Ramanan Krishnamoorti

Polymer-Silicate Nanocomposites: Model Systems for Confined Polymers and Polymer Brushes

The static and dynamic properties of polymer-layered silicate nanocomposites are discussed, in the context of polymers in confined spaces and polymer brushes. A wide range of experimental techniques as applied to these systems are reviewed, and the salient results from these are compared with a mean field thermodynamic model and non-equilibrium molecular dynamics simulations.

Rheology of polymer layered silicate nanocomposites

Abstract Layered silicate based polymer nanocomposites have gained significant technological interest because of the recent commercialization of nylon 6 and polypropylene based materials. Aside from the natural interests in understanding and improving the processing of these hybrids, viscoelastic measurements have also proven to be a sensitive tool to probe the mesoscale structure and the strength of polymer–nanoparticle interactions.

Nanocomposites: Structure, Phase Behavior, and Properties

It is well recognized that nanocomposites formed by adding nanoparticles to polymers can have significantly enhanced properties relative to the native polymer. This review focuses on three aspects that are central to the outstanding problem of realizing these promised property improvements. First, we ask if there exist general strategies to control nanoparticle spatial distribution. This is an important question because it is commonly accepted that the nanoparticle dispersion state crucially affects property improvements. Because ideas on macroscale composites suggest that optimizing different properties requires different dispersion states, we next ask if we can predict a priori the particle dispersion and organization state that can optimize one (or more) properties of the resulting nanocomposite. Finally, we examine the role that particle shape plays in affecting dispersion and hence property control. This review focuses on recent advances concerning these underpinning points and how they affect measurable properties relevant to engineering applications.

Temperature dependence of polymer crystalline morphology in nylon 6/montmorillonite nanocomposites

Abstract The influence of nanodispersed montmorillonite layers and process history on the crystal structure of nylon 6 between room temperature and melting is examined with simultaneous small- and wide-angle X-ray scattering and modulated differential scanning calorimetry. For the examined process history, nylon 6 exhibits predominantly α-phase behavior from room temperature to melting, with a gradual shift in chain–chain and sheet–sheet spacings from ∼100°C to melting. In contrast, the presence of aluminosilicate layers stabilizes a dominant γ-crystal phase, which persists, essentially unmodified, until melting. The temperature dependence of the total crystallinity and the relative fractions of α- and γ-phases is strongly dependent on the layered silicate content and the interaction between the nylon 6 and the aluminosilicate layers. Additionally, the temperature dependence of the α- and γ-phases imply that the γ-phase is preferentially in the proximity of the silicate layers, whereas the α-phase exists away from the polymer–silicate interphase region: In general, process history and use-temperature will determine the relative fraction of the crystalline polymer phases in semi-crystalline polymer nanocomposites, and thus have significant influence on the stability of the crystalline region at elevated temperatures.

Shear response of layered silicate nanocomposites

The linear and nonlinear melt state viscoelastic properties for a series of layered silicate based intercalated polymer nanocomposites are studied to elucidate the role of highly anisotropic nanometer thick layers in altering the flow properties of such hybrids. The steady shear viscosities for the nanocomposites exhibit enhanced shear-thinning at all shear rates, with the viscosity at high shear rates being almost independent of silicate loading and comparable to that of the unfilled polymer. Further, the elasticity, as measured by the first normal stress difference, when compared at constant shear stress is surprisingly independent of the silicate loading and identical to that of the unfilled polymer. This unique combination of unfilled polymerlike viscosity and elasticity for these filled nanocomposites, is attributed to the ability of the highly-anisotropic layered silicates to be oriented in the flow direction and results in a minimal contribution by the silicate layers to both the viscosity and the ...

Structure and dynamics of carbon black-filled elastomers

The linear and nonlinear melt viscoelastic properties for a series of carbon black-filled polymer composites were studied. Complementary tapping-mode atomic force microscopy (AFM) studies were used to examine the dispersion and structural correlations of the filler particles in these composites. The low-frequency dependence of the linear viscoelastic moduli gradually changes from liquidlike behavior for the unfilled polymer to pseudosolid character for composites with more than 9 vol % carbon black filler. The plateau modulus, inferred from the linear viscoelastic response, exhibits a somewhat discontinuous change at about 9 vol % filler. On the basis of the linear viscoelastic response, we postulate that the carbon black filler forms a continuous percolated network structure beyond 9 vol % filler, considerably lower than that expected from theoretical calculations for overlapping spheres and ellipsoids. We suggest that the lower threshold for percolation is due to the polymer mediation of the filler structure, resulting from the low functionality of the polymer and, consequently, few strong polymer–filler interactions, allowing for long loops and tails that can either bridge filler particles or entangle with one another. Furthermore, the strain amplitude for the transition from linear behavior to nonlinear behavior of the modulus for the composites with greater than 9 vol % filler is independent of frequency, and this critical strain amplitude decreases with increasing filler concentration. Complementary AFM measurements suggest a well-dispersed carbon black structure with the nearest neighbor distance showing a discontinuous decrease at about 9 vol % filler, again consistent with the formation of a filler network structure beyond 9 vol % carbon black.

