Metal and Alloy Nanoparticles by Amine-Borane Reduction of Metal Salts by Solid-Phase Synthesis: Atom Economy and Green Process

A new solid state synthetic route has been developed toward metal and bimetallic alloy nanoparticles from metal salts employing amine-boranes, as the reducing agent. During the reduction, amine-borane plays a dual role: acts as a reducing agent and reduces the metal salts to their elemental form and simultaneously generates a stabilizing agent in situ which controls the growth of the particles and stabilizes them in the nanosize regime. Employing different amine-boranes with differing reducing ability (ammonia borane (AB), dimethylamine borane (DMAB), and triethylamine borane (TMAB)) was found to have a profound effect on the particle size and the size distribution. Usage of AB as the reducing agent provided the smallest possible size with best size distribution. Employment of TMAB also afforded similar results; however, when DMAB was used as the reducing agent it resulted in larger sized nanoparticles that are polydisperse too. In the AB mediated reduction, BNHx polymer generated in situ acts as a capping agent whereas, the complexing amine of the other amine-boranes (DMAB and TMAB) play the same role. Employing the solid state route described herein, monometallic Au, Ag, Cu, Pd, and Ir and bimetallic CuAg and CuAu alloy nanoparticles of <10 nm were successfully prepared. Nucleation and growth processes that control the size and the size distribution of the resulting nanoparticles have been elucidated in these systems.

Manifestation of intermediate phase in mechanical properties: Nano-indentation studies on Ge-Te-Si bulk chalcogenide glasses

Nano-indentation studies have been undertaken on bulk Ge15Te85-xSix glasses (0 <= x <= 9), to estimate hardness, H and elastic modulus, E. It is found that E and H increase initially with the increase in the atomic percent of Si. Further, a plateau is seen in the composition dependence of E and H in the composition range 2 <= x <= 6. It is also seen that the addition of up to 2 at% Si increases the density rho of the glass considerably; however, further additions of Si lead to a near linear reduction in rho, in the range 2 <= x <= 6. Beyond x=6, rho increases again with Si content. The variation of molar volume V-m brings out a more fascinating picture. A plateau is seen in the intermediate phase suggesting that the molecular structure of the glasses is adapting to keep the count of constraints fixed in this particular phase. The observed variations in mechanical properties are associated with the Boolchand's intermediate phase in the present glassy system, in the composition range 2 <= x <= 6, suggested earlier from calorimetric and electrical switching studies. The present results reveal rather directly the existence of the intermediate phase in elastic and plastic properties of chalcogenide glasses. (C) 2012 Elsevier Ltd. All rights reserved.

Thermodynamics of TmRhO3, Phase Equilibria, and Chemical Potentials in the System Tm-Rh-O

Phase equilibria in the system Tm-Rh-O at 1200 K is established by isothermal equilibration of selected compositions and phase identification after quenching to room temperature. Six intermetallic phases (Tm3Rh, Tm7Rh3, Tm5Rh3, Tm3Rh2, TmRh, TmRh2 +/-delta) and a ternary oxide TmRhO3 are identified. Based on experimentally determined phase relations, a solid-state electrochemical cell is devised to measure the standard free energy of formation of orthorhombic perovskite TmRhO3 from cubic Tm2O3 and beta-Rh2O3 in the temperature range from (900 to 1300) K. The results can be summarized as: Delta G(f,ox)(o) +/- 104/J.mol(-1) = -46474 + 3.925(T/K). Invoking the Neumann-Kopp rule, the standard enthalpy of formation of TmRhO3 from its constituent elements at 298.15 K is estimated as -1193.89 (+/- 2.86) kJ.mol(-1). The standard entropy of TmRhO3 at 298.15 K is evaluated as 103.8 (+/- 1.6) J.mol(-1).K-1. The oxygen potential-composition diagram and three-dimensional chemical potential diagram at 1200 K and temperature-composition diagrams at constant partial pressures of oxygen are computed from thermodynamic data. The compound TmRhO3 decomposes at 1688 (+/- 2) K in pure oxygen and at 1583 (+/- 2) K in air at standard pressure.