Mechanism of Glowing

Solid fuel is consumed in the absence of a visible flame and without the
formation of volatile fuel gases. Glowing combustion is the rapid, flameless
combustion of carbonaceous pyrolysis residues accompanied by visible
incandescence. Glow is a special type of glowing combustion where the
fuel is the carbonaceous residue formed during or after flaming
combustion. Smouldering is slightly different in that it is a primary
combustion process in which formation of carbonaceous residue and its
oxidation occur consecutively in two interrelated steps. It is a relatively low
temperature process with temperatures as low as 530oC. The initial stage
consists of pyrolytic or thermo-oxidative degradation of polymer to form a
high specific surface area char and is accompanied by formation of volatile
organic compounds; the second stage is solid state oxidation which
volatilises the carbon and is the source of heat for further smouldering to
occur.

Dr. Awni Alkhazaleh

 Glowing combustion is really the oxidation of carbon, which is the main
constituent of the charred residue and is known to be catalysed by many metal
ions. Sodium, potassium, calcium, magnesium and many transition metals,
particularly manganese and iron are known to be smoulder and glow accelerators.
Metal oxides catalyse oxidation of carbon so that the ignition temperature is much
lower in their presence and burning proceeds much more rapidly.

Oxidation of carbon takes place through both of the following reactions :

C(s) + O2 (g) CO2 (g) H = - 394.95 kJ mol-1

Since the first reaction involves liberation of 110.45 kJ mol-1 and second one
394.95 kJ mol-1, the additional release of 284.5 kJ mol-1 in the latter reaction is
more likely to promote self-sustaining glowing. In the first reaction, the energy
liberated is considerably less and is insufficient to propagate the oxidation of
carbon, once the initiating source is removed. Hence, it is thought that smoulder
and glow retardants accelerate the formation of CO and inhibit the formation of
CO2 either directly from carbon or by subsequent conversion of CO to CO2 by
following reaction :
C(s) + 1/2 O2 (g) CO (g) H = - 110.45 kJ mol-1
Dr. Awni Alkhazaleh
 CO(g) + 1/2 O2 (g) CO2 (g) H = - 284.5 kJ mol-1

Glowing combustion is nearly flameless and smokeless combustion such as

found in a bed of burning charcoal in which the primary reaction is that of carbon
with oxygen to produce carbon monoxide. The pale blue flame often seen in a bed
of burning charcoal is due to gas-phase combustion of CO. Afterglow, as the term
implies, is a glow in material after the removal of external source of fire exposure
or termination of flaming of the material. Smouldering combustion is to 'burn and
smoke without flame'. A characteristic that distinguishes smouldering from
glowing combustion is that smouldering may proceed in materials that have not
undergone prior conversion to a char residue. Smouldering combustion is usually
observed in materials of high surface to weight ratios, e.g., paper, cotton fabrics,
sawdust, coal, etc.

Dr. Awni Alkhazaleh

 Flame Retardant Compounds
Flame retardants are usually compounds containing halogens, phosphorus,
nitrogen, sulphur, boron and metals in different combinations. When two
compounds function as flame retardants, the result may be additive, synergistic or
antagonistic. An additive effect is the sum of the effects of two components
measured independently. A synergistic effect is an observed effect greater than the
additive effect and an antagonistic effect is one, which is less than an additive
effect. Flame retardants are chemical compounds that are added to polymers to
reduce their flammability by two alternative means : 1) to change the combustion
characteristics of the polymer so that it will be more difficult to ignite or 2) once
ignited, to cause the fire to die out or cause the material to burn more slowly so
that the flame spread and rate of heat release are lowered.

Flame retardant compounds, in order to be useful, must fulfill a complex set of

requirements, many of which are specific for each material and derived product. In
principle, a flame retardant added to a polymer should :
•Reduce flammability compared to unmodified polymer to a level specified for a
particular end use.
•Reduce (or at least not increase) smoke generation.
Dr. Awni Alkhazaleh
• Not increase toxicity of combustion products
• Be efficient al low loading level in the polymer
• Be totally compatible with the polymer
• Process easily in all processing equipment normally used for the particular
polymer
• Be retained in the product through normal use i.e., not volatilise (or otherwise
leave) the polymer
• Be low in cost

Mode of action
Depending upon their nature, flame retardants can act chemically and /or
physically in the solid, liquid or gas phase. They function by interfering with
particular stage of combustion (heating, decomposition, ignition or flame spread)
of the polymer. The various ways in which a flame retardant can act physically or
chemically are described below.

Dr. Awni Alkhazaleh

Physical Action

There are several ways in which combustion can be retarded by physical action:
•Thermal effect : Endothermic processes by flame retardant additives which are
either capable of dissipating large quantities of heat internally or conducting this
energy away from the flame front. Hence, they cool the substrate to temperature
below that required for combustion.

•Formation of protective layer (coating) : Upon contact with flame a viscous film
of molten salt is formed on the surface of polymer matrix. This film acts as a shield
between substrate and oxygen; also entraps pyrolysis gases, hence flame
propagation is stopped. Heat transfer is also impeded.

• Dilution of gases : The incorporation of inert substances (fillers) and additives

which evolve inert gases on decomposition dilute the flammable gases by
blanketing the substrate with a so-called inert atmosphere.

Dr. Awni Alkhazaleh

Chemical Action

The most significant chemical reaction interfering with combustion process takes
place either in the solid or gas phase.
•Reaction in the gas phase : Some flame retardant chemicals generate free
radicals during their thermal decomposition process, which react with those
produced from the polymer, forming stable non - reactive compounds. The
exothermic processes are thus stopped, the system cools down and supply of
flammable gases is reduced and eventually completely suppressed.

•Reaction in the condensed phase : This type of mechanism is applicable to char-

forming polymers, e.g., cellulose. Flame retardants acting in the condensed phase
usually act as Lewis acids and catalyse dehydration reactions of polymer leading to
cyclizing and cross-linking and ultimately carbonaceous char formation. More char
is formed at the expense of combustible volatile gases, hence flame propagation is
stopped.

Dr. Awni Alkhazaleh