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-2,6-
benzobisoxazole 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 Of the fibres that played a significant part in the

manufacture of technical usage in 1990, i.e. the
The demands of the market for high performance fibres polyolefins, polyamide, polyester and glass fibres, the
are for ‘faster, stronger, lighter, safer’ textiles. Fortu- most significant growth in 2000 was enjoyed by the
nately, high performance and high temperature resistant polyolefins and glass fibres. The aramid and carbon
fibres have been developed to aid in allowing products fibres also experienced high growth rates, but still
to meet these challenges. High-performance fibres are remain marginal in tonnage terms (Table 1).4
driven by special technical functions that require The European situation, in 1990 and 2000 in terms of
specific physical properties unique to these fibres. fibre consumption by the whole textile industry,
They usually have very high levels of at least one of illustrates the importance of technical fibres (Fig. 1).
the following properties: tensile strength, operating This shows that the strong growth in the technical textile
temperature, heat resistance, flame retardancy and usage sector rose from 22% to 36% of fibre usage. All
chemical resistance.1 Each of these fibres has a other sectors declined in a more or less significant way,
unique combination of properties which allows it especially the clothing sector which lost practically ten
to fill a niche in the upper end of the high-perform- points. Technical textiles are gaining on clothing in
ance fibre spectrum. Whereas commodity fibres are terms of importance within the sector, with 36% against
routinely produced in the hundreds of millions of 37.5% market shares respectively in 2000.
kilogrammes, or even in the billions, most high- Finally the field covered by technical textiles is
performance materials are produced in the low characterized by its complexity, the variety of the
millions of kilogrammes, often in the hundreds of sectors in which they are used and of the materials
thousands. Applications include uses in the aerospace, employed. All natural or chemical fibres and all textile
biomedical, civil engineering, construction, protective technologies can be employed to satisfy the current
apparel, geotextiles and electronic areas. The resistance market needs. However, during the past few years, the
to heat and flame is one of the main properties position of chemical fibres has been dominant with the
of interest for determining the working conditions of emergence of very high performances fibres such as
the fibres.2 Zylon1, PIPD or M5 and PEEK1 (see below) starting
Technical textiles are now a global industry, and to contribute significantly.
no longer the preserve of a few industrialized countries. In this paper, high performance fibres are reviewed
All regions and all industries in the world make first, in terms of heat resistance and flammability. In the
use of technical textiles, even if there is no local literature the most common parameter used to measure
manufacturing. Europe and North America remain a the flammability of fibres is the limiting oxygen index.
major supplier of these textiles, and consume two thirds ((LOI) and is a relative indication of flammability. It is
of the total.3 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

Received 29 May 2002

Copyright # 2002 John Wiley & Sons, Ltd. Accepted 26 July 2002
156 S. BOURBIGOT AND X. FLAMBARD

temperature resistant fibres. For this discussion, these

Table 1. Types and quantities of technical fibres used in Europe latter are classified as a synthetic fibres with a
X 1000 tonnes 1990 2000 Change
continuous operating temperature ranging from 1808C
to 3008C (or higher) and a degradation temperature
Polypropylene 325 1145 +252% higher than 3508C. The flame retardant ability of the
Polyethylene 10.5 55 +424% fibres is only defined by the LOI test.
Polyamide 97 142 +46% The principal classes of high performance fibres
Polyester 235 415 +77%
Polyacrylonitrile 2 26 +1200%
considered here according to our definitions are derived
Glass 67 115 +72% from rigid-rod polymers (lyotropic liquid crystalline
Carbon 0.5 3 +500% polymers and heterocyclic rigid-rod polymers), modified
Meta-aramid 1 3.5 +250% carbon fibres, synthetic vitreous fibres, phenolic fibres,
Para-aramid 1 15 +1400% poly(phenylene sulphide) fibres and others. This part
focuses only on the specific thermal and fire perfor-
mances 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

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 polyamide-
Figure 1. Consumption by the full European textile chain: evolution of
imide fibre which is also classified in the meta-aramid
technical textiles versus others sectors. family (see Table 2).16 The fibre has a thermal
conductivity twice as low as any other aramid fibre.16,17
specimen continues to burn for a definite time or until a The principal market niche for meta-aramids is that
specified amount of specimen is consumed5). Generally, of heat-resistant materials.14,18 They are naturally non-
fibres with a LOI greater than 25 vol.% are said to be flammable thanks to their aromatic structures including
flame retardant. Nevertheless, the LOI test although not high C/H ratios and high contents of aromatic double
very representative of a fire, allows us to rate the bonds. They were commercialized for applications
materials quantitatively. The approach that we have requiring unusually high thermal and flame resistance.
developed is to evaluate fibres using the cone calorimeter Nomex fibre retains useful properties at temperatures as
as a fire model.6,7 The major advantage of the cone high as 3708C. It has low flammability and has been
calorimeter is to measure the rate of heat release which is found to be self-extinguishing when removed from the
the quantity of most concern in predicting the course of flame. On exposure to a flame, a meta-aramid fabric
the fire and its effect.8 Other parameters, such as smoke hardens, starts to melt, discolours, and chars thereby
opacity and carbon oxides evolution, can be measured forming a protective coating. An outstanding character-
and can be considered as well. This last aspect is istic is also low smoke generation on burning. The LOI
examined in the second part of this work. The reaction for m-aramid fabrics lies between 30 and 32 vol.%. It
to fire of some high performance fibres are evaluated has a weight loss at 4508C (Fig. 2) and a use temperature
using the cone calorimeter and their heat resistance is of 3708C.
studied by thermal analysis. Indeed, the fire behaviour
of a material depends on processes occurring in both Para-aramid. In the 1970s, researchers at DuPont
condensed and gas phases and on the processes of heat reported that the processing of extended chain all
and mass transfer. These processes strongly depend on para-aromatic polyamides from liquid crystalline solu-
the degradation reactions occurring in the condensed tions produced ultrahigh strength, ultrahigh modulus
phase.9 Even if there is confusion between the tempera- fibres.15,19,20 The greatly increased order and the long
ture resistance and the flame retardant ability, it can be relaxation times in the liquid crystalline state compared
expected that a fibre with a high degradation tempera- with conventional systems led to fibres with highly
ture will have good flame retardancy. oriented domains of polymer molecules. The most
common lyotropic aramid fibres comprise poly(p-
phenylene terephtalamide) (PPTA) which is marketed
as Kevlar by DuPont or as Twaron by Teijin (formerly
REVIEW OF HIGH PERFORMANCE FIBRE developed by Akzo) (see Table 2).18
BEHAVIOUR The conventional market for PPTA is body armour,
cables and composites for sports and space applica-
Before exploring the details of the high performance tions.15 The continuous operating temperature of PPTA
fibres, it is important to define the parameters of high in air is up to 1908C. PPTA degrades in air above 4008C

