Cryogenics 50 (2010) 84–88

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Cryogenics
journal homepage: www.elsevier.com/locate/cryogenics

Mechanical and thermal expansion properties of glass fibers reinforced PEEK

composites at cryogenic temperatures
X.X. Chu a,b, Z.X. Wu a,b, R.J. Huang a,b, Y. Zhou a, L.F. Li a,*
a
The Key Laboratory of Cryogenics, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, PR China
b
Graduate University of Chinese Academy of Sciences, Beijing 100039, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Polyetheretherketone (PEEK) has been widely used as matrix material for high performance composites.
Received 11 August 2009 In this work, 30% chopped glass fibers reinforced PEEK composites were prepared by injection molding,
Received in revised form 6 November 2009 and then the tensile, flexural and impact properties were tested at different temperatures. The modulus,
Accepted 3 December 2009
strength and specific elongation of glass fibers reinforced PEEK at room temperature, 77 K and 20 K have
been compared. And the fracture morphologies of different samples were investigated by scanning elec-
tron microscopy (SEM). The results showed a dependence of mechanical properties of glass fibers rein-
Keywords:
forced PEEK composites on temperature. The coefficient of thermal expansion of unfilled PEEK and
PEEK
Glass fiber
glass fibers reinforced PEEK were also investigated from 77 K to room temperature. The results indicated
Mechanical properties that the thermal expansion coefficient (CTE) of PEEK matrix was nearly a constant in this temperature
Thermal expansion region, and it can be significantly decreased by adding glass fibers.
Low temperature Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction
Polyetheretherketone (PEEK) is an important engineering mate-
rial. As a typical high performance semicrystalline thermoplastic
polymer, PEEK has received significant attentions in recent years.
This is due to its high mechanical strength and elastic modulus,
good combination of thermal and mechanical properties, chemical
inertness, high toughness, easy processing, high wear resistance
and friction coefficient [1–3]. This thermoplastic has a melting
point of 608 K, and glass transition of 417 K. It can be used contin-
uously up to 520 K without any permanent loss of mechanical
properties. PEEK and its composites are good candidate materials
for a variety of structural applications in aerospace, biomechanics,
automotive and chemical industries. In space application, PEEK is
applied for replacing aluminum because of its superior perfor-
mance at high temperatures. In addition, PEEK is also one of a
new generation of engineering polymers which has good cryogenic
properties.
Since glass fibers (GFs) have high strength, high flexural modu-
lus and low expansion rate, they are the most common fiber rein-
forcements in thermoplastics to reduce the expansion rate and
increase the flexural modulus of PEEK [4–7]. For cryogenic engi-
neering applications, the mechanical properties of PEEK compos-
ites are highly related to the changes of temperature. A few
researchers focus on the performance of glass fibers reinforced
* Corresponding author. Tel.: +86 10 82543699.
E-mail address: laifengli@mail.ipc.ac.cn (L.F. Li).
PEEK around room temperature [8,9]. However, the results about
the mechanical and thermal properties obtained from room tem-
perature cannot simply be transferred to the cryogenic case. Thus,
it is important and necessary to study the relative properties at
cryogenic temperature of GFs/PEEK for cryogenic engineering
applications. So far, to our best knowledge, few researchers focus
their attentions on the changes of strength and modulus of GFs/
PEEK composites at low temperatures. In addition, as is well-
known to everyone, the most of materials expand on heating while
contract on cooling. Such a volumetric change may cause problems
in processing of casting and injection moldings, where contractions
occurring upon cooling to operating temperatures can cause frac-
ture or defects so as to lower the performance. The mismatch of
thermal expansion coefficients at cryogenic temperature always
brings serious problems. Therefore how to control the thermal
expansion of materials is very important in cryogenic engineering.
In this work, PEEK containing 30% short-cutting glass fibers in
volume fraction were produced by injection molding. Their
mechanical properties and thermal expansion coefficients were
studied at room and cryogenic temperatures. SEM observation of
the fracture surfaces is performed to get insight into the strength-
ening and toughening mechanisms of GFs/PEEK after testing.
2. Experiment processes
The PEEK matrix (PEEK 150PF) was supplied by ICI company,
UK. The short-cutting glass fibers were supplied by Research Insti-
tute of Synthetic Crystals, Nanjing. The diameter and length of

