FIRE AND MATERIALS
Fire Mater. 2002; 26: 155–168 (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: [email protected]
The heat and flame resistance of high performance fibres are reviewed according to the literature data. The
performance is discussed considering the physical and chemical structure of the fibres. Some selected high
performance fibres are then evaluated using the cone calorimeter as a fire model to provide realistic data on the fire
behaviour of the fibres. 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 fire, low smoke and good heat resistance) and
offer a good combination between heat and flame resistance and mechanical properties. Copyright # 2002 John
Wiley & Sons, Ltd.
INTRODUCTION
The demands of the market for high performance fibres
are for ‘faster, stronger, lighter, safer’ textiles. Fortunately, high performance and high temperature resistant
fibres have been developed to aid in allowing products
to meet these challenges. High-performance fibres are
driven by special technical functions that require
specific physical properties unique to these fibres.
They usually have very high levels of at least one of
the following properties: tensile strength, operating
temperature, heat resistance, flame retardancy and
chemical resistance.1 Each of these fibres has a
unique combination of properties which allows it
to fill a niche in the upper end of the high-performance fibre spectrum. Whereas commodity fibres 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 flame is one of the main properties
of interest for determining the working conditions of
the fibres.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 fibres that played a significant part in the
manufacture of technical usage in 1990, i.e. the
polyolefins, polyamide, polyester and glass fibres, the
most significant growth in 2000 was enjoyed by the
polyolefins and glass fibres. The aramid and carbon
fibres 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
fibre consumption by the whole textile industry,
illustrates the importance of technical fibres (Fig. 1).
This shows that the strong growth in the technical textile
usage sector rose from 22% to 36% of fibre usage. All
other sectors declined in a more or less significant 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 field 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 fibres and all textile
technologies can be employed to satisfy the current
market needs. However, during the past few years, the
position of chemical fibres has been dominant with the
emergence of very high performances fibres such as
Zylon1, PIPD or M5 and PEEK1 (see below) starting
to contribute significantly.
In this paper, high performance fibres are reviewed
first, in terms of heat resistance and flammability. In the
literature the most common parameter used to measure
the flammability of fibres is the limiting oxygen index.
((LOI) and is a relative indication of flammability. 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 fibres 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 fibres. For this discussion, these
latter are classified as a synthetic fibres with a
continuous operating temperature ranging from 1808C
to 3008C (or higher) and a degradation temperature
higher than 3508C. The flame retardant ability of the
fibres is only defined by the LOI test.
The principal classes of high performance fibres
considered here according to our definitions are derived
from rigid-rod polymers (lyotropic liquid crystalline
polymers and heterocyclic rigid-rod polymers), modified
carbon fibres, synthetic vitreous fibres, phenolic fibres,
poly(phenylene sulphide) fibres and others. This part
focuses only on the specific thermal and fire performances of the fibres. Other properties are extensively
discussed in Hearle’s book.10
Table 2 presents a collation of all fibre chemical
structures, properties and applications for all fibres
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 definite time or until a
specified amount of specimen is consumed5). Generally,
fibres with a LOI greater than 25 vol.% are said to be
flame retardant. Nevertheless, the LOI test although not
very representative of a fire, allows us to rate the
materials quantitatively. The approach that we have
developed is to evaluate fibres using the cone calorimeter
as a fire 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 fire 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 fire of some high performance fibres are evaluated
using the cone calorimeter and their heat resistance is
studied by thermal analysis. Indeed, the fire 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 flame retardant ability, it can be
expected that a fibre with a high degradation temperature will have good flame retardancy.
REVIEW OF
BEHAVIOUR
HIGH
PERFORMANCE
FIBRE
Before exploring the details of the high performance
fibres, it is important to define the parameters of high
Copyright # 2002 John Wiley & Sons, Ltd.
