FIRE AND MATERIALS

Fire Mater. 2002; 26: 155168 (DOI: 10.1002 /fam.799)

Heat Resistance and Flammability of High Performance

Fibres: A Review
Serge Bourbigot* and Xavier Flambard
Laboratoire de G!enie et Mat!eriaux Textiles (GEMTEX), UPRES EA2461, Ecole Nationale Sup!erieure des Arts et Industries Textiles
(ENSAIT), BP 30329, 59056 Roubaix Cedex 01, France
E-mail: serge.bourbigot@ensait.fr

The heat and ame resistance of high performance bres are reviewed according to the literature data. The
performance is discussed considering the physical and chemical structure of the bres. Some selected high
performance bres are then evaluated using the cone calorimeter as a re model to provide realistic data on the re
behaviour of the bres. They are also examined in terms of heat resistance using combined TGA/DSC. The results
are discussed and compared with literature data. Heterocyclic rigid-rod polymers (poly (p-phenylene-2,6benzobisoxazole or PBO (Zylon1) and poly(2,6-diimidazo (4,5-b:40 ,50 -e) pyridinylene-1,4 (2,5-dihydroxy) phenylene
or PIPD (M5)) exhibit the best performance (little or contribution to re, low smoke and good heat resistance) and
offer a good combination between heat and ame resistance and mechanical properties. Copyright # 2002 John
Wiley & Sons, Ltd.

INTRODUCTION
The demands of the market for high performance bres
are for faster, stronger, lighter, safer textiles. Fortunately, high performance and high temperature resistant
bres have been developed to aid in allowing products
to meet these challenges. High-performance bres are
driven by special technical functions that require
specic physical properties unique to these bres.
They usually have very high levels of at least one of
the following properties: tensile strength, operating
temperature, heat resistance, ame retardancy and
chemical resistance.1 Each of these bres has a
unique combination of properties which allows it
to ll a niche in the upper end of the high-performance bre spectrum. Whereas commodity bres are
routinely produced in the hundreds of millions of
kilogrammes, or even in the billions, most highperformance materials are produced in the low
millions of kilogrammes, often in the hundreds of
thousands. Applications include uses in the aerospace,
biomedical, civil engineering, construction, protective
apparel, geotextiles and electronic areas. The resistance
to heat and ame is one of the main properties
of interest for determining the working conditions of
the bres.2
Technical textiles are now a global industry, and
no longer the preserve of a few industrialized countries.
All regions and all industries in the world make
use of technical textiles, even if there is no local
manufacturing. Europe and North America remain a
major supplier of these textiles, and consume two thirds
of the total.3

Of the bres that played a signicant part in the

manufacture of technical usage in 1990, i.e. the
polyolens, polyamide, polyester and glass bres, the
most signicant growth in 2000 was enjoyed by the
polyolens and glass bres. The aramid and carbon
bres also experienced high growth rates, but still
remain marginal in tonnage terms (Table 1).4
The European situation, in 1990 and 2000 in terms of
bre consumption by the whole textile industry,
illustrates the importance of technical bres (Fig. 1).
This shows that the strong growth in the technical textile
usage sector rose from 22% to 36% of bre usage. All
other sectors declined in a more or less signicant way,
especially the clothing sector which lost practically ten
points. Technical textiles are gaining on clothing in
terms of importance within the sector, with 36% against
37.5% market shares respectively in 2000.
Finally the eld covered by technical textiles is
characterized by its complexity, the variety of the
sectors in which they are used and of the materials
employed. All natural or chemical bres and all textile
technologies can be employed to satisfy the current
market needs. However, during the past few years, the
position of chemical bres has been dominant with the
emergence of very high performances bres such as
Zylon1, PIPD or M5 and PEEK1 (see below) starting
to contribute signicantly.
In this paper, high performance bres are reviewed
rst, in terms of heat resistance and ammability. In the
literature the most common parameter used to measure
the ammability of bres is the limiting oxygen index.
((LOI) and is a relative indication of ammability. It is
the minimum concentration of oxygen at which the test

*Correspondence to: Laboratoire de G!enie et Materiaux Textiles (GEMTEX), UPRES EA2461, Ecole Nationale Sup!erieure des Arts et Industries
Textiles (ENSAIT), B.P. 30329, 59056 Roubaix Cedex 01, France
Contract/grant sponsor: FLAMERET; contract/grant number: G5RD-CT-1999-00120

Copyright # 2002 John Wiley & Sons, Ltd.

Received 29 May 2002

Accepted 26 July 2002

156

S. BOURBIGOT AND X. FLAMBARD

Table 1. Types and quantities of technical bres used in Europe

X 1000 tonnes

1990

2000

Change

Polypropylene
Polyethylene
Polyamide
Polyester
Polyacrylonitrile
Glass
Carbon
Meta-aramid
Para-aramid

325
10.5
97
235
2
67
0.5
1
1

1145
55
142
415
26
115
3
3.5
15

+252%
+424%
+46%
+77%
+1200%
+72%
+500%
+250%
+1400%

temperature resistant bres. For this discussion, these

latter are classied as a synthetic bres with a
continuous operating temperature ranging from 1808C
to 3008C (or higher) and a degradation temperature
higher than 3508C. The ame retardant ability of the
bres is only dened by the LOI test.
The principal classes of high performance bres
considered here according to our denitions are derived
from rigid-rod polymers (lyotropic liquid crystalline
polymers and heterocyclic rigid-rod polymers), modied
carbon bres, synthetic vitreous bres, phenolic bres,
poly(phenylene sulphide) bres and others. This part
focuses only on the specic thermal and re performances of the bres. Other properties are extensively
discussed in Hearles book.10
Table 2 presents a collation of all bre chemical
structures, properties and applications for all bres
reviewed below.
Lyotropic liquid crystalline polymers

Figure 1. Consumption by the full European textile chain: evolution of

technical textiles versus others sectors.

specimen continues to burn for a denite time or until a

specied amount of specimen is consumed5). Generally,
bres with a LOI greater than 25 vol.% are said to be
ame retardant. Nevertheless, the LOI test although not
very representative of a re, allows us to rate the
materials quantitatively. The approach that we have
developed is to evaluate bres using the cone calorimeter
as a re model.6,7 The major advantage of the cone
calorimeter is to measure the rate of heat release which is
the quantity of most concern in predicting the course of
the re and its effect.8 Other parameters, such as smoke
opacity and carbon oxides evolution, can be measured
and can be considered as well. This last aspect is
examined in the second part of this work. The reaction
to re of some high performance bres are evaluated
using the cone calorimeter and their heat resistance is
studied by thermal analysis. Indeed, the re behaviour
of a material depends on processes occurring in both
condensed and gas phases and on the processes of heat
and mass transfer. These processes strongly depend on
the degradation reactions occurring in the condensed
phase.9 Even if there is confusion between the temperature resistance and the ame retardant ability, it can be
expected that a bre with a high degradation temperature will have good ame retardancy.

