Composites Science and Technology 70 (2010) 20772085

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Composites Science and Technology

journal homepage: www.elsevier.com/locate/compscitech

Fatigue damage behaviors of carbon ber-reinforced epoxy composites containing nanoclay

Sha Ullah Khan a, Arshad Munir b, Rizwan Hussain b, Jang-Kyo Kim a,
a b

Department of Mechanical Engineering, Hong Kong University of Science and Technology Clear Water Bay Kowloon, Hong Kong National Engineering and Scientic Commission, P.O. Box 2801, Islamabad, Pakistan

a r t i c l e

i n f o

a b s t r a c t
The effects of nanoclay inclusion on cyclic fatigue behavior and residual properties of carbon ber-reinforced composites (CFRPs) after fatigue have been studied. The tensiontension cyclic fatigue tests are conducted at various load levels to establish the S-N curve. The residual strength and modulus are measured at different stages of fatigue cycles. The scanning electron microscopy (SEM) and scanning acoustic microscopy (SAM) are employed to characterize the underlying fatigue damage mechanisms and progressive damage growth. The incorporation of nanoclay into CFRP composites not only improves the mechanical properties of the composite in static loading, but also the fatigue life for a given cyclic load level and the residual mechanical properties after a given period of cyclic fatigue. The corresponding fatigue damage area is signicantly reduced due to nanoclay. Nanoclay serves to suppress and delay delamination damage growth and eventual failure by improving the ber/matrix interfacial bond and through the formation of nanoclay-induced dimples. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 13 February 2010 Received in revised form 19 June 2010 Accepted 5 August 2010 Available online 11 August 2010 Keywords: A. Nanoclay A. Carbon ber B. Fatigue B. Interfacial strength C. Damage tolerance

1. Introduction Carbon ber-reinforced composites (CFRPs) are widely used as structural material in load bearing applications because of high strength and stiffness, dimensional and thermal stability, and corrosion resistance. Fatigue is known to be one of the primary reasons for failure in many structural materials, including CFRPs [13]. When subject to cyclic loading, CFRPs exhibit gradual degradation of the mechanical and structural performance as a result of damage accumulation. The nature of fatigue damage in CFRPs is very complicated and is quite different from those of isotropic materials. The damage states are closely related to the anisotropy and heterogeneity which leads to the formation of different stress levels depending on the lay-up sequence and orientation of laminate. The fatigue damage modes in CFRPs include combinations of interfacial debonding, matrix cracking, delamination, ber breakage, etc. Early work on unidirectional CFRP laminates under tensile fatigue loading displayed a high degree of resistance before sudden catastrophic failure [4]. However, when the matrix was more highly loaded such as laminates with off-axis ber orientations, the response was completely different: there were multiple mechanisms of failure throughout the material involving combinations of ber and matrix damage interaction. The fatigue behavior of on-axis specimens was inuenced by the stochastic breakage of brittle ber
Corresponding author. Tel.: +852 23587207; fax: +852 23581543.
E-mail address: mejkkim@ust.hk (J.-K. Kim). 0266-3538/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.compscitech.2010.08.004

bundles, whereas that of off-axis angle-ply was strongly affected by the inelastic shear deformation and crack propagation of the ductile polymer matrix [5]. Similar conclusions were drawn in a recent study where the failure modes were as much related to the cyclic stress as to the off-axis angle [6]. For on-axis specimens the failure modes were ber-dominated and matrix-dominated when high and low cyclic stresses, respectively, were applied. In sharp contrast, for off-axis specimens the failure mode was always matrixdominated irrespective of the stress level. Thermosetting epoxy resin systems are widely employed as matrix materials for composites in many elds such as aerospace, automotive and microelectronics. Toughening of epoxies has been one of the topics most extensively studied because of the brittle nature of epoxies and their widespread applications for engineering components. Understanding the fatigue crack propagation behaviors of epoxy composites has been of great importance because such composites are often used for engineering components that are subject to cyclic loading. Curtis [7] found that the toughened resin system can improve the tensile fatigue response in the low cycle fatigue regime, while in the high-cycle fatigue range the fatigue performance of the toughened epoxy is inferior to that of standard epoxy-based composites. Epoxy matrices with a high ductility exhibited a higher compressive fatigue resistance [8]. The mode I delamination fatigue crack growth was studied of interlayer/interleaf-toughened CFRP laminates [9]. The heterogeneous interlayer with ne polyamide particles increased the crack growth resistance.

