Flexural fatigue behavior of synthesized graphene/carbon-nanober/
epoxy hybrid nanocomposites
M.M. Shokrieh a, , M. Esmkhani a , A.R. Haghighatkhah a , Z. Zhao b a Composites Research Laboratory, Center of Excellence in Experimental Solid Mechanics and Dynamics, School of Mechanical Engineering, Iran University of Science and Technology, Tehran 16846-13114, Iran b School of Chemical Engineering, Shandong University of Technology, 255049 Zibo, Shandong, PR China a r t i c l e i n f o Article history: Received 8 February 2014 Accepted 8 May 2014 Available online 2 June 2014 Keywords: Flexural bending fatigue Hybrid nanocomposites Graphene nanosheet Carbon nanober a b s t r a c t In the present research, effects of adding a combination of synthesized graphene nanosheets and carbon nanobers (CNFs) on the exural fatigue behavior of epoxy polymer have been investigated. Graphene nanosheets are synthesized based on a changing magnetic eld. The exural bending fatigue life of 0.5 wt.% of graphene/CNF/epoxy hybrid nanocomposites has been considered at room temperature. The samples were subjected to different displacement amplitudes fatigue loadings. Due to the addition of hybrid nanoparticles, a remarkable improvement in fatigue life of epoxy resin was observed in com- parison with results obtained by adding 0.25 wt.% graphene or 0.25 wt.% CNF into the resin. Experimental observations show that at a strength ratio equal to 43% by using 0.5 wt.% of hybrid nanoparticles; 37.3-fold improvement in exural bending fatigue life of the neat epoxy was observed. While, enhance- ment of adding only graphene or CNF was 27.4 and 24-fold, respectively. 2014 Elsevier Ltd. All rights reserved. 1. Introduction The exural fatigue behavior of composites and nanocompos- ites has been carried out by many researchers [14]. For compos- ites under displacement-controlled condition, Paepegem and Degrieck developed an experimental setup for bending fatigue loading [1]. They adopted a residual stiffness model which describes the fatigue damage behavior of the composite material [2]. Also, Paepegem and Degrieck [3] used a nite element approach for composites fatigue life prediction. El Mahi et al. [4] studied the exural fatigue behavior of the sandwich composite materials using three-point bend test and the derived approach permitted to predict the fatigue life of the sandwich composite materials while avoiding the large number of experiments that would normally required in fatigue testing. A survey in the avail- able literature reveals that the addition of nanoparticles can improve the fatigue behavior of composites under displacement control loading and has been carried out by many researchers [58]. Ramkumar and Gnanamoorthy [5] studied the stiffness and exural fatigue life improvements of polymer matrix reinforced nanocomposites with nanoclay. They described the effect of adding nanoclay llers on the exural fatigue response of Polyamide-6 (PA6). Rajeesh et al. [6] considered the inuence of humidity on the exural fatigue behavior of commercial grade polyamide-6 granules and hectorite clay nanocomposites. Timmaraju et al. [7] considered the inuence of the environment on the exural fatigue behavior of polyamide 66/hectorite nano- composites. They also found the effect of initial imbibed moisture content on the exural fatigue behavior of polyamide 66/hectorite nanocomposites conducted under deection control method using a custom-built, table-top exural fatigue test rig at a laboratory condition [8]. In the literature, it was also found that the presence of multi-nanoparticles in composites improves the properties of nanocomposites. Some researchers used hybrid llers in order to have a perfect potential of both llers. For instance as a rst group, a combination of micro rubber and nanosilica has been used to improve the fracture toughness and fatigue behavior of [915]. Liang and Pearson [9] used two different sizes of nanosilica (NS) particles, 20 nm and 80 nm in diameter, and carboxyl terminated butadiene acrylonitrile (CTBN) which was blended into a lightly cross-linked, DGEBA/piperidine epoxy system in order to investi- gate the toughening mechanisms. It was shown that addition of small amount of NS particles into CTBN, caused increase of the fracture toughness. Manjunatha et al. [1015] investigated the fati- gue behavior of reinforced composites by adding a combination of micro rubber and nano-silica particles into epoxy matrix in several states. For instance, they [10] studied the tensile fatigue behavior http://dx.doi.org/10.1016/j.matdes.2014.05.040 0261-3069/ 2014 Elsevier Ltd. All rights reserved.
