Studies on the deposition and characterization of silicon oxide films for optical coating applications

Silicon oxide films were deposited by reactive evaporation of SiO. Parameters such as oxygen partial pressure and substrate temperature were varied to get variable and graded index films. Films with a refractive index in the range 1.718 to 1.465 at 550 nm have been successfully deposited. Films deposited using ionized oxygen has the refractive index 1.465 at 550 nm and good UV transmittance like bulk fused quartz. Preparation of graded index films was also investigated by changing the oxygen partial pressure during deposition. A two layer antireflection coating at 1064nm has been designed using both homogeneous and inhomogeneous films and studied their characteristics.

Form, Content, and Magnetism in Iron Oxide Nanocrystals

Monodisperse iron oxide nanocrystals with spherical and cubic morphologies, of comparable dimensions, have been prepared by the thermal decomposition of FeOOH. The lattice spacings of both forms agree with that of magnetite, Fe(3)O(4). The two, however, exhibit very different blocking temperatures. Nanocrystals of cubic morphology are superparamagnetic above 190 K while the spherical nanocrystals at a lower temperature, 142 K. The higher blocking temperatures in particles of cubic morphology are shown to be a consequence of exchange bias fields. We show that in the present iron oxide nanocrystals the exchange bias fields originate from the presence of trace amounts of wustite, FeO. A Reitveld refinement analysis of the X-ray diffraction patterns shows that nanocrystals of cubic morphology have a higher FeO content. The higher FeO content is responsible for the larger exchange bias fields that in turn lead to a higher blocking temperature for nanocrystals with cubic morphology.

Conductance of a photochromic molecular switch with graphene leads

We report a full self-consistent ab initio calculation of the conductance of a diarylethene-based molecular switch with two graphene electrodes. Our results show the contributions of the resonant states of the molecule, of the electrode density of states, and of graphene unique features, such as edge states. The conductivities are found to be significantly different for the two photochromic isomers at zero and finite applied bias. Further we point out the possibility of causing the switching by the application of a large potential difference between the two electrodes.

Direct evidence of redox interaction between metal ion and support oxide in Ce(0.98)Pd(0.02)O(2-delta) by a combined electrochemical and XPS study

A combined electrochemical method and X-ray photo electron spectroscopy (XPS) has been utilized to understand the Pd(2+)/CeO(2) interaction in Ce(1-x)Pd(x)O(2-delta) (x = 0.02). A constant positive potential (chronoamperometry) is applied to Ce(0.98)Pd(0.02)O(2-delta) working electrode which causes Ce(4+) to reduce to Ce(3+) to the extent of similar to 35%, while Pd remains in the +2 oxidation state. Electrochemically cycling this electrode between 0.0-1.2 V reverts back to the original state of the catalyst. This reversibility is attributed to the reversible reduction of Ce(4+) to Ce(3+) state. CeO(2) electrode with no metal component reduces to CeO(2-y) (y similar to 0.4) after applying 1.2 V which is not reversible and the original composition of CeO(2) cannot be brought back in any electrochemical condition. During the electro-catalytic oxygen evolution reaction at a constant 1.2 V for 1000 s, Ce(0.98)Pd(0.02)O(2-delta) reaches a steady state composition with Pd in the +2 states and Ce(4+) : Ce(3+) in the ratio of 0.65 : 0.35. This composition can be denoted as Ce(0.63)(4+)Ce(0.35)(4+)Pd(0.02)O(2-delta-y) (y similar to 0.17). When pure CeO(2) is put under similar electrochemical condition, it never reaches the steady state composition and reduces almost to 85%. Thus, Ce(0.98)Pd(0.02)O(2-delta) forms a stable electrode for the electro-oxidation of H(2)O to O(2) unlike CeO(2) due to the metal support interaction.