Copyright # 2002 John Wiley & Sons, Ltd. Fire Mater. 2002; 26: 155–168
 Table 2. Description and properties of high temperature resistant fibres

Chemical name or designation Generic name Chemical structure Trade name LOI (vol.-%) Continuous Applications
operating
temperature
(8C)

Poly(tetra-fluoroethylene) PTFE Teflon1 95 260 Aerospace and automotive

F F (DuPont) applications, food processing,
* C C * Toyoflon1 agricultural machinery
n
(Toyobo)
F F

Copyright # 2002 John Wiley & Sons, Ltd.

Poly(p-phenylene-2,6- PBO O O Zylon1 56–68 310 Protective clothing, heat resistant
benzobiso-xazole) * * (Toyobo) felt, sling, fragmentation barrier
n
N N

Poly(2,6-diimidazo(4,5-b:40 ,50 -e) PIPD OH H M5 > 50 } Protective clothing, composite

pyridi-nylene-1,4 (2,5-dihydroxy)- N N N (Magellan materials, stealth materials,
phenylene) * * Systems aerospace applications
n
N N International)
HO H

Oxidized poly(acrylonitrile) OPF Pyromex1 45–60 200 Aerospace structures, automotive

fibre (Toho Tenax), engine, ballistic material, heating
N O N H Lastan1 elements, thermal protection
(Asahi),
H N N H PANOX1
(SGL
H N N Carbon Group)

N H
HEAT AND FLAME RESISTANCE OF HIGH PERFORMANCE FIBRES

Elongatable carbonaceous EDF EDF (Dow) 45–55 200 Insulative material

H N
Dow fibre
N
N
N H
H N
N
157

Fire Mater. 2002; 26: 155–168

 158

Table 2. (Continued)

Poly(2,20 -(m-phenylene)-5,50 - PBI N N PBI 41 250 Firefighter protective clothing,

bisbenzimi-dazole) (Celanese) industrial workers apparel, fire
* n * blockers
N N
H H

Poly(phenylene sulfphide) PPS Ryton1
40 280 Reinforcing materials, filtration,

* S (Phillips protective clothing, insulators
n *
Petroleum Co.)
Procon1

Copyright # 2002 John Wiley & Sons, Ltd.

(Toyobo)

O O
Polyimide PI P84TM 38 260 Fire protective clothing, filtration
* N N O * (Inspec
n
Fibres)

O O

O
Poly(ether-etherketone) PEEK PEEK1 35 250 High temperature materials
* C O O n * (Zyex)

OH OH OH
OH
Phenolic fibre Phenolic or C C Kynol1 30–34 200 Fire protective apparel, fire
S. BOURBIGOT AND X. FLAMBARD

CH2 OH
C C OH H2 H2
novoloid H2 H2 (Nippon blockers, composite reinforcement
fibre CH2 CH2 CH 2OH CH2 H2 C Kynol Inc)

C O C C CH2 OH C C
H2 H2 H2 H2 H2
OH OH OH OH OH

Melamine fibre Melamine Three-dimensional melamine-based network Basofil1 30–32 200 Fire protective clothing, insulative
fibre (BASF) materials, fire blockers

N N

N N N N

N N N C N N N
H2

Fire Mater. 2002; 26: 155–168

 O O
Poly(p-phenylene PPTA N N C C Kevlar1 28–30 190 Protective clothing, composite
terephtal-amide) n* (DuPont) reinforcement, ropes and cables
H H Twaron
(Teijin)

Poly(m-phenylene PMIA Nomex1 30–32 200 Fire protective clothing, filtration,

H H O O
isophtal-amide) (DuPont) thermal resistant furnishing
* N N C C n * Conex1
(Teijin)

Polyamide-imide PAI O Kermel1 30–32 200 Fire and heat protective clothing,

Copyright # 2002 John Wiley & Sons, Ltd.

