Chemischer Transport von Eisensulfid (IV) Die Charakterisierung des Eisensulfids mittels röntgenographischer Methoden

The phase and analytical compositions of iron sulphide obtained by chemical transport reactions are determined by X-ray techniques. Utilizing the angle position of the (104)-reflex it is possible to determine 0,1 Mol%-differences in composition needing only small amounts of samples. The different compositions of solids in dissolution zone and deposition zone are verified. The lower limit of the range of homogeneity was determined to be 1.001 ± 0.003 between 200°C and 1000°C, not dependent on temperature.     

Role of Te valence on phases crystallized in K2O–Nb2O5–TeO2 glasses

Differences in crystalline phases between glass-ceramics and sintered ceramics in the K₂O–Nb₂O₅–TeO₂ system have been examined, particularly to obtain information on the role of Te valence on crystallization behaviors of TeO₂-based glasses. In glasses or glass-ceramics, the valence of Te⁴⁺ is retained even during heat-treatment up to around 600°C, leading to the formation of crystalline phases containing Te⁴⁺, e.g., the face-centered cubic crystalline phase. In a powder sintering method, Te⁴⁺ is easily oxidized to Te⁶⁺ during sintering at around 600°C in air and compounds such as KNbTeO₆ in which Te⁶⁺ is present are formed.     

Electrochemical Deposition of CdTe Layers. Their Structure and Electrical Properties

CdTe layers have been deposited catodically on nickel substrates from an aqueous solution of CdSO₄ and TeO₂. The degree of erystallinity increases with increasing temperature and decreasing deposition potential. The structure of the layers is cubic with 〈111〉 or 〈110〉 texture which is determined by TeO₂ concentration predominantly. Amorphous phase is found in deposits prepared at higher deposition potential or at lower temperatures of bath (60 °C). After annealing at 200 °C the amorphous deposits crystallized and pure tellurium appeared in diffraction spectra. The resistivity of the films was determined by means of I—V characteristics. Films with deposition potentials (−500 to −400) mV vs SCE are p-type conductivity whereas at lower potentials (down to − 700 mV vs. SCE) the n-type material is formed.     

Mass spectrometric study on chemical transport of VO2

The analysis of gas in the chemical transport reaction of VO₂ using TeCl₄ as a transport agent was carried out with a quadrupole mass spectrometer. In the transport reaction from 600 to 500°C, it was found that the oxygen and vanadium of VO₂ were transported in the form of VOCl₃ and TeOCl₂ gases; the transport reaction was $\text{VO}{}_2\text{+}\text{3}\text{2}\text{TeCl}{}_4\text{= VOCl}{}_3\text{+ TeOCl}{}_2\text{+}\text{1}\text{2}\text{TeCl}{}_2$. The transport reaction from 900°C to 800°C was assumed to be $\text{VO}{}_2\text{+}\text{3}\text{2}\text{TeCl}{}_2\text{= VOCl}{}_3\text{+}\text{1}\text{2}\text{O}{}_2\text{+}\text{3}\text{4}\text{TeCl}{}_2$. In the transport at high temperature, the oxygen partial pressure estimated from the mass spectrum was considerably higher than that in equilibrium with VO₂ phase. In this paper a study of the chemical transport of the system VO₂-TeCl₄ is presented.     

An Electron Probe Microanalyzer Investigation on Phase Reactions during Firing of Iron Ore Pellets

Processes during the firing of pellets consisting of siderite concentrate and Ca(OH)₂ have been studied by means of X-ray diffractometer and microanalyzer. When temperature is higher than 400°C thermal siderite decomposition starts, producing haematite and calcite being observed up to 600°C with the technique of oscillating X-ray detector. With increasing temperature CaO which arises from calcite doesn't react with SiO₂ up to 750°C; Fe₂O₃ grains grow. Above 1000°C CaO is dissolved in Fe oxides, and ferrite of CF type is formed. At temperatures higher than 1130°C a new phase is forming, presumedly a ferrite CF₂. Results of the study of this phase being stable up to 1250°C are reported.     

Structure and morphological stability of (Lu1–xEux)2O3 thin films

(Lu_1–xEu_x)₂O₃ smooth, crack‐free, transparent films were prepared by the Pechini sol–gel method and a spin‐coating technique. Thermogravimetric analysis, differential thermal analysis and FITR spectroscopy were used to study the chemical processes during annealing of the films. Film structure, morphology and optical properties were investigated. X‐ray diffraction (XRD) analysis reveals the cubic phase of (Lu_1–xEu_x)₂O₃ films annealed in the 600–1000 °C temperature range. Smooth and crack‐free films with thicknesses of 250–1000 nm were obtained in the 600–800 °C temperature range. The thickness upper limit (1000 nm) of morphological stability of films (Lu_1–xEu_x)₂O₃ on sapphire substrates has been studied.     