Meta-aramid. Poly(m-phenylene isophtalamide) was
the first aramid fibre launched on the market (see Table
2).11–13 This meta-aramid fibre was commercialized by
DuPont under the trademark Nomex1 in 1967.14 Teijin
also introduced a similar fibre (trademark Conex1) in
the early 1970s.15
Kermel1, commercialized by Rhodia, is a polyamideimide fibre which is also classified in the meta-aramid
family (see Table 2).16 The fibre has a thermal
conductivity twice as low as any other aramid fibre.16,17
The principal market niche for meta-aramids is that
of heat-resistant materials.14,18 They are naturally nonflammable 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 flame resistance.
Nomex fibre retains useful properties at temperatures as
high as 3708C. It has low flammability and has been
found to be self-extinguishing when removed from the
flame. On exposure to a flame, 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
fibres.15,19,20 The greatly increased order and the long
relaxation times in the liquid crystalline state compared
with conventional systems led to fibres with highly
oriented domains of polymer molecules. The most
common lyotropic aramid fibres 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: 155–168
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
H
N
N
N
O
N H
N
H N
N
H N
N
N H
N
N H
N
O
OH
*
H N
F
n
N H
N
HO
F
C C
F
H N
*
*
*
F
Chemical structure
Table 2. Description and properties of high temperature resistant fibres
N
N
H
N
O
n
*
n
*
> 50
56–68
EDF (Dow)
45–55
Pyromex1
45–60
(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: 155–168
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
O
O
OH
N
CH2
n
*
OH
O
C
H2
OH
C
N
OH
CH2
OH
O
O
C
H2
OH
CH2 OH
CH 2OH
C
H2
O
H
H
S
N
N
N
OH
CH2
OH
C
H2
OH
CH2 OH
O
N
N
N
N
N
N C N
H2
N
N
N
N
N
Three-dimensional melamine-based network
*
*
*
*
N
C
H2
OH
H2 C
O
n
n
n
*
*
*
41
Basofil1
(BASF)
Kynol1
(Nippon
Kynol Inc)
PEEK1
(Zyex)
P84TM
(Inspec
Fibres)
30–32
30–34
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: 155–168
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
O
O
H O
N C
H
C
N C
C
N
N C
N
O
H O
H
H
C
H
N
N
O
O
n
n*
*
O
H
N C
CH2
C
O
C
O
*
C n*
O
n
Technora1
(Teijin)
Kermel1
(Rhodia)
Nomex1
(DuPont)
Conex1
(Teijin)
Kevlar1
(DuPont)
Twaron
(Teijin)
25
30–32
30–32
28–30
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: 155–168
160
S. BOURBIGOT AND X. FLAMBARD
N
S
S
N
*
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 flame. 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 fibre into the high performance fibre market. Technora1 is based on the 1:1
copolyterephtalamide of 3,40 -diaminodiphenyl ether and
p-phenylenediamine (see Table 2).15,21
The fine 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)22–25 and poly(p-phenylene-2,6-benzobisoxazole)
(PBO) (see Table 2).26–29
PBZT and PBO were initially prepared at the Air
Force Materials Laboratory in the US Air Force
Ordered Polymer Program.30,31 Only PBO fibre 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 fibre spinning
technology. The rigid-rod like nature of PBO polymer
chain makes the processing of polymer difficult, whereas
excellent physical properties of the fibre originate from
the rigid conformation. The development of production
technology on fibre 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 fibre. 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 fibres 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 flame resistance and is selfextinguishing when removed from the flame. On
exposure to a flame, formation of char is observed at
the surface which may act as a protective shield. The
LOI of PBO is much higher than aramid fibres, 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).39–42 PBI
fibre is marketed by Celanese (USA) and the main
current textile applications of PBI are protective
clothing, fire 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 flame. On exposure to
flame or high heat flux, it forms a tough char in high
yield (to 80 wt.%).42 After the char is formed, the
charred fabric retains its integrity and flexibility with
little shrinkage. Its LOI is greater than 41 vol.%.43 PBI
fibre 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: 155–168
161
HEAT AND FLAME RESISTANCE OF HIGH PERFORMANCE FIBRES
referenced to as M5) (see Table 2).45–51 It has the ability
to form hydrogen bonds between adjacent chains. PIPD
was first developed by Akzo Nobel Central Research,
and now it is being developed by Magellan Systems
International. Potential applications using M5 fibre are
envisioned in five major areas: personnel protection, fire
resistance, advanced composite materials and tethering/
advanced fabrics.52
PIPD has extremely high fire resistance properties like
the other rigid-rod polymeric fibres.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 flux 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 flame retardant. PIPD fibre varieties formed a char
layer only at the surface of the fibre, while protecting the
rest of the fibre. It is believed that the superior
performance of PIPD fibres may be partly due to the
fact that the crystal structure of PIPD contains about
21% water.
