Materials Science and Engineering A 448 (2007) 264268

Effect of clay surface modication and concentration on the tensile performance of clay/epoxy nanocomposites
S.R. Ha a , S.H. Ryu b , S.J. Park c , K.Y. Rhee d,
b

Graduate School of Mechanical Engineering, KyungHee University, Yongin 449-701, Republic of Korea Industrial Liaison Research Institute, College of Environment and Applied Chemistry, KyungHee University, Yongin 449-701, Republic of Korea c Department of Chemistry, Inha University, 253, Incheon 402-751, Republic of Korea d Center for Media Transport System, Industrial Liaison Research Institute, School of Mechanical and Industrial System Engineering, KyungHee University, Yongin 449-701, Republic of Korea Received 24 June 2006; accepted 14 October 2006

Abstract In this study, the effect of montmorillonite (MMT) clay modication and concentration on the tensile behavior of MMT/epoxy nanocomposite was investigated. MMT was surface-modied using 3-aminopropyltriethoxysilane. MMT/epoxy nanocomposite samples were fabricated by mixing the unmodied and the surface-modied MMT of 2, 6, and 10 wt%, respectively, with epoxy resin. XRD analysis was performed to determine the increase of spacing between layers, after the modication. Tensile tests were performed on the MMT/epoxy nanocomposite specimens with and without the MMT modication. The results showed that the d-spacing between layers increased by more than 55% with the 3-aminopropyltriethoxysilane modication of MMT. For unmodied MMT/epoxy nanocomposite, as the concentration of clay increased the elastic modulus increased, but the tensile strength was not affected signicantly. For surface-modied MMT/epoxy nanocomposite, both the elastic modulus and the tensile strength increased as the concentration of clay increased. Tensile strength and elastic modulus of surface-modied MMT/epoxy nanocomposite were larger than those of unmodied MMT/epoxy nanocomposite, and the modication effect increased with clay concentration. This occurred due to the increased exfoliation of clays along with the improved interfacial strength by the surface modication. 2006 Elsevier B.V. All rights reserved.
Keywords: Montmorillonite; MMT/epoxy nanocomposite; XRD; SEM; Elastic modulus; Tensile strength

1. Introduction It is well known that polymer clay nanocomposite (PCN) offers the advantages of superior mechanical properties, gas permeability, thermal expansion coefcient, and ame retardant compared with pristine polymers. PCN material is generally fabricated by mixing a polymer with inexpensive layered silicate clays. The layered clays are made of high aspect ratio platelets that are one nanometer thick and several hundred nanometers long and wide. The material property of PCN is known to be signicantly affected by the uniform dispersion of clay particles in a polymer matrix. The dispersion of clay particles in the matrix depends on the intercalation and the exfoliation of the clay particles. An intercalated nanocomposite normally is interlayered by molecular layers of polymer in a crystallograph-

Corresponding author. Tel.: +82 31 201 2565; fax: +82 31 202 6693. E-mail address: rheeky@khu.ac.kr (K.Y. Rhee).

ically regular fashion, regardless of the clay-to-polymer ratio, while exfoliation is achieved by delaminating the layers. Numerous studies have been performed for better dispersion of the clay particles in different polymer matrixes and to characterize their effect on the mechanical behavior of PCN materials [14]. Zerda and Lesser [5] used surface-modied montmorillonite (MMT) by a long chain alkylammonium salt and determined the modication effect on the tensile properties of MMT/epoxy nanocomposites. Their result showed that the surface-modication of MMT improved tensile modulus, but corresponding reduction in tensile strength and strain to failure. Zheng et al. [6] modied MMT using three different surfactants and determined tensile properties of MMT/EPDM (ethylenepropylene-diene rubber). It was found that the tensile strength varied from 17 to 25 MPa, while the elastic modulus varied from 2.5 to 3.9 MPa depending on the modifying surfactant. In addition, the effect of MMT concentration on the mechanical behavior of MMT/polymer nanocomposite was extensively investigated by many researchers [79]. Yasmin et al. [10] deter-