Corresponding author. Tel./fax: +98 21 7720 8127.
E-mail address: Shokrieh@iust.ac.ir (M.M. Shokrieh). Materials and Design 62 (2014) 401408 Contents lists available at ScienceDirect Materials and Design j our nal homepage: www. el sevi er . com/ l ocat e/ mat des of modied micron-rubber and nano-silica particle epoxy poly- mers. They [11] also addressed the tensile fatigue behavior of a glass-ber reinforced-plastic (GFRP) with participation of rubber micro-particles and silica nano-particles. They [12] also observed the enhanced capability to withstand longer crack lengths, due to the improved toughness together with the retarded crack growth rate, to enhance the total fatigue life of the hybrid-modied epoxy polymer. Also, Manjunatha et al. [13] enhanced the fatigue behavior of ber reinforced plastic composites by means of 9 wt.% of rubber microparticles and 10 wt.% of silica nanoparticles and showed the fatigue life under WISPERX load sequence was about 45 times higher than that of the neat composites. Manjunatha et al. [14] also used another hybridization of car- boxyl-terminated butadieneacrylonitrile rubber microparticles and silica nanoparticles to increase the tensile fatigue behavior of GFRP composites at a stress ratio equal to 0.1. Manjunatha et al. [15] conducted fatigue crack growth test on a thermosetting epoxy polymer which was hybrid-modied by incorporating 9 wt.% of CTBN rubber micro particles and 10 wt.% of silica nano-particles. The fatigue crack growth rate of the hybrid epoxy polymer was observed to be signicantly lower than that of the unmodied epoxy polymer. In the next category, applying carbon nanotubes (CNTs) with dif- ferent nanoparticles as hybrid llers were taken into account in the literature [1619] to improve the fatigue behavior, mechanical and electrical properties of reinforced composites. Bger et al. [16] appointed silica and MWCNT hybrid nanoparticles to increase the high cycle fatigue life of epoxy laminates and nally reported that the life was increased by several orders of magnitude in number of load cycles. Fritzsche et al. [17] investigated the CNT based elas- tomer-hybrid-nanocomposites prepared by melt mixing and showed promising results in electrical, mechanical and fracture-mechanical properties. Witt et al. [18] improved mechan- ical properties such as tensile strength and strain to failure of a conductive silicone rubber composite using both CNTs and carbon black (CB). Al-Saleh Mohammed and Walaa Saadeh [19] fabricated a nanostructured hybrid polymeric materials based on CNTs, CB and CNFs and investigated electrical properties and electromagnetic interference shielding effectiveness in the X-band frequency range. The other various hybrid nanoparticles were discussed in the literature are considered here as the last category [20,21]. Jen et al. [20] applied hybrid Magnesium/carbon ber to increase the fatigue life of nanocomposite laminates. On the other hand, apply- ing carbon nanotubes (CNT) and graphite nanoplatelets (GNPs) to epoxy nanocomposites was shown by Li et al. [21]. It was repre- sented that the exural mechanical as well as electrical properties of the neat resin was marginally changed by hybridization. This survey reveals that the effect of hybrid particles is mostly positive and can improve the static and dynamic properties of composites. However, it is gured out that in case of displacement control fatigue loading condition, there is a lack of research on this issue for hybrid nanollers/epoxy nanocomposites. Therefore, in the present research, the exural fatigue behavior of graphene/ CNF/epoxy hybrid nanocomposites under displacement control exural loading is investigated and compared with those of the pure epoxy resin. 