Flame retardance combustion

C.F. Cullis, Combustion of Flexible Polyurethane Foams. Mechanism and Evaluation of Flame Retardance , Combust Flame 24 (2), 217-30 (1975) CA 83, 82287 (1975)... 

Hutzinger O, Dumler R, Lenoir D, Teufl C, Thoma H (1989), Chemosphere 18 1235-1242. PBDD and PBDF from brominated flame retardants combustion equipment, analytical methodology and synthesis of standards"... 

The use of flame retardants came about because of concern over the flammabiUty of synthetic polymers (plastics). A simple method of assessing the potential contribution of polymers to a fire is to examine the heats of combustion, which for common polymers vary by only about a factor of two (1). Heats of combustion correlate with the chemical nature of a polymer whether the polymer is synthetic or natural. Concern over flammabiUty should arise via a proper risk assessment which takes into account not only the flammabiUty of the material, but also the environment in which it is used. 

In order for a soHd to bum it must be volatilized, because combustion is almost exclusively a gas-phase phenomenon. In the case of a polymer, this means that decomposition must occur. The decomposition begins in the soHd phase and may continue in the Hquid (melt) and gas phases. Decomposition produces low molecular weight chemical compounds that eventually enter the gas phase. Heat from combustion causes further decomposition and volatilization and, therefore, further combustion. Thus the burning of a soHd is like a chain reaction. For a compound to function as a flame retardant it must intermpt this cycle in some way. There are several mechanistic descriptions by which flame retardants modify flammabiUty. Each flame retardant actually functions by a combination of mechanisms. For example, metal hydroxides such as Al(OH)2 decompose endothermically (thermal quenching) to give water (inert gas dilution). In addition, in cases where up to 60 wt % of Al(OH)2 may be used, such as in polyolefins, the physical dilution effect cannot be ignored. 

Chemical Interaction. Halogens and some phosphoms flame retardants act by chemical interaction. The flame retardant dissociates into radical species that compete with chain propagating and branching steps in the combustion process. 

In poly(ethylene terephthalate) (14—16) and poly(methyl methacrylate) (17—19), the mechanism of action of phosphoms flame retardants is at least partly attributable to a decrease in the amount of combustible volatiles and a corresponding increase in nonvolatile residue (char). In poly(methyl methacrylate), the phosphoms flame retardant appears to cause an initial cross-linking through anhydride linkages (19). 

The amount and physical character of the char from rigid urethane foams is found to be affected by the retardant (20—23) (see Foams Urethane polymers). The presence of a phosphoms-containing flame retardant causes a rigid urethane foam to form a more coherent char, possibly serving as a physical barrier to the combustion process. There is evidence that a substantial fraction of the phosphoms may be retained in the char. Chars from phenohc resins (qv) were shown to be much better barriers to pyrolysate vapors and air when ammonium phosphate was present in the original resin (24). This barrier action may at least partly explain the inhibition of glowing combustion of char by phosphoms compounds. 

Toxicology. Two factors should be considered when discussing the toxicity of flame-retardant materials the toxicity of the compounds themselves and the effect of the flame retardants on combustion product toxicity. 

Effects on Combustion Toxicology. There appears to be no documented case of any type of fine retardant contributing to human fine casualties. A survey of data from small-scale combustion or pyrolysis experiments revealed no consistent pattern of decrease or increase in the yields of toxic gases (CO, HCN) when phosphoms flame retardants were present (152,153). 

Laboratory experiments using rodents, or the use of gas analysis, tend to be confused by the dominant variable of fuel—air ratio as well as important effects of burning configuration, heat input, equipment design, and toxicity criteria used, ie, death vs incapacitation, time to death, lethal concentration, etc (154,155). Some comparisons of polyurethane foam combustion toxicity with and without phosphoms flame retardants show no consistent positive or negative effect. Moreover, data from small-scale tests have doubtful relevance to real fine ha2ards. 

E. D. Wed and A. M. Aaronson, "Phosphoms Flame Retardants— Some Effects on Smoke and Combustion Products," lecture at University of Detroit Polymer Conference on Recent Advances in Combustion and Smoke Retardance of Polymers, Mich., May 1976. 

Thermal Theory. The thermal approach to flame retardancy can function in two ways. Eirst, the heat input from a source may be dissipated by an endothermic change in the retardant such as by fusion or sublimation. Alternatively, the heat suppUed from the source maybe conducted away from the fibers so rapidly that the fabric never reaches combustion temperature. 

