Layered silicates, intercalation

It has been also reported that the layer silicate intercalates can undergo an organic solid-state reaction within the interlayer region, such a reaction can be considered as highly regiospecific due to the distinct surface properties such as surface acidity or layer charge [5-7]. Moreover, size- and shape-selective layer silicates have been prepared [8,9] and the catalytic properties investigated in recent years [10]. 

The XRD patterns for various possible arrangements of layered silicates in biopolymers are shown in Figure 1. For an itmniscible arrangement (microcomposite) of layered clays in a biopolymer matrix, the structure of the layered silicate in the composite is not affected. Thus, XRD pattern for the microcomposite should remain same as that obtained for the pure layered silicate. Intercalation of the polymer... 

The nano-scale structures in polymer layered-silicate nano-composites can be thoroughly characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). XRD is used to identify intercalated structures. XRD allows quantification of changes in layer spacing and the most commonly used to probe the nano-composite structure and... 

Vaia, R.A., Ishii, H. and Giannelis, E.P. 1993. Synthesis and properties of two dimensional nanostructures by direct intercalation of polymer melts in layered silicates. Chemistry of Material 5 1694-1696. 

Since the possibility of direct melt intercalation was first demonstrated [11], melt intercalation has become a method of preparation of the intercalated polymer/ layered silicate nanocomposites (PLSNCs). This process involves annealing, statically or under shear, a mixture of the polymer and organically modified layered fillers (OMLFs) above the softening point of the polymer. During annealing, the polymer chains diffused from the bulk polymer melt into the nano-galleries between the layered fillers. 

In characterizing layered silicate, including layered titanate (HTO), the surface charge density is particularly important because it determines the interlayer structure of the intercalants as well as the cation exchange capacity (CEC). Lagaly proposed a method of calculation consisting of total elemental analysis and the dimensions of the unit cell [15] ... 

The most significant class of inorganic supports, which is used for the direct ion exchange of positively charged transition-metal complexes, are smectite clays. Pin-navaia has introduced the use of these swelling, layered silicate clays for catalysis. Other clays include montmorillonite, bentonite, and laponite. As shown by Pinna-vaia, cationic transition-metal complexes can be readily exchanged (intercalated) into the solvated interlayers of these silicates (Eq. (1)) [117] ... 

R. A. Vaia, E. P. Giannelis, Polymer melt intercalation in organically-modified layered silicates Model predictions and experiment, Macromolecules, vol. 30, pp. 8000-8009, 1997. 

Tennakoon DTB, Thomas JM, Tricker MJ, et al. 1974. Smface and intercalate chemistry of layered silicates. Part 1. General introduction and uptake of benzidine and related organic molecrtles by montmorillonite. J Chem Soc Dalton Trans 20 2207-2211. 

Pantoustier, N., Alexandre, M., Degee, P, Calberg, C., Jerome, R., Henrist, C., et al. (2001). Poly(3-caprolactone) layered silicate nanocomposites effect of clay surface modifiers on the melt intercalation process. e-Polymer, 9, 1-9. 

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. 

Das et al. [89] observed that both sulfur and peroxide vulcanizations of NBR filled with organoclay lead to intercalated-exfoliated structures of the layered silicate. They also reported that the use of excess stearic acid could lead to exfoliation of the clay layers in NBR when cured with sulfur. 

Fig. 4 Mechanism of exfoliation and intercalation of layered silicate in XNBR...

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