Layered-silicate polymer properties

D. Garcia-Lopez, I. Gobernado-Mitre, J. F. Fernandez, J. C. Merino, and J. M. Pastor, Influence of clay modification process in PA6-layered silicate nanocomposite properties. Polymer, 46 (2005), 2758-65. 

M. Alexandre and P. Dubois, Polymer-layered silicate nanocomposites, properties and uses of a new class of materials. Materials Science and Engineering R Reports, 28 (2000), 1-63. 

Finnigan B, Martin D, Halley P, Truss R, Campell K. Morphology and properties of thermoplastic polyurethane nanocomposites incorporating hydrophilic layered silicates. Polymer 2004 45 2249-2260. 

Polymer layered-silicate day nano-composites (PLCN) attracted lately major interests into the industry and academic fields, since they usually show improved properties with comparison by virgin polymers or their conventional micro and macro-composites. Improvements induded increase in strength, heat resistance (Giannelis, 1998), flammability (Gilman, 2000) and a decrease in gas permeability (Xu et ah, 2001) as well as an increase in biodegradability (Sinha et al., 2002). 

However, the field of polymer day silicate has only started to speed up recently, mixing the appropriate modified layered silicate with synthetic layered silicates has long been known (Theng, 1979). The interest in these materials came from two important findings, first has been reported by Toyota research group of a Nylon-6 (N6)/Na-MMT nano-composites (Okada et ah, 1990) where very small amounts of layered silicate loadings resulted in the improvements of thermal and mechanical properties and second the findings of Vaia et ah (1993) about the... 

Giannelis, E.P. 1998. Polymer- layered silicate nanocomposites synthesis, properties and applications. Applied Organometallic Chemistry 12 675-680. 

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. 

Of particular interest are the recently developed nanocomposites consisting of a polymer and layered silicate because they often exhibit remarkably improved mechanical and other properties [3] when compared with pure polymer or conventional composites (both micro- and macro-composites). A primary progress in... 

The rheological properties of insitu polymerized nanocomposites with end-tethered polymer chains were first described by Krisnamoorti and Giannelis [33]. The flow behavior of PCL- and Nylon 6-based nanocomposites differed extremely from that of the corresponding neat matrices, whereas the thermorheological properties of the nanocomposites were entirely determined by the behavior of the matrices [33]. The slope of G (co) and G"(co) versus flxco is much smaller than 2 and 1, respectively. Values of 2 and 1 are expected for linear mono-dispersed polymer melts, and the large deviation, especially in the presence of a very small amount of layered silicate loading, may be due to the formation of a network structure in the molten... 

Ahmadi SJ, Huang YD, Li W (2004) Synthetic routes, properties and future applications of polymer-layered silicate nanocomposites. J Mater Sci 39 1919-1925... 

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. 

On the other hand, Bhattacharya et al. have reported the plasticization effect of organically modified layered silicates on dynamic mechanical properties [13]. In this work, nanocomposites of SBR have been prepared using various nanofillers like modified and unmodified montmorillonite, SP, hectorite etc. It has been observed that the Tg shifts to lower temperature in all the nanocomposites, except for systems from hectorite and NA. This is due to the fact that clay layers form capillaries parallel to each other as they become oriented in a particular direction. Due to wall slippage of the unattached polymer through these capillaries, the Tg is lowered, which could be even more in the absence of organo-modifiers [13]. A similar type of plasticization effect is also noted in the case of the low... 

Krishnamoorti R, Silva AS (2000) Rheological properties of polymer layered-silicate nanocomposites. In Pinnavaia TJ, Beall G (eds) Polymer nanocomposites. Wiley, New York Ren J, Silva AS, Krishnamoorti R (2000) Macromolecules 33 3739... 

The dynamic mechanical thermal analyzer (DMTA) is an important tool for studying the structure-property relationships in polymer nanocomposites. DMTA essentially probes the relaxations in polymers, thereby providing a method to understand the mechanical behavior and the molecular structure of these materials under various conditions of stress and temperature. The dynamics of polymer chain relaxation or molecular mobility of polymer main chains and side chains is one of the factors that determine the viscoelastic properties of polymeric macromolecules. The temperature dependence of molecular mobility is characterized by different transitions in which a certain mode of chain motion occurs. A reduction of the tan 8 peak height, a shift of the peak position to higher temperatures, an extra hump or peak in the tan 8 curve above the glass transition temperature (Tg), and a relatively high value of the storage modulus often are reported in support of the dispersion process of the layered silicate. 

X. Kornmann, R. Thomann, R. Miilhaupt, J. Finter, and L. Bergliind, Synthesis of amine-cured, epoxy-layered silicate nanocomposites The influence of the silicate surface modification on the properties, J. Appl. Polym. Sci. 86, 2643—2652 (2002). 

S. S. Ray, K. Yamada, M. Okamoto, and K. Ueda, New polylactide-layered silicate nanocomposites. 2. Concurrent improvements of material properties, biodegradability and melt rheology, Polymer 44, 857—866 (2003). 

For more than a decade, numerous research studies have been carried out on the flame-retardant properties conferred by nanoparticles and mainly by organo-modified layered silicates (OMLS). Earlier work at Cornell University and National Institute of Standards and Technology in the United States showed that nanocomposites containing OMLS reduced polymer flammability and enhanced the formation of carbonaceous residue (char).14 Owing to a strong increase in polymer viscosity, impairing processability, and also due to the breakdown of ultimate mechanical properties, the acceptable rate of incorporation for nanoparticles to improve flame retardancy is generally restricted to less than 10 wt %. 

The FR properties of polymer-layered silicate nanocomposites have been studied for a wide range of polymers, especially for organomodified montmorillonites (OMMT) in thermoplastics. Depending on the nature of the polymer, the decomposition pathway and decomposition products may change.8 A major consequence of the introduction of modified clays is the formation or the enhancement of charred structure, caused by cross-linking processes possibly catalyzed by the nanoparticles. 

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