Composite Structures 73 (2006) 303309

www.elsevier.com/locate/compstruct

Eects of cure cycles on void content and mechanical properties

of composite laminates
Ling Liu *, Bo-Ming Zhang, Dian-Fu Wang, Zhan-Jun Wu
Center for Composite Materials, Harbin Institute of Technology, Harbin 150001, PR China

Available online 9 April 2005

Abstract

Various curing cycles were designed to evaluate the eects of dierent pressure induced voids on some mechanical properties of
carbon/epoxy laminates and optimum cure pressure time. A series of [0/90]3s laminates with varying void contents were fabricated
and a characterization of void distribution, size, and shape within the laminates was obtained using ultrasonic c-scan and optical
metallography techniques. Short beam shear, three-point exure and tensile testing were used for mechanical evaluation and the
results correlated to void volume fraction and ultrasonic absorption coecient. The experimental results have shown that there
exists an optimum time for applying pressure. The proposed grading evaluation method of ultrasonic inspection is helpful for
the nondestructive examination of composites. Also, changes in mechanical performance due to porosity are consistent with previ-
ously published studies.

2005 Elsevier Ltd. All rights reserved.

Keywords: Composites; Autoclave curing; Void content; Mechanical strength; Ultrasonic inspection

1. Introduction formance signicantly. So the cure cycle pressure is usu-

One of the most often used production procedures for
fabricating a high-performance structural laminate is the
autoclave curing process. The presence of voids in the
nal part is an unavoidable fact. They are formed primar-
ily due to the mechanical air entrapment during the lay-up
and moisture absorbed during the material storing. The
inclusion of voids in the nal part will have a detrimental
impact on the mechanical properties of the composites
[17]. Hence, the removal of voids is quite critical in many
advanced composite aerospace structures.
Some of the cure cycle parameters such as tempera-
ture and pressure have been found to aect the void con-
tent of carbon/epoxy laminates. The temperature
schedule recommended by the manufacturers should
avoid any modication that will alter the structural per-
*
Corresponding author. Tel.: +86 451 8641 4323.
E-mail address: liulingworld@mail.tongji.edu.cn (L. Liu).
ally considered as the process parameter to be optimized
[68]. The magnitude of cure pressures and the moment
of applying pressures will have important eect on the
void content of the laminates. If those two factors are se-
lected properly, then the entrapped air, water vapor and
excessive resin will be squeezed out from the laminates,
and laminates with low porosity and high performance
will be achieved.
However, it may result in serious economical conse-
quence due to excessively high acceptance levels for de-
sign performance requirements. In many composite
applications, the void content is quite critical and levels
above about 1% are not tolerable, such as in advanced
composite dynamic aerospace structures. In other appli-
cations, levels of 5% and higher can be tolerated [5]. For
advanced composites, because of the wide range of
microstructural and macrostructural options available,
even within a given processing technology, the cost dif-
ference between alternative designs can be enormous [9].
It is possible to obtain 90% of the performance at 60%

0263-8223/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compstruct.2005.02.001
304 L. Liu et al. / Composite Structures 73 (2006) 303309

of the cost, the last 10% of performance being 40% of 200

12 viscosity
the cost [10]. The engineer can cut production costs by -------- temperature
d
knowing the acceptable void level for the particular 10 160
application. Loosening the quality control standards g f e c

Temperature (C)
Viscosity (Pa.s)
8 b
translates to a lower cost end product [5]. 120
Therefore, establishing the acceptable level of voids is 6
a
a critical issue in designing composite structures. So, 80
structural composite components must be inspected 4