Thermodynamics of oxide sulfate melts: The system PbO PbSO4

Activities in the PbO-PbSO4 melts at 1253 K have been measured by emf and gas-equilibration techniques. The activity of PbO was directly obtained from the emf of the solid oxide cell, Pt, Ni-NiO/CaO-ZrO2/Auo.92PbO.08, PbOx-PbSO4(1-x), Ir, Pt for 1.0 >XPbO > 0.6. The melt and the alloy were contained in closed zirconia crucibles. Since the partial pressure of SO2 gas in equilibrium with the melt and alloy was appreciable (>0.08 atm) atXPbO < 0.6, activities at lower PbO concentrations were derived from measurements of the weight gain of pure PbO under controlled gas streans of Ar + SO2 + O2. The partial and integral free energies of mixing at 1253 K were calculated and found to fit a subregular model: ΔGEPbO =X2PbSO4 {-42,450 + 20,000X2PbSO4} J mol-1 ΔGEPbO =X2pbSO {-12,450 - 20,000XPbS} J mol-1 ΔGEpbSOXPbSO4 {-32,450XPbS - 22,450XPbSO4 } J mol-1. The standard free energy of formation of liquid PbSO4 from pure liquid PbO and gaseous SO3 at 1 atm at 1253 K was evaluated as -88.02 (±0.72) kJ mol-1.

Gibbs free energies of formation of indium (III) oxide and sulphate

Emf measurements on the galvanic cell Pt, Ta, In + In,O, / Tho,-Y,03 / Cu + C+O, Pt were used to obtain the standard free energy of formation of 1%03fr om 600 to 900°C. Differential thermal analysis was used to detect the decomposition of In2(S0,), under controlled SO2 + O2 + Ar mixtures in thqtemperature range 640-8wC. X-ray diffraction analysis indicated that the decomposition product was 1%03 without an oxywlphate intermediate. The following equations were obtained for the variation of the standard free-energy change(Jlmole) with temperature:

Sulphur potential measurements with a two phase sulphide oxide electrolyte

The open circuit potentials of the galvanic cell,Pt (or Au)¦(Ar + H2S + H2)primeparCaS + ZrO2(CaO)par (Ar + H2S+ H2)Prime£t (or Au) has been measured in the temperature range 1000 to 1660 K and PH2S:PH 2 ratios from 1.73×10–5 to 2.65×10–1. The solid electrolyte consists of a dispersion of calcium sulphide in a matrix of calcia-stabilized zirconia. The surface of the electrolyte is coated with a thin layer of calcium sulphide to prevent the formation of water vapour by reaction of hydrogen sulphide with calcium oxide or zirconia present in the electrolyte. The use of a lsquopoint electrodersquo with a catalytically active tip was necessary to obtain steady emfs. At low temperatures and high sulphur potentials the emfs agreed with the Nernst equation. Deviations were observed at high temperatures and low sulphur potentials, probably due to the onset of significant electronic conduction in the oxide matrix of the electrolyte. The values of oxygen and sulphur potentials at which the electronic conductivity is equal to ionic conductivity in the two-phase electrolyte have been evaluated from the emf response of the cell. The sulphide-oxide electrolyte is unsuitable for sulphur potential measurements in atmospheres with high oxygen potentials, where oxidation of calcium sulphide may be expected.

Alloy/Oxide Equilibria in Iron--Vanadium--Oxygen and Iron--Niobium--Oxygen Systems

An experimental characterization of three-phase equilibria in Fe--V--O and Fe--Nb--O systems at 1823, 1873 and 1923K has been carried out using a solid state cell and by analysis of quenched samples. The oxygen potentials corresponding to these three-phase equilibria were monitored by a solid state cell incorporating Y sub 2 O sub 3 doped ThO sub 2 with Cr + Cr sub 2 O sub 3 as reference electrode. Similar measurements were carried out for Fe--Nb--O alloys in equilibrium with a mixture of FeNb sub 2 O sub 6 and NbO sub 2 . These measurements permit evaluation of interaction parameters (e exp V sub O = --6590/T + 2.892 and e exp Nb sub O = --4066/T + 1.502) and activity coefficients of vanadiun and niobium in dilute solution (ln gamma exp O sub V = --35 320/T + 12.68 and ln gamma sub Nb exp O = --12 386/T + 4.34) in liquid iron. The results obtained in this study resolve a number of discrepancies in thermodynamic data reported in the literature, especially regarding the activity coefficients of V and Nb and the stability ranges for V sub 2 O sub 3 and VO sub 1+x . 18 ref.--AA

