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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-


cles into the matrices are of practical importance for successful
Epoxies have been widely used and thus subjected to extensive applications of nanoparticle-modied matrices in bre-reinforced
investigations over the past few decades. Soft modiers such as composites.
rubber have been found to clearly increase the fracture toughness Some quantitative assessment of the inuence of rigid nanopar-
of epoxies, but to signicantly reduce strength, modulus and glass ticles on the brematrix adhesion in bre-reinforced composites
transition temperature (Tg). The incorporation of rigid nanollers, has been undertaken, but with inconsistent results. Yang et al.
such as nanoclays, TiO2, Al2O3, or silica nanoparticles into epoxies [12] applied an emulsion sizing containing pre-treated nano-SiO2
has been demonstrated to signicantly improve the mechanical particles on the surface of carbon bres, and performed single bre
properties of the epoxies without sacricing their basic properties fragmentation tests and short beam shear tests on the bres. Their
[15]. Particularly in recent years, silica nanoparticles produced by results indicated that nanosilica emulsion sizing signicantly im-
solgel processes have attracted extensive research interest [68]. proved interfacial shear strength. However, Lew et al. [13] found
Due to the tiny uniform size (20 nm in diameter) and uniform that the breepoxy interface was not affected by the incorpora-
distribution of nanosilica particles, epoxy resins containing such tion of up to 2% SiO2 nanoparticles. Godara et al. [14] dispersed car-
particles have relatively low viscosity, which makes them suitable bon nanotubes (CNTs) in a bre sizing formulation and applied the
for resin infusion (RI), resin transfer moulding (RTM), and other sizing on the surfaces of E-glass bres and also in the matrix of a
cost-effective manufacturing processes to fabricate bre-rein- glass/epoxy composite. Their results from single bre push-out
forced composite laminates [911]. tests conducted on unidirectional composite specimens indicated
In bre-reinforced composite materials, the adhesion quality that the carbon nanotubes in the sizing resulted in higher interfa-
between bres and the matrix plays a major role in the overall per- cial shear strength, whereas the incorporation of CNTs in the ma-
formance of the materials. It is thus necessary to be aware of the trix was less effective. Uddin and Sun [15] investigated the
effects of the incorporated nanoparticles on the brematrix bond- strength of a unidirectional glass/epoxy composite with matrix
ing behaviour. Therefore, studies investigating the variations in modied by silica nanoparticles and found that nanosilica particles
improved the tensile strength and modulus in the transverse direc-
Corresponding author. tion. Quaresimin and Varley [16] showed that three different com-
E-mail address: lin.ye@sydney.edu.au (L. Ye). 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, epoxy resin, Araldite-F (Ciba-Geigy, Australia), to form silica-con-
which was believed to be a result of the bre tows preventing opti- taining epoxy suspensions.
mal dispersion of the nanoclay particles in the matrices. T300 carbon bres (FGI Fibre Glass International, Australia)
The interfacial properties of certain brematrix systems can be with a nominal diameter of 7 lm were used in the form of bre
evaluated by micro-mechanical testing techniques or by macro- tows (bundles) for preparing TFB specimens.
mechanical testing methods. Micro-mechanical techniques, such
as single bre pull-out and bre fragmentation tests, have certain 2.2. Preparation of TFB specimens
limitations to their use, and have not yet been standardized. Alter-
natively, macro-mechanical testing methods can be used to indi- The TFB specimens were prepared using a silicon rubber mould
rectly assess brematrix interfacial adhesion, but they require as shown in Fig. 1. The dimensions of a TFB specimen were based
the production of bulk composite laminates, which is time-consum- on tensile testing standard ASTM D638 [20]. Before casting the re-
ing and costly. Transverse tensile testing of unidirectional compos- sin into the rubber mould, one carbon bre bundle containing 3000
ites in the direction perpendicular to the bres can be used to bres was spread evenly and transversely placed into cuts that had
correlate the interfacial strength variation when bre surface condi- been made to the walls of the rubber moulds in the middle of the
tions vary [17]. It is necessary, however, to fabricate unidirectional mould. The depth of the cuts was equal to the thickness of the
bre-reinforced composites for such testing. A transverse bre bun- specimen to be prepared. The Araldite-F epoxy was rst mixed
dle (TFB) test method has been proposed to assess the brematrix with nanosilica-containing Nanopox XP 22/0616 using a mechani-
interfacial adhesion without the need to manufacture the actual cal mixer, stirring for 30 min at 60 C. The resulting weight per-
composite [18,19] and has been successfully applied to certain - centages of nanosilica in the mixtures were 0, 2, 4, 10 and
brematrix systems in which the coefcients of thermal expansion 20 wt%, respectively. After that, degassing of the mixtures was per-
(CTEs) of the bres were comparable to those of the matrices [20]. formed in a vacuum oven to eradicate any entrapped air bubbles.
