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Accelerated environmental ageing study of polyester/glass fiber reinforced

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Article  in  Composites Part B Engineering · April 2008

DOI: 10.1016/j.compositesb.2006.10.004

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Composites: Part B 39 (2008) 467–475

www.elsevier.com/locate/compositesb

Accelerated environmental ageing study of polyester/glass

fiber reinforced composites (GFRPCs)
b,*
Dionysis E. Mouzakis , Helen Zoga a, Costas Galiotis a,b

a
Mechanics of Materials Laboratory, ICEHT/FORTH, P.O. Box 1414, Patras, Greece
b
Department of Materials Science, University of Patras, Greece

Received 1 October 2006; accepted 17 April 2007

Available online 22 May 2007

Abstract

The failure of polymer matrix composites upon exposure to the environment has been assessed in the present study. In order to inves-
tigate the combined action of temperature, humidity and UV radiation on polymers and composites, an environmental ageing chamber
has been constructed and tested. The accelerated environmental ageing was based on two kinds of alternating cycles, which provided
humidity, temperature and ultraviolet radiation. The materials examined were isophthalic polyester and isophthalic polyester reinforced
with a glass fiber random mat onto which glass fibers were knitted at 0/90 (GFRPC) at a total volume fraction of approximately 20%.
Dynamic mechanical analysis, for a range of temperatures and frequencies under tensile and three-point bending loadings, revealed that
the aged materials gained in stiffness, whereas a small deterioration in strength was found. Scanning electron microscopy studies per-
formed before and after environmental chamber conditioning revealed that some microcracks had occurred on the surface of the spec-
imens. Nevertheless, the length of these microcracks was less than the critical value of 0.1 mm, required for crack propagation.
 2007 Elsevier Ltd. All rights reserved.

Keywords: A. Polymer-matrix composites (PMCs); B. Environmental degradation; B. Thermomechanical; D. Mechanical testing

1. Introduction volume. The latter can lead to accumulation of hydroscopic

Glass fiber isophthalic polyester composites (GFRPC)
are materials widely used in applications such as blades
for wind turbines, construction structures, boat hulls, etc.
The study of the exposure of such materials to environmen-
tal conditions such as varying temperature, humidity,
ultraviolet radiation, etc. is of outmost importance, in
order to assess the impact of these important ageing factors
on their mechanical behavior.
As far as water is concerned, absorption through poly-
mer matrices usually follows Fick’s law [1–3] and its effect
is detrimental for certain material properties. For example,
absorbed water has been found to disrupt the interfacial
bonds, to occupy the voids of the composite (or polymer)
[4,5] and, thus, cause changes in the overall free matrix
*
Corresponding author. Tel.: +30 2610 969944; fax: +30 2610 965223.
E-mail address: mouzakis@upatras.gr (D.E. Mouzakis).
stresses that can crack and fail the resin. Also water sorp-
tion may cause hydrolysis and physical ageing. Changes
in the resin can be either reversible (plasticization and swell-
ing) or irreversible (dissolution, hydrolysis and microcrack-
ing). The chemical composition of the resin appears to affect
the equilibrium content of water. Iso- and ortho-phthalic
polyesters are different in this sense. Of course this affects
the mechanical performance; the larger the water content,
the greater the hydrolysis or the swelling stresses [6–8].
Moreover, another irreversible effect is the creation of a sec-
ondary cross-linking in the matrix, due to a specific kind of
hydrogen bond that forms between resin and water mole-
cules. This phenomenon depends on the chemical structure
of the resin, the temperature and the total period of expo-
sure to water [9]. Finally, the diffusion of water into poly-
mers and composites may lead to the leaching of some
resin molecules of low molecular weight, which can also
lead to an irreversible stiffening of these materials [8,10].

