Calcium ruthenates: Determination of Gibbs energies of formation using electrochemical cells

Metallic Ru has been found to coexist separately with CaO, RuO2, and the interoxide phases, Ca2RuO4, Ca3Ru2O7, and CaRuO3, present along the pseudobinary system CaO-RuO2. The standard Gibbs energies of formation (Df((ox))G(o)) of the three calcium ruthenates from their component oxides have been measured in the temperature range 925-1350 K using solid-state cells with yttria-stabilized zirconia as the electrolyte and Ru+RuO2 as the reference electrode. The standard Gibbs energies of formation (Deltaf((ox))G(o)) of the compounds can be represented by Ca2RuO4:Deltaf((ox))G(o)/J mol(-1)=-38,340-6.611 T (+/-120), Ca3Ru2O7 : Df((ox))G(o)/J mol(-1)=-75,910-11.26 T (+/-180), and CaRuO3 : Deltaf((ox))G(o)/J mol(-1)=-35,480-3.844 T(+/-70). The data for Ca2RuO4 corresponds to the stoichiometric composition, which has an orthorhombic structure, space group Pbca, with short c axis ("S'' form). The structural features of the ternary oxides responsible for their mild entropy stabilization are discussed. A three-dimensional oxygen potential diagram for the system Ca-Ru-O is developed as a function of composition and temperature from the results obtained. Using the Neumann-Kopp rule to estimate the heat capacity of the ternary oxides relative to their constituent binary oxides, the standard enthalpies of formation of the three calcium ruthenates from the elements and their standard entropies at 298.15 K are evaluated. (C) 2003 The Electrochemical Society.

Training Young Minds for Nanoscience and Technology: Issues and Challenges

This article explores issues and challenges in the field of education in nanoscience and technology with special emphasis with respect to India, where an expanding programme of research in nano science and technology is in place. The article does not concentrate on actual curricula that are needed in nano science and technology education course. Rather it focuses on the desirability of nanoscience and technology education at different levels of education and future prospect of students venturing into this within the economic and cultural milieu of India. We argue that care is needed in developing the education programme in India. However, the risk is worth taking as the education on nanoscience and technology can bridge the man power gap not only in this area of technology but also related technologies of hardware and micro electronics for which the country is a promising destination at global level. This will also unlock the demographical advantage that India will enjoy in the next five decades.

Tailoring of Structural Morphology of Silver Nanowires in Electrochemical Growth

Noble metal such as Ag normally exists in an fcc crystal structure. However as the size of the material is decreased to nanometer lengthscales, a structural transformation from that of its bulk state can be expected with new atomic arrangements due to competition between internal packing and minimization of surface energy. In many previous studies, it has been shown that silver nanowires (AGNWs) grown inside anodic alumina (AAO) templates by ac or dc electrochemical deposition from silver salts or complexes, adopt fcc structure and below some critical diameter ∼ 20 nm they may acquire hcp structure at low temperature. This is, however, critically dependant on the nature of confinement, as AgNWs grown inside nanotube confinement with subnanometer diameter have been reported to have fcc structure. Hence the question of the crystal structure of metal nanowires under combined influence of confinement, temperature and deposition condition remains open. In this abstract we show that the alternative crystal structures of AGNWs at room temperature can be achieved with electrochemical growth processes under specific conditions determined by the deposition parameters and nature of confinement. We fabricated AgNWs of 4H hexagonal structure with diameters 30 – 80 nm inside polycarbonate (PC) templates with a modified dc electrodeposition technique, where the nanowires were grown at deposition potentials as low as 10 mV in 2 M silver nitrate solution[1]. We call this low-potential electrodeposition (LPED) since the electrodeposition process occurs at potential much less than the standard Nernst potential (770 mV) of silver. Two types of electrodes were used – stainless steel and sputtered thin Pt film, neither of which had any influence on the crystal structure of the nanowires. EDS elemental analysis showed the nanowires to consist only of silver. Although the precise atomic dynamics during the LPED process is unclear at present, we investigated this with HRTEM (high-resolution transmission electron microscopy) characterization of nanowires grown over various deposition times, as well as electrical conductivity measurements. These experiments indicate that nanowire growth does not occur through a three-dimensional diffusion controlled process, as proposed for conventional over-potential deposition, but follow a novel instantaneous linear growth mechanism. Further experiments showed that, (a) conventional electrochemical growth at a small over-potential in a 2 mM AgNO3 solution yields nanowires with expected fcc structure inside the same PC templates, and (2) no nanowire was observed under the LPED conditions inside hard AAO templates, indicating that LPED-growth process, and hcp structure of the corresponding nanowires depend on deposition parameters, as well as nature of confinement.

Role of Management Decision Variables in Determining Technology Progress and Technical Efficiency in Indian Electronic Industry

This paper analyses the influence of management on Technical Efficiency Change (TEC) and Technological Progress (TP) in the communication equipment and consumer electronics sub-sectors of Indian hardware electronics industry. Each sub-sector comprises 13 sample firms for two time periods.The primary objective is to determine the relative contribution of TP and TEC to TFP Growth (TFPG) and to establish the influence of firm specific operational management decision variables on these two components. The study finds that both the sub-sectors have strived and achieved steady TP but not TEC in the period of economic liberalisation to cope with the intensifying competition. The management decisions with respect to asset and profit utilization, vertical integration, among others, improved TP and TE in the sub-sectors. However, R&D investments and technology imports proved costly for TFP indicating inadequate efforts and/or poor resource utilisation by the management. Management was found to be complacent in terms of improving or developing their own technology as indicated by their higher dependence on import of raw materials and no influence of R&D on TP.

