Publications

Field-structured composites (FSCs) were produced by hosting micron-sized gold-coated nickel particles in a pre-polymer and allowing the mixture to cure in a magnetic field environment. The feasibility of controlling a composite's electrical conductivity using feedback control applied to the field coils was investigated. It was discovered that conductivity in FSCs is primarily determined by stresses in the polymer host matrix due to cure shrinkage. Thus, in cases where the structuring field was uniform and unidirectional so as to produce chainlike structures in the composite, no electrical conductivity was measured until well after the structuring field was turned off at the gel point. In situations where complex, rotating fields were used to generate complex, three-dimensional structures in a composite, very small, but measurable, conductivity was observed prior to the gel point. Responsive, sensitive prototype chemical sensors were developed based on this technology with initial tests showing very promising results.

The use of triaxial magnetic fields to create a variety of isotropic and anisotropic magnetic particle/polymer composites with significantly enhanced magnetic susceptibilities was analyzed. It was shown that a rich variety of structures can be created because both the field amplitudes and frequencies can be varied. It was found that the susceptibility anisotropy of these composites can be controlled over a wide range by judicious adjustment of the relative field amplitudes. The results show that with coherent particle motions, magnetostatic energies that are quite close to the ground state can be achieved.

Abstract not provided.

We describe the synthesis of highly magnetic iron nanoparticles using a novel surfactant, a {beta}-diketone. We have produced 6 nm iron nanoparticles with an unusually high saturation magnetization of more than 80% the value of bulk iron. Additionally, we measured a particle susceptibility of 14 (MKS units), which is far above the value possible for micron-scale spherical particles. These properties will allow for formation of composites that can be highly structured by magnetic fields.

We demonstrate through experiment and simulation that when mono-domain Fe nanoparticles are formed into chains by the application of a magnetic field, the susceptibility of the resulting structure is greatly enhanced (11.4-fold) parallel to the particle chains and is much larger than transverse to the chains. Simulations show that this significant enhancement is expected when the susceptibility of the individual particles approaches 5 in MKS units, and is due to the spontaneous magnetization of individual particle chains, which occurs because of the strong dipolar interactions. This large enhancement is only possible with nanoparticles, because demagnetization fields limit the susceptibility of a spherical multi-domain particle to 3 (MKS). Experimental confirmation of the large susceptibility enhancement is presented, and both the enhancement and the susceptibility anisotropy are found to agree with simulation. The specific susceptibility of the nanocomposite is 54 (MKS), which exceeds the highest value we have obtained for field-structured composites of multi-domain particles by a factor of four.

Abstract not provided.

We report high-pressure liquid chromatography (HPLC) and transmission electron microscopy (TEM) studies of the size distributions of nanosize gold clusters dispersed in organic solvents. These metal clusters are synthesized in inverse micelles at room temperature, and those investigated range in diameter from 1 to 10 nm. HPLC is sensitive enough to discern changes in hydrodynamic volume corresponding to only 2 carbon atoms of the passivating agent or metal core size changes of less than 4 angstrom. We have determined for the first time how the total cluster volume (metal core + passivating organic shell) changes with the size of the passivating agent.

Abstract not provided.

Steady shear 3-D simulations of electro- and magnetorheology in a uniaxial field are presented. These large scale simulations are three dimensional, and include the effect of Brownian motion. In the absence of thermal fluctuations, the expected shear thinning viscosity is observed in steady shear, and a striped phase is seen to rapidly form in a uniaxial field, with a shear slip zone in each sheet. However, as the influence of Brownian motion increases, the fluid stress decreases, especially at lower Mason numbers, and the striped phase eventually disappears, even when the fluid stress is still high. To account for the uniaxial steady shear data the author proposes a microscopic chain model of the role played by thermal fluctuations on the rheology of ER and MR fluids that delineates the regimes where an applied field can impact the fluid viscosity, and gives an analytical prediction for the thermal effect.

The authors have used a nonionic inverse micelle synthesis technique to form nanoclusters of platinum and palladium. These nanoclusters can be rendered hydrophobic or hydrophilic by the appropriate choice of capping ligand. Unlike Au nanoclusters, Pt nanoclusters show great stability with thiol ligands in aqueous media. Alkane thiols, with alkane chains ranging from C{sub 6} to C{sub 18} were used as hydrophobic ligands, and with some of these they were able to form 2-D and/or 3-D superlattices of Pt nanoclusters as small as 2.7 nm in diameter. Image processing techniques were developed to reliably extract from transmission electron micrographs (TEMs) the particle size distribution, and information about the superlattice domains and their boundaries. The latter permits one to compute the intradomain vector pair correlation function of the particle centers, from which they can accurately determine the lattice spacing and the coherent domain size. From these data the gap between the particles in the coherent domains can be determined as a function of the thiol chain length. It is found that as the thiol chain length increases, the gaps between particles within superlattice domains increases, but more slowly than one might expect, possibly indicating thiol chain interdigitation.

The authors have investigated the formation of 2-D and 3-D superlattices of Au nanoclusters synthesized in nonionic inverse micelles, and capped with alkyl thiol ligands, with alkane chains ranging from C{sub 6} to C1{sub 18}. The thiols are found to play a significant role in the ripening of these nanoclusters, and in the formation of superlattices. Image processing techniques were developed to reliably extract from transmission electron micrographs (TEMs) the particle size distribution, and information about the superlattice domains and their boundaries. The latter permits one to compute the intradomain vector pair correlation function, from which one can accurately determine the lattice spacing and the coherent domain size. From these data the gap between the particles in the coherent domains can be determined as a function of the thiol chain length. It is found that as the thiol chain length increases, the nanoclusters become more polydisperse and larger, and the gaps between particles within superlattice domains increases. Annealing studies at elevated temperatures confirm nanocluster ripening. Finally, the effect of the particle gaps on physical properties is illustrated by computing the effective dielectric constant, and it is shown that the gap size now accessible in superlattices is rather large for dielectric applications.