Multiscale modeling and simulation of polymer nanocomposites

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.

Nanoindentation in polymer nanocomposites

The mechanics of nanocomposites is critical in the design of nanomaterials with desirable properties In this paper, the mechanics of polymer−clay nanocomposites is studied using a designed polymer and solution nanocomposite synthesis A copolymer latex, with function groups that strongly interact with the surface of the clay nanoplatelet and glass-transition temperature lower than room temperature, was synthesized Uniformly dispersed nanocomposites were then generated using water as the intercalation agent through the solution process The chain mobility in the nanocomposites is greatly reduced as studied by dynamic mechanical thermal analysis (DMTA) and dielectric thermal analysis (DETA) The modulus of the composite increases significantly The modulus enhancement strongly relates to the volume of the added clay as well as the volume of the constrained polymer This modulus enhancement follows a power law with the content of the clay and is modeled well by Mooney's equation for this soft-polymer-based

Mechanics of Polymer−Clay Nanocomposites

Developments of nano materials and technologies on asphalt materials – A review

Molecular interactions in intercalated organically modified clay and clay–polycaprolactam nanocomposites: Experiments and modeling

Insight into molecular interactions between constituents in polymer clay nanocomposites

This paper describes a multiscale approach used to model polymer clay nanocomposites (PCNs) based on a new altered phase concept. Constant-force steered molecular dynamics (SMD) is used to evaluate nanomechanical properties of the constituents of intercalated clay units in PCNs, which were used in the finite element model. Atomic force microscopy and nanoindentation techniques provided additional input to the finite element method (FEM) model. FEM is used to construct a representative PCN model that simulates the composite response of intercalated clay units and the surrounding polymer matrix. From our simulations we conclude that, in order to accurately predict mechanical response of PCNs, it is necessary to take into account the molecular-level interactions between constituents of PCN, which are responsible for the enhanced nanomechanical properties of PCNs. This conclusion is supported by our previous finding that there is a change in crystallinity of polymeric phase due to the influence of intercalated clay units. The extent of altered polymeric phase is obtained from observations of a zone of the altered polymeric phase surrounding intercalated clay units in the "phase image" of PCN surface, obtained using an atomic force microscope (AFM). An accurate FEM model of PCN is constructed that incorporates the zone of the altered polymer. This model is used to estimate elastic modulus of the altered polymer. The estimated elastic modulus for the altered polymer is 4 to 5 times greater than that of pure polymer. This study indicates that it is necessary to take into account molecular interactions between constituents in nanocomposites due to the presence of altered phases, and furthermore provides us with a new direction for the modeling and design of nanocomposites.

Altered phase model for polymer clay nanocomposites.

In studying the morphology, molecular interactions, and physical properties of organically modified montmorillonite (OMMT) and polymer clay nanocomposites (PCNs) through molecular dynamics (MD), the construction of the molecular model of OMMT and PCN is important. Better understanding of interaction between various constituents of PCN will improve the design of polymer clay nanocomposite systems. MD is an excellent tool to study interactions, which require accurate modeling of PCN under consideration. Previously, the PCN models were constructed by different researchers on the basis of specific criteria such as minimum energy configuration, density of the polymer clay nanocomposite, and so forth. However, in this article we describe the development of models combining experimental and conventional molecular modeling to develop models, which are more representative of true intercalated PCN systems. The models were used for studying the morphological interactions and physical properties. These studies gave useful information regarding orientation of organic modifiers, area of coverage of organic modifiers over the interlayer clay surface, interaction of organic modifiers with clay in OMMT, interaction among different constituents of PCN, conformational and density change, and actual proportion of mixing of polymer with clay in PCN. We have X-ray diffraction and photoacoustic Fourier transform infrared spectroscopy to verify the model.

A molecular model for epsilon-caprolactam-based intercalated polymer clay nanocomposite: Integrating modeling and experiments.

In this work, using photoacoustic Fourier transform infrared spectroscopy (FTIR) we have studied the structural distortion of clay crystal structure in organically modified montmorillonite (OMMT) and polymer clay nanocomposites (PCN). To study the effect of organic modifiers on the distortion of crystal structure of clay, we have synthesized OMMTs and PCNs containing same polymer and clay but with three different organic modifiers (12-aminolauric acid, n-dodecylamine, and 1,12-diaminododecane), and conducted the FTIR study on these PCNs. Our previous molecular dynamics (MD) study on these PCNs reveals that significant nonbonded interactions (van der Waals, electrostatic interactions) exist between the different constituents (polymer, organic modifier, and clay) of nanocomposites. Previous work based on X-ray diffraction (XRD) and differential scanning calorimetry (DSC) on the same set of PCNs shows that crystallinity of polymer in PCNs have changed significantly in comparison to those in pristine polymer; and, the nonbonded interactions between different constituents of PCN are responsible for the change in crystal structure of polymer in PCN. In this work to evaluate the structural distortion of crystal structure of clay in OMMTs and PCNs, the positions of bands corresponding to different modes of vibration of Si-O bonds are determined from the deconvolution of broad Si-O bands in OMMTs and PCNs obtained from FTIR spectra. Intensity and area under the Si-O bands are indicative of orientation of clay crystal structures in OMMTs and PCNs. Significant changes in the Si-O bands are observed from each vibration mode in OMMTs and PCNs containing three different organic modifiers indicating that organic modifiers influence the structural orientation of silica tetrahedra in OMMTs and PCNs. Deconvolution of Si-O bands in OMMTs indicate a band at approximately 1200 cm(-1) that is orientation-dependent Si-O band. The specific changes in intensity and area under this band for OMMTs with three different organic modifiers further confirm the change in structural orientation of silica tetrahedra of OMMTs by organic modifiers. Thus, from our work it is evident that organic modifiers have significant influence on the structure of polymer and clay in PCNs. It appears that in nanocomposites, in addition to strong interactions at interfaces between constituents, the structure of different phases (clay and polymer) of PCN are also altered, which does not occur in conventional composite materials. Thus, the mechanisms governing composite action in nanocomposites are quite different from that of conventional macro composites.

Debashis Sikdar

Papers

Molecular interactions in intercalated organically modified clay and clay–polycaprolactam nanocomposites: Experiments and modeling

Insight into molecular interactions between constituents in polymer clay nanocomposites

Altered phase model for polymer clay nanocomposites.

A molecular model for epsilon-caprolactam-based intercalated polymer clay nanocomposite: Integrating modeling and experiments.

Molecular interactions alter clay and polymer structure in polymer clay nanocomposites.