for manufacturing induced defects such as voids that 2

40
may have detrimental eects on the structural response. A B

Ultrasonic inspection is the most used nondestructive 0

technique to detect the presence of manufacturing de-
fects in composite parts. For quality control purposes,
it is natural to dene the maximum acceptable void con-
tents in terms of ultrasonic attenuation rather than di-
rectly establishing a maximum percentage of voids in
the material [1]. Therefore, a practical model should be
able to predict the porosity levels of the laminate
through the ultrasonic attenuation levels.
The research presented in this paper is part of an
investigation aimed at obtaining an optimal cure cycle
as well as evaluating the eects of pressure conditions
on the void contents and mechanical properties. Two
groups of experiments were carried out according to
rheological and DSC tests: the rst group was designed
to assess the eects of dierent cure pressures on the
void contents of the laminates; the second group was
performed to determine the optimum time of applying
autoclave pressures. Ultrasonic attenuation and micro-
scopic inspection was carried out to analyze the distribu-
tion, size and shape of voids. Void contents were
measured according to the ASTM 3171 standard test.
Short beam shear, three-point exure and tensile testing
were used for mechanical evaluation.
2. Experimental procedures
2.1. Material and cure cycle design
2.1.1. Material
The material under research was T700/TDE85 car-
bon ber reinforced epoxy prepreg. The initial ber vol-
ume fraction Vf is 60 2 vol% and the prepreg, ber and
0 30 60 90 120 150 180 210
Time (min)
Fig. 1. Plot of viscosity versus time and temperature.
2.1.3. DSC test
The DSC test was performed from 47 C to 277 C at
the rate of 10 C/min on a dierential scanning calorim-
eter (PE DSC-7). The rate of heat generation was plot-
ted versus temperature as shown in Fig. 2.
2.2. Fabrication of laminates
Rheological and DSC tests were performed to deter-
mine the moment at which the cure pressure must be in-
creased. According to the test results, two groups of cure
pressure cycles were selected to assess the inuence of
voids on the mechanical properties. One group kept
the rst isothermal time as 120 min and changed the
autoclave pressures, those pressures are set as 0.0, 0.1,
0.2, 0.4 and 0.6 MPa. The second group selected the
temperature to be held at 120 C for 30 min (a),
60 min (b), 0 min (c), and 120 min (d). The autoclave
pressure was increased to 0.2 MPa at the end of the
dwell time. The times at which the pressure was applied
were chosen with respect to the minimum viscosity and
the gelation points. The pressure inside the vacuum bag
was 0.1 MPa and remained so throughout the entire
cycle for all experiments.
14
Heat of reaction (Mcal/sec)