REVIEW OF
BEHAVIOUR

HIGH

PERFORMANCE

FIBRE

Before exploring the details of the high performance

bres, it is important to dene the parameters of high
Copyright # 2002 John Wiley & Sons, Ltd.

Meta-aramid. Poly(m-phenylene isophtalamide) was

the rst aramid bre launched on the market (see Table
2).1113 This meta-aramid bre was commercialized by
DuPont under the trademark Nomex1 in 1967.14 Teijin
also introduced a similar bre (trademark Conex1) in
the early 1970s.15
Kermel1, commercialized by Rhodia, is a polyamideimide bre which is also classied in the meta-aramid
family (see Table 2).16 The bre has a thermal
conductivity twice as low as any other aramid bre.16,17
The principal market niche for meta-aramids is that
of heat-resistant materials.14,18 They are naturally nonammable thanks to their aromatic structures including
high C/H ratios and high contents of aromatic double
bonds. They were commercialized for applications
requiring unusually high thermal and ame resistance.
Nomex bre retains useful properties at temperatures as
high as 3708C. It has low ammability and has been
found to be self-extinguishing when removed from the
ame. On exposure to a ame, a meta-aramid fabric
hardens, starts to melt, discolours, and chars thereby
forming a protective coating. An outstanding characteristic is also low smoke generation on burning. The LOI
for m-aramid fabrics lies between 30 and 32 vol.%. It
has a weight loss at 4508C (Fig. 2) and a use temperature
of 3708C.
Para-aramid. In the 1970s, researchers at DuPont
reported that the processing of extended chain all
para-aromatic polyamides from liquid crystalline solutions produced ultrahigh strength, ultrahigh modulus
bres.15,19,20 The greatly increased order and the long
relaxation times in the liquid crystalline state compared
with conventional systems led to bres with highly
oriented domains of polymer molecules. The most
common lyotropic aramid bres comprise poly(pphenylene terephtalamide) (PPTA) which is marketed
as Kevlar by DuPont or as Twaron by Teijin (formerly
developed by Akzo) (see Table 2).18
The conventional market for PPTA is body armour,
cables and composites for sports and space applications.15 The continuous operating temperature of PPTA
in air is up to 1908C. PPTA degrades in air above 4008C
Fire Mater. 2002; 26: 155168

Copyright # 2002 John Wiley & Sons, Ltd.

PTFE

PBO

Poly(tetra-fluoroethylene)

Poly(p-phenylene-2,6benzobiso-xazole)

Elongatable carbonaceous
Dow fibre

Oxidized poly(acrylonitrile)
fibre

EDF

OPF

Poly(2,6-diimidazo(4,5-b:40 ,50 -e)

PIPD
pyridi-nylene-1,4 (2,5-dihydroxy)phenylene)

Generic name

Chemical name or designation

N H

H N

H N

N H

N H

OH

H N

N H

HO

C C

H N

Chemical structure

Table 2. Description and properties of high temperature resistant bres

> 50

5668

EDF (Dow)

4555

Pyromex1
4560
(Toho Tenax),
Lastan1
(Asahi),
PANOX1
(SGL
Carbon Group)

M5
(Magellan
Systems
International)

Zylon1
(Toyobo)

95

Teflon1
(DuPont)
Toyoflon1
(Toyobo)

200

200

310

260

LOI (vol.-%) Continuous

operating
temperature
(8C)

Trade name

Insulative material

Aerospace structures, automotive

engine, ballistic material, heating
elements, thermal protection

Protective clothing, composite

materials, stealth materials,
aerospace applications

Protective clothing, heat resistant

felt, sling, fragmentation barrier

Aerospace and automotive

applications, food processing,
agricultural machinery

Applications

HEAT AND FLAME RESISTANCE OF HIGH PERFORMANCE FIBRES

157

Fire Mater. 2002; 26: 155168

PBI

PPS

PI

PEEK

Phenolic or
novoloid
fibre

Melamine
fibre

Poly(2,20 -(m-phenylene)-5,50 bisbenzimi-dazole)

Poly(phenylene sulfphide)

Polyimide

Poly(ether-etherketone)

Phenolic fibre

Melamine fibre

Table 2. (Continued)

Copyright # 2002 John Wiley & Sons, Ltd.

C
H2
C
H2

C O C
H2
H2

OH

CH2

OH

C
H2

OH

OH

CH2

OH

C
H2

OH

CH2 OH

CH 2OH

C
H2

OH

CH2

OH

C
H2
OH

CH2 OH

N
N

N
N
N C N
H2

N
N

N
N
N

Three-dimensional melamine-based network

C
H2
OH

H2 C

41

Basofil1
(BASF)

Kynol1
(Nippon
Kynol Inc)

PEEK1
(Zyex)

P84TM
(Inspec
Fibres)

3032

3034

35

38

Ryton1

40
(Phillips
Petroleum Co.)
Procon1
(Toyobo)

PBI
(Celanese)

200

200

250

260

280

250

Fire protective clothing, insulative

materials, fire blockers

Fire protective apparel, fire

blockers, composite reinforcement

High temperature materials

Fire protective clothing, filtration

Reinforcing materials, filtration,

protective clothing, insulators

Firefighter protective clothing,

industrial workers apparel, fire
blockers

158
S. BOURBIGOT AND X. FLAMBARD

Fire Mater. 2002; 26: 155168

PPTA

PMIA

PAI

Copolymer
p-aramid
fibre

Poly(p-phenylene
terephtal-amide)

Poly(m-phenylene
isophtal-amide)

Polyamide-imide

Copoly(p-phenylene-3,4oxidiphenylene- terephtalamide)

Copyright # 2002 John Wiley & Sons, Ltd.

