Polymer nanocomposites clay structure

Provided in this chapter is an overview on the fundamentals of polymer nanocomposites, including structure, properties, and surface treatment of the nanoadditives, design of the modifiers, modification of the nanoadditives and structure of modified nanoadditives, synthesis and struc-ture/morphology of the polymer nanocomposites, and the effect of nanoadditives on thermal and fire performance of the matrix polymers and mechanism. Trends for the study of polymer nanocomposites are also provided. This covers all kinds of inorganic nanoadditives, but the primary focus is on clays (particularly on the silicate clays and the layered double hydroxides) and carbon nanotubes. The reader who needs to have more detailed information and/or a better picture about nanoadditives and their influence on the matrix polymers, particularly on the thermal and fire performance, may peruse some key reviews, books, and papers in this area, which are listed at the end of the chapter. 

Most of the previous studies on flame retardation of polymer nanocomposites are focused on the relationship between macroscopic morphologies of chars and the flammability properties. Fang et al. studied the relationship between evolution of the microstructure, viscoelasticity and graphitization degree of chars and the flammability of polymers during combustion (68). The flame retar-dancy of ABS/clay /MWNTs nanocomposites was strongly affected by the formation of a network structure. Flammability properties... 

The characterization of the physical and chemical changes that occur in montmorillonite/PDMS nanocomposite elastomers as they are thermally aged is reported. Broadband Dielectric Spectroscopy (BDS) was used to track changes in the physical interaction between the polymer and clay associated with increases in non-oxidative thermal stability (as determined by TGA). The evolution of volatile siloxane species from the elastomers was characterized with Thermal Volatilization Analysis (TVA). Results suggest that the improved thermal stability and the increases in polymer/clay association are a result of significant re-structuring of the polymer network. 

Intercalated composites in an intercalated composite the insertion of polymer into the clay structure occurs in a crystallographically regular fashion, regardless of the clay to polymer ratio. An intercalated nanocomposite is normally interlayered by only a few molecular layers of polymer and properties of the composite typically resemble those of ceramic materials. 

Choudhaiy, S., Sengwa, R. J. (2014). Intercalated clay structures and amorphous behavior of solution cast and melt pressed poly(ethylene oxlde)-clay nanocomposites,/ Appl. Polym. Set, 131(4), DOI 10.1002/ app.39898. 

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. 

The mechanism of the improvement of thermal stability in polymer nanocomposites is not fully understood. It is often stated [126-129] that enhanced thermal stabihty is due to improved barrier properties and the torturous path for volatile decomposition products, which hinders their diffusion to the surface material where they are combusted. Other mechanisms have been proposed, for example, Zhu et al. [130] recently proposed that for polypropylene-clay nanocomposites, it was the structural iron in the dispersed clay that improved thermal stability by acting as a trap for radicals at high temperatures. 

The dispersion of clay platelets (exfoliation and intercalation level of the silicate layers) and surface area of silicate platelets have the potential to alter the rheological behavior of the nanocomposites. In-situ polymerized nano composites exhibit more exfoliated structure than the composites prepared by the melt blending technique. Irrespective of the processing parameter, the nanocomposites show shear thinning behavior at high shear rate (Figure 9.14), whereas the pristine polyamide exhibits Newtonian behavior (i.e., the viscosity remains almost the same). It has also been reported that the polymer nanocomposite possesses higher steady shear viscosity than pristine polyamide at low shear rates. 

Figure 2.5 Structures of polymer (rubber) clay nanocomposites.

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. 

---