C (Rhodia) insulators
N CH2 n *
* N C C
H O O

Copoly(p-phenylene-3,4- Copolymer O O O O Technora1 25 200 Reinforced plastics, rope and

H
* N N C C m N O N C C n*
oxidiphenylene- terephtal- p-aramid H H H (Teijin) cable, protective clothing,
amide) fibre reinforcement of construction
materials
HEAT AND FLAME RESISTANCE OF HIGH PERFORMANCE FIBRES
159

Fire Mater. 2002; 26: 155–168

160 S. BOURBIGOT AND X. FLAMBARD

N S
* n *
S N

Figure 3. Chemical structure of PBZT.

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 degrada-
Figure 2. Remaining mass versus temperature of Nomex under air and tion of PBO34,35 and PBZT36 is reported to be 6008C in
nitrogen flow.14 air. This temperature is over 7008C in an inert atmo-
sphere. In isothermal aging studies in air at 3438C, PBO
and PBZT retain ca 90% of their weight after 200 h. At
and does not melt below this temperature. During 3718C in air, PBO and PBZT retain ca 78% and 71% of
ignition, PPTA does not melt but glows. No after the original weight, respectively. The operating tem-
burning is observed after removal from the flame. PPTA perature of these two fibres is up to 3508C.15 PBZT and
yields char above 4508C. The LOI for PPTA fabrics lies PBO degrade without the observation of crystalline
between 28 and 30 vol.%. melting points or glass-transition temperatures. PBO
also has a very high flame resistance and is self-
Copolymer para-aramid. Although para-aramids are extinguishing when removed from the flame. On
high in strength, there is some problem with chemical exposure to a flame, formation of char is observed at
resistance. Homopolymer para-aramids have relatively the surface which may act as a protective shield. The
weak resistance to strong acids and bases. PPTA cannot LOI of PBO is much higher than aramid fibres, 68
be bleached with chlorine and are often not approved vol.%.32 The combustion gases of PBO consist of
for food handling protective gloves. In 1985, Teijin carbon oxides and water, with smaller amounts of toxic
introduced Technora1 fibre into the high perform- gases such as hydrogen cyanide, sulphur and nitrogen
ance fibre market. Technora1 is based on the 1:1 oxides.32,37,38
copolyterephtalamide of 3,40 -diaminodiphenyl ether and
p-phenylenediamine (see Table 2).15,21 Polybenzimidazole. Polybenzimidazoles (PBI) are a
The fine surface structure of Technora1 copolymer class of thermally stable polymers, typically condensed
allows much higher chemical resistance than PPTA. from aromatic bis-o-diamines and dicarboxylates.
Copolymer para-aramids have the advantages of in- Poly(2,20 -(m-phenylene)-5,50 -bisbenzimidazole) is the
creased abrasion resistance and steam resistance } polybenzimidazole on which most attention has been
useful properties in many protective applications. focused over the past 30 years (see Table 2).39–42 PBI
Technora1 has a decomposition temperature of fibre is marketed by Celanese (USA) and the main
5008C.18 It can be used at 2008C for long periods of current textile applications of PBI are protective
time and, even at 2508C, it maintains more than half of clothing, fire blockers and space materials.43
its tensile strength measured at room temperature.15 The PBI is a thermoplastic polymer with a high glass
LOI of Technora1 is 25 vol.%, its ignition point is temperature (4508C). Its degradation temperature is
about 6508C and its heat of combustion is 28.5 kJ/g.21 reported to be 5808C in air and is over 10008C in
nitrogen. The continuous operating temperature is up to
Heterocyclic rigid-rod polymers
2508C. PBI does not burn in air and it does not support
burning after removal from the flame. On exposure to
Polybenzazole. A family of p-phenylene-heterocyclic
flame or high heat flux, it forms a tough char in high
rigid-rod and extended chain polymers includes
yield (to 80 wt.%).42 After the char is formed, the
poly(p-phenylene-2,6-benzobisthiazole) (PBZT)
charred fabric retains its integrity and flexibility with
(Fig. 3)22–25 and poly(p-phenylene-2,6-benzobisoxazole)
little shrinkage. Its LOI is greater than 41 vol.%.43 PBI
(PBO) (see Table 2).26–29
fibre has also negligible heat release rate measured by
PBZT and PBO were initially prepared at the Air
the Ohio State University Heat Release Apparatus
Force Materials Laboratory in the US Air Force
(OSU test).44 The 2 min average heat release is less than
Ordered Polymer Program.30,31 Only PBO fibre showed
10 kW/m2. It releases little smoke up to its decomposi-
attractive properties and great economic potentiality.
tion temperature. Its optical smoke density (Ds ) is 2
Dow acquired the patent license from Stanford Re-
compared with 8 for aramids. When exposed in air to
search Institute, and then developed a new synthesis
temperatures below its decomposition point, PBI emits
route of monomer, polymerization and fibre spinning
carbon oxides and water with traces of sulphur dioxide
technology. The rigid-rod like nature of PBO polymer
and hydrogen cyanide.42
chain makes the processing of polymer difficult, whereas
excellent physical properties of the fibre originate from
the rigid conformation. The development of production Polypyridobisimidazole. Recently a new member of the
technology on fibre spinning ran into serious obstacles. rigid-rod polymer family was synthesized. This new
In 1991, Dow decided to work with Toyobo (Japan). polymer is the poly(2,6-diimidazo(4,5-b:40 ,50 -e)pyridiny-
Their joint development bore fruit in 1994 as the lene-1,4(2,5-dihydroxy)phenylene) (PIPD or also

