Sathish K. Sukumaran

Multilevel structure of reinforcing silica and carbon

Using small-angle x-ray (SAXS), neutron (SANS), x-ray diffraction and light scattering, we study the structure of colloidal silica and carbon on length scales from 4 A < q-1 < 107 A where q is the magnitude of the scattering vector. These materials consist of primary particles of the order of 100 A, aggregated into micron-sized aggregates that in turn are agglomerated into 100 µ agglomerates. The diffraction data show that the primary particles in precipitated silica are composed of highly defective amorphous silica with little intermediate-range order (order on the scale of several bond distances). On the next level of morphology, primary particles arise by a complex nucleation process in which primordial nuclei briefly aggregate into rough particles that subsequently smooth out to become the seeds for the primaries. The primaries aggregate to strongly bonded clusters by a complex process involving kinetic growth, mechanical disintegration and restructuring. Finally, the small-angle scattering (SAS) data lead us to postulate that the aggregates cluster into porous, rough-surfaced, non-mass-fractal agglomerates that can be broken down to the more strongly bonded aggregates by application of shear. We find similar structure in pelletized carbon blacks. In this case we show a linear scaling relation between the primary and aggregate sizes. We attribute the scaling to mechanical processing that deforms the fractal aggregates down to the maximum size able to withstand the compaction stress. Finally, we rationalize the observed structure based on empirical optimization by filler suppliers and some recent theoretical ideas due to Witten, Rubenstein and Colby.

Efficient on the fly calculation of time correlation functions in computer simulations

Time correlation functions yield profound information about the dynamics of a physical system and hence are frequently calculated in computer simulations. For systems whose dynamics span a wide range of time, currently used methods require significant computer time and memory. In this paper, we discuss the multiple-tau correlator method for the efficient calculation of accurate time correlation functions on the fly during computer simulations. The multiple-tau correlator is efficacious in terms of computational requirements and can be tuned to the desired level of accuracy. Further, we derive estimates for the error arising from the use of the multiple-tau correlator and extend it for use in the calculation of mean-square particle displacements and dynamic structure factors. The method described here, in hardware implementation, is routinely used in light scattering experiments but has not yet found widespread use in computer simulations.

Quantitative investigations of aggregate systems

Nanomaterials with disordered, ramified structure are increasingly being used for applications where low cost and enhanced performance are desired. A particular example is the use in printed electronics of inorganic conducting and semiconducting nanoparticles. The electrical, as well as other physical properties depend on the arrangement and connectivity of the particles in such aggregate systems. Quantification of aggregate structure and development of structure/property relationships is difficult and progress in the application of these materials in electronics has mainly been empirical. In this paper, a scaling model is used to parameterize the structure of printed electronic layers. This model has chiefly been applied to polymers but surprisingly it shows applicability to these nanolayers. Disordered structures of silicon nanoparticles forming aggregates are investigated using small angle x-ray scattering coupled with the scaling model. It is expected that predictions using these structural parameters can be made for electrical properties. The approach may have wide use in understanding and designing nano-aggregates for electronic devices.

Towards novel wound dressings: antibacterial properties of zinc oxide nanoparticles and electrospun fiber mats of zinc oxide nanoparticle/poly(vinyl alcohol) hybrids

Abstract Zinc oxide (ZnO) nanoparticles possess antibacterial properties. Being less toxic to humans than silver, they are attractive as antibacterial agents in biomedical applications. In this study, we focus on the influence of the size of ZnO nanoparticles on their antibacterial action against strains of three bacteria: one Gram-negative, Escherichia coli and two Gram-positive, Bacillus subtilis and Staphylococcus aureus. The antibacterial efficacy of the nanoparticles increases with decreasing particle size. A major contributor to antibacterial action is the oxidative stress induced by the ZnO. To understand the relationship between antibacterial action and induced oxidative stress, we measured the dependence of the nanoparticle diameter on H2O2 concentration. Even at a fixed nanoparticle concentration, the H2O2 concentration increased with decreasing nanoparticle diameter. This is qualitatively similar to the dependence of the antibacterial activity on the nanoparticle diameter. In addition, in the presence of ZnO nanoparticles, we detected increased quantities of endogenous H2O2 in the E. coli. For use as antibacterial wound dressings, we fabricated nonwoven fiber mats from poly(vinyl alcohol) (PVA)/ZnO nanoparticle suspensions. The antibacterial efficacy of the PVA/ZnO electrospun fiber mats also increased with a decrease in the diameter and an increase in the concentration of the ZnO nanoparticles.

Slip at the interface between immiscible polymer melts I: method to measure slip

Slip at the interface between immiscible polymer melts remains poorly understood. A method that relies solely on rheological measurements to obtain the interfacial slip velocity uses the slip-induced deviation in the flow variables. To use the method, accurate estimates of the flow variables under the assumption of no-slip are necessary. Although such estimates can be easily derived under some cases, in general, this is not straightforward. Therefore, methods to determine the interfacial slip velocity without using estimates for the flow variables under no-slip conditions are desirable. In this work, we focus on investigations of slip at the interface between two immiscible polymer melts undergoing two-phase coaxial flow. To enable such investigations, we have adapted the Mooney method, usually used to investigate wall slip, to investigate polymer/polymer interfacial slip. Using this method, we have measured the slip velocity at the interface between polypropylene and polystyrene as a function of the interfacial stress. To determine the validity of the modified Mooney method, we also determine the slip velocity using the slip-induced deviation in the flow variables. To enable this determination, we use polypropylene and polystyrene with almost identical shear rate-dependent viscosities over a range of shear rates. The slip velocity obtained from the modified Mooney method displayed excellent agreement with that determined using the deviation from no-slip. In agreement with prior work, the dependence of the slip velocity on the interfacial stress is a power-law. Our investigation spans a sufficiently wide range of interfacial stress to enable the direct observation of two power-law regimes and also the transition between the two regimes. We also find that the power-law exponent of approximately 3 at low stresses decreases to approximately 2 at high stresses.