ARTIGO 48 BARBOT FINAL Revisto Final 30 09

J. Coat. Technol. Res.
, 14 (1) 1–20, 2017

DOI 10.1007/s11998-016-9815-3
REVIEW PAPER
Intumescent coatings: A review on recent progress

Ravindra G. Puri, A. S. Khanna
American Coatings Association 2016
Abstract Fire is a serious threat to people and the Abbreviations

structures they build. There is a continuous develop- IFR Intumescent fire retardant
ment of newer methods and materials to prevent its APP Ammonium polyphosphate
effects on them. Nowadays, a lot of attention is being
PER Pentaerythritol
paid in the design of public and commercial buildings by
incorporating fire safety. Passive fireproofing of high- MEL Melamine
rise structures has become very important due to the use AFP Active fire protection
of steel in load bearing mode and has attracted PFP Passive fire protection
increased attention after the collapse of the WTC GRP Glass fiber-reinforced polyester
towers. Conventional passive fireproofing materials MF Melamine-formaldehyde
include concrete covering, gypsum board and cementi- PVA Poly vinyl acetate
tious coatings which have a poor aesthetic. Intumescent
EVA Ethylene vinyl acetate
fire-resistive coatings are a newer type of passive
fireproofing coatings usually applied as thin film and DP Degree of polymerization
they swell many times their original thickness forming DAHP Di-ammonium hydrogen phosphate
an insulating char which acts as a barrier between the MP Melamine phosphate
fire and the structural steel. It prevents the temperatures EDAP Ethylene diamine phosphate
of the steel members from reaching a critical value and DPER Dipentaerythritol
helps in maintaining the integrity of the structure in fire TPER Tri pentaerythritol
event. They are the preferred choice for passive fire PEPA Pentaerythritol phosphate
protection of load bearing steel frame structures of
architects and designers as they offer aesthetic appear- PEPAMP Pentaerythritol phosphate blend with
ance, flexibility, speed of application, and ease of melamine phosphate
inspection and maintenance. The present review covers THEIC Tris (hydroxyethyl) isocyanurate
recent developments in the field of intumescent coatings PETA Poly-ethylene terephthalamide
with a major emphasis on organic intumescent coatings. MC Maleated cyclodexdrin
The role of various ingredients, their interactions in ZHS Zinc hydroxystannate
intumescent coatings, effects of various pigments, CES Chicken eggshell
binders and additives are discussed briefly.
ATH Aluminum tri hydrate
Keywords Intumescent coatings, Passive fireproofing, PP Polypropylene
Fire safety RPU Rigid polyurethane
CNT Carbon nanotubes
OMMT Organically modified montmorillonite
LDH Layered double hydroxides
R. G. Puri (&), A. S. Khanna
Department of Metallurgical Engineering and Materials EG Expandable graphite
Science, Indian Institute of Technology Bombay, Powai, IPTS 3-Isocyanatopropyltriethoxysilane
Mumbai 400076, India
e-mail: [email protected]
1
J. Coat. Technol. Res., 14 (1) 1–20, 2017
Introduction buildings. There is wider acceptance of the use of steel

framed structures in the design of new multistoried
Fire is destructive in nature and there is always a great risk buildings by architects because of rapid design, quick
associated with it. Catastrophic fire can result in the loss of fabrication, and erection which speeds up construction.
wealth, possessions and even life. In recent years, Although the steel is not susceptible to fire, it has a
increasing attention is paid to fire safety regulations and serious limitation and loses approximately 50% of its
there is high demand to reduce the fire hazard associated load bearing capability at around 500C. In an extreme
with combustibles such as wood, plastics, textiles, etc.1 fire event, an unprotected steel structure may collapse
Newer methods and materials are in continuous due to a loss in mechanical properties at extremely
development for preventing and reducing the effects of high temperature during the fire. Therefore, a major
fire. Inherently flame-retardant materials and flame- design consideration in high-rise buildings during a fire
retardant-incorporated materials such as coatings, event is to prevent fire-induced structural collapse by
composites, firestops and intumescent coatings are providing a suitable passive fireproofing system which
currently used to provide protection against fire.2 provides sufficient time to evacuate humans and
Intumescent coatings are the recent developments in valuables.6
the passive fireproofing of load bearing structures. In
the past, Vandersall and Hao et al. reviewed intumes-
cent coatings.3,4 Weil reviewed fire-protective and fire-
Traditional passive fireproofing coatings
retardant coatings with major emphasis on intumescent
coatings.5 However in recent years, the scientific
Traditionally, passive fireproofing coatings are mainly
community has focused extensively on research of
of a cementitious type. They are usually categorized
intumescent coatings, and due to the large number of
as dense concrete and lightweight cementitious coat-
publications in recent years, there is a need to review
ings. They are based on portland cement, vermiculite,
the current progress in the field. The present review
gypsum and other materials. On construction sites
focuses on the recent developments mainly in the field
during application, they are mixed in water with
of intumescent coatings. Some attention is also given to
fillers, binders and are applied by spraying at a
polymers and composite systems which may be useful
thickness of few inches. They provide fire protection
in developing coating formulations.
by thermal insulation effects and water release from a
few minutes to several hours. They have low cost and
Fire protection systems are easier in application but have some serious
limitations in terms of their weight, thickness and
Although the regulations and standard operating poor aesthetics. Since they have poor aesthetics,
procedures in the event of a fire are laid down by building architects are reluctant to use them on
many government and private agencies, there still is a visually exposed steel sections.7 They have a tendency
need to educate society about prevention and rapid to crack and dislodge in a fierce fire. Their poor
response in the event of a fire. The following few surface finish allows moisture to penetrate and
methods are usually applied for fire prevention: accumulate, promoting corrosion which limits their
performance.8
• Fire prevention by awareness
It includes fire safety education, fire drills, fire
service response and emergency evacuation etc. Intumescent coatings
• Active fire protection (AFP)
It is the action to control and extinguish the fire by Intumescent coatings have been used as passive fire
fire fighting systems, extinguishers, sprinklers, etc. protection for over 20 years to protect structural steel
They can be further modified by installing detection in high-rise buildings to avoid fire-induced structural
systems and acoustic alarms. collapse. An intumescent coating swells on exposure to
• Passive fire protection (PFP) fire in a controlled manner several times their original
This limits and controls the fire once it has thickness, producing a carbonaceous protective char.
occurred, for example, using The char acts as heat transfer barrier to physically and
thermally protect the coated steel structure (Fig. 1).
(i) Fire retarding chemicals
Intumescent coatings can swell upto 100 times on
(ii) Modified fire rated fabricated structure
heating (from 1-mm to 10-cm-thick foam). In the event
(iii) Intumescent coatings.
of fire, they can act as passive fire protection for steel
which loses half of its load bearing capacity above
500C limiting structural damage and prolonging
Why structural steel needs fire protection? evacuation time during fire breakout, preventing the
loss of lives and property.9
Currently, structural steel is used extensively in the Intumescent coatings are increasingly used because
construction of high-rise commercial and industrial they provide a high-quality finish and also have good
2
dioxide and water is a major limitation. On environ-

Fire
mental exposure, they gradually lose their intumes-
cence, adhesion and become brittle.
Char K2 SiO3 nH2 O ! K2 SiO3 þ nH2 O
Na2 SiO3 nH2 O ! Na2 SiO3 þ nH2 O
An alkali silicate fire-protective coating with an acidic

Intumescent coating curing agent was investigated for the effect of relative
humidity on intumescence, water sensitivity and water
absorption. Atmospheric CO2 reacts with the coating
resulting in cracking and aging. It is suggested that
Fig. 1: Structural protection using intumescent coatings over-coating prolongs the aging.13 An inorganic coat-
ing composition has been reported containing sodium
fire ratings on buildings requiring high fire protection, silicate, potassium silicate and silicon carbide powder
like stadiums, skyscrapers, multistoried buildings. Most applied to the substrate, typically aluminum intu-
high-rise and steel-framed constructions use intumes- mesces at high temperatures and forms a heat insulat-
cent coatings to protect them from the fire. A char with ing char and retains this structure for prolonged
enhanced strength can help to protect the steel periods at temperatures up to 1000C.14 Mostly sili-
structure exposed to heat or fire and remain stable in cates are preferred in interior applications and in fire
high wind velocities. stops because of their poor water resistance. Making an
Inorganic intumescent coatings based on soluble intumescent powder and mixing it with a binder is also
alkali silicates were widely used in earlier days because one method of using them. A product using lithium–
of their low cost but they have serious drawbacks in sodium-potassium silicate composition having an intu-
durability and water resistance. Due to their aesthetics mescent range above 195C, suitable as a coating or
and performance, nowadays organic thin film intumes- firestop has already been reported.15 Phosphosilicate
cent coatings are becoming more popular. coatings formulated by incorporation of up to 5%
An organic intumescent coating consists of the sodium phosphate in the alkali silicate coating shows
following ingredients: high temperature resistance and is useful in fuel fires.
Exposure of these coatings to high temperatures results
• Carbon donor or char former, e.g., Pentaerythritol; in polymerization of silicate to crystalline silica.16 Fire
• Acid donor or catalyst, e.g., Ammonium polyphos- and heat protection of glass fiber-reinforced polyester
phate (APP); (GRP) composites using intumescent silicate coating is
• Blowing agent, e.g., Melamine; also reported. The inclusion of intumescent surface
• Binder, e.g., Polyvinyl acetate, Epoxy. barriers results in less temperature rise within the core
GRP composites.17 An intumescent inorganic silicate
fibrous material containing CaO, MgO, Al2O3, and
Organic intumescent coatings are thin film intumes- calcium magnesium silicate along with an acrylic or
cent coatings that swell considerably when exposed to polyvinyl acetate is used in a coating or mastic.18 An
heat. They have a good quality finish and can also be top- aqueous fire barrier composition can be prepared by a
coated if required for outdoor exposure. They have polymer latex and an intumescent agent that includes
many advantages like ease of application, aesthetic, granular alkali metal silicate.19 A fire-retardant, intu-
flexibility but have a limitation of sometimes forming a mescent, ceramic coating for structural steel and wood
fluffy char which may dislodge at high wind velocities.10 is prepared by mixing a finely ground borate compound
to sodium silicate solution then drying, pulverizing and
adding it to a second sodium silicate solution.20 A low-
Intumescent silicate coatings cost intumescent composition using alkali silicate,
microspheres and frit materials is said to have been
Inorganic intumescents are based on alkali silicates. stable for several years.21 A self-curing alkali metal-
They find their main application in fire protection of based intumescent composition having alkali metal
wood. They have limited application as coatings and silicate has been reported.22 An intumescent aqueous
are mainly used as firestops. They swell on exposure to composition of alkali silicate, clay, and inorganic
fire mainly due to the endothermic loss of water of materials like hydrated aluminum oxide, hydrated
hydration and their ability to melt forming solid rigid borate, carbonates, bicarbonates can be applied to
foam mainly consisting of hydrated silica.11,12 Envi- metal, wooden and polymeric materials and shown to
ronmental and health concerns with their use are provide a thermal barrier when exposed to high
decreased as only water vapor is released during temperatures.23 The intumescent composition contain-
intumescence, but their sensitivity to both carbon ing sodium silicate, cenospheres, water, and sodium
3
tetradecyl sulfate is also reported for wood structural strained in the melted matrix making it swell and
panels for protection against high temperatures and forming an insulating multi-cellular protective char
heat exposure for longer duration.24 layer. This carbonaceous char shield restricts the
transfer of heat from the source to the substrate and
prevents further degradation of the underlying mate-
Organic intumescent coatings rial (Fig. 2).4,25
The sequence of the intumescence process and
Organic intumescent coatings are thin film intumescent reactions are given as follows:
coatings and are based on an acid catalyst, e.g., ammo-
nium polyphosphate (APP), a char former e.g., pen- 1. Softening and melting of the polymeric binder.
taerythritol (PER) and a blowing agent, e.g., melamine 2. Releasing of inorganic acids.
(MEL) in solventborne or waterborne binders. These [250 C
kinds of coatings are more weather stable and water ðNH4 PO3 Þn !ðHPO3 Þn
nNH3
resistant than alkali silicate-based coatings. They are
favored by architects and designers for passive fire 3. Carbonization of char formers (e.g., of polyalco-
protection of steel-framed structures as they provide a hols).
finish that does not detract from the appearance of the
exposed steelwork as in the case of cementitious ðHPO3 Þn þCx ðH2 OÞm ! ½Cx þðHPO3 Þn mH2 O
coatings. They are increasingly used today in modern
day airports, skyscrapers, sports complexes, shopping 4. Release of gaseous products by blowing agents
malls, hotels and other places, and enabled the architect (e.g., melamine).
to create and design elements using the steel itself.
NH2 N NH2
Intumescence mechanism O2
NH3 N2 + H2O
The intumescence process usually takes place in N N
following steps: a mineral acid is released by breaking
the acid source which results in dehydration and NH2
carbonization of char formers. Further, the blowing
agent decomposes to release gases which get con- 5. Foaming and expansion of the mixture.
6. Crosslinking and solidification of char.
There are three intumescent ingredients: an acid
Post heating source, a carbon source and a blowing agent. The
intumescent coating has to be formulated and opti-
mized so as to form an efficient protective char. The
During heating
protective and heat barrier properties of the char are
Fully expanded largely influenced by its structure. A coating should
char form a large char volume, thick and continuous inner
Blowing
Pre heating
char structure. The char should be compact, and should
Melting
have smaller cell size and narrower cell size distribu-
Virgin zone
Protected
tion. The cells should be closed like solid foam. The
substrate coating should have other performance properties to
withstand the service environment in the long term26
Fig. 2: Schematic representation of intumescence process (Figs. 3, 4).
Fig. 3: Intumescent coatings char
4
>250°C
(NH4PO3)n (HPO3)n +n NH3
Polyphosporic acid
+ Binder Dehydration
(HPO3)n + H3PO4
+ Char former x
Char
Fig. 5: APP response to fire and its interactions with other

