Nanocomposites nanoclay

Keywords Eco-friendly Polymer Nanocomposite Nanoclay Montomorillionite... 

Harikrishnan,G.,T. U. Patro, andD.V. Khakhar. 2006. Polyurethane foam-clay nanocomposites Nanoclays as cell openers. Ind. Eng. Chem. Res. 45 7126-7134. 

Thorough study of nanocomposites has revealed clearly that nanoclays can provide certain advantages in properties in comparison to their conventional filler counterparts. Properties which have been shown to undergo substantial improvements include ... 

The data provided by Toyota Research Group of Japan on polyamide-MMT nanocomposites indicate tensile strength improvements of approximately 40%-50% at 23°C and modulus improvement of about 70% at the same temperature. Heat distortion temperature has been shown to increase from 65°C for the unmodified polyamide to 152°C for the nanoclay-modified material, all the above having been achieved with just a 5% loading of MMT clay. Similar mechanical property improvements were presented for polymethyl methacrylate-clay hybrids [27]. 

They have studied the properties of NR-epoxidized natural rubber (ENR) blend nanocomposites also. Vulcanization kinetics of natural mbber-based nanocomposite was also smdied. The effect of different nanoclays on the properties of NR-based nanocomposite was studied. The tensile properties of different nanocomposites are shown in Figure 2.7 [33]. 

This is a nonpolar rubber with very little unsamration. Nanoclays as well as nanotubes have been used to prepare nanocomposites of ethylene-propylene-diene monomer (EPDM) rubber. The work mostly covers the preparation and characterization of these nanocomposites. Different processing conditions, morphology, and mechanical properties have been smdied [61-64]. Acharya et al. [61] have prepared and characterized the EPDM-based organo-nanoclay composites by X-ray diffracto-gram (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy... 

This is another important and widely used polymer. Nanocomposites have been prepared based on this rubber mostly for flame-retardancy behavior. Blends with acrylic functional polymer and maleic anhydride-grafted ethylene vinyl acetate (EVA) have also been used both with nanoclays and carbon nanotubes to prepare nanocomposites [65-69]. 

ENGAGE is an ethylene-octene copolymer. Ray and Bhowmick [70] have prepared nanocomposites based on this copolymer. In this study, the nanoclay was modified in situ by polymerization of acrylate monomer inside the gallery gap of nanoclay. ENGAGE was then intercalated inside the increased gallery gap of the modified nanoclay. The nanocomposites prepared by this method have improved mechanical properties compared to that of the conventional counterparts. Preparation and properties of organically modified nanoclay and its nanocomposites with ethylene-octene copolymer were reported by Maiti et al. [71]. Excellent improvement in mechanical properties and storage modulus was noticed by the workers. The results were explained with the help of morphology, dispersion of the nanofiller, and its interaction with the mbber. 

FIGURE 2.9 X-ray diffractogram (XRD) spectra of unmodified and modified nanoclays and styrene-butadiene rubber (SBR)-based nanocomposites with styrene content of (a) 15% and 40% and (b) 23%. (From Sadhu, S. and Bhowmick, A.K., J. Polym. Set, Part B Polym. Phys., 42, 1573, 2(304. Courtesy of Wiley InterScience.)... 

Fluoroelastomer-based nanocomposites were prepared using various nanoclays and their different properties were studied [93-98]. 

When a solvent diffuses across a neat polymer, it must travel the thickness of the sample (do). When the same solvent diffuses through a nanocomposite film with nanoclays, its path length is increased by the distance it must travel around each clay layer it strikes. According to Lan et al. [99] the path length of a gas molecule diffusing through an exfoliated nanocomposite is... 

This is a highly polar polymer and crystalline due to the presence of amide linkages. To achieve effective intercalation and exfoliation, the nanoclay has to be modified with some functional polar group. Most commonly, amino acid treatment is done for the nanoclays. Nanocomposites have been prepared using in situ polymerization [85] and melt-intercalation methods [113-117]. Crystallization behavior [118-122], mechanical [123,124], thermal, and barrier properties, and kinetic study [125,126] have been carried out. Nylon-based nanocomposites are now being produced commercially. 

B. de Bievre and K. Nakamura, UBE Europe. Polyamide Nanoclay Hybrids at UBE. Nanocomposites 2002. Conference Paper. January 2002. 

Effects of nanoclay and silica in mbber matrices have been discussed in earlier chapters. Recently, several other nanofillers have been investigated and have shown a lot of promise. All these fillers have not been investigated on rubbers extensively, although they have great potential to do so in the days to come. In this chapter, we have compiled the current research on mbber nanocomposites having nanofillers other than nanoclay and nanosilica. Further, this chapter provides a snapshot of the current experimental and theoretical tools being used to advance our understanding of mbber nanocomposites. 

