Phase relations in the system Cu─Ho─O and stability of Cu2Ho2O5

The phase relations in the system Cu-Ho-O have been determined at 1300 K using X-ray diffraction, optical microscopy, and electron microprobe analysis of samples equilibrated in evacuated quartz ampules and in pure oxygen. Only one ternary compound, Cu2Ho2O5, was found to be stable. The Gibbs free energy of formation of this compound has been measured using the solid-state cell Pt,Cu2O + Cu2Ho2O5 + Ho2O3/(Y2O3)ZrO2/CuO + Cu2O,Pt in the temperature range of 973 to 1350 K. For the formation of Cu2Ho2O5 from its binary component oxides, 2CuO(s) + Ho2O3(S) --> Cu2Ho2O5(s) DELTAG-degrees = 11190 - 13.8T(+/- 120) J-mol-1 Since the formation is endothermic, CU2Ho2O5 becomes thermodynamically unstable with respect to CuO and Ho2O3 below 810 K. When the oxygen partial pressure over Cu2Ho2O5 is lowered, it decomposes according to the reaction 2Cu2Ho2O5(s) --> 2Ho2O3(s) + 2Cu2O(S) + O2(g) for which the equilibrium oxygen potential is given by DELTAmu(O2) = - 238510 + 160.2T(+/- 450) J.mol-1 The decomposition temperature at an oxygen partial pressure of 1.52 x 10(4) Pa was measured using a combined DTA-TGA apparatus. Based on these results, an oxygen potential diagram for the system Cu-Ho-O at 1300 K is presented.

Non-linear optical response of rutile-related oxides, LiM(V)M(VI)O(6), and their derivatives obtained by ion-exchange and intercalation

Polycrystalline samples of oxides of the general formula LiM(V)M(VI)O(6) (M(V) = Nb, Ta; M(VI) = Mo, W), crystallizing in a non-centrosymmetric (space group P (4) over bar 2(1)m) trirutile structure, exhibit second harmonic generation (SHG) of 1064 nm radiation with efficiencies 15-45 times that of alpha-quartz; interestingly, the SHG response is retained by the protonated derivatives HM(V)M(VI)O(6) . xH(2)O, and their n-alkylamine intercalates as well.

Phase equilibria in the system CaO-CoO-SiO2 and Gibbs energies of formation of the quaternary oxides CaCoSi2O6, Ca2CoSi2O7, and CaCoSiO4

Phase relations in the pseudoternary system CaO-CoO-SiO2 have been established at 1323 K. Three quaternary oxides were found to be stable: CaCoSi2O6 with clinopyroxene (Cpx), Ca2CoSi2O7 with melilite (Mel), and CaCoSiO4 with olivine (Ol) structures. The Gibbs energies of formation of the quaternary oxides from their component binary oxides were measured using solid-state galvanic cells incorporating yttria-stabilized zirconia as the solid electrolyte in the temperature range of 1000-1324 K. The results can be summarized as follows: CoO (rs) + CaO (rs) + 2SiO(2) (Qtz) --> CaCoSi2O6 (Cpx), Delta G(f)(0) = -117920 + 11.26T (+/-150) J/mol CoO (rs) + 2CaO (rs) + 2SiO(2) (Qtz) --> Ca2CoSi2O7 (Mel), Delta G(f)(0) = -192690 + 2.38T (+/-130) J/mol CoO (rs) + CaO (rs) + SiO2 (Qtz) --> CaCoSiO2 (Ol), Delta G(f)(0) = -100325 + 2.55T (+/-100) J/mol where rs = rock salt (NaCl) structure and Qtz = quartz. The uncertainty limits correspond to twice the standard error estimate. The experimentally observed miscibility gaps along the joins CaO-CoO and CaCoSiO4-Co2SiO4 were used to calculate the excess free energies of mixing for the solid solutions CaxCo1-xO and (CayCo1-y)CoSiO4:Delta G(E) = X(1 - X)[31975X + 26736 (1 - X)] J/mol and Delta G(E) = 23100 (+/-250) Y(1 - Y) J/mol. A T-X phase diagram for the binary CaO-CoO was computed from the thermodynamic information; the diagram agrees with information available in the literature. The computed miscibility gap along the CaCoSiO4-Co2SiO4 join is associated with a critical temperature of 1389 (+/-15) K. Stability fields for the various solid solutions and the quaternary compounds are depicted on chemical-potential diagrams for SiO2, CaO, and CoO at 1323 K.