ingredients
Fig. 4: SEM image of (a) char surface (b) internal of char
showing cell size distribution
chain structure of polyphosphate with the elimination
of ammonia, water, and releasing polyphosphoric acid.
Polyphosphoric acid then reacts with pentaerythritol
As discussed earlier, the intumescent coating con- forming cyclic phosphoric acid esters which also act as
sists of three major ingredients, i.e., acid source, char blowing agents.25,29 During this process, melamine and
former and blowing agent. The examples of various polyphosphoric acid also combine to form melamine
intumescent ingredients are given in Table 1.2,27 polyphosphate and dipolyphosphate and further,
polyphosphoric acid dehydrates to phosphorus pentox-
ide. Cyclic phosphoric acid esters of char formers also
Interaction of acid source-char former-blowing act as the blowing agents. Glycerol as a char former
agent results in an ester with a low temperature of decom-
position in the coating and shows the best performance
The intumescent process is triggered by an acid- in the fire test.30
liberating catalyst, e.g., ammonium polyphosphate
(APP) releasing acid above 250C in the event of a
fire. The acid reacts with the char former, e.g., polyol Ammonium polyphosphate (APP) and its
resulting in its dehydration and forming carbonaceous modifications
char (Fig. 5). The blowing agent, e.g., melamine,
decomposes and releases gases in the molten mass APP is most widely used acid source in intumescent
resulting in foaming which then solidifies making a formulations. However, water sensitivity and poor
heat transfer barrier. Camino et al. studied in detail the compatibility with the binder are some of its limita-
degradation of APP. APP loses ammonia and water tions. The properties of ammonium polyphosphate
when heated. However at higher temperatures, depend on the number of monomer units and degree of
crosslinking occurs through P–O–P and P–N–P struc- branching. APP with shorter chains (n < 100) has more
tures.28 The reaction takes place with the disruption of water sensitivity and less thermal stability than with
Table 1: Examples of various components of intumescent systems

Acid source Char formers Blowing agent
Inorganic acids Pentaerythritol, Dipentaerythritol, Tripentaerythritol, Melamine