However, the major complication of the TFB testing was the effect Piperidine hardener (SigmaAldrich, Australia) was then added
of residual stresses, particularly in boundary regions between the - into the mixtures in a ratio of 100:5 (epoxy: hardener) by weight,
bre bundles and the bulk matrix. These residual stresses were gen- while stirring slowly. Next, the mixture was cast into specimen
erated during the cooling process from the curing temperature to cavities in the preheated silicon rubber moulds and cured at
ambient temperature, due to the mismatch in the CTEs of the matrix 120 C for 16 h. Once the specimens had been cooled and removed
and the bres and the cure volume shrinkage (CVS) due to the curing from the moulds they were milled using a surface grinder on both
of the epoxy matrix from liquid to solid state, which complicated top and bottom surfaces to ensure their atness and smoothness.
interpretation of the TFB testing data and even resulted in prema- Fig. 2 illustrates a polished cross-section of an untested TFB
ture failure of test specimens [18,19]. Nevertheless, it is still possible specimen. It can be seen that the impregnation of the matrix resin
to use TFB tests to evaluate the brematrix adhesion for carbon - in the bre bundle was very good and the distribution of the bres
bre reinforced epoxy composites with nanoparticle-modied matri- of the bre bundle in the matrix was basically uniform. The thick-
ces if further investigations are carried out to correlate the residual ness of the bre bundle in the matrix was around 400 lm (be-
stresses with the brematrix interfacial properties. tween the dotted lines in Fig. 2). The average bre volume
In this study, a TFB test method was adopted to assess the bre fraction within the bre bundle region was 61.5%, measured by
matrix interfacial adhesion of bre-reinforced composites with dif- the image analysis method using an optical microscope.
ferent amounts of silica nanoparticles in the matrix, using nite
element analysis (FEA) for data interpretation. The tensile proper- 2.3. Tensile tests
ties of the TFB specimens were measured and the fracture surface
and breepoxy interfacial region were examined by scanning Tensile tests for the dog-bone-shaped TFB specimens and also
electron microscopy (SEM) and transmitting electron microscopy the neat epoxy specimens were carried out on an Instron testing
(TEM). The residual stresses at the brematrix interface in the machine (Model 5567). A longitudinal extensometer (Instron,
specimens were determined by FEA and then correlated with the Model 2630-112, gauge length of 50 mm) and a transverse exten-
results obtained from TFB testing to identify the effect of nanosilica someter (Epsilon, Model 3575-100-LT) were used to measure the
particles on the brematrix interfacial strength of carbon bre- strains in both the longitudinal and transverse directions. All ten-
reinforced epoxy composites. 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-
2. Experimental imens were successfully tested for each group of specimens with
different amount of silica nanoparticles incorporated.
2.1. Materials
2.4. Measurement of CTE and CVS
Different amounts of a SiO2 nanoparticle dispersed epoxy
(Nanopox XP 22/0616, Hanse-Chemie AG, Germany) were The CTEs of the cured epoxy matrices without/with nanosilica
separately mixed with a diglycidyl ether of bisphenol A (DGEBA) particles were determined by a dynamic mechanical analyser (TA

Fig. 1. Schema of a TFB specimen.


J. Zhang et al. / Composites: Part A 55 (2013) 3544 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.
Fig. 2. Optical micrograph of the bre bundle region in a TFB specimen.