uncured resin densities are also known. 12 C

10
2.1.2. Rheological Tests
The viscosity was measured on an improved NDJ-7 8
rheometrics. The procedure consists of simulating the 6
temperature conditions of the manufacture recom-
4
mended cure cycle. The temperature was increased to
120 C at a rate of 2 C/min and was held for 2 h. Then 2
it was further increased to 160 C at the same rate and 0
0 50 100 150 200 250 300
held for some hours. Finally it was cooled to room tem-
Temperature (C)
perature. The results of viscosity, plotted versus time
and temperature, are shown in Fig. 1. Fig. 2. Heat of reaction as a function of temperature.
 L. Liu et al. / Composite Structures 73 (2006) 303309
So the rst group included ve plates and the second
group included four plates. Three laminates with 12
plies, [0, 90]3s, were manufactured as described above
for each of the cure routes considered, respectively. Each
plate was approximately 300 mm (length) 300 mm
(width) 2 mm (thickness).
2.3. C-scan ultrasonic inspection
All the laminates were inspected using immersion c-
scan ultrasonic testing. The scanning was carried out
using the double-through-transmission technique. The
probes were transported by an automation M400D sys-
tem (host machine is SONIC138VFD) that generated
a quantized c-scan record of the plate with a working
frequency is 5 MHz. An actual size map of the plate
was generated after scanning, associating a color to each
attenuation level. This feature was used to identify areas
of constant porosity level. Three independent scans of
each plate were performed to measure the absorption
coecient of the selected areas with approximately uni-
form porosity level. The average value of these measure-
ments is considered as the absorption coecient of the
samples, respectively.
2.4. Assessment of void content
After c-scan inspection, specimens were cut and their
densities were determined in order to estimate the void
content. The density of each composite sample was
determined using the water displacement method by
measuring its weight in air and in water. The void con-
tent was measured by matrix digestion in heated concen-
trated sulfuric acid according to the ASTM 3171
standard test. The void content measurement was made
with three test pieces on each plates and the average was
taken to be as the normal void content. Specimens with
dierent porosities levels ranging from 0 to 3.5% were
obtained for this carbon/epoxy laminates.
2.5. Microstructural analysis
Optical microscopy and image analysis were em-
ployed to characterize the void location, void size, and
void shape in the carbon/epoxy laminates. A ZEISS
MC80DX Microscope equipped with a camera and an
image processing system was used for all analyses. The
samples were mounted, polished, and photographed at
various magnications (80 to 200) via the optical
microscope. Typical photomicrographs appear in Fig. 7.
2.6. Mechanical testing
To assess the inuence of voids on the mechanical
strength of the T700/TDE85 carbon epoxy laminates,
short beam shear (ASTM D2344), three-point exure
305
(ASTM D790) and tensile testing (ASTM D3039) were
used for mechanical evaluation. Five mechanical prop-
erties were measured: interlaminar shear strength
(ILSS), exural strength, exural modulus, tensile
strength and tensile modulus. Each test for those prop-
erties included ve to twelve specimens. The relationship
between void content and mechanical properties was
then determined by correlating the experimental data.
3. Results and discussion
3.1. Cure cycles and void contents
Rheological tests provide some information used to
determine the moment at which the pressure must be in-
creased. The results are shown in Fig. 1. It shows that
there exists one minimum viscosity platform (from point
of A to B) in the viscosity versus time curve. At the end
of the platform the viscosity increases quickly with time
or temperature owing to the initiation of cure reactions.
To conrm this view, a DSC test was performed to give
some useful information for determining the optimum
time for applying pressure (Fig. 2). It has been shown
that the initiation of resin reaction in Fig. 2 (point C)
corresponding to the increasing point of resin viscosity
in Fig. 1 (point B).
Physically, void removal by pressurization is feasible
in that pressurization results in void dissolution [11,12].
Eorts were made to describe the eects of cure pressure
conditions on void contents. A set of cure cycle pres-
sures, 0.0, 0.1, 0.2, 0.4 and 0.6 MPa, were used. The void
content of each type of laminate is plotted in Fig. 3 as a
function of the cure pressure. It shows that an exponen-
tial decrease tting curve can realistically characterize
the relationship between the void content and cure pres-
sure. This result is similar to the work of Olivier and
Tang et al. [6,7]. Therefore, an applied autoclave pres-
sure is necessary to reduce the void percentage down
to an acceptable level. So, for a particular application,
4.0
3.5
3.0
Void content (%)
2.5
2.0
1.5
1.0
0.5
0.0
0.0 0.2 0.4 0.6 0.8
Pressure (MPa)
Fig. 3. Measured void contents as a function of cure pressures.
306 L. Liu et al. / Composite Structures 73 (2006) 303309
we can determine an appropriate magnitude of curing
pressure according to the void levels required when the
other process parameters remain unchanged.
In fact, the cure temperature cycle, marked with a, b,
c and d in Fig. 1, is a conservative temperature cycle rec-
ommended by the manufacturer which is mainly used
for match die processes. Experiments were carried out
to show whether the rst dwell time is the optimum
time. Hence, the time for increasing the autoclave pres-
sure within the range of minimum viscosity was set as
30, 60, 90 and 120 min. Fig. 4 shows the results of void
contents varying with the rst dwell time. It shows that
the optimum moment of applying pressure is not
120 min but 90 min. There exists one time span for
applying autoclave pressures, and if the level of porosity
limits to less than 1.5%, the time span would be chosen
between the 50 and 90 min. While the last span from 90
to 120 min can be pass over. Here we are concerned only
3.0
2.5
Void content (%)
2.0
1.5
1.0
0.5
0.0
0 30 60 90 120
Dwell time (min)
Fig. 4. Measured void contents as a function of the rst dwell time.
Fig. 5. C-scan showing areas with dierent void contents: (a) cure pressure is 0.0 MPa, (b) cure pressure is 0.6 MPa, (c) presentation of grey level and
its porosity.
with the values of porosity and do not take the mechan-
ical properties of the laminates into account. The resin
viscosity aects the resin ow and also aects the trans-
port of voids and, to a limited degree, their formation
and growth. Experimental results show that the resin
can ow fully in the time span from 50 to 90 min and
an improved and optimum cure cycle was obtained
namely a, b, e and d shown in Fig. 1. This improved cure
cycle can obviously shorten the time of processing in a
cost-eective manner.
3.2. Ultrasonic attenuation
Fig. 5 shows a c-scan of the laminates studied using a
double-through-transmission technique with pressures
0.0 MPa (a) and 0.6 MPa (b). It shows the distribution
and location of porosity. Fig. 5(c) gives the presentation
of grey levels associated with each attenuation level, de-
noted as the echo amplitude 100807570656055
50(1) 0%. The area of porosity corresponding to each
echo amplitude mentioned above is obtained as 0.0,
1.0, 1.3, 1.6, 1.9, 2.3, 2.7, 3.1 and 18.9% (this value cor-
responds to the echo amplitude 1%). It was calculated
from the experimental results of ultrasonic attenuation.
So, the area porosity levels of above are aected by fre-
quency and echo amplitude of ultrasonic inspection,
material types such as the ber and matrix, and the
thickness of the composite laminates and so on. This
method is a quantitative grading evaluation criterion
that will be greatly useful in engineering applications.
150 The calibration of the absorption coecient to the
porosity determined by acid digestion is shown in
Fig. 6, where the attenuation coecient is measured in
 L. Liu et al. / Composite Structures 73 (2006) 303309 307