1359-8368/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesb.2006.10.004
468 D.E. Mouzakis et al. / Composites: Part B 39 (2008) 467–475
On the other hand, temperature and UV radiation can
either impose scission of the chemical bonds of the matrix
(i.e. main C–C chain scission), leading to photo/thermo-
oxidation and crazing of the material [11–15], or lead to
polymer post-curing [7,14,16–19]. Salted water (or NaCl
saline solution) has proved to have similar effects compared
to distilled water. Salt molecules lead to hydrolysis and
scission of the chemical bonds of the interphase [20]. It also
contributes to the leaching of low molecular weight mole-
cules, which can, thus, lead to embrittlement and stiffening
of the polymer matrix [21,22]. Moreover, salt crystals inhi-
bit the diffusion of water, by blocking the paths through
which water diffuses into the material. In comparison, dis-
tilled water is absorbed to a greater extent compared to
salted water [20,23].
In order to investigate the combined effect of tempera-
ture, humidity and ultraviolet radiation on the properties
of isophthalic polyester/glass fiber composite materials,
the construction of an environmental accelerated ageing
chamber was undertaken. This chamber would provide
accelerated ageing by alternating cycles of temperature,
humidity and UV radiation. The changes in the mechanical
and viscoelastic behavior of the aged materials vis-à-vis the
virgin samples were not only examined by tensile and three
point bending tests, but also by dynamic mechanical anal-
ysis (DMA). The fracture surfaces of the specimens were
examined by scanning electron microscopy and useful con-
clusions were drawn.
2. Experimental
2.1. Environmental accelerated ageing chamber (EA2C)
Three ASTM standards were used as guidelines for the
construction of the environmental chamber namely, (a)
Fig. 1. The alternating temperature, humidity and UV-radiation cycles during the accelerated environmental ageing procedure.
ASTM D1151-90: standard test method for effect of mois-
ture and temperature on adhesive bonds (b) ASTM D5229/
D5229M-92: standard test method for moisture absorption
properties and equilibrium conditioning of polymer matrix
composite materials and (c) ASTM G53-96: standard prac-
tice for operating light and water exposure apparatus (fluo-
rescent UV-condensation type) for exposure of nonmetallic
materials.
The ASTM G53-96 provided the main guidelines. This
standard prescribes the following two-step procedure in
order to have an accelerated, simulated environmental
impact on polymers and composite materials:
Step A: Specimen preconditioning
Specimens are stored at about 50% relative humidity
conditions, at 23 C without UV for 7 days.
Step B: Specimen main ageing procedure
Specimens are subjected to alternating cycles of UV–B
(302 nm) and condensation according to the following
scheme: 4 h UV–B at 60 C without condensation followed
by 4 h condensation (98% RH) at 50 C. This cycle is
repeated for about 1008 h or 42 days (6 weeks). The above,
simulated, environmental ageing protocol is schematically
shown in Fig. 1.
A cubical PMMA chamber shown in Fig. 2A of approx-
imately 1 · 1 · 1 m3, was devised, featuring two program-
mable ‘‘logic’’ controllers (PLC’s) in order to maintain
exact control of the temperature, humidity and ultraviolet
radiation. The chamber featured digital monitoring of all
needed operational parameters. The inside walls were
painted by epoxy marine lacquer (gel-coat), in order to pro-
tect the chamber material itself from ageing. Humidity
inside the chamber was provided, through a flexible tube,
by an ultrasonic humidifier, which was supplied by distilled
water. The real-time recorded temperature–relative humid-
ity curves are incorporated in Fig. 2B.
 D.E. Mouzakis et al. / Composites: Part B 39 (2008) 467–475
Fig. 2. The environmental accelerated ageing chamber (EA2C) and the real-time recorded temperature humidity cycles.
2.2. Materials
The isophthalic polyester was prepared by mixing 100 g
resin with 1.1 g methyl ethyl ketone (MEK) peroxide initi-
ator and pouring it into moulds of rectangular and dumb-
bell shape. After 24 h, the resin was placed inside an oven
and post-cured, at 30 C, for 24 h. Concerning GFRPC, it
was provided in ca. 600 · 600 mm2 plaques of 1 mm thick-
ness, at ca. Vf = 20%. The reinforcement consisted of a
random glass fiber mat onto which 0–90 glass rovings were
stitched.
It has to be stated that before placing all specimens
inside the ageing chamber, they were sealed with a special
elastomeric sealant resin around the edges, to prevent
moisture absorption, in other than through the thickness
direction. In this way, Fickian diffusion of moisture inside
the material was ensured. The specimens were not sub-
jected to any special preconditioning prior to the initiation
of the chamber cycles, since the conditions maintained in
the storage room, where the materials were kept, were
almost identical to those of the preconditioning phase.
Upon completion of the environmental ageing campaign
(42 days) the materials were removed from the chamber
and carefully sealed in a plastic bag to ensure that they will
keep the absorbed moisture. In addition, some aged speci-
mens of both materials were cut properly and dried for a
whole week, at 40 C, under vacuum, in order to provide
comparison data against the humid-aged specimens.
2.3. Experimental techniques
2.3.1. Dynamic mechanical analysis (DMA)
In order to find out the exact impact of the environmen-
tal ageing on the viscoelastic behavior of the materials,
thermal and frequency scans were performed on small bars
of ca. 60 · 12 · 1 mm3 for the composite and 60 · 12 ·
4 mm3 for the polymer materials respectively. The machine
469
was a Q800 type of TA instruments. Test mode was three
point bending under controlled strain. Temperature was
set between 35 and +200 C, with constant frequency of
1 Hz, during temperature scans. Frequency scans were also
performed varying from 1 to 30 Hz, at a constant temper-
ature of 25 C. Preloading was set at 0.125 N and strain
amplitude was 15 lm. Each material was tested in its pris-
tine, aged but saturated in water and aged but in dried
conditions.
2.3.2. Static tensile tests
Static tensile tests were performed on an MTS 20KN
universal testing machine per ASTM D3039/D3039 M-
94a, at 2 mm/min crosshead speed, for the composite mate-
rial and ASTM D638-76, at 1 mm/min, for the isophthalic
polyester. Tensile strain was measured by strain gauges
attached along the specimen longitudinal axis. The speci-
men dimensions were 250 · 25 · 1 mm3 for the composite
material and dumbbells of 165 mm total length and 5 mm
thickness for the polymer. A number of 10 specimens were
used for extracting the average mechanical properties for
the pristine, the dried-aged and the humid-aged (saturated)
specimens, respectively. The experiments took place at
ambient temperature and relative humidity conditions.
2.3.3. Three point bending tests
Three point bending (3PB) tests were performed on an
MTS 20KN universal testing machine per DIN (EN ISO
178), at 2 mm/min crosshead speed, while preloading was
set at 10 N. A number of eight specimens were used for
extracting the average mechanical properties for the pris-
tine and humid-aged (saturated) composite material, after
the ageing in the environmental chamber. The dimensions
of the samples were 80 · 20 · 2 mm3 and the experiments
took place at room conditions. Measurements of force/
deflection were taken every 0.5 s and were transformed into
the equivalent values of stress/strain out of which the
470 D.E. Mouzakis et al. / Composites: Part B 39 (2008) 467–475