Carbon precursor and elongatable carbonaceous fibres
Carbon precursor. Carbon precursor fibres are partially
carbonized fibres which transform into carbon or
graphite fibre when they undergo further carbonization
in an inert atmosphere at high temperature.53,54 They
are produced by thermal stabilization of acrylic fibre at
2008–3008C 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
fibre.55,56 The stabilized fibre is called oxidized PAN
fibre (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 fire blockers.
Due to the unique structure of OPF, the fibres have
non-flammable and non-melting characteristics. The
LOI lies between 45 and 60 vol.%. They do not melt
or adhere under direct exposure to intensive flame. The
decomposition temperature of OPF is higher than 3008C
and the products of degradation are hydrogen cyanide,
ammonia, carbon oxides and water.
Elongatable carbonaceous fibre. The extreme brittleness,
high modulus and low elongation of standard carbon
fibres restricts them to being woven only on specially
adapted weaving machines. To overcome these drawbacks, a modification of carbon fibre technology was
developed using less stringent carbonizing conditions
and only partially carbonizing the precursor fibres, and
improved textile fibre properties have been achieved
(Fig. 4).60
Copyright # 2002 John Wiley & Sons, Ltd.
N
O
N H
H N
H N
N H
N
450 - 750°C
N
H N
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 4508–7508C, preferably 5258–
5958C, to give fibres having 69–70% C, 19% N, and a
density less than 2.5 g/ml. This fibre is marketed by Dow
(USA).
Elongatable Dow Fibre (EDF) exhibits very good
ignition-resistance, flame retardancy and fire blocking
properties. Its LOI lies between 45 and 55 vol.%.
Previous results with ignition resistant blends, where
such fibres as aramids or PBI are used as the high LOI
fibres, show that they need at least 65%, and typically
85%, fibre content to pass the vertical burn test for
lightweight nonwoven batting. In contrast only 7–20%
of either EDF mixed with flammable natural and
synthetic fibres allow the blends to pass such tests while
still retaining most of the base natural or synthetic fibre
properties. Blends of 50/50 EDF/polyester also passed
the FAA airlines ignition resistance tests with zero flame
length and no after-burn.
Carbon fibre. Though a large number of polymeric
precursors have been tried for modern carbon fibres, 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 fibres 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 fibres under the trademark Besfight157 or
Toray (Japan) under the trademark Torayca1.61
Carbon fibres are extremely resistant to high temperatures: their melting temperature is 40008C. They can
also be considered as flame 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 filtration of molten
iron.
Vitreous fibre
Man-made vitreous fibres comprise a number of glass
and speciality glass fibres and also, refractory ceramic
fibres. All these fibres are flame retardant since they do
not burn even at very high temperatures.62
Glass fibre. A wide range of glass compositions is
available to suit many textile fibres.62,63 Glass fibres
made from various compositions have softening points
in the range 650–9708C. At temperatures above 8508C,
these fibres partially devitrify and form polycrystalline
Fire Mater. 2002; 26: 155–168
162
S. BOURBIGOT AND X. FLAMBARD
material that melts at 1225–13608C, which is high
enough to contain the fires for several hours.