*

N
H

O
C m N
H

H O

N C
H

N C

C
N

N C

N
O

H O

n*

O
H
N C

CH2

C n*

Technora1
(Teijin)

Kermel1
(Rhodia)

Nomex1
(DuPont)
Conex1
(Teijin)

Kevlar1
(DuPont)
Twaron
(Teijin)

25

3032

3032

2830

200

200

200

190

Reinforced plastics, rope and

cable, protective clothing,
reinforcement of construction
materials

Fire and heat protective clothing,

insulators

Fire protective clothing, filtration,

thermal resistant furnishing

Protective clothing, composite

reinforcement, ropes and cables

HEAT AND FLAME RESISTANCE OF HIGH PERFORMANCE FIBRES

159

Fire Mater. 2002; 26: 155168

160

S. BOURBIGOT AND X. FLAMBARD

N

Figure 3. Chemical structure of PBZT.

Figure 2. Remaining mass versus temperature of Nomex under air and

nitrogen flow.14

and does not melt below this temperature. During

ignition, PPTA does not melt but glows. No after
burning is observed after removal from the ame. PPTA
yields char above 4508C. The LOI for PPTA fabrics lies
between 28 and 30 vol.%.
Copolymer para-aramid. Although para-aramids are
high in strength, there is some problem with chemical
resistance. Homopolymer para-aramids have relatively
weak resistance to strong acids and bases. PPTA cannot
be bleached with chlorine and are often not approved
for food handling protective gloves. In 1985, Teijin
introduced Technora1 bre into the high performance bre market. Technora1 is based on the 1:1
copolyterephtalamide of 3,40 -diaminodiphenyl ether and
p-phenylenediamine (see Table 2).15,21
The ne surface structure of Technora1 copolymer
allows much higher chemical resistance than PPTA.
Copolymer para-aramids have the advantages of increased abrasion resistance and steam resistance }
useful properties in many protective applications.
Technora1 has a decomposition temperature of
5008C.18 It can be used at 2008C for long periods of
time and, even at 2508C, it maintains more than half of
its tensile strength measured at room temperature.15 The
LOI of Technora1 is 25 vol.%, its ignition point is
about 6508C and its heat of combustion is 28.5 kJ/g.21
Heterocyclic rigid-rod polymers
Polybenzazole. A family of p-phenylene-heterocyclic
rigid-rod and extended chain polymers includes
poly(p-phenylene-2,6-benzobisthiazole)
(PBZT)
(Fig. 3)2225 and poly(p-phenylene-2,6-benzobisoxazole)
(PBO) (see Table 2).2629
PBZT and PBO were initially prepared at the Air
Force Materials Laboratory in the US Air Force
Ordered Polymer Program.30,31 Only PBO bre showed
attractive properties and great economic potentiality.
Dow acquired the patent license from Stanford Research Institute, and then developed a new synthesis
route of monomer, polymerization and bre spinning
technology. The rigid-rod like nature of PBO polymer
chain makes the processing of polymer difcult, whereas
excellent physical properties of the bre originate from
the rigid conformation. The development of production
technology on bre spinning ran into serious obstacles.
In 1991, Dow decided to work with Toyobo (Japan).
Their joint development bore fruit in 1994 as the
Copyright # 2002 John Wiley & Sons, Ltd.

development of a unique spinning technology, opening

the way to the production of PBO bre. Commercial
production started in 19981 under the trademark
Zylon.32,33
In thermogravimetric analyses, the onset of degradation of PBO34,35 and PBZT36 is reported to be 6008C in
air. This temperature is over 7008C in an inert atmosphere. In isothermal aging studies in air at 3438C, PBO
and PBZT retain ca 90% of their weight after 200 h. At
3718C in air, PBO and PBZT retain ca 78% and 71% of
the original weight, respectively. The operating temperature of these two bres is up to 3508C.15 PBZT and
PBO degrade without the observation of crystalline
melting points or glass-transition temperatures. PBO
also has a very high ame resistance and is selfextinguishing when removed from the ame. On
exposure to a ame, formation of char is observed at
the surface which may act as a protective shield. The
LOI of PBO is much higher than aramid bres, 68
vol.%.32 The combustion gases of PBO consist of
carbon oxides and water, with smaller amounts of toxic
gases such as hydrogen cyanide, sulphur and nitrogen
oxides.32,37,38
Polybenzimidazole. Polybenzimidazoles (PBI) are a
class of thermally stable polymers, typically condensed
from aromatic bis-o-diamines and dicarboxylates.
Poly(2,20 -(m-phenylene)-5,50 -bisbenzimidazole) is the
polybenzimidazole on which most attention has been
focused over the past 30 years (see Table 2).3942 PBI
bre is marketed by Celanese (USA) and the main
current textile applications of PBI are protective
clothing, re blockers and space materials.43
PBI is a thermoplastic polymer with a high glass
temperature (4508C). Its degradation temperature is
reported to be 5808C in air and is over 10008C in
nitrogen. The continuous operating temperature is up to
2508C. PBI does not burn in air and it does not support
burning after removal from the ame. On exposure to
ame or high heat ux, it forms a tough char in high
yield (to 80 wt.%).42 After the char is formed, the
charred fabric retains its integrity and exibility with
little shrinkage. Its LOI is greater than 41 vol.%.43 PBI
bre has also negligible heat release rate measured by
the Ohio State University Heat Release Apparatus
(OSU test).44 The 2 min average heat release is less than
10 kW/m2. It releases little smoke up to its decomposition temperature. Its optical smoke density (Ds ) is 2
compared with 8 for aramids. When exposed in air to
temperatures below its decomposition point, PBI emits
carbon oxides and water with traces of sulphur dioxide
and hydrogen cyanide.42
Polypyridobisimidazole. Recently a new member of the
rigid-rod polymer family was synthesized. This new
polymer is the poly(2,6-diimidazo(4,5-b:40 ,50 -e)pyridinylene-1,4(2,5-dihydroxy)phenylene) (PIPD or also
Fire Mater. 2002; 26: 155168

