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M. B U G G Y , A. C A R E W
Department of Materials Science and Technology, University of Limerick,
Limerick, Ireland
The static and dynamic mechanical properties of carbon fibre-reinforced PEEK (APC-2)
laminates subjected to long-term thermal ageing and cycling treatments have been studied
using three-point bend flexure tests. Results are discussed with respect to morphological
changes and degradation analysis. SIN curves were modelled using fatigue modulus
degradation data. Ageing laminates at high temperatures, for long time periods, between the
glass transition temperature, T9, and the melting temperature, Tin, caused a significant
reduction in mechanical properties. However, for short ageing periods, a crystal-perfection
process occurs which enhanced the low stress level fatigue resistance of both laminate
geometries.
1. Introduction
APC-2 is a thermoplastic-based composite reinforced
with carbon fibres. The matrix material polyetheretherketone (PEEK) is a semicrystalline polymer
whose micro-structure and, therefore, its mechanical
properties are influenced by the composite's previous
thermal history and manufacturing process [1,
2]. Changes in the overall crystal content, spherulitic
size and distribution and crystal orientation have been
reported for various processing routes [3]. A marked
reduction in delamination toughness was exhibited by
AS4/PEEK for cooling rates below 3 ~ min-1 [4].
This is believed to be a result of weak regions (uncrystallized) between highly ordered transcrystalline
layers [5]. Others found that the rate of cooling from
the melt is a much more important indicator of tensile
properties than measured per cent crystallinity values
[6]. Slow cooling and cooling more quickly from the
melt resulted in the same degree of crystallinity but
produced large differences in mechanical properties.
This highlights the importance of understanding and
controlling the matrix crystal structure.
Barton et al. [7] suggested that the performance of
APC-2 is not greatly dependent on thermal history
provided the matrix is adequately crystallized, i.e.
30%. However, post-annealing (ageing) improved the
transverse flexural properties slightly. Thermal analysis of these laminates revealed the introduction of a
secondary endothermic melting peak positioned just
above the annealing temperature [8, 9]. A number of
investigations into annealing effects on the mechanical
properties of P E E K have revealed the beneficial
effects of annealing and suggest that annealing enhanced the growth of secondary crystals corresponding to the lower melting endotherm previously
0022-2461
2. Experimental procedure
Laminates were produced by a two-stage compression-moulding process recommended by ICI [14] in
order to achieve optimum crystallinity. Statically tested laminates measured 50 m m x 12 m m x 1 mm and
both (0)s and (0/90)2 s laminate geometries were tested.
Flexural testing was performed on an Instron 4302 at
a crosshead speed of 1.3 m m m i n -1 and an aspect
ratio of 32/1. Flexural fatigue laminates measured
30 mm x 40 mm x 2 mm and both (0)16 and (0/90)4s
geometries were tested. Static strengths were measured. Fatigue testing was carried out at stress levels of
between 70% and 95% static strength. A stress ratio of
0.1 and a test frequency of 5 Hz were used in all cases
and a number of tests were carried out at each stress
level. Fatigue testing was performed on a Dartec
M100RE servohydraulic straining frame using a
50 kN load cell controlled by a 9500 Texas Instruments computer. Jig dimensions conformed to British
standards BS 2782: Part 3; Method 304E and all tests
were carried out at room temperature (RT).
Ageing temperatures of 120, 250 and 310 ~ were
selected. The lower temperature of 120 ~ was chosen
because it allows physical ageing of the polymer to
occur [15] and because it is considered to represent
1925
1926
2.30
106
0.024
(0/90)25
1.67
69.5
0.024
2.5
k+,,
2.0
Q..
(,..9
v
,,t"
1.5
rO3
=
1.0
LL
0.5
A
0.0
10
20
30
40
50
Time (wk)
60
70
8O
3.1. Fatigue
A fatigue modulus degradation model developed by
Hwang and Han [19], was directly applied to flexural
fatigue results generated by Dillon and Buggy 1-20],
for APC-2 laminates. This mathematical model was
also applied to laminates tested in this paper. As
previously reported [20], cross-ply laminates appear
to have a higher fatigue resistance up to 105-106 cycles
compared with unidirectional laminates, when their
SIN curves are normalized with respect to flexural
strength, Fig. 2. This is believed to result from greater
loading nose stress intensification in the unidirectional
system causing a rapid build-up of compressive matrix
damage. In general, the shape of the SIN curves
suggest that the fatigue properties are heavily fibre
dominated, especially for unidirectional laminates.
