Polymer Degradation and Stability 77 (2002) 279–284

www.elsevier.com/locate/polydegstab

Wool/para-aramid fibres blended in spun yarns as

heat and fire resistant fabrics
Xavier Flambarda,*, Serge Bourbigota, Manuela Ferreiraa,
Bernard Vermeulena, Franck Poutchb
a
Laboratoire de Génie et Matériaux Textiles (GEMTEX), UPRES EA2461, Ecole Nationale Supérieure des Arts et Industries Textiles (ENSAIT),
BP 30329, 59056 Roubaix Cedex 01, France
b
Centre de Recherche et d’Etude sur les Procédés d’Ignifugation des Matériaux (CREPIM), Parc de la Porte Nord, Rue Christophe Colomb,
62700 Bruay-la-Buissiére, France

Received 12 October 2001; received in revised form 28 January 2002; accepted 3 February 2002

Abstract
Knitted textiles, obtained with yarn-by-yarn blending of wool and poly-p-phenylenediamine-terephthalamide (PPTA) high perfor-
mance fibres, allow improved fire retardance performance and thermal stability by synergistic effects. Blends of wool with PPTA fibres in
spun yarns (intimate mixing) are studied in order to investigate better synergistic effects due to the intimate contact between fibres. Those
yarns, made and knitted in our laboratory, give exceptional results according to RHR (rate of heat release) peak and thermal sta-
bility. A mechanism of action explaining the enhanced performance is proposed. # 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Textile blends; Fire resistance; Knitted textiles; Thermal stability; PPTA; Wool; Spun yarn

1. Introduction requires high flame and heat resistant textiles (seat cov-
erings in aircraft) which should have a combination of
Textiles are in many elements constituting the interior other acceptable properties including a good handle.
of public transportation (buses, aircraft, cars, trains In recent work [2] we have shown that blends of wool
etc.). These structures are composed of fibres assembled with PPTA (poly-p-phenylenediamine-terephthalamide),
to make yarns and then to manufacture textile struc- made yarn by yarn knitted side by side, allow improve-
tures about which transportation legislation is very ment of the FR performance and the thermal stability
strict for safety reason. However, the flame retardant of the whole textile and that synergistic effects are
treatments suitable for these mainly wool-containing observed in terms of RHR peak. The thermal stability
fabrics are generally not permanent to dry cleaning and of the high performance PPTA fibres is much higher
laundry treatments [1]. The most popular of these textile than wool [2,3]. It was proposed that the first step of the
structures are woven and knitted structures made of degradation of wool can be assigned to the melting and
fibres of increased resistance to ignition as well as coat- the formation of char. This molten char can coat the
ings applied to bottom layers of covering or to the sur- PPTA fibres and slow down their degradation.
face of the first layer of filling material. At the same This melt was obtained by assembling different yarns
time, textiles used for these applications require other of wool with yarns of PPTA. As we have seen in the last
specific properties such as dyeability, good handle, etc. paragraph, the thermal stability is obtained by a char
This is why, wool is particularly used in interiors of formation. We proposed, in this work, to increase the
buses or cars as seat fabrics for its comfort and col- fibre contacts to enhance the interaction between wool
ouration properties, coupled with a low level of inherent and PPTA. An intimate blend was made by a spinning
flame resistance. The market, however, increasingly process which perfectly homogenizes the final product.
The thread obtained is a spun yarn with fibres of PPTA
* Corresponding author. Tel.: +33-3-20-25-64-78; fax: +33-3-20-
and wool of known percentage.
27-25-97. The originality of our present study is to use technical
E-mail address: xavier.fl[email protected] (X. Flambard). the fibres, PPTA, to manufacture textile structures for
0141-3910/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S0141-3910(02)00062-9
280 X. Flambard et al. / Polymer Degradation and Stability 77 (2002) 279–284

Table 1
Fibre characteristics

Diameter/linear Length Count of

density of fibres (mm)b sliver (ktex)

Wool 26.26 mm 71.3 25.62

Kevlar 29 (PPTA) 1.81 dtexa 91.8 3.88
a
dtex: Weight in decigrams of 1000 m of fibre.
b Fig. 1. Double woven rib knitted with blend of spun yarns.
Length (mm): the mean fibre length deduced from the propor-
tions, in terms of count, of the fibres in the silver.

