Polymer/clay-based nanocomposites intercalation

The most commonly studied polymer nanocomposites are clay-based nanocomposites, mainly with montmorillonite (MMt) as layered silicate filler (Scheme 15.12). Upon incorporation of organomodihed clays (organoclays) into a polymer matrix, two nanomorphologies (Scheme 15.13) can be obtained, either intercalation of the polymer chain in between the clay platelets keeping the stacking of the sheets, or exfoliation of the clay platelets with a disordered dispersion of the inorganic sheets in the polymer. 

The present chapter is devoted mainly to the phase morphology reported for silicate clay-based nanocomposites. Many of the selected TEM photomicrographs show exfoliated and intercalated states of clay in various polymer matrices. 

Many different polymers have already been used to synthesize polymer-clay nanocomposites. In this section, an overview of the advances that have been made during the last 10 years in the intercalation and the delamination of organoclay in different polymeric media is given. The discussion mainly covers the work involving thermoset nanocomposites along with a brief discussion about thermoplastic-based 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. 

The procedure to obtain nanocomposites based on unsaturated polyester resins leads to improvements in the order of 120% in the flexural modulus, 14% in flexural strength and 57% increase in tensile modulus with 4.7% of clay slurry content. Thermal stability augments and the gelation temperature increases to 45 °C, as compared to that of the resin (Fig. 31.6). It seems that adding water to the MMT allows better intercalation of polymer chains into the interlamellar space. Because clay is first suspended in water, this improves dispersion and distribution of the particles in the resin matrix. Longer gelation times lead to more uniform and mechanically stronger structures and to yield stresses (Fig. 31.7). Enhanced polymer-clay interactions are revealed by XPS in this case (Fig. 31.8). 

Besides melt intercalation, described above, in situ intercalative polymerization of E-caprolactone (e-CL) has also been used [231] to prepare polycaprolactone (PCL)-based nanocomposites. The in situ intercalative polymerization, or monomer exfoliation, method was pioneered by Toyota Motor Company to create nylon-6/clay nanocomposites. The method involves in-reactor processing of e-CL and MMT, which has been ion-exchanged with the hydrochloride salt of aminolauric acid (12-aminodecanoic acid). Nanocomposite materials from polymers such as polystyrene, polyacrylates or methacrylates, styrene-butadiene rubber, polyester, polyurethane, and epoxy are amenable to the monomer approach. 

Three main types of structures, which are shown in Fig. 5.3, can be obtained when a clay is dispersed in a polymer matrix (1) phase-separated structure, where the polymer chains did not intercalate the clay layers, leading to a structure similar to those of a conventional composite, (2) intercalated structure, where the polymer chains are intercalated between clay layers, forming a well ordered multilayer structure, which has superior properties to those of a conventional composite, and (3) structure exfoliated, where the clay is completely and uniformly dispersed in a polymeric matrix, maximizing the interactions polymer-clay and leading to significant improvements in physical and mechanical properties [2, 50-52]. Production of nanocomposites based on polymer/clay can be done basically in three ways (a) in situ polymerization, (b) prepared in solution and (c) preparation of the melt or melt blending [53]. 

H. Sh. Xia, M. Song, Characteristic length of dynamic glass transition based on polymer/clay intercalated nanocomposites. Thermo. Acta 2005, 429, 1. 

Sibold, N., Dufour, C., Gourbilleau, R, Metzner, M. N., Lagreve, C., Le Puart, L., Madec, P. J., and Pham, T. N. 2007. Montmorillonite for clay-polymer nanocomposites Intercalation of tailored compounds based on succinic anhydride, acid and acid salt derivatives A review. Applied Clay Science 38 130-138. 

Solution casting has been widely used as a nanocomposite processing method since solvent intercalation is the simplest way to prepare PLA/clay nanocomposites. But, a solvent where polymer is soluble and nanofillers are highly dispersible is necessary. The preparation of PLA-based nanocomposites by this method normally results in good dispersion of the nanofillers within the polymer matrix, and consequently in enhanced properties, as has successfully been demonstrated by some authors. 

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