0921-5093/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.msea.2006.10.052

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mined the effect of MMT concentration on the elastic modulus and the tensile strength of MMT/epoxy nanocomposite. Their result showed that elastic modulus increased with increasing MMT concentration, while the tensile strength was lower than that of pure epoxy. A similar result on the tensile behavior of MMT/epoxy nanocomposite was obtained by Velmurugan and Mohan [11]. They reported that elastic modulus increased, but tensile strength decreased with increasing MMT concentration. In this study, the effect of MMT modication using 3aminopropyltriethoxysilane and MMT concentration on the tensile behavior of MMT/epoxy nanocomposite was investigated. XRD analysis was performed to determine the increase of spacing of layers after the modication of MMT. Tensile tests were performed on the MMT/epoxy nanocomposite specimens, with and without the MMT modication, to characterize the improvement of tensile behavior due to the modication of MMT. SEM analysis was also performed on fracture surface after tensile tests. 2. Experimental 2.1. Materials The matrix used in this study was a three-component epoxy resin system from Kukdo Chemical (Korea), where epoxy DGEBA (YD-115), anhydride hardner (PAA), and accelerator (DY070) were mixed in the ratios of 100:50:30, respectively. The reinforcing materials were unmodied and 3amonopropyltriethoxysilane-modied MMT clays. Unmodied MMT clay, Cloisite Na+ , was obtained from Southern Clay Products Inc. (USA). 3-Aminopropyltriethoxysilane was obtained from Aldrich Chemical Company Inc. (USA). One gram of clay was dispersed in 100 ml of solvent at 25 C, using a mechanical stirrer. One gram of 3-aminopropyltriethoxysilane dissolved in 100 ml of distilled water was added to the clay dispersion under constant stirring, and stirring was continued for 30 min. Then, it was ltered off and dried at 60 C under vacuum. 2.2. Fabrication of MMT/epoxy nanocomposite MMT/epoxy nanocomposite samples were fabricated by mixing the MMT of 2, 6, and 10 wt%, respectively, with epoxy resin. The epoxy resin was heated to 110 C and, then, the required amount of MMT was mixed with the epoxy by stirring at 200 rpm for 3 h, using a mechanical stirrer. Next, the mixture was degassed in a vacuum oven at room temperature for 3 h. The nanocomposite plates were machined as the dog-bone tensile samples, according to ASTM D 638 [12]. Thickness and gauge length of the tensile specimens are 5 and 40 mm, respectively. For the sake of convenience, the samples made of unmodied MMT were abbreviated as Na+ -MMT and the samples made of modied MMT were abbreviated as SM-MMT. 2.3. Characterization X-ray diffraction measurement was performed on MMT and MMT/epoxy nanocomposite, using a Mac-science X-ray

diffractometer equipped with a back monochromator operating at 40 kV and a copper cathode as the X-ray source ( = 1.54 A). Five samples were tested for XRD analysis. Tensile tests were carried out using an Instron testing machine at a crosshead speed of 0.5 mm/min at room temperature. At least four tests were performed for each content of clay to ensure the reliability of test results. The fracture surfaces of tensile specimens were examined using a SEM (Leica Cambridge, England). The fracture surfaces were gold coated prior to SEM investigation and examined at 3 kV. 3. Results and discussion Fig. 1 shows X-ray diffraction patterns of the unmodied MMT powder and the surface-modied MMT powder with 3amonopropyltriethoxysilane in distilled water, which shows the d-spacing. As shown in the gure, for an unmodied MMT, a sharp peak occurred at around 2 = 7.0 , in which the d-spacing The surface-modied MMT with was calculated to be 12.8 A. 3-amonopropyltriethoxysilane, however, shifts the peak to the lower 2 value at around 4.2 , which corresponds to a d-spacing Therefore, the d-spacing of modied MMT value of 20.8 A. than that of the unmodied MMT. is larger by about 8.0 A The diffraction patterns of Na+ -MMT and SM-MMT samples with 10 wt% are shown in Fig. 2. For a SM-MMT sample, the sharp peak shifted to lower angle (2 = 3.5 ), which indicates an intercalated structure with an increase (20%) in d-spacing. It can be seen from the gure that for a Na+ -MMT sample, however, the sharp peak did not shift much and occurred at around 2 = 6.3 . This corresponds to a d-spacing value of (10% increase) and indicates that the unmodied 14.1 A MMT worked as a ller with a small increase in d-spacing. Fig. 3 shows typical stressstrain curves of the Na+ -MMT sample and the SM-MMT sample, when the concentration of MMT is 10 wt%. As shown in the gure, the stress increased almost linearly with strain before reaching the maximum stress for both specimens. This linear stressstrain behavior was also observed for 2 and 6 wt% samples. A point to be noted in Fig. 3 is that the strain to failure of SM-MMT is considerably larger

Fig. 1. X-ray diffraction patterns of the Na+ -MMT and SM-MMT powders.