0
0.5
1
2
4
8
16
32
48
76
Flexural strain
Unidir.
Cross-ply
Unidir.
Cross-ply
Unidir.
Cross-ply
106.0
100.3
69.5
68.3
2296
2311
1670
1690
0.024
0.022
0.024
0.024
1561
1592
1594
1597
976
543
172
0.024
0.022
0.020
0.021
0.014
0.008
0.006
0.022
0.023
0.021
0.020
0.013
0.007
0.005
97.6
98.9
113.1
113.5
111.9
98.6
63.8
70.3
67.6
74.2
77.3
76.8
68.6
38.9
2409
2120
2364
2446
1523
826
373
TABLE III The effects of thermal cycling APC-2 laminates from room temperature to 250 ~ on their mechanical properties
Time (wk)
0
0.5
2
4
8
16
32
48
76
Flexural strain
Unidir.
Cross-ply
Unidir.
Cross-ply
Unidir.
Cross-ply
106.0
99.7
69.5
70.8
2296
2240
1670
1535
0.024
0.022
0.024
0.021
97.7
98.5
71.3
67.9
2406
2356
1702
1550
0.025
0.028
0.024
0.023
1565
1135
543
243
0.020
0.015
0.009
0.005
0.019
0.015
0.008
0.005
112.6
t08.7
100.8
59.7
76.1
75.0
71.0
45.6
2209
1574
913
346
32 wk
Weight loss of
composite (%)
0.2
( = 0.6 matrix)
0.8
( = 2.4 matrix)
Flexural strength
(MPa)
2446
1523
Flexural modulus
(GPa)
113.5
Ill.9
Crystallinity (%)
(DSC)
25
42
Crystallinity (%
(XRD)
25
26
Strain
Fractography
0.20
0.14
Ductility excellent
Reduced ductility
Neutral axis
is central
Neutral axis
shifted towards
compressive surface
1 927
TABLE V The effects of ageing of APC-2 laminates at 310 ~ on the mechanical properties
Time (wk)
0
0.5
I
2
4
7
8
Flexural strain
Unidir.
Cross-ply
Unidir.
Cross-ply
Unidir.
Cross-ply
106.0
96.7
74.2
88.2
64.6
20.0
12.8
69.5
66.2
65.2
67.8
31.0
12.3
2296
2252
1575
984
976
527
386
1670
1600
1513
626
413
289
-
0.024
0.022
0.022
0.016
0.015
0.028
-
0.024
0.023
&023
0.010
0.005
0.016
1.0
1.0
0.9
0.9
0.8
~- 0.8
c-
0.7
0.7
0.6
0.6
X
~0.5
--- 0.5-
0.4
0.4-
0.3
0.3.
0.2
0.2
0.1
0.1
0.0
0
--+- I
1
-I
0.0
I l l l l - I I l ~ l l l t
control unidirec-
1,0
0.9
0.80.75 0.6X
0.50.4
E 0.3
0.2
0.10.0
1928
Acknowledgement
1,0
0.90.8t-
References
0.7-
1.
X
Q
,+-
O,6-
"- 0.52.
'~ 0 . 4 E
0.3-
3.
4.
:~ 0.20.1
5.
0.0
I I
I I I
I
6
6.
7
for (
---)
t wk, ( - - - ) 2 wk, ( - - - - - )
4 wk; (
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
4. Conclusion
Ageing laminates at a temperature below the Tg of
the matrix revealed no significant property changes.
Ageing at higher temperatures between Tg and Tin,
caused a marked reduction in flexural properties. This
is considered to result from matrix degradation. However, ageing for short time periods enhanced the low
stress level fatigue resistance of the composite. Thermal cycling at such temperatures exhibits similar
trends but at a slower rate.
19.
20.
21.
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Received 28 September
and accepted 19 October 1993
1929