Copyright # 2002 John Wiley & Sons, Ltd. Fire Mater. 2002; 26: 155–168
 HEAT AND FLAME RESISTANCE OF HIGH PERFORMANCE FIBRES 161

referenced to as M5) (see Table 2).45–51 It has the ability

to form hydrogen bonds between adjacent chains. PIPD N O N H
was first developed by Akzo Nobel Central Research, H N
H N N H 450 - 750°C N
and now it is being developed by Magellan Systems N
International. Potential applications using M5 fibre are H N N N 2 atmosphere N H
H N
envisioned in five major areas: personnel protection, fire N H N
resistance, advanced composite materials and tethering/
advanced fabrics.52
OPF EDF
PIPD has extremely high fire resistance properties like
the other rigid-rod polymeric fibres.52 This is due to its Figure 4. Synthesis of elongatable Dow fibre (EDF) from oxidized PAN
lack of a true melting point, the rigidity of the chain and fibre (ODF).
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 Any standard precursor material can be used, but the
external heat flux of 75 kW/m2 (implying a surface preferred material is wet spun. The OPF is treated in a
temperature of about 8908C) give a peak heat release nitrogen atmosphere at 4508–7508C, preferably 5258–
(PHRR) rate of 44 kW/m2 associated with a time to 5958C, to give fibres having 69–70% C, 19% N, and a
ignition (TTI) of 77 s (PHRR and TTI of PBO=48 kW/ density less than 2.5 g/ml. This fibre is marketed by Dow
m2 and 56 s; PHRR and TTI of p-aramid=205 kW/m2 (USA).
and 20 s). This means that PIPD shows a great potential Elongatable Dow Fibre (EDF) exhibits very good
as a flame retardant. PIPD fibre varieties formed a char ignition-resistance, flame retardancy and fire blocking
layer only at the surface of the fibre, while protecting the properties. Its LOI lies between 45 and 55 vol.%.
rest of the fibre. It is believed that the superior Previous results with ignition resistant blends, where
performance of PIPD fibres may be partly due to the such fibres as aramids or PBI are used as the high LOI
fact that the crystal structure of PIPD contains about fibres, show that they need at least 65%, and typically
21% water. 85%, fibre content to pass the vertical burn test for
lightweight nonwoven batting. In contrast only 7–20%
Carbon precursor and elongatable carbonaceous fibres of either EDF mixed with flammable natural and
synthetic fibres allow the blends to pass such tests while
Carbon precursor. Carbon precursor fibres are partially still retaining most of the base natural or synthetic fibre
carbonized fibres which transform into carbon or properties. Blends of 50/50 EDF/polyester also passed
graphite fibre when they undergo further carbonization the FAA airlines ignition resistance tests with zero flame
in an inert atmosphere at high temperature.53,54 They length and no after-burn.
are produced by thermal stabilization of acrylic fibre at
2008–3008C in air. The mechanism of stabilization is Carbon fibre. Though a large number of polymeric
basically interpreted as intermolecular ring deformation precursors have been tried for modern carbon fibres, the
of the nitrile group and oxidation. The stabilization is
three main precursors used commercially in order of
accompanied by stretching to induce the high molecular decreasing current use are PAN, coal-based pitch and
orientation required for obtaining a high modulus rayon.54 The major application of carbon fibres is in
fibre.55,56 The stabilized fibre is called oxidized PAN
polymeric matrix composites; however, they are also
fibre (OPF) in the market (see chemical structure used in metal matrix and carbon matrix composites. As
Table 2). It is commercialized by several companies, examples, Toho Tenax (Japan) produces several grades
such as Toho Rayon Ltd (Japan) under the name
of carbon fibres under the trademark Besfight157 or
Pyromex1,57 SGL Carbon Group (UK and Germany) Toray (Japan) under the trademark Torayca1.61
under the name PANOX158 or by Asahi (Japan) under Carbon fibres are extremely resistant to high tem-
the name Lastan1.59 The applications of OPF are peratures: their melting temperature is 40008C. They can
friction materials, protective clothing and fire blockers. also be considered as flame resistant since they will burn
Due to the unique structure of OPF, the fibres have only at very high temperatures. They hence represent a
non-flammable and non-melting characteristics. The choice material for applications at extremely high
LOI lies between 45 and 60 vol.%. They do not melt
temperatures, for example in the filtration of molten
or adhere under direct exposure to intensive flame. The iron.
decomposition temperature of OPF is higher than 3008C
and the products of degradation are hydrogen cyanide, Vitreous fibre
ammonia, carbon oxides and water.
Man-made vitreous fibres comprise a number of glass
Elongatable carbonaceous fibre. The extreme brittleness, and speciality glass fibres and also, refractory ceramic
high modulus and low elongation of standard carbon fibres. All these fibres are flame retardant since they do
fibres restricts them to being woven only on specially not burn even at very high temperatures.62
adapted weaving machines. To overcome these draw-
backs, a modification of carbon fibre technology was Glass fibre. A wide range of glass compositions is
developed using less stringent carbonizing conditions available to suit many textile fibres.62,63 Glass fibres
and only partially carbonizing the precursor fibres, and made from various compositions have softening points
improved textile fibre properties have been achieved in the range 650–9708C. At temperatures above 8508C,
(Fig. 4).60 these fibres partially devitrify and form polycrystalline

