99-1

99
!Ire-Refardanf[!Ire-
ResIsfIve CoafIngs
99.1 Conventional Paints ..........................................................99-1
99.2 Fiie-Retaidant Paints ........................................................99-1
99.3 Fiie-Retaidation Mechanism............................................99-2
99.4 Fiie-Resistive Intumescent Coatings................................99-3
99.5 Miscellaneous Coatings ....................................................99-4
Refeiences .....................................................................................99-5
Paint-type coatings can be divided into thiee geneial classes: conventional paints, vainishes, and enamels;
fie-ietaidant coatings foimulated with halogen compounds with oi without special flleis; and intumes-
cent coatings designed to foam upon application of heat oi ßame foi development of an adheient fie-
iesistive cellulai chai.
99.1 Cunventiuna! Paints
Non-ßame-ietaidant coatings usually give a low ßame spiead iating ovei asbestos-cement boaid, steel,
oi cement block. When the coatings aie tested ovei wood and othei ßammable mateiials, ßame spiead
iatings similai to those of the substiate aie obtained.
1
The fie-ietaidant effectiveness of paints is highly dependent on the spieading iate oi thickness of the
coating as well as the composition. When conventional paints aie applied at the heavy iate common foi
fie-ietaidant coatings, they give ßame spiead indices compaiable to those of fie-ietaidant paints. Foi
example, coating of latex and ßat alkyd paints applied to tempeied haidboaid at an effective spieading
iate of 250 ft
2
/gal ieduced the ßame spiead index of the uncoated substiate by factois of 3 and 5,
iespectively.
2
99.2 Fire-Retardant Paints
Fiie-ietaidant coatings aie paiticulaily useful in maiine applications. Ships aie painted iepeatedly to
maintain maximum coiiosion piotection. As the layeis of paint build, they pose a fie hazaid even though
the substiate is steel. In the event of fie, the paint may catch fie, melt, diip, and cause seveie injuiy and
damage to the vessel. Coatings aie theiefoie foimulated that do not sustain combustion; they should not
spiead the ßame by iapid combustion noi contiibute a signifcant amount of fuel to the fie.
Polyvinyl chloiide containing 57% by weight chloiine is self-extinguishing. Howevei, it is not a good
vehicle foi a ßame-ietaidant coating because of its high melting point. This can be loweied substantially
by copolymeiization with othei vinyl monomeis such as vinyl acetate. To make these copolymeis useful,
addition of plasticizeis and coalescing solvents is often necessaiy to give suitable application and pei-
}oseph Creen
íMC Cor¡ororíon
© 2006 by Taylor & Erancis Group, LLC
99-2 Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
foimance piopeities. These additions dilute the oveiall concentiation of chloiine theieby ieducing the
ßame ietaidancy.
3
Fiie-ietaidant coatings aie based piimaiily on chloiinated alkyds, alumina tiihydiate, oi a combination
of chloiinated paiaffns and antimony tiioxide. Table 99.1 and Table 99.2 give typical foimulations. Flame
spiead test iesults depend both on the substiate and the thickness of the flm.
4
99.3 Fire-Retardatiun Mechanism
The combustion of gaseous fuel is believed to pioceed by a fiee iadical mechanism:
The H, OH, and O iadicals aie chain caiiieis and take pait in a numbei of ieactions in the ßame zone.
The function of halogen containing compounds as ßame ietaidants has been explained by the iadical
tiap theoiy and takes place in the gas phase. In the foiegoing ieactions, libeiated HCI oi HBi competes
foi the iadical species that aie ciitical foi ßame piopagation:
The active chain caiiieis aie ieplaced with the much less active halogen iadical, slowing the iate of
eneigy pioduction and helping ßame extinguishments.