Measurement of the Gibbs energy of formation of URh3 using an oxide solid electrolyte

The Gibbs' energy offormation of the intermetallic compound URh3has been measured in the temperature range 980 to 1320 K using an oxide solid state cell incorporating yttria-doped thoria as the solid electrolyte and a mixture of manganese and manganese oxide as the reference electrode. The cell can be represented as Pt, Mn + MnO I (Y203)Th02 I Rh + URh3 + U02 + x' Rh, Pt The reversible emf of the cell was a linear function of temperature E = 15.60 +0.0237 T (±0.8) mY. Using auxiliary thermodynamic data for MnO and U02+ x the Gibbs' energy of formation of URh3 from component metals has been computed. The results can be expressed by the equation L'.G?< URh3 > = -316240 + 13.22 T (± 3000) J mol-1. The "third-law" enthalpy of formation of URh3at 298 K is -293.2 (± 4) kJ mol-1, significantly more negative than the value of -181.5 kJ mol-1 calculated using Miedema's model.

Physical chemistry of the reduction of calcium oxide with aluminium in vacuum

The physical chemistry of "aluminothermic" reduction of calcium oxide in vacuum is analyzed. Basic thermodynamic data required for the analysis have been generated by a variety of experiments. These include activity measurements in liquid AI-Ca alloys and determination of the Gibbs energies of formation of calcium aluminates. These data have been correlated with phase relations in the Ca-AI-0 system at 1373 K. The various stages of reduction, the end products and the corresponding equilibrium partial pressures of calcium have been established from thermodynamic considerations. In principle, the recovery of calcium can be improved by reducing the pressure in the reactor. However,, the cost of a high vacuum system and the enhanced time for reduction needed to achieve higher yields makes such a practice uneconomic. Aluminum contamination of calcium also increases at low pressures. The best compromise is to carry the reduction up to the stage where 3CaO-Al,O, is formed as the product. This corresponds to an equilibrium calcium partial pressure of 31.3 Pa at 1373 K and 91.6 Pa at 1460 K. Calcium can be extracted at this pressure using mechanical pumps in approximately 8 to 15 hr, depending on the size and the fill ratio of the retort and porosity of the charge briquettes.

Alloy oxide equilibria in the system Ca Al O at 1373 K

The tie lines delineating equilibria between different oxides of the Ca-Al-O system and liquid Ca-Al alloy has been determined at 1373 K. Equilibration of the alloy with two adjacent oxide phases in the CaO-Al2O3 pseudo-binary system was established in a closed cell made of iron. Equilibrium oxide phases were confirmed by x-ray analysis and alloy compositions were determined by chemical analysis. The compound 12CaO.7Al2O3 Ca12Al14O33 was found to be a stable phase in equilibrium with calcium alloys. The experimental diagram is consistent with that calculated from the free energies of formation of the oxide phases and activities in liquid Ca-Al alloys at 1373 K reported in the literature.

Synthesis, characterization and spectroscopy of composites of graphene with CdSe and CdS nanoparticles

Nanocomposites of few-layer graphene with nanoparticles of CdSe and CdS have been synthesized by two different methods, one involving ultrasonication of a mixture of graphene and the chalcogenide nanoparticles, and another involving assembly at the organic-aqueous interface. The nanocomposites have been examined by electron microscopy, electronic absorption and photoluminescence spectroscopies as well as Raman spectroscopy. Electron microscopy reveals that the nanoparticles are dispersed on the graphene surface. Raman spectra show the presence of definitive electronic interaction between the nanoparticles and graphene depending on the capping agent. Photoluminescence spectra are markedly influenced by the interaction of the nanoparticles with the graphene surface, depending on the capping agent.