DMA 2980) with temperature scanning from ambient temperature 4. Results and discussion
to 130 C at a heating rate of 3 C/min. A compression xture was
used for the DMA measurement using specimens with dimensions 4.1. Tensile properties of TFB specimens
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 A summary of the tensile test results obtained at ambient tem-
with the xture during measurements. The data processing proce- perature for the TFB specimens is presented in Table 1, together
dures used in a previous study [21] were adopted in this study to with the transverse tensile testing results of the unidirectional car-
obtain CTEs of the cured epoxies. bon bre/epoxy composite laminates [11]. A comparison of the
The CVS of the epoxies with different silica content was mea- typical tensile strainstress curves of the TFB specimens with dif-
sured by comparing the volume change of the epoxy matrices be- ferent amounts of nanosilica is shown in Fig. 4. From Fig. 4, it
fore and after curing, using a high resolution camera. The mixture can be seen that TFB specimens failed in a brittle manner and their
of epoxy and hardener was lled into a nely-scaled 50 ml glass failure occurred suddenly with little plastic deformation. In Fig. 4a,
cylinder with an inner diameter of 20 mm. The cylinder was posi- the effective modulus of the TFB specimen, with the neat epoxy as
tioned vertically in a hot oil bath at 120 C until the mixture was the matrix, retains the same value as that of the neat epoxy, though
fully cured. The volume change of the mixture in the cylinder a carbon bre bundle was inserted in the middle. For the TFB spec-
was then determined by comparing the volumes before and after imens with matrices containing different amounts of nanosilica,
the curing, from photographs taken by the high resolution camera. 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
3. Determination of thermal residual stresses by FEA method similar, around 2022 MPa, as shown in Fig. 4b.
The tensile test results shown in Table 1 indicate that: (a) the
A 2D FEA was conducted using a commercial program, ABAQUS, transverse strength of the TFB specimen using neat epoxy is
to elaborate distributions and magnitudes of thermal residual around 20 MPa, much lower than the tensile strength of the neat
stresses in the TFB specimens as a result of the curing and cooling epoxy (66 MPa), (b) the tensile strength of the TFB specimens is
process from the curing temperature to the ambient temperature. not obviously affected by the inclusion of nanosilica particles,
The 2D FE model was considered in a plain strain state. The and (c) there are differences (10 MPa) between the tensile

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.)
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 ticles are seen on the bre surface. Further investigation using TEM
of the unidirectional composite specimens using the same bres shows similar ndings. As shown in Fig. 7, the nanoparticles are
and matrices. uniformly dispersed in the matrix and no nanosilica particles are
SEM was used to examine the fracture surfaces of the TFB spec- clustered around the brematrix interfaces. It is concluded, there-
imens containing different amounts of nanosilica particles. As fore, that the presence of nanosilica particles does not greatly affect
shown in Fig. 5, the fracture surfaces for all TFB specimens look the adhesion between the bres and the epoxy matrices.
similar at low magnication. Fibre surfaces and grooves left in As mentioned previously, there are gaps (10 MPa) between
the matrix on the fracture surfaces are smooth, with almost no ma- the tensile strengths of the TFB specimens and the transverse ten-
trix resin stuck on bres. At high magnication, as shown in Fig. 6, sile strengths of the unidirectional composite specimens using the
the nanosilica particles can be clearly seen in the matrix in both the same amounts of nanosilica in the matrices. This may be attributed
secondary electron and back-scatter images. However, no nanopar- 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 material properties of the nanosilica modied epoxies were
the stiff nanosilica particles embed between the polymer chains
obtained from both mechanical tests and DMA measurements. It
and prevent the chains from sliding.
should be note that resin ow and compaction usually began be-
fore curing shrinkage and they might not have such a signicant
4.3. FE analysis of TFB specimen contribution to nal residual stresses. As indicated by White and
Hahn [23], when a matrix is in its low viscosity state the residual
The elastic moduli of the all matrices were determined by stress induced in curing may vanish due to stress relaxation. In
means of a dynamic mechanical analyser (TA DMA 2980) with the current simulation, therefore, only a small portion of CVS mea-
temperature scanning from ambient temperature to 150 C at a sured experimentally was considered as a function of the CTEs of
heating rate of 2 C/min. As reported in a previous study [22], matrices in the temperature range of 120100 C, on the basis of
due to the variations in loading modes and test conditions, there the procedure adopted in a previous study [19], as shown in
were discrepancies between the absolute values of the elastic Table 5.