2. Materials specication 2.1. Epoxy resin In the present research, ML-526 (Bisphenol-A) epoxy resin was selected because of its low viscosity and extensive industrial appli- cations to fabricate the specimens. The low viscosity of the matrix makes the dispersion of additives easier. Physical and mechanical properties of ML-526 epoxy resin are shown in Table 1. The curing agent was HA-11 (Polyamine). The ML-526 resin and the HA-11 polyamine hardener were supplied by Mokarrar Company, Iran. 2.2. Nanoparticles In this research, graphene nanoplatelets (GPL) and CNF are utilized as carbon based nanollers. The graphene nanoplatelets (GPL) were synthesized with a stirring grinding driven by changing the magnetic eld as shown in Fig. 1. The steel needles with a weak magnetism are used as grinding media and four NdFeB permanent magnets are inserted into a motor-driven disc (Fig. 1). When the disc is made of steel, the magnetic stainless steel needles are attracted by the permanent magnets (Fig. 1a and b). By increasing the rotational speed, the magnetic stainless steel needles y up and collide with each other with a high frequency under the changing attraction and repulsion forces of the high speed rotating perma- nent magnets (Fig. 1c). When a rigid grinding chamber lled with a certain amount of graphite powder is set on the disc, there are high frequent collisions and shears between the grinding chamber and magnetic stainless steel needles, which can nally result in a strong collision and shear forces. Graphite in the chamber will be crushed into ultra-ne powder under the action of these strong forces and then the powder will be prepared efciently. Physical properties of synthesized graphene powders are shown in Table 2. The TEM image of the synthesized GPL powder is shown in Fig. 2. The D, G and 2D bands of Raman spectra of the synthesized GPLs powder are demonstrated in Fig. 3. The CNF was supplied by Grupo Antolin SL, Spain. The physical properties of CNF are represented in Table 3. The Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) images of CNF nanoparticles are illustrated in Fig. 4. 3. Specimen preparation The polymer nanocomposite reinforced with 0.5 wt.% of graphene/CNF hybrid nanoparticles/epoxy nanocomposites was prepared as described below. Firstly, epoxy resin was mixed with 0.25 wt.% CNF and stirred for 10 min at 2000 rpmand then the mix- ture was sonicated via 14 mm diameter probe-sonicator (Hielscher UP400S) at output power of 200 W and 12 kHz frequency. The mix- ture was sonicated for 60 min. It is worth mentioning that during the sonication, the mixture container was kept by the aid of ice- bath to prevent the overheating of the suspension to keep the tem- perature around 40 C. Secondly, suspension was mixed with 0.25 wt.% GPL under same condition within 30 min by the sonica- tion. After sonication, the hardener at a ratio of 15:100 was added to the mixture and stirred gently for 5 min. Then, it was vacuumed at 1 mbar for 10 min to remove any trapped air. Six samples were prepared and cured at room temperature for 48 h and followed by 2 h at 80 C and 1 h at 110 C for post curing. The approach was used to disperse GPL/CNF hybrid nanoparti- cles into epoxy resin, is adopted from a combination of supplemen- tary research [22]. Time for sonication depends on the ller contents and has been dened based on experiments until llers remain intact. For CNF llers, Shokrieh et al. [22] investigated the suitable time for sonication versus contents of the ller and pointed out for 0.25 wt.% CNF materials, the optimum value of son- ication with regard to Fig. 5, was found around 90 min with the same compartment and conditions. Also, the optimum sonication time for 0.25 wt.% GPL was equal to 30 min. In addition, to inspect the dispersion state of nanollers, a new technique based on scan- ning electron microscopy, which utilizes the burn-off test, was introduced to visualize the dispersion state of nanollers [23]. 