2.2. Blend principle

Table 2 For this study, we produced yarns with a count of 36

Real percentage of wool/PPTA blends tex (Nm 28) and with variable amounts of PPTA fibres
Blends of Real percentage added (0, 10, 20, 30, 50 and 75%).
wool/PPTA in the blend (%) The blend principle adopted is that by compensation,
and consists in distributing the constituents to be blen-
90/10 87.9/12.1
80/20 76.0/24.0
ded in the form of different slivers, but having the same
70/30 65.5/34.5 length. These can then form a lap intended to feed the
50/50 44.3/55.7 head of a gill-box which, depending on the number of
25/75 21.2/78.8 pinned fallers (5 needles/cm) and the number of passes,
allows a pre-blend to be produced. After this phase has
been completed, the slivers obtained enter the worsted
spinning preparation cycle in order to obtain a roving.
transportation. These fibres present very high mechan- After spinning, the single yarns were all subjected for 20
ical and thermal performance as well as very good minutes to vapour treatment at 80  C.
resistance to fire [4,5]. But they are not generally The real percentage of the different yarns was verified
employed for this end-use because they have a poor UV by dissolution of wool fibres in NaOH [9]. The weight of
resistance, a bad handle and they are very difficult to the remaining PPTA fibres was measured and the exact
dye. It is proposed that blending PPTA fibres with nat- quantity of PPTA and wool in the blend calculated. The
ural fibres will protect them from UV by reducing their results are given in Table 2.
exposure to incident light.
Blends, yarn by yarn, give very good FR behaviours, 2.3. Knitting process
and in this work, we manufacture spun yarns in inti-
mate mixing (fibre by fibre) in order to obtain more Spun yarns were knitted on an automatic rectilinear
contacts between fibres to enhance thermal and FR machine gauge 7—Shima Seiki SES 122 FF. A different
behaviour. We examine the heat resistance of spun percentage can be obtained by knitting different blen-
blended yarns by TGA and we also investigate the flame ded yarns. The texture used is a double woven rib
resistance by using a cone calorimeter after assembling (Fig. 1). The samples had a surface weight of
them to knitted fabrics. 1.08  0.05 kg/m2.

2.4. Cone calorimetry by oxygen consumption

2. Experimental
Samples were exposed to a Stanton Redcroft Cone
2.1. Materials Calorimeter at heat flux equalling 75 kW/m2. This flux
corresponds to flashover conditions [10,11]. This flux
PPTA fibres were Kevlar1 type 29 supplied by the has been used because of the high fire performance of
company DuPont De Nemours (USA). The fibres used our fabrics, with a lower heat flux, the samples would
in this study have the characteristics listed in Table 1. not have burned. The samples are put between two cut
The diameter of wool fibres was determined using a steel sheets. The surface exposed to the external heat
Fibre Fitness Meter (Air Flow) [6], and the linear den- flux is 99 cm2. Our method does not correspond to
sity of PPTA fibres using a Vibroskop [7]. We mea- any standard. We obtained conventional data [Rate of
sured the fibre length on a Wira, Fibre Diagram Heat Release (RHR), volume of smoke production
Machine [8]. The count of each sliver has been determined (VSP) [12], . . .] using software developed in our
by weighing 5 m. laboratory. The experiments were repeated three times.
 X. Flambard et al. / Polymer Degradation and Stability 77 (2002) 279–284 281

Fig. 2. RHR curves of spun blends wool/PPTA (external heat flux=75 kW/m2).

Fig. 3. FIGRA curves of spun blends wool/PPTA (external heat flux=75 kW/m2).

