B. Viswanath

Controlled synthesis of plate-shaped hydroxyapatite and implications for the morphology of the apatite phase in bone

A general methodology for predicting the conditions for the formation of plate-shaped structures by precipitation has been developed. The method has been applied for understanding the morphology of hydroxyapatite formed under different synthetic conditions. Morphology diagram has been developed in the form of pH-T diagrams to predict regions where plate-shaped hydroxyapatite is expected to form. The validity of the morphology diagram has been tested by critical experiments carried out at different conditions coupled with detailed microstructural analysis. Different morphologies ranging from single crystalline sheets, rods to equiaxed particles of hydroxyapatite are achieved by tuning the driving force of the precipitation reactions by varying the parameters such as pH and temperature in the absence of capping/surfactant agents. The synthesis and analysis presented here have important implications for understanding the plate-shaped morphology of apatite crystals that exist in the bone.

Nanoporous Pt with high surface area by reaction-limited aggregation of nanoparticles.

Nanoporous structures with high active surface areas are critical for a variety of applications. Here, we present a general templateless strategy to produce such porous structures by controlled aggregation of nanostructured subunits and apply the principles for synthesizing nanoporous Pt for electrocatalytic oxidation of methanol. The nature of the aggregate produced is controlled by tuning the electrostatic interaction between surfactant-free nanoparticles in the solution phase. When the repulsive force between the particles is very large, the particles are stabilized in the solution while instantaneous aggregation leading to fractal-like structures results when the repulsive force is very low. Controlling the repulsive interaction to an optimum, intermediate value results in the formation of compact structures with very large surface areas. In the case of Pt, nanoporous clusters with an extremely high specific surface area (39 m2/g) and high activity for methanol oxidation have been produced. Preliminary investigations indicate that the method is general and can be easily extended to produce nanoporous structures of many inorganic materials.

High-surface step density on dendritic pd leads to exceptional catalytic activity for formic acid oxidation.

Dendritic Pd with corrugated surfaces, obtained by a novel AC technique, exhibits an exceptionally high catalytic activity for the oxidation of formic acid because of the presence of a high density of surface steps. The formation of twinned dendrites leads to a predominance of exposed 111 facets with a high density of surface steps as evident from high resolution electron microscopy investigations. These surface sites provide active sites for the adsorption of the formic acid molecules, thereby enhancing the reaction rate. Control experiments by varying the time of deposition reveal the formation of partially grown dendrites at shorter times indicating that the dendrites were formed by growth rather than particle attachment. Our deposition method opens up interesting possibilities to produce anisotropic nanostructures with corrugated surfaces by exploiting the perturbations involved in the growth process.

High-speed roll-to-roll manufacturing of graphene using a concentric tube CVD reactor

We present the design of a concentric tube (CT) reactor for roll-to-roll chemical vapor deposition (CVD) on flexible substrates, and its application to continuous production of graphene on copper foil. In the CTCVD reactor, the thin foil substrate is helically wrapped around the inner tube, and translates through the gap between the concentric tubes. We use a bench-scale prototype machine to synthesize graphene on copper substrates at translation speeds varying from 25 mm/min to 500 mm/min, and investigate the influence of process parameters on the uniformity and coverage of graphene on a continuously moving foil. At lower speeds, high-quality monolayer graphene is formed; at higher speeds, rapid nucleation of small graphene domains is observed, yet coalescence is prevented by the limited residence time in the CTCVD system. We show that a smooth isothermal transition between the reducing and carbon-containing atmospheres, enabled by injection of the carbon feedstock via radial holes in the inner tube, is essential to high-quality roll-to-roll graphene CVD. We discuss how the foil quality and microstructure limit the uniformity of graphene over macroscopic dimensions. We conclude by discussing means of scaling and reconfiguring the CTCVD design based on general requirements for 2-D materials manufacturing.

Mechanical properties of tricalcium phosphate single crystals grown by molten salt synthesis

Mechanical properties of flux-grown tricalcium phosphate (TCP) single crystals ranging in size from 50 to 75microm have been characterized by performing micro- and nanoindentation on their facets. Notwithstanding the inherent brittleness and anisotropy, these single crystals exhibit nanoscale plasticity in the form of pile-up around the edges of indents. A similar plastic response was observed in hydroxyapatite (HA) single crystals during nanoindentation in an earlier study. The hardness and elastic modulus obtained during nanoindentation are discussed in comparison with the polycrystalline forms of both TCP and HA found in the literature. The indentation fracture toughness values of TCP single crystals were found to be higher than those of HA single crystals. The higher values are attributed not only to the difference in crystal structure and corresponding differences in surface energy, but also to extensive crack bridging by ligament formation across crack faces during crack propagation.