402 M.M. Shokrieh et al. / Materials and Design 62 (2014) 401408 4. Calculation of the bending stress In this study, high cycle fatigue properties of nanocomposites are measured by a modied cantilever beam bending test. A typical fatigue life test specimen for the cantilever beam bending test is shown in Fig. 6. The presented specimen is designed based on ASTM: B593-96 standard and the method presented by Ramkumar and Gnanamoorthy [5]. The wide end of the specimen is clamped to a bed plate, while the narrow end is cyclically deected (see, Fig. 6(a)). To catch reliable results of the exural fatigue strength, the gage area of the specimen is designed based on the stress con- centration concept (Fig. 6(b)). The stress concentration of the critical location of the specimen has the maximum magnitude; therefore the failure will start from this area. For the wedge-shaped beam as applied specimen, the cross section is not uniform and dened by means of a parameter called local B according to Eq. (1). (Fig. 7): Bx B 0 L 0 : L 0 x 1 where L 0 is the length of the specimen and B 0 is the width at the base of the wedge-shaped beam. Therefore, the magnitude of the second moment of area of the cross section depends on the position along the x-axis as Eq. (2): Ix B 0 : L 0 x : H 3 12: L 0 2 where H is the thickness of the beam. Finally, the maximum tension or compression stress at a given cross section for small Table 1 Properties of ML-526 epoxy resin. Physical properties Mechanical properties Viscosity at 25 C (centipoise) Glass transition temperature (C) Tensile modulus (GPa) Tensile strength (MPa) 1190 72 2.6 60 Fig. 1. GPL synthesis method. (a and b) Still condition; (c) moving condition. Table 2 GPL nanoparticles specications. Nanoparticle Diameter (nm) Thickness (nm) Specic surface area (m 2 /g) GPL 40120 35 500 Fig. 2. The transmissionelectron microscopy (TEM) of the synthesized graphene nanoplatelets. Fig. 3. Raman spectra of synthesized graphene nanoplatelets, D, G and 2D bands. Table 3 CNF specications. Properties Unit Value Fiber diameter (TEM) nm 2080 Fiber length (SEM) lm >30 Bulk density g/cc >1.97 Apparent density g/cc 0.060 Surface energy mJ/m 2 100 Graphitization degree % 70 Electrical resistivity O m 1 10 3 Metallic particles content % 68 M.M. Shokrieh et al. / Materials and Design 62 (2014) 401408 403 displacements within elastic deformation behavior is calculated according to the following equation [24]: r max
z 0 E H L 2 0 3 where r max is the maximum stress, H is the thickness of the beam, z 0 is the displacement at point x = L 0 and E is the Youngs modulus. The relation between the displacement z 0 at the tip and the maximum stress r max for a small deformation is linear. 5. Test equipment 5.1. Static testing instruments The Santam universal testing machine STM-150 was utilized to perform bending tests in accordance with the ASTM:D790. The cross-head speed for bending tests was 16 mm/min. To analyze hybrid nanoparticles, gold sputtered samples were used. The eld-emission scanning electron microscopy (FESEM) photographs were taken by using Zeiss-Germany Sigma microscope. 5.2. Experimental setup for exural bending fatigue The pure epoxy and reinforced polymer specimens are mounted into a xed cantilever, constant deection type fatigue testing machine. The machine called BFM-110 is designed and manufac- tured based on a developed version of a testing machine designed by Paepegem and Degrieck [1] and shown in Fig. 8. The specimen is held at one end, acting as a cantilever beam and cycled until a com- plete failure is achieved. The number of cycles to failure is recorded Fig. 4. (a) SEM and (b) TEM images of CNF, prepared by Grupo Antolin SL, Spain. Fig. 5. Viscosity (mPa s) versus sonication time (min) of 0.25 wt.