European Polymer Journal 43 (2007) 28562865

EUROPEAN POLYMER JOURNAL

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Macromolecular Nanotechnology

Shape memory and mechanical properties of cross-linked polyethylene/clay nanocomposites

Sayena Rezanejad, Mehrdad Kokabi
MACROMOLECULAR NANOTECHNOLOGY
*
Polymer Engineering Group, Chemical Engineering Department, Faculty of Engineering, Tarbiat Modares University, P.O. Box 14115-143, Tehran, Islamic Republic of Iran Received 8 October 2006; received in revised form 7 April 2007; accepted 23 April 2007 Available online 5 May 2007

Abstract Shape memory polymer (SMP) such as cross-linked low-density polyethylene (XLDPE), can return from its temporary shape to the original (permanent) shape upon heating. SMP in comparison with shape memory alloy (SMA) and shape memory ceramic (SMC) has lower stiness, so generates lower recovery force when it is being used as an actuator. Also, when SMP is reinforced with traditional micro-llers, it often loses its shape memory eect due to the high weight fraction of ller (2030%). To overcome these disadvantages, nanoclays can be used. The smart resultant nanocomposite, even in small clay loading level (010 wt.%), shows higher modulus, strength, and the other physical properties such as higher recovery force, required to act as an actuator. In this work, the eect of modied montmorillonite on mechanical and shape memory properties as well as the force generation of a shape memory cross-linked low density polyethylene were investigated. The results show that the modulus of elasticity, the recovery temperature, the recovery force and force recovery rate increase with increasing organoclay in nanocomposites, but nal recovery strain decreases slightly. 2007 Elsevier Ltd. All rights reserved.
Keywords: Nanocomposite; Shape memory eect; Low density polyethylene; Organoclay; Actuator; Smart polymer

1. Introduction Smart/intelligent/adaptive systems are composed of three basic elements: sensors, actuators, and control processors [1]. An intelligent material can respond adaptively to an environmental stimulus, such as a change in temperature and loading [2].

* Corresponding author. Tel.: +98 21 8801 1001; fax: +98 21 8800 6544. E-mail address: mehrir@modares.ac.ir (M. Kokabi).

Smart materials have been the subject of much investigation in recent years. Shape memory materials are dened by their potential to store a deformed (temporary) shape and recover the original (permanent) shape [3]. The shape memory behaviour is typically induced by a change in temperature and has been observed in metals, ceramics, and polymers [4]. Shape memory polymers have many advantages over shape memory counterparts in easy processing, low density, high shape recovery, high recoverable strain, and low manufacturing cost. Especially, their

0014-3057/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.eurpolymj.2007.04.031

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recoverable strain is of an order of 100%, while shape memory metals or ceramics can recover only about 10% or 1%, respectively [5]. All shape memory polymers have a two phase structure [3]: 1. Hard phase (segment) which retains the permanent shape of the shape memory article does not melt or soften in the transition temperature of soft segments. These segments could be cross-linked rigid local structures or entanglements which will not disentangle in the recovery temperature. 2. Soft phase (segment) which upon heating becomes soft and acts as a switch to remember the original (permanent) shape of the article. The ability of shape memory polymers to spontaneously recover large strains in restricted environments has been exploited in numerous applications, such as heat-shrink tubing, deployable aerospace structures, microsystems, and biomedical devices. Deformation (i.e., strain energy) is stored by a reversible morphological change or a suppression of molecular relaxation [6]. Theoretically, the stored energy can also be used to exert force, but to achieve this, the performance of such materials has to be increased by enhancing the rubbery modulus (elastic modulus above glass transition temperature) [7]. Typically, micro-scale llers such as chopped carbon, glass or Kevlar bres are used to enhance the rubbery modulus [2]. Ni et al. found that the tensile strength besides thermo-mechanical stress of PU/ bre glass composites became higher by incremental increase of bre weight fraction, but nal recovery strain decreased [7]. Recently, some interesting results have been reported using nanocomposites such as polymeric nanocomposites [5]. Studies have shown that constrained bending recovery force of shape memory polymer could be increased by 50% with the addition of 20 wt.% of SiC [8,9]. Zheng found that shape recovery time was shorter for poly (D,L-lactide)/ hydroxyapatite composites in comparison with neat polymers [10]. Also the work done by Koerner et al. shows uniform dispersion of 15 vol.% of carbon nanotubes in a thermoplastic elastomer yields nanocomposites that can store and subsequently release, through remote means, up to 50% or more recovery stress than the pristine resin. The anisotropic nanotubes increase the rubbery modulus by a factor of

Fig. 1. 3DS stressstraintemperature relations in the typical thermomechanical cycles [8].