Gel-glass transformation in the SiO2Fe2O3 system

Gel-glass transformation has been studied by Mössbauer spectroscopy, DTA-TG analyses and X-ray diffractometry for four compositions in the SiO₂Fe₂O₃ system (A: 5 wt% Fe₂O₃, B: 10 wt% Fe₂O₃, C: 20 wt% Fe₂O₃, D: 40 wt% Fe₂O₃).The gels were prepared by the hydrolysis of silicon tetraethoxide and iron triethoxide and successively dried and heated in oxygen in the temperature range 40–1000°C.Samples A and B gave typical amorphous X-ray patterns up to 700°C; heating at higher temperature yielded the precipitation of quartz, cristobalite and hematite in sample A, cristobalite and hematite in sample B. Crystallization was also detected by DTA in sample A for which X-ray diffraction exhibited a larger effect.In samples C and D crystallization took place starting from 300°C with the precipitation of hematite, which remained the only crystalline phase up to 1000°C.The presence of hematite was confirmed by the obtained Mössbauer spectra which showed the characteristic sextet. The apportion of iron ions in the Fe³⁺ and Fe²⁺ oxidation states was also determined, together with the attribution of the probable coordination states for Fe³⁺ ions.Complex magnetic structure appeared in samples treated above 800°C.     

Electrochemical performance of B and M phases VO2 nanoflowers

VO₂ exists in four phases, among which, the M/R phase VO₂ is well known for its reversible metal‐semiconductor phase transition at about 68 °C, and VO₂ (B) is a promising candidate cathode material to be applied in aqueous lithium‐ion battery owing to its proper electrode potential and layered structure. In this study, VO₂ (B) nanoflowers was synthesized via one‐step hydrothermal process and then successfully transformed into the VO₂ (M) by heat treatment. Electrochemical behaviors of the two samples were evaluated by cycling discharge and cyclic voltammetry (CV). The results showed that flower‐like VO₂ (B) had the first discharge capacity of 180.33 mAhg‐1, an outstanding value of 52.8% for the capacity retention after 50 cycles. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of nonstoichiometric zirconium carbide whiskers by chemical vapor deposition

Nonstoichiometric zirconium carbide crystals with various compositions were prepared by chemical vapor deposition. Two gaseous mixtures, zirconium tetrachloride and argon, toluene and hydrogen, were introduced to the reaction zone where a graphite substrate was heated between 1200 and 1400°C. The deposition rate was proportional to the partial pressure of toluene. The compositional ratio of n_C/n_Zr in the gaseous mixture from 2.0 to 6.0 was found to be optimum for producing needle-like crystals. Needle-like crystal with smaller size were formed when the ratio of n_C/n_Zr was smaller than 2.0, and less needle-like crystals accompanied with more carbon were also produced when the ratio of n_C/n_Zr was larger than 6.0. The temperature of the substrate suitable for the growth of needle crystals was in the range from 1250 to 1300°C. The lattice constants of the products varied as a function of the ratio of n_C/n_Zr in the gaseous mixtures.     

Intermediates and transport phenomena in two‐temperature synthesis of ZnGeP2

High quality semiconducting ternary compound ZnGeP₂ was synthesized by a modified two‐temperature technique using high purity elemental zinc, germanium and phosphorus as the starting materials. Transport phenomena of zinc and phosphorus vapors and the major reaction intermediates, taking place in ZnGeP₂ formation, were studied by interrupting the synthesis process using quenching technique as well as by adjusting the temperatures of cold and hot zones. The powder X‐ray diffraction analysis showed that the major reaction intermediates were ZnP₂, Zn₃P₂, and GeP, which proportions were changed at the different temperature stages. ZnP₂ was formed in the temperature gradient region and ZnGeP₂ was formed in the hot zone when the temperature of the hot zone was higher than 900 °C. The 520‐1040 °C temperature profile was chosen for the ZnGeP₂ synthesis and charge amount per run reached 200 g. The powder X‐ray diffraction pattern of the synthesized ZnGeP₂ compound was in agreement with the standard pattern of ZnGeP₂. These results demonstrated that the synthesized ZnGeP₂ compound was a single phase. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Conductivity stabilization by metal and oxide additives in ceramics on the basis of VO2 and glass V2O5–P2O5

