Electrohydrodynamic flow and colloidal patterning near inhomogeneities on electrodes.

Current density inhomogeneities on electrodes (of physical, chemical, or optical origin) induce long-range electrohydrodynamic fluid motion directed toward the regions of higher current density. Here, we analyze the flow and its implications for the orderly arrangement of colloidal particles as effected by this flow on patterned electrodes. A scaling analysis indicates that the flow velocity is proportional to the product of the applied voltage and the difference in current density between adjacent regions on the electrode. Exact analytical solutions for the streamlines are derived for the case of a spatially periodic perturbation in current density along the electrode. Particularly simple asymptotic expressions are obtained in the limits of thin double layers and either large or small perturbation wavelengths. Calculations of the streamlines are in good agreement with particle velocimetry experiments near a mechanically generated inhomogeneity (a "scratch") that generates a current density larger than that of the unmodified electrode. We demonstrate that proper placement of scratches on an electrode yields desired patterns of colloidal particles.

Functionalized graphene sheets for polymer nanocomposites.

Polymer-based composites were heralded in the 1960s as a new paradigm for materials. By dispersing strong, highly stiff fibres in a polymer matrix, high-performance lightweight composites could be developed and tailored to individual applications. Today we stand at a similar threshold in the realm of polymer nanocomposites with the promise of strong, durable, multifunctional materials with low nanofiller content. However, the cost of nanoparticles, their availability and the challenges that remain to achieve good dispersion pose significant obstacles to these goals. Here, we report the creation of polymer nanocomposites with functionalized graphene sheets, which overcome these obstacles and provide superb polymer-particle interactions. An unprecedented shift in glass transition temperature of over 40 degrees C is obtained for poly(acrylonitrile) at 1 wt% functionalized graphene sheet, and with only 0.05 wt% functionalized graphene sheet in poly(methyl methacrylate) there is an improvement of nearly 30 degrees C. Modulus, ultimate strength and thermal stability follow a similar trend, with values for functionalized graphene sheet- poly(methyl methacrylate) rivaling those for single-walled carbon nanotube-poly(methyl methacrylate) composites.

Electrically driven flow near a colloidal particle close to an electrode with a Faradaic current.

To elucidate the nature of processes involved in electrically driven particle aggregation in steady fields, flows near a charged spherical colloidal particle next to an electrode were studied. Electrical body forces in diffuse layers near the electrode and the particle surface drive an axisymmetric flow with two components. One is electroosmotic flow (EOF) driven by the action of the applied field on the equilibrium diffuse charge layer near the particle. The other is electrohydrodynamic (EHD) flow arising from the action of the applied field on charge induced in the electrode polarization layer. The EOF component is proportional to the current density and the particle surface (zeta) potential, whereas our scaling analysis shows that the EHD component scales as the product of the current density and applied potential. Under certain conditions, both flows are directed toward the particle, and a superposition of flows from two nearby particles provides a mechanism for aggregation. Analytical calculations of the two flow fields in the limits of infinitesimal double layers and slowly varying current indicate that the EOF and EHD flow are of comparable magnitude near the particle whereas in the far field the EHD flow along the electrode is predominant. Moreover, the dependence of EHD flow on the applied potential provides a possible explanation for the increased variability in aggregation velocities observed at higher field strengths.

Enhanced resonator sensitivity with nanostructured porous silica coatings.

We present a strategy to increase the sensitivity of resonators to the presence of specific molecules in the gas phase, measured by the change in resonant frequency as the partial pressure of the molecule changes. We used quartz crystals as the resonators and coated them with three different thin films (<1 microm thick) of porous silica: silica xerogel, silica templated by an ordered hexagonal phase of surfactant micelles, and silica templated by an isotropic L3 phase surfactant micellar system. We compared the sensitivity of coated resonators to the presence of water vapor. The crystals coated with hexagonal phase-templated silica displayed a sensitivity enhancement up to 100-fold compared to an uncoated quartz crystal in the low-pressure regime where adsorption played a dominant role. L3 phase-templated silica displayed the highest sensitivity (up to a 4000-fold increase) in the high partial pressure regimes where capillary condensation was the main accumulation mechanism. Three parameters differentiate the contributions of these coatings to the sensitivity of the underlying resonator: (i) specific surface area per unit mass of the coating, (ii) accessibility of the surfaces to a target molecule, and (iii) distribution in the characteristic radii of curvature of internal surfaces, as measured by capillary condensation.

Orientational order of molecular assemblies on inorganic crystals.

Surfactant micelles form oriented arrays on crystalline substrates although registration is unexpected since the template unit cell is small compared to the size of a rodlike micelle. Interaction energy calculations based on molecular simulations reveal that orientational energy differences on a molecular scale are too small to explain matters. With atomic force microscopy, we show that orientational ordering is a dynamic, multimolecule process. Treating the cooperative processes as a balance between van der Waals torque on a large, rodlike micellar assembly and Brownian motion shows that orientation is favored.

Assembly of colloidal aggregates by electrohydrodynamic flow: Kinetic experiments and scaling analysis.

Electric fields generate transverse flows near electrodes that sweep colloidal particles into densely packed assemblies. We interpret this behavior in terms of electrohydrodynamic motion stemming from distortions of the field by the particles that alter the body force distribution in the electrode charge polarization layer. A scaling analysis shows how the action of the applied electric field generates fluid motion that carries particles toward one another. The resulting fluid velocity is proportional to the square of the applied field and decreases inversely with frequency. Experimental measurements of the particle aggregation rate accord with the electrohydrodynamic theory over a wide range of voltages and frequencies.

