Composites: Part A 55 (2013) 3544

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Effect of nanoparticles on interfacial properties of carbon breepoxy

composites
Jianing Zhang a, Shiqiang Deng a, Yulong Wang b, Lin Ye a,, Limin Zhou c, Zhong Zhang d
a
Centre for Advanced Materials Technology, School of Aerospace, Mechanical and Mechatronic Engineering, The University of Sydney, NSW 2006, Australia
b
Aerospace System Engineering Shanghai, Shanghai, China
c
Department of Mechanical Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, China
d
National Centre for Nanoscience and Technology, No. 11 Beiyitiao, Zhongguancun, Beijing 100190, China

a r t i c l e i n f o a b s t r a c t

Article history: This study assessed the effect of rigid nanoparticles on brematrix adhesion in bre-reinforced polymer
Received 17 April 2013 composites by means of a transverse bre bundle (TFB) test method with the bre bundle transversely
Received in revised form 8 August 2013 embedded in the middle of the TFB specimens. Fracture surfaces of the TFB specimens were examined
Accepted 11 August 2013
by scanning electron microscopy and transmitting electron microscopy to identify dispersion and mor-
Available online 21 August 2013
phologies of nanoparticles on and near the brematrix interfaces. A nite element analysis was con-
ducted to identify the distribution and magnitude of the thermal residual stresses within the TFB
Keywords:
specimen to correlate the TFB tensile strength with the bre/matrix interfacial strength. The coefcient
A. Carbon bre
A. Polymermatrix composites
of thermal expansion and cure volume shrinkage of matrices with different amounts of nanosilca parti-
B. Fibre/matrix bond cles were experimentally evaluated and were included in the FE simulation. Results showed that the
addition of nanosilica particles in the epoxy matrix did not noticeably affect the interfacial bonding
behaviour between bres and matrix.
2013 Elsevier Ltd. All rights reserved.

1. Introduction brematrix adhesion due to the incorporation of nanosilica parti-

Epoxies have been widely used and thus subjected to extensive
investigations over the past few decades. Soft modiers such as
rubber have been found to clearly increase the fracture toughness
of epoxies, but to signicantly reduce strength, modulus and glass
transition temperature (Tg). The incorporation of rigid nanollers,
such as nanoclays, TiO2, Al2O3, or silica nanoparticles into epoxies
has been demonstrated to signicantly improve the mechanical
properties of the epoxies without sacricing their basic properties
[15]. Particularly in recent years, silica nanoparticles produced by
solgel processes have attracted extensive research interest [68].
Due to the tiny uniform size (20 nm in diameter) and uniform
distribution of nanosilica particles, epoxy resins containing such
particles have relatively low viscosity, which makes them suitable
for resin infusion (RI), resin transfer moulding (RTM), and other
cost-effective manufacturing processes to fabricate bre-rein-
forced composite laminates [911].
In bre-reinforced composite materials, the adhesion quality
between bres and the matrix plays a major role in the overall per-
formance of the materials. It is thus necessary to be aware of the
effects of the incorporated nanoparticles on the brematrix bond-
ing behaviour. Therefore, studies investigating the variations in
Corresponding author.
E-mail address: lin.ye@sydney.edu.au (L. Ye).
cles into the matrices are of practical importance for successful
applications of nanoparticle-modied matrices in bre-reinforced
composites.
Some quantitative assessment of the inuence of rigid nanopar-
ticles on the brematrix adhesion in bre-reinforced composites
has been undertaken, but with inconsistent results. Yang et al.
[12] applied an emulsion sizing containing pre-treated nano-SiO2
particles on the surface of carbon bres, and performed single bre
fragmentation tests and short beam shear tests on the bres. Their
results indicated that nanosilica emulsion sizing signicantly im-
proved interfacial shear strength. However, Lew et al. [13] found
that the breepoxy interface was not affected by the incorpora-
tion of up to 2% SiO2 nanoparticles. Godara et al. [14] dispersed car-
bon nanotubes (CNTs) in a bre sizing formulation and applied the
sizing on the surfaces of E-glass bres and also in the matrix of a
glass/epoxy composite. Their results from single bre push-out
tests conducted on unidirectional composite specimens indicated
that the carbon nanotubes in the sizing resulted in higher interfa-
cial shear strength, whereas the incorporation of CNTs in the ma-
trix was less effective. Uddin and Sun [15] investigated the
strength of a unidirectional glass/epoxy composite with matrix
modied by silica nanoparticles and found that nanosilica particles
improved the tensile strength and modulus in the transverse direc-
tion. Quaresimin and Varley [16] showed that three different com-
mercially available organo-modied layered silicates decreased