161

HEAT AND FLAME RESISTANCE OF HIGH PERFORMANCE FIBRES

referenced to as M5) (see Table 2).4551 It has the ability

to form hydrogen bonds between adjacent chains. PIPD
was rst developed by Akzo Nobel Central Research,
and now it is being developed by Magellan Systems
International. Potential applications using M5 bre are
envisioned in ve major areas: personnel protection, re
resistance, advanced composite materials and tethering/
advanced fabrics.52
PIPD has extremely high re resistance properties like
the other rigid-rod polymeric bres.52 This is due to its
lack of a true melting point, the rigidity of the chain and
the strong chain-to-chain interaction. PIPD does not
burn in air and is self-extinguishing. Its LOI is reported
to be greater than 50 vol.%. Cone calorimeter data at an
external heat ux of 75 kW/m2 (implying a surface
temperature of about 8908C) give a peak heat release
(PHRR) rate of 44 kW/m2 associated with a time to
ignition (TTI) of 77 s (PHRR and TTI of PBO=48 kW/
m2 and 56 s; PHRR and TTI of p-aramid=205 kW/m2
and 20 s). This means that PIPD shows a great potential
as a ame retardant. PIPD bre varieties formed a char
layer only at the surface of the bre, while protecting the
rest of the bre. It is believed that the superior
performance of PIPD bres may be partly due to the
fact that the crystal structure of PIPD contains about
21% water.
Carbon precursor and elongatable carbonaceous bres
Carbon precursor. Carbon precursor bres are partially
carbonized bres which transform into carbon or
graphite bre when they undergo further carbonization
in an inert atmosphere at high temperature.53,54 They
are produced by thermal stabilization of acrylic bre at
20083008C in air. The mechanism of stabilization is
basically interpreted as intermolecular ring deformation
of the nitrile group and oxidation. The stabilization is
accompanied by stretching to induce the high molecular
orientation required for obtaining a high modulus
bre.55,56 The stabilized bre is called oxidized PAN
bre (OPF) in the market (see chemical structure
Table 2). It is commercialized by several companies,
such as Toho Rayon Ltd (Japan) under the name
Pyromex1,57 SGL Carbon Group (UK and Germany)
under the name PANOX158 or by Asahi (Japan) under
the name Lastan1.59 The applications of OPF are
friction materials, protective clothing and re blockers.
Due to the unique structure of OPF, the bres have
non-ammable and non-melting characteristics. The
LOI lies between 45 and 60 vol.%. They do not melt
or adhere under direct exposure to intensive ame. The
decomposition temperature of OPF is higher than 3008C
and the products of degradation are hydrogen cyanide,
ammonia, carbon oxides and water.
Elongatable carbonaceous bre. The extreme brittleness,
high modulus and low elongation of standard carbon
bres restricts them to being woven only on specially
adapted weaving machines. To overcome these drawbacks, a modication of carbon bre technology was
developed using less stringent carbonizing conditions
and only partially carbonizing the precursor bres, and
improved textile bre properties have been achieved
(Fig. 4).60
Copyright # 2002 John Wiley & Sons, Ltd.

N H
H N

H N

N H

450 - 750C
N

H N

N 2 atmosphere

N H
H N
N

N H

OPF

EDF

Figure 4. Synthesis of elongatable Dow fibre (EDF) from oxidized PAN

fibre (ODF).

Any standard precursor material can be used, but the

preferred material is wet spun. The OPF is treated in a
nitrogen atmosphere at 45087508C, preferably 5258
5958C, to give bres having 6970% C, 19% N, and a
density less than 2.5 g/ml. This bre is marketed by Dow
(USA).
Elongatable Dow Fibre (EDF) exhibits very good
ignition-resistance, ame retardancy and re blocking
properties. Its LOI lies between 45 and 55 vol.%.
Previous results with ignition resistant blends, where
such bres as aramids or PBI are used as the high LOI
bres, show that they need at least 65%, and typically
85%, bre content to pass the vertical burn test for
lightweight nonwoven batting. In contrast only 720%
of either EDF mixed with ammable natural and
synthetic bres allow the blends to pass such tests while
still retaining most of the base natural or synthetic bre
properties. Blends of 50/50 EDF/polyester also passed
the FAA airlines ignition resistance tests with zero ame
length and no after-burn.
Carbon bre. Though a large number of polymeric
precursors have been tried for modern carbon bres, the
three main precursors used commercially in order of
decreasing current use are PAN, coal-based pitch and
rayon.54 The major application of carbon bres is in
polymeric matrix composites; however, they are also
used in metal matrix and carbon matrix composites. As
examples, Toho Tenax (Japan) produces several grades
of carbon bres under the trademark Besght157 or
Toray (Japan) under the trademark Torayca1.61
Carbon bres are extremely resistant to high temperatures: their melting temperature is 40008C. They can
also be considered as ame resistant since they will burn
only at very high temperatures. They hence represent a
choice material for applications at extremely high
temperatures, for example in the ltration of molten
iron.
Vitreous bre
Man-made vitreous bres comprise a number of glass
and speciality glass bres and also, refractory ceramic
bres. All these bres are ame retardant since they do
not burn even at very high temperatures.62
Glass bre. A wide range of glass compositions is
available to suit many textile bres.62,63 Glass bres
made from various compositions have softening points
in the range 6509708C. At temperatures above 8508C,
these bres partially devitrify and form polycrystalline
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162