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Although many research efforts have been directed toward understanding the mechanisms of fatigue in polymer matrix composites, the effects of nanoparticles on their fatigue performance is still not fully understood. The addition of 1 wt% of carbon nanotubes (CNTs) to the matrix of glass ber-epoxy composite laminates improved their high-cycle fatigue life by a remarkable 60 250% [10]. Even more impressively, the addition of 2 and 5 wt% multi-walled CNTs enhanced the fatigue performance of physiologically maintained methyl methacrylatestyrene copolymer (MMA-co-sty) by 565 and 593%, respectively [11]. Zhang et al. [3] demonstrated an order of magnitude reduction in fatigue crack propagation rate for an epoxy system with the addition of 0.5 wt% of CNTs. The crack-tip bridging and frictional pull-out mechanisms were responsible for the suppression of fatigue in the nanocomposite. Other types of nanollers also gave rise to improved fracture properties. For example, the introduction of SiO2 particles increased both the initiation fracture toughness and the corresponding cyclic fatigue behavior of epoxy [12]. Al2O3 and TIO2 nanoparticles improved the exural strength, stiffness and fracture toughness as well as the fatigue crack propagation resistance of the epoxy [13]. The incorporation of organoclay in polyurethane elastomers showed signicantly improved fatigue life in addition to more than 150% increase in static strength and failure strain [14]. Many studies have devoted to improving the mechanical properties of ber-reinforced composites by adding nanoclay. In addition to mechanical properties, clay-epoxy nanocomposites have shown wide array of property improvements with only very low fractions of clay, including the enhanced thermal stability [15,16], reduced moisture and gas permittivity [17] and superior ame retardancy [18]. The nanoclay, in particular, exhibited ameliorating effects on fracture and fatigue resistance of carbon ber composites (CFRPs): e.g. increased mode 1 delamination resistance [19], enhanced impact damage resistance and tolerance [20] and better static and impact fracture toughness [21]. However, very few studies have appeared in the open literature on fatigue performance of hybrid CFRP composites containing nanoclay. As a continuation of our previous studies on clay-CFRP hybrid composites [1921], this work specically studies the fatigue performance of CFRP composites affected by the incorporation of nanoclay. The S-N curves and the residual properties of hybrid composites after tensiontension cyclic loads of different levels were specically evaluated.

