Zirconia-Related Phases in the Zirconia/Titanium Diffusion Couple After Annealing at 1100°–1550°C

A diffusion couple of 3 mol% Y₂O₃–ZrO₂ and titanium was isothermally annealed in argon at temperatures between 1100° and 1550°C. The phases and microstructure in the ceramic side were investigated using scanning electron microscopy and transmission electron microscopy, both attached to an energy-dispersive spectrometer. After annealing at 1100°C/6 h, zirconia grains did not grow conspicuously and evolved only traces of oxygen, resulting in t -ZrO_{2− x} but not α-Zr. At temperatures above 1300°C, a significant amount of oxygen evolved from zirconia, reducing the O/Zr ratio, such that α-Zr was excluded from t -ZrO_{2− x} during cooling, yielding a higher O/Zr ratio (≈2). When held at 1550°C/6 h, zirconia grains grew rapidly. The α-Zr was segregated on grain boundaries during cooling by the exsolution of zirconium from ZrO_{2− x} , while twinned t '-ZrO_{2− x} or lenticular t -ZrO_{2− x} , which was embedded in ordered c- ZrO_{2− x} , was found. The ordered c -ZrO_{2− x} was identified by the     {113} superlattice reflections of its electron diffraction patterns.     

Oxidation of CVD Si3N4 at 1550° to 1650°C

A thermo gravimetric study of the oxidation behavior of chemically vapor-deposited amorphous and crystalline Si₃N₄ (CVD Si₃N₄) was made in dry oxygen (0.1 MPa) at 1550° to 1650°C. The specimens were prepared under various deposition conditions using a mixture of SiCl₄, NH₃, and H₂ gases. The crystalline CVD Si₃N₄ indicated a parabolic oxidation kinetics over the whole temperature range, whereas the amorphous CVD Si₃N₄ changed from a parabolic to a linear law with increased temperature. The oxidation mechanism is discussed in terms of the activation energy for the oxidation and the microstructure of the formed oxide films.     

Reaction Between Titanium and Zirconia Powders During Sintering at 1500°C

Zirconia–titanium (ZrO₂–Ti) composites have been considered potential thermal barrier graded materials for applications in the aerospace industry. Powder mixtures of Ti and 3 mol% Y₂O₃ partially stabilized ZrO₂ in various ratios were sintered at 1500°C for 1 h in argon. The microstructures of the as-sintered composites were characterized by X-ray diffraction and transmission electron microscopy/energy-dispersive spectroscopy. Ti reacted with and was mutually soluble in ZrO₂, resulting in the formation of α-Ti(O, Zr), Ti₂ZrO, and/or TiO. These oxygen-containing phases extracted oxygen ions from ZrO₂, whereby oxygen-deficient ZrO₂ was generated. For relatively small Ti/ZrO₂ ratios, specimens with ≤30 mol% Ti, TiO were formed as oxygen could be sufficiently supplied by excess ZrO₂. For the specimens with ≥50 mol% Ti, lamellar Ti₂ZrO was precipitated in α-Ti(Zr, O), with no TiO being found. Both m -ZrO_{2− x} and t -ZrO_{2− x} were found in specimens with ≤50 mol% Ti; however, only c -ZrO_{2− x} was formed in the specimen with 70 mol% Ti. As ZrO₂ was gradually dissolved into Ti, yttria was retained in ZrO₂ because of the very limited solubility of yttria in α-Ti(O, Zr) or TiO. The concentration of retained yttria and the degree of oxygen deficiency in ZrO₂ increased with the Ti content. The complete dissolution of ZrO₂ into Ti was followed by the precipitation of Y₂Ti₂O₇ in the specimen with 90 mol% Ti.     

Kinetics of the UO2-C-N2 Reaction at 1700°C

The mechanism of the reaction of UO₂ with carbon in the presence of N₂ at 1700°C and the rate of formation of the carbonitride product were determined. Uranium carbonitride forms at specific O₂ and N₂ chemical potentials by reactions such as (1) UO₂( s ) + 0.67HCN( g )→UO_1.33N_0.45( s ) + 0.67CO( g ) + 0.11N₂( g ) + 0.335H₂( g ) and (2) UO_1.33N_0.45( s ) + 1.58HCN( g )→UO_0.25N_0.75( s ) + 1.33CO( g ) + 0.79H₂( g ) + 0.64N₂( g ). At P _H2=2×10^-5 atm, HCN formed, permitting a gas-phase transport of reactions not observed in the UO₂-C reaction. Reaction (1) is completed in 0.01 to 0.1 of the time for complete conversion to carbonitride; reaction (2), which proceeds as soon as oxynitride is available, is controlled by solid-state diffusion across the carbonitride layers after they become continuous on the entire specimen. The reaction rates and product compositions depend on the P _N2 and P_CO in the system.     