Structural and optical properties of RF sputtered Bi2VO5.5 thin films

Thin films of Bismuth Vanadate Bi2VO5.5 (BiV) have been deposited on amorphous quartz and polycrystalline silicon substrates by r.f. sputtering technique and characterised for their structural and optical properties. The os-deposited films at room temperature are found to be amorphous and transparent over the spectral range of 0.55 mu m to 12 mu m. Post-deposition annealing at 400 degrees C in air shows the formation of the BiV crystalline phase. The optical constants namely refractive index. extinction coefficient and optical bandgap of both amorphous and crystalline films have been determined. The refractive index of the as-deposited film is around 2.4 at 0.7 mu m and drops to 2.26 at 1.56 mu m. The optical bandgap of the material has been determined from the computed values of the absorption coefficients.

Interaction of Bacillus polymyxa with some oxide minerals with reference to mineral beneficiation and environmental control

Interaction of Bacillus polymyxa with calcite, hematite, corundum and quartz resulted in significant surface chemical changes not only of the cells but also in the minerals. Both the cell surfaces as well as quartz particles were rendered more hydrophobic after mutual interaction, whilst the rest of the minerals exhibited enhanced hydrophilicity after interaction with the bacteria. The bacteria were also observed to be capable of dissolving calcite, hematite and corundum and biosorbing the dissolved metal ions to varying extents. An excess of polysaccharides could be observed on biotreated calcite, hematite and corundum while the predominance of a protein-based metabolic product was evident on quartz surfaces. The utility of bioprocessing in the beneficiation of the above minerals through bioflotation and bioflocculation is demonstrated. (C) 1997 Elsevier Science Ltd.

Surface modification and biobeneficiation of some oxide minerals using Bacillus polymyxa

The interaction of Bacillus polymyxa and minerals such as hematite, corundum and quartz resulted in significant surface chemical changes, both on the cell surfaces and on the interacted oxide minerals. After such treatment, quartz was rendered relatively more hydrophobic, while hematite and corundum were rendered more hydrophilic. Biopretreatment was observed to be beneficial in the separation of silica from hematite and alumina by both selective flocculation and flotation. The possible role of bacterial adhesion and metabilites in the biobeneficiation process is illustrated.

Role of corundum-adapted strains of Bacillus polymyxa in the separation of hematite and alumina

Strains of Bacillus polymyxa, preadapted and grown in the presence of corundum, were found to be capable of the efficient separation of hematite from alumina. Results of rests peformed using binary hematite-corundum and ternary hematite-quartz-corundum mixtures in the presence of cells and metabolic products separated from the adapted bacterial culture indicated that more than 99% of the hematite could he efficiently separated through selective flocculation after desliming. It was found that alumina-specific bioproteins and other nonproteinaceous compounds were secreted by bacterial cells after adaptation to the mineral. The utility of this bioprocessing is demonstrated in the removal of iron from bauxite ores through selective flocculation in the presence of the adapted bacteria.

Fluorescence and visual sensing of nitroaromatic explosives using electron rich discrete fluorophores

Several pi-electron rich fluorescent aromatic compounds containing trimethylsilylethynyl functionality have been synthesized by employing Sonogashira coupling reaction and they were characterized fully by NMR (H-1, C-13)/IR spectroscopy. Incorporation of bulky trimethylsilylethynyl groups on the peripheral of the fluorophores prevents self-quenching of the initial intensity through pi-pi interaction and thereby maintains the spectroscopic stability in solution. These compounds showed fluorescence behavior in chloroform solution and were used as selective fluorescence sensors for the detection of electron deficient nitroaromatics. All these fluorophores showed the largest quenching response with high selectivity for nitroaromatics among the various electron deficient aromatic compounds tested. Quantitative analysis of the fluorescence titration profile of 9,10-bis(trimethylsilylethynyl) anthracene with picric acid provided evidence that this particular fluorophore detects picric acid even at ppb level. A sharp visual detection of 2,4,6-trinitrotoluene was observed upon subjecting 1,3,6,8-tetrakis (trimethylsilylethynyl) pyrene fluorophore to increasing quantities of 2,4,6-trinitrotoluene in chloroform. Furthermore, thin film of the fluorophores was made by spin coating of a solution of 1.0 x 10(-3) M in chloroform or dichloromethane on a quartz plate and was used for the detection of vapors of nitroaromatics at room temperature. The vapor-phase sensing experiments suggested that the sensing process is reproducible and quite selective for nitroaromatic compounds. Selective fluorescence quenching response including a sharp visual color change for nitroaromatics makes these fluorophores as promising fluorescence sensory materials for nitroaromatic compounds (NAC) with a detection limit of even ppb level as judged with picric acid.

