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Composites: Part B 39 (2008) 467475


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Accelerated environmental ageing study of polyester/glass


ber 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 ber random mat onto which glass bers 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 stiness, 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


stresses that can crack and fail the resin. Also water sorp-
Glass ber isophthalic polyester composites (GFRPC) tion may cause hydrolysis and physical ageing. Changes
are materials widely used in applications such as blades in the resin can be either reversible (plasticization and swell-
for wind turbines, construction structures, boat hulls, etc. ing) or irreversible (dissolution, hydrolysis and microcrack-
The study of the exposure of such materials to environmen- ing). The chemical composition of the resin appears to aect
tal conditions such as varying temperature, humidity, the equilibrium content of water. Iso- and ortho-phthalic
ultraviolet radiation, etc. is of outmost importance, in polyesters are dierent in this sense. Of course this aects
order to assess the impact of these important ageing factors the mechanical performance; the larger the water content,
on their mechanical behavior. the greater the hydrolysis or the swelling stresses [68].
As far as water is concerned, absorption through poly- Moreover, another irreversible eect is the creation of a sec-
mer matrices usually follows Ficks law [13] and its eect ondary cross-linking in the matrix, due to a specic kind of
is detrimental for certain material properties. For example, hydrogen bond that forms between resin and water mole-
absorbed water has been found to disrupt the interfacial cules. This phenomenon depends on the chemical structure
bonds, to occupy the voids of the composite (or polymer) of the resin, the temperature and the total period of expo-
[4,5] and, thus, cause changes in the overall free matrix sure to water [9]. Finally, the diusion of water into poly-
mers and composites may lead to the leaching of some
*
Corresponding author. Tel.: +30 2610 969944; fax: +30 2610 965223. resin molecules of low molecular weight, which can also
E-mail address: mouzakis@upatras.gr (D.E. Mouzakis). lead to an irreversible stiening 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) 467475

On the other hand, temperature and UV radiation can ASTM D1151-90: standard test method for eect of mois-
either impose scission of the chemical bonds of the matrix ture and temperature on adhesive bonds (b) ASTM D5229/
(i.e. main CC chain scission), leading to photo/thermo- D5229M-92: standard test method for moisture absorption
oxidation and crazing of the material [1115], or lead to properties and equilibrium conditioning of polymer matrix
polymer post-curing [7,14,1619]. Salted water (or NaCl composite materials and (c) ASTM G53-96: standard prac-
saline solution) has proved to have similar eects compared tice for operating light and water exposure apparatus (uo-
to distilled water. Salt molecules lead to hydrolysis and rescent UV-condensation type) for exposure of nonmetallic
scission of the chemical bonds of the interphase [20]. It also materials.
contributes to the leaching of low molecular weight mole- The ASTM G53-96 provided the main guidelines. This
cules, which can, thus, lead to embrittlement and stiening standard prescribes the following two-step procedure in
of the polymer matrix [21,22]. Moreover, salt crystals inhi- order to have an accelerated, simulated environmental
bit the diusion of water, by blocking the paths through impact on polymers and composite materials:
which water diuses into the material. In comparison, dis- Step A: Specimen preconditioning
tilled water is absorbed to a greater extent compared to Specimens are stored at about 50% relative humidity
salted water [20,23]. conditions, at 23 C without UV for 7 days.
In order to investigate the combined eect of tempera- Step B: Specimen main ageing procedure
ture, humidity and ultraviolet radiation on the properties Specimens are subjected to alternating cycles of UVB
of isophthalic polyester/glass ber composite materials, (302 nm) and condensation according to the following
the construction of an environmental accelerated ageing scheme: 4 h UVB at 60 C without condensation followed
chamber was undertaken. This chamber would provide by 4 h condensation (98% RH) at 50 C. This cycle is
accelerated ageing by alternating cycles of temperature, repeated for about 1008 h or 42 days (6 weeks). The above,
humidity and UV radiation. The changes in the mechanical simulated, environmental ageing protocol is schematically
and viscoelastic behavior of the aged materials vis-a-vis the shown in Fig. 1.
virgin samples were not only examined by tensile and three A cubical PMMA chamber shown in Fig. 2A of approx-
point bending tests, but also by dynamic mechanical anal- imately 1 1 1 m3, was devised, featuring two program-
ysis (DMA). The fracture surfaces of the specimens were mable logic controllers (PLCs) in order to maintain
examined by scanning electron microscopy and useful con- exact control of the temperature, humidity and ultraviolet
clusions were drawn. radiation. The chamber featured digital monitoring of all
needed operational parameters. The inside walls were
2. Experimental painted by epoxy marine lacquer (gel-coat), in order to pro-
tect the chamber material itself from ageing. Humidity
2.1. Environmental accelerated ageing chamber (EA2C) inside the chamber was provided, through a exible tube,
by an ultrasonic humidier, which was supplied by distilled
Three ASTM standards were used as guidelines for the water. The real-time recorded temperaturerelative humid-
construction of the environmental chamber namely, (a) ity curves are incorporated in Fig. 2B.