Copyright # 2002 John Wiley & Sons, Ltd. Fire Mater. 2002; 26: 155–168
162 S. BOURBIGOT AND X. FLAMBARD

material that melts at 1225–13608C, which is high about 7008C, they are completely carbonized, with a
enough to contain the fires for several hours. carbon yield of about 558–60%. This weight loss occurs
without melting, and only a fraction of the compara-
Ceramic fibres. Ceramic fibres are mostly used as tively small volume of volatiles produced is combusti-
refractory fibres in uses over 10008C and are character- ble.71 The remaining carbon char is amorphous (glassy)
ized by a polycrystalline, rather than amorphous, in structure. The LOI of Kynol1 fibres is reported in the
structure. These fibres have exceptional high tempera- range 30–34 vol.%.72 When exposed to flame Kynol1
ture characteristics. Different compositions result in fibres do not melt but gradually char until completely
modifying end use temperatures from about 10508C or carbonized, without losing their original fibre structure.
higher for the kaolin-based products to 14258C and Finally, water and CO2 evolve as the main products of
above for the zirconium-containing materials. decomposition.
Sulphur-containing fibres
Melamine. Although melamine is considered unreac-
tive, its symmetry and functionality make it suitable for
Because of the chemical structure of poly(phenylene
use as a building block in condensation reactions with
sulphide) (PPS) does not fall into any of the standard
formaldehyde. It results in a cross-linked, non-thermo-
polymer classes, the Federal Trade Commission granted
plastic polymer of melamine units joined by methylene
the fibre the new generic name of Sulfar (see Table 2).64–68
and dimethylene ether linkages. In the polymerization
PPS fibres are marketed by Phillips Petroleum Co.
reaction, methylol derivatives of melamine react with
(USA) under the trademark Ryton169 and by Toyobo
each other to form a three-dimensional structure. The
(Japan) under the trademark Procon1.32 The main
resulting network structure gives melamine fibres the
applications of PPS fibres are heat and chemical
same characteristics of other melamine based products:
resistant filters, papermaking felts, insulators, reinfor-
heat stability, solvent resistance, and flame resistance
cing materials and protective clothing. They exhibit
(see Table 2).70,73 Melamine fibre is marketed by BASF
good flame retardancy (LOI is about 40 vol.%) and its
(Germany) under the trademark Basofil1. Since mela-
operating temperature is up to 2608C.17,18,69
mine fibres are heat and flame resistant, they typically
Miscellaneous fibres target hot gas filtration and safety and protective
apparel markets.74 Because of its variable denier and
There are a number of fibres which are used in non- staple length, low tensile strength and difficulty in
conventional textile applications and cannot be classi- processing, melamine fibres are generally blended with
fied in the sections considered above. stronger fibres such as aramids. It is more often used in
needled products or yarns made from wrapped spinning
Phenolic. Phenolic (or also referenced as novoloid) techniques, though recent advances have led to satisfac-
fibres are cured phenol-aldehyde fibres made by acid- tory ring spun yarns, blended with other fibres, such as
catalysed cross-linking of melt-spun novolac resin to para-aramids, suitable for weaving into firemen’s turn-
form a fully cross-linked, three-dimensional, amorphous out gear.
‘network’ polymer structure similar to that of thermo- TGA of melamine fibres reveals that the main
setting phenolic resins (see chemical structure Table degradation temperature of the fibres occurs at 3708C
2).70,71 Chemically, the fibres contain approximately in air and that the residue is 34 wt.% at 6008C. Their
76% carbon, 18% oxygen, and 6% hydrogen. The only continuous use temperature is 2008C. The LOI lies
commercially available phenolic fibres are the so-called between 30 and 32 vol.%.18 Basofil fibre offers good
Kynol1 fibres marketed by Nippon Kynol Inc (Japan). heat and flame protection in comparison with some
They are used in a wide variety of flame- and chemical- other high performance fibres when measuring thermal
resistant textiles and papers, in composites, gaskets and protective performance (TPP)75 as shown in Fig. 5. The
friction materials, and as precursors for carbon and main evolving gases are carbon oxides, water, nitride
activated-carbon fibres textiles, and composites.72 oxides and a small amount of hydrogen cyanide.
Thermogravimetric analysis (TGA) indicates that
upon heating above 2508C in the absence of oxygen, Fluorocarbon. Fluorocarbon fibres are based on poly
Kynol1 fibres undergo gradual weight loss until, at (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
 HEAT AND FLAME RESISTANCE OF HIGH PERFORMANCE FIBRES 163