Ceramic fibres. Ceramic fibres are mostly used as
refractory fibres in uses over 10008C and are characterized by a polycrystalline, rather than amorphous,
structure. These fibres 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 fibres
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 fibre the new generic name of Sulfar (see Table 2).64–68
PPS fibres 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 fibres are heat and chemical
resistant filters, papermaking felts, insulators, reinforcing materials and protective clothing. They exhibit
good flame retardancy (LOI is about 40 vol.%) and its
operating temperature is up to 2608C.17,18,69
Miscellaneous fibres
There are a number of fibres which are used in nonconventional textile applications and cannot be classified in the sections considered above.
Phenolic. Phenolic (or also referenced as novoloid)
fibres are cured phenol-aldehyde fibres 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 fibres contain approximately
76% carbon, 18% oxygen, and 6% hydrogen. The only
commercially available phenolic fibres are the so-called
Kynol1 fibres marketed by Nippon Kynol Inc (Japan).
They are used in a wide variety of flame- and chemicalresistant textiles and papers, in composites, gaskets and
friction materials, and as precursors for carbon and
activated-carbon fibres textiles, and composites.72
Thermogravimetric analysis (TGA) indicates that
upon heating above 2508C in the absence of oxygen,
Kynol1 fibres undergo gradual weight loss until, at
about 7008C, they are completely carbonized, with a
carbon yield of about 558–60%. 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 fibres is reported in the
range 30–34 vol.%.72 When exposed to flame Kynol1
fibres do not melt but gradually char until completely
carbonized, without losing their original fibre 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 fibres the
same characteristics of other melamine based products:
heat stability, solvent resistance, and flame resistance
(see Table 2).70,73 Melamine fibre is marketed by BASF
(Germany) under the trademark Basofil1. Since melamine fibres are heat and flame resistant, they typically
target hot gas filtration and safety and protective
apparel markets.74 Because of its variable denier and
staple length, low tensile strength and difficulty in
processing, melamine fibres are generally blended with
stronger fibres 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 fibres, such as
para-aramids, suitable for weaving into firemen’s turnout gear.
TGA of melamine fibres reveals that the main
degradation temperature of the fibres 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 Basofil fibre offers good
heat and flame protection in comparison with some
other high performance fibres 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 fibres are based on poly
(tetrafluorethylene) (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: 155–168
163
HEAT AND FLAME RESISTANCE OF HIGH PERFORMANCE FIBRES
fluorine bonds are extremely strong, and provide the
polymer with a very high thermal and flame resistance
(LOI = 95 vol.%).77 PTFE fibres are marketed by
DuPont (USA) under the trademark Teflon1.76
Polyimide. Polyimide (PI) fibres are manufactured by
polycondensation of an anhydride with aromatic
diisocyanates in high polar solvents such as dimethylformamide or dimethylacetamide (see Table 2).78–81 The
thermal properties of PI fibres are characterized by the
glass transition temperature of 3158C which enables a
fibre application temperature of 2508C.79,82 Recently,
NASA has developed a new technology via a melt
extrusion process to produce these PI fibres.83 The fibres
have a glass transition temperature of between 2408C
and 2708C. Melt extruding the fibres 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 fibres are only produced
by Inspec Fibres (Austria) under the trademark
P84TM .82 The main applications of these fibres are
protective clothing, high temperature filtration and
thermal insulation.
PI fibres do not melt but decompose and carbonize at
elevated temperatures.84 TGA reveals that at 3508C, the
weight loss of PI fibres is about 5 wt.%, and at 5008C a
value is attained after 70 min.Their continuous operating temperature is reported to be 2808C. PI fibres 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 flexibility to inherently rigid polymer chains
without incurring too radical reduction in thermal/
thermooxidative stability. Poly(ether-ether-ketone)
(PEEK1) was the first polyketone synthesized in
1979,84–86 and other related materials have also been
developed.87–88 Nevertheless, only PEEK1 fibres 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 fibre 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 fibres (as Basofil1) and polyamideimide fibres (as Kermel1) were supplied respectively by
Kynol GmbH (Germany), BASF (Germany) and
Rhodia (France). Recycled oxidized polyacrylonitrile
fibres 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)
Multifilament (90 tex)
TECH (Technora):
Nm 2/28 spun yarn (72 tex)
PIPD (M5):
Multifilament (92 tex)
Phenolic fibre (Kynol):
Nm 2/28 spun yarn (72 tex)
Melamine fibre (Basofil): 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 flux equalling 75 kW/m2. This flux
corresponds to flashover 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 flux 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 fire
growth rate index (FIGRA) (see the definition91) were
obtained using a software developed in our laboratory.