Fig. 1. The alternating temperature, humidity and UV-radiation cycles during the accelerated environmental ageing procedure.
D.E. Mouzakis et al. / Composites: Part B 39 (2008) 467475 469

Fig. 2. The environmental accelerated ageing chamber (EA2C) and the real-time recorded temperature humidity cycles.

2.2. Materials was a Q800 type of TA instruments. Test mode was three
point bending under controlled strain. Temperature was
The isophthalic polyester was prepared by mixing 100 g set between 35 and +200 C, with constant frequency of
resin with 1.1 g methyl ethyl ketone (MEK) peroxide initi- 1 Hz, during temperature scans. Frequency scans were also
ator and pouring it into moulds of rectangular and dumb- performed varying from 1 to 30 Hz, at a constant temper-
bell shape. After 24 h, the resin was placed inside an oven ature of 25 C. Preloading was set at 0.125 N and strain
and post-cured, at 30 C, for 24 h. Concerning GFRPC, it amplitude was 15 lm. Each material was tested in its pris-
was provided in ca. 600 600 mm2 plaques of 1 mm thick- tine, aged but saturated in water and aged but in dried
ness, at ca. Vf = 20%. The reinforcement consisted of a conditions.
random glass ber mat onto which 090 glass rovings were
stitched. 2.3.2. Static tensile tests
It has to be stated that before placing all specimens Static tensile tests were performed on an MTS 20KN
inside the ageing chamber, they were sealed with a special universal testing machine per ASTM D3039/D3039 M-
elastomeric sealant resin around the edges, to prevent 94a, at 2 mm/min crosshead speed, for the composite mate-
moisture absorption, in other than through the thickness rial and ASTM D638-76, at 1 mm/min, for the isophthalic
direction. In this way, Fickian diusion of moisture inside polyester. Tensile strain was measured by strain gauges
the material was ensured. The specimens were not sub- attached along the specimen longitudinal axis. The speci-
jected to any special preconditioning prior to the initiation men dimensions were 250 25 1 mm3 for the composite
of the chamber cycles, since the conditions maintained in material and dumbbells of 165 mm total length and 5 mm
the storage room, where the materials were kept, were thickness for the polymer. A number of 10 specimens were
almost identical to those of the preconditioning phase. used for extracting the average mechanical properties for
Upon completion of the environmental ageing campaign the pristine, the dried-aged and the humid-aged (saturated)
(42 days) the materials were removed from the chamber specimens, respectively. The experiments took place at
and carefully sealed in a plastic bag to ensure that they will ambient temperature and relative humidity conditions.
keep the absorbed moisture. In addition, some aged speci-
mens of both materials were cut properly and dried for a 2.3.3. Three point bending tests
whole week, at 40 C, under vacuum, in order to provide Three point bending (3PB) tests were performed on an
comparison data against the humid-aged specimens. MTS 20KN universal testing machine per DIN (EN ISO
178), at 2 mm/min crosshead speed, while preloading was
2.3. Experimental techniques set at 10 N. A number of eight specimens were used for
extracting the average mechanical properties for the pris-
2.3.1. Dynamic mechanical analysis (DMA) tine and humid-aged (saturated) composite material, after
In order to nd out the exact impact of the environmen- the ageing in the environmental chamber. The dimensions
tal ageing on the viscoelastic behavior of the materials, of the samples were 80 20 2 mm3 and the experiments
thermal and frequency scans were performed on small bars took place at room conditions. Measurements of force/
of ca. 60 12 1 mm3 for the composite and 60 12 deection were taken every 0.5 s and were transformed into
4 mm3 for the polymer materials respectively. The machine the equivalent values of stress/strain out of which the
470 D.E. Mouzakis et al. / Composites: Part B 39 (2008) 467475

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
=1Hz
were studied. Table 1 shows the average static mechanical
properties, in tension, of isophthalic polyester, which were
0.45
tan [-]

