The surge of interest in and scientific publications on the structure and properties of nanocomposites has made it rather difficult for the novice to comprehend the physical structure of these new materials and the relationship between their properties and those of the conventional range of composite materials. Some of the questions that arise are: How should the reinforcement volume fraction be calculated? How can the clay gallery contents be assessed? How can the ratio of intercalate to exfoliate be found? Does polymerization occur in the clay galleries? How is the crystallinity of semi-crystalline polymers affected by intercalation? What role do the mobilities of adsorbed molecules and clay platelets have? How much information can conventional X-ray diffraction offer? What is the thermodynamic driving force for intercalation and exfoliation? What is the elastic modulus of clay platelets? The growth of computer simulation techniques applied to clay materials has been rapid, with insight gained into the structure, dynamics and reactivity of polymer–clay systems. However these techniques operate on the basis of approximations, which may not be clear to the non-specialist. This critical review attempts to assess these issues from the viewpoint of traditional composites thereby embedding these new materials in a wider context to which conventional composite theory can be applied. (210 references)

A critical appraisal of polymer-clay nanocomposites.

Recently, biopolymer-based nanocomposites have been replacing synthetic polymer composites for various biomedical applications. This is often because of the biocompatible and biodegradable behavior of natural polymers. Several studies have been reported pertaining to the synthesis and characterization of chitosan(chi)/montmorillonite(MMT) and chitosan (chi)/hydroxyapatite (HAP) for tissue engineering applications. In the present work, a biopolymer-based novel nanocomposite chitosan/montmorillonite (MMT)/hydroxyapatite (HAP) was developed for biomedical applications. The composite was prepared from chitosan, unmodified MMT and HAP precipitate in aqueous media. The properties of the composites were investigated using x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM) and thermogravimetric analysis (TGA). Nanomechanical properties were measured using nanoindentation. Cell culture experiments were also conducted in order to ascertain the biocompatibility of the composite. The XRD results indicate that an intercalated structure was formed with an increase in d-spacing of montmorillonite. FTIR studies provide the evidence of molecular interaction among the three different constituents of the composite. AFM images show well-distributed nanoparticles in the chitosan matrix. The composites also exhibit a significant enhancement in nanomechanical property as compared to pure chitosan as well as the chi/HAP and chi/MMT composites. The TGA results indicate that an intercalated nanocomposite was formed with improved thermal properties even compared to chi/MMT composites. The results of cell culture experiments show that the composite is biocompatible and has a better cell proliferation rate compared to chi/HAP composites. This work represents the design of a novel clay-chitosan-hydroxyapatite composite with improved mechanical properties that has potential applications in bone tissue engineering.

http://iopscience.iop.org/article/10.1088/1748-6041/3/3/034122/pdf

Synthesis and characterization of a novel chitosan/montmorillonite/hydroxyapatite nanocomposite for bone tissue engineering

Review of fundamental principles in modelling unsaturated soil behaviour

Molecular dynamics simulation of hydroxyapatite : polyacrylic acid interfaces

Understanding protein-inorganic surface interactions is central to the rational design of new tools in biomaterial sciences, nanobiotechnology and nanomedicine. Although a significant amount of experimental research on protein adsorption onto solid substrates has been reported, many aspects of the recognition and interaction mechanisms of biomolecules and inorganic surfaces are still unclear. Theoretical modeling and simulations provide complementary approaches for experimental studies, and they have been applied for exploring protein-surface binding mechanisms, the determinants of binding specificity towards different surfaces, as well as the thermodynamics and kinetics of adsorption. Although the general computational approaches employed to study the dynamics of proteins and materials are similar, the models and force-fields (FFs) used for describing the physical properties and interactions of material surfaces and biological molecules differ. In particular, FF and water models designed for use in biomolecular simulations are often not directly transferable to surface simulations and vice versa. The adsorption events span a wide range of time- and length-scales that vary from nanoseconds to days, and from nanometers to micrometers, respectively, rendering the use of multi-scale approaches unavoidable. Further, changes in the atomic structure of material surfaces that can lead to surface reconstruction, and in the structure of proteins that can result in complete denaturation of the adsorbed molecules, can create many intermediate structural and energetic states that complicate sampling. In this review, we address the challenges posed to theoretical and computational methods in achieving accurate descriptions of the physical, chemical and mechanical properties of protein-surface systems. In this context, we discuss the applicability of different modeling and simulation techniques ranging from quantum mechanics through all-atom molecular mechanics to coarse-grained approaches. We examine uses of different sampling methods, as well as free energy calculations. Furthermore, we review computational studies of protein-surface interactions and discuss the successes and limitations of current approaches.

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Modeling and simulation of protein–surface interactions: achievements and challenges

Pyrophyllite is the precursor to other smectite-group minerals which exhibit swelling. The mineral structure of pyrophyllite can lead to other minerals in the smectite group, including montmorillonite, through appropriate isomorphous substitutions. In this work, an atomic model of the pyrophyllite interlayer was constructed. The response of the interlayer was evaluated using steered molecular dynamics simulations. In steered molecular dynamics, external forces were applied to individual atoms to study the response of the model to applied forces. In this work, forces are applied to the surface clay atoms to evaluate the displacement vs. applied stress in the interlayer between clay layers. This paper describes the construction of the model, the simulation procedure, and the results of the simulations which show that under the applied loading, deformation occurs mainly in the interlayer. The clay layers show relatively little deformation. The results show that the relationship between applied stress and displacement of the interlayer is linear. The stress-deformation relationship for the interlayer is presented.

Modeling the response of pyrophyllite interlayer to applied stress using steered molecular dynamics

The mechanical response of the interlayer of hydrated montmorillonite was evaluated using steered molecular dynamics. An atomic model of the sodium montmorillonite was previously constructed. In the current study, the interlayer of the model was hydrated with multiple layers of water. Using steered molecular dynamics, external forces were applied to individual atoms of the clay surface, and the response of the model was studied. The displacement versus applied stress and stress versus strain relationships of various parts of the interlayer were studied. The paper describes the construction of the model, the simulation procedure, and results of the simulations. Some results of the previous work are further interpreted in the light of the current research. The simulations provide quantitative stress deformation relationships as well as an insight into the molecular interactions taking place between the clay surface and interlayer water and cations.

Evolution of Mechanical Response of Sodium Montmorillonite Interlayer with Increasing Hydration by Molecular Dynamics

Mechanical properties of the sodium montmorillonite interlayer intercalated with amino acids.

To accurately model and understand the mechanism of the evolution of microstructure during swelling, it is extremely important to model the mechanical response of smectite clay interlayers. The mec...

Steven R. Schmidt

Papers

Modeling the response of pyrophyllite interlayer to applied stress using steered molecular dynamics

Evolution of Mechanical Response of Sodium Montmorillonite Interlayer with Increasing Hydration by Molecular Dynamics

Mechanical properties of the sodium montmorillonite interlayer intercalated with amino acids.

Molecular modeling of the mechanical behavior and interactions in dry and slightly hydrated sodium montmorillonite interlayer

An insight into clay-water molecular interactions in the interlayer of Na-montmorillonite subject to external stress