Experimental Study and Thermodynamic Re-optimization of the FeO-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> System

Phase equilibria and thermodynamic data in the FeO-Fe₂O₃-SiO₂ system were critically reviewed. New experiments were undertaken to resolve discrepancies found in previous data. The liquid oxide/slag phase was described using the modified quasichemical model. New optimized parameters of the thermodynamic models for the Gibbs energies of slag and other phases in the selected system were obtained. The new parameters reproduce all available phase equilibria and thermodynamic data within the experimental error limits from 298 K (25 °C) to above the liquidus temperatures at all compositions and oxygen partial pressures from metal saturation to 1 atm of O₂. This study was carried out as part of the development of a self-consistent thermodynamic database for the Al-Ca-Cu-Fe-Mg-Si-O-S multi-component system.     

Effect of hydrogen intercalation on the critical parameters of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>

The effect of hydrogenation at T = 150 and 200°C on the electrophysical properties of highly textured YBa₂Cu₃O _y ceramics with different oxygen content has been investigated. Like hydration, hydrogenation results in the deterioration of these properties. However, in samples with high oxygen contents (y = 6.96) hydrogenated at T = 150°C after oxidation (400°C) or recovery annealing with subsequent oxidation, the critical current density and first critical field increase compared to the initial state. The improvement of the properties occurs mainly in a magnetic field applied perpendicularly to the c axis. As after hydration, this is connected with the formation of planar defects in the course of low-temperature annealing. In addition, in the process of the hydrogenation, the partial reduction of copper occurs with the formation of microinclusions of Cu₂O and other products of chemical decomposition, which are extra pinning centers of magnetic vortices.     

High-Temperature Oxidation of Nickel-Based Cermet Coatings Containing WC and Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Nanosized Particles

This paper investigates the high-temperature oxidation of cermet coatings composed of two types of nanosized particles (WC and a mixture of WC and Al₂O₃) incorporated in nickel and produced by co-electrodeposition. For this purpose, high-temperature oxidation tests were conducted at three temperatures (500, 600, and 700 °C) in dry air with 6 time intervals up to 96 h and mass changes at each specific time interval was measured. Statistical techniques were used to calculate the oxidation rate constants (k) and growth-rate time constants (a) for all coatings. The confidence intervals associated with tests were also calculated. The results showed linear to sub-parabolic oxidation rates for coatings composed of only WC particles and sub-liner to liner oxidation rates for coating with both WC and Al₂O₃ particles. The reduction in oxidation rates for coatings with both WC and Al₂O₃ particles were correlated to the addition of Al₂O₃ particles in the matrix.     

Oxidation Kinetics of UZr<Subscript>2.3</Subscript> and U<Subscript>2</Subscript>Ti Alloys in Dry Air

The isothermal oxidation behavior of UZr_2.3 and U₂Ti alloys in dry air was studied by thermogravimetric technique in the temperature ranges of 773–848 and 548–623 K, respectively. The oxidation products were found to be U₃O₈ and ZrO₂ for UZr_2.3 and U₃O₈ and TiO₂ for U₂Ti by X-ray diffraction analysis. The oxidation kinetics were found to best fit into linear rate law for both the alloys in the temperature range of investigation and the lowest value of α (0.11 for UZr_2.3 and 0.12 for U₂Ti), which corresponds to the fraction of completed reaction. The linear rate constants (k) were evaluated from the oxidation data. The activation energies of oxidation reactions were calculated using the Arrhenius equation and found to be 161 kJ mol^?1 for UZr_2.3 and 88 kJ mol^?1 for U₂Ti.     

Effect of water intercalation on the structure and electrophysical properties of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6.9</Subscript>

The influence of water vapors and plastic deformation on the structure and electrophysical properties of YBa₂Cu₃O_6.9 (123) has been studied. It has been established that, at T = 200°C, the introduction of water into the structure of YBa₂Cu₃O_6.9 leads to its transition into a defect tetragonal phase of the 124 type as a result of the formation of planar stacking faults. After annealing at T = 930°C, these defects are partially retained and are efficient centers of pinning in the magnetic fields applied perpendicularly to the c axis, which makes it possible to increase (by an order of magnitude) the critical current density in the high-textured ceramics at 77 K in the external magnetic field of 5–10 T. The plastic deformation of the hydrated ceramics favors the reverse transition of the arising 124 phase to the 123 phase at T = 930°C and is accompanied by a recrystallization of the material, which leads to the appearance of a texture and an increase the critical current density.     