1359-835X/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.compositesa.2013.08.005
36 J. Zhang et al. / Composites: Part A 55 (2013) 3544
the transverse tensile strength of carbon breepoxy composites,
which was believed to be a result of the bre tows preventing opti-
mal dispersion of the nanoclay particles in the matrices.
The interfacial properties of certain brematrix systems can be
evaluated by micro-mechanical testing techniques or by macro-
mechanical testing methods. Micro-mechanical techniques, such
as single bre pull-out and bre fragmentation tests, have certain
limitations to their use, and have not yet been standardized. Alter-
natively, macro-mechanical testing methods can be used to indi-
rectly assess brematrix interfacial adhesion, but they require
the production of bulk composite laminates, which is time-consum-
ing and costly. Transverse tensile testing of unidirectional compos-
ites in the direction perpendicular to the bres can be used to
correlate the interfacial strength variation when bre surface condi-
tions vary [17]. It is necessary, however, to fabricate unidirectional
bre-reinforced composites for such testing. A transverse bre bun-
dle (TFB) test method has been proposed to assess the brematrix
interfacial adhesion without the need to manufacture the actual
composite [18,19] and has been successfully applied to certain -
brematrix systems in which the coefcients of thermal expansion
(CTEs) of the bres were comparable to those of the matrices [20].
However, the major complication of the TFB testing was the effect
of residual stresses, particularly in boundary regions between the -
bre bundles and the bulk matrix. These residual stresses were gen-
erated during the cooling process from the curing temperature to
ambient temperature, due to the mismatch in the CTEs of the matrix
and the bres and the cure volume shrinkage (CVS) due to the curing
of the epoxy matrix from liquid to solid state, which complicated
interpretation of the TFB testing data and even resulted in prema-
ture failure of test specimens [18,19]. Nevertheless, it is still possible
to use TFB tests to evaluate the brematrix adhesion for carbon -
bre reinforced epoxy composites with nanoparticle-modied matri-
ces if further investigations are carried out to correlate the residual
stresses with the brematrix interfacial properties.
In this study, a TFB test method was adopted to assess the bre
matrix interfacial adhesion of bre-reinforced composites with dif-
ferent amounts of silica nanoparticles in the matrix, using nite
element analysis (FEA) for data interpretation. The tensile proper-
ties of the TFB specimens were measured and the fracture surface
and breepoxy interfacial region were examined by scanning
electron microscopy (SEM) and transmitting electron microscopy
(TEM). The residual stresses at the brematrix interface in the
specimens were determined by FEA and then correlated with the
results obtained from TFB testing to identify the effect of nanosilica
particles on the brematrix interfacial strength of carbon bre-
reinforced epoxy composites.
2. Experimental
2.1. Materials
Different amounts of a SiO2 nanoparticle dispersed epoxy
(Nanopox XP 22/0616, Hanse-Chemie AG, Germany) were
separately mixed with a diglycidyl ether of bisphenol A (DGEBA)
Fig. 1. Schema of a TFB specimen.
epoxy resin, Araldite-F (Ciba-Geigy, Australia), to form silica-con-
taining epoxy suspensions.
T300 carbon bres (FGI Fibre Glass International, Australia)
with a nominal diameter of 7 lm were used in the form of bre
tows (bundles) for preparing TFB specimens.
2.2. Preparation of TFB specimens
The TFB specimens were prepared using a silicon rubber mould
as shown in Fig. 1. The dimensions of a TFB specimen were based
on tensile testing standard ASTM D638 [20]. Before casting the re-
sin into the rubber mould, one carbon bre bundle containing 3000
bres was spread evenly and transversely placed into cuts that had
been made to the walls of the rubber moulds in the middle of the
mould. The depth of the cuts was equal to the thickness of the
specimen to be prepared. The Araldite-F epoxy was rst mixed
with nanosilica-containing Nanopox XP 22/0616 using a mechani-
cal mixer, stirring for 30 min at 60 C. The resulting weight per-
centages of nanosilica in the mixtures were 0, 2, 4, 10 and
20 wt%, respectively. After that, degassing of the mixtures was per-
formed in a vacuum oven to eradicate any entrapped air bubbles.
Piperidine hardener (SigmaAldrich, Australia) was then added
into the mixtures in a ratio of 100:5 (epoxy: hardener) by weight,
while stirring slowly. Next, the mixture was cast into specimen
cavities in the preheated silicon rubber moulds and cured at
120 C for 16 h. Once the specimens had been cooled and removed
from the moulds they were milled using a surface grinder on both
top and bottom surfaces to ensure their atness and smoothness.
Fig. 2 illustrates a polished cross-section of an untested TFB
specimen. It can be seen that the impregnation of the matrix resin
in the bre bundle was very good and the distribution of the bres
of the bre bundle in the matrix was basically uniform. The thick-
ness of the bre bundle in the matrix was around 400 lm (be-