2510) at an ultrahigh frequency for 3 h to further disperse the clay, while maintaining the resin temperature at 75 C using a hot water bath. After sonication, the translucent color of the epoxy/clay mixture indicates uniform distribution of organoclays, partly conrming the efciency of the sonication conditions used. The mixture was degassed in a vacuum oven followed by addition of curing agent, and the mixture was stirred while avoiding the formation of bubbles. Twelve ply laminates of 30 cm square were prepared by hand lay-up of carbon fabrics with a stacking sequence [0/ 90]3S on a steel mould plate. To keep fabrics well aligned, necessary precautions were taken during hand lay-up. The molded laminates were wrapped with bleeders and peel plies within Teon dam all around, which was cured at 80 C for 2 h and at 150 C for 8 h, followed by post-cure at 160 C for 2 h in a vacuum hot press (Technical Machine Product Corp). The high cure temperature excursions for long durations were aimed at complete cure of the resin. The cured composite laminates were cut, by a diamond wheel, at 45 off-axis directions to obtain a resultant stacking sequence of [45]3S. Introduction of clay into epoxy inevitably increases the viscosity of the resin, which may result in composite laminates thicker than those without clay. To lower the viscosity and thus to avoid the thickness variation, the resin was heated to 75 C during the whole processing steps, including shear mixing, sonication and degassing, as well as before hand lay-up after mixing with the hardener. A uniform laminate thickness and a constant ber volume fraction were further assured through the use of Teon dams of required thickness and a constant pressure of 0.32 MPa during curing. The volume fraction of carbon bers, Vf, was consistently maintained at about 0.55 for both the composites with and without nanoclay, which was determined from the known weights and densities of the composite constituents. 2.2. Characterization, static and cyclic fatigue tests The static tensile tests were conducted according to the specication, ASTM D3039, on a universal testing machine (MTS Sintex 10/D) to determine the tensile strength and modulus. Rectangular specimens of 230 mm long 20 mm wide 2.5 mm thick were loaded at a crosshead speed of 2 mm/min. An extensometer with gauge length of 25 mm was attached to the specimen to monitor the strain during loading. The tensiontension cyclic fatigue tests were conducted according to the specication, ASTM D3479, on a universal testing machine (25 KN servo-hydraulic Instron 1300). The tests were conducted at room temperature on a load control mode at a stress ratio of 0.1, and with constant-amplitude sine-wave loading. To determine the fatigue S-N curves, the maximum stress levels were kept at 80, 70, 60 and 45% of the corresponding ultimate tensile strength (UTS) of the composite. A test frequency of 2 Hz was used which was low enough to minimize the effect of adiabatic heating. Rectangular specimens, 230 mm long, 20 mm wide and 2.5 mm thick, were cut from the composite plates, and end tabs made of glass fabrics and 40 mm long were bonded at both ends of the specimen to avoid failure around the gripping device during the tests. At least four specimens were tested for each set of loading conditions. The residual properties of the composites were measured after different periods of fatigue loading at a maximum load equivalent to 60% of the ultimate tensile strength of the composite. Static tensile tests were conducted on the pre-cycled specimens to measure the residual tensile strength and modulus. The tests followed the same procedure as those for the static tensile properties on virgin specimens. The scanning electron microscopy (SEM) was used to examine the surface morphologies of the static and fatigue fractured specimens and thus to identify the different failure mechanisms involved in CFRPs with and without nanoclay. The scanning

2. Experiments 2.1. Materials and fabrication of composite laminates The laminate composites were fabricated from unidirectional carbon ber and organoclay lled epoxy resin. The epoxy resin system was basically the same as that employed in our previous studies [1921]: a diglycidyl ether of bisphenol A (DGEBA) epoxy (Epon828, supplied by Shell Corp) mixed with 1,3-phenylenediamine (supplied by Aldrich) hardener at a ratio of 100:14.5 by weight. Unidirectional carbon fabric (supplied by Taiwan electrical insulators) with a unit weight of 200 g/m2 was used as the main reinforcement for composite laminates. The organoclay, Nanomer I30P (supplied by Nanocor), is an octadeclyamine modied montmorillonite suitable for dispersion in epoxy resins [17]. The organoclay was dried overnight at 75 C in an oven prior to use. The epoxy in a glass beaker was heated at 75 C to lower the viscosity and the organoclay was added. The organoclay content was varied between 0, 3, and 5 wt% of the epoxy resin-hardener mixture. Mixing was conducted at a shear rate of 3000 rpm for 1 h using a high speed shear mixer (Ross Mixer). The mixture was subjected to sonication using an ultrasonicator (Branson