(storage) modulus and the modulus of elasticity measured via con- During FE simulation, the thermal history and external tensile
ventional mechanical tests. Therefore, the values of the elastic loading of a TFB specimen were considered in a time frame con-
moduli of the matrices at room temperature were taken from the taining three arbitrary load steps. The rst two steps reected
tensile testing results, while those at elevated temperatures were the cooling-down phase from 120 C to 100 C, in which the CVS
derived from the DMA tests and calibrated by the mechanical test- was considered, then further to 23 C, when no external stress
ing results on the basis of procedures detailed in the previous work was applied, only the internal stresses induced by the CTE mis-
[22]. match of the bres and the matrix. In the third step, the external
The CTEs and Poissons ratios of the matrices and the carbon - stress was increased from 0 to 20 MPa, and the temperature was
bre were assumed to be independent of temperature. Also, we as- kept constant at 23 C.
sume that the Poissons ratios of epoxy matrix with different Fig. 8 illustrates the stress distributions (in MPa) around the
nanosilica content remain the same as that of the neat epoxy boundary region between the bres and the bulk neat epoxy in a
(0.418). The modulus of elasticity, Poissons ratio, and CTEs of the TFB specimen after curing when it was cooled from 120 C to
carbon bre were adopted from the literature [18]. Table 3 shows 23 C, before an external stress was applied. It can be seen that,
the material properties used for FE simulation for the unmodied in the absence of external stress, the residual thermal stresses
matrix (neat epoxy) and the anisotropic carbon bre. Compared are much higher in regions between the carbon bres adjacent to
to the neat epoxy, the modied epoxies had increased moduli, as the bulk epoxy. Because of the combined effect of CVS and the dif-
shown in Table 4, due to the incorporation of nanosilica particles ference in CTE between the matrix and the bres, high Mises stres-
[6]. Therefore, residual stresses in the different TFB specimens with ses are built up in matrix locations between the bres, particularly
different amounts of nanosilica were estimated by the variations of between the rst row bres adjacent to the bulk matrix. The high-
matrix moduli, curing shrinkage and thermal contraction. 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 men is greatly increased, around twice that of the specimens
only a tensile stress of 20 MPa, assuming that there were no ther- subjected to applied stress alone.
mal residual stresses involved. As shown in Fig. 9, without consid- Fig. 11 shows the thermal residual stress distributions (Mises
ering thermal residual stresses, the highest stresses are distributed stress) along the vertical line in the middle of the model for pure
on the bres in the rst row adjacent to the bulk epoxy, the highest and 20% nanosilica modied epoxies in a TFB specimen, and the
value of Mises stress being around 38 MPa. The stress gradually de- thermal residual stresses along the horizontal line on the rst
creases for bres distant from the brematrix boundary. High row in the boundary region of the bres and bulk matrix are shown
stresses also exist near the left and right edges of the specimen. in Fig. 12. It can be seen that the thermal residual stresses in the
When a tensile stress, for example 20 MPa, is applied to the area between two adjacent bres are very high. However, around
model with the presence of thermal residual stresses, the concen- the central location of the bre bundle, the stresses are more uni-
trated stresses are superimposed on the thermal residual stresses, form and are much lower. It can also be seen that the thermal
as shown in Fig. 10. As a result of the combined stress, the stress residual stress and the combined stress for the matrix with 20%
magnitude is greatly increased. From Fig. 10, it can be seen that nanosilica are lower than those of the neat epoxy in a TFB speci-
the highest stresses exist within the bres in the rst row adjacent men due to the lower CVS and CTE of the materials.
to the bulk matrix and also in bres near the specimen edges, with Once the external stress reaches a critical level, cracks are more
the highest Mises stress being around 71 MPa. likely to initiate at locations (bre, matrix or brematrix inter-
Table 6 provides a comparison of the maximum Mises stresses face) where the strength is the lowest. Compared with the bre
in a TFB specimen in three conditions: (a) with thermal residual and the matrix, the brematrix interface is usually the weakest
stresses; (b) with application of a transverse stress (20 MPa), but location, especially for the carbon breepoxy composites in the
no thermal residual stresses; and (c) with both thermal residual current study, so that brematrix interfacial cracking may appear
stresses and applied stress. It can be seen that with thermal resid- rst at locations in the boundary between the bre-rich area and
ual stress, the magnitude of stress concentration in the TFB speci- 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 the cracks generated between the bres in the rst row were the
brittle nature of the matrix. Therefore, the tensile failure strength most critical ones that led to nal failure [24].