tween the dotted lines in Fig. 2). The average bre volume
fraction within the bre bundle region was 61.5%, measured by
the image analysis method using an optical microscope.
2.3. Tensile tests
Tensile tests for the dog-bone-shaped TFB specimens and also
the neat epoxy specimens were carried out on an Instron testing
machine (Model 5567). A longitudinal extensometer (Instron,
Model 2630-112, gauge length of 50 mm) and a transverse exten-
someter (Epsilon, Model 3575-100-LT) were used to measure the
strains in both the longitudinal and transverse directions. All ten-
sile tests were carried out using a 1 kN load cell with a cross-head
rate of 1 mm/min at ambient temperature (23 C). At least six spec-
imens were successfully tested for each group of specimens with
different amount of silica nanoparticles incorporated.
2.4. Measurement of CTE and CVS
The CTEs of the cured epoxy matrices without/with nanosilica
particles were determined by a dynamic mechanical analyser (TA
 J. Zhang et al. / Composites: Part A 55 (2013) 3544
Fig. 2. Optical micrograph of the bre bundle region in a TFB specimen.
DMA 2980) with temperature scanning from ambient temperature
to 130 C at a heating rate of 3 C/min. A compression xture was
used for the DMA measurement using specimens with dimensions
of 10  10  8 mm. A tiny compressive force of 0.1 N was applied
for all CTE measurements in order to keep the specimen in contact
with the xture during measurements. The data processing proce-
dures used in a previous study [21] were adopted in this study to
obtain CTEs of the cured epoxies.
The CVS of the epoxies with different silica content was mea-
sured by comparing the volume change of the epoxy matrices be-
fore and after curing, using a high resolution camera. The mixture
of epoxy and hardener was lled into a nely-scaled 50 ml glass
cylinder with an inner diameter of 20 mm. The cylinder was posi-
tioned vertically in a hot oil bath at 120 C until the mixture was
fully cured. The volume change of the mixture in the cylinder
was then determined by comparing the volumes before and after
the curing, from photographs taken by the high resolution camera.
3. Determination of thermal residual stresses by FEA method
A 2D FEA was conducted using a commercial program, ABAQUS,
to elaborate distributions and magnitudes of thermal residual
stresses in the TFB specimens as a result of the curing and cooling
process from the curing temperature to the ambient temperature.
The 2D FE model was considered in a plain strain state. The
Fig. 3. Geometry and meshes of the 2D model for a TFB specimen. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version
of this article.)
37
stress-free temperature of the fully cured sample was set at
120 C. The interface between the bre and the matrix in the model
was considered to be perfectly bonded, without the use of any
interface elements. The cross-section of the bres was idealized
to be round and the bres were closely packed in the bre bundle
region.
Fig. 3 illustrates the geometry and the meshes of the 2D model
used in this study. For simplicity, a miniature TFB specimen was
simulated with dimensions of 135.5  200 lm. As the boundary
region between the bre-rich area and the bulk epoxy was the area
of interest, ner meshes were used at the bre surfaces and inter-
bre regions. Generally, four node linear quadrilateral elements
(CPE4R) were used. The total numbers of elements and nodes for
the model were 258,748 and 259,466, respectively. The nodes
along the bottom edge of the model are xed in y direction, allow-
ing motion only in x direction, and the node at the left bottom cor-
ner of the model is constrained in both x and y directions to
prevent the rigid body motion.
4. Results and discussion
4.1. Tensile properties of TFB specimens
A summary of the tensile test results obtained at ambient tem-
perature for the TFB specimens is presented in Table 1, together
with the transverse tensile testing results of the unidirectional car-
bon bre/epoxy composite laminates [11]. A comparison of the
typical tensile strainstress curves of the TFB specimens with dif-
ferent amounts of nanosilica is shown in Fig. 4. From Fig. 4, it
can be seen that TFB specimens failed in a brittle manner and their
failure occurred suddenly with little plastic deformation. In Fig. 4a,
the effective modulus of the TFB specimen, with the neat epoxy as
the matrix, retains the same value as that of the neat epoxy, though
a carbon bre bundle was inserted in the middle. For the TFB spec-
imens with matrices containing different amounts of nanosilica,
although their tensile moduli are relatively higher with an increase
in concentration of nanosilica, due to the reinforcing effect of the
nanoparticles on the matrices, their failure strengths are roughly
similar, around 2022 MPa, as shown in Fig. 4b.
The tensile test results shown in Table 1 indicate that: (a) the
transverse strength of the TFB specimen using neat epoxy is
around 20 MPa, much lower than the tensile strength of the neat
epoxy (66 MPa), (b) the tensile strength of the TFB specimens is
not obviously affected by the inclusion of nanosilica particles,
and (c) there are differences (10 MPa) between the tensile
38 J. Zhang et al. / Composites: Part A 55 (2013) 3544