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with a 35 MHz probe in a through-transmission mode. Both the neat CFRP composites and the hybrid composites containing 5 wt% nanoclay were examined before loading and after 5 K, 10 K, 20 K, 25 K and 30 K fatigue cycles. For ease of understanding only two colors, black and grey, were used to present the damage state and a threshold value of 10% was used as the border line between the two colors. 3. Results and discussion 3.1. Static tensile properties Fig. 1 presents a typical TEM image of nanocomposites with 5 wt% clay content, indicating a mixture of full intercalation and partial exfoliation. Representative stressstrain curves obtained from the static tensile tests are shown in Fig. 2. All materials exhibited a typical bilinear stressstrain behavior before failure. As reported previously [2224], the tensile stressstrain curves for angle-ply specimens are non-linear due to the signicant contribution of the polymer matrix. It is clearly seen that both the yield strength and the failure strain increased with increasing the clay content. Fig. 3 summarizes the static tensile strength and modulus of clay-CFRP hybrid composites containing varying clay contents. Both the tensile strength and modulus increase continuously with increasing clay content, which is again a reection of the composite property signicantly affected by the matrix property. This observation is generally consistent with the exural properties reported earlier [21] although the exural strength tended to be marginally reduced at a high clay content due to the potential lack of dispersion of clay. The fracture surface morphologies as shown in Fig. 4 exhibited sharp contrast between the composites without and with 5 wt% nanoclay. Interfacial debonding between the ber and matrix, as well as limited deformation of matrix material are the major failure mechanisms observed in the composites without clay. The fracture surface was generally smooth and featureless indicating brittle failure. Meanwhile, the clay-CFRP hybrid composites revealed improved bermatrix interfacial bonding due to the presence of nanoclay in the matrix material that maximizes the stress transfer between matrix and ber. The modied epoxy adhered well to the long carbon bers and the fracture surface was rougher and textured, quite similar to those observed from the interlaminar fracture surfaces [19]. It is thought that the octadecylamine modier used for I.30P organoclay had alkyl and amine groups that are functionally compatible with carbon bers to give rise to strong adhesion [20]. Similar amine groups have been extensively used to functionalize carbon nanotubes/nanobers for polymer compos-

Fig. 1. Typical TEM image of nanocomposite containing 5 wt.% clay, showing dispersion state of nanoclay.

acoustic microscopy (SAM, Sonix Micro-Scan System) was employed to characterize the progressive fatigue damage growth at different stages of fatigue cycles. A focused acoustic beam was scanned over the damaged laminate using a transducer equipped

Fig. 2. Representative stressstrain curves of clay-CFRP hybrid composites.

Fig. 3. Tensile properties of clay-CFRP hybrid composites containing varying clay contents.

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Fig. 4. Fracture surface morphologies of CFRP composites: (a and b) without clay and (c and d) with 5 wt.% clay.

ite applications, which may also be responsible for the improved adhesion between the modied epoxy and ultra-high molecular weight polyethylene bers [25]. It is well known that the properties of the composites with [45]S ply orientation are dominated by the in-plane shear properties, which is further conrmed by the general view of the failed specimen shown in Fig. 5a. The interlaminar shear and in-plane shear are considered to be the matrix dominated properties [26]. It was noted (Fig. 2) that the presence of nanoclay in the matrix not only increased the apparent yield stress but also the strain to failure, which is consistent with the previous observations of improved interlaminar shear strength (ILSS) [19,27] and in-plane shear strength of ber composites [28].

3.2. Fatigue life and residual strength Fig. 6 presents the S-N data of clay-CFRP hybrid composite at varying clay contents. For the same level of maximum applied stress, the clay-CFRP hybrid composite exhibited much longer fatigue life than the composite without clay at all the stress levels tested. A maximum improvement of about 74% in fatigue life was achieved with 3 wt% clay when cyclic fatigue was carried out at a load equivalent to 45% of the tensile strength of the specimen. Results indicated that nanoclay modication produced more improvement in fatigue life at a low stress or a high cycle regime and was less potent in improving life at high stress levels. At high

Fig. 5. Images of the failed specimens from (a) static tension and (b) cyclic fatigue.

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throughout the whole fatigue life. Judging from the typical images of failed specimens in Fig. 5b, in-plane shear, instead of ber breakage, is the primary failure mode. Since no stochastic ber failure was involved, erratic changes in the residual strength and modulus were not observed, further details of the latter will be discussed in Section 3.4. 3.3. Fatigue damage index Amongst several methods to characterize the extent of damage arising from cyclic fatigue, the fatigue damage index was employed in this study. The fatigue damage index, D, is dened as:

D1
Fig. 6. S-N Curves of clay-CFRP hybrid composites with varying clay contents.

