Natural rubber-clay nanocomposites

The effect of polymer-filler interaction on solvent swelling and dynamic mechanical properties of the sol-gel-derived acrylic rubber (ACM)/silica, epoxi-dized natural rubber (ENR)/silica, and polyvinyl alcohol (PVA)/silica hybrid nanocomposites was described by Bandyopadhyay et al. [27]. Theoretical delineation of the reinforcing mechanism of polymer-layered silicate nanocomposites has been attempted by some authors while studying the micromechanics of the intercalated or exfoliated PNCs [28-31]. Wu et al. [32] verified the modulus reinforcement of rubber/clay nanocomposites using composite theories based on Guth, Halpin-Tsai, and the modified Halpin-Tsai equations. On introduction of a modulus reduction factor (MRF) for the platelet-like fillers, the predicted moduli were found to be closer to the experimental measurements. 

Unlike polymer-clay nanocomposites, in rubber-clay nanocomposites complete exfoliation of clay layers results in disappearance of the diffraction maxima in their XRD patterns. However, this can also occur due to other reasons, like extremely low concentration of clay materials in the composites, crystal defects, etc. The majority of the reports on rubber-clay nanocomposites display the intercalated or swollen nature of the clay structures. The presence of the basal reflections in the XRD patterns of such type of nanocomposites indicates that the clay crystal structure is not destroyed completely. But, shifting of their positions to lower 26 values is interpreted as an expansion of the interlayer region by the macromolecular rubber chains. Besides, broadening of the characteristic reflections in nanocomposites is often related to the defects in the crystal layer stacking caused by the interlayer polymeric species. 

The extent of clay dispersion and clay-polymer interaction is crucial in determining the formation of natural rubber based nanocomposites. Due to the low polarity and high viscosity of natural rubber, direct blending of clay nanoparticles into natural rubber will only yield micro-scale composites. Thus, it is more effective to blend clay nanoparticles into another polymer component before blending with natural rubber. 

Compared to the vast literature on most of the thermoplastic or thermosetting polymer-clay nanocomposites, reports of rubber-clay nanocomposites are much more limited. Much more research is needed to understand the complex nature of these nanocomposites and to identify the factors that have the most significant influence on their physical, mechanical, thermal, barrier, and dynamic mechanical properties. The several examples of rubber-clay nanocomposite that have been covered in this chapter indicate that to date rubber nanocomposite research has largely concentrated on the natural rubber, ethylene propylene diene rubber, styrene-butadiene rubber, and nitrile rubbers. The main factors found to influence final properties were type of clay and its treatment, clay... 

FIGURE 2.7 Effect of various clays on natural rubber (NR)-based nanocomposites (at 4 phr loading). (From Bhattacharya and Bhowmick, Unpublished data.)... 

Mondragon et al. [250] used unmodified and modified natural mbber latex (uNRL and mNRL) to prepare thermoplastic starch/natural rubber/montmorillonite type clay (TPS/NR/Na+-MMT) nanocomposites by twin-screw extrusion. Transmission electron microscopy showed that clay nanoparticles were preferentially intercalated into the mbber phase. Elastic modulus and tensile strength of TPS/NR blends were dramatically improved as a result of mbber modification. Properties of blends were almost unaffected by the dispersion of the clay except for the TPS/ mNR blend loading 2 % MMT. This was attributed to the exfoliation of the MMT. 

This is Volume 2 of Natural Rubber Materials and it covers natural rubber-based composites and nanocomposites in 27 chapters. It focuses on the different types of fillers, the filler matrix reinforcement mechanisms, manufacturing techniques, and applications of natural rubber-based composites and nanocomposites. The first 4 chapters deal with the present state of art and manufacturing methods of natural rubber materials. Two of these chapters explain the theory of reinforcement and the various reinforcing nanofillers in natural rubber. Chapters 5 to 19 detail the natural rubber composites and nanocomposites with various fillers sueh as siliea, glass fibre, metal oxides, carbon black, clay, POSS and natural fibres ete. Chapters 20-26 discuss the major characterisation techniques and the final ehapter covers the applications of natural rubber composites and nanoeomposites. By covering recent developments as well as the future uses of rubber, this volume will be a standard reference for scientists and researchers in the field of polymer chemistry for many years to come. 

Table 2.1 presents a summary of the information available in the scientific literature for C and OC dispersion in isoprene rubbers. The state of dispersion depends on the clay type, pristine or organically modified, and on the blending technology adopted. Table 2.2 shows that nanocomposites are formed with a pristine clay only through emulsion blending. In fact, the inorganic nature of clay layers hinders their compatibility with the rubber matrix. 

A. Jacob, P. Kurian and A. S. Aprem, Transport Properties of Natural Rubber Latex Layered Clay Nanocomposites, Journal of Applied Polymer Science, 2008, 108, 2623. 

Kong et al. [115] synthesized hy melt-intercalation silicone rubber (SR)/clay nanocomposites using synthetic Fe-montmoriUonite (Fe-MMT) and natural Na-MMT which were modified by cetyltrimethylammoniumbromide, surfactant. They obtained exfoliated and intercalated nanocomposites. With TGA and mechanical performance found that with the presence of iron significantiy increased the onset temperarnre of thermal degradation in SR/Fe-MMT nanocomposites. In addition, the thermal stability, gel fraction and mechanical property of SR/Fe-MMT were different from the SR/Na-MMT nanocomposites, so the iron not only in thermal degradation but also in the vulcanization process acted as an antioxidant and radicals trap. A new flame-retardant system, SR/Fe-OMT based on an EVA matrix, was examined Fang et al. [ 116]. The experimental analyses showed that the exfoliated Fe-OMT had better dispersion in the EVA matrix than Na-OMT, and it was more effective in improving... 

This technique has found the following applications in addition to those discussed in Sections 10.1 (resin cure studies on phenol urethane compositions) [65], 12.2 (photopolymer studies [66-68]), and 13.3 (phase transitions in PE) [66], Chapter 15 (viscoelastic and rheological properties), and Section 16.4 (heat deflection temperatures) epoxy resin-amine system [67], cured acrylate-terminated unsaturated copolymers [68], PE and PP foam [69], ethylene-propylene-diene terpolymers [70], natural rubbers [71, 72], polyester-based clear coat resins [73], polyvinyl esters and unsaturated polyester resins [74], polyimide-clay nanocomposites [75], polyether sulfone-styrene-acrylonitrile, PS-polymethyl methacrylate (PMMA) blends and PS-polytetrafluoroethylene PMMA copolymers [76], cyanate ester resin-carbon fibre composites [77], polycyanate epoxy resins [78], and styrenic copolymers [79]. 

An alternative method of producing natural rubber based clay reinforced nanocomposites with outstanding properties is by using a spray drying technique. In this technique the siUcate layers of clay will be well dispersed in an irradiated polymer latex and this mixture will be sprayed through hot air to produce micrometre-sized liquid droplets. When the solvent is fully evaporated, micrometre-sized polymer spheres with delaminated clay silicate layers on their surface are produced. These spheres can later be melt blended with natural rubber to produce ternary nanocomposites. It is noteworthy that exfoliation of nanofillers can still be achieved without modification of the nanofiller surface, thus the expensive modification process can be eliminated. 

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