fluorine bonds are extremely strong, and provide the Kynol1), melamine fibres (as Basofil1) and polyamide-
polymer with a very high thermal and flame resistance imide fibres (as Kermel1) were supplied respectively by
(LOI = 95 vol.%).77 PTFE fibres are marketed by Kynol GmbH (Germany), BASF (Germany) and
DuPont (USA) under the trademark Teflon1.76 Rhodia (France). Recycled oxidized polyacrylonitrile
fibres were supplied by Achille Bayard (France). The
Polyimide. Polyimide (PI) fibres are manufactured by yarns used in this study have the following character-
polycondensation of an anhydride with aromatic istics:
diisocyanates in high polar solvents such as dimethyl-
formamide or dimethylacetamide (see Table 2).78–81 The
PBO (Zylon): Nm 2/34 spun yarn (60 tex)
thermal properties of PI fibres are characterized by the
PPTA (Kevlar): Nm 2/28 spun yarn (72 tex)
glass transition temperature of 3158C which enables a
Multifilament (90 tex)
fibre application temperature of 2508C.79,82 Recently,
TECH (Technora): Nm 2/28 spun yarn (72 tex)
NASA has developed a new technology via a melt
PIPD (M5): Multifilament (92 tex)
extrusion process to produce these PI fibres.83 The fibres
Phenolic fibre (Kynol): Nm 2/28 spun yarn (72 tex)
have a glass transition temperature of between 2408C
Melamine fibre (Basofil): Staple (2.2 dtex)
and 2708C. Melt extruding the fibres eliminates the need
PAI (Kermel): Staple (2.2 dtex)
for volatiles such as acid and harsh solvents, making the
Recycled oxidized PAN: Nm 1/14 Spun yarn (72 tex)
whole process more environmentally friendly than
solution spinning. NASA says that the process is also
inexpensive. Nevertheless, PI fibres are only produced Processing
by Inspec Fibres (Austria) under the trademark
P84TM .82 The main applications of these fibres are Fibres were knitted on an automatic rectilinear
protective clothing, high temperature filtration and machine gauge 7. The texture used is a double woven
thermal insulation. rib. The fabrics had the surface weight equalling
PI fibres do not melt but decompose and carbonize at 1.08  0.05 kg/m2.
elevated temperatures.84 TGA reveals that at 3508C, the
weight loss of PI fibres is about 5 wt.%, and at 5008C a Cone calorimetry by oxygen consumption
value is attained after 70 min.Their continuous operat-
ing temperature is reported to be 2808C. PI fibres also Samples were exposed to a Stanton Redcroft cone
exhibits a good LOI of 38 wt.%.17 calorimeter at a heat flux equalling 75 kW/m2. This flux
corresponds to flashover conditions. The samples were
Poly(ketone). Polyketones represent another interesting mounted between two cut steel sheets placed on the
group of polymers which possess useful high tempera- usual holder of the cone calorimeter (Fig. 6). The
ture properties. The ether link is used to promote an surface exposed to the external heat flux was 9  9 cm2.
added flexibility to inherently rigid polymer chains Our method does not correspond to any standard.
without incurring too radical reduction in thermal/ Conventional cone calorimetry data (rate of heat release
thermooxidative stability. Poly(ether-ether-ketone) (RHR), volume of smoke production (VSP) (see the
(PEEK1) was the first polyketone synthesized in computation90), CO and CO2 evolution, and the fire
1979,84–86 and other related materials have also been growth rate index (FIGRA) (see the definition91) were
developed.87–88 Nevertheless, only PEEK1 fibres can be obtained using a software developed in our laboratory.
found in the market under the trademark PEEK The experiments were repeated three times. When
marketed by Zyex1 (UK) (see Table 2).89 The main measured at 75 kW/m2 flux, the RHR and VSP values
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

EXPERIMENTAL

Materials

Poly(p-phenylene-2,6-benzobisoxazole) (PBO) fibres

were supplied by Toyobo (Japan) as Zylon1. Poly p-
phenylenediamine-terephtalamide fibers (PPTA) fibres
are Kevlar129. Co-poly(p-phenylene-3,4-oxidipheny-
lene-terephtalamide) fibres (TECH) were supplied by
Tejin (Japan) as Technora1. Poly(2,6-diimidazo[4,5-
b:40 ,50 -e]pyridinylene-1,4(2,5-dihydroxy)phenylene)
(PIPD or M5) fibres were supplied as multifilament by Figure 6. Home made cone calorimeter holder used in the experi-
Magellan (USA) (hot drawn yarn). Phenolic fibres (as ments.

Copyright # 2002 John Wiley & Sons, Ltd. Fire Mater. 2002; 26: 155–168
164 S. BOURBIGOT AND X. FLAMBARD

were reproducible to within  10% and CO, CO2 were (TTI of PPTA spun yarn=30 s; TTI of PPTA multi-
reproducible to within  15%. The results presented in filament=25 s) and the RHR peaks (RHR peak of
the following section are averages. The cone data PPTA spun yarn=255 kW/m2; RHR peak of PPTA
reported in this work are the average of three replicated multifilament=290 kW/m2) are similar, but the curves
experiments. after the RHR peaks are significantly different. The two
plateaux assigned to the glowing of the samples92 do not
Thermal analysis have the same duration (
300 s between 100 and 400 s
for PPTA spun yarn and
600 s between 200 and 800 s
Simultaneous TGA/DSC measurements were per- for PPTA multifilament).
formed using a Netzsch STA 449C Jupiter instrument RHR curves of the knitted high performance fabrics
under air flow (50 ml/min) from 208C to 12008C. at 75 kW/m2 show that three categories of fibres can be
Samples (about 5 mg) were placed in Pt crucibles with distinguished (Fig. 8). The p-aramid fibres (PPTA and
a cap on the top (the cap had a hole in the centre). The TECH) have a RHR peak value of about 300 kW/m2
calibration in temperature and in energy was made using and a time to ignition at 25 s, while the Kynol and
standards: biphenyl, KClO4, K2CrO4, BaCO3 and recycled oxidized PAN fibres have a lower RHR peak
benzoic acid. 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
HEAT AND FLAME RESISTANCE 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
The overview of the heat and fire resistance of the PAN and Kynol have moderately high RHR values with
high performance fibres shows that the flame retardancy short times to ignition.
of the fibre is high according to the LOI test (see Table FIGRA is a good indicator of the contribution to fire
2). The LOI test does not provide any data on the flame growth of a material and FIGRA curves of the fibres
behaviour of the fibre in a real fire scenario but only studied are shown in Fig. 9. The FIGRA of PBO is close
indications on the flammability of the fibre in particular to zero which means that PBO does not contribute to
conditions. Here, we consider that LOI alone is not the propagation of fire. FIGRA curves of p-aramids
sufficient for quantifying and predicting the flame (PPTA and TECH) exhibit only one peak respectively at
behaviour of these fibres in a real fire. Other parameters 40 s (FIGRA=500 W/s) and at 30 s (FIGRA=700 W/s)
must be considered such as the heat release rate, time to and after 100 s, values for the two fibres become close to
ignition and heat of combustion. This part evaluates the zero. PPTA and TECH would contribute, therefore, to
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 300 300

resistance and, recycled oxidized PAN and Kynol for

RHR (kW/m²)
RHR (kW/m²)