corresponding mechanical properties were calculated

Polyester-Virgin
according to the testing protocols. 5000 Polyester-ECH
Polyester-ECD

Storage Modulus [MPa]

v=1 Hz
2.3.4. Scanning electron microscopy (SEM) 4000
Surfaces and fracture surfaces of the virgin and aged
panels of GFRPC, before and after the completion of three 3000
point bending tests, were investigated by means of scanning
electron microscopy employing a JEOL 5200 SEM at 2000
25 kV accelerating voltage, after sputtering with gold.
Images taken were digitally stored for a further study. 1000

3. Results and discussion 0

-50 0 50 100 150 200

3.1. Isophthalic polyester resin Temperature [oC]

In order to obtain a clear view of the impact of ageing

on the composite material matrix, specimens made from 0.75 Polyester-Virgin
pure isophthalic polyester, were aged separately and the Polyester-ECH
Polyester-ECD
corresponding static and dynamical mechanical responses 0.60
ν=1Hz
were studied. Table 1 shows the average static mechanical
properties, in tension, of isophthalic polyester, which were
0.45
tanδ [-]

derived from the samples of pristine, humid-aged (ECH)

and dried-aged (ECD) polyester, respectively. These speci-
mens were all aged inside the EA2C.
As is evident from the data reported in Table 1, the ten-
sile strength rult of isophthalic polyester appears to be
decreasing as the environmental ageing increases. Further-
more, a small increase of the elastic modulus and decrease
in the failure strain, eult of the aged polymer (humid and
dried) can also be observed. These changes are indicative
of embrittlement in the case of the aged polymer.
Fig. 3 presents the thermal scans for the polyester sam-
ples. It appears that up to 100 C, within the glass transi-
tion region, the storage modulus (E 0 , Fig. 3a) of the
environmentally aged samples of isophthalic polyester
increases as compared to the pristine material. However,
no differences can be observed between the storage modu-
lus values of the humid and dried samples. On the other
hand, the damping constant, tan d, of the aged samples
(Fig. 3b) are marginally higher than that of the virgin spec-
imen, showing no difference again between the humid and
the dried aged samples. The irreversible increase of storage
modulus, implies that some kind of permanent stiffening
occurs in the aged material. Moreover, a slight increase
in the Tg of the aged polymer, (Tg of the virgin polyester
is at about 100 C) and also a narrowing of the peak can
be observed. These changes in the Tg, imply a decreased
Table 1
Average tensile mechanical properties of the virgin, humid, (ECH) and
dried (ECD) environmentally aged isophthalic polyester specimens,
respectively
Polyester rult (MPa) E (GPa) eult (%)
Virgin 47.27 ± 3.3 2.37 ± 0.04 2.52 ± 0.25
ECH 47.08 ± 4.94 2.59 ± 0.04 2.18 ± 0.28
ECD 45.01 ± 5.50 2.67 ± 0.07 1.99 ± 0.35
0.30
0.15
0.00
-50 0 50 100 150 200
Temperature [ oC]
Fig. 3. DMA thermal scans for the isophthalic polyester matrix samples.
(a) Storage modulus and (b) tan d vs temperature, respectively, ECH:
aged-humid specimens, ECD: aged and post-dried specimens.
material mobility, which complies with the stiffening
observed during tensile testing. In the rubbery state, no dif-
ferences were observed between the viscoelastic behavior of
the virgin and aged isophthalic polyester.
The most plausible explanation of the irreversible
increase in E 0 that occurred in the aged polymer is a possi-
ble post-curing that took place during the ageing proce-
dure. This happened due to a combination of UV–B
radiation and high temperature, which were not severe
enough to break the chemical bonds of the polymer [11–
15], but in contrast, they contributed to the creation of free
radicals to the molecules of unsaturated isophthalic polyes-
ter which had not already reacted, and thus, to a further
cross-linking [7,14,16–19].
Furthermore, in epoxy resins, water has proved to be