Phosphoric Starch Urea
Sulfuric Dextrins Urea–formaldehyde
Boric Sorbitol Melamine formaldehyde
Ammonium salts Mannitol Dicyandiamide
Phosphates, polyphosphates Phenol–formaldehyde resins
Borates, polyborates Methylol melamine
Sulfates Char-forming polymers
Halides
Phosphates of amine
Melamine phosphate
Melamine pyrophosphate
Urea with phosphoric acids
Other phosphates
Tricresyl phosphate
Alkyl phosphates
Haloalkyl phosphates
5
longer chains (n > 1000). There are two main classes of much better flame retardancy.46 Zheng et al. synthe-
APP: Crystal phase I (APP I) and Crystal phase II sized microencapsulated ammonium polyphosphate via
(APP II). APP I having phosphate units generally a two-step surface polymerization process using 4, 4¢-
lower than 100 is a linear chain with the lower diphenylmethane diisocyanate (MDI), melamine
decomposition temperature of approximately 150C (MEL) and pentaerythritol (PER), which introduces
and has higher water solubility. APP II with number of the carbon source and blowing agent into the micro-
phosphate units higher than 1000 has a branched capsules simultaneously. The microencapsulation com-
structure and much higher molecular weight than APP bines the flame-retardant system (APP/PER/MEL) in
I. The thermal stability of APP II is higher with one compound and also improves its compatibility,
decomposition temperature of approximately 300C water resistance and flame retardancy.47 The degree of
and has less water solubility than APP I. Surface polymerization (DP) of APP also influences fire
modification of APP with melamine can be helpful in protection of intumescent coating. The fire protection
overcoming the poor water resistance and low com- of the coating significantly improved with the increase
patibility with polymeric binders. Some of the ammo- of DP. The improvement was significant when DP was
nium cations in APP get replaced by melamine less than 100 but slows when DP was more than 100.48
increasing its water resistance.31 Microencapsulated
ammonium polyphosphate (MCAPP) with a mela-
mine–formaldehyde (MF) resin coating layer leads to Other phosphates and phosphorus compounds
reduction in water absorption and gives a still more
water-resistant APP. It also increases its compatibility Many other phosphorus compounds are also useful in
in the matrix and gives higher thermal stability.32,33 intumescent coatings and polymeric systems. Other
Most of the reported studies on the surface modifica- phosphates such as mono-, di-ammonium phosphates
tion of APP are in the composite system but can also may have higher water solubility and are not generally
be useful in formulating coating. In microencapsulated preferred in coatings but may found some use in other
APP, the shell can have additional effect as a char polymeric systems. However, ammonium dihydrogen
former or blowing agent and it may also prevent water phosphate and partially substituted ammonium
from coming in contact with the acid source. Tang et al. polyphosphates in fireproofing formulations are shown
synthesized glycidyl methacrylate microencapsulated to enhance adhesion of foamed coke to the metal
ammonium polyphosphate which shows better flame surface.49 Synthesis of hybrid salt composition with
retardancy, thermal stability, and better dispersion in substantially reduced solubility and low thermal acti-
the epoxy matrix.34 Microencapsulated ammonium vation temperature is reported by the interaction of
polyphosphate with a urea-melamine–formaldehyde mono ammonium phosphate, phosphoric acid and
resin prepared by in situ polymerization shown to melamine.50 Commercial polyurea coating containing
increase water resistance of composites.35 Many other microcapsules of di-ammonium hydrogen phosphate
materials like PVA-melamine–formaldehyde resin, (DAHP) with polyester-polyurethane shells has been
hydroxyl silicone oil, polyurethane, and epoxy can be shown to involve the smallest quantity of smoke and
used for the microencapsulation of APP.36–38 Compos- carbon monoxide.51,52 Ammonium polyphosphate is
ites containing them are reported to have better the most widely used acid source in intumescent
thermal stability and water resistance.39–41 Microen- formulation but other salts, e.g., melamine phosphate
capsulation with cellulose acetate butyrate enhances (MP), melamine pyrophosphate also find use.
the water resistance of APP and its compatibility with MP has slightly less solubility in water and is a
ethylene vinyl acetate. The results also conclude that it suitable choice in combination with APP. Various
increases interfacial adhesion, mechanical, electrical melamine phosphates differ in their stabilities and
and thermal stability of the system.42 Sol–gel encapsu- water solubility. Melamine phosphate and pyrophos-
lated ammonium polyphosphate (APP) has better phates have higher residues than APP at higher
water resistance and also its epoxy resin composites temperatures. Melamine pyrophosphate is thermally
have better flame retardancy because of a synergistic more stable and also has less water solubility.
effect between polysiloxane and APP. The results Melamine pyrophosphate has better water resistance
demonstrate that the silanes hydrolyze and condense and gives char with better thermal barrier properties
forming a dense layer on the surface of ammonium than melamine phosphate. They form an infusible
polyphosphate. They react with the hydroxyl groups on residue of phosphorus oxynitride having extremely
the surface forming a new Si–O–P bond.43,44 APP high thermal stability when heated.53,54 Different
modification with ethanolamine (ETA) improves its crystal types of melamine orthophosphates have dif-
flame-retardancy via ion exchange reaction. Ethanola- ferent behaviors when incorporated in epoxy intumes-
mine-modified ammonium polyphosphate (ETA-APP) cent coatings.55 Melamine phosphate starts to
thus formed acts as the acid source, blowing agent and decompose at about 250C and converts to melamine
also has excellent charring property.45 Ethylene dia- pyrophosphate, releasing small amount of melamine.56
mine-modified ammonium polyphosphate forms some MP contains both acid source and blowing agent and is
stable structures such as P–N–C and C–N which useful in combination with char-forming polymers.
dramatically increases its charring ability resulting in Fireproof coating composing of melamine salts or
6
guanidine salt and microencapsulated melamine with mostly reported charring agent in combination with
stability in a tropical environment is reported.57 A fire- APP as an acid source in intumescent formulations. Its
retardant additive containing a mixture of melamine lower melting point is advantageous in early intumes-
polyphosphate (MP)/dipentaerythritol (DPER) has cence; however, its water solubility restricts its use
been used for preparing waterborne intumescent fire- sometimes for weather stable applications. Dipentaery-
resistive coating. The results confirmed that the MP/ thritol and tripentaerythritol although more expensive
DPER mixture and the coating have similar thermal are somewhat less soluble. The comparison of pen-
degradation behavior. They degrade, releasing non- taerythritol with its dimer and trimer shows that
flammable gases and form phosphorus oxide contain- pentaerythritol intumesces earlier. The embrittlement
ing intumescent char layer at high temperature.58 An temperature is, however, higher for di- and tripen-
intumescent coating is also formulated using dicyandi- taerythritol and has resistance to the wind and cracking
amide phosphate along with pentaerythritol, especially of char at high temperature, especially on curved
as a clearcoat for wood and wood-related surfaces.59 surfaces.73 Other char former as replacements for the
An intumescent polymer composition with pentaery- pentaerythritol such as tris (hydroxyethyl) isocyanu-
thritol phosphate is reported where pentaerythritol rate (THEIC) is also reported. THEIC, a derivative of
phosphate (PEPA) functions as both an acid source triazine, and its derivatives serve as the charring agent.
and a carbonific.60 Pentaerythritol phosphate (PETA) There is a synergistic interaction between APP and
and its blend with melamine phosphate (PEPAMP) act THEIC but water solubility limits its use.74 THEIC,
as an intumescent additive and are shown to produce when used along with long chain amine in intumescent
equal amount of char; however, PEPAMP produces flame-retardant compositions, reduces its blooming
less stable char.61,62 Ethyl diamine phosphate has an tendency.75 Formals of pentaerythritol and dipentaery-
advantage of its relatively high phosphorus content. It thritol are the by-products in their frequently used
is also inexpensive and does not require the use of production processes and cheap carbon sources as a
synergists in order to provide sufficient effective- partial replacement.76 Char-forming ingredients such
ness.63,64 Chloroalkyl phosphates and phosphonates as starches, sugars and cellulose having pendant
find major use as flame retardants.65,66 It is obvious hydroxyl groups are cheaper char formers and find
that both chlorine and phosphorus contribute to the use in intumescent formulations.77,78 Alongi et al.
flame retardancy. They may also be useful in intumes- prepared a cyclodextrin nanosponge compound which
cent coating formulations. The organic phosphate or acts as a carbon source and also helps in foam
phosphonate acts as blowing agent and charring formation.79 Poly-hexa methylene terephthalamide
catalyst by releasing phosphorus acids and can also (PA6T) is a novel charring agent in combination with
be useful as plasticizer improving coating properties.67 ammonium polyphosphate (APP). A synergistic inter-
Intumescent formulations using monophosphates such action takes place between PA6T and APP, which aids
as tris (2-chloroethyl) phosphate are shown to have in char formation. The results revealed the formation
better flexibility due to its plasticizing effect.68 Clear of uniform and compact intumescent char after com-
intumescent lacquers for metal, wood and textiles can bustion.80 Maleated cyclodexdrin (MC) and its metal
also be synthesized by reaction of the polyphosphoric salts (Metal MC) in poly (vinyl alcohol) show
acid with polyols forming partial esters and further improved thermal stability of the composites. It is
curing with epoxy and amino resins.69 Pentaerythritol concluded that during degradation the metal ions
phosphate alcohol aryl phosphonate and phosphate enhances formation of organized and compact char.81
compounds contain both char former and acid source. Bi(4-methoxy-1-phospha-2, 6, 7-trioxabicyclo [2.2.2]-
They may contain from one to three pentaerythritol octane-1-sulfide) phenylphosphate (BSPPO) is re-
phosphate and are useful as flame retardants.70 Intu- ported as a novel halogen-free charring agent having
mescent coatings for fiberglass mats can be prepared excellent charring ability.82 Alkali lignin and urea-
by mixed glycerol/pentaerythritol acid phosphate as a modified lignin as a carbonization agent in intumescent
base, cured with amino resin.71 Ma et al. synthesized formulations are also reported. The results showed that
poly (diamino diphenyl methane spiro cyclic pentaery- the urea-modified lignin with APP has better flame
thritol bisphosphonate) (PDSPB), having a high ther- retardancy and thermal stability as compared with
mal stability. The phosphate ester releases phosphoric virgin lignin.83
acid and forms a complex P–O–Ph and aro-
matic/graphitic structure having improved fire perfor-
mance.72 Melamine and other blowing agents
Melamine is the most widely used blowing agent in
Various char-forming ingredients intumescent formulations. Its action mainly takes place
by its degradation at high temperature, releasing gases
The major role of char former is to form a carbona- and volatile products. Various melamine compounds
ceous char by dehydration in the presence of acid like melamine phosphate and polyphosphate also find
source. In literature, pentaerythritol has been the use as blowing agents. The TGA data of melamine
7
suggest that it sublimes completely at about 250– intumescent charred layer.94 N-alkoxy-hindered
350C. Melamine, apart from its role as a blowing amine-containing silane (Si-NORs), prepared by sol
agent, also interacts with ammonium polyphosphate.84 gel reaction combining N-alkoxy-hindered amine and
Costa et al. demonstrated that on heating, melamine silane coupling, are shown to improve significantly the
undergoes condensation with liberation of ammonia thermal stability, UV stability, mechanical properties,
and forms insoluble products. Upon heating in a close compatibility and residual char structure.95 Zinc
system ammonia is eliminated and fused ring struc- hydroxyl stannate (ZHS) and Ferrous disulfide (FeS2)
tures, e.g., melam, melem and melon are formed.85,86 can also improve the char yields of intumescent
The sublimed melamine and ammonia are poor fuels systems. They could promote formation of stable,
and flame inhibitors and act as flame retardants in the homogeneous, and compact intumescent char and thus
gaseous phase. Melamine phosphate formed by the protect the underlying polymer from degradation.96,97
interaction of melamine with ammonium polyphos- Zinc and nickel salts and oxides can enhance the
phate also acts as an acid source. performance of the intumescent system. ZnSO4Æ7H2O
Various phosphorus compounds of melamine such can optimize the intumescent process and strengthens
as phosphate, pyrophosphate and polyphosphate are the char layer under combustion conditions.98 Sup-
useful flame retardants. In addition to an acid source, ported nickel catalyst (Ni-Cat) improves the flame
they are also useful as blowing agents in intumescent retardancy of IFR system based on APP and PER in
formulations.87 Urea can also act as a blowing agent polypropylene (PP) matrix. The catalyst was shown to
but is shown to reduce the intumescence in APP-PER act synergistically and changes the char microstructure
mixture because of less amount of gases evolved during and improves the thermal stability.99 Zeolite in intu-
decomposition.88 Dicyandiamide and guanidine can mescent formulations results in the formation of
also be a useful blowing agent along with melamine in stable structures with the polymer and helps in stabi-
intumescent formulations. lizing intumescent protective shield. It enhances the
stability of the phosphocarbonaceous species and
hinders the formation of small molecules in the
Catalysts and synergists in intumescent polyaromatic network.100,101 Spent refinery catalyst is
also reported as synergistic agent in intumescent
formulations formulations. The use of finest catalyst exhibits a
higher amount of residue at high temperature and
In addition to the acid catalyst used in typical
low heat release rates. Silica–aluminates are found to
intumescent formulations, many other compounds like
be more efficient than silica or alumina alone.102
amines and metal oxides show catalytic and synergistic
effects. Most of the reported catalysts are in non-
coating systems but are useful in developing coatings.
Epoxy resin showed improved flame retardancy Influence of binder in intumescent coatings
through the addition of APP with metal compounds.
It is reported that the flame retardancy is affected by Various studies have reported on the role of the binder
the composition of metal compounds (metal ions and in intumescent formulations. The binders, besides
ligands/anions) and the mass ratios of APP to metal providing typical protective performance, also have
compounds.89 Metals like iron, magnesium, aluminum, to degrade over the same temperature range as other
and zinc also influence the thermal degradation of intumescent fire retardant additives in the formulation
paraffin/intumescent flame retardants (IFR) system so as to produce intumescence, leading to a carbona-
and could also increase the char yield.90 Calcium ceous char. Additionally, it must have a melt viscosity
gluconate monohydrate is a new base-catalyzed intu- which would not be too low to cause the molten
mescent compound. It forms low-density closed-cell coating to slump leading to dislodging of char during
carbonaceous foam when exposed to heat. The volume intumescence, nor too high to prevent the expansion of
expansion can be as high as two hundred times the the foam. The polymer melt should be so viscoelastic
original volume.91 Cerium (IV) phosphate with intu- that the gases released during the intumescence pro-
mescent flame retardant in styrene butadiene rubber cess should remain contained within it, forming a
acts synergistically and results in the formation of foamed char. Some binder also aids in char formation
compact charring layers.92 La2O3 promotes formation process. They have synergistic interaction with ammo-
of a homogenous and compact intumescent char layer nium polyphosphate and produce thermally more
and shows a synergistic effect in the flame retardancy stable chars.
and smoke suppression of IFR system.93 Sheng et al. A range of polymeric resins can be used as a binder
reported excellent improvement in flammability due to in intumescent coatings. Selection of binder also
the catalytic carbonization effect of LaMnO3 in the depends upon the service environment to which the
intumescent flame-retardant system. The incorporation coating is exposed and its expected durability. Water-
of LaMnO3 improves the thermal stability and it also borne acrylics are used mostly in dry, internal loca-
acts as the nuclei to induce the formation of the tions, solventborne acrylics in internal or sheltered
continuous, compact, and smooth condensed phase external locations while solvent-less or solventborne
8
epoxy coatings find use in any location where high intumescent composition curable by free radical poly-
weatherability and protective performance are antici- merization is reported to be useful in these condi-
pated. Thermoplastic binders have good char-forming tions.117–119 Waterborne intumescent fire-retardant
behavior compared to thermosets. Polyvinyl acetate varnish prepared from phosphate resin acid (PRA)
emulsion is mostly preferred in waterborne while and cold cured amino resin is reported. The fire
epoxies are in solventborne intumescent formulations. retardancy test demonstrated that a high phosphorus
The combination of binders also gives good perfor- content is useful to fire retardancy of coatings, but the
mance. Chlorinated rubber with chlorinated paraffin quality of the char formed has a major role.120
gives good performance and withstands aging in a Intumescent coatings to the metal of acrylic binder
conventional APP-PER-MEL formulation. In addition with copolymerizable acid monomers such as a
to their fire retardancy, the halogen-containing mate- methacrylic, maleic, fumaric or itaconic acid is claimed
rials also act as a plasticizer and flexibilizer for the to have improved metal adhesion.121 The combination
dried coating.103 Phosphorus-containing styrene-acrylic of self-crosslinking polyacrylate emulsion and silicone
copolymers are shown to form a dense swollen char. emulsion improves the fire protection of the coating
The results demonstrated that along with thermal significantly. The silicone emulsion improves the ther-
stability, the crosslinking degree of the binder has an mal stability of the coating and increases the char
important role in the performance of intumescent residue at high temperature.122 A self-crosslinking
coatings.104 A copolymer with substituted styrene has silicone acrylate when added to epoxy emulsion leads
good reactivity with APP and shows enhanced thermal to increase in the fire protection. It increases the
stability. Copolymers of 2-ethylhexyl acrylate p-methyl crosslinking degree of the binder and reduces perme-
styrene are relatively efficient in thin film intumescent ation of water and migration of intumescent ingredi-
coating. Linear and crosslinked copolymers, more ents increasing its corrosion resistance.123 Fire-
particularly those synthesized from monomers having resistance behavior of the intumescent coating based
good reactivity with ammonium polyphosphate, greatly on silicone-epoxy resin containing intumescent addi-
improve the thermal insulation of char.105–109 The tives is also evaluated. Intumescent coatings based on
addition of a chloroparaffin in intumescent paints this resin forms a thermally stable thin ceramic-like
improves flame-retardant properties of polyvinyl acet- layer, which improves the thermal insulation properties
ate. A condensed heterocyclic system is formed by of the char.124 Gardelle et al. evaluated silicone-based
C=C bonds. When combining it with melamine, it binder in the intumescent coating. It is shown that the
reacts with the polyene on a large temperature range, incorporation of a mixture of poly dimethyl siloxane
forming a condensed heteroaromatic structure having and silica-coated by silane as a modifier in the silicone
high thermal stability.110 Polymers like polyamide-6 act results in the formation of char having low thermal
as a carbonization agent in an intumescent formula- conductivity after swelling. Incorporation of expand-
tion. Insertion of this additive system in EVA leads to able graphite, organoclay, and calcium carbonate in
a significant improvement of the fire performance of silicone-based coatings results in improved perfor-