The experiments were repeated three times. When
measured at 75 kW/m2 flux, the RHR and VSP values
EXPERIMENTAL
Materials
Poly(p-phenylene-2,6-benzobisoxazole) (PBO) fibres
were supplied by Toyobo (Japan) as Zylon1. Poly pphenylenediamine-terephtalamide fibers (PPTA) fibres
are Kevlar129. Co-poly(p-phenylene-3,4-oxidiphenylene-terephtalamide) fibres (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) fibres were supplied as multifilament by
Magellan (USA) (hot drawn yarn). Phenolic fibres (as
Copyright # 2002 John Wiley & Sons, Ltd.
Figure 6. Home made cone calorimeter holder used in the experiments.
Fire Mater. 2002; 26: 155–168
164
S. BOURBIGOT AND X. FLAMBARD
Simultaneous TGA/DSC measurements were performed using a Netzsch STA 449C Jupiter instrument
under air flow (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 fire resistance of the
high performance fibres shows that the flame retardancy
of the fibre is high according to the LOI test (see Table
2). The LOI test does not provide any data on the flame
behaviour of the fibre in a real fire scenario but only
indications on the flammability of the fibre in particular
conditions. Here, we consider that LOI alone is not
sufficient for quantifying and predicting the flame
behaviour of these fibres in a real fire. Other parameters
must be considered such as the heat release rate, time to
ignition and heat of combustion. This part evaluates the
reaction to fire and the heat resistance of selected high
performance fibres: PPTA as reference of the high
performance fibres, TECH for its unique mechanical
properties, PBO and PIPD for their unique flame
resistance and, recycled oxidized PAN and Kynol for
their good cost to performance ratio.
Reaction to fire
300
300
RHR (kW/m²)
Thermal analysis
(TTI of PPTA spun yarn=30 s; TTI of PPTA multifilament=25 s) and the RHR peaks (RHR peak of
PPTA spun yarn=255 kW/m2; RHR peak of PPTA
multifilament=290 kW/m2) are similar, but the curves
after the RHR peaks are significantly 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 multifilament).
RHR curves of the knitted high performance fabrics
at 75 kW/m2 show that three categories of fibres can be
distinguished (Fig. 8). The p-aramid fibres (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 fibres have a lower RHR peak
value of about 150 kW/m2 but a very short time to
ignition at 3 s. Finally, PBO fibres exhibit a RHR peak
(flat plateau between 100 and 500 s) of only 40 kW/m2
and a very long time to ignition at 100 s. This result
confirms the very high flame resistance of PBO in
comparison with the other fibres. Recycled oxidized
PAN and Kynol have moderately high RHR values with
short times to ignition.
FIGRA is a good indicator of the contribution to fire
growth of a material and FIGRA curves of the fibres
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 fire. 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 fibres become close to
zero. PPTA and TECH would contribute, therefore, to
RHR (kW/m²)
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
0
100
Fibres are evaluated as knitted samples of spun yarn
or multifilament 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
0
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/m²)
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: 155–168
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/m²)
fire 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 fibre, it means that its contribution to the rate of fire
could be high because it ignites so easily. One reason for
this is the presence of yarn defects which create fibrils 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 significant from
PPTA and TECH fibres (Fig. 10). PPTA and TECH
fibres 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
fire 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 fires.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 fibres. 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
fibres in multifilament yarns at external heat flux of
75 kW/m2 are presented in Fig. 13. They show that
PIPD fibres 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.
fibres demonstrating that PIPD has a very high fire
resistance and is at least as outstanding as PBO fibres.