of the TFB specimen is closely related to the failure strength of As mentioned previously, the low failure strength of the TFB
the brematrix interface. specimens in comparison with their matrix resins was attributed
The mechanisms just described can be conrmed by optical to the stress concentration in the matrix adjacent to the bres.
microscopy of the cross-section of a fractured specimen and SEM The presence of thermal residue stresses further increased the
observation of the fracture surface, as shown in Figs. 5 and 13. Mul- stress concentration. When a transverse tensile load is applied, -
tiple microcracks are believed to initiate rst in the bre-rich area bres act as hard inclusions in the matrix. Depending on the mod-
in the TFB specimen after the tensile load is increased to a critical ulus of the bre and the bre volume fraction of the composite,
level (Fig. 13a). These microcracks coalesce and propagate near the brematrix interface the local radial stress in the sur-
(Fig. 13b), and result in transverse failure of the TFB specimen rounding matrix is much higher than the applied stress [25], so
(Fig. 13c). that interfacial cracking occurs, causing premature failure of the
It should be noted that the FE simulation indicates that the TFB specimens. Therefore, the brematrix interfacial bonding
interfacial cracking most likely appears in the rst row of bres strength is indeed much greater than the applied stress. Table 7
adjacent to the bulk epoxy. Indeed, as shown in Fig. 13a, multiple shows the FE analysis results using the failure strength of TFB
cracks were initiated prior to the nal failure of the specimen, but 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- are smaller than those around the boundary region between the -
men with the neat epoxy matrix, the local stress concentrations bre bundle and the bulk epoxy, similar to the stress state of the
can be as high as 71.3 MPa, instead of being the failure strength transverse tensile specimen.
of the TFB specimen (20.3 MPa). Therefore, the interfacial bonding It should be noted that the tensile strengths obtained from both
strength may reach about the same level as the highest stress the transverse tensile tests of the unidirectional composites and
concentrations. It can also be seen that the presence of nanosilica the TFB tests are not direct measurements of the brematrix
particles in the matrices reduces the stress concentration around interfacial strength. However, both the tests are sensitive to varia-
the bres by about 10% for 20% silica. However, the failure tions in the interfacial bonding strength [17,20,26], so that their re-
strength of the TFB specimens with different amounts of nanosil- sults can be easily correlated into the brematrix interfacial
ica remains almost the same, indicating that the presence of properties once their thermal histories and CVS are determined.
nanosilica in the matrix does not obviously alter the brematrix In particular, the TFB method provides a simple and quick ap-
bonding conditions in the composites. proach for the assessment of brematrix adhesion in bre-rein-
As previously shown in Table 1, compared with the transverse forced composites.
strength of unidirectional carbon breepoxy composites, the ten-
sile strength of the corresponding TFB specimens is lower, which is 5. Conclusions
attributed to the residual stress concentrations caused by the
microscopic nonuniformity of the materials in the boundary re- In this work, TFB tests were successfully used to assess the ef-
gion. In a unidirectional composite, the bres are uniformly dis- fect of silica nanoparticles incorporated into epoxy matrices on
tributed in the matrix, so that the residual stresses generated by the quality of brematrix adhesion in carbon bre reinforced
the CVS of the matrix and the differences in the CTEs of matrix epoxy composites. FE analysis was used to determine the distribu-
and bres are also uniform in a test specimen. As previously shown tion and magnitude of thermal residual stresses which were gener-
in Fig. 11, the thermal residual stress distributions in the central ated by the combination of CVS and the mismatch in the CTE of
location of the bre bundle of a TFB specimen are uniform and 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- 10 wt% and 20 wt% silica nanoparticles in matrix resins. Compos Part A
Appl S 2011;42(12):194350.
ysis results with the tensile strengths of the TFB specimens, it was
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