TABLE 99.1 Foimulation foi a Fiie-Retaidant Latex Paint
Ingiedient Paits by Weight
Polyvinyl acelate copolymei emulsion
(55% solids)
20
Chloiinated paiaffn 5
Antimony oxide 11
Titanium dioxide 22
Mica 9
Thickeneis, etc. 3
Watei 30
TABLE 99.2 Foimulation foi an Alkyd-Based Paint
Ingiedient Paits by Weight
Long oil alkyd 22
Chloiinated paiaffn 7
Antimony oxide 6
Titanium dioxide 29
Micionized talc 7
Whiting 11
White spiiit diiei, etc. 18
CH O CH H
H O OH O
CO OH CO H
4 2 3 2
2
2

O
CH X HX CH
H HX H X
OH HX H O X
O HX OH X
4 3
2
2
© 2006 by Taylor & Erancis Group, LLC
ííreFerordonr/ííreFe·í·ríve Cooríng· 99-3
Antimony oxide is known as a ßame-ietaidant syneigist when used in combination with halogen
compounds. Volatile antimony oxyhalide (SbOX) and/oi antimony tiihalide (SbX
3
) foim in the con-
densed phase and tianspoit the halogen into the gas phase.
Phosphoius compounds aie also used as piimaiy ßame ietaidants. The ßame-ietaidant mechanism
foi phosphoius compounds vaiies with the type of compound, the polymei, and the combustion con-
ditions.
5
Foi example, some phosphoius compounds decompose to phosphoiic acids and polyphos-
phates. A viscous suiface glass foims and shields the substiate fiom the ßame. If the phosphoiic acid
ieacts with the polymei (e.g., to foim a phosphate estei), subsequent decomposition iesults in a dense
suiface chai. The coatings that foim seive as a physical baiiiei to heat tiansfei fiom the ßame to the
substiate and to diffusion of gases; in othei woids, the substiate is isolated fiom heat, ßame, and oxygen.
This is the mechanism foi fie-iesistive intumescent coatings discussed below.
Tiiaiyl phosphate esteis aie theimally stable, high boiling (>350C) mateiials. They can volatilize
without signifcant decomposition into the ßame zone, wheie they decompose. Flame inhibition ieac-
tions, similai to the halogen iadical tiap theoiy, have been pioposed.
6
Alumina tiihydiate (ATH) oi magnesium hydioxide inhibits ignition by absoiption of heat due to
decomposition, ieleasing laige volumes of watei of hydiation (>30%).
99.4 Fire-Resistive Intumescent Cuatings
Intumescent paints and mastics swell and chai when exposed to heat and ßame, giving a caibonaceous
foam that insulates the substiate fiom heat, aii, and fie. This may delay the onset of combustion of a
wood oi plastic substiate oi delay the heat buildup and tensile loss of stiuctuial steel. In the lattei case,
thick coatings oi mastics aie used. These coatings aie consideied to be fie iesistive and signifcantly
moie effective than fie-ietaidant coatings. The foimei offei piotection to the substiate. Intumescent
coatings iequiie thiee basic ingiedients: a caibonifc oi caibon pioducei such as pentaeiythiitol oi othei
polyol, an acid ieleasing agent such as a phosphate, and a spumifc oi gas pioducei such as melamine.
Polyols such as staich and dipentaeiythiitol (less watei sensitive) aie caibonifcs. Othei acid pioduceis
and theii tempeiatuies of decomposition aie ammonium polyphosphate (215C), monoammonium
phosphate (417C), and melamine phosphate (300C); spumifcs include uiea (130C), dicyandiamide
(210C), and melamine (300C).
7
When the coating oi mastic is heated, the decomposing phosphate foims phosphoiic acid. This
esteiifes the hydioxyl gioups of the polyol, which subsequently decomposes, foiming watei and a
caibonaceous chai, iegeneiating the phosphoiic acid. As the chai foims, the paint bindei softens and
the spumifc decomposes, libeiating nonßammable gases. These gases expand the softened bindei into
a foam. A iigid caibonaceous foam is foimed as chaiiing of both caibonifc and bindei iesin is completed.
4
When used as a thick mastic coating on stiuctuial steel, such mateiials can pievent the steel fiom
A unique intumescent coating containing no watei-sensitive polyols is composed of p,p -oxybis(ben-
zenesulfonamide) in a vinyl chloiide-vinylidene chloiide copolymei bindei. The addition of melamine
pyiophosphate impioves the homogeneity of the system.
9
Dipentaeiythiiol can also be added to impiove
the homogeneity.
10
H PO HPO PO etc
H PO HPO
H HPO H PO
OH PO
3 4 2
2
.
HHPO O
© 2006 by Taylor & Erancis Group, LLC
Table 99.3 and Table 99.4 give examples of intumescent systems.
ieaching the failuie point foi 3 houis, as indicated in Table 99.5.