% CNF/epoxy nanocomposites [22]. Fig. 6. (a) Schematic of specimen clamping procedure and (b) schematic picture of the bending fatigue specimen. Fig. 7. Schematic view of a beam, with coordinates. 404 M.M. Shokrieh et al. / Materials and Design 62 (2014) 401408 as a measure of the fatigue life during the test. Generally, the shaft of the motor has a rotational speed of 01450 rpm. The power is transmitted via a V-belt to the second shaft, which provides a fatigue testing frequency between 2 and 20 Hz and gives the pos- sibility to investigate the inuence of the frequency in this range of values. The power transmission through a V-belt ensures that the motor and the measuring system are electrically isolated. The second shaft bears a crank-linkage mechanism, which is shown in Fig. 8. Hence the sample is loaded as a cantilever beam. The amplitude of the imposed displacement is a controllable parameter and the adjustable crank allows choosing between single-sided and fully reversed bending, i.e., the deection can vary from zero to a maximum deection in one direction, or in two opposite Fig. 8. The experimental setup for the displacement controlled exural bending fatigue loading. 110 Pure epoxy resin 0.25 wt.% CNF 0.25 wt.% GPL 0.5 wt.% Hybrid F l e x u r a l
S t r e n g t h
( M P a ) 80 90 100 110 120 130 121 118 123 Fig. 9. Flexural strength (MPa) for pure epoxy resin, 0.25 wt.% GPL, 0.25 wt.% CNF and 0.25 wt.% of GPL plus 0.25 wt.% of CNF hybrid nanoparticles epoxy nanocomposites. Pure epoxy resin 0.25 wt.% CNF 0.25 wt.% GPL 0.5 wt.% Hybrid F l e x u r a l
S t i f f n e s s
( G P a ) 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.00 3.18 3.40 3.43 Fig. 10. Flexural stiffness (GPa) for pure epoxy resin, 0.25 wt.% GPL, 0.25 wt.% CNF and 0.25 wt.% of GPL plus 0.25 wt.% of CNF hybrid nanoparticles epoxy nanocomposites. Fig. 11. Drawing of the specimen (dimensions in mm). Fig. 12. Flexural bending stress vs. number of cycles to failure for neat epoxy resin, 0.25 wt.% GPL, 0.25 wt.% CNF, 0.25 wt.% of GPL plus 0.25 wt.% of CNF hybrid nanoparticles epoxy nanocomposites, at a frequency equal to 5 Hz. M.M. Shokrieh et al. / Materials and Design 62 (2014) 401408 405 directions, respectively. The maximum deection is measured by a displacement dial gauge at the back of the lower clamp. The num- ber of cycles to failure should be counted directly for each test specimen. A counting signal was generated once per cycle by a PES-R18PO3MD reector speed sensor which was supplied by IBEST Electric, Ltd., China. The counting signal was transferred to the counter fabricated by RASAM Madar electronic Company, Iran. In this setup, there are two parallel stands with counting system implemented separately. To stop the counter of speed sensors, at the bottom of each specimen a thin wire as an electrical contact are used and after failure, the damaged specimen drops down and disconnects the wire and stops the counting system. Therefore, after failure of both specimens, control system acts and turns off the main current of the machine completely. 6. Results and discussions 6.1. Static bending strength Calculation of the maximum bending stress has been repre- sented and Eq. (3) was valid when specimen is subjected to a small and linear deformation. The static bending strength of GPL/epoxy nanocomposites for 0.25 wt.% of GPL content was found 118 MPa and it was 121 MPa for 0.25 wt.% CNF/epoxy nanocomposites [22]. Also, the static exural modulus of 0.25 wt.% graphene/epoxy nanocomposites was demonstrated 3.4 GPa and for 0.25 wt.% of CNF content was 3.18 GPa [22]. While, the static bending strength and modulus of neat epoxy resin were 110 MPa and 3 GPa, respectively. For 0.25 wt.% of GPL plus 0.25 wt.% of CNF (i.e., 0.5 wt.