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25 and improve shape xity by enhancing strain induced crystallization [11]. A typical pre-deformation and recovery cycle for shape memory polymers was described by Gall in three steps (Fig. 1) [8]. First the SMP material has to be heated to an elevated temperature. In the rst step of the cycle (step 1) sample is deformed to a desired strain (em). In the second step (step 2) SMP is cooled to x the temporary shape. At the lower temperature, the SMP molecular chain segments are frozen in a temporary position and upon removing the constraint the induced shape is retained. In the nal step, the SMP structure is heated up to transition temperature. In this step the two limiting cases of constraint are applied: unconstrained recovery (free recovery of strain upon heating in the absence of external limit as in step 3a) and constrained recovery (generation of recovery stress upon heating in SMP xed at the pre-deformation strain (step 3b)). Low density polyethylene (LDPE) by volume has the highest production in world plastics industry. Its rather poor properties can be improved by crosslinking [12]. Cross-linked polyethylene deforms easily above its crystalline melting point and this deformation can be xed by cooling. On heating, it may restore to its original shape. Therefore, cross-linked LDPE can be put into the class of shape memory polymers particularly used in the heat-shrinkable products, packaging, and electrical industries [13]. Previous works on polyolen nanocomposites show that the addition of clay to polyolen matrix will eect physical properties such as crystallinity [1416], and increase the mechanical properties such

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as modulus [17,18] and dynamic mechanical properties (E 0 /E00 ) [19]. These will enhance shape memory eect in the nanocomposites. In this work, the dependency of mechanical and shape memory properties of cross-linked LDPE/ clay nanocomposite on the weight fraction of clay was investigated. 2. Experimental 2.1. Materials Organically modied clay (Org-MMT) Cloisite intergallary spacing, ion exchanged 15A with 31.5 A by dimethyl dehydrogenated tallow ammonium bromide were provided by Southern Clay Products. Low density polyethylene (LDPE) grade LF0200 with MFI of 1.6 g/10 min and density of 0.923 g/ml, was obtained from Bandar Imam Petrochemical Company, Iran. Irganox 1010 antioxidant with density of 1.45 g/ml was purchased from Ciba Geigy Co. Dicumyl peroxide (DCP) with purity of 98% and density of 1.02 g/ml was obtained from Hercules Co. 2.2. Preparation of LDPE/Org-MMT compound LDPE and 3, 5, 8 and 10 wt.% Cloisite 15A were melt blended in a Brabender Plasticorder with a chamber of 50 cm3 and roller blades at 170 C. The screw speed was kept at a low speed of 30 rpm for the rst 5 min, and then increased to 60 rpm for 25 min to obtain a well mixed system. Then the compound was removed from the chamber and cooled to room temperature. 2.3. Preparation of cross-linked LDPE/Org-MMT Nanocomposites compound obtained from previous section were mixed with 0.5 wt.% DCP and 0.1 wt.% antioxidant at 130 C and a screw speed of 50 rpm for 8 min. Original shape of the article was obtained by curing under a hot press at 180 C and 80 ton pressure. 2.4. Instrumentation X-ray diraction (XRD) patterns were performed using a Philips X-Pert apparatus with . Transmission electron microscopy k = 1.5404 A (TEM) image was obtained at 200 kV with a Philips