99-4 Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
Pitt-Chai (PPG Industiies) coating is a two-component epoxy-polyamide pioduce designed foi stiuc-
tuial steel. This intumescent epoxy coating iequiies no ieinfoicement and piovides up to 3 houis of fie
piotection.
11
99.5 Misce!!aneuus Cuatings
Magnesium oxychloiide mastics will piotect steel by ieleasing laige quantities of watei upon heating and
by ie
used in exteiioi applications.
12
Polystyiene foam block can be piotected against fie foi specifed time peiiods. Building plastics
containing gypsum and peilite and an expanded veimiculite, Poitland cement, and limestone coating
aie paiticulaily effective in piotecting polystyiene foam block against the heat of a simulated mine fie.
13
Foi an insight into potential methods of ßame ietaiding polyuiethane and epoxy coatings, an analogy
with plastic ßame ietaidants can be made. The most common way to achieve ßame-ietaidant polyuie-
thanes is by the addition of halogen, phosphoius, chloiophosphate, oi chloiophosphonate compounds.
Reactive halogen and phosphoius diols have also been used. Epoxy iesins aie geneially ßame ietaided
using the ieactive tetiabiomobisphenol A. Use of phosphoius-halogen compounds has been iepoited.
TABLE 99.3 Foimulation foi a Typical Intumescent
Emulsion Paint
Ingiedient Paits by Weight
Polyvinyl acetate latex 18
Ammonium polyphosphate 22
Pentaeiythiitol 12
Staich 3
Dicyandiamide 16
Titanium dioxide 4
Watei 25
TABLE 99.4 Foimulation foi a Typical Intumescent
Solvent-Thinnei Paint
Ingiedient Paits by Weight
Vinyl toluene-butadiene copolymei 7
Ammonium polyphosphate 28
Dipentaeiythiitol 8
Melamine 9
Chloiinated paiaffn 9
Titanium dioxide 6
Mineial spiiits 33
TABLE 99.5 Ratings on Steel Column
Coating Thickness (in) Rating (h)
0.31 1
0.39 1.5
0.58 2
0.78 2.5
0.97 3
Scurce. Fiom Seinei, J. A., and T. A. Waid,
Pcly. Paint Cclcur }., 178(4207), 75-78 (Feb-
iuaiy 10, 1988).
© 2006 by Taylor & Erancis Group, LLC
ííreFerordonr/ííreFe·í·ríve Cooríng· 99-5
Relerences
1. C. A. Hafei, Final Repoit, Pioject No. 3-294-26, Southwest Reseaich Institute, San Antonio, TX,
1970.
2. D. Gioss and J. J. Loftus, Fire Res. Abstr. Rev., 3(3), 151-158 (1961).
3. W. S. Chang, R. L. Sciiven, and R. B. Ross, in Flame Retardant Pclymeric Materials, Vol. 1. M.
Lewin, S. M. Atlas, and E. M. Peaice, Eds. New Yoik: Plenum Piess, 1975, pp. 399-447.
4. A. G. Walkei, Prcceedings cf the Fire Retardant Chemical Asscciaticn Meeting, Pinehuist, NC,
Octobei 27-30, 1985, pp. 51-61.
5. J. Gieen, Plast. Ccmpd., 10(3), 47 (May/June 1987).
6. J. W. Hastie, }. Res. U.S. Natl. Bur. Stand., 77A(6), 733 (1973).
7. J. A. Shelton and M. G. Bivok, Mater. Design, 5, 41-42 (Febiuaiy/Maich 1984).
8. J. A. Seinei and T. A. Waid, Pcly. Paint Cclcur }., 178(4207), 75-78 (Febiuaiy 10, 1988).
9. S. H. Roth, J. Gieen, and J. J. Seipel, U.S. Patent 3,714,081 (Januaiy 30, 1973).
10. S. H. Roth, J. Gieen, and J. J. Seipel, U.S. Patent 3,714,082 (Januaiy 30, 1973).
11. Mcdern Paint Ccatings, pp. 188-190, Octobei 1984.
12. S. I. Kawallei, Cil Gas }., 71(4), 78-80 (1973).
13. S. J. Luzik, Fire Techncl., 22, 311-328 (1986).
© 2006 by Taylor & Erancis Group, LLC