S. BOURBIGOT AND X. FLAMBARD

material that melts at 122513608C, which is high

enough to contain the res for several hours.
Ceramic bres. Ceramic bres are mostly used as
refractory bres in uses over 10008C and are characterized by a polycrystalline, rather than amorphous,
structure. These bres have exceptional high temperature characteristics. Different compositions result in
modifying end use temperatures from about 10508C or
higher for the kaolin-based products to 14258C and
above for the zirconium-containing materials.
Sulphur-containing bres
Because of the chemical structure of poly(phenylene
sulphide) (PPS) does not fall into any of the standard
polymer classes, the Federal Trade Commission granted
the bre the new generic name of Sulfar (see Table 2).6468
PPS bres are marketed by Phillips Petroleum Co.
(USA) under the trademark Ryton169 and by Toyobo
(Japan) under the trademark Procon1.32 The main
applications of PPS bres are heat and chemical
resistant lters, papermaking felts, insulators, reinforcing materials and protective clothing. They exhibit
good ame retardancy (LOI is about 40 vol.%) and its
operating temperature is up to 2608C.17,18,69
Miscellaneous bres
There are a number of bres which are used in nonconventional textile applications and cannot be classied in the sections considered above.
Phenolic. Phenolic (or also referenced as novoloid)
bres are cured phenol-aldehyde bres made by acidcatalysed cross-linking of melt-spun novolac resin to
form a fully cross-linked, three-dimensional, amorphous
network polymer structure similar to that of thermosetting phenolic resins (see chemical structure Table
2).70,71 Chemically, the bres contain approximately
76% carbon, 18% oxygen, and 6% hydrogen. The only
commercially available phenolic bres are the so-called
Kynol1 bres marketed by Nippon Kynol Inc (Japan).
They are used in a wide variety of ame- and chemicalresistant textiles and papers, in composites, gaskets and
friction materials, and as precursors for carbon and
activated-carbon bres textiles, and composites.72
Thermogravimetric analysis (TGA) indicates that
upon heating above 2508C in the absence of oxygen,
Kynol1 bres undergo gradual weight loss until, at

about 7008C, they are completely carbonized, with a

carbon yield of about 55860%. This weight loss occurs
without melting, and only a fraction of the comparatively small volume of volatiles produced is combustible.71 The remaining carbon char is amorphous (glassy)
in structure. The LOI of Kynol1 bres is reported in the
range 3034 vol.%.72 When exposed to ame Kynol1
bres do not melt but gradually char until completely
carbonized, without losing their original bre structure.
Finally, water and CO2 evolve as the main products of
decomposition.
Melamine. Although melamine is considered unreactive, its symmetry and functionality make it suitable for
use as a building block in condensation reactions with
formaldehyde. It results in a cross-linked, non-thermoplastic polymer of melamine units joined by methylene
and dimethylene ether linkages. In the polymerization
reaction, methylol derivatives of melamine react with
each other to form a three-dimensional structure. The
resulting network structure gives melamine bres the
same characteristics of other melamine based products:
heat stability, solvent resistance, and ame resistance
(see Table 2).70,73 Melamine bre is marketed by BASF
(Germany) under the trademark Basol1. Since melamine bres are heat and ame resistant, they typically
target hot gas ltration and safety and protective
apparel markets.74 Because of its variable denier and
staple length, low tensile strength and difculty in
processing, melamine bres are generally blended with
stronger bres such as aramids. It is more often used in
needled products or yarns made from wrapped spinning
techniques, though recent advances have led to satisfactory ring spun yarns, blended with other bres, such as
para-aramids, suitable for weaving into remens turnout gear.
TGA of melamine bres reveals that the main
degradation temperature of the bres occurs at 3708C
in air and that the residue is 34 wt.% at 6008C. Their
continuous use temperature is 2008C. The LOI lies
between 30 and 32 vol.%.18 Basol bre offers good
heat and ame protection in comparison with some
other high performance bres when measuring thermal
protective performance (TPP)75 as shown in Fig. 5. The
main evolving gases are carbon oxides, water, nitride
oxides and a small amount of hydrogen cyanide.
Fluorocarbon. Fluorocarbon bres are based on poly
(tetrauorethylene) (PTFE) (see Table 2).76 The carbon-

Figure 5. Basofil versus PBI, Nomex and P84 fibres when tested usingTPP test apparatus according to75 (combined convective and radiative heat flux
equalling 83.6 kW/m2 for 20 s).74

Copyright # 2002 John Wiley & Sons, Ltd.

Fire Mater. 2002; 26: 155168

163

HEAT AND FLAME RESISTANCE OF HIGH PERFORMANCE FIBRES

uorine bonds are extremely strong, and provide the

polymer with a very high thermal and ame resistance
(LOI = 95 vol.%).77 PTFE bres are marketed by
DuPont (USA) under the trademark Teon1.76
Polyimide. Polyimide (PI) bres are manufactured by
polycondensation of an anhydride with aromatic
diisocyanates in high polar solvents such as dimethylformamide or dimethylacetamide (see Table 2).7881 The
thermal properties of PI bres are characterized by the
glass transition temperature of 3158C which enables a
bre application temperature of 2508C.79,82 Recently,
NASA has developed a new technology via a melt
extrusion process to produce these PI bres.83 The bres
have a glass transition temperature of between 2408C
and 2708C. Melt extruding the bres eliminates the need
for volatiles such as acid and harsh solvents, making the
whole process more environmentally friendly than
solution spinning. NASA says that the process is also
inexpensive. Nevertheless, PI bres are only produced
by Inspec Fibres (Austria) under the trademark
P84TM .82 The main applications of these bres are
protective clothing, high temperature ltration and
thermal insulation.
PI bres do not melt but decompose and carbonize at
elevated temperatures.84 TGA reveals that at 3508C, the
weight loss of PI bres is about 5 wt.%, and at 5008C a
value is attained after 70 min.Their continuous operating temperature is reported to be 2808C. PI bres also
exhibits a good LOI of 38 wt.%.17
Poly(ketone). Polyketones represent another interesting
group of polymers which possess useful high temperature properties. The ether link is used to promote an
added exibility to inherently rigid polymer chains
without incurring too radical reduction in thermal/
thermooxidative stability. Poly(ether-ether-ketone)
(PEEK1) was the rst polyketone synthesized in
1979,8486 and other related materials have also been
developed.8788 Nevertheless, only PEEK1 bres can be
found in the market under the trademark PEEK
marketed by Zyex1 (UK) (see Table 2).89 The main
applications are aerospace components and conveyor
systems.
PEEK1 bre has a glass transition temperature of
1438C and a melting point of 3438C. Its continuous
operating temperature is 2508C. It exhibits a LOI of 35
vol.%.17