Understanding surfactant aided aqueous dispersion of multi-walled carbon nanotubes

Dispersions of multi-walled carbon nanotubes (MWNTs) assisted by surfactant adsorption were prepared for a number of ionic and non-ionic surfactants including sodium 4-dodecylbenzenesulfonate (NaDDBS), hexadecyl(trimethyl)azanium bromide (CTAB), sodium dodecane-1-sulfonate (SDS), Pluronic® F68, Pluronic® F127, and Triton® X-100 to examine the effects of nanotube diameter, surfactant concentration, and pH on nanotube dispersability. Nanotube diameter was found to be an important role in surfactant adsorption rendering single-walled carbon nanotube studies as unreliable in predicting MWNT dispersive behavior. Similar to other reports, increasing surfactant concentrations resulted in a solubility plateau. Quantification of nanotube solubility at these plateaus demonstrated that CTAB is the best surfactant for MWNTs at neutral pH conditions. Deviations from neutral pH demonstrated negligible influence on non-ionic surfactant adsorption. In contrast, both cationic and anionic surfactants were found to be poor dispersing aids for highly acidic solutions while, CTAB remained a good surfactant under strongly basic conditions. These pH dependent results were explained in the context of nanotube surface ionization and Debye length variation.

Partitioning of Nonsteroidal Antiinflammatory Drugs in Lipid Membranes: A Molecular Dynamics Simulation Study

Using the potential of mean constrained force method, molecular dynamics simulations with atomistic details were performed to examine the partitioning and nature of interactions of two nonsteroidal antiinflammatory drugs, namely aspirin and ibuprofen, in bilayers of dipalmitoylphosphatidylcholine. Two charge states (neutral and anionic) of the drugs were simulated to understand the effect of protonation or pH on drug partitioning. Both drugs, irrespective of their charge state, were found to have high partition coefficients in the lipid bilayer from water. However, the values and trends of the free energy change and the location of the minima in the bilayer are seen to be influenced by the drug structure and charge state. In the context of the transport of the drugs through the bilayer, the charged forms were found to permeate fully hydrated in contrast to the neutral forms that permeate unhydrated.

INSIGHT INTO NSAID-INDUCED MEMBRANE ALTERATIONS, PATHOGENESIS AND THERAPEUTICS: CHARACTERIZATION OF INTERACTION OF NSAIDS WITH PHOSPHATIDYLCHOLINE

Nonsteroidal anti-inflammatory drugs (NSAIDs) are one of the most widely consumed pharmaceuticals, yet both the mechanisms involved in their therapeutic actions and side-effects, notably gastrointestinal (GI) ulceration/bleeding, have not been clearly defined. In this study, we have used a number of biochemical, structural, computational and biological systems including; Fourier Transform InfraRed (FTIR). Nuclear Magnetic Resonance (NMR) and Surface Plasmon Resonance (SPR) spectroscopy, and cell culture using a specific fluorescent membrane probe, to demonstrate that NSAIDs have a strong affinity to form ionic and hydrophobic associations with zwitterionic phospholipids, and specifically phosphatidylcholine (PC), that are reversible and non-covalent in nature. We propose that the pH-dependent partition of these potent anti-inflammatory drugs into the phospholipid bilayer, and possibly extracellular mono/multilayers present on the luminal interface of the mucus gel layer, may result in profound changes in the hydrophobicity, fluidity, permeability, biomechanical properties and stability of these membranes and barriers. These changes may not only provide an explanation of how NSAIDs induce surface injury to the GI mucosa as a component in the pathogenic mechanism leading to peptic ulceration and bleeding, but potentially an explanation for a number of (COX-independent) biological actions of this family of pharmaceuticals. This insight also has proven useful in the design and development of a novel class of PC-associated NSAIDs that have reduced GI toxicity while maintaining their essential therapeutic efficacy to inhibit pain and inflammation.

Polymers in confined environments

Phase Transitions of Polymer Blends and Block Copolymer Melts in Thin Films.- Flexible Polymers in Nanopores.- Polymer-Silicate Nanocomposites: Model Systems for Confined Polymers and Polymer Brushes.- Normal and Shear Forces Between Polymer Brushes.- Surface-Anchored Polymer Chains: Their Role in Adhesion and Friction.- Molecular Transitions and Dynamics at Polymer / Wall Interfaces: Origins of Flow Instabilities and Wall Slip.