Resistance of High-Nickel,Heat-Resisting Alloys to Air and to Supercritical CO<Subscript>2</Subscript> at High Temperatures

The reduction behaviour of wustite-type iron oxide scale on a low-carbon, low-silicon steel by dissolved carbon in the steel at 650–900 °C under pure nitrogen was studied. It was found that dissoved carbon in the steel examined was able to react with the wustite scale on the surface, leading to reduction of this scale. It was also found that the scale reduction rate was the most rapid within 750–800 °C, followed by that at 700 °C and then at 850 °C, whereas the rates were essentially zero at 650 and 900 °C. Decarburization occurred to the steel as a result of scale reduction, and the degree of decarburization at 750–800 °C was also the most severe. The rate of scale–carbon reaction was primarily controlled by carbon diffusion through the decarburization layer as the calculated carbon permeability, defined as the product of carbon diffusivity and the carbon concentration difference across the decarburization layer, also reached its maximum within 750–800 °C. Scale reduction led to the formation of pores at the scale–steel interface as a result of volume shrinkage when wustite was reduced to iron, but the porosity volume was smaller than calculated at 800–850 °C, which could have an inhibiting effect on the scale–carbon reaction. The calculated volume of CO + CO₂ gases generated as a result of scale–carbon reactions was about 100 times the calculated porosity volume. It was believed that the wustite scale was permeable to CO and/or CO₂, allowing the much larger volume of CO and CO₂ gases to escape through the scale layer.     

Thermal Spray Deposition,Phase Stability and Mechanical Properties of La<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript>/LaAlO<Subscript>3</Subscript> Coatings

This paper deals with the deposition of La₂Zr₂O₇ (LZO) and LaAlO₃ (LAO) mixtures by air plasma spray (APS). The raw material for thermal spray, single phase LZO and LAO in a 70:30 mol.% ratio mixture was prepared from commercial metallic oxides by high-energy ball milling (HEBM) and high-temperature solid-state reaction. The HEBM synthesis route, followed by a spray-drying process, successfully produced spherical agglomerates with adequate size distribution and powder-flow properties for feeding an APS system. The as-sprayed coating consisted mainly of a crystalline LZO matrix and partially crystalline LAO, which resulted from the high cooling rate experienced by the molten particles as they impact the substrate. The coatings were annealed at 1100 °C to promote recrystallization of the LAO phase. The reduced elastic modulus and hardness, measured by nanoindentation, increased from 124.1 to 174.7 GPa and from 11.3 to 14.4 GPa, respectively, after the annealing treatment. These values are higher than those reported for YSZ coatings; however, the fracture toughness (K _IC) of the annealed coating was only 1.04 MPa m^0.5.     

Viscosity and Structure of CaO-SiO<Subscript>2</Subscript>-P<Subscript>2</Subscript>O<Subscript>5</Subscript>-Fe<Subscript>t</Subscript>O System with Varying P<Subscript>2</Subscript>O<Subscript>5</Subscript> and FeO Content

A rotary viscosimeter and Raman spectrum were employed to measure the viscosity and structural information of the CaO-SiO₂-P₂O₅-Fe_tO system at 1673 K. The experimental data have been compared with the calculated results using different viscosity models. It shows that the National Physical Laboratory (NPL) and Pal models fit the CaO-SiO₂-P₂O₅-FeO_t system better. With the P₂O₅ content increasing from 5% to 14%, the viscosity increases from 0.12 Pa s to 0.27 Pa s. With the FeO content increasing from 30% to 40%, the viscosity decreases from 0.21 Pa s to 0.12 Pa s. Increasing FeO content makes the complicated molten melts become simple, and increasing P₂O₅ content will complicate the molten melts. The linear relation between viscosity and structure parameter Q(Si + P) was obtained by regression analysis. The calculated viscosity by using the optimized NPL and Pal model are almost identical with the fitted values.     