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Fig. 2. X-ray diffraction patterns of the Na+ -MMT and SM-MMT samples with 10 wt% concentration.

Fig. 4. Variation of elastic modulus for the Na+ -MMT and SM-MMT samples as a function of the clay concentration.

than that of the Na+ -MMT. It is believed that this phenomenon occurs due to the improved dispersion of MMT and interfacial bonding strength with epoxy matrix. When a deformation is externally applied, the clay is rearranged in the direction of the deformation. The applied stress is mostly carried by clay layer so that the more dispersed clay layer and the improved interfacial strength restrain the matrix cracking. To understand the effects that the 3-amonopropyltriethoxysilane modication and concentration of MMT have on the elastic modulus of MMT/epoxy nanocomposite, the elastic modulus of the SM-MMT sample was compared with that of the Na+ -MMT sample as a function of MMT concentration. The elastic modulus was determined by measuring the slope in the beginning of the linear region in the stressstrain curve. Fig. 4 shows the change in elastic modulus of MMT/epoxy nanocomposites for the two cases according to the concentration increase of MMT. It can be seen from the gure that in both cases, the elastic modulus increases with the concentration of MMT. The main reason for increasing elastic modulus of MMT/epoxy nanocom-

Fig. 3. Typical stressstrain curves of the Na+ -MMT and SM-MMT samples with 10 wt% concentration.

posites with increasing MMT concentration can be explained as follows. When a load is applied to the MMT/epoxy nanocomposite, the applied load is transferred through the epoxy to the MMT, with a high elastic modulus. In this case, the clay strengthens nanocomposite by resisting the applied force and, as a result, inhibits the deformation of nanocomposite. The inhibiting effect on deformation increases with the concentration of MMT. Fig. 4 also shows that the elastic modulus of the SM-MMT sample is larger than that of the Na+ -MMT sample, regardless of the concentration of MMT. In particular, it is seen that when the concentration of clay is 2 wt%, the difference of elastic modulus between the Na+ -MMT and the SM-MMT specimens is not big, but the difference of elastic modulus between the two samples increases with the concentration. Specically, the difference of averaged elastic modulus between the two samples was about 11% for 2 wt% concentration and about 22% for 10 wt% concentration. The reason, why the difference of elastic modulus between the two cases increases with the concentration of clay, is explained in the next section. The tensile strength of the SM-MMT sample was compared with that of the Na+ -MMT sample as a function of clay concentration, to understand the effects that the silane modication and the concentration of clay have on the tensile strength of MMT/epoxy nanocomposite. The value of tensile strength was determined as the maximum stress value. Fig. 5 shows the variation of tensile strength in the two cases as a function of the clay concentration. As shown in Fig. 5, the tensile strength increases with increasing concentration of clay for the SM-MMT sample, while in the case of the Na+ -MMT sample, the tensile strength is almost not affected by the clay concentration. A number of studies have been carried out on the effect of clay concentration on tensile strength, and the research results are presented differently depending on the researchers. Qi et al. [13] reported that the tensile strength of MMT/epoxy nanocomposite was lower than that of pure epoxy and decreased with increasing clay concentration. On the other hand, Hiroaki et al. [14] studied the tensile strength of amine-cured diglycidyl ether of bisphenol A based nanocomposites reinforced by organomontmorillonite clay nanoplatelets.

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Fig. 5. Variation of tensile strength for the Na+ -MMT and SM-MMT samples as a function of the clay concentration.

Fig. 6. Variation of hardness for the Na+ -MMT and SM-MMT samples as a function of the clay concentration.