0011-2275/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cryogenics.2009.12.003
 X.X. Chu et al. / Cryogenics 50 (2010) 84–88
glass fibers were 9 lm and 3 mm respectively. Because the rein-
forcement of PEEK composites was dependent on the GFs volume
fraction and the interface bonding situation between GFs and PEEK,
the ratio of GFs and PEEK was important. In our preliminary works
we found doping 30% volume fraction of GFs in PEEK matrix dis-
played the best enhancement effect, so in this study we chose
30% GFs as the filler. The mixture of PEEK and glass fibers was
achieved by twin-screw-extruders at about 660 K with standard
screw configurations. The composites were finally manufactured
using an injection molding machine at a barrel temperature of
660 K. The injection pressure was kept constant at 1400 bar, and
the mould temperature was fixed at 330 K. A constant injection
speed was applied at all the process.
Tensile and flexural test were carried out using MTS-SANS
CMT5504 testing machine at 20 K, 77 K and room temperature.
The cross-head speeds are 2 mm/min and 1 mm/min for tensile
and flexural testing respectively. Impact test was carried out using
MTS-SANS ZBC2000 testing machine. Impact specimens were im-
mersed in cryogenic liquids for over 5 min and then impact testing
was completed in seconds after taking the specimens out from the
cryostat. Five specimens were tested for each composition to im-
prove the reproducibility. The geometries and dimensions of the
specimens for the experiments were shown in Fig. 1. The tensile,
flexural, impact test and the calculation of experimental results
were in accordance with the national standards as GB/T 1447-
2005, GB/T 1449-2005 and GB/T 1451-2005 respectively.
Thermal expansion coefficient (CTE) of PEEK was measured
using the strain gauge technique in self-designed experimental de-
vice from 77 K to room temperature. In our measurement, quartz
was used as a reference specimen because of its low CTE, and
120 X strain gauge were bonded to the surface of specimen with
ultra thin low temperature resistant glue, so that the strain gauge
and the specimen have the same strain when the temperatures
vary. As the relative change in length DL/L of strain gauge could
be detected electrically by the relationship DL/L = (1/KS) DR/R,
where KS is the gauge factor, DR/R is the relative change in the elec-
trical resistance of strain gauge. So strain gauges in sample and
quartz were connected to form a half-bridge circuit to measure
Fig. 1. The geometries and dimensions of the specimens for (a) tensile and (b) flexural and impact.
85
the DR/R, and the strain DL/L was collected by computer. Conse-
quently the CTE of GFs/PEEK can obtain from the slope of strain-
temperature curves.
The fracture surfaces of GFs/PEEK composites were examined
by SEM (Hitichi S-4300). Before SEM examination, the fracture sur-
face were cleaned with alcohol and then coated with a thin gold
layer to improve image quality.
3. Results and discussion
3.1. Mechanical performance
The tensile, flexural and impact test results of 30% chopped
glass fibers reinforced PEEK are shown in Table 1. The data are
based upon the average of five testing specimens. From Table 1,
it is found that the mechanical performances are dependent on
temperatures, which are illustrated in Fig. 2. From Table 1 and
Fig. 2 we can see that the tensile strength and modulus tend to in-
crease as temperature decreases from 295 K to 20 K. These results
are very similar to those for other polymer materials [10,11]. It can
be imagined out that molecules are more closely compacted and
the binding forces between molecules are high at cryogenic tem-
perature which makes the positive contributions to the tensile
strength and Young’s modulus. The interface adhesion between
glass fibers and PEEK matrix becomes stronger because of the ther-
mal shrinkage of PEEK matrix and tight clamping of the GFs by the
PEEK matrix at cryogenic temperature.
As expected, the tensile strength, tensile modulus and impact
ductility at low temperatures are much higher than those at ambi-
ent temperature. Furthermore, it is observed that the elongation
and deflection at break at low temperature are much lower than
that at ambient temperature. It is well-known that for an engineer-
ing material, crack propagation would proceed along the weakest
paths in the matrix. At cryogenic temperatures (20 K and 77 K),
the matrix becomes more brittle, and the glass fibers would play
a less role in resisting the propagation of cracks. As a result, cracks
would more easily occur in the matrix and the failure strains and
deflection are much lower at cryogenic temperatures than that at
86 X.X. Chu et al. / Cryogenics 50 (2010) 84–88

Table 1
Tensile, bending and impact test results of 30% chopped glass fiber reinforced PEEK.