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


and dried-aged (ECD) polyester, respectively. These speci-
mens were all aged inside the EA2C. 0.30
As is evident from the data reported in Table 1, the ten-
sile strength rult of isophthalic polyester appears to be 0.15
decreasing as the environmental ageing increases. Further-
more, a small increase of the elastic modulus and decrease
0.00
in the failure strain, eult of the aged polymer (humid and
dried) can also be observed. These changes are indicative -50 0 50 100 150 200
of embrittlement in the case of the aged polymer. Temperature [ oC]
Fig. 3 presents the thermal scans for the polyester sam- Fig. 3. DMA thermal scans for the isophthalic polyester matrix samples.
ples. It appears that up to 100 C, within the glass transi- (a) Storage modulus and (b) tan d vs temperature, respectively, ECH:
tion region, the storage modulus (E 0 , Fig. 3a) of the aged-humid specimens, ECD: aged and post-dried specimens.
environmentally aged samples of isophthalic polyester
increases as compared to the pristine material. However,
no dierences can be observed between the storage modu- material mobility, which complies with the stiening
lus values of the humid and dried samples. On the other observed during tensile testing. In the rubbery state, no dif-
hand, the damping constant, tan d, of the aged samples ferences were observed between the viscoelastic behavior of
(Fig. 3b) are marginally higher than that of the virgin spec- the virgin and aged isophthalic polyester.
imen, showing no dierence again between the humid and The most plausible explanation of the irreversible
the dried aged samples. The irreversible increase of storage increase in E 0 that occurred in the aged polymer is a possi-
modulus, implies that some kind of permanent stiening ble post-curing that took place during the ageing proce-
occurs in the aged material. Moreover, a slight increase dure. This happened due to a combination of UVB
in the Tg of the aged polymer, (Tg of the virgin polyester radiation and high temperature, which were not severe
is at about 100 C) and also a narrowing of the peak can enough to break the chemical bonds of the polymer [11
be observed. These changes in the Tg, imply a decreased 15], but in contrast, they contributed to the creation of free
radicals to the molecules of unsaturated isophthalic polyes-
Table 1 ter which had not already reacted, and thus, to a further
Average tensile mechanical properties of the virgin, humid, (ECH) and cross-linking [7,14,1619].
dried (ECD) environmentally aged isophthalic polyester specimens, Furthermore, in epoxy resins, water has proved to be
respectively
responsible for the creation of a secondary network of
Polyester rult (MPa) E (GPa) eult (%) cross-links between free hydroxyls (OH) of the main chain
Virgin 47.27 3.3 2.37 0.04 2.52 0.25 of the resin. Therefore, water molecules do not act as plast-
ECH 47.08 4.94 2.59 0.04 2.18 0.28 icizers, as expected, but in contrast make the polymer some-
ECD 45.01 5.50 2.67 0.07 1.99 0.35
what stier. This is also marked by a shift of the Tg at higher
D.E. Mouzakis et al. / Composites: Part B 39 (2008) 467475 471

temperatures [24]. This kind of cross-linking may exist in aged material. The overall conclusion drawn here, is that
the materials studied here, as well, as a result of water mol- there is a number of mechanisms which can be held as
ecules forming multiple hydrogen bonds with the polyester responsible for causing an irreversible stiening of the mate-
resin network. Although isophthalic polyester resin does rial during the environmental ageing procedure. Stiening
not contain free OH along its main chain, it does contain of the composite material matrix when exposed to the envi-
free OH and H at the end of each main chain, which ronment can lead to non-predictable behavior of a structure
could be responsible for the creation of such hydrogen such as eigenfrequency shifting and/or deterioration of over-
bonds with water molecules as it happens in epoxy resins all structural damping and thus to life-span degradation.
[25,26]. A proposed mechanism is shown in Chemical To support our ndings with respect to material
Equation 1. Also, the oxygen of the carbonyl group, cobalt dynamic behavior under changing load frequency, DMA
[26], hydroquinone [27] or other additives found in commer- scans were performed in a limited frequency spectrum.
cial polymers may also be responsible for this phenomenon. Fig. 4 shows the DMA frequency spectra at the glassy state
Finally, the reacting chemicals of the chemical reaction of of the material (25 C). An irreversible increase of the stor-
isophthalic polyester contain free OH and it is envisaged age moduli (Fig. 4a) and decrease of tan d (Fig. 4b) is obvi-
that if they are in excess, they may contribute to the forma- ous again for the aged material. These ndings support our
tion of hydrogen bonds. These hydrogen bonds possess conclusions above regarding the irreversible stiening of
higher activation energies and are, therefore, harder to the matrix.
remove. The formation of this kind of bonds depends on In summary, changes in the mechanical properties of the
the exposure temperature and time; higher temperatures aged polymer, compared to the virgin, seem to be less dis-
and longer exposure times promote the creation of large tinct in tensile mode of testing while DMA tests provided
numbers of these bonds [9]. Also, exposing the polymer to more detailed results. This could be attributed to the fact
humidity, as in our occasion, and not immersing it to water, that ageing mainly occurs on the surface of the material
facilitates this eect due to the higher mobility of water mol- and 3PB results are sensitive to changes in the surface of
ecules when in the gaseous state [26,2]. the specimen. On the other hand, tensile tests concern the
Another mechanism related to water sorption, is the entire cross section of the specimen and not its surface
occupation of the voids of the material [4] or the possible mainly. Thus, because DMA tests were performed in the
leaching of low molecular weight molecules [8,10]. These 3PB mode they delivered the results of ageing on the matrix
also lead to an irreversible increase in the stiness of the in an unambiguous way.