4.0 morphology of the voids are determined by the used

data
3.5 fit of data processing parameters and physical properties of the re-
sin. However, the void content is a volume characteristic
3.0
and void locations and sizes must be taken into account
Void content (%)

2.5 in order to predict the inuence of voids on mechanical

2.0 properties. So, optical assessment of void content in-
1.5 creased our understanding of the void sensitivity of
strength.
1.0

0.5 3.4. Mechanical properties analysis

0.0
1.6 1.8 2.0 2.2 2.4 2.6 2.8
As has been shown in the previous section, the cure
Absorption coefficient (db/mm)
pressure has a signicant eect on the void content. In
Fig. 6. Correlation between void contents and absorption coecient. turn, the void content (and cure pressure) inuences
the mechanical properties. The measured ILSS, exural
and tensile strengths and moduli are presented in Figs. 8
dB/mm and depends on the internal condition of the
and 9. As was shown both the strengths and moduli de-
laminate, particularly, on the void content according
crease with increasing void content. However, the drop-
to Almeida and Nogueira Neto [3]. As expected the
o rate is dierent; the decreasing percentage for ILSS is
smallest absorption coecient correspond to the low
the largest. The exural modulus seems to decreased
porosity laminates. This suggests that a greater void
asymptotically with increasing void contents. As for
content causes increased attenuation and a linear corre-
lation between the porosity and absorption coecient
can be observed for laminates with porosity range from
Cure pressure (MPa)
0 to 3.5%.
0.6 0.4 0.2 0.1 0.0

3.3. Optical image analysis shear strength

100 flexural strength
tensile strength
Strength fraction (%)

95
A better characterization of pore size, shape, and
location within the laminates was obtained using stan- 90
dard optical metallography techniques. A photomicro-
85
graph of a sample of low porosity laminate is shown
in Fig. 7(a), which has the void content of 0.6% with 80
the curing pressure 0.6 MPa. In this gure, the voids
75
are shown as holes and most of them are spherical.
Fig. 7(b) shows the occurrence of much larger and at- 70
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
tened and elongated voids distributed in the samples
Void content (%)
with cure pressure 0.0 MPa. As can be seen, the voids
occur mostly at the ply interface. The dierences in the Fig. 8. Relationship between strength and void content (or pressure).

Fig. 7. Photomicrograph of voids with dierent cure pressures. (a) with curing pressure 0.6 MPa, (b) with curing pressure 0 MPa.
308 L. Liu et al. / Composite Structures 73 (2006) 303309

Cure pressure (MPa)

1.2% 0.9% 2.0%
0.6 0.4 0.2 0.1 0.0 100
2.2%

Modulus fraction (%)

100
95
Modulus fraction (%)

95

90
90

85 85 flexural modulus
tensile modulus

80 flexural modulus 80
tensile modulus 0 30 60 90 120
75
Dwell time (min)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Void content (%) Fig. 11. Relationship between modulus and the rst isothermal time.

Fig. 9. Relationship between modulus and void content (or pressure).