Test Tensile strength Tensile modulus Elongation at Flexural strength Flexural modulus Deflection at break Impact strength
temperature (K) (MPa) (GPa) break (%) (MPa) (GPa) (mm) (kJ/m2)
20 200 18.1 1.98 346 14.6 3.67 23.7
77 192 15.7 2.16 381 13.5 4.78 19.5
295 139 11.6 2.49 408 12.6 5.35 17.9

ambient temperature. However, the flexural strength of GF/PEEK

composite has a slightly decrease as it is cooling down. This may
be attributed to that the better ductility of GFs at room tempera-
ture than cryogenic temperature. As seen in Table 1, the deflection
increases accompanying the temperature increases. Even though
the flexural strength is lower, as expected, the flexural modulus
at cryogenic temperature is higher than that at room temperature
due to the tight arrangement of PEEK molecules.
A further comparison of the properties of GFs/PEEK composites
at different temperatures were presented below in Fig. 3 by the
tensile stress–strain curves and in Fig. 4 by flexural load–deflection
curves. From the stress–strain curves in Fig. 3 we can observe that
the tensile strength at cryogenic temperature was higher than
those at room temperature. And the tensile strain was increased
with the temperature increased from 20 K to 295 K. That was to
say the tensile strength and elongation at break of GFs/PEEK were
a function of temperature. These can be mainly attributed to the
following reasons. For one thing, because of the thermal shrinkage
of PEEK matrix, the GFs/PEEK matrix interface adhesion was stron-
Fig. 3. Stress–strain curves of 30% glass fibers reinforced PEEK at 20 K, 77 K and
ger at low temperature than at room temperature, leading to a
295 K.
higher composite strength. For another, the molecules of polymer
matrix was tightly frozen at cryogenic temperature, resulting in a
higher strength than that at room temperature. However, at the tensile testing, the direction of load when flexural or impacting
same time, with it was cooled down the GFs/PEEK matrix became was vertical to the specimens.
more brittle. When the load reached the critical intensity of com- The fractured surfaces of PEEK composites examined by SEM
posites, the brittle fracture accrued and the composites fractured are illustrated in Fig. 5. As seen in all the photographs, the glass fi-
in a sudden, leading to a lowest elongation at 20 K. From the bers were dispersed orderly in matrix. Short pull-out lengths of the
load–deflection curves we can obtain the similar conclusions. Just fibers were the evidence of strong fiber/matrix interfacial bond.
like the temperature dependence of elongation, the lower the tem- Image (a)–(c) were the fractured morphology after tensile tests
perature it was, the smaller deflection it exhibited. However, the at 295 K, 77 K and 20 K respectively. It can be seen in these three
fracture load was a little lower at cryogenic temperature. This images that glass fibers were pulled out in tensile tests. Specimens
may also be contributed to the brittleness of matrix with the tem- fractures at low temperatures as (b) and (c) exhibited the effect of
perature decreased, and the influence of brittleness was more sig- pulling more intuitive. This was because with the temperature de-
nificant to flexure and impact than to tensile, because unlike the creased the PEEK matrix became more brittle. From the short fibers
in photograph (c) and the small hole in (b), we can easily image the

Fig. 2. Tensile modulus, flexural modulus, impact strength and elongation at break Fig. 4. Load–deflection curves of 30% glass fibers reinforced PEEK at 20 K, 77 K and
as a function of temperature. 295 K.
 X.X. Chu et al. / Cryogenics 50 (2010) 84–88 87

Fig. 5. SEM micrographs taken from the fracture morphology of chopped glass fibers reinforced PEEK: (a) tensile fracture at 295 K, (b) tensile fracture at 77 K, (c) tensile
fracture at 20 K, (d) flexural fracture at 295 K, (e) flexural fracture at 77 K and (f) flexural fracture at 20 K.

