Pre-edge analysis of X-rays absorption spectra in TiO2 modified films

The thesis is mainly focused on the pre-edge analysis of XAS spectra of Ti HCF sample hexacyanocobaltate and hexacyanoferrate samples doped on a Indium Tin Oxide (ITO) thin film. The work is aimed at the determination of Ti oxidation state, as well as indication of various coordination number in the studied samples. The experiment have been conducted using XAFS (X-ray absorption fine structure)beamline at Elettra synchrotron, Trieste (Italy) under supervision of Professor Marco Giorgetti, Department of Industrial Chemistry, University of Bologna. The Master thesis accreditation to fullfill the ASC Master of Advanced Spectroscopy in Chemistry Degree requirement.

Geochemical analysis of minerals from sediment core CRP-2 in the Ross Sea, Antarctica

Distribution patterns, petrography, whole-rock and mineral chemistry, and shape and fabric data are described for the most representative basement lithologies occurring as clasts (granule to bolder grain-size class) from the 625 m deep CRP-2/2A drillcore. A major change in the distribution pattern of the clast types occurs at c. 310 mbsf., with granitoid-dominated clasts above and mainly dolerite clasts below; moreover, compositional and modal data suggest a further division into seven main detrital assemblages or petrofacies. In spite of this variability, most granitoid pebbles consist of either pink or grey biotite±hornblende monzogranites. Other less common and ubiquitous lithologies include biotite syenogranite, biotite-hornblende granodiorite, tonalite, monzogranitic porphyries (very common below 310 mbsf), microgranite, and subordinately, monzogabbro, Ca-silicate rocks, biotite-clinozoisite schist and biotite orthogneiss (restricted to the pre-Pliocene strata). The ubiquitous occurrence of biotite±hornblende monzogranite pebbles in both the Quaternary-Pliocene and Miocene-Oligocene sections, apparently reflects the dominance of these lithologies in the onshore basement, and particularly in the Cambro-Ordovician Granite Harbour Igneous Complex which forms the most extensive outcrop in southern Victoria Land. The petrographical features of the other CRP-2/2A pebble lithologies are consistent with a supply dominantly from areas of the Transantarctic Mountains facing the CRP-2/2A site, and they thus provide further evidence of a local provenance for the supply of basement clasts to the CRP-2/2A sedimentary strata.

Hydrothermal synthesis of single crystallin strontium titanate nanocubes

Strontium titanate nanocubes with an average edge length of 150mm have been successfully synthesized from a simple hydrothermal system. Characterization techniques such as X-ray powder diffraction analysis, scanning electron microscopy and energy-dispersive analysis of X-rays were used to investigate the products. The results showed that as-prepared powders are pure SrTiO3 with cubic shape, which consists with the growth habit of its intrinsic crystal structure. These uniform nanocubes with high crystallinity will exhibit superior physical properties in the practical applications. Furthermore, during the experimental process, it has been found that the dilute acid washing process is very important to obtain high pure SrTiO3.

Phase Relations in the System La-Rh-O and Thermodynamic Properties of LaRhO3

Phase relations in the system La-Rh-O at 1223 Ii have been determined by examination of equilibrated samples by optical and scanning electron microscopy, powder X-ray diffraction (XRD), and energy-dispersive analysis of X-rays (EDAX). Only one ternary oxide, LaRhO3, with distorted orthorhombic perovskite structure (Pbnm, a = 0.5525, b = 0.5680, and c = 0.7901 nm) was identified. The alloys and intermetallics along the La-Rh binary are in equilibrium with La2O3. The thermodynamic properties of LaRhO3 were determined in the temperature range 890 to 1310 K, using a solid-state cell incorporating yttria-stabilized zirconia as the electrolyte. A new four-compartment design of the emf cell was used to enhance the accuracy of measurement. For the reaction 1/2La(2)O(3) + 1/2Rh(2)O(3) --> LaRhO3, Delta G degrees = - 70 780 + 4.89T (+/- 90) J.mol(-1) The compound decomposes on heating to a mixture of La2O3, Ph and O-2. The calculated decomposition temperatures are 1843 (+/- 5) K in pure O-2 and 1728 (+/- 5) K in air at a pressure of 1.01 x 10(5) Pa. The phase diagrams for the system La-Rh-O at different partial pressures of oxygen are calculated from the thermodynamic information.