% of GPL/ CNF) hybrid nanoparticles/epoxy nanocomposites based on ASTM: D790, static tests to measure the exural strength and stiffness have been conducted and eventually, 123 MPa for the strength and 3.43 GPa for the stiffness were found. The exural strength and stiffness were presented in Figs. 9 and 10. 6.2. Cyclic exural bending fatigue life There is not a special standard test method for epoxy matrix and epoxy based nanocomposites under exural bending stress in fati- gue. The ASTM: B59396 and a publication of Ramkumar and Gnanamoorthy [5] are for copper alloy spring material, lled ther- moplastic nanocomposites, respectively. In our experiments, the test setup frequency was 5 Hz. The effective length of the specimen subjected to the bending is 32.84 mm. The drawing and picture of the used specimen in current research are shown in Fig. 11. Although the BFM-110 testing machine is capable of apply- ing the reversal bending fatigue loading, however in the present study, the specimens were subjected to zero-bending fatigue load- ing conditions. The exural bending stress versus the number of cycles for the neat epoxy resin, 0.25 wt.% GPL nanoparticles, Fig. 13. Flexural stress ratio (%) vs. number of cycles to failure for neat epoxy resin, 0.25 wt.% GPL, 0.25 wt.% CNF, 0.25 wt.% of GPL plus 0.25 wt.% of CNF hybrid nanoparticles epoxy nanocomposites, at a frequency equal to 5 Hz. Fig. 14. FESEM of the fractured surface. (a) 0.25 wt.% GPL/epoxy nanocomposites, (b) 0.25 wt.% CNF/epoxy nanocomposites (c) and (d) 0.5 wt.% of GPL/CNF hybrid nanoparticles epoxy nanocomposites. 406 M.M. Shokrieh et al. / Materials and Design 62 (2014) 401408 0.25 wt.% CNF nanoparticles, 0.5 wt.% of GPL/CNF hybrid nanoparti- cles epoxy nanocomposites, at a frequency equal to 5 Hz is illus- trated in Fig. 12. The strength ratios (the bending stress normalized by the bending strength) versus number of cycles to failure is presented in Fig. 13. For instance, the experimental obser- vations show that at the strength ratio equal to 43% by using 0.5 wt.% of hybrid nanoparticles; 37.3-fold improvement in exural bending fatigue life of the neat epoxy was observed. While, enhancement of adding only graphene or CNF was 27.4 and 24-folds, respectively. The enhancement of the fatigue life for composites at presence of nanollers has been stated in literature. For instance, Ramkumar and Gnanamoorthy [5] expressed that the nanoclay addition can be attributed to enhanced modulus coupled with reduced dissipation factor and improved surface hardness. The brillated appearance of the lled nanocomposite fracture surface suggests that addition of nanoller promotes the toughening and inuences the crack propagation characteristics of pure polymer. Ramanathan et al. [25] argued that the micrometer-size dimensions, high aspect ratio and two-dimensional sheet geometry of the graphenes make them effective in deecting cracks in bending. In addition, hydrogen bonding interaction or an enhanced nanollerpolymer mechani- cal interlocking due to the wrinkled morphology of graphenes are additional factors that can contribute to composite reinforce- ment. Whilst, Raee et al. [26] pointed out that this enhancement may be related to their high specic surface area, enhanced nano- llermatrix adhesion/interlocking arising from their wrinkled (rough) surface. 6.3. Dispersion and morphology analysis The improvement of the fatigue life of hybrid nanocomposites can be explained by a close look at the fracture surfaces of the damaged specimens. The fracture surface of specimens 0.25 wt.% GPL/epoxy, 0.25 wt.% CNF/epoxy and 0.5 wt.% of GPL/CNF hybrid nanoparticles epoxy nanocomposites were evaluated and presented in Fig. 14. As depicted in Fig. 14(a), dispersion of GPL was observed and shown that the dispersion was not sufcient and the stiffness of reinforced composites with GPL improved and the strength was not inuenced like the stiffness. Also, as shown in Fig. 14(b), the fracture surface of 0.25 wt.