responsible for the creation of a secondary network of
cross-links between free hydroxyls (OH) of the main chain
of the resin. Therefore, water molecules do not act as plast-
icizers, as expected, but in contrast make the polymer some-
what stiffer. This is also marked by a shift of the Tg at higher
 D.E. Mouzakis et al. / Composites: Part B 39 (2008) 467–475
temperatures [24]. This kind of cross-linking may exist in
the materials studied here, as well, as a result of water mol-
ecules forming multiple hydrogen bonds with the polyester
resin network. Although isophthalic polyester resin does
not contain free OH along its main chain, it does contain
free OH and H at the end of each main chain, which
could be responsible for the creation of such hydrogen
bonds with water molecules as it happens in epoxy resins
[25,26]. A proposed mechanism is shown in Chemical
Equation 1. Also, the oxygen of the carbonyl group, cobalt
[26], hydroquinone [27] or other additives found in commer-
cial polymers may also be responsible for this phenomenon.
Finally, the reacting chemicals of the chemical reaction of
isophthalic polyester contain free –OH and it is envisaged
that if they are in excess, they may contribute to the forma-
tion of hydrogen bonds. These hydrogen bonds possess
higher activation energies and are, therefore, harder to
remove. The formation of this kind of bonds depends on
the exposure temperature and time; higher temperatures
and longer exposure times promote the creation of large
numbers of these bonds [9]. Also, exposing the polymer to
humidity, as in our occasion, and not immersing it to water,
facilitates this effect due to the higher mobility of water mol-
ecules when in the gaseous state [26,2].
Another mechanism related to water sorption, is the
occupation of the voids of the material [4] or the possible
leaching of low molecular weight molecules [8,10]. These
also lead to an irreversible increase in the stiffness of the
HO CH2 CH2 OH + HO CO CH CH CO OH
O CH2 CH2 O CO CO O CH2 CH2 O CO CH CH
O CH2 CH 2 O CO CO O CH2 CH2 O CO CH CH
O CH CH2
.
O CH2 CH2 O CO CO O CH2 CH2 O CO CH CH
Chemical Equation 1. A proposed mechanism of hydrogen bond formation with the polyester matrix.
471
aged material. The overall conclusion drawn here, is that
there is a number of mechanisms which can be held as
responsible for causing an irreversible stiffening of the mate-
rial during the environmental ageing procedure. Stiffening
of the composite material matrix when exposed to the envi-
ronment can lead to non-predictable behavior of a structure
such as eigenfrequency shifting and/or deterioration of over-
all structural damping and thus to life-span degradation.
To support our findings with respect to material
dynamic behavior under changing load frequency, DMA
scans were performed in a limited frequency spectrum.
Fig. 4 shows the DMA frequency spectra at the glassy state
of the material (25 C). An irreversible increase of the stor-
age moduli (Fig. 4a) and decrease of tan d (Fig. 4b) is obvi-
ous again for the aged material. These findings support our
conclusions above regarding the irreversible stiffening of
the matrix.
In summary, changes in the mechanical properties of the
aged polymer, compared to the virgin, seem to be less dis-
tinct in tensile mode of testing while DMA tests provided
more detailed results. This could be attributed to the fact
that ageing mainly occurs on the surface of the material
and 3PB results are sensitive to changes in the surface of
the specimen. On the other hand, tensile tests concern the
entire cross section of the specimen and not its surface
mainly. Thus, because DMA tests were performed in the
3PB mode they delivered the results of ageing on the matrix
in an unambiguous way.
-H2O
+ HO CO CO OH
RT
CO O CH2 CH2 O
O OH
CH3 C CH2 CH3
O OH
.
CO O CH2 CH2 O
CH 3 C CH 2 CH 3
O OH
CH
CH2
CO O CH2 CH2 O
O
CH3 C CH2 CH 3
O OH
472 D.E. Mouzakis et al. / Composites: Part B 39 (2008) 467–475