Origin of carrier-type reversal in Pb-Ge-Se glasses: A detailed thermal, electrical, and structural study

A long-standing and important problem in glass science has been carrier-type reversal (CTR) in semiconducting glasses. This phenomenon is exhibited by Pb-Ge-Se glasses also. It has been addressed here by carrying out detailed electrical, thermal, and spectroscopic investigations. PbxGe42-xSe58 (x = 0-20) glasses were prepared by a two stage melt-quenching process and characterized using x-ray diffraction, high-resolution electron microscropy, and energy dispersive analysis of x-rays. Thermoelectric power and high-pressure electrical resistivity have been measured. IR, Raman, and X-ray adsorption near edge structure spectroscopies have been used for examining the glass structures as well as differential scanning calorimetry (DSC) for studying the thermal properties. A structural model based on the chemical nature of the constituents has been proposed to account for the observed properties of these glasses. Effect of Pb incorporation on local structures and qualitative consequences on the energy band structures of Ge-Se glasses has been considered. The p -->n transition has been attributed to the energetic disposition of the sp(3)d(2) band of Pb atoms, which is located closely above the lone pair band of selenium. This feature makes Pb unique in the context of p -->n transition of chalcogenide glasses. The model can be extended successfully to account for the CTR behavior observed in Bi containing chalcogenide glasses also.

The effect of mischmetal addition on the structure and mechanical properties of a cast Al-7Si-0.3Mg alloy containing excess iron (up to 0.6 Pct)

The effect of Fe content (0.2 to 0.6 pct) on the microstructure and mechanical properties of a cast Al-7Si-0.3Mg (LM 25/356) alloy has been investigated. Further, 1 pct mischmetal (MM) additions (a mixture of rare-earth (RE) elements) were made to these alloys, and their mechanical properties at room and at elevated temperatures (up to 200 degreesC) were evaluated. A structure-property correlation on this alloy was attempted using optical microstructure analysis, fractographs, X-ray diffraction, energy-dispersive analysis of X-rays (EDX), and quantitative metallography by image analysis. An increase in Fe content increased the volume percentage of Fe-bearing intermetallic compounds (beta and pi phases), contributing to the lower yield strength (YS), ultimate tensile strength (UTS), percentage elongation, and higher hardness. An addition of 1 pct MM to the alloys containing 0.2 and 0.6 pct Fe was found to refine the microstructure; modify the eutectic silicon and La, Ce, and Nd present in the MM; form different intermetallic compounds with Al, Si, Fe, and Mg; and improve the mechanical properties of the alloys both at room and elevated temperatures.

System Nd-Pd-O: Phase diagram and thermodynamic properties of oxides using a solid-state cell with advanced features

An isothermal section of the phase diagram for the system Nd-Pd-O at 1350 K has been established by equilibration of samples representing 13 different compositions and phase identification after quenching by optical and scanning electron microscopy, x-ray diffraction, and energy dispersive analysis of x-rays. The binary oxides PdO and NdO were not stable at 1350 K. Two ternary oxides Nd4PdO7 and Nd2Pd2O5 were identified. Solid and liquid alloys, as well as the intermetallics NdPd3 and NdPd5, were found to be in equilibrium with Nd2O3. Based on the phase relations, three solidstate cells were designed to measure the Gibbs energies of formation of PdO and the two ternary oxides. An advanced version of the solid-state cell incorporating a buffer electrode was used for high-temperature thermodynamic measurements. The function of the buffer electrode, placed between reference and working electrodes, was to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. Yttria-stabilized zirconia was used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MP a as the reference electrode. Electromotive force measurements, conducted from 950 to 1425 K, indicated the presence of a third ternary oxide Nd2PdO4, stable below 1135 (±10) K. Additional cells were designed to study this compound. The standard Gibbs energy of formation of PdO (†f G 0) was measured from 775 to 1125 Kusing two separate cell designs against the primary reference standard for oxygen chemical potential. Based on the thermodynamic information, chemical potential diagrams for the system Nd-Pd-O were also developed.