Conductivity behavior during the temperature cycling through the phase transition temperature of VO₂ (T_t = 68 °C) was investigated in glass-ceramics based on VO₂ and vanadium phosphate glass (VPG) for compositions without and with Cu and SnO₂ additives. Copper and SnO₂ additives stabilize the conductivity of glass-ceramics at temperature cycling. For ceramics (wt%) (80 − y)VO₂–5Cu–15VPG–ySnO₂ the best stabilizing effect takes place when SnO₂ content is in the interval 35 wt% < y < 50 wt%. Ceramics with such SnO₂ content keeps a stable value of the conductivity change (∼10²) in the vicinity of VO₂ phase transition temperature and shows the conductivity decrease no more than of 2.5 times after 3000 thermal cycles. The reasons of conductivity stabilizing in VO₂-based glass-ceramics with additives of Cu and SnO₂ are being discussed. The analysis resting on the percolation theory has shown the increase of conductivity stability in VO₂-based glass-ceramics when the VO₂ volume fraction and the average size of VO₂ crystallites decrease and the ceramics surface tension increases.     

GeO2/SiO2-glasses from gels to increase the oxidation resistance of porous silicon containing ceramics

GeO₂/SiO₂-glasses with relatively high expansion coefficients (between 5 and 7.3 × 10^?6 °C^?1) were prepared by hydrolysis of metal alkoxides (tetramethoxy silane+tetraethoxy germane as well as mixtures of the silane with GeO₂-powder) with subsequent heat treatment up to 1000°C. It is shown that the preparation of thin films on glasses and ceramics is possible but also that this technique can be used for liquid infiltration of porous SiC- and Si₃N₄-materials to increase the oxidation behaviour in the temperature range 1000 to 1400°C. In the case of molybdenumdisilicide as a ceramic material it is shown that the catastrophic inner oxidation in the low temperature range (600 to 800°C) of porous specimens (tested with plasma-sprayed MoSi₂-layers on refractory metals) can be hindered if these materials are infiltrated and heat treated.     

Effect of Thermal Annealing on Structural Properties,Morphologies and Electrical Properties of TiO2 Thin Films Grown by MOCVD

TiO₂ thin films, were deposited on Si(100) and Si(111) substrates by metalorganic chemical vapor deposition at 500 °C, and have been annealed for 2 min, 30 min and 10 hours at the temperature from 600 °C to 900 °C, in oxygen and air flow, respectively. XRD and atomic force microscopy characterized the structural properties and surface morphologies of the films. As‐deposited films show anatase polycrystalline structure with a surface morphology of regular rectangled grains with distinct boundaries. Rutile phase formed for films annealed above 600 °C, and pure rutile polycrystalline films with (110) orientation can be obtained after annealing under adequate conditions. Rutile annealed films exhibit a surface morphology of equiaxed grains without distinct boundaries. The effects of substrate orientation, annealing time and atmosphere on the structure and surface morphology of films have also been studied. Capacitance‐Voltage measurements have been performed for films deposited on Si(100) before and after annealing. The dielectric properties of TiO₂ films were greatly improved by thermal annealing above 600 °C in oxygen.     

Zu dem Transportsystem V-O-Te-Cl und dem Transportverhalten der Vanadinoxide mit TeCl4(II). Der chemische Transport der Magnéliphasen VnO2n–1, des V6O13 und des V2O5

It was reported on the transport system V O Te Cl and on the transport behaviour of VO₂ in a previous paper. This paper deals with the chemical transport of Magnéli phases V_nO_2n–1, and of V₆O₁₃, and of V₂O₅. Resulting from the composition of the gas phase over the solid phases in the presence of TeCl₄ the chronological sequence of the transported phases as well as the direction and rate of transport are calculated. These results are compared with experiments. All of the oxides are obtained without deposition of any other phases. Their phase boundaries are determined. The dependence on temperature is investigated for the upper phase boundary of V₂O₃.     

The effect of calcination temperature on the crystallinity of TiO2 nanopowders

TiO₂ nanopowders have been prepared using 0.1 M titanium tetraisopropoxide (TTIP) in varied pH aqueous solution containing TMC and NP-204 surfactants. Only the powder acquired from a solution of pH=2 has a regular particle size distribution. Anatase phase powders are obtained by calcination in nitrogen in the 250–500°C temperature range. When calcined at 400°C, the diameter of the nanoparticles is approximately 10 nm with a specific surface area of 106.9 m²/g. As the calcination temperature is increased, the particle size increases. Rutile phase powders are formed at calcination temperatures above 600°C.     

