pickup for each base paper could then be estimated using DWR
measurements with starch. Surface size viscosity affected the porosity of the surface
sized paper, and porosity of the base paper affected the starch pickup.
SCT strength of surface sized paper depended on base paper SCT strength and the
applied starch amount. A more porous base paper was weaker in Z-direction, as
expected.
M. Lagus: Hydrophobic surface sizing of testliner 55
The sizing effect correlated with wettability of the base paper, and DWR
measurements with starch. The easier the base paper was to wet and the more starch it
absorbed in DWR measurements, the stronger was the sizing effect.
Sizing effect was further affected by the SSA particle size, SSA hydrophobicity, and
PAC usage. Smaller SSA particles gave a stronger sizing effect, which is logical given
the increased surface coverage due to the larger specific surface area. A more
hydrophobic SSA also generally gave a higher sizing effect, but with the use of PAC,
the hydrophobicity of the SSA lost significance.
The results indicate that base paper properties can be optimized for starch pickup and
surface sizing effect. The costs of applying excess SSA and excess starch to the paper
surface could thus be decreased. Further studies are recommended on adjusting the
base paper properties to improve sizing effect and on SSA particle interaction with the
paper surface, especially in combination with PAC or other promoters. Printability and
gluability of surface sized testliner should also be considered in further studies.
M. Lagus: Hydrophobic surface sizing of testliner 56
Målet för detta diplomarbete var att närma sig en förståelse för
hydrofobiseringsmekanismen i ytlimning av testliner. Först undersöktes och
optimerades en laboratoriemetod för ytlimning och sedan testades 45 olika
ytlimningsmedel på åtta olika baspapper. Baspappren och ytlimningsmedlen
analyserades och resultaten undersöktes för korrelation med stärkelseupptagning och
ytlimningseffekt.
Baspappren som användes i arbetet var fem olimmade testliners, en testliner med
utspädd ytlimningsstärkelse, en olimmad kraftliner och ett kopieringspapper. Två
modifierade lågviskositetsstärkelser från Roquettes ”Stabilys A” produktsortiment
användes, den ena med något högre viskositet. Stärkelsernas struktur simulerar
enzymatiskt konverterad stärkelse. Båda stärkelserna var i pulverform och kokades
med jetkokare i 134ºC till en bestämd torrhalt. Ytlimningsmedlen inkluderade både
kommersiella referensprodukter och utvecklingsprodukter. Två av ytlimningsmedlen
testades på alla baspapper och alla ytlimningsmedel testades på testliner 1, de flesta
både med och utan polyaluminiumklorid (PAC).
Liner baspapprens Z-styrka korrelerade väl med luftpermeabiliteten, så att ett mer
poröst papper var svagare. Kopieringspappret hade högre Z-styrka trots hög
luftpermeabilitet, men råmaterialet och produktionsprocessen skiljer sig också från
liners. Kraftlinern och testlinern med stärkelse var, som förväntat, starkast i Z-
riktning, eftersom nyfibrer är starkare än returfibrer och har bättre bindningspotential
mellan fibrerna och stärkelsen limmar ihop testlinern för högre styrka. Mätt med
kvicksilverporosimetri korrelerade porositeten med kompressionsstyrkan för alla
baspapper. Kompressionsstyrkan för ytlimmat papper var beroende av baspapprets
styrka och den applicerade stärkelsemängden, så att kompressionsstyrkan ökade
logiskt med större mängder stärkelse. För testliner 1 mättes en kompressionsstyrka
på 1,5 kN/m med 40 kg/t stärkelse, vilket är ett typiskt värde för kommersiella liners
av samma ytvikt.
Dessa resultat antyder att genom pappersanalys kan baspappret optimeras för
stärkelseupptagning och limningseffekt. Kostnaderna för att applicera ett överskott
av stärkelse och ytlimningsmedel kunde därmed minskas. Ytterligare studier
rekommenderas av justering av pappersegenskaper för ytlimningseffekt och av
ytlimningspartiklarnas interaktion med pappersytan, speciellt i kombination med
PAC eller andra främjande tillsatsmedel. Tryckbarhet och limbarhet av ytlimmad
testliner borde också betraktas i fortsatta studier.
M. Lagus: Hydrophobic surface sizing of testliner 61
References
Andersson, L., Ridgway, C.J. & Gane, P.A.C. 2013, "Defining the mechanism of
sizepress starch penetration in filled unsized fibrous products - a traditional
technology revisited", vol. Nordic Pulp & Paper Research Journal Vol 28, no. 4,
pp. 547-558.