Electrically guided assembly of planar superlattices in binary colloidal suspensions.

Binary colloidal suspensions are assembled into planar superlattices using ac electric fields. Either triangular or square-packed arrays form, depending on the frequency and relative particle concentrations. The frequency dependence is striking since superlattices develop at low and high frequencies but not at intermediate frequencies. We explain the low frequency behavior (<3 kHz) in terms of induced-dipole repulsion balanced by attraction resulting from electrohydrodynamic (EHD) flow. At high frequencies (20-200 kHz), EHD flow is negligible but aggregation occurs since dipole-dipole interactions become attractive.

Continuous crystalline carbonate apatite thin films. A biomimetic approach.

In contrast to extensive studies on hydroxyapatite thin films, very little has been reported on the thin films of carbonated apatite (dahllite). In this report, we describe the synthesis and characterization of a highly crystalline dahllite thin film assembled via a biomimetic pathway. A free-standing continuous precursor film of carbonated calcium phosphate in an amorphous phase was first prepared by a solution-inhibited templating method (template-inhibition) at an air-water interface. A stearic acid surface monolayer acted as the template, while a carbonate-phosphate solution composed a binary inhibition system. The precursor film formed at the air/water interface was heated at 900 degrees C and transformed into a dense crystalline film that retained the overall shape of the precursor. The crystalline phase was characterized by XRD and IR to be a single-phase carbonate apatite, with carbonate substitutions in both type A (OH-) and type B (PO4(3-)) lattice positions.

Self-assembled ceramics produced by complex-fluid templation.

This review examines the use of self-assembly in the fabrication of ceramic mesostructures, emphasizing the use of amphiphilic surfactants and block copolymers. The association between this area of research and biomimetics is discussed, linking developments in synthetic self-assembly with biomineralization. The fabrication of hierarchical structures through the use of simultaneous processing is shown to be a necessary condition for applications of this new technology.

Quantum impurities and the neutron resonance peak in YBa2Cu3O7: Ni versus Zn.

The influence of magnetic (S=1) and nonmagnetic (S=0) impurities on the spin dynamics of an optimally doped high temperature superconductor is compared in YBa2(Cu0.97Ni0.03)3O7 (Tc=80 K) and YBa2(Cu0.99Zn0.01)3O7 (Tc=78 K). In the Ni-substituted system, the magnetic resonance peak (which is observed at Er approximately 40 meV in the pure system) shifts to lower energy with a preserved Er/Tc ratio while the shift is much smaller upon Zn substitution. By contrast Zn, but not Ni, restores significant spin fluctuations around 40 meV in the normal state. These observations are discussed in the light of models proposed for the magnetic resonance peak.

Inclined-Field Structure, Morphology, and Pinning of the Vortex Lattice in Microtwinned YBa2Cu3O7.

A detailed small-angle neutron scattering study of the vortex lattice in a single crystal of YBa(2)Cu(3)O(7) was made for a field of 0.5 tesla inclined at angles between 0 and 80 degrees to the crystalline c axis. The vortex lattice is triangular for all angles, and for angles less than or equal to 70 degrees its orientation adjusts itself to maximize the pinning energy to densely and highly regularly spaced twin planes. These observations have important implications for the microscopic flux-pinning mechanism, and hence for the critical current achievable in YBa(2)Cu(3)O(7). For large angles (about 80 degrees) the vortex lattice consists of independent chains in the orientation predicted by anisotropic London theory.

Dispersion of Small Ceramic Particles (Al(2)O(3)) with Azotobacter vinelandii.

The high surface charge of small ceramic particles such as alumina particles prevents them from dispersing evenly in aqueous suspensions and forming high-density compacts. However, suspensions of 400-nm-diameter alumina particles treated with alginate from the bacterium Azotobacter vinelandii were well dispersed. The alginate bound firmly to the particle surface and could not be removed by repeated washing with distilled water (2.82 mg of the bacterial alginate adsorbed to 1 g of the alumina particles). Furthermore, A. vinelandii grew and produced alginate in the presence of up to 15% (vol/vol) alumina particles. These results suggest that an in situ process using this bacterium to coat ceramic particles with alginate might be developed. In in situ processing experiments, the particle-packing densities were significantly increased and the viscosities of 5 and 10% (vol/vol) suspensions were reduced 4- and 60-fold, respectively, over those of controls. The bacteria were readily removed from the alumina particles by washing.

The silica-alumina system: stable and metastable equilibria at 1.0 atmosphere.

Diffusion couples, consisting of sapphire and fused silica, which were annealed in the temperature range from 1678 degrees to 2003 degrees C and analyzed by electron beam microprobe, have provided data on the stable phase equilibrium of the silica-alumina system. Under stable equilibrium conditions, the intermediate compound of this system, mullite (3Al(2)O(3) . 2SiO(2)), melts incongruently at 1828 degrees +/- 10 degrees C and its solid solution field extends from 70.5 to 74.0 percent (by weight) alumina. The stable phase diagram is a composite of the two binary eutectic diagrams: silica-mullite in the absence of alumina and silica-alumina in the absence of mullite. Under metastable conditions, mullite melts congruently at approximately 1890 degrees +/- 10 degrees C and its solid solution field extends to approximately 83.2 percent (by weight) alumina.