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Article history:
Received 23 April 2010
Received in revised form 23 August 2010
Accepted 26 August 2010
Available online 15 September 2010
Keywords:
A. Particle-reinforced composites
B. Mechanical properties
B. Thermal properties
C. Residual stress
Fiber Bragg grating
a b s t r a c t
The inuence of SiO2 nanoparticles and rubber micro-llers on the mechanical and thermal responses of
an epoxy based composite is investigated using classical quantitative thermo-mechanical testing (tensile
tests, DMTA, TMA), microstructural analysis (Micro-CT, TEM, SEM microscopy) as well as distributed optical sensing in order to determine different residual strain elds generated during processing. The results
show that the tensile modulus of the compounds increases with the addition of SiO2 and decreases with
the rubber content, following estimates of the HashinShtrikman model. The coefcient of thermal
expansion appears to be insensitive to the particles content in the temperature range investigated.
The residual strains generated during processing are inuenced by the rubber content that introduces
a strong relief, with respect to the one generated by the neat resin, whereas the silica content tends to
increase their level.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
Epoxy resins are versatile because of the large number of potential epoxy resin/curing agent combinations, each one of them giving a different molecular structure of the nal thermoset material.
They have widespread application, one of which is their use as
matrices of reinforced composites materials. Epoxies have in general good mechanical and thermal properties, however, highly
cross linked epoxy systems are usually brittle, which limit their
usefulness in applications requiring high impact and fracture
strengths. As a consequence, the search for toughened epoxy
matrices has become the subject of numerous recent publications,
and several formulations have been developed [14].
Epoxy resins can be substantially toughened by the addition of a
rubbery phase, although the improvement in toughness appears
commonly to be accompanied by a signicant loss in elastic modulus, strength and glass transition temperature [5,6]. Rigid llers
such as alumina [7], titanium dioxide [8] and clay [9] have been
added to the epoxies to increase their stiffness, strength and thermal properties but they have also demonstrated a favourable
toughening effect. It is possible to increase the toughness of an
epoxy resin by up to 100% using selected rigid llers, normally
sized in the range of nanometers. However, this toughening effect
seems to be moderate when being compared with the toughness of
Corresponding author.
E-mail address: john.botsis@ep.ch (J. Botsis).
0266-3538/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2010.08.019
2169
residual stress elds only in a limited amount of points. Nondestructive techniques such as based on Moir interferometry
[23], photo-elasticity [24] and other non-contact full-eld deformation measurement techniques have been proposed, however, a
relatively large specimen is required.
The present work is concentrated on investigating easy to process rubber toughened and nanoparticles reinforced epoxy matrices, with possibly enhanced stiffness/toughness balance as well
as good thermal properties, and with low residual stresses. The
microstructure of these composites is observed by electron microscopy and the mechanical properties are evaluated using standard
mechanical testing procedures. Cylindrical specimens with a
centrally located optical ber with a long ber Bragg grating
(FBG) are produced from the composites. The shrinkage as a result
of curing, produces compressive strains on the FBG which is
recorded by means of the optical low coherence reectometry
(OLCR)-based technique [25]. Such strains allow to determine the
residual strains and to evaluate the coefcient of thermal
expansion (CTE) of certain epoxy ller combination.
2. Experimental
2.1. Material components
The epoxy resins used are all Diglycidyl ether of Bisphenol A
(DGEBA) modied with Hexadioldiglycidyl ether. The three
materials used in this study are: (a) CeTePox VP 823-30R, neat
epoxy resin (EP), delivered by Chemicals and Technologies for
Polymers GmbH [26]. (b) CeTePox VP 823-33R: This master batch
epoxy resin is a suspension containing SiO2 nanoparticles
(Chemicals and Technologies for Polymers GmbH). The dispersed
phase consists of surface-modied, spherical nano-SiO2 with
diameters under 50 nm and an extremely narrow particle size
distribution, obtained from a solgel chemical process. The
particles are agglomerate-free and homogeneously distributed in
the epoxy resin. This behaviour permits the resin to maintain a
relatively low viscosity even at a high ller content [27]. (c) Albidur
EP 2240 A: Master batch epoxy resin, modied with reactive
silicone rubber (SR) micro-particles by Nanoresins GmbH. The elastomer fraction is a special silicon rubber addition with a particle
size of 0.13 lm, nely distributed as a separate phase in the uid
resin. Albidur EP 2240-A is totally compatible with other epoxy
resins and also with the most diverse curing agents. The silicone
elastomer particles have an organic shell structure comprising
reactive groups. The reaction curing rules the hydrophobicity of
the nal particles and can be used to adjust the polarity of the
formulation [28,29]. The main properties of these materials are
summarized in Table 1. The curing agent is Cetepox V 823-2H
and is based on cycle aliphatic polyamine, also supplied by
Table 1
Material properties.
Resins
Aspect
CeTePox VP 823-30R
Transparent uid
CeTePox VP 823-33R
Whitish uid
Albidur EP 2240 A
White uid
0.581
1.148
0
1160
0.485
1.249
19.125
1330
0.3180.345
1.081.12
40
30,00045,000
Aspect
Curing agent
Clear colorless liquid
H equivalent weight
Boiling point
Density
Eq./100 g
C
g/cm3
50.7
240
0.931
2170
T3 = 80 C
Table 2
Compositions of the nanocomposites and hybrid compounds in vol.%, and their
designations.