Kynol1), melamine bres (as Basol1) and polyamideimide bres (as Kermel1) were supplied respectively by
Kynol GmbH (Germany), BASF (Germany) and
Rhodia (France). Recycled oxidized polyacrylonitrile
bres were supplied by Achille Bayard (France). The
yarns used in this study have the following characteristics:
PBO (Zylon):
PPTA (Kevlar):

Nm 2/34 spun yarn (60 tex)

Nm 2/28 spun yarn (72 tex)
Multilament (90 tex)
TECH (Technora):
Nm 2/28 spun yarn (72 tex)
PIPD (M5):
Multilament (92 tex)
Phenolic bre (Kynol):
Nm 2/28 spun yarn (72 tex)
Melamine bre (Basol): Staple (2.2 dtex)
PAI (Kermel):
Staple (2.2 dtex)
Recycled oxidized PAN: Nm 1/14 Spun yarn (72 tex)
Processing
Fibres were knitted on an automatic rectilinear
machine gauge 7. The texture used is a double woven
rib. The fabrics had the surface weight equalling
1.08  0.05 kg/m2.
Cone calorimetry by oxygen consumption
Samples were exposed to a Stanton Redcroft cone
calorimeter at a heat ux equalling 75 kW/m2. This ux
corresponds to ashover conditions. The samples were
mounted between two cut steel sheets placed on the
usual holder of the cone calorimeter (Fig. 6). The
surface exposed to the external heat ux was 9  9 cm2.
Our method does not correspond to any standard.
Conventional cone calorimetry data (rate of heat release
(RHR), volume of smoke production (VSP) (see the
computation90), CO and CO2 evolution, and the re
growth rate index (FIGRA) (see the denition91) were
obtained using a software developed in our laboratory.
The experiments were repeated three times. When
measured at 75 kW/m2 ux, the RHR and VSP values

EXPERIMENTAL
Materials
Poly(p-phenylene-2,6-benzobisoxazole) (PBO) bres
were supplied by Toyobo (Japan) as Zylon1. Poly pphenylenediamine-terephtalamide bers (PPTA) bres
are Kevlar129. Co-poly(p-phenylene-3,4-oxidiphenylene-terephtalamide) bres (TECH) were supplied by
Tejin (Japan) as Technora1. Poly(2,6-diimidazo[4,5b:40 ,50 -e]pyridinylene-1,4(2,5-dihydroxy)phenylene)
(PIPD or M5) bres were supplied as multilament by
Magellan (USA) (hot drawn yarn). Phenolic bres (as
Copyright # 2002 John Wiley & Sons, Ltd.

Figure 6. Home made cone calorimeter holder used in the experiments.

Fire Mater. 2002; 26: 155168

164

S. BOURBIGOT AND X. FLAMBARD

Simultaneous TGA/DSC measurements were performed using a Netzsch STA 449C Jupiter instrument
under air ow (50 ml/min) from 208C to 12008C.
Samples (about 5 mg) were placed in Pt crucibles with
a cap on the top (the cap had a hole in the centre). The
calibration in temperature and in energy was made using
standards: biphenyl, KClO4, K2CrO4, BaCO3 and
benzoic acid.

HEAT AND FLAME RESISTANCE

The overview of the heat and re resistance of the
high performance bres shows that the ame retardancy
of the bre is high according to the LOI test (see Table
2). The LOI test does not provide any data on the ame
behaviour of the bre in a real re scenario but only
indications on the ammability of the bre in particular
conditions. Here, we consider that LOI alone is not
sufcient for quantifying and predicting the ame
behaviour of these bres in a real re. Other parameters
must be considered such as the heat release rate, time to
ignition and heat of combustion. This part evaluates the
reaction to re and the heat resistance of selected high
performance bres: PPTA as reference of the high
performance bres, TECH for its unique mechanical
properties, PBO and PIPD for their unique ame
resistance and, recycled oxidized PAN and Kynol for
their good cost to performance ratio.
Reaction to re

300

300
RHR (kW/m)

Thermal analysis

(TTI of PPTA spun yarn=30 s; TTI of PPTA multilament=25 s) and the RHR peaks (RHR peak of
PPTA spun yarn=255 kW/m2; RHR peak of PPTA
multilament=290 kW/m2) are similar, but the curves
after the RHR peaks are signicantly different. The two
plateaux assigned to the glowing of the samples92 do not
have the same duration (
300 s between 100 and 400 s
for PPTA spun yarn and
600 s between 200 and 800 s
for PPTA multilament).
RHR curves of the knitted high performance fabrics
at 75 kW/m2 show that three categories of bres can be
distinguished (Fig. 8). The p-aramid bres (PPTA and
TECH) have a RHR peak value of about 300 kW/m2
and a time to ignition at 25 s, while the Kynol and
recycled oxidized PAN bres have a lower RHR peak
value of about 150 kW/m2 but a very short time to
ignition at 3 s. Finally, PBO bres exhibit a RHR peak
(at plateau between 100 and 500 s) of only 40 kW/m2
and a very long time to ignition at 100 s. This result
conrms the very high ame resistance of PBO in
comparison with the other bres. Recycled oxidized
PAN and Kynol have moderately high RHR values with
short times to ignition.
FIGRA is a good indicator of the contribution to re
growth of a material and FIGRA curves of the bres
studied are shown in Fig. 9. The FIGRA of PBO is close
to zero which means that PBO does not contribute to
the propagation of re. FIGRA curves of p-aramids
(PPTA and TECH) exhibit only one peak respectively at
40 s (FIGRA=500 W/s) and at 30 s (FIGRA=700 W/s)
and after 100 s, values for the two bres become close to
zero. PPTA and TECH would contribute, therefore, to

RHR (kW/m)

were reproducible to within  10% and CO, CO2 were

reproducible to within  15%. The results presented in
the following section are averages. The cone data
reported in this work are the average of three replicated
experiments.

200

200

100

100

Fibres are evaluated as knitted samples of spun yarn

or multilament yarns. Even if the knitted structure is
the same, these two kinds of samples may not be
compared because it leads to different results. Figure 7
shows the comparison of the RHR curves of the two
PPTA fabrics. It is observed that the times to ignition

50

25

75
Time (s)

100

125

0
0

100

200

300
Time (s)

PPTA

TECH

Oxidised recycled PAN

Kynol

400

500

600

PBO

Figure 8. RHR curves (external heat flux=75 kW/m2) of selected

knitted high performance fibres in spun yarn.