5600 in the mechanical properties of the aged composite. This

is to be expected since that tensile modulus data are pre-
dominantly governed by the fiber properties. However,
5200
the data of Table 2 indicate: (a) slight stiffening of the com-
Storage Modulus [MPa]

posite in the presence of water possibly emanating from the

4800 stiffening of the resin which accounts for 80% of composite
volume and (b) strength reduction upon removal of the
water in the aged samples.
4400 DMA scans provided more clear evidence of ageing for
the composite. Phenomena similar to those observed for
4000 Polyester-Virgin the pure isophthalic polyester matrix aged samples, were
Polyester-ECH also noticed for the GFRPC, as well. In the temperature
Polyester-ECD regime up to 100 C (Tg of the polyester matrix), there is
3600 ( T=25 °C) again a slight irreversible increase in the storage moduli
of the aged composite, both in dried and humid (saturated
0 8 16 24 32 in moisture) states (Fig. 5a), accompanied by a decrease in
Frequency [Hz]
the tan d (Fig. 5b). This should be attributed, similarly as in
0.060
the case of the polyester matrix, to the combined action of
UV, temperature and humidity, which seem to impose a

0.054
12000 GFRPC-ECH
GFRPC-Virgin
0.048 Polyester-Virgin GFRPC-ECD
Polyester-ECH 10000
tanδ [-]

v=1 Hz
Storage Modulus [MPa]

Polyester-ECD
(T=25 °C)
0.042 8000

6000
0.036

4000
0.030
0 6 12 18 24 30
2000
Frequency [Hz]

Fig. 4. DMA frequency scans for the isophthalic polyester matrix 0

samples. (a) Storage modulus and (b) tan d vs frequency, respectively, -50 0 50 100 150 200
ECH: aged-humid specimens, ECD: aged and post-dried specimens. Temperature [ oC]

3.2. Glass fiber reinforced isophthalic polyester composite 0.30 GFRPC-ECH

(GFRPC) GFRPC-Virgin
GFRPC-ECD
0.25
v=1 Hz
Table 2 summarizes the average values for the tensile
mechanical properties of the pristine GFRPC, aged 0.20
GFRPC (ECH) in saturated and dried GFRPC (ECD)
tanδ [-]

conditions respectively. According to Table 2, it is obvious 0.15

that the average values of rult, eult and E of GFRPC, before
and after the environmental ageing, are followed by rela- 0.10
tively large standard deviations. Consequently, no strong
evidence can be derived concerning changes that occurred 0.05

0.00
Table 2
Average tensile mechanical properties of the virgin, humid (ECH) and -50 0 50 100 150 200
dried (ECD) environmentally aged GFRPC’s, respectively
Temperature [oC]
GFRPC rult (MPa) E (GPa) eult (%)
Fig. 5. DMA thermal scans of the pristine GFRPC, environmentally
Virgin 156.79 ± 15.06 11.81 ± 0.36 1.82 ± 0.19
aged-saturated (GFRPC-ECH) and dried (GFRPC-ECD) conditions,
ECH 169.34 ± 15.12 13.26 ± 1.18 1.73 ± 0.34
respectively. (a) Storage moduli (E 0 ) vs temperature and (b) material
ECD 149.94 ± 5.68 11.63 ± 0.33 1.87 ± 0.08
damping constant (tan d) vs temperature.
 D.E. Mouzakis et al. / Composites: Part B 39 (2008) 467–475 473

post-curing effect by several acting mechanisms. In addi-

a
tion, the coupling agents (silanes) containing hydroxyl 16000
groups used as glass fiber sizing, promote the creation of
the secondary kind of cross-linking. In this sense, the crea-