-H2O
HO CH2 CH2 OH + HO CO CH CH CO OH + HO CO CO OH

RT
O CH2 CH2 O CO CO O CH2 CH2 O CO CH CH CO O CH2 CH2 O
O OH
CH3 C CH2 CH3
O OH

.
O CH2 CH 2 O CO CO O CH2 CH2 O CO CH CH CO O CH2 CH2 O
O CH CH2
CH 3 C CH 2 CH 3
O OH

CH
.
CH2
O CH2 CH2 O CO CO O CH2 CH2 O CO CH CH CO O CH2 CH2 O
O
CH3 C CH2 CH 3
O OH

Chemical Equation 1. A proposed mechanism of hydrogen bond formation with the polyester matrix.
472 D.E. Mouzakis et al. / Composites: Part B 39 (2008) 467475

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 ber properties. However,
5200
the data of Table 2 indicate: (a) slight stiening of the com-
Storage Modulus [MPa]

posite in the presence of water possibly emanating from the


4800 stiening 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
tan [-]

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 ber 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)
tan [-]

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 GFRPCs, 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) 467475 473

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


a
tion, the coupling agents (silanes) containing hydroxyl 16000
groups used as glass ber 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 ber 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 bers, as conrmed by Hodzic et al. for b 0.055 GFRPC-Virgin
glass/polyester composites [30]. They have conrmed 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 eect could lead to an increased tan d (material
damping) at high temperatures. Should this be the govern- 0.040
Tan

ing eect, 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 bers 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 exural 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 stiening 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 specically, 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, conrms 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 stiening
properties in 3PB tests of the pristine GFRPC and environ- eect of the GFRPC attributed to several mechanisms,
mentally aged GFRPC, in saturated conditions (ECH). which mainly promotes a post-curing eect on the polymer
Static 3PB tests showed small dierences 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) 467475

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- Regarding isophthalic polyester matrix, the experimental
face of the aged tensile specimens can be easily seen in data revealed that, after exposure, the polymer matrix
the microphotographs of Fig. 7. Nevertheless, the length became stier in an irreversible way. This happened mainly
of the noticed microcracks appears smaller than the critical because of the post-curing of the material, caused by tem-
value of 0.1 mm, required for crack propagation and there- perature and UV radiation. Also, the secondary cross-link-
fore did not possibly aect the tensile strength of the com- ing via hydrogen bonding, the occupation of the voids of
posite. Also, these microcracks do not appear scattered the materials and the possible leaching of low molecular
along the whole surface of the aged composite material. weight molecules due to water absorption, are considered
The fracture surfaces of three point bending specimens the main factors that contributed to the increase of stiness.
on pristine and aged condition are shown in Fig. 8. No dis- As far as the GFPC is concerned, the main ageing
tinct dierences could be stated from these microphoto- parameter was again matrix stiening, due to UV radia-
graphs with respect to matrix or ber failure. Fracture tion, temperature and water. In addition, a kind of interfa-
surfaces for aged and pristine specimens are dominated cial degradation was observed for the composite material,
by matrix fracture and multiple ber fragmentation, which during DMA scanning at high temperatures, possibly
are typical for these types of composites. Also, no evidence because of expansion of water molecules at the interface
of interfacial debonding phenomena is present. combined with hydrolysis. In addition, SEM images on
the surface of the composite, before and after the ageing
4. Conclusions of the material in the environmental chamber, revealed that
some microcracks had occurred on its surface. Neverthe-
An environmental chamber that can simulate acceler- less, the length of these microcracks was less than the crit-
ated ageing on polymers and composites was constructed ical value of 0.1 mm, required for crack propagation and,
and tested. This chamber provided two alternative cycles, as a result, they should not aect the tensile strength of
including a combination of stable conditions of tempera- the composite. No specic dierences or ndings could be
ture, humidity and UVB radiation. The materials aged stated for the fracture surfaces of the virgin and aged three
in this chamber were isophthalic polyester and GFPC. point bend composite specimens.
D.E. Mouzakis et al. / Composites: Part B 39 (2008) 467475 475

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