Nano Archive

Counterintuitive effect of molecular strength and role of molecular rigidity on mechanical properties of layer-by-layer assembled nanocomposites

Podsiadlo, Paul and Tang, Zhiyong and Shim, Bong Sup and Kotov, Nicholas A. (2007) Counterintuitive effect of molecular strength and role of molecular rigidity on mechanical properties of layer-by-layer assembled nanocomposites. NANO LETTERS, 7 (5). pp. 1224-1231.

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Molecular engineering of multilayered composites by layer-by-layer assembly (LBL) made possible easy replication of mechanical properties of nacre. Taking advantage of the ability of LBL to finely control the structure of the composite, one can further improve the mechanical properties of the multilayers, e.g., increase the strength and stiffness, and gain better understanding of the nanoscale and molecular scale mechanics of the materials critical for a variety of advanced technologies. In this study, we have replaced poly(diallyldimethylammonium chloride) (PDDA) (sigma(UTS) similar to 12 MPa, E similar to 0.2 GPa) with a much stronger polysaccharide polycation, chitosan (CH, sigma(UTS) similar to 108 MPa, E similar to 2 GPa), considering that its superior molecular strength will improve the macroscale mechanical properties of the nanocomposite: strength and stiffness. Free-standing films of the CH and montmorillonite (MTM) have been successfully made, and the resulting films revealed high uniformity with very high loading of MTM closely comparable to that in the natural nacre, similar to 80 wt %. Contrary to our expectations and theoretical predictions, the CH-MTM composite revealed lower strength and stiffness than those of PDDA-MTM and lower strength than CH polymer itself: sigma(UTS) approximate to 80 MPa and E approximate to 6 GPa. Analysis of the morphology of adsorbing CH chains with atomic force microscopy revealed highly elongated molecules, which is opposite to the observations made for PDDA. Plane-to-plane adhesion showed a factor of similar to 4 lower strength when compared to PDDA-MTM nanocomposite. Altogether these facts support the conclusion that CH lacks flexibility necessary for strong adhesion and efficient load transfer between the organic matrix and MTM platelets. High rigidity of the CH chains does not allow them to acquire a conformation necessary for maximizing the interfacial attraction with nanoscale component of the composite. These observations create an important foundation in the experimental design of the high-performance nanocomposite materials.

Item Type:Article
Subjects:Material Science > Functional and hybrid materials
Material Science > Nanochemistry
ID Code:2277
Deposited By:Anuj Seth
Deposited On:06 Jan 2009 12:11
Last Modified:06 Jan 2009 12:11

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