300

250

150

Spun yarn

100

Multifilament yarn

FIGRA (W/s)

RHR (kW/m)

2000

200
1500

1000

500

50

0
0

25

50
Time (s)

75

100

0
0

200

400

600

800

1000

Time (s)

Figure 7. Comparison of knitted fabrics of PPTA in spun yarn and multifilament yarn.

Copyright # 2002 John Wiley & Sons, Ltd.

PPTA

TECH

Oxidised recycled PAN

Kynol

PBO

Figure 9. FIGRA curves (external heat flux=75 kW/m2) of selected

knitted high performance fibres in spun yarn.

Fire Mater. 2002; 26: 155168

165

HEAT AND FLAME RESISTANCE OF HIGH PERFORMANCE FIBRES

Figure 12. Evolution of CO2 (external heat flux=75 kW/m2) of selected

knitted high performance fibres in spun yarn.

300
250
M5 multi
RHR (kW/m)

re spread during their combustion. Kynol has the same

FIGRA peak as PPTA but it occurs at shorter times
(20 s). The FIGRA peak of recycled oxidized PAN is
high (2000 W/s) and occurs during the ignition. For this
last bre, it means that its contribution to the rate of re
could be high because it ignites so easily. One reason for
this is the presence of yarn defects which create brils at
the surface of the fabric which ignite easily.
Smoke obscuration is very close to zero in the cases of
PBO, Kynol and recycled PAN but it is signicant from
PPTA and TECH bres (Fig. 10). PPTA and TECH
bres respectively evolve smoke with peaks at 0.007 m3/s
(35 s) and at 0.009 m3/s (30 s). PBO, Kynol and recycled
PAN do not contribute to the smoke obscuration during
re whereas the smoke production of burning p-aramids
is comparatively higher. This illustrates the potentially
lower smoke hazard presented by this former group in
real res.93
Figs. 11 and 12 show the evolution of carbon oxides
and the amounts evolved by PPTA (CO peaks) are
always higher than for the other bres. It suggests that
incomplete combustion reactions are favoured for
PPTA (Fig. 11). The evolution of carbon dioxide leads
to the same conclusions made above with regard to
respective RHR curves (Figure 12).
Finally, RHR curves of knitted PPTA and PIPD
bres in multilament yarns at external heat ux of
75 kW/m2 are presented in Fig. 13. They show that
PIPD bres should present a superior behaviour in
comparison with PPTA. RHR peak of PIPD is only
50 kW/m2 in comparison with 300 kW/m2 for PPTA

200
PPTA multi
150
100
50
0
0

200

400

600

800

1000

Time (s)

Figure 13. RHR curves (external heat flux=75 kW/m2) of PIPD (M5)
and PPTA fabrics in multifilament yarn.

bres demonstrating that PIPD has a very high re

resistance and is at least as outstanding as PBO bres.
0.01

Heat resistance

VSP (m3/s)

0.008
0.006
0.004
0.002
0
0

25

50
Time (s)

PPTA

TECH

Oxidised recycled PAN

Kynol

75

100
PBO

Figure 10. VSP curves (external heat flux=75 kW/m2) of selected

knitted high performance fibres in spun yarn.

Figure 11. Evolution of CO (external heat flux=75 kW/m2) of selected

knitted high performance fibres in spun yarn.

Copyright # 2002 John Wiley & Sons, Ltd.

TG curves (Fig. 14) show that PBO bres have a

much better heat resistance than the other bres. PBO
bres degrade in a one step apparent process at about
6008C to give 2 wt.% residue at 8008C. PPTA degrades
via two apparent steps. The rst one starts at 2008C and
the second one (the main stage) starts at 5008C. TECH
and Kermel decomposes via only one apparent step
which starts at about the same temperature as the
second step of PPTA (about 5008C). Kynol exhibits the
same behaviour as TECH and Kermel but its decomposition temperature is lower than these latter bres
(
3508C). Two degradation steps are observed for
Basol. The rst one is abrupt and occurs at 3808C, and
the second one occurs at 5508C after slowly decreasing
between 3808 and 5508C. Recycled oxidised PAN
degrades slowly from 3008 to 7008C. All bres have a
2 wt.% residue at 8008C.
Under nitrogen ow (inert atmosphere), the degradation of the high performance bres begins at higher
temperatures than under air (
3508C for recycled
oxidized PAN,
4008C for Basol,
4508C for Kynol,

5008C for TECH and Kermel,
5508C for PPTA and

7008C for PBO). High amounts of residue are formed
which are stable up to 15008C (55 wt.% for Kynol, 50
wt.% for recycled oxidised PAN, 44 wt.% for Kermel,
38 wt.% for PPTA, 37 wt.% for TECH, 12 wt.% for
Basol and 65 wt.% for PBO). It is to be noted that
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166

S. BOURBIGOT AND X. FLAMBARD

Remaining mass (wt.-%)

100
80
60
40
20
0
200

400

800

600
Temperature (C)

PPTA

TECH

PBO

Oxidised recycled PAN

Kermel

Kynol

Basofil

Figure 14. TG curves of selected high performance fibres under air

(heating rate=108C/min).

Basol has a comparatively low thermal stability under

an inert atmosphere in comparison with the other high
performance bres and this shows the strong inuence
of oxygen present in the bre structure itself on the
thermal degradation of the bres. This last consideration is important when recalling that polymeric substrates heated by an external source are pyrolysed with
the generation of combustible fuels in a zone where there
is depletion of oxygen.94
Using simultaneous TGA/DSC, the values of the
enthalpies of decomposition can be estimated by
integrating DSC curves in the temperature range
of decomposition of the bres (Table 3). The
thermo-oxidative decompositions of the bres are
exothermic and can be assigned to oxidation reactions. The enthalpies of decomposition of all
bres are of the same order of magnitude. It should be
noted that these values are in the same order of
magnitude as the heat of combustion of common
organic polymers.99 In particular, the heats of combustion of PPTA, TECH and PBO are measured to be
26 kJ/g, 28.5 kJ/g and 28 kJ/g, respectively95 and are
close to those measured in Table 3 by simultaneous
TGA/DSC.