the material.111 Molecular weight of binder can also mance. This is due to interactions of calcium carbonate
affect fire protection of the intumescent coating. High and silicone matrix which increases the thermal stabil-
molecular weight can improve the thermal stability of ity of the resin and forms a protective ceramic layer of
the coating and improve the antioxidation property of calcium silicate.125,126 The concentration of binder used
the char at high temperature. It is observed that the in the formulation also influences char expansion and
higher melt viscosity with increasing molecular weight its antioxidation behavior.127
may reduce the expansion speed of the coating leading
to an increase in the cell size of the char layer.
However, loose and uneven foam structure may be Various pigments in intumescent formulations
formed with excessive high molecular weight signifi-
cantly reducing the fire performance.112 A combination A variety of pigments are used in the intumescent
of thermosetting and thermoplastic binders can be a formulation. Apart from their role as a typical coating
suitable choice. Mostly, thermosetting binder is an ingredient, they are also useful in improving the fire
epoxy resin. Various thermoplastic binders i.e., ketonic performance of coatings. Use of titanium dioxide is
resin, hydrogenated castor oil are used to modify melt reported in many intumescent formulations. Its use in
viscosity.113,114 A cost-effective and environmentally the intumescent formulation is not only as a white
friendly polymer emulsion using phosphonate or pigment but is shown to interact with intumescent
phosphate monomer along with acrylic and additives. The addition of pigments in intumescent
methacrylic monomers is also reported to be useful in formulation results in the formation of close cells,
intumescent paints.115 Epoxidized polysulphide-based narrower cell size distribution and compact char
intumescent composition forms a substantially structure which improves fire protection. Titanium
stable and protective carbonaceous char.116 Due to dioxide-containing intumescent coatings often show
high thickness, slow drying remains a major problem the formation of white expanded foam on the exterior
with intumescent coatings particularly in water-based surface, which is mainly titanium pyrophosphate and is
formulations when the relative humidity is high. An the result of the interaction of APP with TiO2.
9
Horacek et al. proposed that the formation of titanium ing char integrity.135 Inert fillers like zirconium silicate
pyrophosphate is due to the reaction of P2O5 with TiO2 help in the reinforcement of char. It is also reported
in the intumescent coating.30 Li et al. reported that fire that its addition results in an increase in residual weight
resistance of coating containing rutile-TiO2 is much of char and release of less gaseous products.136 Inor-
longer than that of the anatase-TiO2. It is suggested ganic compounds e.g., borides, nitrides, or carbides of
that the difference may be due to size distribution and Titanium, Zirconium, or other metals are chemically
crystalline forms of TiO2. Anatase-TiO2 is also con- inert and have a much higher thermal decomposition
verted to rutile-TiO2 at high temperature (above temperature. They serve as a filler and stabilize char in
900C).128 intumescent formulations.137 Glass flake as a modifier
in intumescent coatings improves the fire protection
2TiO2 þ ðNH4 Þ4 P4 O12 ! 2TiP2 O7 þ 4NH3 þ 2H2 O and water resistance of the coatings. Coatings modified
with glass flake restrict the migration of APP and PER
in the presence of water, maintain their fixed ratio and
Inorganic oxides form a highly reflective glassy layer have an excellent intumescent effect and fire protec-
on the surface of the char by interacting with phos- tion.138
phates. These compositions are effective at continu- Refractory fibers like alumina and silica increase the
ously maintained high temperatures for a long duration strength of the residual char and also improve the fire-
under severe environmental conditions, with reduced protective performance for a longer duration.129 Addi-
degradation of the mechanical properties.129 It is tion of nepheline syenite in the formulation has been
claimed that Molybdenum trioxide (MoO3) and ferric reported to increase performance against high temper-
oxide (Fe2O3) improve the outer and inner surface ature fuel fires.139 Synthetic glasses also have been
structure of the residual char and enhance the thermal shown to increase the performance of intumescent
stability of the intumescent APP–PER–MEL coat- coatings. The incorporation of vitreous fillers resulted
ings.130 Fumed silica (SF) as a binder and chicken in char stabilization, decreasing in optical density of
eggshell (CES) as flame-retardant filler have been smoke emitted and their toxicity index.119,140 Ceno-
incorporated to synthesize water-based intumescent spheres as a filler in water-based intumescent formu-
coatings. The coating showed improved adhesion to lation form a ceramifying layer of silicophosphates and
the steel substrate by adding fumed silica and provided aluminophosphates and protect the underlying char
longer-lasting protection.131 Liu et al. reported the use improving the fire performance.141 Koo et al. incorpo-
of sepiolite as a synergistic agent in the intumescent rated and compared high-temperature ceramic fibers
flame-retardant system. The addition of sepiolite in and minerals in water-based epoxy intumescent sys-
polypropylene results in low heat release rate, total tems.142 The high-temperature ceramic fibers are easier
smoke, and CO2 production.132 Intumescent flame- to incorporate than minerals and enhance the tough-
retardant ethylene–vinyl acetate (EVA/IFR) compos- ness of the char. Formulations with alumina, carbon,
ites containing lanthanide oxide, iron oxide, their glass and aramid fibers are shown to increase the char
mixture, and nanocrystalline lanthanum ferrite strength.143 Use of wollastonite, kaolin clay, alumina,
(LaFeO3) are also reported. It is confirmed that they eggshell biofiller as an intumescent filler is also
act as effective additives functioning both as flame reported. The incorporation of filler results in even
retardants and smoke suppressants. LaFeO3 could foaming and improved adhesion strength. The easy
promote the formation of the homogeneous and availability and good fire-protective performance of
compact intumescent char layer.133 alumina make it a good choice. The coatings contain-
ing egg shell fillers are shown to have excellent fire
protection, water resistance, thermal stability and
Other additives, fillers, and fibers in intumescent adhesion strength.144–148 Different kinds of inorganic
formulations fillers incorporated into intumescent coatings are
shown to have significant differences in the intumes-
Many inorganic fillers and fibers find use in intumescent ratio, char morphology and thermal shielding
cent formulations. They increase char residue of the performance. It is found that the high melt viscosity
coatings at high temperatures. Selecting the right resulting from incorporation of inorganic fillers hinders
combination of flame-retardant fillers also strongly the polymer chains from rotation and relaxation and
influence the fire protective as well as other properties influences the intumescent behavior which leads to
of the coatings. Fillers such as magnesium hydroxide lower intumescent ratio and poor fire performance.149
are reported to increase bonding strength to the metal
surface due to its effective interface adhesion.134
Addition of inorganic fillers results in reinforcement Use of fire-retardant additives in intumescent
of the char which improves the fire-protective perfor- formulations
mance, maintaining it for a longer time. Some inor-
ganic fillers react with APP or with its degradation Boron-containing additives are most common in the
products and leads to the formation of thermally intumescent formulation and are well known to
stable phosphate compounds which helps in maintain- increase the fire-protective performance of the
10
intumescent coatings. Interaction of boron compounds is a formation of ceramified char of silicon network in a
with intumescent additives results in formation of a polyaromatic structure which acts as a thermal barrier
vitreous layer over the surface of intumescent char. A at the surface and limits heat and mass transfer leading
low-density epoxy intumescent coating for steel against to a limited heat release rate.156 Use of nanoparticle in
hydrocarbon fires containing boric acid is shown to improving water resistance is also reported. Studies
have good performance.150 Jimenez et al. reported on showed that about 4% of surface modified nano-size
the use of boric acid and coated ammonium polyphos- silica have improved the water resistance of APP-PER-
phate (pure ammonium polyphosphate coated with MEL coatings.157 Organically modified montmoril-
THEIC) as flame retardants in an intumescent epoxy- lonite (OMMT) used as nano-filler is claimed to
based formulation. Boric acid reacts with coated improve the fire protection, water and corrosion
ammonium polyphosphate and forms borophosphate resistance of waterborne intumescent fire-retardant
which provides superior mechanical resistance to the coating. It is due to the barrier effect of parallel-
char and also enhances adhesion of char to the steel arranged OMMT which significantly slows down the
substrate.151 Colemanite (2CaOÆ3B2O3.5H2O), a com- migration and solvation of fire retardant additives.158
mercial borate mineral, is shown to act as synergistic Intumescent coatings prepared with organo-clays
agent in an intumescent PP system. It is suggested that added with different types of Cloisite 30B, 10A and
colemanite decomposes to CaO and B2O3 at high 15A in different concentrations (1%, 3%, 5%, and
temperature which can react with flame retardants 10%) have shown significant enhancement in the fire
forming a thermally resistant layer.152 Boric acid along retardancy. The formation of phosphocarbonous struc-
with ammonium polyphosphate gave best results from ture in the char enhances the fire performance.159 The
various intumescent formulations developed for steel addition of different nanoclays influences the char
in hydrocarbon fire based on thermoset epoxy-amine formation, its height, mass and structure along with its
resin system. Boric acid reacts with APP to form fracture behavior and hence influences its fire protec-
borophosphate. It increases thermal protection as well tion.160 Flame-retardant nano-coatings by the addition
as gives better adhesion and mechanical strength to the of nano-size layer double hydroxides (nano-LDHs)
char.151,153 An intumescent epoxy coating is claimed to and titanium dioxide (nano-TiO2) to APP-PER-MEL
have improved fire protection by incorporation of zinc systems have also been reported. Nano-LDHs lead to
borate or zinc oxide along with it.68 the formation of an intercalated nanostructure of the
char and mixed metal oxides (Al2O3 and MgAl2O4)
during thermal decomposition. The intercalated nanos-
tructure enhances the antioxidation property of the
Use of nanoparticles in intumescent formulations char. APP and layered double hydroxide (LDH) show
a synergistic effect on flame-retardant properties of
The addition of nano-scale additives has shown to poly vinyl alcohol.161 It is reported that only specific
enhance the fire protection performance of the intu- amounts (1.5%) of nano-LDHs could significantly
mescent coatings. Various nano-additives like nano- improve its char layer structure and fire-resistant
clays, e.g., montmorillonite, hectorite, saponite, dou- properties.162 The intumescent degree decreases with
ble-layered Mg Al hydroxides improve thermal shield- increasing LDH content, thus giving poor thermal
ing performance of intumescent coatings. Carbon shielding performances. However, it also depends on
nanotubes (CNT), metals nanoparticles of silica, alu- the functionalization of the LDH.163,164 Nano-alu-
minum, and titanium, fullerenes, silsesquioxane are minum hydroxide in intumescent PP leads to the
shown to perform synergistically in improving the formation of a more intact and homogeneous char
performance of intumescent coatings. during combustion. It also interacts with the degrada-
The introduction of CNT into intumescent formu- tion products of APP giving aluminum metaphosphate,
lation increases the thermal stability up to certain which provides a synergistic effect in the condensed
temperature range, but then causes a severe deterio- phase.165 Fumed silica in APP-based intumescent
ration in performance due to the interaction of the coatings is shown to have a beneficial effect. Silicon
network structure and the intumescent carbonaceous migrates on the surface in the heating process and
char. The increase in the concentration of MWCNT three-dimensional interpenetrating networks were
results in cracking of the char due to complex inter- formed leading to the formation of a physically strong
actions between MWCNTs and IFR on heating in charred surface layer.163,166,167 Dong et al. reported the
PP.154 MWCNT may be effective as a flame retardant use of nano-sized boron nitride in the waterborne
in polymer nanocomposites, but are not suitable for intumescent coating.168 It is demonstrated that nano-
intumescent coatings due to their degradation at high sized boron nitride improves the cell size distribution,
temperature.155 CNTs do not have enhanced reaction foam structure and the mechanical strength of the char
in APP system while organically modified polyhedral layer improving its heat insulation. Polymer flame-
oligomeric silsesquioxane (OMPOSS) in combination retardant composition which forms a homogeneous
with APP provides a large synergistic effect. Polyhe- foamy char using nano-graphene is also reported.169
dral oligomeric silsesquioxane also claimed to act as a Cyclodextrin nanosponges are also claimed as novel
flame retardant for thermoplastic polyurethane. There green flame retardants. The nanosponge architectures
11
keep phosphorus derivatives embedded and generate of water and ions through the coating and, therefore,
phosphoric acid directly in situ at high temperatures. helps in reducing water sensitivity of the coating.175
As a result, they dehydrate, resulting in char formation Polyurethane/EG coating, which is obtained by poly
and thus significantly increasing fire protection.170 condensation of an isocyanate with a polyol, eliminates
drawbacks such as the loss of mechanical properties or
processing difficulties improving fire retardancy of
Expandable graphite (EG)-based intumescent polymers.176 Boric acid modification ensures a uniform
H3BO3 distribution over the surface, thereby consid-
coatings erably improving the fire protection of the material.177
Grafting 3-isocyanatopropyltriethoxysilane (IPTS) to
EG is a new class of intumescent additives having an
EG as coupling agent reacts with a polymer matrix,
exfoliated structure intercalated with acid intercalating
resulting in increased thermal stability and flame
agents (H2SO4 or HNO3) into the graphite crystal
retardancy.178 Gardelle et al. have reported on cur-
structure (Fig. 6). Under fire at high temperatures, the
able-silicone-based coatings containing EG and organ-
intercalated agents release gases and expansion takes
oclay. It is observed that the presence of the non-
place in a perpendicular direction to the carbon layers
degraded silicone matrix, coating of graphite pellets by
in the crystal structure.171,172 Current research demon-
silicone and also the organoclay increases the cohesion
strated that EG can be a useful additive in improving
of the char.179,180 Higher addition of EG may result in
flame-retardant properties of the coatings.
poor bonding of coating.181 It is also reported that
An intumescent coating for steel conduits using
titanium-based catalyst gives higher fire protection and
expandable graphite and glass or ceramic micro
better mechanical properties to the char than the tin
balloons is reported.173 Expandable graphite modified
catalyst in intumescent silicone coatings. It is con-
by polyethylene glycol improves the thermal shielding
firmed that during crosslinking, tin migrates to the
performance of the intumescent coating. It is reported
surface leading to a low thermal stability and thus, low
that adding modified EG increases cell size of the char
fire performances while titanium catalyst interacts with
layer and also narrows the cell size distribution.174
the silicone network forming Si–O–Ti linkage, increas-
Most of the flame-retardant additives in APP–PER–
ing the thermal stability of the matrix and thus
MEL coatings are water sensitive, and thus during
enhancing the fire performance of the coating.182
water immersion, the compositional changes result in
the reduction of the fire performance of coatings. The
unique structure of graphite flakes with specific paral- Performance testing of fire-protective
lel-arrangement acts as a hindrance to the permeation intumescent coatings
No two fire conditions are similar. The extent of
temperature rise mainly depends on the type and
quantity of fuel, availability of oxygen, and ambient
conditions. Thus, for testing, fire performance of this
kind of coatings standard fire curves have been
defined.183 In fire-resistance design of structures and
– tall buildings, performance-based structural fire engi-
HSO4
neering is mostly accepted method of structural design.
HSO4
– This makes it important to understand the performance
H2SO4 of these coatings under a range of potential designed fire
conditions. Other methods for determining the heat
transfer to structural elements are by using heat flux-
time curves and temperature–time curves. The fire
resistance of building structures is mainly decided by
the time within which the structural members achieves a
critical temperature which reduces their load bearing
capacity. In many countries, the critical temperature for
H2SO4 –
H2SO4 HSO4
–
steel structures is 500–550C, above which it starts losing
HSO4
its mechanical properties.184,185
The use of an intumescent coating on structural steel
may prolong the fire rating time from few minutes to
several hours. Apart from the formulation, the perfor-
mance also depends on the thickness of the coatings,
types of steel sections, e.g., I section, hallow sections
and their orientation, e.g., beams, columns. The tests
are carried out in the large test furnace nearly
Fig. 6: Expandable graphite structure (3 m 9 4 m 9 6 m) where the conditions of tempera-
12
ture and load are simulated. The temperature of the ings provide good protection against fire. An intumes-
furnace, as well as the inside of the steel core, is cent coating containing sodium, potassium, and lithium
measured by well-placed thermocouples and the test is silicate was formulated containing expandable graphite
carried out according to various fire curves. British and silicon carbide. The expanded char and time–
standard BS 476 part 20, 21 and ISO 834 describes the temperature profile of the coating are shown in Figs. 7,
test method for intumescent coatings in cellulosic fire 8. The back panel temperature of these coatings on
exposure. Other standard test curves include UL 1709 aluminum substrates after 60 min was 180C. The char
for hydrocarbon fire and ISO 22899 for jet fire. The produced was very tough and expansion was 15 times
increase of temperature in the furnace follows the of the original thickness. Increasing the coating thick-
dependency as per the relation given below.186,187 ness resulted in better fire rating thus increasing the
evacuation time. However, the mechanical properties
T T0 ¼ 345 Log ð8t þ 1Þ; of the coatings were not good and the coating had poor
application properties.
where t is the time in minutes, T is the furnace The inorganic-based intumescent coating was thus
temperature (C) within time t, T0 is the initial furnace modified with organic binders to overcome the draw-
temperature (C). backs. An epoxy-based silicate intumescent coating
An essential requirement for the intumescent coat- showed a good fire performance with a back panel
ing to protect steel is that it should remain intact in the temperature of 180C at the end of 60 min. The char
event of a fire. Adhesion and cohesion of char in fire was strong but the application of the coating was still
scenario are also important issues. The durability of not adequate (Figs. 9, 10).
coatings is important for effective fire protection in a In order to further improve the application proper-
long run. Poor protection can lead to corrosion and ties of the silicate-based intumescent coatings, water-
possibly structural failure in fire and expensive main- based emulsions were introduced into the formulation
tenance cost. The major ingredients ammonium along with organoclay, aluminum hydroxide, silicon
polyphosphate, pentaerythritol, and melamine are carbide, and zinc borate. The coating showed excellent
water sensitive and need careful formulation. For
testing durability of the coatings, many standard 220
coating tests are used. NORSOK M-501 and European
200
Technical Approval Guidance ETAG 18-2 are some to
mention here. The panels are exposed to the specified 180
exposure environment according to these test proce- 160