Er Eo

stress levels the nanoparticles are less resistive in suppressing the rapidly propagating cracks. This was explained on the basis of stress intensities or strain densities [10,11]. At high stress levels the fatigue crack grow at a rapid rate and at several fronts because of the high stress intensity and high strain density, respectively. The nanoparticles become relatively ineffective in slowing down the onset or subsequent growth of damage at high stress intensities. Fig. 7 shows the residual tensile strength and modulus measured after a given number of cycles. The residual properties exhibited a gradual decrease with increase in number of cycles with small variations between specimens. The nanoclay-modied composite showed higher residual properties than those without

where E is the modulus of specimen, with the subscripts o and r referring to the undamaged state and residual value after a certain fatigue life. D varies between 0 and I, and a low D value means little modulus reduction due to fatigue. Thus, D is a macroscopic measure of fatigue damage because the structural changes on the microscopic scale (due to matrix cracks, ber/matrix interfacial failure, etc.) are characterized by a macroscopic reduction of the modulus [2932]. Fig. 8 shows the damage index, D, plotted a function of fatigue cycles for hybrid composites containing different clay contents. It can be seen that at the early stage of fatigue (say, 0 12.5 k cycles) the hybrid composites in general exhibited marginally more damage than the neat composites. After the initial damage period, the hybrid composite specimens sustained a relatively longer stable period with low damage indices for the rest of fatigue life. The nal failure took place much earlier in the neat composite than the clay-CFRP hybrid composites; and the higher was the clay content, the longer was the fatigue life, with the exception of the hybrid composites containing 5 wt% clay. The diminishing improvement in fatigue life at clay contents higher than 3 wt% is attributed to the higher possibility of forming unwanted agglomerates of a relatively large size. The early stage is generally considered as the crack initiation stage. The hybrid composites have a large number of interfaces due to the presence of nanoclay, and there are many weak interfaces between the clay galleries. The cleavage of clay tactoids or the inter-gallery debonding might have occurred during this early stage of fatigue generating micro or nanoscale cracks. It is likely, however, that these micro or nanocracks took signicantly longer time to coalesce and propagate to form critical damage than in the neat CFRP composites. Other important toughening mechanisms responsible for the enhanced crack growth resistance offered by nanoclay have been identied previously [18 21,27,33,34]. Nanoclay can serve as the trigger for crack deection,

Fig. 7. Residual fatigue properties: (a) strength and (b) modulus.

Fig. 8. Fatigue damage variable, D, plotted as function of fatigue life.

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pinning, as well as crack arrest mechanisms, which signicantly increase the fracture toughness. These mechanisms could also be operative to retard fatigue failure by preventing or slowing the damage buildup through fatigue crack growth, especially at the later stage of fatigue.

3.4. Fatigue damage mechanisms Fig. 9 shows SEM micrographs of fractured specimens that were fatigued at 80%, 60% and 45% of UTS of the CFRP composites without and with 5 wt% clay. Both composites showed a number of

Fig. 9. SEM images showing fatigue fracture surfaces of the specimens failed at different maximum stress levels: (a) neat CFRP composites and (b) 5 wt.% clay-CFRP hybrid composites.

Fig. 10. SEM micrographs of 5 wt.% clay-CFRP hybrid composite, showing improved bermatrix and particlematrix interfacial bonding.

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dimples on the fracture surface. The dimples are formed as results of highly localized deformation around matrix defects, microvoids or nanoparticles [35,36]. It is interesting to note that the size of these dimples in general increased in both width and depth with decreasing the stress level applied during fatigue or alternatively with an increase in fatigue life. The mechanisms behind the formation and growth of dimples can be explained as follows: microcrackes are formed during the early stage of fatigue loading at some weak locations where there are high stress concentrations. Localized plastic deformation occurs due to the strain concentration around these microcracks, which in turn promotes the formation of dimples. The lower the applied stress level, the longer this stage lasts. Dimples grow in a stable fashion with increasing number of fatigue cycles before they coalescence into major cracks and nal

failure. At high stress levels, they tend to coalescence rapidly, leading to premature fracture without extensive growth of deep and wide dimples. These observations suggest that the elongation or stretching of the localized deformation zones or dimples is highly dependent on the applied stress. Indeed, the morphology of the nanoclay-induced dimples is considerably different from those present in neat composite. The neat composites had generally wider and shallower dimples than the nanoclay hybrid composites. There was signicant difference in size of these dimples for a given maximum stress level, especially at a low stress or high cycle regime: e.g. at 45% of UTS level these cavities are about 46 and 23 lm wide in the neat and hybrid composites, respectively. For a given fractured cross-sectional area, there were more dimples of smaller sizes in the hybrid sys-

Fig. 11. SAM images showing progressive fatigue damage growth at different stages of fatigue life.