Table 1
Tensile test results for the TFB tensile specimens and unidirectional carbon bre/epoxy composite laminates.

Specimen matrix composition Tensile strength (MPa) Modulus (MPa) Poissons ratio
Neat epoxy 65.8 1.9 2940 100 0.41 0.03
TFB-neat epoxy 20.3 7.3 2950 370 0.45 0.09
TFB-2% silica 21.1 4.6 3000 350 0.43 0.03
TFB-4% silica 20.5 7.0 3030 290 0.40 0.04
TFB-10% silica 21.1 0.4 3030 520 0.43 0.02
TFB-20% silica 22.1 1.6 3380 210 0.37 0.03
UD-CF/neat epoxya 31.1 0.7 11200 500
UD-CF/10% silicaa 32.6 3.1 11400 500
UD-CF/20% silicaa 36.8 1.7 12700 800
a
Unidirectional CF/EP composites [11].

strength of the TFB specimens and the transverse tensile strength
of the unidirectional composite specimens using the same bres
and matrices.
SEM was used to examine the fracture surfaces of the TFB spec-
imens containing different amounts of nanosilica particles. As
shown in Fig. 5, the fracture surfaces for all TFB specimens look
similar at low magnication. Fibre surfaces and grooves left in
the matrix on the fracture surfaces are smooth, with almost no ma-
trix resin stuck on bres. At high magnication, as shown in Fig. 6,
the nanosilica particles can be clearly seen in the matrix in both the
secondary electron and back-scatter images. However, no nanopar-
ticles are seen on the bre surface. Further investigation using TEM
shows similar ndings. As shown in Fig. 7, the nanoparticles are
uniformly dispersed in the matrix and no nanosilica particles are
clustered around the brematrix interfaces. It is concluded, there-
fore, that the presence of nanosilica particles does not greatly affect
the adhesion between the bres and the epoxy matrices.
As mentioned previously, there are gaps (10 MPa) between
the tensile strengths of the TFB specimens and the transverse ten-
sile strengths of the unidirectional composite specimens using the
same amounts of nanosilica in the matrices. This may be attributed
to the residual stresses concentrations caused by microscopic