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CM200 electron microscope. The sample was embedded in an epoxy matrix and ultra-microtomed with a diamond knife on a Coreichart OMUS microtome at room temperature to give 60100 nm thick section. The section was transferred from water to Cu grades of 400 meshes. To measure the gel content, samples in the form of ne granules were weighed and extracted with boiling xylene for 16 h at 140 C according to ASTM D2765. Dierential thermal analysis (DTA) was performed on a PL-STA 1500. Samples were heated from 25 C to 200 C at a heating rate of 10 C/ min, and then cooled to room temperature at the same rate. A Netzch 242C dynamic mechanical analyzer (DMA) was used in tension mode with 1 Hz frequency and dynamic force of 4 mN. Samples were heated from 100 C to +100 C with a heating rate of 2 C/min. To measure the tensile properties of nanocomposites, a tensile device with HBM load-cell and Scott 55 amplier which had a heating chamber was used at four dierent temperatures (25, 60, 108 and 150 C) and cross-head speed of 1.063 mm/s. To measure the thermo-mechanical properties of the products mentioned before, the samples with 15 mm width, 1.3 mm thickness and 50 mm length were heated up to 150 C and stretched up to dierent pre-deformation strains (em) and then cooled instantaneously. Then, the deformed samples were examined at the dierent conditions. 2.4.1. Non-isothermal constant strain The samples were heated from 25 C to 150 C at the constant strain equal to em and generation of stress in the sample was recorded by the load cell. 2.4.2. Isothermal constant strain The samples were left at 108 C instantaneously and the generation of stress with time was recorded. 2.4.3. Non-isothermal free strain recovery The deformed samples were heated from 25 C to 150 C in an oven and the free recovery of the samples was determined as follows: Free recovery strain Lt Lr =Lt Li ; 1

where Lt = temporary length: length of deformed sample, Lr = recovery length: length of sample during recovery that changes upon heating, Li = initial length: original length of undeformed sample, and

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Scheme 1. Setup used to measure recovering length.

to measure Lr a setup similar to that shown in Scheme 1 was employed. By increasing the temperature, the sample begins to shrink, thus pulls the wire and needle. Displacement of the needle is equal to the length change of the sample. 3. Results and discussion 3.1. Structure of nanocomposites In the formation process of nanocomposite, polymer chains are inserted in the interlayer space of layered silicates to force them take distance from each other. XRD is a suitable means to evaluate this process. According to the Braggs equation 2d sinh = nk, every peak in XRD pattern is related to a distance (d), so the rst peak observed in the 2h below 5 is attributed to d001 or interlayer spacing. The XRD patterns of PE/Org-MMT nanocomposites are shown in Fig. 2 and XRD data calculated from the (0 0 1) peaks are summarized in Table 1. As is observed in Fig. 2 and Table 1, there is a strong peak at the position of 2.75 for OrgMMT, which corresponds to a d-spacing of 3.15 nm. After melt blending with PE the position of the (0 0 1) peak shifts to lower angles (higher d001) for each sample. The viscosity of the matrix of nanocomposites will increase with increasing of clay content, thus the exerted shear stress to the layers will increase and clay layers will separate easier up to the sample with 5 wt.% of clay which has 3.7 nm d-spacing. But, after this point, the increasing clay content probably results in stacking layers and separation

Fig. 2. XRD patterns of PE/Org-MMT nanocomposites and Org-MMT (Cloisite 15A).

Table 1 XRD data for PE/Org-MMT nanocomposites Sample code Org-MMT (cloisite 15A) PE3 PE5 PE8 PE10 2h 2.75 2.6 2.49 2.73 2.79 d-Spacing (nm) 3.1 3.3 3.7 3.2 3.1

of these layers may become more dicult. For this reason, basal spacing will decrease. Finally no increase could be observed in a 10 wt.% specimen in which nanocomposite would not be actually formed. In most cases, TEM is combined with XRD to testify the microstructure of nanocomposites. It is convenient to observe the dispersion of Org-MMT in the PE matrix by TEM. Fig. 3 is the TEM micrograph of PE5, in which the dark lines are the layers of Org-MMT. According to the result obtained from XRD, most of Org-MMT in PE5 system still is parallel to each other and intercalation of PE chains only increases the interlayer space. From the low magnication images one can see that the clay is well distributed in PE matrix and from the high magnication images the intercalated clay with PE chains can be observed. These results further show the intercalation eect of PE is limited. It is due to its non-polar character even for an OrgMMT being modied with C-16.

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Scheme 2. Schematic diagram of clay layers and macro-radicals.