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 fibres have a
much better heat resistance than the other fibres. PBO
fibres degrade in a one step apparent process at about
6008C to give 2 wt.% residue at 8008C. PPTA degrades
via two apparent steps. The first 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 fibres
(3508C). Two degradation steps are observed for
Basofil. The first 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 fibres have a
2 wt.% residue at 8008C.
Under nitrogen flow (inert atmosphere), the degradation of the high performance fibres begins at higher
temperatures than under air (3508C for recycled
oxidized PAN, 4008C for Basofil, 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
Basofil and 65 wt.% for PBO). It is to be noted that
Fire Mater. 2002; 26: 155–168
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).
Basofil has a comparatively low thermal stability under
an inert atmosphere in comparison with the other high
performance fibres and this shows the strong influence
of oxygen present in the fibre structure itself on the
thermal degradation of the fibres. 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 fibres (Table 3). The
thermo-oxidative decompositions of the fibres are
exothermic and can be assigned to oxidation reactions. The enthalpies of decomposition of all
fibres 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 fibres examined show that all
exhibit high flame 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 fibres
Fibre
Enthalpy of
decomposition (J/g)
Temperature range of
computation (8C)
PPTA
TECH
Kermel
Oxidized recycled PAN
PBO
22200
25000
21000
19500
21000
400–650
400–700
300–700
250–700
450–800
Copyright # 2002 John Wiley & Sons, Ltd.
natural fibres (e.g. cotton, wool) or with other common
synthetic fibres (e.g. nylons, polyester, acrylic). Three
categories of fibres can be distinguished, rated according
to their performance. The first group is PBO and PIPD.
These fibres have a very low RHR and in the conditions
of post-flashover (external heat flux >50 kW/m2) would
not to be expected to spread fire (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 fibres are in the second
group because they have a moderate RHR (5150 kW/
m2). Recycled oxidized PAN fibres exhibit a comparatively high FIGRA value because of surface fibres
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 fibres which have comparatively high RHR values (300 kW/m2), they contribute
to the fire growth (moderate FIGRA values) and they
evolve smoke but maintain high LOI (>27 vol.%)
values. This work shows that the high performance
fibres can be ranked according to realistic quantitative
parameters of fire, and so provides useful specifications
for using fibres in special configurations. Table 4
provides a brief overview of the performance of the
fibres in comparison with PPTA (PPTA is taken as
standard because it is the widely used high performance
fibre). The fibres studied may be ranked in three groups
as follows:
1. Minimal or no contribution to fire and no smoke :
PBO and PIPD,
2. Low contribution to fire and low smoke : Kynol and
recycled oxidized PAN,
3. Significant contribution to fire 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 flexible 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 flame resistance. In
contrast to PBO and PIPD, p-aramid fibres have
phenylene groups linked by amide bridges. These
bridges (-CONH-) lead to a reduction in thermal
stability of the fibres which, consequently, yield flammable molecules upon heating. Finally, Kynol and
recycled oxidized PAN fibres are cross-linked networks
with methylene (Kynol) or ether (recycled oxidized
PAN) bridges. These flexible 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 fire performance of Kynol
and recycled oxidized PAN fibres 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: 155–168
167
HEAT AND FLAME RESISTANCE OF HIGH PERFORMANCE FIBRES
Table 4. Performance of selected high performance fibres 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 flame resistance
of high performance fibres presently available on the
market. Literature and original data have been reported
and the main conclusion is that heteroaromatic polymeric fibres are the most outstanding halogen-free
fibres. In particular, PBO and PIPD exhibit unique
flame retardancy and these two fibres present significant
advances in high performance fibre technology because
they offer the right combination of unique heat and
flame resistance with exceptional mechanical properties.
It is predicted that future technological development will
focus on the emergence and exploitation of heterocyclic
polymer fibres. It is also anticipated that the market will
provide these fibres at an acceptable cost to performance
ratio.
CONCLUSION
Acknowledgements
It can be seen that the newer organic fibres offer very
significant competition in terms of flame 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
specific end-uses and partly on establishing very costeffective processing routes. The promise of significant
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 Modified 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) fibre and for supplying
M5 fibres. 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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