dures and are then fire tested against a non-exposed
Temperature °C
140
sample.188
120
100
6.5 mm
Work done in our lab at IIT Bombay 80
4.5 mm
60 2 mm
Various inorganic- and organic-based intumescent
40
coatings were developed in our laboratory at IIT
Bombay. Some of the findings of the work are 20
described below: 0 20 40 60 80 100 120

The coatings were developed using sodium, potas- Time (min)
sium, and lithium silicates along with other fire-
retardant additives. It was observed that only alkali Fig. 8: Time–temperature profile of silicate intumescent
silicate-based coatings cannot provide fire protection coatings
for more than 20 min and are not suitable for extreme
conditions. Expandable graphite-based silicate coat-
Fig. 9: Epoxy silicate intumescent coatings (a) before and

Fig. 7: Char of silicate intumescent coatings (b) after fire testing
13
240 The developed intumescent silicate coatings have

2 mm Epoxy silicate coating excellent expansion and char strength but are poor in
220
mechanical properties, over-coating ability and have a
200
severe problem with moisture absorption in the humid
180 atmosphere leading to severe corrosion. Currently, we
160 are working on the development of both waterborne
Temperature °C
140 and solventborne organic thin film intumescent coat-

120 ings. Various formulations are developed for improve-
ment in char fragility and mechanical strength. The
100
developed formulations also have a good fire rating
80 and corrosion resistance. APP modifications in water-
60 based emulsions and epoxy systems with various
40 incorporated additives like nano-clays, metal nano-
20 particles and vitreous fillers helped in improving the
0
properties of the intumescent coatings. In addition,
0 10 20 30 40 50 60 various test methods were designed for laboratory
Time (min) testing of the intumescent coatings, e.g., small-scale
testing for adhesion and strength of char.
Fig. 10: Time–temperature profile of intumescent epoxy
silicate coatings
Conclusion
Intumescent coatings provide passive fire protection
with a rating of few minutes to several hours and are
consistently used by architects and designers. In
addition, they also offer aesthetic appearance and ease
of application. They can be formulated for use in
cellulosic fire and hydrocarbon fire including jet fire
and are effective in prolonging fire-induced structural
collapse. The present review focuses several aspects of
Fig. 11: Silicate acrylic intumescent formulation intumescent coatings i.e., their classifications, compo-
sition variations and effect of several additives. The use
of appropriate ingredients in formulation is of para-
200 mount importance as it largely influences the fire
180
shielding performance. High-temperature stable fillers,
nano-metal oxides, and clays modify the morphology
160 of the intumescent char and increase thermal stability.
The nano-additives are effective only at low concen-
140
trations.
Temperature °C
120 Modern day intumescent coatings provide effective

passive fire protection in the event of a fire but still
100 have some pitfalls. Lower fire ratings and application
80
involving several layers with long drying times make
the use of these coatings difficult on site. Due to use of
60 water sensitive ingredients in the formulations, the
outdoor exposed coatings have poor corrosion resis-
40
tance. The ingredients leach out of the coating in moist
20 environments and the coatings lose their intumescence
with time. The carbonaceous char formed may have
0 10 20 30 40 50 60 poor cohesive strength and fragility and may dislodge
Time (min) due to mechanical disturbances of falling objects
Fig. 12: Time–temperature profile of silicate acrylic intu-
during a fire event.
mescent Use of nanofillers and nano-clays, surface modifica-
tion of ammonium polyphosphate, and formulating
with vitreous fillers are some of the promising
intumescent property with higher expansion and strong approaches in the formulation of high-performance
char and good application properties (Figs. 11, 12). intumescent coatings.
14
References 24. Craig Lipka, JP, Roger Youngs, ‘‘Intumescent Coating