(1) shear strength data
(2) flexural strength data
100 (3) tensile strength data
the tensile modulus, there appears to be little decrease fit of (1)

Strength fraction (%)

with increasing porosity shown in Fig. 9. 95 fit of (2)
fit of (3)
In Figs. 10 and 11, the plots of strengths and modulus
versus the rst dwell time at which the cure pressure is 90

increased, shows the existence of an optimum time for

85
applying pressure. As expected, the maximum strength
and modulus correspond to the minimum void contents. 80
It can be seen that if the required performance is 90%,
then the b-stage in Fig. 1 requires only 50 min (at the 75
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
end of which pressure increases to 0.2 MPa), which Void content (v%)
can completely meet these three requirements. While,
if those performance requirements are 100%, then the Fig. 12. Relationship between strength and void content.
time will be chosen as 90 min. Fig. 11 shows a similar
trend as Fig. 10.
Figs. 12 and 13 present the strength and modulus re- 100
sults for all sample laminates. As expected, the perfor- 95
Modulus fraction (%)

mance values decreases with the porosity of the

90
laminates (or with the absorption coecient). It can be
seen in Fig. 12 that the ILSS values are very sensitive 85
to the void content. There is a decrease of 18% in ILSS 80
when the void content goes from 0.6 to 3.2% and in the 75 (1) flexural modulus data
range from 0 to 3. 5%, each 1% increase in void content (2) tensile modulus data
70 fit of (1)
decreases ILSS by 6% for this material. The result indi- fit of (2)
cates that the drop-o rate of ILSS closely follows the 65
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Void content (v%)

Fig. 13. Relationship between modulus and void content.

1.2% 0.9%
100
(void content) 2.0% strength drop-o rate found in the literature results [5].
2.2%
Strength fraction (%)

95 With the increase of void content, a higher void sensitiv-

ity of ILSS is obtained that is mainly due to the decrease
90 of ply interface area with increasing voids.
The exural strength and modulus were measured in
85
a three point bending test. The experimental results
shear strength show that the strength falls by 22% for a void content
80 flexural strength
tensile strength of 3.2% (see Fig. 12). For exural modulus, this reduc-
75 tion is 18% (in Fig. 13). The quantied value of the
0 30 60 90 120
exural strength fall o determined in this work was
Dwell time (min)
7% per percent void. In the case of exural modulus
Fig. 10. Relationship between strength and the rst isothermal time. the similar drop-o trend occurs again.
 L. Liu et al. / Composite Structures 73 (2006) 303309
The results of tensile strength measurements are re-
ported in Fig. 12. The tensile strength decreases by
14% when the void content increases from 0.6 to 3.2%
and the drop-o rate is 4% in the porosity range from
0 to 3.5% for this material. The decrease of tensile
strength versus porosity can be mainly attributed to
the local ber deformation observed during the optical
analysis of voids. As for tensile modulus, there appear
to be a little decrease with increasing porosity shown
in Fig. 13. This is due largely to the very high ber vol-
ume fractions after curing (6572%). Therefore, the ten-
sile modulus is insensitive to the void content.
4. Conclusions
A composite laminate produced by dierent cure
pressures presented various void contents from 0 to
3.5%. An exponentially decreasing relationship is ob-
tained between the void content and cure pressure.
For quality control purposes, an appropriate curing
pressure should be applied during the cure cycle accord-
ing to the acceptable void levels. An optimum curing cy-
cle has been established by altering the moment of
applying pressure within the range of minimum viscos-
ity. It can cost-eectively shorten the cure cycle by
nearly 1 h if appropriate pressure is applied.
The grading evaluation criterion obtained mainly
from ultrasonic inspection and optical image analysis
can be very useful in engineering application of compos-
ite structures. The results suggest that both the strength
and modulus decrease with increasing porosity. A higher
void sensitivity for ILSS, exural strength and exural
modulus are obtained, and tensile strength decreases rel-
atively slowly, while the tensile modulus is insensitive to
the void content. Further work on this subject can pre-
dict the compressive strength and fatigue life of the lam-
inates, and verify the grading evaluation criterion of
ultrasonic inspection.
309
Acknowledgements
The author gratefully acknowledges engineer Sheng
Wulan and Lu Mingkun for their support in this re-
search. The author also gratefully acknowledges Na-
tional Natural Science Foundation of China for its
support (Grant No. 10372027).
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