Fig. 4. Typical tensile strainstress curves of TFB specimens: (a) neat epoxy and the TFB specimen with neat epoxy matrix; (b) TFB specimens with matrices containing
different amounts of nanosilica. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)
 J. Zhang et al. / Composites: Part A 55 (2013) 3544 39

Fig. 5. SEM images for fracture surface of various TFB specimens at low magnications.

Fig. 6. SEM photographs of fracture surfaces of the TFB specimen with matrix containing 20 wt% nanosilica: (a) and (b) secondary electron images; (c) and (d) back-scattered
electron images. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

Fig. 7. TEM photographs of brematrix interfacial region in the TFB specimen with epoxy matrix containing 20 wt% nanosilica particles.
40 J. Zhang et al. / Composites: Part A 55 (2013) 3544

Table 2 Table 4
CVSs of epoxies with different silica content. Elastic modulus for neat epoxy matrix with different silica content.
Silica content (wt%) CVS (%) Silica content (%) E (MPa)
0 2.24 (23 C) (60 C) (99 C)
2 2.21
4 2.18 0 2860 2500 16
10 2.08 2 2880 2500 16
20 1.80 4 2930 2550 18
10 3140 2638 23
20 3480 2800 28

nonuniformity of the materials at the boundary region [18]. This

can be claried by nite element (FE) analysis around the bound-
ary region of the bres and the bulk neat epoxy in a TFB specimen. Table 5
CTEs of epoxies with different silica content.

Silica content (%) a2 (120100 C) (1/K) a2 (9923 C) (1/K)

4.2. The CVS of the epoxy matrix with different silica contents
6 6
0 55.4  10 36.7  10
6 6
2 55.1  10 36.7  10
The CVS values of the epoxies with different silica content are 6 6
4 54.8  10 36.7  10
shown in Table 2. It can be seen that the CVS decreases gradually 10 52.3  10 6
35.0  10 6

from 2.24% to 1.80% when the silica content is increased from zero 20 45.0  10 6
30.0  10 6

to 20 wt%. In conrmation, the addition of nanoparticles reduces

the shrinkage of curing, which may be attributed to the fact that
the stiff nanosilica particles embed between the polymer chains
and prevent the chains from sliding.
4.3. FE analysis of TFB specimen
The elastic moduli of the all matrices were determined by
means of a dynamic mechanical analyser (TA DMA 2980) with
temperature scanning from ambient temperature to 150 C at a
heating rate of 2 C/min. As reported in a previous study [22],
due to the variations in loading modes and test conditions, there
were discrepancies between the absolute values of the elastic
(storage) modulus and the modulus of elasticity measured via con-
ventional mechanical tests. Therefore, the values of the elastic
moduli of the matrices at room temperature were taken from the
tensile testing results, while those at elevated temperatures were
derived from the DMA tests and calibrated by the mechanical test-
ing results on the basis of procedures detailed in the previous work
[22].
The CTEs and Poissons ratios of the matrices and the carbon -
bre were assumed to be independent of temperature. Also, we as-
sume that the Poissons ratios of epoxy matrix with different
nanosilica content remain the same as that of the neat epoxy
(0.418). The modulus of elasticity, Poissons ratio, and CTEs of the
carbon bre were adopted from the literature [18]. Table 3 shows
the material properties used for FE simulation for the unmodied
matrix (neat epoxy) and the anisotropic carbon bre. Compared
to the neat epoxy, the modied epoxies had increased moduli, as
shown in Table 4, due to the incorporation of nanosilica particles
[6]. Therefore, residual stresses in the different TFB specimens with
different amounts of nanosilica were estimated by the variations of
matrix moduli, curing shrinkage and thermal contraction.
The material properties of the nanosilica modied epoxies were
obtained from both mechanical tests and DMA measurements. It
should be note that resin ow and compaction usually began be-
fore curing shrinkage and they might not have such a signicant
contribution to nal residual stresses. As indicated by White and
Hahn [23], when a matrix is in its low viscosity state the residual
stress induced in curing may vanish due to stress relaxation. In
the current simulation, therefore, only a small portion of CVS mea-
sured experimentally was considered as a function of the CTEs of
matrices in the temperature range of 120100 C, on the basis of
the procedure adopted in a previous study [19], as shown in
Table 5.
During FE simulation, the thermal history and external tensile
loading of a TFB specimen were considered in a time frame con-
taining three arbitrary load steps. The rst two steps reected
the cooling-down phase from 120 C to 100 C, in which the CVS
was considered, then further to 23 C, when no external stress
was applied, only the internal stresses induced by the CTE mis-
match of the bres and the matrix. In the third step, the external
stress was increased from 0 to 20 MPa, and the temperature was
kept constant at 23 C.
Fig. 8 illustrates the stress distributions (in MPa) around the
boundary region between the bres and the bulk neat epoxy in a
TFB specimen after curing when it was cooled from 120 C to
23 C, before an external stress was applied. It can be seen that,
in the absence of external stress, the residual thermal stresses
are much higher in regions between the carbon bres adjacent to
the bulk epoxy. Because of the combined effect of CVS and the dif-
ference in CTE between the matrix and the bres, high Mises stres-
ses are built up in matrix locations between the bres, particularly
between the rst row bres adjacent to the bulk matrix. The high-
est Mises stress generated could be as high as 46 MPa.