Composition and Process for Fire-Retardant Wood Product
1. Saxena, NK, Gupta, DR, ‘‘Development and Evaluation of Having Intumescent Coating.’’ US Patent US20100223878
Fire Retardant Coatings.’’ Fire Technol., 26 (4) 329–341 A1
(1990) 25. Camino, G, Costa, L, Martinasso, G, ‘‘Intumescent Fire-
2. Bourbigot, S, Duquesne, S, ‘‘Fire Retardant Polymers: Retardant Systems.’’ Polym. Degrad. Stab., 23 (4) 359–376
Recent Developments and Opportunities.’’ J. Mater. (1989)
Chem., 17 (22) 2283–2300 (2007) 26. Camino, G, Costa, L, ‘‘Mechanism of Intumescence in Fire
3. Vandersall, H, ‘‘Intumescent Coating Systems, Their Devel- Retardant Polymers.’’ Rev. Inorg. Chem., 8 (1–2) 69–100
opment and Chemistry.’’ J. Fire Flammabil., 2 (2) 97–140 (1986)
(1971) 27. Camino, G, ‘‘Flame Retardants: Intumescent Systems.’’ In:
4. Hao, J, Chow, WK, ‘‘A Brief Review of Intumescent Fire Pritchard, G (ed.) Plastics Additives, pp. 297–306. Springer,
Retardant Coatings.’’ Arch. Sci. Rev., 46 (1) 89–95 (2003) Dordrecht (1998)
5. Weil, ED, ‘‘Fire-Protective and Flame-Retardant Coat- 28. Camino, G, Costa, L, Trossarelli, L, ‘‘Study of the Mech-
ings—A State-of-the-Art Review.’’ J. Fire Sci., 29 (3) 259– anism of Intumescence in Fire Retardant Polymers: Part
296 (2011) V—Mechanism of Formation of Gaseous Products in the
6. Fire Protection of Structural Steel in High-Rise Buildings. Thermal Degradation of Ammonium Polyphosphate.’’
www.fire.nist.gov/bfrlpubs/build04/PDF/b04047.pdf Ac- Polym. Degrad. Stab., 12 (3) 203–211 (1985)
cessed February 2016 29. Camino, G, Costa, L, Trossarelli, L, Costanzi, F, Landoni,
7. Challener, C, ‘‘Fire Safety with Specialty Coatings.’’ JCT G, ‘‘Study of the Mechanism of Intumescence in Fire
CoatingsTech., 4 (9) 78 (2007) Retardant Polymers: Part IV—Evidence of Ester Forma-
8. Mike Reed, GM, US Coatings, Intumescent Coating vs. tion in Ammonium Polyphosphate-Pentaerythritol Mix-
Cementitious Coating. Coatings World (March 2015) tures.’’ Polym. Degrad. Stab., 8 (1) 13–22 (1984)
9. Horacek, H, Pieh, S, ‘‘The Importance of Intumescent 30. Horacek, H, ‘‘Reactions of Stoichiometric Intumescent
Systems for Fire Protection of Plastic Materials.’’ Polym. Paints.’’ J. Appl. Polym. Sci., 113 (3) 1745–1756 (2009)
Int., 49 (10) 1106–1114 (2000) 31. Cao, K, Wu, S-L, Wang, K-L, Yao, Z, ‘‘Kinetic Study on
10. Kirbyshire, A, Stewart, A, A Fire Protective Coating. Surface Modification of Ammonium Polyphosphate with
WO2011151649 A1 Melamine.’’ Ind. Eng. Chem. Res., 50 (14) 8402–8406 (2011)
11. Bulewicz, EM, Pelc, A, Kozlowski, R, Miciukiewicz, A, 32. Wu, K, Wang, Z, Liang, H, ‘‘Microencapsulation of
‘‘Intumescent Silicate-Based Materials: Mechanism of Ammonium Polyphosphate: Preparation, Characterization,
Swelling in Contact with Fire.’’ Fire Mater., 9 (4) 171–175 and its Flame Retardance in Polypropylene.’’ Polym.
(1985) Comp., 29 (8) 854–860 (2008)
12. Langille, KB, Nguyen, D, Bernt, JO, Veinot, DE, Murthy, 33. Wu, K, Wang, Z, ‘‘Intumescent Flame Retardation of EVA
MK, ‘‘Mechanism of Dehydration and Intumescence of Using Microencapsulated Ammonium Polyphosphate and
Soluble Silicates.’’ J. Mater. Sci., 26 (3) 695–703 (1991) Pentaerythritols.’’ Polym. Plast. Technol. Eng., 47 (3) 247–
13. Veinot, DE, Langille, KB, Nguyen, D, Bernt, JO, ‘‘Soluble 254 (2008)
Silicate-Based Coatings for Fire Protection.’’ Fire Technol., 34. Tang, Q, Wang, B, Shi, Y, Song, L, Hu, Y, ‘‘Microencap-
25 (3) 230–240 (1989) sulated Ammonium Polyphosphate with Glycidyl
14. Dat T. Nguyen, DEV, James Foster, ‘‘Inorganic Intumes- Methacrylate Shell: Application to Flame Retardant Epoxy
cent Fire Protective Coatings.’’ US patent US4888057 A Resin.’’ Ind. Eng. Chem. Res., 52 (16) 5640–5647 (2013)
15. Langille, KB, Nguyen, DT, Veinot, DE, Bernt, JO, ‘‘Intu- 35. Wu, K, Wang, Z, Hu, Y, ‘‘Microencapsulated Ammonium
mescent powder.’’ US patent US 6645278 B2 Polyphosphate with Urea–Melamine–Formaldehyde Shell:
16. Langille, KB, Nguyen, D, Bernt, JO, Veinot, DE, Murthy, Preparation, Characterization, and its Flame Retardance in
MK, ‘‘Constitution and Properties of Phosphosilicate Coat- Polypropylene.’’ Polym. Adv. Technol., 19 (8) 1118–1125
ings.’’ J. Mater. Sci., 28 (15) 4175–4182 (1993) (2008)
17. Kandare, E, Chukwudolue, C, Kandola, BK, ‘‘The Use of 36. Chen, X, Jiao, C, Zhang, J, ‘‘Microencapsulation of
Fire-Retardant Intumescent Mats for Fire and Heat Pro- Ammonium Polyphosphate with Hydroxyl Silicone Oil
tection of Glass Fibre-Reinforced Polyester Composites: and Its Flame Retardance in Thermoplastic Polyurethane.’’
Thermal Barrier Properties.’’ Fire Mater., 34 (1) 21–38 J. Therm. Anal. Calorim., 104 (3) 1037–1043 (2011)
(2010) 37. Wu, K, Song, L, Wang, Z, Hu, Y, ‘‘Microencapsulation of
18. Wainwright, R, Evans, KA, ‘‘Intumescent Compositions.’’ Ammonium Polyphosphate with PVA–Melamine–Formalde-
US Patent US5532292 A hyde Resin and Its Flame Retardance in Polypropylene.’’
19. Erismann, D, Vesley, G, ‘‘Aqueous Intumescent Fire Polym. Adv. Technol., 19 (12) 1914–1921 (2008)
Barrier Composition.’’ US Patent US20020171068 A1 38. Lei, Z, Cao, Y, Xie, F, Ren, H, ‘‘Study on Surface
20. Youngs, RW, ‘‘Intumescent Ceramic Fire Retardant Coat- Modification and Flame Retardants Properties of Ammo-
ing Containing Intumescent Ceramic Particles.’’ US Patent nium Polyphosphate for Polypropylene.’’ J. Appl. Polym.
US7045080 B1 Sci., 124 (1) 781–788 (2012)
21. Batdorf, VH, ‘‘Inorganic Based Intumescent System.’’ US 39. Ni, J, Song, L, Hu, Y, Zhang, P, Xing, W, ‘‘Preparation and
Patent US5786095 A Characterization of Microencapsulated Ammonium
22. Kalbskopf, R and Trojer, F, ‘‘Method of Forming a Fire- Polyphosphate with Polyurethane Shell by In Situ Poly-
Resistant Silicate Coating.’’ US Patent US4179535 A merization and Its Flame Retardance in Polyurethane.’’
23. Dimanshteyn, FA, ‘‘Intumescent Coatings, Alkali Metal Polym. Adv. Technol., 20 (12) 999–1005 (2009)
Silicate, Gas Releasing Inorganic Particles.’’ US Patent 40. Liu, L, Zhang, Y, Li, L, Wang, Z, ‘‘Microencapsulated
US5035951 Ammonium Polyphosphate with Epoxy Resin Shell:
15
Preparation, Characterization, and Application in EP Sys- 56. Fudang, S, Zhiming, D, Xiaomin, C, Linshuang, Z, Ye, Y,
tem.’’ Polym. Adv. Technol., 22 (12) 2403–2408 (2011) Linming, LI, ‘‘Experimental Study on Fires Extinguishing
41. Chen, M, Xu, Y, Chen, X, Ma, Y, He, W, Yu, J, Zhang, Z, Properties of Melamine Phosphate Powders.’’ Proc. Eng.,
‘‘Thermal stability and combustion behavior of flame- 84 535–542 (2014)
retardant polypropylene with thermoplastic polyurethane- 57. Pirig, WD, Rothkamp, S, Thewes, V, ‘‘Intumescent Coating
microencapsulated ammonium polyphosphate.’’ High Per- Stable Under Tropical Conditions.’’ US Patent US6054513 A
formance Polymers (2014) 58. Wang, G, Yang, J, ‘‘Thermal Degradation Study of Fire
42. Wang, B, Tang, Q, Hong, N, Song, L, Wang, L, Shi, Y, Hu, Resistive Coating Containing Melamine Polyphosphate and
Y, ‘‘Effect of Cellulose Acetate Butyrate Microencapsu- Dipentaerythritol.’’ Prog. Org. Coat., 72 (4) 605–611 (2011)
lated Ammonium Polyphosphate on the Flame Retar- 59. Ward, DA, ‘‘Fire Protection & Retardant Coatings.’’
dancy, Mechanical, Electrical, and Thermal Properties of European Patent EP2093263 B1
Intumescent Flame-Retardant Ethylene-Vinyl Acetate 60. Chyall, LJ, Hodgen, HA, Vyverberg, FJ, Chapman, RW,
Copolymer/Microencapsulated Ammonium Polyphos- ‘‘Intumescent Polymer Compositions.’’ US Patent
phate/Polyamide-6 Blends.’’ ACS Appl. Mater. Interf., 3 US6905693 B2
(9) 3754–3761 (2011) 61. Balabanovich, AI, ‘‘Thermal Decomposition Study of
43. Qu, H, Wu, W, Hao, J, Wang, C, Xu, J, ‘‘Inorganic-Organic Intumescent Additives: Pentaerythritol Phosphate and Its
Hybrid Coating-Encapsulated Ammonium Polyphosphate Blend with Melamine Phosphate.’’ Thermochim. Acta, 435
and Its Flame Retardancy and Water Resistance in Epoxy (2) 188–196 (2005)
Resin.’’ Fire Mater., 38 (3) 312–322 (2014) 62. Zhou, S, Song, L, Wang, Z, Hu, Y, Xing, W, ‘‘Flame
44. Qu, H, Hao, J, Wu, W, Zhao, X, Jiang, S, ‘‘Optimization of Retardation and Char Formation Mechanism of Intumes-
Sol–Gel Coatings on the Surface of Ammonium Polyphos- cent Flame Retarded Polypropylene Composites Contain-
phate and its Application in Epoxy Resin.’’ J. Fire Sci., 30 ing Melamine Phosphate and Pentaerythritol Phosphate.’’
(4) 357–371 (2012) Polym. Degrad. Stab., 93 (10) 1799–1806 (2008)
45. Shao, ZB, Deng, C, Tan, YL, Chen, MJ, Chen, L, Wang, 63. Huggard, MT, White, PS, ‘‘An Alkyl Diamine Phosphate.’’
YZ, ‘‘Ammonium Polyphosphate Chemically Modified with US Patent US5137937 A
Ethanolamine as an Efficient Intumescent Flame Retardant 64. Rhodes, MS, Izrailev, L, Tuerack, J and Rhodes, PS,
for Polypropylene.’’ J. Mater. Chem. A, 2 (34) 13955–13965 ‘‘Enhancing the Flame Retardancy of Nitrogenous Phos-
(2014) phorus and/or Sulfonate Flame Retardants, Activated with
46. Shao, Z-B, Deng, C, Tan, Y, Chen, M-J, Chen, L, Wang, Y- a Char Forming Catalyst and/or a Phase Transfer Catalyst.’’
Z, ‘‘Flame Retardation of Polypropylene via a Novel US Patent US6733697 B2
Intumescent Flame Retardant: Ethylenediamine-Modified 65. Sergei, VL, Edward, DW, ‘‘Recent Progress in Flame
Ammonium Polyphosphate.’’ Polym. Degrad. Stab., 106 88– Retardancy of Polyurethane and Polyisocyanurate Foams.’’
96 (2014) Fire. Polym. IV, pp. 280–290. American Chemical Society,
47. Zheng, Z, Qiang, L, Yang, T, Wang, B, Cui, X, Wang, H, (2005)
‘‘Preparation of Microencapsulated Ammonium Polyphos- 66. Green, J, ‘‘A Review of Phosphorus-Containing Flame
phate with Carbon Source- and Blowing Agent-Containing Retardants.’’ Journal of Fire Sciences, 10 (6) 470–487 (1992)
Shell and Its Flame Retardance in Polypropylene.’’ J. 67. Weil, ED, Phosphorus-Based Flame Retardants. Flame-
Polym. Res., 21 (5) 1–15 (2014) Retardant Polymeric Materials. Springer, New York, 1978
48. Wang, G, Wang, Y, Yang, J, ‘‘Influences of Polymerization 68. Nugent, RM, Ward, TA, Greigger, PP and Seiner, JA,
Degree of Ammonium Polyphosphate on Fire Protection of ‘‘Flexible intumescent coating composition.’’ US Patent
Waterborne Intumescent Fire Resistive Coating.’’ Surf. US5108832 A
Coat. Technol., 206 (8–9) 2275–2280 (2012) 69. Aslin, CD, ‘‘Composition with Integral Intumescence
49. Zav’yalov, DE, Zybina, OA, Mitrofanov, VV, Mnat- Properties.’’ US Patent US5387655 A
sakanov, SS, ‘‘Comparative Study of the Behavior of 70. Telschow, JE, ‘‘Pentaerythritol Phosphate Alcohol-Con-
Ammonium Phosphate in Fireproofing Intumescent For- taining Phosphonate and Phosphite Compounds.’’ US
mulations.’’ Russ. J. Appl. Chem., 85 (1) 150–152 (2012) Patent US5536862 A
50. Hill, JE, ‘‘Intumescent Coating and Method of Manufac- 71. Göbelbecker, SD, Nägerl, HDD, Danker, GJ, Kirk, D,
ture.’’ US Patent US5225464 A ‘‘Intumescent Composition of the Two-Components-Type.’’
51. Giraud, S, Bourbigot, S, Rochery, M, Vroman, I, Tighzert, European Patent EP0614944 A2
L, Delobel, R, Poutch, F, ‘‘Flame Retarded Polyurea with 72. Ma, H, Fang, Z, ‘‘Synthesis and Carbonization Chemistry of
Microencapsulated Ammonium Phosphate for Textile a Phosphorous–Nitrogen Based Intumescent Flame Retar-
Coating.’’ Polym. Degrad. Stab., 88 (1) 106–113 (2005) dant.’’ Thermochim. Acta, 543 130–136 (2012)
52. Vroman, I, Giraud, S, Salaün, F, Bourbigot, S, ‘‘Polypropy- 73. Andersson, A, Lundmark, S, Maurer, FHJ, ‘‘Evaluation
lene Fabrics Padded with Microencapsulated Ammonium and Characterization of Ammoniumpolyphosphate–Pen-
Phosphate: Effect of the Shell Structure on the Thermal taerythritol-Based Systems for Intumescent Coatings.’’ J.
Stability and Fire Performance.’’ Polym. Degrad. Stab., 95 Appl. Polym. Sci., 104 (2) 748–753 (2007)
(9) 1716–1720 (2010) 74. Jenewein, EDI, Pirig, WD, ‘‘Flame-Retardant Coating
53. Weil, E, McSwigan, B, ‘‘Melamine Phosphates and Composition.’’ European Patent EP0735119 B1
Pyrophosphates in Flame Retardant Coatings: Old Products 75. Knox, CL, Damle, SB, ‘‘Intumescent Flame Retardant
with New Potential.’’ J. Coat. Technol., 66 (839) 75–82 (1994) Composition.’’ US Patent US5227416
54. Weil, ED, Choudhary, V, ‘‘Flame-Retarding Plastics and 76. Adrian, H’’, Per-Erik, V, ‘‘Intumescent Coating and Use
Elastomers with Melamine.’’ J. Fire Sci., 13 (2) 104–126 Thereof.’’ WO2006096112 A1
(1995) 77. Gestner, RE, Harshbarger, DM, ‘‘Low Density Fire Barrier
55. Kay, M, Price, AF, ‘‘Fire Test Behaviour of Various Crystal Material and Method of Making’’ US 6153668 A
Types of Melamine Phosphate in Intumescent Formula- 78. Réti, C, Casetta, M, Duquesne, S, Bourbigot, S, Delobel, R,
tions.’’ Fire Mater., 6 (3–4) 119–121 (1982) ‘‘Flammability Properties of Intumescent PLA Including
16
Starch and Lignin.’’ Polym. Adv. Technol., 19 (6) 628–635 95. Cao, K, Wu, S-L, Qiu, S-L, Li, Y, Yao, Z, ‘‘Synthesis of N-
(2008) Alkoxy Hindered Amine Containing Silane as a Multifunc-
79. Alongi, J, Pošković, M, Frache, A, Trotta, F, ‘‘Novel Flame tional Flame Retardant Synergist and Its Application in
Retardants Containing Cyclodextrin Nanosponges and Intumescent Flame Retardant Polypropylene.’’ Ind. Eng.
Phosphorus Compounds to Enhance EVA Combustion Chem. Res., 52 (1) 309–317 (2012)
Properties.’’ Polym. Degrad. Stab., 95 (10) 2093–2100 96. Wang, L, Hu, Y, Song, L, Yuen, RKK, ‘‘Investigation of
(2010) Thermal and Combustion Properties for Intumescent
80. Liu, Y, Yi, J, Cai, X, ‘‘The Investigation of Intumescent Flame-Retardant Ethylene-Viny Acetate Composites Con-
Flame-Retarded Polypropylene Using Poly(hexamethylene taining Ferrous Disulfide.’’ Ind. Eng. Chem. Res., 51 (46)
terephthalamide) as Carbonization Agent.’’ J. Therm. Anal. 15082–15088 (2012)
Calorim., 107 (3) 1191–1197 (2012) 97. Su, X, Yi, Y, Tao, J, Qi, H, ‘‘Synergistic Effect of Zinc
81. Feng, J, Zhang, X, Ma, S, Xiong, Z, Zhang, C, Jiang, Y, Hydroxystannate with Intumescent Flame-Retardants on
Zhu, J, ‘‘Syntheses of Metallic Cyclodextrins and Their Use Fire Retardancy and Thermal Behavior of Polypropylene.’’
as Synergists in a Poly(Vinyl Alcohol)/Intumescent Flame Polym. Degrad. Stab., 97 (11) 2128–2135 (2012)
Retardant System.’’ Ind. Eng. Chem. Res., 52 (8) 2784–2792 98. Wu, N, Ding, C, Yang, R, ‘‘Effects of Zinc and Nickel Salts
(2013) in Intumescent Flame-Retardant Polypropylene.’’ Polym.
82. Huang, J, Zhang, Y, Yang, Q, Liao, X, Li, G, ‘‘Synthesis Degrad. Stab., 95 (12) 2589–2595 (2010)
and Characterization of a Novel Charring Agent and Its 99. Song, R, Zhang, B, Huang, B, Tang, T, ‘‘Synergistic Effect
Application in Intumescent Flame Retardant polypropy- of Supported Nickel Catalyst with Intumescent Flame-
lene System.’’ J. Appl. Polym. Sci., 123 (3) 1636–1644 (2012) Retardants on Flame Retardancy and Thermal Stability of
83. Zhang, R, Xiao, X, Tai, Q, Huang, H, Hu, Y, ‘‘Modification Polypropylene.’’ J. Appl. Polym. Sci., 102 (6) 5988–5993
of Lignin and Its Application as Char Agent in Intumescent (2006)
Flame-Retardant Poly(lactic acid).’’ Polym. Eng. Sci., 52 100. Bourbigot, S, Le Bras, M, Delobel, R, Tremillon, J-M,
(12) 2620–2626 (2012) ‘‘Synergistic Effect of Zeolite in an Intumescence Process.
84. Taylor, AP, Sale, FR, ‘‘Thermoanalytical Studies of Intu- Study of the Interactions Between the Polymer and the
mescent Systems.’’ Makromol. Chem. Macromol. Symp., 74 Additives.’’ J. Chem. Soc. Faraday Trans., 92 (18) 3435–
(1) 85–93 (1993) 3444 (1996)
85. Costa, L, Camino, G, ‘‘Thermal Behaviour of Melamine.’’ 101. Bourbigot, S, Le Bras, M, Delobel, R, Decressain, R,
J. Ther. Anal., 34 (2) 423–429 (1988) Amoureux, J-P, ‘‘Synergistic Effect of Zeolite in an
86. Wirnhier, E, Mesch, MB, Senker, J, Schnick, W, ‘‘Forma- Intumescence Process: Study of the Carbonaceous Struc-
tion and Characterization of Melam, Melam Hydrate, and a tures Using Solid-State NMR.’’ J. Chem. Soc. Faraday
Melam-Melem Adduct.’’ Chemistry, 19 (6) 2041–2049 Trans., 92 (1) 149–158 (1996)
(2013) 102. Estevão, LRM, Le Bras, M, Delobel, R, Nascimento, RSV,
87. Thewes, V, Pirig, WD, ‘‘Flame-Retardant Coating ‘‘US ‘‘Spent Refinery Catalyst as a Synergistic Agent in Intu-
Patent US 6251961 B1 mescent Formulations: Influence of the Catalyst’s Particle
88. Camino, G, Costa, L, Trossarelli, L, ‘‘Study of the Mech- Size and Constituents.’’ Polym. Degrad. Stab., 88 (3) 444–
anism of Intumescence in Fire Retardant Polymers: Part 455 (2005)
III—Effect of Urea on the Ammonium Polyphosphate- 103. Levine, HS, ‘‘Intumescent Heat-and Fire-Resistant Com-
Pentaerythritol System.’’ Polym. Degrad. Stab., 7 (4) 221– position and Substrate Coated Therewith.’’ US Patent US
229 (1984) 5,356,568