High temperature behavior of periodic mesoporous ethanesilica glasses prepared from a bridged silsesquioxane and a non-ionic triblock copolymer

Periodic mesoporous organosilicas (PMOs) with 2D-hexagonal structure have been prepared by the sol–gel route in acidic conditions from a bissilylated reactive as a silica-modified source, namely 1,2-bis(triethoxysilyl)ethane (BTEE), and Pluronic^® P123 non-ionic surfactant as a templating agent. Pyrolysis of the PMO material was performed under inert atmosphere up to 1000 °C in order to assess the possibility to transform the hybrid network into a porous SiOC glass network. The pyrolysis process has been mainly followed by ²⁹Si and ¹³C solid state NMR. Thermal degradation of the pore network was followed by XRD and TEM and measured by N₂ adsorption–desorption experiments. This study shows that despite the Si–C bonds cleavage occurring after 600 °C causes a phase separation into silica and free carbon, an ordered structure is retained up to 1000 °C with a remaining specific surface area.     

An X‐ray powder diffraction study of the microstructural evolution on heating 3:2 and 2:1 mullite single‐phase gels

Single‐phase gels with compositions 3Al₂O₃·2SiO₂ and 2Al₂O₃·SiO₂ were prepared by gelling mixtures of aluminium nitrate and tetraethylorthosilicate. Gels were fast heated at different temperatures between 900°C and 1600°C. The phase transformation and microstructural changes of both mullite precursor gels over the temperature range were followed by X‐ray powder diffraction (XRD), lattice parameter determination (LP), and scanning and transmission electron microscopies (SEM and TEM). The distribution of crystallite sizes and strains were determined by linewidth refinements of X‐ray diffraction patterns using the integral breadth method of Langford and the Warren‐Averbach analysis. XRD of both heated gels showed the formation of crystalline mullite single phase. Some amount of glassy phase coexisted with mullites at low temperatures, i. e. below 900°C. The compositional range of mullites formed on heating gels at temperatures between 900°C and 1600°C was dependent on the starting nominal composition of gels. SEM and TEM micrographs of both heated gels below 1200°C showed the formation of small, discrete, prismatic, well‐shaped nanocrystals in a very ordered arrangement. The size of these nanocrystals was dependant on the nominal composition of gels and increased on rising the heating temperature of gel precursors. The microstructural features obtained from linewidth refinement results of X‐ray diffraction patterns also allowed to suggest the formation of prismatic a little elongated nanocrystals at temperatures below 1200°C. Microstrain values were small and only displayed a relatively significant value for mullites processed at 900°C. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Phase separation in GeGeO2 glasses

De Neufville prepared homogeneous glasses ranging in composition from pure GeO₂ to GeO by quenching bulk samples from the melt and by vapor deposition. For compositions in the range of 10–20 mol % excess Ge dissolved in GeO₂, he found that phase separation into amorphous Ge rich and amorphous GeO₂ phases occurred. The results reported here on a 7.5 mol % excess Ge composition using differential scanning calorimetry have shown that a two-step phase separation mechanism is operative. A homogeneous GeGeO₂ glass phase separates at 450°C into amorphous GeO₂ and amorphous GeO. The GeO phase separates at 570°C into crystalline Ge and amorphous GeO₂. The heat measured at 570°C is equal to the sum of the heats of phase separation of GeO and crystallization of Ge. The amorphous GeO₂ crystallizes at 670°C with a heat of crystallization of 4.65 kcal/mol (± 0.5). Additional support for a two-step phase separation mechanism is provided by kinetic arguments based on the viscosity dependence on composition and on the structure of the amorphous GeO phase and its stability relative to the homogeneous GeGeO₂ glass.     

Spray pyrolysis deposition and characterization of highly (100) oriented magnesium oxide thin films

Transparent dielectric thin films of MgO has been deposited on quartz substrates at different temperatures between 400 and 600°C by a pneumatic spray pyrolysis technique using Mg(CH₃COO)₂·4H₂O as a single molecular precursor. The thermal behavior of the precursor magnesium acetate is described in the results of thermogravimetry analysis (TGA) and differential thermal analysis (DTA). The prepared films are reproducible, adherent to the substrate, pinhole free and uniform. Amongst the different spray process parameters, the substrate temperature effect has been optimized for obtaining single crystalline and transparent MgO thin films. The films crystallize in a cubic structure and X‐ray diffraction measurements have shown that the polycrystalline MgO films prepared at 500°C with (100) and (110) orientations are changed to (100) preferred orientation at 600°C. The MgO phase formation was also confirmed with the recorded Fourier Transform Infrared (FTIR) results. The films deposited at 600°C exhibited highest optical transmittivity (>80%) and the direct band gap energy was found to vary from 4.50 to 5.25 eV with a rise in substrate temperature from 500 to 600°C. The measured sheet resistance and the resistivity of the film prepared at 600°C were respectively 10¹³Ω/□ and 2.06x10⁷Ω cm. The surface morphology of the prepared MgO thin films was examined by atomic force microscopy. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)