DISCUSSION
The high performance bres examined show that all
exhibit high ame retardancy (high LOI, low RHR and
low smoke) and good heat resistance (temperature of
degradation higher than 3508C) in comparison with

Table 3. Enthalpy of decomposition in air of Kermel, recycled

oxidized PAN, PPTA, TECH and PBO bres
Fibre

Enthalpy of
decomposition (J/g)

Temperature range of
computation (8C)

PPTA
TECH
Kermel
Oxidized recycled PAN
PBO

22200
25000
21000
19500
21000

400650
400700
300700
250700
450800

Copyright # 2002 John Wiley & Sons, Ltd.

natural bres (e.g. cotton, wool) or with other common

synthetic bres (e.g. nylons, polyester, acrylic). Three
categories of bres can be distinguished, rated according
to their performance. The rst group is PBO and PIPD.
These bres have a very low RHR and in the conditions
of post-ashover (external heat ux >50 kW/m2) would
not to be expected to spread re (from their low FIGRA
values); also they have high LOI values (>50 vol.%),
and they do not evolve smoke (
0.000 m3/s). Kynol
and recycled oxidized PAN bres are in the second
group because they have a moderate RHR (5150 kW/
m2). Recycled oxidized PAN bres exhibit a comparatively high FIGRA value because of surface bres
present which should be corrected using an optimized
yarn process production, while the value for Kynol
is low ; both have good LOI values (>30 vol.%),
and they evolve little smoke (50.002 m3/s). The third
group is the p-aramid bres which have comparatively high RHR values (
300 kW/m2), they contribute
to the re growth (moderate FIGRA values) and they
evolve smoke but maintain high LOI (>27 vol.%)
values. This work shows that the high performance
bres can be ranked according to realistic quantitative
parameters of re, and so provides useful specications
for using bres in special congurations. Table 4
provides a brief overview of the performance of the
bres in comparison with PPTA (PPTA is taken as
standard because it is the widely used high performance
bre). The bres studied may be ranked in three groups
as follows:
1. Minimal or no contribution to re and no smoke :
PBO and PIPD,
2. Low contribution to re and low smoke : Kynol and
recycled oxidized PAN,
3. Signicant contribution to re and smoke : PPTA
and TECH.
According to the above ratings, the heterocyclic
rigid-rod polymers (PBO and PIPD) exhibit the best
performance. Both polymers have highly conjugated
structures which are heteroaromatic. Moreover, they
do not have exible groups mid-chain which would
otherwise lead to the reduction of their thermal
stability. These factors provide high levels of stability
to the polymer, and promote high ame resistance. In
contrast to PBO and PIPD, p-aramid bres have
phenylene groups linked by amide bridges. These
bridges (-CONH-) lead to a reduction in thermal
stability of the bres which, consequently, yield ammable molecules upon heating. Finally, Kynol and
recycled oxidized PAN bres are cross-linked networks
with methylene (Kynol) or ether (recycled oxidized
PAN) bridges. These exible groups lead to the
reduction in thermal stability as for the p-aramids,
but the stabilizing character of the cross-linked
network may enhance char yield (see Fig. 15). It
follows hat the better re performance of Kynol
and recycled oxidized PAN bres in comparison
with p-aramids may be assigned to the formation of
higher yields of char. These enhanced chars can act
as insulative shields when burning, and can protect
underlying substrates.
Fire Mater. 2002; 26: 155168

167

HEAT AND FLAME RESISTANCE OF HIGH PERFORMANCE FIBRES

Table 4. Performance of selected high performance bres compared with PPTA

PPTA

C
O
N
E
!

TGA
LOI
RHR
FIGRA
VSP
CO
same performance, % %

PBO

PIPD

Kynol

!
%%
}
!
%%
%%
!
%%
%%
!
%%
}
!
%%
}
!
%
}
much better, % better, & worse, & & much

Recycled oxidized PAN

&&
&
!
}
%
%
&
&&
%%
%%
%
%
worse, - not determined.

TECH

%
!
!
&
&
%

Figure 15. TG curves of selected high performance fibres under nitrogen (heating rate=108C/min).

This work has presented the heat and ame resistance

of high performance bres presently available on the
market. Literature and original data have been reported
and the main conclusion is that heteroaromatic polymeric bres are the most outstanding halogen-free
bres. In particular, PBO and PIPD exhibit unique
ame retardancy and these two bres present signicant
advances in high performance bre technology because
they offer the right combination of unique heat and
ame resistance with exceptional mechanical properties.
It is predicted that future technological development will
focus on the emergence and exploitation of heterocyclic
polymer bres. It is also anticipated that the market will
provide these bres at an acceptable cost to performance
ratio.

CONCLUSION

Acknowledgements

It can be seen that the newer organic bres offer very

signicant competition in terms of ame resistance and
of other properties (included mechanical, electrical and
chemical properties). Future expansion of their use
depends partly on the exploitation of these properties in
specic end-uses and partly on establishing very costeffective processing routes. The promise of signicant
further improvements in properties and/or the possibility of cost reduction with processing, synthesis and cost
of monomers continues to excite research in this area.

This work was partially supported by the European project

FLAMERET (New Surface Modied Flame Retarded Polymeric
Systems to Improve Safety in Transportation and Other Areas
registered under the number No. G5RD-CT-1999-00120). The
authors thank Professor Sikkema from Magellan International
System for helpful discussion on PIPD (M5) bre and for supplying
M5 bres. Mr Franck Poutch from CREPIM is grateful acknowledged
for helpful discussion on the cone calorimeter. The authors are
indebted to Mr Dubusse from CREPIM for his skilful experimental
assistance in cone calorimeter, and to Mrs Sabine Chlebicki from
GEMTEX for her skilful experimental assistance in TGA/DSC
experiments.

Remaining mass (wt.-%)

100
80
60
40
20
0
100

300

500

700
900
Temperature (C)

1100

1300

PPTA

TECH

PBO

Kynol

Recycled oxidised PAN

Basofil

1500

Kermel

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