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Phosphorus/Halogen Synergism: Dr. Awni Alkhazaleh

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20 views4 pages

Phosphorus/Halogen Synergism: Dr. Awni Alkhazaleh

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graduationp19
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The nitrogen compounds used as synergists, have some flame retardant property

in their own right. Their synergistic combination with phosphoric acids, when
exposed to flame, leads to the production of intumescent chars which because of
good thermal insulating characteristics tend to protect the underlying combustible
substrate.

Phosphorus/Halogen Synergism

Phosphorus compounds enhance the effectiveness of the halogens by forming


phosphorus oxyhalides which are more effective radical traps than halogens
alone. In addition , they have high boiling points and higher specific gravities and
therefore remain longer in the flame zone. Because of their higher molecular
weights phosphorus halides form layer over the condensed phase, protecting it
from the air required for combustion. Furthermore, phosphorus compounds aid
the decomposition of the halogen compounds, thereby releasing more halogen
species to the flame zone.

Dr. Awni Alkhazaleh


Inorganic Flame Retardants

Most of inorganic flame retardants unlike organic retardants, act by physical means.
Antimony trioxide is an exception which, in presence of halogenated compounds
act chemically in vapour phase. Inorganic flame retardants are usually used as
additives and are required in relatively large amounts. The main features of their
action are:

• Dilution of the polymer in the condensed phase, hence, decrease the amount of
available fuel.

• If used as fillers, increase the amount of thermal energy required to raise the
temperature of polymer to pyrolysis level, due to their high heat capacities.

• All inorganic compounds decompose endothermally liberating water and non-


flammable gases like CO2, SO2, etc. Endothermic process of decomposition and
released water help in cooling down the substrate, whereas, inert gases help in
diluting the fuel gases and shielding the surface of polymer against oxygen attack.
Some of them like borates, can make glassy film on the surface of the polymer.

Dr. Awni Alkhazaleh


Some examples are discussed here :

Boron compounds : The most widely used boron flame retardants are mixture of
boric acid and borax, zinc borate, sodium borate, calcium borate and barium
metaborate. They are very successful flame retardants for cellulosic textiles, wood
and paper. These compounds decompose endothermally releasing water and
forming a glassy coating on the surface of the substrate :
On heating, the mixture dissolves in its own water of hydration, swells to form a
frothy substance, dehydrates again and fuse into clear melt. The melt which is
mainly B2O3 softens at 325 0C and starts to flow above 500 0C. This melt acts as a
shield between fuel and substrate. Furthermore, boric acid like other Lewis acids,
catalyses dehydration reactions of cellulose leading to more char formation and
suppression of flammable gases. Borates act mainly in the condensed phase.

Alumina trihydrate : It is most widely used flame retardant because of its low cost
and is easy to incorporate into plastics. It contains a significant amount of water
(34.5% of its weight) and on heating starts releasing it in the temperature range of
180 - 200 0C. This endothermic reaction absorbs the heat and cools the substrate
below its decomposition temperature. Liberated water vapours dilute the
flammable gases and form a protective layer on the polymer surface.
Dr. Awni Alkhazaleh
Other inorganic compounds : Magnesium hydroxide and magnesium carbonate
are other flame retardants which act similar to aluminium trihydrate. Magnesium
hydroxide decomposes at about 320 0C producing water (31% of its weight). It is
used in polyolefins. It also promotes char formation and reduces smoke
formation. Magnesium carbonate releases carbon dioxide (36.1% of its weight) in
addition to water (20.2%) starting at 230 0C. Chalk, a filler is also used for flame
retarding plastics. It does not decompose up to 9000C and acts purely by the
diluting effect by reducing the amount of combustible material available per unit
volume. Other inert fillers are quartz flour, alumina, kaolin, talc, etc.

As mentioned earlier red phosphorus is also used as flame retardant for plastics
and polyurethane foams. Most probably phosphorus during combustion process
oxidises to phosphoric acid or phosphorus pentoxide. The latter acts by formation
of glassy film on the surface of the substrate as mentioned in the earlier section.

Dr. Awni Alkhazaleh

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