Nanoclay particles by virtue of their particulate nature are emerging as effective heterogeneous nucleating agents for polyesters. The nanoclay particles in PET/montmorillonite nanocomposites impart to PET a higher crystallization rate without the need for expensive nucleating agents. 

Nanocomposites General Motors and Basell Polyolefins continue the development of nanocomposites for high-volume applications in external trim parts such as body panels. Three grades of TPO-based nanocomposites reinforced with 2.5% nanoclay have been commercialized by Basell Polyolefins. The first application of these nanocomposites was a low-volume minivan step option. 

The most important materials developed are nanocomposites and nanotubes. Fabrication of the first nanocomposites was inspired by nature (biomineralisation). Nanocomposites based on nanoclays and plastics are seen as ideal materials for improved barrier properties against oxygen, water, carbon dioxide and volatiles [37]. This makes them in particular suitable for retaining flavours in foods. The technology is rather straightforward using commercially available nanoclays and extrusion processing. 

Choudhury et al. [36] in their work on hydrogenated nitrile butadiene rubber (HNBR)-nanoclay systems showed the thermodynamic aspects of nanocomposite formation using the mean-field-lattice-based description of polymer melt intercalation, which was first proposed by Vaia and Giannelis [37]. Briefly, the free... 

In subsequent discussion, we will demonstrate the use and interpretation of some of these techniques. Figure 2a shows typical XRD traces of nanocomposite systems of styrene butadiene rubber (SBR) containing unmodified and modified nanoclay, describing an exfoliated and intercalated nanocomposite [5]. photographs of these systems are also given in the same figure (Fig. 2b, c). In the present case, the information obtained from both the techniques is complimentary. 

Values of Example were calculated for the constituting domains of SEBS (PS and PEB) and for the nanoclay regions in the SEBS/clay nanocomposite using (6) and are provided in Table 2. The modulus of the clay platelets was found to be 100 MPa, whereas the modulus for PS and PEB blocks was determined to be 22 and 12 MPa, respectively. These modulus values tallied with the slow strain-rate macromechanical tensile data of 26 MPa for the SEBS/clay nanocomposite (Table 2). The lower calculated modulus values of nanoclays compared to the literature might be due to adhering soft rubber on the nanoclays, which reduces the overall modulus of clay regions in the composite. 

Fig. 4 Effect of nanoclay loading on neat SEBS a Lorentz -corrected SAXS profiles (vertically shifted for better clarity) showing effect of nanoclay arrows indicate peak positions, b Lengths corresponding to first- and second- order scattering vector positions along with the 2D SAXS patterns for each sample of clay-loaded nanocomposites...

The same group carried out ATRP of EA in bulk at 90°C in the presence of organically modified nanoclay as an additive. They found remarkable enhancement in the rate of polymerization as compared with the ATRP of EA without nanoclay. Interestingly, the resulting nanocomposites had exfoliated clay particles, as evident from WAXD and studies [80]. 

Figure 7 shows the representative bright field HRTEM images of nanocomposites of NR and unmodified montmorillonite (NR/NA) prepared by different processing and curing techniques. It is apparent that the methodology followed to prepare the nanocomposites by latex blending facilitates the formation of exfoliated clay structure, even with unmodified nanoclays. It has been reported in the literature that hydration of montmorillonite clay leads to extensive delamination and breakdown of silicate layers [94, 95]. It has also been shown that NA disperses fully into the individual layers in its dilute aqueous dispersion (clay concentration <10%)... 

The lowering of die swell values has a direct consequence on the improvement of processability. It is apparent that the processability improves with the incorporation of the unmodified and the modified nanofillers. Figure lOa-c show the SEM micrographs of the surface of the extrudates at a particular shear rate of 61.2 s 1 for the unfilled and the nanoclay-filled 23SBR systems. The surface smoothness increases on addition of the unmodified filler, and further improves with the incorporation of the modified filler. This has been again attributed to the improved rubber-clay interaction in the exfoliated nanocomposites. 

Rubber-based nanocomposites were also prepared from different nanofillers (other than nanoclays) like nanosilica etc. Bandyopadhyay et al. investigated the melt rheological behavior of ACM/silica and ENR/silica hybrid nanocomposites in a capillary rheometer [104]. TEOS was used as the precursor for silica. Both the rubbers were filled with 10, 30 and 50 wt% of tetraethoxysilane (TEOS). The shear viscosity showed marginal increment, even at higher nanosilica loading, for the rubber/silica nanocomposites. All the compositions displayed pseudoplastic behavior and obeyed the power law model within the experimental conditions. The... 

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