Storage Modulus [MPa]

tion of hydrogen bonds can not be ruled out as in the case 15000
of the plain resin [6,28,29]. Furthermore, the increase in the
storage modulus of the aged composite appears to a some- GFRPC-Virgin
14000
what less extent than it was for the aged polymer. As men- GFRPC-ECH
tioned above, this happens because the storage modulus of GFRPC-ECD
a composite material mainly depends on the fiber and not (T=25 °C)
13000
on the resin.
On the other hand, above 100 C, data trends are
reversed; the values of storage modulus become lower 12000
and the values of tan d higher for the aged composite, espe-
cially the saturated material, in comparison with the pris- 0 6 12 18 24 30
tine sample. This can be possibly due to the presence of Frequency [Hz]
an expanded interphase region of increased ductility
around the glass fibers, as confirmed by Hodzic et al. for b 0.055 GFRPC-Virgin
glass/polyester composites [30]. They have confirmed via GFRPC-ECH
nano-scratching that ageing in water enlarges the inter- 0.050 GFRPC-ECD
phase region by at least a factor of two. This larger inter- (T=25 °C)
phase region shows increased ductility according to them 0.045
[30] and this effect could lead to an increased tan d (material
damping) at high temperatures. Should this be the govern- 0.040
Tan δ

ing effect, then the Tg of such an enlarged interphase should

0.035
lay somewhat lower than the pure matrix Tg. Indeed, a sec-
ondary peak, in the form of a shoulder appears at around 0.030
80 C for all specimens as seen in Fig. 5b.
Additionally, the tan d(T ) spectra show a third peak that 0.025
appears at around 150 C for the GFRPC-ECH sample,
which can be attributed to the Tg of adhesion promoters 0.020
(silanes). Silanes are applied on the surface of glass fibers 0 5 10 15 20 25 30
as a treatment to a great extent in order to contribute to Frequency (Hz)
the creation of strong interfacial bonds in the composite Fig. 6. DMA frequency scans of the pristine GFRPC, environmentally
[6,28,29]. The Tg of the matrix appears at about 125 C, aged in saturated (GFRPC-ECH) and dried (GFRPC-ECD) conditions,
according to tan d curves. Alternatively, the third peak that respectively. (a) Storage moduli (E 0 ) vs frequency and (b) material
damping constant (tan d) vs frequency.
appears at around 150 C could be due to the evaporation
of water molecules, captured at the enlarged, due to water
absorption, interphase. Table 3
The frequency related viscoelastic response of the com- The average flexural mechanical properties of the virgin and humid (ECH)
posite, which is depicted in Fig. 6, leads once more to the environmentally aged GFRPC in 3PB mode
conclusion that a kind of irreversible stiffening takes place GFRPC rult (MPa) E (GPa) eult (%)
in the composite, after the environmental ageing procedure Virgin 265.99 ± 5.09 15.81 ± 0.55 2.07 ± 0.61
is completed in the EA2C. More specifically, the spectra of ECH 259.49 ± 8.61 16.92 ± 0.63 1.79 ± 0.31
Fig. 6a, obtained at the glassy state of the material (25 C),
show an increase in the storage modulus and a decrease in
the tan d data (Fig. 6b) for the aged GFRPC, with little dif- virgin and aged GFRPC samples, confirms the conclusions
ference between the water-saturated and dried samples. derived from DMA and tensile testing. Accelerated envi-
Table 3 includes the average values for the mechanical ronmental ageing is accompanied by a relative stiffening
properties in 3PB tests of the pristine GFRPC and environ- effect of the GFRPC attributed to several mechanisms,
mentally aged GFRPC, in saturated conditions (ECH). which mainly promotes a post-curing effect on the polymer
Static 3PB tests showed small differences between the virgin matrix.
and aged GFRPC samples. Ultimate strength data rult,
seems to degrade slightly, whereas there is a small rise in 3.2.1. Scanning electron microscopy (SEM)
the bending modulus of the aged samples. Finally, the fail- SEM scans provided valuable evidence of the EA2C
ure strain eult is somewhat decreased after the ageing proce- impact on the polymer and composite specimens. Fig. 7
dure. The overall picture delivered by the 3PB tests on the depicts the virgin and environmentally aged surface of
474 D.E. Mouzakis et al. / Composites: Part B 39 (2008) 467–475

Fig. 7. SEM microphotography of the pristine (left) and aged (right) GFRPC surfaces, respectively.