They showed that the tensile strength was improved only when 2.5% clay nanoplatelets were added to the epoxy because of the large plastic behavior. Lan and Pinnavaia [15] observed more than a 10-fold increase in tensile strength and modulus by the addition of only 15% of the exfoliated organoclay. A point to be noticed in Fig. 5 is that the difference of tensile strength between the two cases increases as the clay concentration increases. If the concentration of clay was 2 wt%, the average difference of tensile strength between the two samples was within 3%, but for 10 wt%, the average difference of tensile strength was about 25%. The reason, why the effect of silane modication of clay increases with clay concentration, is explained as follows. Firstly the exfoliation effect of clay increases due to silane modication and, therefore, the distance between the layers increases. In other words, with the gap between layers widening, the amount of epoxy inserted between layers increases. Second, the interfacial strength between clay and epoxy increases due to the silane modication. Fig. 6 shows the change in hardness of MMT/epoxy nanocomposites for the two cases, according to the clay concentration. As shown in the gure, for both cases the hardness increases as the clay concentration increases. The reason for that

is that the clay dispersed within the epoxy prevents crystals on the surface of epoxy from being damaged by an external force and also prevents microcracks existing inside the epoxy from growing up to the surface. The gure shows that the average hardness of SM-MMT specimen is higher than that of the Na+ MMT specimen at the same clay concentration. This also occurs because the clay was well-dispersed within the epoxy matrix and the adhesion strength between clay and epoxy matrix was increased by the 3-amonopropyltriethoxysilane modication. Fracture surfaces of the Na+ -MMT and the SM-MMT samples were observed using SEM and compared with each other. Fig. 7(a and b) shows the typical fracture surfaces of 2 and 10 wt% Na+ -MMT samples, respectively. Low magnication (500) micrographs were presented as they showed a better view of clay dispersion in the nanocomposite. As shown in the gures, clay is agglomerated in different sizes and debonded from the epoxy matrix. Voids are formed around the clay, due to the low interfacial strength between unmodied clay and epoxy matrix, in both samples. The fracture surface of 10 wt% sample has smaller and rougher fracture pieces compared with that of the 2 wt% sample. This indicates that the agglomerated clay acted as crack initiation site and epoxy matrix was fractured in a cleavage

Fig. 7. Typical fracture surfaces of Na+ -MMT samples for 2 wt% (a), and 10 wt% (b) concentrations.

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Fig. 8. Typical fracture surfaces of SM-MMT samples for 2 wt% (a), and 10 wt% (b) concentrations.

mode. Fig. 8(a and b) shows the typical fracture surfaces of 2 and 10 wt% SM-MMT samples, respectively. As shown in the gure, the fracture surfaces of SM-MMT samples are similar to those of the Na+ -MMT samples. Therefore, cleavage fracture occurred in the epoxy matrix and the surface became rougher as the clay concentration increased. It can be seen from Figs. 7(b) and 8(b) that the clay of the SM-MMT sample is more uniformly distributed than that of the Na+ -MMT sample. Furthermore, there are more holes (dark area) in the Na+ -MMT sample, which could be attributed to small clay pieces that were pulled out during testing or micro-voids that formed during fabrication. 4. Conclusion In this study MMT was modied using 3aminopropyltriethoxysilane, and MMT/epoxy nanocomposite was fabricated by changing the concentration of clay in three steps. This was done to investigate the effects that the modication and the concentration of clay have on the tensile characteristics of MMT nanocomposite. The conclusions obtained from this study are as follows. First the d-spacing between layers increased by more than 55% as a result of the 3-aminopropyltriethoxysilane modication of MMT. Second, in the case of Na+ -MMT, as the concentration of clay increased the elastic modulus increased, but the tensile strength was not affected signicantly. On the other hand, in the case of SM-MMT, both the elastic modulus and the tensile strength increased as the concentration of clay increased. Third, the SM-MMT sample had higher tensile characteristics than the Na+ -MMT sample at the same clay concentration, and the mod-

ication effect increased with increasing clay concentration. This is judged to be caused by increased exfoliation of clay along with the improved interfacial strength between clay and epoxy. Acknowledgement This work is supported by the Basic Research Program (Grant R01-2005-000-10388-0) of the Korea Science and Engineering Foundation. References
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