Table 3
Material parameters for neat epoxy matrix and carbon bre.

Neat epoxy (23 C) Neat epoxy (60 C) Neat epoxy (99 C) Carbon bre
E1 (MPa) 2860 2500 16 235000
E2 (MPa) 2860 2500 16 15,000
E3 (MPa) 2860 2500 16 15,000
m12 0.418 0.418 0.418 0.166
m13 0.418 0.418 0.418 0.166
m23 0.418 0.418 0.418 0.4
6 6 6 6
a1 (1/K) 36.7  10 36.7  10 36.7  10 0.54  10
6 6 6
a2 (1/K) 36.7  10 36.7  10 36.7  10 10.1  10 6
6 6 6
a3 (1/K) 36.7  10 36.7  10 36.7  10 10.1  10 6
 J. Zhang et al. / Composites: Part A 55 (2013) 3544 41

Fig. 8. Residual thermal stress distributions around the boundary region of the bres and the bulk neat epoxy in a TFB specimen before tensile stress is applied. (For
interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

Fig. 9. Stress distributions around the boundary region of the bres and the bulk neat epoxy in a TFB specimen with only tensile stress applied. (For interpretation of the
references to colour in this gure legend, the reader is referred to the web version of this article.)

Using the same model, a FE analysis was conducted by applying
only a tensile stress of 20 MPa, assuming that there were no ther-
mal residual stresses involved. As shown in Fig. 9, without consid-
ering thermal residual stresses, the highest stresses are distributed
on the bres in the rst row adjacent to the bulk epoxy, the highest
value of Mises stress being around 38 MPa. The stress gradually de-
creases for bres distant from the brematrix boundary. High
stresses also exist near the left and right edges of the specimen.
When a tensile stress, for example 20 MPa, is applied to the
model with the presence of thermal residual stresses, the concen-
trated stresses are superimposed on the thermal residual stresses,
as shown in Fig. 10. As a result of the combined stress, the stress
magnitude is greatly increased. From Fig. 10, it can be seen that
the highest stresses exist within the bres in the rst row adjacent
to the bulk matrix and also in bres near the specimen edges, with
the highest Mises stress being around 71 MPa.
Table 6 provides a comparison of the maximum Mises stresses
in a TFB specimen in three conditions: (a) with thermal residual
stresses; (b) with application of a transverse stress (20 MPa), but
no thermal residual stresses; and (c) with both thermal residual
stresses and applied stress. It can be seen that with thermal resid-
ual stress, the magnitude of stress concentration in the TFB speci-
men is greatly increased, around twice that of the specimens
subjected to applied stress alone.
Fig. 11 shows the thermal residual stress distributions (Mises
stress) along the vertical line in the middle of the model for pure
and 20% nanosilica modied epoxies in a TFB specimen, and the
thermal residual stresses along the horizontal line on the rst
row in the boundary region of the bres and bulk matrix are shown
in Fig. 12. It can be seen that the thermal residual stresses in the
area between two adjacent bres are very high. However, around
the central location of the bre bundle, the stresses are more uni-
form and are much lower. It can also be seen that the thermal
residual stress and the combined stress for the matrix with 20%
nanosilica are lower than those of the neat epoxy in a TFB speci-
men due to the lower CVS and CTE of the materials.
Once the external stress reaches a critical level, cracks are more
likely to initiate at locations (bre, matrix or brematrix inter-
face) where the strength is the lowest. Compared with the bre