The Effects of KCl,NaCl and K<Subscript>2</Subscript>CO<Subscript>3</Subscript> on the High-Temperature Oxidation Onset of Sanicro 28 Steel

The present study investigates the early stages in the oxidation process of Sanicro 28 (Fe31Cr27Ni) stainless steel when exposed to an alkali salt (KCl, NaCl or K₂CO₃) for 2 h at 450 and 535 °C. After the exposure, the oxidized samples were analyzed with a combinatory method (CA, XPS and SEM–EDX). It was found that all three salts were corrosive, and the overall oxidation reaction rate was much higher at 535 °C than at 450 °C. There were clear differences in terms of the impact of cations (Na⁺, K⁺) and anions (Cl^?, CO₃ ^2?) on the initial corrosion process at both temperatures. When focusing on the cations, the presence of potassium ions resulted in a higher rate of chromate formation than in the presence of sodium ions. When studying the effect of anions, the oxidation of iron and chromium occurred at higher rates in the presence of both chloride salts than in the presence of the carbonate salt, and chloride salts seemed to possess higher diffusion rate in the gas phase and along the surface than carbonate salts. Moreover, at the higher temperature of 535 °C, the formed chromate reacted further to chromium oxide, and an ongoing oxidation process of iron and chromium was identified with a significantly higher reaction rate than at 450 °C.     

Thermoelectric properties of n-type Bi<Subscript>2</Subscript>Te<Subscript>2.7</Subscript>Se<Subscript>0.3</Subscript> compounds prepared by spark plasma sintering

In this study, the thermoelectric properties of 0.1 wt.% Cdl₂-doped n-type Bi₂Te_2.7Sb_0.3 compounds, fabrieated by SPS in a temperature range of 250°C to 350°C, were characterized. The density of the compounds was increased to approximately 100% of the theoretical density by carrying out consolidation at 350°C. The Seebeck coefficient, thermal conductivity, and electrical resistivity were dependent on a hydrogen reduction process and the sintering temperature. The Seebeck coefficient and the electrical resistivity increased with the reduction process. Also, electrical resistivity decreased and thermal conductivity increased with sintering temperature. The results suggest that carrier density and mobility vary according to the reduction process and sintering temperature. The highest figure of merit, 1.93×10⁻³ K⁻¹, was obtained for the compound consolidated at 350°C for 2 min.     

Activities of Fe,FeO, Fe<Subscript>2</Subscript>0<Subscript>3</Subscript>, and CaO in Simple Slags

The data previously reported for the quantity j = Fe⁺⁺⁺/(Fe⁺⁺+Fe⁺⁺⁺) as a function of oxygen pressure at 1550°C have been used to compute the activities of Fe, FeO, Fe₂O₃, and CaO in slags of the ternary system. Activities of the first three have been obtained also for two quasi-ternaries involving fixed CaO:SiO₂ ratios.     

Dual-Layer Oxidation-Protective Plasma-Sprayed SiC-ZrB<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Carbon Nanotube Coating on Graphite

Graphite is used in high-temperature gas-cooled reactors because of its outstanding irradiation performance and corrosion resistance. To restrict its high-temperature (>873 K) oxidation, atmospheric-plasma-sprayed SiC-ZrB₂-Al₂O₃-carbon nanotube (CNT) dual-layer coating was deposited on graphite substrate in this work. The effect of each layer was isolated by processing each component of the coating via spark plasma sintering followed by isothermal kinetic studies. Based on isothermal analysis and the presence of high residual thermal stress in the oxide scale, degradation appeared to be more severe in composites reinforced with CNTs. To avoid the complexity of analysis of composites, the high-temperature activation energy for oxidation was calculated for the single-phase materials only, yielding values of 11.8, 20.5, 43.5, and 4.5 kJ/mol for graphite, SiC, ZrB₂, and CNT, respectively, with increased thermal stability for ZrB₂ and SiC. These results were then used to evaluate the oxidation rate for the composites analytically. This study has broad implications for wider use of dual-layer (SiC-ZrB₂/Al₂O₃) coatings for protecting graphite crucibles even at temperatures above 1073 K.     