Silicon rubber
0
3
5.5
Nano-SiO2
t3 = 8 h
t1 = 2 h
0_0
3_0
5.5_0
0_3
3_3
5.5_3
0_8
3_8
T4 = 80 C
T0 = 60 C
t2 = 10 min
T1 = 60 C
Gelation
Crosslinking
Fig. 1. (a) Dissolver, (b) vertical mould, and (c) cylindrical specimen section.
2171
kB z kB0
1 pe ez z 1 pe eT af nDT
kB0
Fig. 3. TEM micrographs of the modied epoxy resins containing: (a) 8 vol.% SiO2
(material 0_8 of Table 2) and (b) 3 vol.% SiO2 + 5.5 vol.% SR (material 5.5_3 of
Table 2).
SiO2
1 m
Fig. 4. SEM picture of the fracture surfaces of material 3_8: SR refers to the rubber
particles, and SiO2 represents the nano-llers.
2172
Table 3
Density of silica-rubber modied epoxy resins at 25 C.
Content SiO2 (vol.%)
EP
+3 vol.% SR
3
0
3
8
+5.5 vol.% SR
Density (g/cm )
Std. dev.
Density (g/cm )
Std. dev.
Density (g/cm3)
Std. dev.
1.1524
1.1841
1.2339
0.0003
0.0005
0.0005
1.1479
1.1921
1.2230
0.0010
0.0040
0.0004
1.1432
1.1741
0.0008
0.0006
Fig. 5. Tensile moduli of SiO2 and SR modied epoxy matrices and comparison with
estimates of HashinShtrikman variational model.
Fig. 6. Storage modulus and damping factor as function of temperature for a rubber modied epoxy.
2173
Fig. 7. Residual strains evolution as function of the axial coordinate z for different
ller content and type.
Table 4
Coefcients of thermal expansion for all the materials considered.
CTE (105 C1)
Nano-SiO2
0
Silicon rubber
Fig. 8. Axial strains evolution during thermal cycles for the 0_0 material.
DkB z
1 pe ez z
kB0
where ez(z) is the residual strain along the ber direction (cf.
Fig. 1c). The results for some combination of llers are reported in
0
3
5.5
OLCR
TMA
OLCR
TMA
OLCR
TMA
6.74
6.38
6.67
6.12
6.73
6.79
/
6.46
6.43
5.85
6.58
7.45
/
6.46
/
6.00
6.70
/
Fig. 7, where three zones are clearly distinguishable. Zone I, for negative values of z, represents strains measured by the grating outside
the specimens; since these measurements are taken at room temperature no strains are applied to this part. Zone II, presents a steep
gradient of axial deformation, caused by the presence of the specimen edge and zone III a homogeneous strain level on the ber in
most cases.
With respect to the data corresponding to 0_0 (i.e., pure epoxy)
(Fig. 7), it can be seen that the introduction of rubber particles
reduces the residual strains, at z = 20 mm, by about 37% for the
5.5_0 mixture. Conversely the addition of 3 vol.% ceramic nanoparticles to this latter material resulted in a slight increase of this
residual eld (5.5_3). These results can be explained by considering
the difference in the material properties of the constituent llers.
Interestingly, an increase of the SiO2 content does not signicantly
affect the residual strain (3_8). The introduction of llers results
also in a drastic change of the shape of the axial strain along the
ber. This characteristic is highlighted by the comparison of
compositions 3_8, 5.5_3 and 0_0 in zones II and III which appear
to be affected by the llers as compared to pure epoxy (i.e., 0_0).
Note that for the material 0_8, a steep change of the axial strains
is recorder in zone III and is attributed to an interface failure as
discussed later.
3.4. Effect of temperature on residual strains
After the residual strain calculations at room temperature, selected specimens of each mixture were submitted to a series of
two similar heating proles, consisting of four temperature plateaus with: P1 = 31.5 C, P2 = 39 C, P3 = 48 C and P4 = 58 C, with
a maximum oscillation of 0.3 C. The range of these temperatures
2174
(a)
(b)
FD
FD
Fig. 10. lCT-pictures of ber debonding (FB) in the range of the uncoated part of the optical ber, where FBG was supposed to take place: (a) 2D section through the
composite cylinder and (b) 3D section (specimen 0_8).
has been chosen so that the highest temperature was below the
glass transition temperature of the epoxy. The temperature was
recorded, during the whole test, using K-type thermocouples
placed underneath the specimens, in direct contact with them.
Once the temperature in the furnace was stabilized at each plateau,
the specimens were allowed to reach equilibrium for more than
1 h. Afterwards, at least ve OLCR measurements were recorded
at each temperature.
To calculate the thermal strains, (1) is used. Since the residual
strains represented by the rst term of the right hand side of the
equation are known, the second term, representing the thermal
strains developed by the specimen during the thermal cycle, can
be easily calculated knowing the specimen temperature and the
wavelength shifts from the OLCR measurements. Results for the
neat resin conguration are reported in Fig. 8. Considering globally
the reported curves, it becomes clear that, for a given temperature,
the thermal cycles do not induce any modications on the epoxy
and the strain transfer to the ber, especially towards the centre
of the specimen (zone III). Some slight changes are visible in zone
II, indicating a small strain relief. This behaviour is also similar in
all the other samples, independently of the particle content.
eT z am af DT
Acknowledgements
One of us, K. Friedrich, is grateful to the laboratory of applied
mechanics and reliability analysis which enabled him to stay at
EPFL as a guest professor during the period of April 1 to May 31,
2009. Further thanks are due to the Swiss National Science Foundation under Grant 200020_124397 for the partial nancial support
of the work.
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