When measured at 75kW/m2 flux, RHR and VSP values ranges of stabilisation and destabilisation of blended
are reproducible to within  10% and CO, CO2 are yarns to be determined [13]. The curves are computed as
reproducible to within  15%. The cone data repor- follows:
ted in this work are the average of three replicated MWool(T): TG curve of pure wool,
experiments. MPPTA(T): TG curve of pure PPTA,
Mexp(x,y)(T): experimental TG curve of the blend wool/
2.5. Thermal analysis PPTA were x and y are respectively the mass percentage
of wool and PPTA in the blend: (x+y)/100=1,
Simultaneous TGA/DSC measurements were per- Mth(x,y)(T): theoretical TG curve computed by linear
formed using a Netzsch STA 449C Jupiter under air combination between the TG curves of wool and PPTA
flow (50 ml/min) from 20 to 1200  C. Samples (about 5
mg) were placed in Pt crucibles with a cap on the top Mth(x,y)(T)=(x.MWool(T)+ y.MPPTA(T))/100
(the cap had a hole in the centre). The calibration in
temperature and in energy was made using standards (x,y)(T): curve of weight difference for each percen-
(biphenyl, KClO4, K2CrO4, BaCO3, benzoic acid). tage of wool and PPTA.
The curves of weight difference, between the experi-
mental and theoretical TG curves, allow the temperature (x,y)(T)=Mexp(x,y)(T) Mth(x,y)(T).
282 X. Flambard et al. / Polymer Degradation and Stability 77 (2002) 279–284

Fig. 4. VSP curves of spun blends wool/PPTA (external heat flux=75 kW/m2).

The (x,y)(T) curves allow the observation of an

eventual increase or decrease in the thermal stability of
the polymer.

3. Results and discussion

3.1. Flame and heat resistance of blended spun yarns

3.1.1. Reaction of blended spun yarns to fire

Fire hazard is associated with a variety of properties Fig. 5. TG curves of spun wool/PPTA blends (10  C/min, air flow).
of a material in a particular scenario. It is determined by
a combination of factors including the material ignit-
ability, the rate at which heat is released from it when it
burns, the total amount of heat that is released, the
flame spread, the smoke production and the toxicity of
the smoke. It has now been established that the property
which most critically defines a fire is the heat release [12].
Fig. 2 shows RHR curves of the spun blends wool/
PPTA. A synergistic effect is observed when the amount
of PPTA reaches 30 wt.% in the blend. Indeed, with at
least 30% of PPTA in the blends, the RHR peak of each
sample is lower than the black line corresponding to the
RHR peak of the virgin PPTA. In the case of the blend Fig. 6. Curves of the weight difference of spun yarn wool/PPTA
processed yarn by yarn, the synergistic effect was blends.
reached for 75 wt.% of PPTA in the blend [2]. It means
that the synergistic effect is enhanced when blends are
proceed fibre by fibre in a blended spun yarn. A per- decreased when the amount of PPTA is increased
centage of 75 wt.% of PPTA, blended yarn by yarn in a (Fig. 3). FIGRA peak of the blends is only lower than
composite yarn, is necessary to obtain the same RHR PPTA for the blend 25/75 but it occurs at shorter time
peak than the one obtained with only 30 wt.% of PPTA (13 against 38 s). The combination wool/PPTA 25/75 is
when the blend is an intimate blend. the most interesting because its FIGRA value is close of
It is significant to note that ignition times of the the one of virgin PPTA. It should be noticed that the short
blends are lower than virgin PPTA and correspond to time to ignition of the blends leads to higher FIGRA.
the one of wool. Whatever the percentage of the blend VSP [12] curves of wool/PPTA blends are presented in
is, the ignition times of the blends are controlled by Fig. 4. The blends always exhibit lower VSP peaks than
wool (about 10 s). virgin PPTA (0.003 against 0.007 m3/s) but the peaks
FIGRA (fire index of growth rate) [14] curves of the occur at shorter times. Curves of blended structures
fabrics show that the contribution to fire growth is show behaviour very close to virgin wool. It is a very
 X. Flambard et al. / Polymer Degradation and Stability 77 (2002) 279–284 283

