Flame Retardant Theory

Antimony oxide by itself is not a fire retardant, and the halogens by themselves, mainly bromine and chlorine, are weak fire retardants. However, when they are combined they become synergistic and are the most effective and most widely used flame retardant system for plastics. Usually three to four parts of halogenated flame retardants are used to one part of antimony oxide on a weight basis. Using more than the 4:1 ratio offers little additional protection. The stoichiometric ratio of chlorine to antimony in antimony trichloride is 3:1. Formulations in different applications will depend on thermal stability, cost, tinting strength, Change in physical properties, smoke considerations, streaking, blend ability, and the flame retardant specification.

Two mechanisms exist in the synergistic system. First is the “free radical capture” process that takes place in the vapor phase. On combustion at a temperature of over 6000 F, the halogen forms hydrochloric or hydrobromic acid that reacts with the antimony oxide to form antimony trichloride, antimony oxychloride, antimony tribromide, or antimony oxybromide. The flame retarding action takes place in the vapor stage above the burning material. It is thought that “free radicals propagate” the flame. But, the antimony trihalides or antimony oxyhalides act as “free radical traps”, and take up free radicals. They inhibit ignition and pyrolysis in the solid, liquid, and vapor phases.

A second process occurs in a solid phase and is the “char process”. The antimony oxide promotes the formation of “char” (essentially carbon) on the substrate which reduces volatile gas formation. The barrier between the substrate and the vapor phase reduces the available oxygen to the underlying substrate. The barrier effect is obtained by almost any inert additive. In plastics there is a cross linking with antimony to produce a more stable thermoset polymer. Additionally in the solid phase, the formation of SbCl3 and SbOCl acts as a dehydrating agent that increases charring. Sometimes phosphorous compounds (TCP), magnesium oxide, alumina trihydrate, molybdic oxide, zinc borate, or zinc oxide are used in combination or in place of antimony oxide to reduce costs, to increase char formation, or to reduce smoke. However, the substitution of the other retardants greatly reduces the flame retardance normally rendered by antimony oxide. Testing of the amounts of the halogen and antimony oxide in each formulation is necessary to optimize the flame retardance and lower costs. Alumina trihydrate is not synergistic with halogenated flame retardants. It functions as a flame retardant by the release of its water of hydration and cannot be used in high temperature processes. Zinc borate, molybdic oxide, zinc oxide, and magnesium oxide can be used in conjunction with antimony oxide to augment char formation and decrease smoke. Replacement of the antimony oxide to meet a smoke requirement compromises the flame retardance.

A relationship exists between particle size and tinting strength. If the particles are very fine (less than 300 nanometers) they are below the visual range and there is no tint strength. However, within the visual range, the smaller the particle size, the higher the tint strength. Or conversely, the larger the particle size, the lower the tint strength.


There are more than 100 test methods for the determination of the flame retardance of materials. Each application has its own method. Some of the more popular test methods are as follows:

ULUL-94Vertical Burn RatePlastics
ASTMASTM-D-635Horizontal Burn RateRigid Plastics
ASTMASTM-E-162Surface FlammabilitySheet laminates, fabrics, tiles, liquids, films
ASTMASTM-E-84Surface Burning CharacteristicsCarpeting, building materials
ASTMASTM-D-1692Flammability plastic foams and sheetingPlastic foams and sheeting
ASTMASTM-D-2863Oxygen Index (O.I.) flammabilityPlastics, textiles, paper etc.
DOTDOT 302MVSSTo establish 4 inch per minute burn ratePlastics in motor vehicles
FAAPar. 25.853FAA regulations for compartment interiorsCompartment interior plastics
NBSAminco smoke density chamberAll materials
NBSFederal Standard 372Flooring radiant panelCarpeting
DOC FF-2-70
Surface Flammability Carpets and RugsCarpets and rugs
DOCDOC FF-4-72Flammability of mattressesMattresses
CSCS-191-53Flammability of clothing and textilesFabrics
CPAICPAI-84Spec. for camping tentsFabrics
TAPPITAPPI-461-M-48Flammability of paperPaper