STUDY OF THE THERMAL AND FIRE BEHAVIOUR OF HIGH

PERFORMANCE FIBRES – APPLICATION TO POLYBENZAZOLE AND

p- ARAMIDE FIBRES

Serge Bourbigot* , Xavier Flambard* , Sophie Duquesne ** and Franck Poutch***

*
Laboratoire de Génie et Matériaux Textiles (GEMTEX),ENSAIT, 9 rue de l'Ermitage BP
30329, 59056 Roubaix Cedex 01, France, ** Laboratoire de Génie des Procédés d’Interactions
Fluides Réactifs Matériaux (GEPIFREM), serge.bourbigot@ensait.fr
ENSCL, 59652 Villeneuve d’Ascq Cedex, France, ***Centre de Recherches et d’Etudes sur les
Procédés d’Ignifugation des Matériaux (CREPIM), 62700 Bruay-la-Buissière, France

INTRODUCTION
Poly(p-phenylene-2,6-benzobisoxazole) (PBO) registered under the trademark Zylon® is
a new high performance fiber (1). It is one of polybenzazoles containing aromatic hetero-cyclic
ring. The polybenzazoles have been firstly developed by US Air Force researchers as super heat
resistant polymer which could surpass traditional aramide fibers. PBO has good flame resistance
and thermal stability among organic fibers and in particular, in comparison with p-aramide
fibers. As an example, the limiting oxygen index (LOI measured according to NF G 07-128) of
PBO is 68 vol.-% whereas the one of p-aramide fibers is only 30 vol.-%.

The paper compares and discusses the fire (using the cone calorimeter as fire model) and
thermal behavior of PBO fibers in comparison with p-aramides (PPT) ones.

EXPERIMENTAL
Materials
PBO fibers were supplied by the company Toyobo (Japan) and is registered under the
trademark Zylon®. PPT fibers are classical Kevlar®. PBO and PPT fibers have been knitted in
spun yarns on an automatic rectilinear machine gauge 7. The texture used is a double weaved rib.
The two samples have the surface weight equaling 1.08 kg/m² (4 yarns knitted together in the
case of PPT and 5 yarns in the case of PBO).

Cone calorimeter
The Stanton Redcroft Cone Calorimeter was used to carry out measurements on samples
following the procedure defined in ASTM 1354-90. The standard procedure used involves
exposing specimens measuring 100 mm x 100 mm x 3 mm thick in horizontal orientation.
External heat fluxes of 50 and 75 kW/m² have been used for running the experiments.

TG analyses
TG analyses were performed using a Setaram MTB 10-8 thermobalance at 10 °C / min
from 20°C to 1200°C under air flow (Air Liquide grade, 5×10-7 m3 /s measured in standard
conditions) and under nitrogen flow (N45 Air Liquide grade, 5×10-7 m3 /s measured in standard
conditions) . Samples (about 10 mg) were placed in vitreous silica pans. Precision on
temperature measurements is ±1,5°C.
RESULTS AND DISCUSSION
Rate of Heat Release (RHR) curves (Fig. 1) of knitted PPT and PBO fibers under two
external heat fluxes (50 and 75 kW/m²) show that PBO fibers present a very good fire behavior
in comparison with PPT fibers. RHR peaks of PBO under 50 kW/m² and 75 kW/m² are
respectively only 60 kW/m² and 150 kW/m² in comparison with 400 kW/m² and 430 kW/m² for
PPT fibers. It demonstrates therefore the high fire resistance of PBO.

TG curves (Fig. 2) show the high heat resistance of PBO fibers in comparison with PPT
fibers. Whatever the atmosphere is, the degradation occurs in one step and the heat resistance of
PBO fibers is always higher. Under air, PPT fibers begin to degrade at about 450°C and form a 3
wt.-% residue at 1200°C whereas PBO fibers degrade at about 600°C and form a 3 wt.-% residue
at 1200°C. Under nitrogen, the degradation of fibers begins at higher temperature (about 550°C
for PPT and about 700°C for PBO). High amount residues are formed stable up to 1200°C (38
wt.-% for PPT and 65 wt.-% for PBO). It is then shown the strong influence of oxygen on the
thermal degradation of the fibers.

100
500
90

400 PPT 50 kW/m² 80

Remaining mass (wt.-%)

70 PBO (nitrogen)
PBO 50 kW/m²
RHR (kW/m²)

300 60

50
PPT 75 kW/m²
40
PPT (nitrogen)
200
PBO 75 kW/m² 30
PBO (air)
100 20
PPT (air)
10

0 0
0 200 400 600 800 1000 1200
0 250 500 750 1000 1250 1500
Time (s) Temperature (°C)

Fig. 1 RHR curves of knitted PPT and PBO fibers Fig. 2 TG curves of PPT and PBO fibers under
nitrogen (dashed lines) and air (plain lines)

CONCLUSION
The investigation of the fire performance of the PPT and PBO fibers using the cone calorimeter
has shown the excellent behavior of PBO in comparison with PPT. This behavior is confirmed
by TG analysis. The thermal stability (under pyrolytic or thermo-oxidative conditions) of PBO is
150°C higher than this one of PPT. Moreover it is shown the strong influence of oxygen on the
thermal degradation of the fibers.

References
(1) Kitagawa, T., Murase, H. and Yabuki, K., Morphological study on poly-p-
phenylenebenzobisoxazole (PBO) fiber, J. Polym. Sci. Part B : Polym. Phys., 1998, 36, 39.