Microbially induced flotation of alumina, silica/calcite from haematite

Selective separation of haematite from alumina and silica/calcite was achieved through microbiologically induced flotation and flocculation in presence of Bacillus subtilis. Bacterial metabolites containing extracellular proteins were characterized from mineral-grown bacterial cell free extract. Bacteria can adhere to mineral surfaces and influence subsequent flotation of the minerals. Cells and metabolic products of bacteria were used in flotation, flocculation and adsorption studies on oxide minerals. Bacteria functions as a stronger depressant for haematite. Selective affinity of the bacterial cells towards the mineral surface was observed through adsorption studies. Bacterial byproduct like extracellular protein (EP) was isolated from bacteria. The protein profile of the EP of bacterial cells grown in presence and absence of minerals (haematite, corundum, quartz and calcite) was also studied. The role of such proteins in selective mineral separation was demonstrated through microbially induced selective flotation. This study has demonstrated the utility and amenability of microbially induced mineral beneficiation through the use of bacterially generated metabolic products and mineral-grown bacterial cells. (C) 2011 Elsevier B.V. All rights reserved.

New transparent crystallized glasses with optical nonlinear LiBGeO4 crystals

Crystallization behaviors of the glass with a composition of 25Li(2)O.25B(2)O(3).50GeO(2) corresponding to lithium borogermanate LiBGeO4 have been examined. It has been confirmed that the LiBGeO4 crystalline phase is formed at the surface of heat-treated glasses. The second harmonic (SH) generation is found from transparent surface crystallized glasses, demonstrating for the first time that the LiBGeO4 phase shows optical nonlinearity. The SH intensity of LiBGeO4 crystallites (powdered state) prepared through crystallization is about ten times as large as that of pulverized alpha-quartz. The SH intensity of transparent crystallized glasses (bulk state) with crystalline layers of 3-4.5 mum thickness increases with increasing heat treatment temperature (540-560degreesC) and time (1-6 h), and the maximum SH intensity among the samples studied is in the order of 1/10 in comparison with that of alpha-quartz single crystal. The transparent crystallized glass obtained by heat treatment at 550alphaC for 3 h exhibits a clear and fine Maker fringe pattern, indicating a highly orientation of LiBGeO4 crystals at the surface.

The use of a fibre anemometer in turbulent flows

Quartz fibre anemometers have been used (as described in subsequent papers) to survey the velocity field of turbulent free convective air flows. This paper discusses the reasons for the choice of this instrument and provides the background information for its use in this way. Some practical points concerning fibre anemometers are mentioned. The rest of the paper is a theoretical study of the response of a fibre to a turbulent flow. An approximate representation of the force on the fibre due to the velocity field and the equation for a bending beam, representing the response to this force, form the basis of a consideration of the mean and fluctuating displacement of the fibre. Emphasis is placed on the behaviour when the spectrum of the turbulence is largely in frequencies low enough for the fibre to respond effectively instantaneously (as this corresponds to the practical situation). Incomplete correlation of the turbulence along the length of the fibre is taken into account. Brief mention is made to the theory of the higher-frequency (resonant) response in the context of an experimental check on the applicability of the low-frequency theory.