Effects of defects generated in ALD TiO<Subscript>2</Subscript> films on electrical properties and interfacial reaction in TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript>/Si system upon annealing in vacuum

Thin TiO₂ layers grown at 130°C on SiO₂-coated Si substrates by atomic layer deposition (ALD) using TTIP and H₂O as precursors were annealed, and the effects of the annealing temperature on the resulting electrical properties of TiO₂ and the interface properties between a Pt electrode and TiO₂ were examined using transmission line model (TLM) structures. The as-deposited TiO₂ thin film had an amorphous structure with OH groups and a high resistivity of 6×10³Ω-cm. Vacuum annealing at 700 °C transformed the amorphous film into an anatase structure and reduced its resistivity to 0.04Ω-cm. In addition, the vacuum-annealing of the TiO₂/SiO₂ structure at 700°C produced free silicon at the TiO₂-SiO₂ interface as a result of the reaction between the Ti interstitials and SiO₂. The SiO₂ formed on the TiO₂ surface caused a Schottky contact, which was characterized by the TLM method. The use of the TLM method enabled the accurate measurement of the resistivity of the vacuum-annealed TiO₂ films and the characterization of the Schottky contacts of the metal electrode to the TiO₂.     

Identification of Mg<Subscript>2</Subscript>Cu particles in Cu-alloyed austempered ductile iron

In the present work, the Mg₂Cu precipitates in copper-alloyed austempered ductile iron (ADI) were identified by analyzing techniques such as TEM and SEM with EDS. It was revealed that, in castings made of ADI-containing copper, highly dispersed particles of Mg₂Cu are formed, whose size does not exceed <1 μm. The research work was carried out on ductile iron that was austenitized at 900 °C, followed by austempering at 380 °C. The microstructure was investigated using various techniques, including optical microscopy, XRD, SEM, and TEM. In addition to this, the exhibited impact properties of castings with Cu, Ni, and Cu+Ni were also determined. This study casts a new light on the formation of the structure of Cu-alloyed ADI. The highly-dispersive and brittle Mg₂Cu particles that are located in the vicinity of the graphite nodules have a negative effect on the impact properties of ADI. It has also been shown that impact strength decreases from levels of 160-180 J (for copper-free ADI) to 90-120 J (for copper-and copper-nickel-alloyed ADI).     

Microstructure and Thermal Properties of Atmospheric Plasma-Sprayed Yb<Subscript>2</Subscript>Si<Subscript>2</Subscript>O<Subscript>7</Subscript> Coating

In the present work, Yb₂Si₂O₇ powder was synthesized by solid-state reaction using Yb₂O₃ and SiO₂ powders as starting materials. Atmospheric plasma spray technique was applied to fabricate Yb₂Si₂O₇ coating. The phase composition and microstructure of the coating were characterized. The density, open porosity and Vickers hardness of the coating were investigated. Its thermal stability was evaluated by thermogravimetry and differential thermal analysis (TG-DTA). The thermal diffusivity and thermal conductivity of the coating were measured. The results showed that the as-sprayed coating was mainly composed of crystalline Yb₂Si₂O₇ with amorphous phase. The coating had a dense structure containing defects, such as pores, interfaces and microcracks. The TG-DTA results showed that there was almost no mass change from room temperature to 1200 °C, while a sharp exothermic peak appeared at around 1038 °C in DTA curve, which indicated that the amorphous phase crystallized. The thermal conductivity of the coating decreased with rise in temperature up to 600 °C and then followed by an increase at higher temperatures. The minimum value of the thermal conductivity of the Yb₂Si₂O₇ coating was about 0.68 W/(m K).     

Solubility of boron in Fe<Subscript>3</Subscript>C and variation of saturation magnetization,curie temperature,and lattice parameter of Fe<Subscript>3</Subscript>(C,B) with composition

Using quantitative metallography, X-ray lattice parameter, and Curie temperature measurements, it was found that at 1000°C 80 pct of the carbon in Fe₃C could be replaced by boron. Based on magnetic data, it is proposed that an electron transfer occurs between the interstitial atoms and the 3d shell of iron. A study of solubility data of interstitial compounds of iron indicates that the solid solubility is not only dependent upon a similarity of atomic size of the interstitial elements, but is determined to a large extent by the influence of the solute atoms on the electron density of the 3d shell of iron.     

