6.
Intumescent Flame Retardants
Intumescence is an interesting phenomenon. The French verb tumere
means "to swell". The Latin equivalent tumescere can be translated as "to
swell up". Therefore tumid or tumescent means swollen or bulging, and the
process of getting to a swollen state is intumescence. In flame retardant
terms, exposure to heat initiates a series of chemical and physical
processes, leading to a tumescent condition. This state is characterised by
a fire-resistant insulating foam. The foam serves to isolate heat and
oxygen from the fuel source, extinguishing the fire (Mount, 1992).
6.1 Condensed phase charring
A complete description of intumescence requires analysis of both chemical
and physical process.
, .
6.1.1 Chemical mechanism of intumescence
A suggested mechanism for char formation is discussed by Mount (1992).
The chemistry is often written in terms of simple acid-catalysed,
dehydration reactions. This is shown in the four reactions below.
46
OH
I
-----CH-CHz-OH ~ ------CH-CHz-O-P=O
I
OH
OH OH
I I
------CH-CH2-0-P=O ~ H3 P0 4 + -------C=CH 2
I I
OH OH
The first two reactions show the depolymerisation catalysed by an acid.
The second two show the dehydration of the polymer when phosphoric
acid is present. Both reactions essentially lead to the same result:
producing -----C=CH 2 fragments at the polymer chain ends. These
fragments condense to form carbon-rich char residues.
Briefly stated, the way the phosphorous compounds work is that they
phosphorylate carbonifics such as pentaerythritol to make polyol
phosphates. These polyol phosphates can then break down to form char
(Weil, 1992). ,.
6.1.2 Physical model of intumescence
Intumescent flame retardants were initially used, in paints and coatings.
Typical formulations contained a phosphorous compound such as
ammonium polyphosphate, a char forming polyol such as pentaerythritol,
along with a blowing agent such as melamine. A binder is also necessary
to keep the compounds in contact with each other.
With such intumescent coatings, one can visualise the burning polymer as
a block consisting of several separate layers. The top char layer, is
47
followed by the intumescent front where the foaming reactions take place.
Below is an unburned polymer coating layer that still contains flame
retardant. The bottom layer represents the polymer substrate that is being
protected by the intumescent coating. The char-foam provides a physical
barrier to heat- and mass transfer, and therefore interferes with the
combustion process (Gilman & Kashiwagi, 1997).
For a mixture to be an efficient intumescent system, three ingredients are
needed (Mount, 1992; Camino, et al., 1989):
• An inorganic acid (dehydrating agent);
• A carbon rich polyhydric material as char former (carbonific); and
• A blowing agent - called a spumific.
The interaction of these components, to form a foamed char is illustrated in
Figure 2.
Acid Carbonific Blov,;ng agent
Catalyst Carbon source Spumific
, .
Gases
Carbon Char
Carbon Foam
Figure 2: chematic diagram of the formation of char during
intumescence (Gilman & Kashiwagi, 1997).
48
The ratios in which the different compounds are present are also of utmost
importance. The optimum ratio must be determined experimentally. One or
more of these substances could be replaced with others of the same class
or group. Further studies showed that more effective intumescent systems
are obtained when two or more of the elements required for intumescence
are incorporated in the same molecular complex (Camino, et al., 1989).
Intumescent flame retardants also work well in bulk polymers, such as
polypropylene (PP) (Montaudo & Puglisi, s.a.).
The effectiveness of the intumescent flame retardants is due to the foamed
char formed on the surface of the burning material (Camino, et al., 1989).
The char acts as a physical barrier against heat transfer to the surface of
the combustible material. Char formation lowers the rate of temperature
increase of the surface beneath the char. (See Figure 1)
The layer of char furthermore hinders the diffusion of oxygen to the site of
combustion. Dripping of the molten plastic is also reduced by char
formation, thereby eliminating a possible ' source of further flame
propagation.
49
t
Mass loss Heat absorption
INTUMESCENT FRONT
UNBURNED FLAME RETARDANT COATING
Figure 1: Schematic diagram of the different layers during the burning
process (Gilman & Kashiwagi, 1997).
Halogenated compounds such as chlorinated paraffin are commonly used
in intumescent coatings as carbonifics. However, they are not widely used
in intumescent flame retardants for plastics. Nitrogen based compounds
are widely used owing to their environmental soundness. This is true for
almost all char forming flame retardant systems (Zaikov & Lomakin, 1996).
Nitrogen based flame retardants have many advantages over other
systems because they produce less smoke and fewer toxic gases. The
smoke is also less corrosive and polymer scrap more re~dily disposable
after use (Horacek & Grabner, 1996). The shift to such environmentally
friendly flame retardants, is of high interest world wide. The market is trying
to move away from halogenated flame retardants, but alternative systems
are usually less effective or more expensive (Mount, 1992).
50
6.2 Mineral filler synergism
It was believed that the addition of inorganic fillers to the compounds used
as flame retardants can improve their efficiency. This is due to the plate-
like microstructure of certain fillers and the consequent stabilising effect
they might have on the cell-structure of the char foam. The addition of
fillers may reduce the amount of intumescent char, but should give the
char a better strength and cell-structure. In the late 1980's a study on the
then common and frequently used inorganic fillers proved to be a
revelation. It was found that the fillers did modify the char structure but
reduced the efficiency of the flame retardant system (Bertelli et aI., 1989).
The chars formed with the added filler were harder and more solid than
those without the fillers, but were of lesser volume. The mechanism used
to explain the modifications in the chemical and physical characteristics of
the char was based on the possibility of the reaction between the acid
phosphorus moieties and the fillers.
Recently, a careful study was made by Hoechst-Celanese comparing the
effect of titanium dioxide (Ti0 2) and stannous oxide (Sn02) on the flame
retardant char forming effect of ammonium polyphosphate in
polypropylene. An intumescent nitrogen containing resin was also used.
Titanium dioxide increased the flame retardancy by giving a stronger and
more cohesive char with higher yield. Stannous oxide on the other hand
was antagonistic, made the char flakier and more porous and did not
enhance the char yield. Titanium dioxide probably functions by a physical
bridging effect in the char, and the negative effect of the stannous oxide is
probably due to some chemical interaction with the phosphorous
compounds (Weil, 1992).
51
6.3 Other intumescent systems
Recent research showed that combinations of silica gel and pentaerythritol
with potassium carbonate are effective char forming flame retardants
(Gilman et al. , 1997; Miller, 1996). Unfortunately, these systems are water-
soluble, making them unsuitable for outdoor use. It should be possible to
convert these systems to intumescent ones.
Other new intumescent systems include the use of expandable graphite
flakes in a special intumescent carrier resin (Miller, 1996). These flakes
expand their initial thickness by up to a hundred times when exposed to
heat. This material is based on natural occurring graphite and is therefore
environmentally friendly. The implementation of nanocomposite clays as
flame retardants in polymers is also being investigated (Gilman &
Kashiwagi, 1997).
, .
52