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tem than in the neat system. Similar dimple patterns were also found near the pre-cracked region of fractured PA/nano-TIO2 and PA/nano-SIO2 composites [35,36] where the density of dimples was much higher and the size was much smaller in the nanocomposites than in the neat PA66. In addition, there is signicant analogy between our ndings and those reported previously on glass ber composites (GFRPs) containing carbon nanotubes (CNTs) [10] in terms of crack density: the addition of CNTs into the composites resulted in a higher density of nanoscale cracks than the composites without CNTs. It is also worth noting that the nanoclay-induced dimples are often divided into sub-partitions as evidenced from Figs. 9b and 10. There appears to be distinct partitioning lines emerging from clay particles in the center to the periphery of the dimples. These dividing walls signicantly increased the density of dimples and the total fracture surface area. The increased surface area implies meandering crack tips during crack growth, consequently resulting in high energy dissipation. The increased number of distinct partitioning lines in hybrid composites containing nanoclay is again an indication of simultaneous initiation and growth of small cracks in a large density, in contrast to larger cracks in a low density in the neat composite. Nevertheless, the static fracture surfaces in both the hybrid and neat composites did not show any sign of these dimples. The rapid crack propagation at a high stress intensity and a high loading speed did not allow the matrix material with enough time to stretch and plastically deform into these dimples. The clay/matrix interfacial bond appears to be very strong even when the clay was agglomerated to a microscale. The strong interfacial bond gave rise to magnication of the strain that the matrix material between the nanoparticles could sustain. 3.5. Characterization of fatigue damage growth The SAM technique was employed in a through-transmission mode [3739] to monitor the progressive damage growth due to cyclic fatigue and the representative SAM images are shown in Fig. 11. The corresponding damage area divided by the total area within the gauge length is plotted as a function of life cycles in Fig. 12. Black color (Fig. 11) represents the sound waves that are less than the threshold value and are absorbed by the composite, thus is an indication of damage. Grey color represents the sound waves that pass through the composites and are received at the receiver unit, and thus is an indication of bonded region. The slight variation in the grey color intensity occurred because of the density variation of ber, matrix and the particle rich areas, which in turn changed the extent of received waves.

Both materials exhibited quite uniform damage distributions over the whole gauge area until damage became more concentrated at the later stage. It is seen that the hybrid composites exhibited slightly more damage than the neat composites at the very early stage of loading at below about 10 k cycles. This observation is functionally very similar to the damage index variation discussed in Section 3.3 (Fig. 8). Except the early stage, the clayCFRP hybrid composite showed in general much less damage than the neat composite throughout the whole fatigue life. The clayCFRP hybrid composites sustained about 15% more damage before nal failure than the neat composites, conrming substantially higher damage-tolerant characteristics. Based on the above observations, the fatigue damage in the laminate composites studied here can be divided into two stages: Stage I for damage initiation and stable damage growth; and Stage II for rapid damage growth to failure. It is seen that the hybrid composites had a longer Stage I period than the neat composites (i.e. approximately 020 k cycles vs 015 k cycles).

4. Conclusions The tensiontension fatigue behavior of clay-CFRP hybrid composite was investigated and the prevalent toughening mechanisms arising from nanoclay were identied. The following conclusions can be highlighted from this study. (1) The static tensile strength and modulus of CFRP composite were signicantly enhanced by the addition of nanoclay. The presence of nanoclay in the matrix increased the apparent yield strength and strain to failure. (2) The clay-CFRP hybrid composites showed better performance in terms of residual tensile strength and modulus than the neat composite after a given fatigue cycle. (3) Fatigue life was signicantly extended with the incorporation of nanoclay to CFRP composite and the maximum improvement was about 74% with 3 wt% clay content. (4) Nanoclay suppressed the fatigue damage growth of CFRP composites in terms of damage area over the whole fatigue life except the very early stage of loading. (5) Improved ber/matrix interfacial bond and nanoclayinduced dimples were identied as underlying toughening mechanisms responsible for the enhanced fatigue life of clay-CFRP hybrid composites.

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