% CNF/epoxy nanocomposites was monitored and found that the dispersion of CNF into epoxy resin was appropriate as observed and was efcient for improving mechanical properties. Fig. 14(c) and (d) show that a combination of both nanollers in the fractured surface and dom- inant failure mechanism is pull-out which leads to a higher strength for nanocomposites. The GPL increased the stiffness of the nanocomposites and the pull-out of the CNT increases the strength. Therefore, hybridization of these nanoparticles promotes the toughening and inuences the crack propagation characteris- tics of the pure polymer which in turn causes a signicant improvement in fatigue life of the nanocomposites. 7. Conclusions In this research, the effect of adding hybrid nanoparticles into epoxy resin was investigated and it was found that hybrid particles can improve the static and dynamic properties of composites. For 0.25 wt.% of GPL plus 0.25 wt.% of CNF (i.e., 0.5 wt.% of GPL/CNF) hybrid nanoparticles/epoxy nanocomposites was achieved 123 MPa. While, the static bending strength of GPL/epoxy nano- composites for 0.25 wt.% of GPL content was found 118 MPa and 121 MPa for 0.25 wt.% CNF/epoxy nanocomposites. The exural fatigue behavior of graphene/CNF hybrid nanocomposites under displacement control exural loading is investigated and results are compared with pure epoxy resin, pure epoxy resin with presence of GPL or CNF nanollers. Due to the addition of hybrid nanoparticles, a remarkable improvement in fatigue life of epoxy resin was observed in comparison with results obtained by adding 0.25 wt.% graphene or 0.25 wt.% CNF into the resin. Also, the strength ratio (the bending stress normalized by the bending strength) versus number of cycles to failure for the neat epoxy resin, 0.25 wt.% GPL nanoparticles, 0.25 wt.% CNF nanoparticles, 0.5 wt.% of GPL/CNF hybrid nanoparticles epoxy nanocomposites have been investigated and the experimental observations show that at the strength ratio equal to 43% by using 0.5 wt.% of hybrid nanoparticles; 37.3-fold improvement in exural bending fatigue life of the neat epoxy was observed. While, enhancement of adding only graphene or CNF was 27.4 and 24-folds, respectively. The improvement of the fatigue life of hybrid nanocomposites can be explained by a close look at the fracture surface. The GPL increased the stiffness of nanocomposites and the pull-out of the CNT increases the strength. Therefore, hybridization of these nanoparti- cles promotes the toughening and inuences the crack propagation characteristics of the pure polymer which in turn causes a signi- cant improvement in fatigue life of nanocomposites. In addition, based on literature, addition of nanoller promotes toughening and inuences the crack propagation characteristics of polymer without nanoparticles. Also, they can be attributed to enhanced modulus coupled with a reduced dissipation factor and improved surface hardness. Acknowledgment The authors thank Professor Van W. Paepegemof the mechanics of materials and structures research group at Ghent University for his suggestions and advice. References [1] Paepegem VW, Degrieck J. Experimental setup for and numerical modeling of bending fatigue experiments on plain woven glass/epoxy composites. Compos Struct 2001;51:18. [2] Paepegem VW, Degrieck J. A new coupled approach of residual stiffness and strength for fatigue of bre reinforced composites. Int J Fatigue 2002;24(7):74762. [3] Paepegem VW, Degrieck J. Fatigue degradation modeling of plain woven glass/ epoxy composites. Compos A 2001;32(10):143341. [4] El Mahi A, Khawar Farooq M, Sahraoui S, Bezazi A. Modeling the exural behavior of sandwich composite materials under cyclic fatigue. Mater Des 2004;25:199208. [5] Ramkumar A, Gnanamoorthy