System Cu-Rh-O: Phase diagram and thermodynamic properties of ternary oxides CuRhO2 and CuRh204

An isothermal section of the phase diagram for the system Cu-Rh-O at 1273 K has been established by equilibration of samples representing eighteen different compositions, and phase identification after quenching by optical and scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersive analysis of X-rays (EDX). In addition to the binary oxides Cu2O, CuO, and Rh2O3, two ternary oxides CuRhO2 and CuRh2O4 were identified. Both the ternary oxides were in equilibrium with metallic Rh. There was no evidence of the oxide Cu2Rh2O5 reported in the literature. Solid alloys were found to be in equilibrium with Cu2O. Based on the phase relations, two solid-state cells were designed to measure the Gibbs energies of formation of the two ternary oxides. Yttria-stabilized zirconia was used as the solid electrolyte, and an equimolar mixture of Rh+Rh2O3 as the reference electrode. The reference electrode was selected to generate a small electromotive force (emf), and thus minimize polarization of the three-phase electrode. When the driving force for oxygen transport through the solid electrolyte is small, electrochemical flux of oxygen from the high oxygen potential electrode to the low potential electrode is negligible. The measurements were conducted in the temperature range from 900 to 1300 K. The thermodynamic data can be represented by the following equations: {fx741-1} where Δf(ox) G o is the standard Gibbs energy of formation of the interoxide compounds from their component binary oxides. Based on the thermodynamic information, chemical potential diagrams for the system Cu-Rh-O were developed.

Investigations on structural and optical properties of co-doped (Ag, Co) ZnO nanoparticles

Undoped and co-doped (Ag, Co) ZnO powders were synthesized by chemical co-precipitation method without using any capping agent. The X-ray diffraction results indicate that the undoped and co-doped ZnO powders have pure hexagonal structure and are consisting of nanosized single-crystalline particles. The size of the nanoparticles increases with increasing Ag concentration from 1 to 5 mol% as compared to that of undoped ZnO. The presence of substitution dopants of Ag and Co in the ZnO host material was confirmed by the Energy dispersive analysis of X-rays (EDAX). Optical absorption measurements indicate blue shift and red-shift in the absorption band edge upon doping concentration of Ag and blue emission was observed by photoluminescence (PL) studies.

Compositional dependence properties change in S40Se60-x,Sb-x alloys

Bulk samples of S40Se60,Sb-x (with x=10, 20, 30 and 40 at. %) were prepared from high purity chemicals by melt quenching technique. The samples compositions were confirmed by using energy dispersive analysis of X-rays. X-ray diffraction studies revealed that all the samples have poly-crystalline phase. The variation in optical properties with compositional has been investigated by X-ray photoelectron spectroscopy and Raman spectroscopy. The optical band gap of the thin films is found to be decreased with composition. Increasing Sb content was found to affect the structural and optical properties of bulk samples. The intensity of core level spectra changes with the addition of Sb clearly interprets the optical properties change due to compositional variation. The Raman shift and new peak formation in these samples clearly show the structural modifications due to Sb addition.

Crystallinity, Magnetic and Electrical Properties of Bi doped LaVO3

We report the results of crystal structure, magnetization and resistivity measurements of Bi doped LaVO3. X-ray diffraction (XRD) shows that if doping Bi in the La site is less than ten percent, the crystal structure of La1-xBixVO3 remains unchanged and its symmetry is orthorhombic. However, for higher Bi doping (>10%) composite compounds are found where the XRD patterns are characterized by two phases: LaVO3+V2O3. Energy-dispersive analysis of the x-ray spectroscopy (EDAX) results are used to find a proper atomic percentage of all samples. The temperature dependence of the mass magnetization of pure and single phase doped samples have transition temperatures from paramagnetic to antiferromagnetic region at TN=140 K. This measurement for bi-phasic samples indicates two transition temperatures, at TN=140 K (LaVO3) and TN=170 K (V2O3). The temperature dependence of resistivity reveals semiconducting behavior for all samples. Activation energy values for pure and doped samples are extracted by fitting resistivity versus temperature data in the framework of thermal activation process.