Fig. 8. SEM microphotographs of the pristine (left) and environmentally aged GFRPC 3PB fracture surfaces (right), respectively.

GFRPC. Some microcracking and microvoids on the sur-
face of the aged tensile specimens can be easily seen in
the microphotographs of Fig. 7. Nevertheless, the length
of the noticed microcracks appears smaller than the critical
value of 0.1 mm, required for crack propagation and there-
fore did not possibly affect the tensile strength of the com-
posite. Also, these microcracks do not appear scattered
along the whole surface of the aged composite material.
The fracture surfaces of three point bending specimens
on pristine and aged condition are shown in Fig. 8. No dis-
tinct differences could be stated from these microphoto-
graphs with respect to matrix or fiber failure. Fracture
surfaces for aged and pristine specimens are dominated
by matrix fracture and multiple fiber fragmentation, which
are typical for these types of composites. Also, no evidence
of interfacial debonding phenomena is present.
4. Conclusions
An environmental chamber that can simulate acceler-
ated ageing on polymers and composites was constructed
and tested. This chamber provided two alternative cycles,
including a combination of stable conditions of tempera-
ture, humidity and UV–B radiation. The materials aged
in this chamber were isophthalic polyester and GFPC.
Regarding isophthalic polyester matrix, the experimental
data revealed that, after exposure, the polymer matrix
became stiffer in an irreversible way. This happened mainly
because of the post-curing of the material, caused by tem-
perature and UV radiation. Also, the secondary cross-link-
ing via hydrogen bonding, the occupation of the voids of
the materials and the possible leaching of low molecular
weight molecules due to water absorption, are considered
the main factors that contributed to the increase of stiffness.
As far as the GFPC is concerned, the main ageing
parameter was again matrix stiffening, due to UV radia-
tion, temperature and water. In addition, a kind of interfa-
cial degradation was observed for the composite material,
during DMA scanning at high temperatures, possibly
because of expansion of water molecules at the interface
combined with hydrolysis. In addition, SEM images on
the surface of the composite, before and after the ageing
of the material in the environmental chamber, revealed that
some microcracks had occurred on its surface. Neverthe-
less, the length of these microcracks was less than the crit-
ical value of 0.1 mm, required for crack propagation and,
as a result, they should not affect the tensile strength of
the composite. No specific differences or findings could be
stated for the fracture surfaces of the virgin and aged three
point bend composite specimens.
 D.E. Mouzakis et al. / Composites: Part B 39 (2008) 467–475 475

