Professional Documents
Culture Documents
This trend article describes some recent work related to the development of ame retardancy
of six common plastic materials, polypropylene, polystyrene, poly(methyl methacrylate),
unsaturated polyester, polyurethane, and epoxy resin. Conventionally, a single re retardant element is used to achieve
re retardancy but in this paper, there is a description of combinations of re retardant elements, including a nano-sized
material.
Introduction
In modern society, there is an
increasing use of plastic materials
to replace metals due to the lighter
weight and high specic strength of
plastic materials. However, the utilization of plastics carries a re risk that is
not seen with metals and this brings
about the need for re retardancy.
Plastic materials, when exposed to
high temperatures, decompose with
the release of heat, smoke, soot, and
toxic volatiles with smoke considered as the primary cause of death in
most res rather than heat.[1] There
are two ways to render a plastic ame
retardant (FR): 1) the plastic can be
blended with FRs (additive approach)
and 2) an FR element can be introduced into the plastic via a chemical
reaction (reactive approach). Both
T. Mariappan, C. A. Wilkie
Department of Chemistry and Fire
Retardant Research Facility, Marquette
University, PO Box 1881, Milwaukee,
WI 53201, USA
E-mail: Charles.wilkie@marquette.edu
wileyonlinelibrary.com
DOI: 10.1002/macp.201200363
1987
Macromolecular
Chemistry and Physics
www.mcp-journal.de
1988
Flame Retardancy of
Polypropylene
Polypropylene (PP) burns readily in air
(LOI = 17%) with melting and dripping
and produces virtually no soot nor
leaves any residual char. PP starts to
degrade thermally above 290 C, via
a random scission mechanism with a
complex mixture of gaseous pyrolysis
products of C4, C5, and C6 hydrocarbon
fragments with only small amounts of
propylene monomer present. The FR
requirements for PP are generally similar to those for other polyolens.[10]
The re retardancy of PP usually relies
on the use of endothermic additives,
which requires about 60% additive
and thus the mechanical properties
are severely impacted, vapor-phase
additives, or intumescent compositions.[11] Many commercially available
FRs are not completely compatible and
tend to bleed out; FRs for PP have to
be thermally stable at the processing
temperature of about 250 C.
Intumescent compositions swell
when heat is applied and thus form
a thick layer of insulating material,
which can limit the ow of heat to
the polymer. The classical intumescent (IFR) composition contains three
basic components, acid [ammonium
polyphosphate (APP), char-former
(pentaerythritol), and blowing agent
(melamine)]. A minimum of 30 wt%
of IFR loading is necessary for
Macromol. Chem. Phys. 2012, 213, 19871995
2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.MaterialsViews.com
Macromolecular
Chemistry and Physics
www.mcp-journal.de
Table 1. LOI and UL94 data of FR lled PP with different loading of sepiolite. (Reproduced
from ref. [19] with permission).
Sample
[wt%]
IFR
[%]
Sepiolite
[wt%]
LOI
[%]
UL 94 test
Dripping
PP - 100
17.6
No rating
Yes
PP - 75
25
34.4
V-1
No
PP - 75
24
36.0
V-0
No
PP - 75
23
35.8
V-0
No
PP - 75
22
35.8
V-1
No
PP - 75
21
32.3
V-2
No
www.MaterialsViews.com
Flame Retardancy
of Polystyrene
Polystyrene (PS) is intrinsically highly
ammable (LOI = 18%) and has a tendency to depolymerize when exposed
to high temperatures, and the volatile
products, styrene monomer, dimer,
and benzene and lower alkyl benzenes, have high fuel value. Since the
fuel is aromatic, it is able to condense
to large polycyclic structures, resulting
in a very smoky or sooty ame. Yang
et al.[29] showed that nanosilica
could effectively improve the ame
retardancy of brominated PS. Beach
et al.[30] found that a low loading of
sulfur could improve the LOI values
of PS lled with triphenylphosphate.
Synergy was observed between
phosphate and bromine re retardants and clay[31,32]; signicant deterioration of mechanical properties is
observed upon the addition of conventional FR but, the addition of clay can
ameliorate this. Improvements in re
performance of PS/IFR composites by
the partial substitution of nanollers,
including clay, OZrP, CNT, Fe2O3, and
nickel catalyst have been reported. The
presence of these additives changes
the structure, yield, and thermal
stability of the char, which leads
to composites with different ammability performance. The claycontaining sample showed the lowest
ammability. OZrP modied with
different salts had various effects,
depending on the cations, on the FR
efciency of IFR system.[33] A synergistic effect of CNT with Deca/Sb2O3
was observed in PS system.[34]
Nyambo et al.[35] showed synergistic effects in both TGA and cone
calorimetry for PS formulations containing both MgAl-LDH and APP.
Physical and chemical interactions
between MgAlLDH and APP are
responsible for the observed synergy in thermal stability and re
1989
Macromolecular
Chemistry and Physics
www.mcp-journal.de
1990
Flame Retardancy of
Unsaturated Polyester
Unsaturated polyester resins are lowmolecular-weight prepolymers or
precursors, which are prepared by the
condensation of a glycol, an unsaturated acid, and a saturated aromatic
acid. Styrene or methyl methacrylate is most commonly employed
as the cross linking agents for the
polyester resin. Cast and glass ber
reinforced resin constitute a large
proportion of the high volume composite materials currently in use.
They are employed in a wide range
of applications such as ooring, surface coatings, boats, transportation,
and buildings; res may arise in these
uses at any time, giving great importance to re hazards.[47] Because of the
aromatic content (styrene) in polyester resins, large amounts of smoke
can be released. When low smoke
www.MaterialsViews.com
Macromolecular
Chemistry and Physics
www.mcp-journal.de
www.MaterialsViews.com
Figure 1. PHRR, TSR, and smoke values of polyester resin containing DBNPG under
35 kW m2. (Reproduced from ref. [56] with permission).
1991
Macromolecular
Chemistry and Physics
www.mcp-journal.de
1992
Materials
Fire
performance
index (FPI)
TPU
0.073
TPU + 5% organoclay
0.130
0.071
0.199
www.MaterialsViews.com
Macromolecular
Chemistry and Physics
www.mcp-journal.de
Table 3 Fire retardancy of epoxy lled with clay and conventional FRs. (Reproduced from
ref. [76] with permission).
Sample
LOI (%) UL 94
1
tig
(S) 3
THE/ML Residue
THE
[MJ m2] [MJ g m2] [%] 2
10
0.2
EP
20.5
HB
102
140
2.4
5.0
EP + Clay
21.2
HB
90
130
2.3
9.2
EP + 5 MB
23.3
HB
60
142
2.4
9.8
EP + Clay + 5 MB
23.5
HB
60
135
2.4
12.5
EP + 10 MB
24.1
HB
53
129
2.3
12.0
EP + 10 APP
23.8
HB
62
105
1.9
15.6
EP + Clay + 10 APP
21.9
HB
63
116
2.2
21.1
EP + 15 APP
28.9
V0
66
84
2.0
35.3
www.MaterialsViews.com
Summary
Nanodimensional materials have
three major areas of application,
enhancing ame retardancy, barrier
1993
Macromolecular
Chemistry and Physics
www.mcp-journal.de
1994
www.MaterialsViews.com
Macromolecular
Chemistry and Physics
www.mcp-journal.de
www.MaterialsViews.com
1995