89. Wang, J-S, Liu, Y, Zhao, H-B, Liu, J, Wang, D-Y, Song, Y- 104. Fan, F, Xia, Z, Li, Q, Li, Z, Chen, H, ‘‘Thermal Stability of
P, Wang, Y-Z, ‘‘Metal Compound-Enhanced Flame Retar- Phosphorus-Containing Styrene–Acrylic Copolymer and Its
dancy of Intumescent Epoxy Resins Containing Ammo- Fire Retardant Performance in Waterborne Intumescent
nium Polyphosphate.’’ Polym. Degrad. Stab., 94 (4) 625–631 Coatings.’’ J. Therm. Anal. Calorim., 114 (3) 937–946 (2013)
(2009) 105. Delobel, R, Duquesne, S, Jama, C, Magnet, S, ‘‘Polymer
90. Zhang, P, Song, L, Lu, H, Wang, J, Hu, Y, ‘‘The Thermal Binder for Intumescent Coatings.’’ WO2004061020 A1
Property and Flame Retardant Mechanism of Intumescent 106. Duquesne, S, Magnet, S, Jama, C, Delobel, R, ‘‘Intumes-
Flame Retardant Paraffin System with Metal.’’ Ind. Eng. cent Paints: Fire Protective Coatings for Metallic Sub-
Chem. Res., 49 (13) 6003–6009 (2010) strates.’’ Surf. Coat. Technol, 180–181 302–307 (2004)
91. Labuschagné, FJWJ, Focke, WW, ‘‘Metal Catalysed Intu- 107. Duquesne, S, Magnet, S, Jama, C, Delobel, R, ‘‘Thermo-
mescence: Characterisation of the Thermal Decomposition plastic Resins for Thin Film Intumescent Coat-
of Calcium Gluconate Monohydrate.’’ J. Mater. Sci., 38 (6) ings—Towards a Better Understanding of Their Effect on
1249–1254 (2003) Intumescence Efficiency.’’ Polym. Degrad. Stab., 88 (1) 63–
92. Qiao, ZH, Yang, W, Song, L, Hu, Y, Kong, FQ, Li, J, Yan, 69 (2005)
HZ, Huang, W, ‘‘Synergistic Effects of Cerium(IV) Phos- 108. Magnet, S, Duquesne, S, Delobel, R, Jama, C, ‘‘Polymer
phate with Intumescent Flame Retardant in Styrene Buta- Binder for Intumescent Coatings.’’ US Patent US7105605
diene Rubber.’’ Plast. Rubb. Comp., 40 (8) 413–419 (2011) B2
93. Li, Y, Li, B, Dai, J, Jia, H, Gao, S, ‘‘Synergistic Effects of 109. Magnet, S, Duquesne, S, Delobel, R, Jama, C, ‘‘Polymer
Lanthanum Oxide on a Novel Intumescent Flame Retar- Binder for Intumescent Coatings. US Patent US20070010
dant Polypropylene System.’’ Polym. Degrad. Stab., 93 (1) 624 A1
9–16 (2008) 110. Ducrocq, P, Duquesne, S, Magnet, S, Bourbigot, S, Delobel,
94. Sheng, Y, Chen, Y, Bai, Y, ‘‘Catalytically Synergistic R, ‘‘Interactions Between Chlorinated Paraffins and Mel-
Effects of Novel LaMnO3 Composite Metal Oxide in amine in Intumescent Paint—Investing a Way to Suppress
Intumescent Flame-Retardant Polypropylene System.’’ Chlorinated Paraffins from the Formulations.’’ Prog. Org.
Polym. Comp., 35 (12) 2390–2400 (2014) Coat., 57 (4) 430–438 (2006)
17
111. Le Bras, M, Bourbigot, S, Revel, B, ‘‘Comprehensive Study 131. Yew, MC, Ramli Sulong, NHR, ‘‘Fire-Resistive Perfor-
of the Degradation of an Intumescent EVA-Based Material mance of Intumescent Flame-Retardant Coatings for
During Combustion.’’ J. Mater. Sci., 34 (23) 5777–5782 Steel.’’ Mater. Des., 34 719–724 (2012)
(1999) 132. Liu, Y, Zhao, J, Deng, C-L, Chen, L, Wang, D-Y, Wang, Y-
112. Wang, G, Yang, J, ‘‘Influences of Molecular Weight of Z, ‘‘Flame-Retardant Effect of Sepiolite on an Intumescent
Epoxy Binder on Fire Protection of Waterborne Intumes- Flame-Retardant Polypropylene System.’’ Ind. Eng. Chem.
cent Fire Resistive Coating.’’ Surf. Coat. Technol., 206 (8–9) Res., 50 (4) 2047–2054 (2011)
2146–2151 (2012) 133. Wang, L, Yang, W, Wang, B, Wu, Y, Hu, Y, Song, L, Yuen,
113. John, SM, Edward, WJ, ‘‘Fire Retardant Intumescent RKK, ‘‘The Impact of Metal Oxides on the Combustion
Coating.’’ WO2002077110 A8 Behavior of Ethylene-Vinyl Acetate Coploymers Contain-
114. Sinclair, M, Watts, J, ‘‘Fire Retardant Intumescent Coat- ing an Intumenscent Flame Retardant.’’ Ind. Eng. Chem.
ing.’’ US Patent US20050101696 A1 Res., 51 (23) 7884–7890 (2012)
115. Zakikhani, M, ‘‘Flame Retardant Polymer Emulsion.’’ US 134. Yew, MC, RamliSulong, NH, Yew, MK, Amalina, MA,
Patent US20070145338 A1 Johan, MR, ‘‘Influences of Flame-Retardant Fillers on Fire
116. Reinheimer, A, ‘‘A Mixture of Curable Addition-Conden- Protection and Mechanical Properties of Intumescent
sation Copolymers.’’ US Patent US20080121851 A1 Coatings.’’ Prog. Org. Coat., 78 59–66 (2015)
117. Green, JD, Allen, W, ‘‘Intumescent Coating Composi- 135. Duquesne, S, Bachelet, P, Bellayer, S, Bourbigot, S,
tions.’’ US Patent US20080224105 A1 Mertens, W, ‘‘Influence of Inorganic Fillers on the Fire
118. Green, JD, Allen, W, Taylor, AP, Butterfield, S, ‘‘Intumes- Protection of Intumescent Coatings.’’ J. Fire Sci., 31 (3)
cent Coating Compositions.’’ US Patent US20090143501 A1 258–275 (2013)
119. Green, JD, Allen, W, Taylor, AP, Butterfield, S, ‘‘Intumes- 136. Ullah, S, Ahmad, F, ‘‘Effects of Zirconium Silicate Rein-
cent Coating Compositions.’’ US Patent WO2006067478 A1 forcement on Expandable Graphite Based Intumescent Fire
120. Ma, Z, Wang, J, Chen, S, Li, X, Ma, H, ‘‘Synthesis and Retardant Coating.’’ Polym. Degrad. Stab., 103 49–62
Characterization of Water Borne Intumescent Fire Retar- (2014)
dant Varnish Based on Phosphate Resin Acid Cold Cured 137. Kobayashi, N, Yoshioki, H, Yoshida, K, Sagawa, K,
Amino Resin.’’ Prog. Org. Coat., 74 (3) 608–614 (2012) Ishihara, S, ‘‘Intumescent Fire-Resistant Coating, Fire-
121. Schmitt, G, Neugebauer, P, Scholl, S, Heeb, H, Reinhard, P Resistant Material, and Process for Producing the Fire-
and KÜHL, G, ‘‘Intumescent Coating Composition with Resistant Material.’’ US Patent US5401793 A
Enhanced Metal Adhesion.’’ US Patent US20120164462 138. Wang, G, Yang, J, ‘‘Influences of Glass Flakes on Fire
122. Dong, Y, Wang, G, Yang, J, ‘‘Influences of Silicone Protection and Water Resistance of Waterborne Intumes-
Emulsion on Fire Protection of Waterborne Intumescent cent Fire Resistive Coating for Steel Structure.’’ Prog. Org.
Fire-Resistive Coating.’’ J. Coat. Technol. Res., 11 (2) 231– Coat., 70 (2–3) 150–156 (2011)
237 (2014) 139. Taylor, AP, Butterfield, S, Green, JD, Allen, W, ‘‘Intumes-
123. Wang, G, Yang, J, ‘‘Influences of Binder on Fire Protection cent Coating Compositions.’’ US Patent US8461244 B2
and Anticorrosion Properties of Intumescent Fire Resistive 140. Olcese, T, Pagella, C, ‘‘Vitreous Fillers in Intumescent
Coating for Steel Structure.’’ Surf. Coat. Technol., 204 (8) Coatings.’’ Prog. Org. Coat., 36 (4) 231–241 (1999)
1186–1192 (2010) 141. Puri, RG, Khanna, AS, ‘‘Effect of Cenospheres on the Char
124. Otáhal, R, Veselý, D, Násadová, J, Zı́ma, V, Němec, P, Formation and Fire Protective Performance of Water-
Kalenda, P, ‘‘Intumescent Coatings Based on an Organic- Based Intumescent Coatings on Structural Steel.’’ Prog.
Inorganic Hybrid Resin and the Effect of Mineral Fibres on Org. Coat., 92 8–15 (2016)
Fire-Resistant Properties of Intumescent Coatings.’’ Pigm. 142. Koo, JH, Ng, PS, Cheung, F-B, ‘‘Effect of High Temper-
Resin Technol., 40 (4) 247–253 (2011) ature Additives in Fire Resistant Materials.’’ J. Fire Sci., 15
125. Gardelle, B, Duquesne, S, Rerat, V, Bourbigot, S, ‘‘Ther- (6) 488–504 (1997)
mal Degradation and Fire Performance of Intumescent 143. Canosa, G, Alfieri, PV, Giudice, CA, ‘‘Hybrid Intumescent
Silicone-Based Coatings.’’ Polym. Adv. Technol., 24 (1) 62– Coatings for Wood Protection against Fire Action.’’ Ind.
69 (2013) Eng. Chem. Res., 50 (21) 11897–11905 (2011)
126. Gardelle, B, Duquesne, S, Vandereecken, P, Bourbigot, S, 144. Zia-ul-Mustafa, M, Ahmad, F, Megat-Yusoff, PSM, Aziz,
‘‘Resistance to Fire of Silicone-Based Coatings: Fire Pro- H, ‘‘The Effect of Wollastonite Filler on Thermal Perfor-
tection of Steel against Cellulosic Fire.’’ J. Fire Sci., 32 (4) mance of Intumescent Fire Retardant Coating.’’ Proc. Adv.
374–387 (2014) Mater. Res., Vol. 970, pp. 328–331 (2014)
127. Yew, MC, Ramli Sulong, NH. ‘‘Effect of Epoxy Binder on 145. Yew, MC, Ramli Sulong, NH, Yew, MK, Amalina, MA,
Fire Protection and Bonding Strength of Intumescent Fire Johan, MR, ‘‘Fire Propagation Performance of Intumescent
Protective Coatings for Steel.’’ Adv. Mater. Res. 168 (2011). Fire Protective Coatings Using Eggshells as a Novel
128. Li, H, Hu, Z, Zhang, S, Gu, X, Wang, H, Jiang, P, Zhao, Q, Biofiller.’’ Sci. World J., 2014, 805094 (2014). doi:10.1155/
‘‘Effects of Titanium Dioxide on the Flammability and 2014/805094
Char Formation of Water-Based Coatings Containing 146. Mohamad, WF, Ahmad, F, Ullah, S, ‘‘Effect of Inorganic
Intumescent Flame Retardants.’’ Prog. Org. Coat., 78 Fillers on Thermal Performance and Char Morphology of
318–324 (2015) Intumescent Fire Retardant Coating.’’ Asian J. Sci. Res., 6
129. Gottfried, S, ‘‘Intumescent Fire-Retardant Composition for (2) 263–271 (2013)
High Temperature and Long Duration Protection.’’ US 147. Yew, MC, RamliSulong, NH, Yew, MK, Amalina, MA,
Patent US5723515 A Johan, MR, ‘‘Eggshells: A Novel Bio-Filler for Intumescent
130. Li, G, Yang, J, He, T, Wu, Y, Liang, G, ‘‘An Investigation Flame-Retardant Coatings.’’ Prog. Org. Coat., 81 116–124
of the Thermal Degradation of the Intumescent Coating (2015)
Containing MoO3 and Fe2O3.’’ Surf. Coat. Technol., 202 148. Ullah, S, Ahmad, F, Shariff, AM, Bustam, MA, ‘‘Synergistic
(13) 3121–3128 (2008) Effects of Kaolin Clay on Intumescent Fire Retardant
18
Coating Composition for Fire Protection of Structural Steel 166. Kozlowski, R, Wesolek, D, Wladyka-Przybylak, M, ‘‘Intu-
Substrate.’’ Polym. Degrad. Stab., 110 91–103 (2014) mescent Fire Retardant and the Method of its Manufac-
149. Fan, F-Q, Xia, Z-B, Li, Q-Y, Li, Z, ‘‘Effects of Inorganic ture.’’ US Patent US20090215926 A1
Fillers on the Shear Viscosity and Fire Retardant Perfor- 167. Chen, Y, Zhan, J, Zhang, P, Nie, S, Lu, H, Song, L, Hu, Y,
mance of Waterborne Intumescent Coatings.’’ Prog. Org. ‘‘Preparation of Intumescent Flame Retardant Poly(buty-
Coat., 76 (5) 844–851 (2013) lene succinate) Using Fumed Silica as Synergistic Agent.’’
150. Hanafin, JW, Bertrand, DC, ‘‘Low Density, Light Weight Ind. Eng. Chem. Res., 49 (17) 8200–8208 (2010)
Intumescent Coating.’’ US Patent US6096812 A 168. Dong, Y, Wang, G, ‘‘Influence of Nano-Boron Nitride on
151. Jimenez, M, Duquesne, S, Bourbigot, S, ‘‘Intumescent Fire Fire Protection of Waterborne Fire-Resistive Coatings.’’ J.
Protective Coating: Toward a Better Understanding of Coat. Technol. Res., 11 (2) 265–272 (2014)
Their Mechanism of Action.’’ Thermochim. Acta, 449 (1–2) 169. Han, SJ, Paquette, MS, Cieslinski, RC, ‘‘Polymer Compos-
16–26 (2006) ite with Intumescent Graphene.’’ US Patent
152. Atikler, U, Demir, H, Tokatlı, F, Tıhmınlıoğlu, F, Balköse, US20110095244 A1
D, Ülkü, S, ‘‘Optimisation of the Effect of Colemanite as a 170. Alongi, J, Poskovic, M, Visakh, PM, Frache, A, Malucelli,
New Synergistic Agent in an Intumescent System.’’ Polym. G, ‘‘Cyclodextrin Nanosponges as Novel Green Flame
Degrad. Stab., 91 (7) 1563–1570 (2006) Retardants for PP, LLDPE and PA6.’’ Carbohydr. Polym.,
153. Jimenez, M, Duquesne, S, Bourbigot, S, ‘‘Characterization 88 (4) 1387–1394 (2012)
of the Performance of an Intumescent Fire Protective 171. Kang, F, Leng, Y, Zhang, T-Y, ‘‘Influences of H2O2 on
Coating.’’ Surf. Coat. Technol., 201 (3–4) 979–987 (2006) Synthesis of H2SO4-GICs.’’ J. Phys. Chem. Solids, 57 (6–8)
154. Du, B, Fang, Z, ‘‘Effects of Carbon Nanotubes on the 889–892 (1996)
Thermal Stability and Flame Retardancy of Intumescent 172. Chen, G, Weng, W, Wu, D, Wu, C, Lu, J, Wang, P, Chen, X,
Flame-Retarded Polypropylene.’’ Polym. Degrad. Stab., 96 ‘‘Preparation and Characterization of Graphite Nanosheets
(10) 1725–1731 (2011) from Ultrasonic Powdering Technique.’’ Carbon, 42 (4)
155. Beheshti, A, Heris, SZ, ‘‘Is MWCNT a Good Synergistic 753–759 (2004)
Candidate in APP–PER–MEL Intumescent Coating for 173. Hallissy, G, Higbie, WG, Camarota, A, Rowen, JB,
Steel Structure?’’ Prog. Org. Coat., 90 252–257 (2016) ‘‘Electrical Distribution System Components with Fire
156. Bourbigot, S, Turf, T, Bellayer, S, Duquesne, S, ‘‘Polyhe- Resistant Insulative Coating.’’ US Patent US6960388 B2
dral Oligomeric Silsesquioxane as Flame Retardant for 174. Wang, G, Yang, J, ‘‘Influences of Expandable Graphite
Thermoplastic Polyurethane.’’ Polym. Degrad. Stab., 94 (8) Modified by Polyethylene Glycol on Fire Protection of
1230–1237 (2009) Waterborne Intumescent Fire Resistive Coating.’’ Surf.
157. Wang, Z, Han, E, Ke, W, ‘‘Effect of Acrylic Polymer and Coat. Technol., 204 (21–22) 3599–3605 (2010)
Nanocomposite with Nano-SiO2 on Thermal Degradation 175. Wang, Z, Han, E, Ke, W, ‘‘Influence of Expandable
and Fire Resistance of APP–DPER–MEL Coating.’’ Graphite on Fire Resistance and Water Resistance of
Polym. Degrad. Stab., 91 (9) 1937–1947 (2006) Flame-Retardant Coatings.’’ Corros. Sci., 49 (5) 2237–2253
158. Wang, J, Wang, G, ‘‘Influences of Montmorillonite on Fire (2007)
Protection, Water and Corrosion Resistance of Waterborne 176. Duquesne, S, Le Bras, M, Bourbigot, S, Delobel, R,
Intumescent Fire Retardant Coating for Steel Structure.’’ Camino, G, Eling, B, Lindsay, C, Roels, T, ‘‘Thermal
Surf. Coat. Technol., 239 177–184 (2014) Degradation of Polyurethane and Polyurethane/Expand-
159. Chuang, C-S, Tsai, K-C, Yang, T-H, Ko, C-H, Wang, M-K, able Graphite Coatings.’’ Polym. Degrad. Stab., 74 (3) 493–
‘‘Effects of Adding Organo-Clays for Acrylic-Based Intu- 499 (2001)
mescent Coating on Fire-Retardancy of Painted Thin 177. Saidaminov, MI, Maksimova, NV, Kuznetsov, NG, Soroki-
Plywood.’’ Appl. Clay Sci., 53 (4) 709–715 (2011) na, NE, Avdeev, VV, ‘‘Fire Protection Performance of
160. Bodzay, B, Bocz, K, Bárkai, Z, Marosi, G, ‘‘Influence of Oxidized Graphite Modified with Boric Acid.’’ Inorg.
Rheological Additives on Char Formation and Fire Resis- Mater., 48 (3) 258–262 (2012)
tance of Intumescent Coatings.’’ Polym. Degrad. Stab., 96 178. Chiang, C-L, Hsu, S-W, ‘‘Novel Epoxy/Expandable Gra-
(3) 355–362 (2011) phite Halogen-Free Flame Retardant Composites—Prepa-
161. Zhao, C-X, Liu, Y, Wang, D-Y, Wang, D-L, Wang, Y-Z, ration, Characterization, and Properties.’’ J. Polym. Res., 17
‘‘Synergistic Effect of Ammonium Polyphosphate and (3) 315–323 (2010)
Layered Double Hydroxide on Flame Retardant Properties 179. Gardelle, B, Duquesne, S, Vandereecken, P, Bourbigot, S,
of Poly(vinyl alcohol).’’ Polym. Degrad. Stab., 93 (7) 1323– ‘‘Characterization of the Carbonization Process of Expand-
1331 (2008) able Graphite/Silicone Formulations in a Simulated Fire.’’
162. Wang, Z, Han, E, Ke, W, ‘‘Influence of Nano-LDHs on Polym. Degrad. Stab., 98 (5) 1052–1063 (2013)
Char Formation and Fire-Resistant Properties of Flame- 180. Gardelle, B, Duquesne, S, Vandereecken, P, Bellayer, S,
Retardant Coating.’’ Prog. Org. Coat., 53 (1) 29–37 (2005) Bourbigot, S, ‘‘Resistance to Fire of Intumescent Silicone
163. Wang, Z, Han, E, Ke, W, ‘‘Effect of Nanoparticles on the Based Coating: The Role of Organoclay.’’ Prog. Org. Coat.,
Improvement in Fire-Resistant and Anti-Ageing Properties 76 (11) 1633–1641 (2013)
of Flame-Retardant Coating.’’ Surf. Coat. Technol., 200 181. Ullah, S, Ahmad, F, Megat-Yuso, P, Binti Azmi, NH, ‘‘A
(20–21) 5706–5716 (2006) Study of Bonding Mechanism of Expandable Graphite
164. Han, Z, Fina, A, Malucelli, G, ‘‘Thermal Shielding Perfor- Based Intumescent Coating on Steel Substrate.’’ J. Appl.
mances of Nano-Structured Intumescent Coatings Contain- Sci., 11 1630–1635 (2011)
ing Organo-Modified Layered Double Hydroxides.’’ Prog. 182. Gardelle, B, Duquesne, S, Vandereecken, P, Bellayer, S,
Org. Coat., 78 504–510 (2015) Bourbigot, S, ‘‘Resistance to Fire of Curable Silicone/
165. Qin, Z, Li, D, Li, Q, Yang, R, ‘‘Effect of Nano-Aluminum Expandable Graphite Based Coating: Effect of the Cata-
Hydroxide on Mechanical Properties, Flame Retardancy lyst.’’ Eur. Polym. J., 49 (8) 2031–2041 (2013)
and Combustion Behavior of Intumescent Flame Retarded 183. Janssens, ML, ‘‘10—Challenges in Fire Testing: A Tester’s
Polypropylene.’’ Mater. Des., 89 988–995 (2016) Viewpoint.’’ In: Horrocks, AR, Price, D (eds.) Advances in
19
Fire Retardant Materials, pp. 233–254. Woodhead Publish- 186. EN 1363-1:2004 Fire Resistance Tests—Part 1, General
ing, Cambridge (2008) Requirements, 49 (2000)
184. Grigonis, M, Mačiulaitis, R, Lipinskas, D, ‘‘Fire Resistance 187. ISO 834:1975. Fire Resistance Tests—Elements of Building
Tests of Various Fire Protective Coatings.’’ Mater. Sci., 17 Products, International Organisation for Standardization,
(1) 93–98 (2011) 25 (1975)
185. BS 476:Part 20:1987. Fire Tests on Building Materials and 188. Sakumoto, Y, Nagata, J, Kodaira, A, Saito, Y, ‘‘Durability
Structures. Part 20. Method for Determination of the Fire Evaluation of Intumescent Coating for Steel Frames.’’ J.
Resistance of Elements of Construction (GeneralPrinciples) (1987) Mater. Civil Eng., 13 (4) 274–281 (2001)
20