Acknowledgement [14] Halim S, Amin MB, Maadhah AG. Handbook of polymer degrada-
tion. Research Institute, King Fahd of Petroleum and Minerals,
Dhahran, Saudi Arabia, New York/Hong Kong: Marcel Dekker,
The authors are grateful to CEC for funding through Inc./Basel; 1992.
the ENERGIE ENK5-CT-2000-00328 (MEGAWIND) [15] Golder, Michael D, Bruce, Mulholland. Improved UV stabilization
project. expands uses for polyester elastomers. Plast Eng 1990;46(6):43–4.
[16] Signor, Vanlandingham M, Chin J. Effects of ultraviolet radiation
References exposure on vinyl ester resins: characterization of chemical, physical
and mechanical damage. Polym Degrad Stabil 2003;79:359–68.
[17] Sakai W, Sadakane T, Nishimoto W, Nagata M, Tsutsumi N.
[1] Ferreira JM, Pires JTB, Costa JD, Errajhi OA, Richardson M.
Photosensitized degradation and crosslinking of linear aliphatic
Fatigue damage and environment interaction of polyester aluminized
polyesters by GPC and ESR. Polymer 2002;43:6231–8.
glass fiber composites. Compos Struct 2007;78(3):397–401.
[18] Li G, Pourmohamadian N, Cygan A, Peck J. Fast repair of laminated
[2] Pavan R, Saravanan V, Dinesh AR, Rao YJ. Hydrothermal effects of
beams using UV curing composites. Compos Struct 2003;60:73–
painted and unpainted glass/epoxy composites—part A: moisture
81.
absorption characteristics. J Reinf Plast Comp 2001;20(12):1036–47.
[19] Grossman E, Gouzman I. Space environment effects on polymers in
[3] Zhang S, Karbhari VM, Mai L-Y, Mai Y-W. Evaluation of property
low earth orbit. Nucl Instrum Methods 2003;208:48–57.
retention in E-glass/vinylester composites after exposure to salt
[20] Bulder BH, Bach PW. A literature survey on the effects of moisture
solution and natural weathering. J Reinf Plast Comp 2000;19(9):
on the mechanical properties of glass and carbon fibre plastic
704–31.
laminates. ECN-C-91-033, 1991.
[4] Papanicolaou GC, Kosmidou ThV, Vatalis AS, Delides CG. A water
[21] Siddaramaiah, Suresh SV, Atul VB, Srinivas D, Girish S. Effect of
absorption mechanism and some anomalous effects on the mechan-
aggressive environments on composite properties. J Appl Polym Sci
ical and viscoelastic behavior of an epoxy system. J Appl Polym Sci
1999;73(5):795–9.
2006;99(4):1328–39.
[22] Bastaki N, Madani H. Material behaviour, effect of local atmosphere
[5] Adamson MF. Foundations of materials science and engineering. 2nd
in bahrain on the mechanical properties of GRP. Polym Test
ed. McGraw-Hill International Editions; 1993, p. 322.
1995;14:263–72.
[6] Schutte CL. Environmental durability of glass fiber composites. Mat
[23] Davies P, Mazeas F, Casari P. Sea water ageing of glass reinforced
Sci Eng R 1994;13:264–324.
composites: shear behaviour and damage modeling. J Compos Mater
[7] Gates T, Grayson M. On the use of accelerated aging methods for
2001;35(15):1343–73.
screening high temperature polymeric composite materials. Am Inst
[24] Zhou J, Lucas JP. Hygrothermal effects of epoxy resin. Part II:
Aeronaut Astronaut 1998;2:925–35.
variations of glass transition temperature, vol. 40. Michigan State
[8] Boinard E, Pethrick RA, Dalzel-Job J, Macfarlane CJ. Influence of
University, East Lansing, MI 48824, USA: Department of Materials
resin chemistry on water uptake and environmental ageing in glass
Science and Mechanics; 1999, p. 5505–12.
fibre reinforced composites-polyester and vinyl ester laminates. J
[25] Belan F, Bellenger V, Mortaigne B. Hydrolytic stability of unsatu-
Mater Sci 2000;35:1931–7.
rated polyester networks with controlled chain ends. Polym Degrad
[9] Zhou J, Lucas JP. Hygrothermal effects of epoxy resin. Part I: the
Stabil 1997;56:93–102.
nature of water in epoxy, vol. 40. Michigan State University, East
[26] Marais St, Metayer M, Nguyen T, Labbe M, Saiter J. Diffusion and
Lansing, MI 48824, USA: Department of Materials Science and
permeation of water through unsaturated polyester resins-influence of
Mechanics; 1999, p. 5505–12.
resin curing. Eur Polym J 2000;36:453–62.
[10] Xiao GZ, Shanahan MER. Swelling of DGEBA/DDA epoxy resin
[27] Mallick PK. Fibre reinforced composites. Materials, manufacturing,
during hydrothermal ageing. Polymer, vol. 39. France: Elsevier
and design. 2nd ed. CRC; 1993.
Science Ltd; 1998, p. 3253–60.
[28] Ward IM, Hadley DW. An introduction to the mechanical properties
[11] López FS, Ferrer C, Salvador MD, Amigo V. Flexural characteristics
of solid polymers. John Wiley & Sons; 1993.
of sunlight-aged polyester composites: influence of processing vari-
[29] Gaur U, Chou CT, Moller B. Effect of hydrothermal ageing on bond
ables. J Test Eval 2002;30(1):20–6.
strength. Composites 1994;25:609–12.
[12] Griffiths R, Ball A. An assessment of the properties and degradation
[30] Hodzic A, Kim JK, Lowe AE, Stachurski ZH. The effects of water
behaviour of glass-fibre-reinforced polyester polymer concrete.
aging on the interphase region and interlaminar fracture toughness
Compos Sci Technol 2000;60:2747–53.
in polymer–glass composites. Compos Sci Technol 1994;64:2185–
[13] Segovia F, Ferrer C, Salvador MD, Amigo V. Influence of processing
95.
variables on mechanical characteristics of sunlight aged polyester–
glass fibre composites. Polym Degrad Stabil 2001;71:179–84.

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