Fig. 3. TEM micrograph of PE/Org-MMT nanocomposite PE5: (a) low magnication, (b) high magnication.

behave like rigid obstacles that prevent cross-linking reaction, and so the cross-link density decreases. This phenomenon is depicted as in Scheme 2. According to the fact that cross-links are the hard segments that guarantee the shape memory eect, decreasing the cross-link density due to the presence of clay will cause a drop in shape memory eect in the specimen and it prevents the sample to return completely back to its original shape, Fig. 4. 3.2.2. Thermal properties Fig. 5 shows the DTA curve of PE/Org-MMT nanocomposites. To avoid overlap between curves, they are shifted in the vertical direction. According to the cooling curves, addition of clay would not extremely change the Tc of the nanocomposites,

3.2. Physical properties of nanocomposites 3.2.1. Cross-link density Cross-link density of the samples was measured and the results were listed in Table 2. It clearly shows a decrease in cross-link density with increasing clay content. To explain this trend, the mechanism of crosslinking by DCP must be realized. By applying heat, rst DCP decomposes to free radicals and then attacks the polymeric chains and converts them to macro-radicals. These macro-radicals react with each other and cross-link [20]. If a polymeric chain is caught between clay layers, it cannot nd another chain to react with it. On the other hand, clay layers
Table 2 Gel content of PE/Org-MMT nanocomposites Sample code PE PE3 PE5 PE8 Gel content 48 46.44 44.67 30.79

Fig. 4. Gel content of nanocomposites.

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Fig. 5. DTA curves of the PE/Org-MMT nanocomposites: (a) cooling curves, (b) heating curves.

thus subjecting the samples to pre-deformation at the same temperature is a right method. From the heating curve it is evident that Tm of the nanocomposites would not change extremely, but in order to compare the degree of crystallinity of the nanocomposites, this curve could be used. The area above the curve in the vicinity of Tm is proportional to the crystallinity. To make the comparison easier, the plots are shifted in the vertical direction. Crystallinity of the samples increases up to nanocomposite PE3 and then begins to decrease. However, the degree of crystallinity of the nanocomposites is higher than neat polymers. Clay layers in the PE matrix will exhibit behaviour somewhat like nucleating agents and thus cause increase in crystallinity. But increasing clay content more than 3 wt.% will increase viscosity of the matrix, and so the propagation of these spherulites will be inhibited and nally the amount of crystallinity will be diminished. 3.2.3. Dynamic mechanical properties Fig. 6 shows the E 0 , E00 and tan d curves of nanocomposites. Curves are in the logarithmic scale.

Fig. 6. DMA results of the PE/Org-MMT nanocomposites (a) E 0 , (b) E00 , (c) tan d.

From these curves, increase in E 0 and E00 is evident (about 300% increase in both of E 0 and E00 ) which means that the incorporation of clay layers in PE matrix increases both the elasticity and plasticity characteristics of the nanocomposites. Increase in elasticity character of the chains is more dramatic which causes increase in stress generation rate in the samples at the recovery process. The amount of tan d of the nanocomposites decreases which means that the damping character of the chains will decrease upon addition of clay layers. As mentioned previously, nanocomposite matrix contains crystal regions, cross-link regions and regions beside clay layers which cause restriction in the mobility of the polymer chains. Chains activation in these regions takes place at dierent

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temperatures. Because of this variety of transitions (mobilities), the tan d curves of these samples are very broad and no sharp transition could be observed. 3.2.4. Tensile properties Tensile test was carried out on the samples at four dierent temperatures, as mentioned in the experimental section. The results are shown in Fig. 7. It is observed that by increasing clay content an increase in elastic modulus (slope of the diagrams in the linear section) besides a decrease in elongation-at-break are observed. The presence of clay layers in the PE matrix will prevent PE chains from free motions thus decreasing the toughness and increasing the brittleness. The modulus of elasticity of the samples at various temperatures was plotted in Fig. 8. Extreme increase in elasticity modulus due to increasing clay content could be observable (143% increase for 8 wt.% clay loading, in comparison with the neat polymer at ambient temperature). Increasing in

Fig. 8. Elasticity modulus of PE/Org-MMT nanocomposites at four dierent temperatures.

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Youngs modulus will cause increase in generated stress in the nanocomposite samples according to Hooks law (r = Ee). 3.3. Shape memory properties of nanocomposites 3.3.1. Free recovery strain Fig. 9 shows the recovery strain obtained from nanocomposites with dierent clay loading levels

Fig. 7. Tensile results of PE/Org-MMT nanocomposites at four dierent temperatures.