and the matrix, the brematrix interface is usually the weakest
location, especially for the carbon breepoxy composites in the
current study, so that brematrix interfacial cracking may appear
rst at locations in the boundary between the bre-rich area and
the bulk matrix. Further coalescence and propagation of these
42 J. Zhang et al. / Composites: Part A 55 (2013) 3544

Fig. 10. Stress distributions around the boundary region of the bres and the bulk neat epoxy in a TFB specimen after tensile stress is applied. (For interpretation of the
references to colour in this gure legend, the reader is referred to the web version of this article.)

cracks will result in instant failure of the TFB specimen due to the
brittle nature of the matrix. Therefore, the tensile failure strength
of the TFB specimen is closely related to the failure strength of
the brematrix interface.
The mechanisms just described can be conrmed by optical
microscopy of the cross-section of a fractured specimen and SEM
observation of the fracture surface, as shown in Figs. 5 and 13. Mul-
tiple microcracks are believed to initiate rst in the bre-rich area
in the TFB specimen after the tensile load is increased to a critical
level (Fig. 13a). These microcracks coalesce and propagate
(Fig. 13b), and result in transverse failure of the TFB specimen
(Fig. 13c).
It should be noted that the FE simulation indicates that the
interfacial cracking most likely appears in the rst row of bres
adjacent to the bulk epoxy. Indeed, as shown in Fig. 13a, multiple
cracks were initiated prior to the nal failure of the specimen, but
the cracks generated between the bres in the rst row were the
most critical ones that led to nal failure [24].
As mentioned previously, the low failure strength of the TFB
specimens in comparison with their matrix resins was attributed
to the stress concentration in the matrix adjacent to the bres.
The presence of thermal residue stresses further increased the
stress concentration. When a transverse tensile load is applied, -
bres act as hard inclusions in the matrix. Depending on the mod-
ulus of the bre and the bre volume fraction of the composite,
near the brematrix interface the local radial stress in the sur-
rounding matrix is much higher than the applied stress [25], so
that interfacial cracking occurs, causing premature failure of the
TFB specimens. Therefore, the brematrix interfacial bonding
strength is indeed much greater than the applied stress. Table 7
shows the FE analysis results using the failure strength of TFB
specimens as the applied stresses to estimate the magnitude of

Table 6
Maximum stresses within TFB specimens under different conditions.

TFB specimen matrix Mises stress (thermal stresses Mises stress (20 MPa alone without consideration of Mises stress (thermal stresses plus
composition alone) (MPa) residual stresses) (MPa) 20 MPa) (MPa)
Neat epoxy 45.91 37.86 71.28
2% Silica 45.83 37.75 71.06
4% Silica 46.14 37.50 70.87
10% Silica 46.22 36.48 69.25
20% Silica 42.03 34.98 63.76

Fig. 11. Mises stress alongside the vertical line in the middle region of the bres and the bulk neat epoxy and 20% nanosilica modied epoxy in a TFB specimen (thermal
residual stresses only).
 J. Zhang et al. / Composites: Part A 55 (2013) 3544 43

Fig. 12. Mises stress on the horizontal line along the boundary region of rst row bres and bulk neat epoxy and 20% nanosilica modied epoxy in a TFB specimen (thermal
residual stresses only).