interesting result compared to a yarn by yarn blended 3.2. Heat resistance of blended spun yarns
structure [2]. In this case, the smoke opacity was as high
as the PPTA alone. When fibres are intimately mixed, In the previous part, we have shown that we can get a
the smoke production is strongly reduced. synergistic effect by combining wool with p-aramid
fibres. It is then interesting to investigate the thermal
stability of the blends. TG curves show that the thermal
stability of spun yarn wool/PPTA blends increases when
the amount of PPTA increases (Fig. 5). The degradation
of the textiles starts at 280  C but the degradation rate
depends on the PPTA content in the blend. The
decomposition occurs in two main steps between 200
and 600  C [3, 15]. The residue is about 1–2 wt.%.
The degradation of PPTA is similar to the 25/75
blend.
To investigate the interactions between wool and
PPTA during the degradation, the curves of the weight
difference are plotted (Fig. 6). All the blends are stabi-
lized in the temperature range 200–560  C. This last
consideration is important because synergistic effect
could be expected between wool and PPTA when the
Fig. 7. TG curves of PPTA fibres under air and nitrogen flow (heating amount of PPTA is high enough. This result could
rate=10  C/min). explain the synergistic effects observed during the cone

Fig. 8. Stitch photographs (50/50 blended yarns) exposed during 30 min at different characteristic temperatures.
284 X. Flambard et al. / Polymer Degradation and Stability 77 (2002) 279–284

experiments. It can happen that an interaction between manufacturing spun yarns made with wool and PPTA
wool and PPTA fibres occurs during the combustion in fibres as an intimate mixture. These blended yarns
order to stabilise the material. This can be explained by improve the FR performance and the thermal stability
the improvement of the FR performance of the wool/ of the whole textile and synergistic effects are shown in
PPTA blends and in particular, in the case of the 70/30, terms of RHR peak reduction.
50/50 and 25/75 blends where the RHR peaks are lower In addition, there is an undeniable economic interest,
than the one of PPTA alone. because, textile structures made with these kinds of
spun yarns yield excellent thermal and mechanical
3.3. Mechanism of action behaviour [16] and ‘‘good handle’’ fabrics, while low-
ering cost.
In order to interpret the mechanism of the synergistic
effects happening during the combustion of the blends
with the cone calorimeter, we took micrographs of the Acknowledgements
fibres after a period in a furnace at different representa-
tive temperatures. This work is supported by the European project
Some knitted structures (50/50 Wool/PPTA) were FLAMERET (‘‘New Surface Modified Flame Retarded
exposed for 30 min at 250, 350, 450 and 550  C and Polymeric Systems to Improve Safety in Transportation
observed using an optical microscope. These tempera- and Other Areas’’ registered under the number No.
tures are chosen at points on the TGA curves of Fig. 5 G5RD-CT-1999–00120). The authors are indebted to
to obtain different degradation phases of the blends. Mr Dubusse from CREPIM for his skilful experimental
The micrographs are shown in Fig. 8. The char deposits, assistance in cone calorimeter experiments. Mrs. Sabine
produced by the wool degradation (dark fibres on the 3 Chlebicki is grateful acknowledged for experimental
first photographs at 250, 350 and 450  C), may hinder assistance in TGA/DSC experiments. Mr. Laurent
oxygen diffusion during the combustion stage. Indeed, Marquaire and Mr. Karim Asses are also acknowledged
PPTA fibres are very sensitive to oxygen during their for working on this project. We also acknowledge Paul
thermal degradation and Fig. 7 shows the degradation Bonte firm for giving PPTA slivers.
of PPTA under air flow in comparison with the degra-
dation of PPTA under nitrogen flow. Under nitrogen
flow, the TG curve is shifted forward 100  C (i.e. The References
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