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• Dilution of
Noncombustible
Gases
– Dicyandiamide and urea
release non-combustible
gases.
– Borax releases water in
high quantities.
Free Radical Trap Theory
• This theory involves:
– Chain Branching Reaction
• The decomposition of the fuel source, i.e. breaking the chemical bonds into high
energy free radicals, is initially done by an external ignition source that starts the cycle.
• Heating of combustible materials results in the generation of hydrogen, oxygen,
hydroxide, and peroxide radicals that are subsequently oxidized with flame.
• If the resulting compound is less readily oxidized than the radical that is removed, the
result is reduced flammability.
Free Radical Trap Theory(Cont’d)
– Bromine and Chlorine are good free radical inhibitors
• Complex with free radicals and stop the combustion mechanism.
– Large amounts are required for practical fire retardancy
• 15-30% by weight
• Halide is regenerated to continue the reaction
– Routes with oxygen are also possible
Major Chemicals
• The main fire retardant chemical classes together with some representative examples
are listed below:
– Inorganics compounds
• Aluminium trihydroxide, ammonium polyphosphate, antimony trioxide.
• Three Classes:
– 1) Aromatics - including tetrabromobisphenol-A, (TBBA), polybrominatedethers (PBDEs)
and Polybrominated biphenyls (PBBs)
– 2) Aliphatics - which tend to have limited use and
– 3) Cycloaliphatics - such as hexabromocyclododecane (HBCD)
• Synergistic Chemicals –
– Antimony Trioxide - (Sb2O3). The synergist acts to improve the activity of the
additive in the polymer, thus lowering the amount of halogenated additive
needed. Antimony oxide acts as a halogen shuttle bringing SbX3 into the vapor
phase
Nitrogen
• Nitrogen based FRs result in char formation by causing the material to swell as
flammable gases are evolved.
• Nitrogen decomposes in the vapor phase to form non-flammable gases such as HNO 2
and HNO3 and also prevents the phosphorous compounds from being pyrolyzed in the
vapor phase.
NH2
HN NH
H2N N NH2
H
Melamime
MDF(Multiple Density
Fiberboard) with
Melamine Coating
Phosphorus Compounds
• Monoamonium and Diamonium phosphates.
– Presence of Nitrogen produces a synergistic effect
• The final way in which these polymers can form char during the burning
process is to form additional rings either by Claisen-Cope or Diels Alder
rearrangement. The following polyamide, similar to Dupont’s Nomex, forms
a more stable benzoxazole structure on heating
Issues with Traditional Retardants
• Persistence
– Resist breakdown in the environment
• Toxicity
– Firefighters at risk
• Dioxins and furans produced at high levels
– European Union banned the use of all polybrominated diphenyl ethers
(PBDEs) and polybrominated biphenyls (PBBs) in electronic products
starting in 2006.
– Halogenated Organic Compounds are considered Persistent Organic
Pollutants(POP)
– Antimony Oxide – possible link to Sudden Infant Death Syndrome.
Green Alternatives
• Non-Halogenated Fire Retardants
– Carbon Nanotubes and Clay
• Synergistic effects improve the flame retardancy of
polymeric materials without the use of toxic
chemicals
• Barrier properties of clay and tensile strength of
carbon nanotubes
– Expectation of high performance characteristics with
reduced use of potentially toxic chemicals
– Researchers have been able to modify the
flammability properties of polymers with
carbon nanotubes
Bromine Free Alternatives
• Most commonly used bromine free alternatives
– Inorganic
• Aluminium Trihydroxide
• Magnesium Hydroxide
• Ammonium Polyphosphate
• Red Phosphorous
• Zinc Borate
– Organophosphorous
• Triphenyl Phosphate
• Tricresyl Phosphate
• Resorcinol bis(diphenyl phosphate)
• Phosphonic Acid (2-((hydroxymethyl) carbamyl)ethyl)- dimethyl ester
• Phosphorous and Nitrogen containing thermosets
– Nitrogen Containing
• Melamine
Bibliography
• LeVan, Susan L. Chemistry of Fire Retardancy. U.S. Department of Agriculture, Forest Service,
Forest Products Laboratory.
• Berger, Michael. “Flame-retardant materials with more nanotechnology and less toxic chemicals.”
Nanowerk, 8/30/2007. Accessed 4/13/09. http://www.nanowerk.com/spotlight/spotid=2445.php
• Blum, Arlene. “Review of The Fire Retardant Dilemma Parts I-VI" (part 2). Green Science Policy
Institute- The Fire Retardant Dilemma: Part VII, January 30, 2009. Accesed 4/14/09.
http://greensciencepolicy.org/assets/Uploads/Jan-30-09-Conf-Presentations/Blum-FRDVII-Jan-
09reduced.pdf
• Janssen, Sarah. “Halogenated Fire Retardants.” Green Science Policy Institute- The Fire
Retardant Dilemma: Part VII, January 30, 2009.
http://greensciencepolicy.org/assets/Uploads/Jan-30-09-Conf-Presentations/Janssen-FRD-
presentation01-09.pdf
• Hepburn, C. Rubber Compounding Ingredients – Need, Theory, and Innovation, Part II. Vol 9
Num 1. 1997.
• Flame Retardants: A General Introduction, Enviornmental Health Criteria 192. United Nations
Enviornment Programme. 1997. http://www.inchem.org/documents/ehc/ehc/ehc192.htm.
• Federal Aviation Association. U.S Department of Transportation. Development and Testing of
Flame Retardant Additives and Polymers. 04/07. 04/17/09.
http://www.tc.faa.gov/its/worldpac/techrpt/ar0725.pdf
Major Chemicals
• Nitrogen
– Barrier
• Phosphorus
– Barrier
• Boron
– Thermal
– Dilution of combustible gases
• Aluminum Trihydrate.
– Thermal
– Dilution of combustible gases