Bajpai, P. 2015, "Chapter 3 - Pulp and Paper Chemicals∗ " in Pulp and Paper Industry,
ed. P. Bajpai, Elsevier, Amsterdam, pp. 25-273.
CEPI 2016, CEPI Key Statistics 2015, Confederation of European Paper Industries.
ERPC 2016, ERPC Monitoring Report 2015, European Recovered Paper Council.
Forsström, U. 2003, Interactions between base paper and coating color in metered
size press coating, Keskuslaboratorio.
Gane, P.A.C. 2001, "Surface treatment: Sizepress tradition, current development and
a pigmented chemical future", vol. Twelfth Fundamental Research Symposium.
Gess, J.M. & Rodriguez, J.M. 2005, The sizing of paper, 3. ed edn, TAPPI Press,
Atlanta, GA.
Hagiopol, C. & Johnson, J.W. 2012, Chemistry of modern papermaking, CRC, Boca
Raton, FL.
Höke, U., Höke, U. & Schabel, S. 2010, Papermaking science and technology. Book
7, Recycled fibre and deinking, 2nd ed., totally updated version edn, Paper
Engineers' Association : Paperi ja puu, Helsinki.
Holik, H. 2013, Handbook of paper and board, 2nd, rev. and enl. ed edn, Wiley-VCH,
Weinheim.
M. Lagus: Hydrophobic surface sizing of testliner 62
Jeong, Y.B., Lee, H.L., Youn, H.J., Jeong, K.H. & Ryu, H. 2012, "Influence of the
Viscosity of Surface Sizing Starch Solutions on Surface Sizing Effect of
Linerboard", Journal of Korea Technical Association of The Pulp and Paper
Industry, vol. 44, no. 5, pp. 54.
Jonhed, A. 2006, Properties of modified starches and their use in the surface treatment
of paper, Karlstad University, Faculty of Technology and Science, Chemical
Engineering.
Lee, H.L., Shin, J.Y., Koh, C., Ryo, H., Lee, D. & Sohn, C. 2002, "Surface sizing with
cationic starch: its effect on paper quality and papermaking process", TAPPI
JOURNAL, vol. 1, no. 1, pp. 34-40.
Lipponen, J. 2005, Surface Sizing With Starch Solutions at High Solids Contents,
Dissertation for the degree of Doctor of Science in Technology, Helsinki
University of Technology, Laboratory of Paper Technology.
Lopes, P., Preciso, C., Sousa, A.M.d. & Ferreira, P. 2010, "Sizing evaluation of
uncoated fine papers", .
M. Lagus: Hydrophobic surface sizing of testliner 63
Maurer, H.W. 2009, "Chapter 18 - Starch in the Paper Industry" in Starch (Third
Edition), eds. J. BeMiller, , & R. Whistler, Academic Press, San Diego, pp. 657-
713.
Nazhad, M.M., Li, K., Sutjipto, E.R. & Pongpattanasuegsa, S. 2008, "Effect of
recycling on paper properties", vol. Tappsa Journal.
Pandian, V.E., van Calcar, D. & Wolff, B.W. 1994, Use of zirconium salts to improve
the surface sizing efficiency in paper making, Google Patents.
Ryu, J. & Lee, H.L. 2007, "Improvement of plybond strength of two-ply sheets by
spraying of starch blends", TAPPI JOURNAL, vol. 6, no. 5, pp. 3-8.
Shirazi, M., Esmail, N., Garnier, G. & van, d.V. 2005, "Starch Penetration into Paper
in a Size Press", Journal of Dispersion Science and Technology, vol. 25, no. 4, pp.
457-468.
Valmet 2017, 2017-last update, OptiSizer Spray - spray sizing for best controllability.
Available: http://www.valmet.com/board-and-paper/board-and-paper-
machines/sizing/spray-application/ [2017, 4/3].
M. Lagus: Hydrophobic surface sizing of testliner 64
Vanier, N.L., El Halal, S.L.M., Dias, A.R.G. & da Rosa Zavareze, E. 2017, "Molecular
structure, functionality and applications of oxidized starches: A review", Food
Chemistry, vol. 221, pp. 1546-1559.
Wygant, R., Kendrick, J. & Walter, J. 2008, "Metered Size Press Pigmentation for
Fiber Reduction", TAPPI/PIMA PaperCon ’08 Conference, May 4-7 2008.
Wygant, R., Lucidi, G. & Kendrick, J. 2009, "Pond Size Press Pigmentation with Platy
Kaolin", TAPPI PaperCon’09 Conference.
Zeng, H. 2013, Polymer Adhesion, Friction, and Lubrication (1), John Wiley & Sons,
Incorporated, Somerset, US.