Producing titanium by reducing TiCl<Subscript>2</Subscript>-MgCl<Subscript>2</Subscript> mixed salt with magnesium in the molten state

In the Kroll process for titanium sponge metal production, TiCl₄ gas is introduced and reacted with molten magnesium metal via a gas-liquid reduction reaction. The magnesium reduction reaction of the mixed salt of TiCl₂-MgCl₂ via a liquid-liquid reaction has been investigated and the results are reported in this article. First, the molten mixed salt was synthesized through chlorination reaction of solid titanium sponge placed in molten MgCl₂ salt, while TiCl₄ gas was bubbled at around 1,173K. Then, the TiCl₂-MgCl₂ was reacted with molten magnesium at similar temperatures. This proposed magnesium reduction reaction of the TiCl₂-MgCl₂ in the molten state may be more efficient, easier to control, and suitable for realizing continuous titanium production. For more information, contact Akio Fuwa, Waseda University, Department of Materials Science and Engineering, Faculty of Science and Engineering, Okubo 3-4-1, Shinjuku-ku, Tokyo, Japan 169-8555; +81-3-5286-3313; fax +81-3-5286-3488; e-mail akiofuwa@waseda.jp.     

Preparation and characterization of nanostructured Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> and Sn<Subscript>0.5</Subscript>-Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript>

Nanostructured Bi₂Se₃ and Sn_0.5-Bi₂Se₃ were successfully synthesized by hydrothermal coreduction from SnCl₂·H₂O and the oxides of Bi and Se. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and field emission scanning electron microscope (FESEM). Bi₂Se₃ powders obtained at 180°C and 150°C consist of hexagonal flakes of 50–150 nm in side length and nanorods of 30–100 nm in diameter and more than 1 μm in length. The product obtained at 120°C is composed of thin irregular nanosheets with a size of 100–200 nm and several nanometers in thickness. The major phase of Sn_0.5-Bi₂Se₃ synthesized at 180°C is similar to that of Bi₂Se₃. Sn_0.5-Bi₂Se₃ powders are primarily nanorod structures, but small amount of powders demonstrate irregular morphologies.     

Elevated Temperature Solid Particle Erosion Performance of Plasma-Sprayed Co-based Composite Coatings with Additions of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and CeO<Subscript>2</Subscript>

In this paper, investigation into solid particle erosion behavior of atmospheric plasma-sprayed composite coating of CoCrAlY reinforced with Al₂O₃ and CeO₂ oxides on Superni 76 at elevated temperature of 600 °C is presented. Alumina particles are used as erodent at two impact angles of 30° and 90°. The microstructure, porosity, hardness, toughness and adhesion properties of the as-sprayed coatings are studied. The effects of temperature and phase transformation in the coatings during erosion process are analyzed using XRD and EDS techniques. Optical profilometer is used for accurate elucidation of erosion volume loss. CoCrAlY/CeO₂ coating showed better erosion resistance with a volume loss of about 50% of what was observed in case of CoCrAlY/Al₂O₃/YSZ coating. Lower erosion loss is observed at 90° as compared to 30° impact angle. The erosion mechanism evaluated using SEM micrograph revealed that the coatings experienced ductile fracture exhibiting severe deformation with unusual oxide cracks. Reinforced metal oxides provide shielding effect for erodent impact, enabling better erosion resistance. The oxidation of the coating due to high-temperature exposure reforms erosion process into oxidation-modified erosion process.     

Synthetically Controlled,Carbon-Coated Co<Subscript>2</Subscript>SnO<Subscript>4</Subscript>/SnO<Subscript>2</Subscript> Composite Anode for Lithium-ion Batteries

The inherent drawbacks of Co₂SnO₄ in demonstrating the closer-to-theoretical capacity value behavior and the inadmissible volume-expansion-related capacity fade behavior have been surpassed by choosing a tailor-made material composition of Co₂SnO₄/SnO₂, prepared at two different temperatures such as 400°C and 600°C to obtain residual carbon-containing and carbon-free compositions, respectively. Among the products, carbon-coated Co₂SnO₄/SnO₂ composite exhibits better electrochemical performance compared with that of the carbon-free product mainly because of the beneficial effect of carbon in accommodating the volume-expansion-related issues arising from the alloying/de-alloying mechanism. A combination of conversion reaction and alloying/de-alloying mechanism is found to play a vital role in exhibiting closer-to-theoretical capacity values. In other words, an appreciable specific capacity value of 834 mAh g^?1 has been exhibited by Co₂SnO₄/SnO₂ anode containing carbon coating, thus, demonstrating the possibility to improve the electrochemical performance of the title anode through carbon coating, which is realized as a result of the addition of carefully manipulated synthesis conditions.