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nal recovery strain (12% decrease for PE8 in comparison with neat polymer). 3.3.2. Recovery stress (force generation) 3.3.2.1. Non-isothermal condition. Fig. 10 shows the force generation in nanocomposites kept at constant strain, while increasing the temperature. This phenomenon is very similar to increasing pressure of gasses with increasing temperature at constant volume PV nRT . Increasing temperature will cause crystalline regions to melt and amorphous chains tend to return back to their original random shape with higher entropy. In this stage, preventing the chain motion (kept at constant strain) generates the force in the samples. Increasing clay content will increase the amount of the generated force in samples during temperature rise. Tensile test results show that increasing clay content enhances elastic modulus and according to Hooks law, i.e., r = Ee, this will cause rise in the generated stress. Thus, increase in modulus may cause an increase in recovery stress of

Fig. 9. Recovery strain curve of nanocomposites with (a) 50%, (b) 100% pre-deformation strain.

at various pre-deformation strains. According to these curves, increasing clay content shifts the recovery temperature (incline point of S-type recovery curve) to higher point and the nal recoverable strain to decrease. DTA results show that increasing clay content increases crystallinity in nanocomposites which causes the recovery temperature to increase. Recovery temperature is the temperature in which polyethylene crystals melt and amorphous chains can return back to their initial random state. Thus, increasing crystallinity will increase the recovery temperature. Additionally, increasing clay content will prevent polymer chains to move freely and hinders their motion, thus prevents them to be recovered completely to their original shape. The other reason in interpreting this observation could be the presence of clay layers without shape memory potential which will properly decrease the total shape memory eect of the nanocomposite so decreasing the

Fig. 10. Recovery stress results of nanocomposites with (a) 50%, (b) 100% pre-deformation strain.

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nanocomposites which makes the polymeric chains to generate higher forces during recovery. Another interesting feature in these curves is increasing the slope of curves by increasing clay content. According to the rubber elasticity theory, the slope of stress curve versus temperature is proportional to the number of cross-links existing in n n the polymeric matrix r V RT a 1 , where V a and a are the number of cross-links per unit volume and stretching ratio, respectively). Recently, Mark [21] has found that n is not only the number of cross-links, but relates to every hard segment that exists in the matrix, for instance in this study, the crystalline regions as well as the clay layers. Thus, increasing clay content and accordingly increasing crystalline regions may cause the slope of these curves to increase. Finally, in these curves a decrease in generated stress after reaching its maximum value could be observed. Trznadel relates this phenomenon to slippage of polymeric chains above each other and their disentanglement [22]. By increasing clay content this decrease will become less and less and completely disappears at 8 wt.% of clay. A schematic presentation of molecules in neat polymer and nanocomposite is given in Scheme 3 (a: neat polymer, b: nanocomposite). Cross-links could not be formed in the surface of the clays, thus the presence of clay layers causes the cross-links to distribute more eciently in the matrix. In a good distributed system, the likelihood of entanglements between two cross-links is higher, thus by stretching, disentanglement is less probable and only congurationally changes would occur in the nanocomposites.

3.3.2.2. Isothermal condition. To compare the rate of stress generation in nanocomposites, a stress recovery test was performed in isothermal condition (at 108 C which is the maximum temperature that nanocomposite with 8 wt.% clay reaches to its maximum recovery stress). The results of the test are shown in Fig. 11.

Fig. 11. Recovery stress at 108 C for nanocomposites with (a) 50%, (b) 100% pre-deformation strain.

Scheme 3. Schematic design of (a) neat polymer chains, (b) nanocomposite chains.

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As it is evident, increasing clay content causes the slope of the curves (rate of stress generation in nanocomposites) to increase. This increase is due to the increased elastic character of the polymeric chains (according to DMA results) which can generate higher stresses in shorter time intervals. 4. Conclusions Produced nanocomposites have intercalated structure as characterized by XRD and TEM. Presence of clay layers in the matrix causes cross-link density to decrease and crystallinity to increase. These layers extremely improve mechanical properties such as storage, loss, and Youngs modulus. Besides these changes, clay layers have strong eect on shape memory properties. The nal recovery strain decreases slightly (about 12%) but due to their improved mechanical properties, recovery stress (force generation) increases extremely (about 200%) in nanocomposites. Increased recovery stress in shape memory crosslinked polyethylene nanocomposite is an advantage to produce high performance light weight actuator with reasonable recovery strains. Acknowledgement The authors thank the Ministry of Science, Research and Technology of Islamic Republic of Iran for the nancial support. References
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