Direct fabrication of graphene on SiO2 enabled by thin film stress engineering

We demonstrate direct production of graphene on SiO2 by CVD growth of graphene at the interface between a Ni film and the SiO2 substrate, followed by dry mechanical delamination of the Ni using adhesive tape. This result is enabled by understanding of the competition between stress evolution and microstructure development upon annealing of the Ni prior to the graphene growth step. When the Ni film remains adherent after graphene growth, the balance between residual stress and adhesion governs the ability to mechanically remove the Ni after the CVD process. In this study the graphene on SiO2 comprises micron-scale domains, ranging from monolayer to multilayer. The graphene has >90% coverage across centimeter-scale dimensions, limited by the size of our CVD chamber. Further engineering of the Ni film microstructure and stress state could enable manufacturing of highly uniform interfacial graphene followed by clean mechanical delamination over practically indefinite dimensions. Moreover, our findings suggest that preferential adhesion can enable production of 2-D materials directly on application-relevant substrates. This is attractive compared to transfer methods, which can cause mechanical damage and leave residues behind.

Nanoscale Heterostructures with Molecular-Scale Single-Crystal Metal Wires

Creating nanoscale heterostructures with molecular-scale (<2 nm) metal wires is critical for many applications and remains a challenge. Here, we report the first time synthesis of nanoscale heterostructures with single-crystal molecular-scale Au nanowires attached to different nanostructure substrates. Our method involves the formation of Au nanoparticle seeds by the reduction of rocksalt AuCl nanocubes heterogeneously nucleated on the substrates and subsequent nanowire growth by oriented attachment of Au nanoparticles from the solution phase. Nanoscale heterostructures fabricated by such site-specific nucleation and growth are attractive for many applications including nanoelectronic device wiring, catalysis, and sensing.

Symmetry and shape issues in nanostructure growth

Symmetry plays a key role in dictating the equilibrium morphology of crystals. However, several growth morphologies that deviate from the point group symmetry are routinely observed under several different growth conditions. In this article, we present a summary of symmetry-breaking mechanisms that are operative for crystals grown from the vapour phase as well as those formed as a result of wet chemical synthesis. This understanding is crucial for rationalizing the variety of morphologies observed during nanocrystal synthesis and also provides a rational framework for the synthesis of anisotropic nanostructures.

Epitaxy, strain, and composition effects on metal-insulator transition characteristics of SmNiO3 thin films

SmNiO3 (SNO) thin films were deposited on LaAlO3 (LAO), SrTiO3, SrLaAlO4, Si, and Al2O3 (sapphire) substrates by RF magnetron sputtering and studies were conducted to understand how film structure and composition influence the insulator-metal transition properties. It is observed that the compressive strain induces the insulator to metal transition (MIT), while tensile strain suppresses it. In the case of non-epitaxial films, semiconducting behavior is obtained on sapphire over a broad temperature range, while on heavily-doped Si substrate; an MIT is seen in out-of-plane resistance measurement. In addition, thickness dependence on the resistance behavior and nickel oxidation state has been examined for epitaxial SNO films on LAO substrates. Fine control of the MIT by modifications to the mismatch strain and thickness provides insights to enhance the performance and the functionality of these films for emerging electron devices.

Exfoliation of α-hydroxides of nickel and cobalt in water

p-Aminobenzoate ion intercalated alpha-hydroxides of nickel/cobalt were synthesized by precipitation using ammonia (pH= approximately 12). Aqueous colloidal suspension of alpha-hydroxide of nickel/cobalt was obtained on washing the precipitate as the pH was reduced to approximately 7. The development of partial positive charge on the amine end of the intercalated anion causes repulsion between the layers leading to exfoliation and colloidal suspension of monolayers in water. While the layers could be restacked from the colloidal suspension in the presence of other anions in the case of alpha-cobalt hydroxide, the exfoliation could not be reversed easily in the case of the nickel analog.