Dehydration or Chemical Theory. In the dehydration or chemical theory, catalytic dehydration of ceUulose occurs. The decomposition path of ceUulose is altered so that flammable tars and gases are reduced and the amount of char is increased ie, upon combustion, ceUulose produces mainly carbon and water, rather than carbon dioxide and water. Because of catalytic dehydration, most fire-resistant cottons decompose at lower temperatures than do untreated cottons, eg, flame-resistant cottons decompose at 275—325°C compared with about 375°C for untreated cotton. Phosphoric acid and sulfuric acid [8014-95-7] are good examples of dehydrating agents that can act as efficient flame retardants (15—17). 

Another valuable characteristic of many phosphazene polymers is their flame-retardant behavior and low smoke generation on combustion (13). This property is utilized in commercial appHcations. 

Flame Retardants. Flame retardants are added to nylon to eliminate burning drips and to obtain short self-extinguishing times. Halogenated organics, together with catalysts such as antimony trioxide, are commonly used to give free-radical suppression in the vapor phase, thus inhibiting the combustion process. Some common additives are decabromodiphenyl oxide, brominated polystyrene, and chlorinated... 

Flame retardants (qv) are incorporated into the formulations in amounts necessary to satisfy existing requirements. Reactive-type diols, such as A/ A/-bis(2-hydroxyethyl)aminomethylphosphonate (Fyrol 6), are preferred, but nonreactive phosphates (Fyrol CEF, Fyrol PCF) are also used. Often, the necessary results are achieved using mineral fillers, such as alumina trihydrate or melamine. Melamine melts away from the flame and forms both a nonflammable gaseous environment and a molten barrier that helps to isolate the combustible polyurethane foam from the flame. Alumina trihydrate releases water of hydration to cool the flame, forming a noncombustible inorganic protective char at the flame front. Flame-resistant upholstery fabric or liners are also used (27). 

Flame Retardants. Because PVC contains nearly half its weight of chlorine, it is inherently flame-retardant. Not only is chlorine not a fuel, but it acts chemically to inhibit the fast oxidation in the gas phase in a flame. When PVC is diluted with combustible materials, the compound combustibiHty is also increased. Por example, plastici2ed PVC with > 30% plastici2er may require a flame retardant such as antimony oxide, a phosphate-type plastici2er, or chlorinated or brominated hydrocarbons (145,146). 

Whilst the development of flame retarders has in the past been largely based on a systematic trial-and-error basis, future developments will depend more and more on a fuller understanding of the processes of polymer combustion. This is a complex process but a number of stages are now generally recognised and were discussed in Chapter 5. 

Many methods have been evolved in recent years for assessing flame retardants and the combustion characteristics of plastics and these have been the subject of comprehensive reviews. " ... 

Some inorganic fillers are used as flame retardants in rubber base formulations. Flame retardants act in two ways (1) limiting or reducing access of oxygen to the combustion zone (2) reacting with free radicals (especially HO ), thus acting as terminator for combustion-propagation reaction. The additives most widely used as flame retardants for polymers are antimony oxides and alumina trihydrate. 

Flame Retardants. Most polymers, because they are organic materials, are flammable. Additives that contain chlorine, bromine, phosphorous or metallic salts reduce the likelihood that combustion will occur or spread. 

Principles and Characteristics Combustion analysis is used primarily to determine C, H, N, O, S, P, and halogens in a variety of organic and inorganic materials (gas, liquid or solid) at trace to per cent level, e.g. for the determination of organic-bound halogens in epoxy moulding resins, halogenated hydrocarbons, brominated resins, phosphorous in flame-retardant materials, etc. Sample quantities are dependent upon the concentration level of the analyte. A precise assay can usually be obtained with a few mg of material. Combustions are performed under controlled conditions, usually in the presence of catalysts. Oxidative combustions are most common. The element of interest is converted into a reaction product, which is then determined by techniques such as GC, IC, ion-selective electrode, titrime-try, or colorimetric measurement. Various combustion techniques are commonly used. 

Substances applied to or incorporated in a combustible material (e.g. organic polymers, nylon, vinyl and rubber, etc.) to reduce flammability. Act by retarding ignition, control/douse burning, reduce smoke evolution. Slow down or interrupt the self-sustained combustion cycle when the heat-flux is limited. Flame retardants (FRs) improve the combustion behaviour and alter the combustion process (cool, shield, dilute, react) so that decomposition products will differ from nonflame retarded articles. FRs are usually divided into three classes ... 

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