200
their good cost to performance ratio.
200
100
Reaction to fire
100 0
0 25 50 75 100 125
Fibres are evaluated as knitted samples of spun yarn Time (s)

or multifilament yarns. Even if the knitted structure is

0
the same, these two kinds of samples may not be 0 100 200 300 400 500 600
compared because it leads to different results. Figure 7 Time (s)
shows the comparison of the RHR curves of the two PPTA TECH PBO
PPTA fabrics. It is observed that the times to ignition Oxidised recycled PAN Kynol

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

300 knitted high performance fibres in spun yarn.

250
2000

200
RHR (kW/m²)

1500
FIGRA (W/s)

150 Spun yarn

1000

100 Multifilament yarn 500

50 0
0 25 50 75 100
Time (s)
0
PPTA TECH PBO
0 200 400 600 800 1000
Time (s) Oxidised recycled PAN Kynol

Figure 7. Comparison of knitted fabrics of PPTA in spun yarn and mul- Figure 9. FIGRA curves (external heat flux=75 kW/m2) of selected
tifilament yarn. knitted high performance fibres in spun yarn.

Copyright # 2002 John Wiley & Sons, Ltd. Fire Mater. 2002; 26: 155–168
 HEAT AND FLAME RESISTANCE OF HIGH PERFORMANCE FIBRES 165

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
Figure 12. Evolution of CO2 (external heat flux=75 kW/m2) of selected
(35 s) and at 0.009 m3/s (30 s). PBO, Kynol and recycled
knitted high performance fibres in spun yarn.
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 300

real fires.93 250

Figs. 11 and 12 show the evolution of carbon oxides M5 multi
and the amounts evolved by PPTA (CO peaks) are

RHR (kW/m²)
200
always higher than for the other fibres. It suggests that PPTA multi
150
incomplete combustion reactions are favoured for
PPTA (Fig. 11). The evolution of carbon dioxide leads 100
to the same conclusions made above with regard to
50
respective RHR curves (Figure 12).
Finally, RHR curves of knitted PPTA and PIPD 0
0 200 400 600 800 1000
fibres in multifilament yarns at external heat flux of
Time (s)
75 kW/m2 are presented in Fig. 13. They show that
PIPD fibres should present a superior behaviour in Figure 13. RHR curves (external heat flux=75 kW/m2) of PIPD (M5)
comparison with PPTA. RHR peak of PIPD is only and PPTA fabrics in multifilament yarn.
50 kW/m2 in comparison with 300 kW/m2 for PPTA

fibres demonstrating that PIPD has a very high fire

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

0.008
Heat resistance
VSP (m3/s)

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

0.004
much better heat resistance than the other fibres. PBO
fibres degrade in a one step apparent process at about
0.002 6008C to give 2 wt.% residue at 8008C. PPTA degrades
0 via two apparent steps. The first one starts at 2008C and
0 25 50 75 100 the second one (the main stage) starts at 5008C. TECH
Time (s)
and Kermel decomposes via only one apparent step
PPTA TECH PBO
which starts at about the same temperature as the
Oxidised recycled PAN Kynol
second step of PPTA (about 5008C). Kynol exhibits the
Figure 10. VSP curves (external heat flux=75 kW/m2) of selected same behaviour as TECH and Kermel but its decom-
knitted high performance fibres in spun yarn. position 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 degrada-
tion 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,
Figure 11. Evolution of CO (external heat flux=75 kW/m2) of selected 38 wt.% for PPTA, 37 wt.% for TECH, 12 wt.% for
knitted high performance fibres in spun yarn. Basofil and 65 wt.% for PBO). It is to be noted that

Copyright # 2002 John Wiley & Sons, Ltd. Fire Mater. 2002; 26: 155–168
166 S. BOURBIGOT AND X. FLAMBARD