process of fibers being pulled out when in tensile tests. Image (d)–
(f) were the flexural fracture micrographs at 295 K, 77 K and 20 K
respectively. It also can be observed that many fibers were frac-
tured in a sudden, but the surfaces were smoother because the
direction of the flexural force was vertical to the samples. Com-
pared with micrographs in different temperatures, it can be ob-
served that fractures in 295 K were rougher than that in 77 K and
20 K. It was due to that with the temperature decreased, there
was a tendency towards increasing of brittleness in the PEEK com-
posites. Cracks would more easily to occur at cryogenic tempera-
ture than that at ambient temperature. So it was also can explain
the fact that elongation and deflection at break were decreased
accompanying with the temperature decreased, which reached to
the minimum at 20 K.
3.2. Thermal expansion coefficient
The linear thermal expansion coefficient is a sensitive measure
of the physical state of a polymer. It is known from earlier works
[12] that the CTE of unfilled PEEK is over 40  106 K1. Glass fiber
has a very low coefficient of thermal expansion, which ranges from
5  106 K1 to 12  106 K1 with different chemical compo-
nents, so it is always used as additives to reduce the CTE of other
polymer matrixes. The DL/L(300 K) obtained for unfilled PEEK and
30% chopped glass fiber reinforced PEEK at different temperatures
are shown in Fig. 6. It is clearly seen that the unfilled PEEK has a
much larger strain than the glass fiber reinforced PEEK with the
temperature decreased. From the slope in this Figure, we obtained
that the average CTE of neat PEEK and 30% glass fiber reinforced
PEEK are 46.5  106 K1 and 14.4  106 K1 respectively in the
temperature range of 77–295 K. This result indicates that the
chopped glass fiber as the filler significantly reduce the thermal
expansion of PEEK composites.
Two models have been used to predict the CTE of GFs/PEEK
composites, including the simple rule-of-mixture (ROM) [13] and
the Turner’s model [14]. The ROM serves as the first-order approx-
imation to the overall calculation of the CTE of the composites.
ac ¼ am V m þ af V f ð1Þ
In this equation ac, am and af represent the CTEs of the composites,
matrix and filler, respectively, and Vm and Vf represent the volume
fraction of matrix and filler respectively. In Turner’s model the
88 X.X. Chu et al. / Cryogenics 50 (2010) 84–88
Fig. 6. Linear thermal expansion of glass fibers reinforced PEEK in a cooling process.
mechanical interaction between the different materials in the com-
posites is taken into account. Turner’s equation is given as
following:
am K m V m þ af K f V f
ac ¼ ð2Þ
KmV m þ Kf V f
where Km and Kf represent the bulk moduli of the matrix and filler,
respectively.
In our study, the glass fiber we used was e-glass fiber with CTE
about 10  106 K1 and modulus about 72 GPa, and the modulus
of unfilled PEEK was about 3.7 GPa. According to the ROM model,
we calculated the CTE of GFs/PEEK composite was 35.6  106 K1,
which was much higher than that we measured in the experiment.
Consequently, in this work it is hard to use ROM to explain the
decrease of CTE. From the Turner’s model, the CTE of composites
we obtained was 13.9  106 K1 at room temperature. At cryogenic
temperature region, the moduli of glass fiber and PEEK matrix
slightly increased, reaching to an average 86 GPa and 4.5 GPa
respectively. With these parameters we calculated the CTE of
composites was 14.0  106 K1 at low temperature. These two cal-
culation were very approximate to our experiment results, which
was 14.4  106 K1. In other words, the Turner’s model can well
predict the behavior of thermal expansion of glass fiber reinforced
PEEK. In the experiment, the chopped glass fibers have a length of
about 3 mm, which is different from other particles in mixtures. Be-
sides, PEEK is semicrystalline, with a crystallinity of 15–35%. It may
therefore be regarded as a two-phase composite consisting of crys-
talline regions embedded in an amorphous matrix. After homoge-
nized by mixing, the glass fibers and PEEK integrated well with
each other, and all the glass fibers formed a net analog. When tem-
perature cooled down, the glass fibers with high modulus and low
CTE inhibited the shrink of PEEK molecules, especially inhibited
the shrink of amorphous regions of PEEK matrix. The high modulus
of glass fiber and the interaction between filler and matrix played an
important role in decreasing the CTE of the PEEK composites. As a re-
sult, the CTE of the composites was far below comparing to the un-
filled PEEK. So the experiment result deviated from the ROM model a
lot.
On the other hand, from the prediction according to Turner’s
model, we can conclude that there was little influence of temper-
ature to the CTE of GFs/PEEK composites. This conclusion was also
identical to our experiment. From the Fig. 6, we can see that the
DL/L(300 K) were nearly linear in the whole measuring temperature
range, indicating the CTE was almost constant. As the glass transi-
tion temperature of PEEK is 417 K, it can conclude that there is
little influence of temperature in this range to CTE of PEEK compos-
ites. As PEEK is expected to be used in many areas, it always needs
to be joined to other components for structure requirement. Exces-
sive thermal mismatch can cause failure in joints with heat parts
and coolant manifolds connected to these structures. Glass fibers
reinforced PEEK can markedly minimize the CTE of PEEK matrix,
as a result, the thermal stresses in braze joints and the problem
of thermal mismatch can be minimized.
4. Conclusions
The temperature dependence of mechanical properties and
thermal expansion coefficient of 30% chopped glass fibers rein-
forced PEEK prepared by injection molding have been studied in
this paper. From the mechanical properties testing we can know
that the tensile strength, tensile modulus, flexural modulus and
impact strength of GF/PEEK at cryogenic temperatures are higher
than those at room temperature. The elongation and deflection at
break obviously increased with the increase of temperature. From
the results it can be found that GF/PEEK has a better ductility at
room temperature than at cryogenic temperature. The fracture sur-
faces were examined by SEM to explain the observation of the frac-
ture behaviors. The results from thermal expansion coefficient
measurement show that the temperature has little influence to
the thermal expansion property of PEEK matrix. And the average
CTEs of neat PEEK and GFs/PEEK from 77 K to 295 K are
46.5  106 K1 and 14.4  106 K1, respectively. It can conclude
that glass fibers as the filler can significantly decrease the CTE of
PEEK matrix.
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