Polymer clay nanocomposites crystal structure

The reinforcement of polypropylene and other thermoplastics with inorganic particles such as talc and glass is a common method of material property enhancement. Polymer clay nanocomposites extend this strategy to the nanoscale. The anisometric shape and approximately 1 nm width of the clay platelets dramatically increase the amount of interfacial contact between the clay and the polymer matrix. Thus the clay surface can mediate changes in matrix polymer conformation, crystal structure, and crystal morphology through interfacial mechanisms that are absent in classical polymer composite materials. For these reasons, it is believed that nanocomposite materials with the clay platelets dispersed as isolated, exfoliated platelets are optimal for end-use properties. 

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. 

This system does not increase the carbon monoxide or soot produced during the combustion, as many commercial FRs do [233]. Other polymer silicate nanocomposites based on a variety of polymers, such as polystyrene, epoxy and polyesters, have been prepared recently by melt intercalation [236]. A direct synthesis of PVA-clay (hectorite) complexes in water solution (hydrothermal crystallization) was reported [237]. It was assumed that the driving force of this phenomenon, at least kinetically, can be described in terms of a simple diffusion reaction of polymers/monomers into clay-layered structures. 

A typical shish-kebab crystalline structure has been foimd by Maiti and Okamoto (2003) and Kim et al. (2001) in polyamide/organoclay nanocomposite and by Choi and Kim (2004) in PP/EPR/talc nanocomposite where a preferential orientation of polymer lamellae perpendicular to the surface of organoclay layers was inspected by TEM measurements. The unique observation of lamellar orientation (Ml the clay layers was ascribed to nucleation and epitaxial crystallization at the interface between layered silicate and polymer matrix especially the surfaces of clay platelets acted as heterogeneous nucleation sites. Orientation of iPP crystals was also enhanced in rPP/PP-MA/o-MMT injection-moulded parts, especially manufactured by dynamic packing injection moulding (Wang et al. 2005). MMT... 

Morales et al. [323] prepared bionanocomposites of PEA (derived from glycohc acid and 6-aminohexanoic add by in situ polymerization) reinforced with OMMTs. The most dispersed structure was obtained by addition of C25A organoclay. Evaluation of thermal stability and crystallization behavior of these samples showed significant differences between the neat polymer and its nanocomposite with C25A. Isothermal and nonisothermal calorimetric analyses of the polymerization reaction revealed that the kinetics was highly influenced by the presence of the silicate particles. Crystallization of the polymer was observed to occur when the process was isothermally conducted at temperatures lower than 145 °C. In this case, dynamic FTIR spectra and WAXD profiles obtained with synchrotron radiation were essential to study the polymerization kinetics. Clay particles seemed to reduce chain mobility and the Arrhenius preexponential factor. 

SPS nanocomposites exhibited an enhanced crystallization rate but had reduced crystallization than the neat polymer. The reason is that clay dispersed in the polymer matrix may serve as a nucleating agent but also hinders the crystal growth of polymer chains as a foreign material [14]. Exfoliated nanocomposites exhibited a faster crystallization and a lower degree of crystallization than intercalated ones. It is quite reasonable since clay in the exfoliated state is much more actively involved in the crystallization. As far as mechanical properties are concerned, the exfoliated structure would give us more enhanced properties than the intercalated one. 

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