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

Remaining mass (wt.-%)
80
synthetic fibres (e.g. nylons, polyester, acrylic). Three
categories of fibres can be distinguished, rated according
60 to their performance. The first group is PBO and PIPD.
These fibres have a very low RHR and in the conditions
40
of post-flashover (external heat flux >50 kW/m2) would
20 not to be expected to spread fire (from their low FIGRA
values); also they have high LOI values (>50 vol.%),
0
200 400 600 800 and they do not evolve smoke (
0.000 m3/s). Kynol
Temperature (°C) and recycled oxidized PAN fibres are in the second
PPTA TECH PBO group because they have a moderate RHR (5150 kW/
Oxidised recycled PAN Kermel Kynol m2). Recycled oxidized PAN fibres exhibit a compara-
Basofil tively high FIGRA value because of surface fibres
Figure 14. TG curves of selected high performance fibres under air
present which should be corrected using an optimized
(heating rate=108C/min). 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 compara-
Basofil has a comparatively low thermal stability under tively high RHR values (
300 kW/m2), they contribute
an inert atmosphere in comparison with the other high to the fire growth (moderate FIGRA values) and they
performance fibres and this shows the strong influence evolve smoke but maintain high LOI (>27 vol.%)
of oxygen present in the fibre structure itself on the values. This work shows that the high performance
thermal degradation of the fibres. This last considera- fibres can be ranked according to realistic quantitative
tion is important when recalling that polymeric sub- parameters of fire, and so provides useful specifications
strates heated by an external source are pyrolysed with for using fibres in special configurations. Table 4
the generation of combustible fuels in a zone where there provides a brief overview of the performance of the
is depletion of oxygen.94 fibres in comparison with PPTA (PPTA is taken as
Using simultaneous TGA/DSC, the values of the standard because it is the widely used high performance
enthalpies of decomposition can be estimated by fibre). The fibres studied may be ranked in three groups
integrating DSC curves in the temperature range as follows:
of decomposition of the fibres (Table 3). The
thermo-oxidative decompositions of the fibres are 1. Minimal or no contribution to fire and no smoke :
exothermic and can be assigned to oxidation re- PBO and PIPD,
actions. The enthalpies of decomposition of all
2. Low contribution to fire and low smoke : Kynol and
fibres are of the same order of magnitude. It should be
noted that these values are in the same order of recycled oxidized PAN,
magnitude as the heat of combustion of common 3. Significant contribution to fire and smoke : PPTA
organic polymers.99 In particular, the heats of combus- and TECH.
tion of PPTA, TECH and PBO are measured to be –
26 kJ/g, 28.5 kJ/g and –28 kJ/g, respectively95 and are According to the above ratings, the heterocyclic
close to those measured in Table 3 by simultaneous rigid-rod polymers (PBO and PIPD) exhibit the best
TGA/DSC. 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
DISCUSSION stability. These factors provide high levels of stability
to the polymer, and promote high flame resistance. In
The high performance fibres examined show that all contrast to PBO and PIPD, p-aramid fibres have
exhibit high flame retardancy (high LOI, low RHR and phenylene groups linked by amide bridges. These
low smoke) and good heat resistance (temperature of bridges (-CONH-) lead to a reduction in thermal
degradation higher than 3508C) in comparison with stability of the fibres which, consequently, yield flam-
mable molecules upon heating. Finally, Kynol and
recycled oxidized PAN fibres are cross-linked networks
with methylene (Kynol) or ether (recycled oxidized
Table 3. Enthalpy of decomposition in air of Kermel, recycled PAN) bridges. These flexible groups lead to the
oxidized PAN, PPTA, TECH and PBO fibres reduction in thermal stability as for the p-aramids,
but the stabilizing character of the cross-linked
Fibre Enthalpy of Temperature range of network may enhance char yield (see Fig. 15). It
decomposition (J/g) computation (8C)
follows hat the better fire performance of Kynol
PPTA 22200 400–650 and recycled oxidized PAN fibres in comparison
TECH 25000 400–700 with p-aramids may be assigned to the formation of
Kermel 21000 300–700
higher yields of char. These enhanced chars can act
Oxidized recycled PAN 19500 250–700
PBO 21000 450–800
as insulative shields when burning, and can protect
underlying substrates.

Copyright # 2002 John Wiley & Sons, Ltd. Fire Mater. 2002; 26: 155–168
 HEAT AND FLAME RESISTANCE OF HIGH PERFORMANCE FIBRES 167

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

PPTA PBO PIPD Kynol Recycled oxidized PAN TECH

TGA ! %% } && & %

LOI ! %% %% ! } !
C RHR ! %% %% % % !
O FIGRA ! %% } & && &
N VSP ! %% } %% %% &
E CO ! % } % % %
! same performance, % % much better, % better, & worse, & & much worse, - not determined.

100 This work has presented the heat and flame resistance
of high performance fibres presently available on the
Remaining mass (wt.-%)

80
market. Literature and original data have been reported
60 and the main conclusion is that heteroaromatic poly-
40 meric fibres are the most outstanding halogen-free
fibres. In particular, PBO and PIPD exhibit unique
20
flame retardancy and these two fibres present significant
0 advances in high performance fibre technology because
100 300 500 700 900 1100 1300 1500 they offer the right combination of unique heat and
Temperature (°C)
flame resistance with exceptional mechanical properties.
PPTA TECH PBO
It is predicted that future technological development will
Kynol Recycled oxidised PAN Basofil
focus on the emergence and exploitation of heterocyclic
Kermel
polymer fibres. It is also anticipated that the market will
Figure 15. TG curves of selected high performance fibres under nitro- provide these fibres at an acceptable cost to performance
gen (heating rate=108C/min). ratio.

CONCLUSION Acknowledgements

It can be seen that the newer organic fibres offer very This work was partially supported by the European project
FLAMERET (New Surface Modified Flame Retarded Polymeric
significant competition in terms of flame resistance and Systems to Improve Safety in Transportation and Other Areas
of other properties (included mechanical, electrical and registered under the number No. G5RD-CT-1999-00120). The
chemical properties). Future expansion of their use authors thank Professor Sikkema from Magellan International
depends partly on the exploitation of these properties in System for helpful discussion on PIPD (M5) fibre and for supplying
specific end-uses and partly on establishing very cost- M5 fibres. Mr Franck Poutch from CREPIM is grateful acknowledged
for helpful discussion on the cone calorimeter. The authors are
effective processing routes. The promise of significant indebted to Mr Dubusse from CREPIM for his skilful experimental
further improvements in properties and/or the possibi- assistance in cone calorimeter, and to Mrs Sabine Chlebicki from
lity of cost reduction with processing, synthesis and cost GEMTEX for her skilful experimental assistance in TGA/DSC
of monomers continues to excite research in this area. experiments.

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