Turbulent free convection above a heated plate inclined at a small angle to the horizontal Journal

An investigation has been made of the structure of the motion above a heated plate inclined at a small angle (about 10°) to the horizontal. The turbulence is considered in terms of the similarities to and differences from the motion above an exactly horizontal surface. One effect of inclination is, of course, that there is also a mean motion. Accurate data on the mean temperature field and the intensity of the temperature fluctuations have been obtained with platinum resistance thermometers, the signals being processed electronically. More approximate information on the velocity field has been obtained with quartz fibre anemometers. These results have been supplemented qualitatively by simultaneous observations of the temperature and velocity fluctuations and also by smoke experiments. The principal features of the flow inferred from these observations are as follows. The heat transfer and the mean temperature field are not much altered by the inclination, though small, not very systematic, variations may result from the complexities of the velocity field. This supports the view that the mean temperature field is largely governed by the large-scale motions. The temperature fluctuations show a systematic variation with distance from the lower edge and resemble those above a horizontal plate when this distance is large. The largescale motions of the turbulence start close to the lower edge, but the smaller eddies do not attain full intensity until the air has moved some distance up the plate. The mean velocity receives a sizable contribution from a ‘through-flow’ between the side-walls. Superimposed on this are developments that show that the momentum transfer processes are complex and certainly not capable of representation by any simple theory such as an eddy viscosity. On the lower part of the plate there is surprisingly large acceleration, but further up the mixing action of the small eddies has a decelerating effect.

Mapping of local electronic properties in nanostructured CMR thin films by Scanning Tunneling Microscopy (STM) and Local Conductance Map (LCMAP)

We have investigated the local electronic properties and the spatially resolved magnetoresistance of a nanostructured film of a colossal magnetoresistive (CMR) material by local conductance mapping (LCMAP) using a variable temperature Scanning Tunneling Microscope (STM) operating in a magnetic field. The nanostructured thin films (thickness ≈500nm) of the CMR material La0.67Sr0.33MnO3 (LSMO) on quartz substrates were prepared using chemical solution deposition (CSD) process. The CSD grown films were imaged by both STM and atomic force microscopy (AFM). Due to the presence of a large number of grain boundaries (GB's), these films show low field magnetoresistance (LFMR) which increases at lower temperatures. The measurement of spatially resolved electronic properties reveal the extent of variation of the density of states (DOS) at and close to the Fermi level (EF) across the grain boundaries and its role in the electrical resistance of the GB. Measurement of the local conductance maps (LCMAP) as a function of magnetic field as well as temperature reveals that the LFMR occurs at the GB. While it was known that LFMR in CMR films originates from the GB, this is the first investigation that maps the local electronic properties at a GB in a magnetic field and traces the origin of LFMR at the GB.

Constitutive Response of Passivated Copper Films: Experiments and Analyses

The constitutive behavior of passivated copper films is studied. Stresses in copper films of thickness ranging from 1000 nm to 40 nm, passivated with silicon oxide on a quartz or silicon substrate, were measured using the curvature method. The thermal cycling spans a temperature range from - 196 to 600°C. It is seen that the strong relaxation at high temperatures normally found in unpassivated films is nonexistent for passivated films. The copper film did not show any rate-dependent effect over a range of heating/cooling rate from 5 to 25°C/min. Further analyses showed that significant strain hardening exists during the course of thermal loading. In particular, the measured stress- temperature response can only be fitted with a kinematic hardening model, if a simple constitutive law within the continuum plasticity framework is to be used. The analytic procedures for extracting the film properties are presented. Implications to stress modeling of copper interconnects in actual devices are discussed.

The effect of nature of raw coal on the adhesion of bacteria to coal surface

The surface properties of coal and solution pH play a major role in determining the adhesion of microorganisms. In this study, three Indian coal samples with different compositions have been used and the adhesion of the bacterium Bacillus polymyxa to these coals has been investigated. It was found that due to the high ash content of coal, the zeta-potential was negative over most of the pH range which is close to the values exhibited by pure quartz as well as B. polymyxa. Similarly, the surface free energy components of coal (derived from contact angle measurements) showed that the electron-donor component increased with ash content. Adhesion experiments revealed that maximum adhesion of the bacterium B. polymyxa occurred on to the coal samples around the point-of-zero-charge of the coal and the bacterium i.e. about pH 2. Further, adhesion was found to be dependent on the ash content and the surface free energy of the coals. (C) 2002 Published by Elsevier Science Ltd.