Fig. 13. Failure mechanism of a TFB specimen: (a) optical micrograph showing the cross-section of a fractured TFB specimen in a bre-rich area, (b) schematic demonstration
of crack coalescence and propagation, and (c) SEM micrograph of the fracture surface of the TFB specimen. (For interpretation of the references to colour in this gure legend,
the reader is referred to the web version of this article.)

Table 7
Comparison of failure strengths of TFB specimens with FEA results.

TFB specimen matrix Failure strength of TFB specimen Mises stress (thermal stresses alone) Mises stress (thermal stresses plus applied stress)
composition (MPa) (MPa) (MPa)
Neat epoxy 20.3 7.3 45.9 71.3
2% Silica 21.1 4.6 45.8 71.1
4% Silica 20.5 7.0 46.1 70.9
10% Silica 21.1 0.4 46.2 69.3
20% Silica 22.1 1.6 42.0 63.8

the brematrix interfacial bonding strength. For the TFB speci-
men with the neat epoxy matrix, the local stress concentrations
can be as high as 71.3 MPa, instead of being the failure strength
of the TFB specimen (20.3 MPa). Therefore, the interfacial bonding
strength may reach about the same level as the highest stress
concentrations. It can also be seen that the presence of nanosilica
particles in the matrices reduces the stress concentration around
the bres by about 10% for 20% silica. However, the failure
strength of the TFB specimens with different amounts of nanosil-
ica remains almost the same, indicating that the presence of
nanosilica in the matrix does not obviously alter the brematrix
bonding conditions in the composites.
As previously shown in Table 1, compared with the transverse
strength of unidirectional carbon breepoxy composites, the ten-
sile strength of the corresponding TFB specimens is lower, which is
attributed to the residual stress concentrations caused by the
microscopic nonuniformity of the materials in the boundary re-
gion. In a unidirectional composite, the bres are uniformly dis-
tributed in the matrix, so that the residual stresses generated by
the CVS of the matrix and the differences in the CTEs of matrix
and bres are also uniform in a test specimen. As previously shown
in Fig. 11, the thermal residual stress distributions in the central
location of the bre bundle of a TFB specimen are uniform and
are smaller than those around the boundary region between the -
bre bundle and the bulk epoxy, similar to the stress state of the
transverse tensile specimen.
It should be noted that the tensile strengths obtained from both
the transverse tensile tests of the unidirectional composites and
the TFB tests are not direct measurements of the brematrix
interfacial strength. However, both the tests are sensitive to varia-
tions in the interfacial bonding strength [17,20,26], so that their re-
sults can be easily correlated into the brematrix interfacial
properties once their thermal histories and CVS are determined.
In particular, the TFB method provides a simple and quick ap-
proach for the assessment of brematrix adhesion in bre-rein-
forced composites.
5. Conclusions
In this work, TFB tests were successfully used to assess the ef-
fect of silica nanoparticles incorporated into epoxy matrices on
the quality of brematrix adhesion in carbon bre reinforced
epoxy composites. FE analysis was used to determine the distribu-
tion and magnitude of thermal residual stresses which were gener-
ated by the combination of CVS and the mismatch in the CTE of
reinforcing bres and the matrix during the cooling process from
44 J. Zhang et al. / Composites: Part A 55 (2013) 3544
the curing to room temperature. From the correlations of FE anal-
ysis results with the tensile strengths of the TFB specimens, it was
possible to determine the brematrix interfacial bonding strength
of the bre-reinforced composites.
The results of this study indicated that the inclusion of nanosil-
ica particles in the epoxy matrices of the bre-reinforced compos-
ites did not signicantly affect brematrix interfacial bonding
strength. Furthermore, the study demonstrated the possibility of
using the TFB test method to evaluate the interfacial bonding
strength of bre-reinforced composites without requiring fabrica-
tion of the actual composite materials.
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