R. Effect of nanoclay addition on the displacement-controlled exural fatigue behavior of a polymer. J Mater Sci 2010;45(15):41807. [6] Rajeesh KR, Gnanamoorthy R, Velmurugan R. Effect of humidity on the indentation hardness and exural fatigue behavior of polyamide 6 nanocomposite. Mater Sci Eng, A 2010;527(12):282630. [7] Timmaraju MV, Gnanamoorthy R, Kannan K. Effect of environment on exural fatigue behavior of polyamide 66/hectorite nanocomposites. Int J Fatigue 2011;33(4):5418. [8] Timmaraju MV, Gnanamoorthy R, Kannan K. Inuence of imbibed moisture and organoclay on tensile and indentation behavior of polyamide 66/hectorite nanocomposites. Compos B Eng 2011;42(3):46672. [9] Liang YL, Pearson RA. The toughening mechanism in hybrid epoxysilica rubber nanocomposites (HESRNs). Polymer 2010;51(21):488090. [10] Manjunatha CM, Taylor AC, Kinloch AJ, Sprenger S. The cyclic-fatigue behaviour of an epoxy polymer modied with micron-rubber and nano- silica particles. J Mater Sci 2009;44(16):448790. [11] Manjunatha CM, Taylor AC, Kinloch AJ, Sprenger S. The effect of rubber micro- particles and silica nano-particles on the tensile fatigue behaviour of a glass- bre epoxy. J Mater Sci 2009;44(1):3425. [12] Manjunatha CM, Jagannatha N, Padamalatha K, Taylor AC, Kinloch AJ. The fatigue and fracture behavior of micron-rubber and nano-silica particles modied epoxy polymer. Int J Nanosci 2012;11(3). 1240002-1-7. [13] Manjunatha CM, Bojja R, Jagannathan N, Kinloch AJ. Enhanced fatigue behavior of a glass ber reinforced hybrid particles modied epoxy nanocomposite under WISPERX spectrum load sequence. Int J Fatigue 2013;54:2531. [14] Manjunatha CM, Sprenger S, Taylor AC, Kinloch AJ. The tensile fatigue behavior of a glass-ber reinforced plastic composite using a hybrid-toughened epoxy matrix. J Compos Mater 2010;44(17):2095109. M.M. Shokrieh et al. / Materials and Design 62 (2014) 401408 407 [15] Manjunatha CM, Jagannatha N, Padamalatha K, Taylor AC, Kinloch AJ. The effect of micron-rubber and nano-silica particles on the fatigue crack growth behavior of an epoxy polymer. Int J Nanosci 2011;10(4):10959. [16] Bger L, Sumeth J, Hedemann H, Schulte K. Improvement of fatigue life by incorporation of nanoparticles in glass bre reinforced epoxy. Compos A Appl Sci Manuf 2010;41(10):141924. [17] Fritzsche J, Lorenz H, Klppel M. CNT based elastomer-hybrid-nanocomposites with promising mechanical and electrical properties. Macromol Mater Eng 2009;294(9):55160. [18] Witt N, Tang Y, Ye L, Fang L. Silicone rubber nanocomposites containing a small amount of hybrid llers with enhanced electrical sensitivity. Mater Des 2013;45:54854. [19] Al-Saleh Mohammed H, Saadeh Walaa H. Hybrids of conductive polymer nanocomposites. Mater Des 2013;52:10716. [20] Jen MHR, Chang CK, Sung YC, Hsu FC. Experiments and simulations. DEStech Publications, Inc.; 2012. p. 1759. [21] Li J, Wong PS, Kim JK. Hybrid nanocomposites containing carbon nanotubes and graphite nanoplatelets. Mater Sci Eng, A 2008;483484:6603. [22] Shokrieh MM, Esmkhani M, Vahedi F, Shahverdi HR. Improvement of mechanical and electrical properties of epoxy resin with carbon nanobers. Iran Polym J 2013;22(10):7217. [23] Shokrieh MM, Saeedi A, Chitsazzadeh M. Evaluating the effects of multi-walled carbon nanotubes on the mechanical properties of chopped strand mat/ polyester composites. Mater Des 2014;56:2749. [24] Berchem K, Hocking MG. A simple plane bending fatigue and corrosion fatigue testing machine. Meas Sci Technol 2006;17:606. [25] Ramanathan T, Abdala AA, Stankovich S, Dikin DA, Herrera-Alonso M, Piner RD, et al. Nat Nanotechnol 2008;3:32731. [26] Raee MA, Raee J, Wang Z, Song H, Yu ZZ, Koratkar N. Enhanced mechanical properties of nanocomposites at low graphene. ACS Nano 2009;3(12): 388490. 408 M.M. Shokrieh et al. / Materials and Design 62 (2014) 401408