ARTIGO 48 BARBOT FINAL Revisto Final 30 09

Uploaded by

Copyright:

Available Formats

ARTIGO 48 BARBOT FINAL Revisto Final 30 09

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

ARTIGO 48 BARBOT FINAL Revisto Final 30 09

Uploaded by

Copyright:

Available Formats

J. Coat. Technol. Res.

, 14 (1) 1–20, 2017

Intumescent coatings: A review on recent progress

American Coatings Association 2016

Abstract Fire is a serious threat to people and the Abbreviations

Introduction buildings. There is wider acceptance of the use of steel

dioxide and water is a major limitation. On environ-

Na2 SiO3 nH2 O ! Na2 SiO3 þ nH2 O

An alkali silicate fire-protective coating with an acidic

Fig. 3: Intumescent coatings char

Fig. 5: APP response to fire and its interactions with other

Table 1: Examples of various components of intumescent systems

Inorganic acids Pentaerythritol, Dipentaerythritol, Tripentaerythritol, Melamine

exposure environment according to these test proce- 160

described below: 0 20 40 60 80 100 120

Fig. 9: Epoxy silicate intumescent coatings (a) before and

240 The developed intumescent silicate coatings have

140 and solventborne organic thin film intumescent coat-

120 Modern day intumescent coatings provide effective

References 24. Craig Lipka, JP, Roger Youngs, ‘‘Intumescent Coating

You might also like