Electrochemical phase formation. Time-dependent nucleation and growth rates

The theory of phase formation is generalised for any arbitrary time dependence of nucleation and growth rates. Some sources of this time dependence are time-dependent potential inputs, ohmic drop and the ingestion effect. Particular cases, such as potentiostatic and, especially, linear potential sweep, are worked out for the two limiting cases of nucleation, namely instantaneous and progressive. The ohmic drop is discussed and a procedure for this correction is indicated. Recent results of Angerstein-Kozlowska, Conway and Klinger are critically investigated. Several earlier results are deduced as special cases. Evans' overlap formula is generalised for the time-dependent case and the equivalence between Avrami's and Evans' equations established.

Necessity for quatum simulation for future technology nodes

In this paper we present and compare the results obtained from semi-classical and quantum mechanical simulation for a double gate MOSFET structure to analyze the electrostatics and carrier dynamics of this device. The geometries like gate length, body thickness of this device have been chosen according to the ITRS specification for the different technology nodes. We have shown the extent of deviation between the semi- classical and quantum mechanical results and hence the need of quantum simulations for the promising nanoscale devices in the future technology nodes predicted in ITRS.

The effect of electrochemical lithiation on physicochemical properties of RF-sputtered Sn thin films

Thin films of Sn were deposited on Pt/Si substrates by sputtering technique and subjected to electrochemical lithiation studies. Electrochemical lithiation of Sn resulted in the formation of Sn-Li alloys of different compositions. Charging of Sn-coated Pt/Si electrodes was terminated at different potentials and the electrodes were examined for physicochemical properties. The scanning electron microscopy and atomic force microscopy images suggested that the Sn films expanded on lithiation. Roughness of the film increased with an increase in the quantity of Li present in Sn-Li alloy. Electrochemical impedance data suggested that the kinetics of charging became sluggish with an increase in the quantity of Li in Sn-Li alloy.

Electrochemical copolymerization of thiophene derivatives; a precursor to photovoltaic devices

This work presents an electrochemical technique for the polymerization and copolymerization of thiophene derivatives like 7,9-dithiophene-2yl-8H-cyclopenta[a]acenaphthalene-8-one and 3-hexylthiophene. The structural characterization of chemically synthesized monomers and electro-chemically synthesized polymers was carried out by nuclear magnetic resonance and Fourier transform infrared spectroscopy. Thermal characterizations indicate that copolymer has increased thermal stability than that of homopolymer. Morphological studies of the polymerized films carried out by scanning electron microscopy shows network structure of copolymer. Optical properties of the homopolymers and copolymer were studied by UV-visible spectrometer and it was observed that band gap of copolymer is less than the homopolymers. HOMO and LUMO levels, band gap values of the respective polymers were also calculated from the cyclic voltammetry technique with various scan rates. By the peak current obtained from various scan rates shows that all polymerization reactions are diffusion controlled process. Charge transfer resistances of polymers were determined using Nyquist plots. Conductivity of synthesized polymers shows higher conductivity for copolymer than homopolymers. (C) 2011 Elsevier Ltd. All rights reserved.

Electrochemical performance of mixed crystallographic phase nanotubes and nanosheets of titania and titania-carbon/silver composites for lithium-ion batteries

The role of homogeneity in ex situ grown conductive coatings and dimensionality in the lithium storage properties of TiO(2) is discussed here. TiO(2) nanotube and nanosheet comprising of mixed crystallographic phases of anatase and TiO(2) (B) have been synthesized by an optimized hydrothermal method. Surface modifications of TiO(2) nanotube are realized via coating the nanotube with Ag nanoparticles and amorphous carbon. The first discharge cycle capacity (at current rate = 10 mA g(-1)) for TiO(2) nanotube and nanosheet were 355 mAh g(-1) and 225 mAhg(-1), respectively. The conductive surface coating stabilized the titania crystallographic structure during lithium insertion-deinsertion processes via reduction in the accessibility of lithium ions to the trapping sites. The irreversible capacity is beneficially minimized from 110 mAh g(-1) for TiO(2) nanotubes to 96 mAh g(-1) and 57 mAhg(-1) respectively for Ag and carbon modified TiO(2) nanotubes. The homogeneously coated amorphous carbon over TiO(2) renders better lithium battery performance than randomly distributed Ag nanoparticles coated TiO(2) due to efficient hopping of electrons. (C) 2011 Elsevier B.V. All rights reserved.

V(2)O(5)-Anchored Carbon Nanotubes for Enhanced Electrochemical Energy Storage

Functionalized multiwalled carbon nanotubes (CNTs) are coated with a 4-5 nm thin layer of V(2)O(5) by controlled hydrolysis of vanadium alkoxide. The resulting V(2)O(5)/CNT composite has been investigated for electrochemical activity with lithium ion, and the capacity value shows both faradaic and capacitive (nonfaradaic) contributions. At high rate (1 C), the capacitive behavior dominates the intercalation as 2/3 of the overall capacity value out of 2700 C/g is capacitive, while the remaining is due to Li-ion intercalation. These numbers are in agreement with the Trasatti plots and are corroborated by X-ray photoelectron spectroscopy (XPS) studies on the V(2)O(5)/CNTs electrode, which show 85% of vanadium in the +4 oxidation state after the discharge at 1 C rate. The cumulative high-capacity value is attributed to the unique property of the nano V(2)O(5)/CNTs composite, which provides a short diffusion path for Lit-ions and an easy access to vanadium redox centers besides the high conductivity of CNTs. The composite architecture exhibits both high power density and high energy density, stressing the benefits of using carbon substrates to design high performance supercapacitor electrodes.