Thermal Expansion of Polycrystalline Ti3SiC2 in the 25°–1400°C Temperature Range

We measured the volume thermal expansion of Ti₃SiC₂ from 25° to 1400°C using high-temperature X-ray diffraction using a resistive heated cell. A piece of molybdenum foil with a 250 μm hole contained the sample material (Ti₃SiC₂+Pt). Thermal expansion of the polycrystalline sample was measured under a constant argon flow to prevent oxidation of Ti₃SiC₂ and the molybdenum heater. From the lattice parameters of platinum (internal standard), we calculated the temperature by using thermal expansion data published in the literature. The molar volume change of Ti₃SiC₂ as a function of temperature in °C is given by: V _M (cm³/mol)=43.20 (2)+9.0 (5) × 10⁻⁴ T +1.8(4) × 10⁻⁷ T ². The temperature variation of the volumetric thermal expansion coefficient is given by: α_v (°C⁻¹)=2.095 (1) × 10⁻⁵+7.700 (1) × 10⁻⁹ T . Furthermore, the results indicate that the thermal expansion anisotropy of Ti₃SiC₂ is quite mild in accordance with previous work.     

Phase Relations and Lattice Constants in the MgO-Al2O3-Ga2O3 System at 1550°C

Phase relations and lattice constants in the MgO–Al₂O₃–Ga₂O₃ system at 1550°C have been determined experimentally. In a large part of this system, only a nonstoichiometric spinel is stable. Compositions as extreme as 12.5 mol% MgO–20.5 mol% Ga₂O₃–67 mol% Al₂O₃ for a homogeneous spinel are possible. In the bordering phase diagrams of MgO–Al₂O₃ and MgO–Ga₂O₃, the composition of the spinel is as high as 63 mol% Al₂O₃ or Ga₂O₃, respectively. The contributions of all simple ionic exchange reactions on the lattice constant of the spinel have been deduced from X-ray diffractometry data.     

Interdiffusion Between Ti3SiC2–Ti3GeC2 and Ti2AlC–Nb2AlC Diffusion Couples

In this work, we report on the interdiffusion of Ge and Si in Ti₃SiC₂ and Ti₃GeC₂, as well as that of Nb and Ti in Ti₂AlC and Nb₂AlC. The interdiffusion coefficient, D _int, measured by analyzing the diffusion profiles of Si and Ge obtained when Ti₃SiC₂–Ti₃GeC₂ diffusion couples are annealed in the 1473–1773 K temperature range at the Matano interface composition (≈Ti₃Ge_0.5Si_0.5C₂), was found to be given by
D _int increased with increasing Ge composition. At the highest temperatures, diffusion was halted after a short time, apparently by the formation of a diffusion barrier of TiC. Similarly, the interdiffusion of Ti and Nb in Ti₂AlC–Nb₂AlC couples was measured in the 1723–1873 K temperature range. The D _int for the Matano interface composition, viz. ≈(Ti_0.5,Nb_0.5)₂AlC, was found to be given by
At 1773 K, the diffusivity of the transition metal atoms was ≈7 times smaller than those of the Si and Ge atoms, suggesting that the former are better bound in the structure than the latter.     

The System MgO-MgCl2-H2O at 23°C

Solubilities of MgO in aqueous HC1 solutions at 23°±3°C were measured and combined with analyses of neat magnesium oxychloride cements, cured in sealed containers, to construct an equilibrium phase diagram for the system MgO-MgCl₂-H₂O. Specific gravities and acidities of solutions saturated with MgO and relative humidities of vapor phases over sealed samples were measured and combined with XRD data to define the compositions in equilibrium with two crystalline phases. Studies of relative reaction rates indicated that the 5–1–8 phase crystallizes more rapidly than the 3·1·8 phase and that cements near the 3·1·8 composition react rapidly with atmospheric CO₂ to form the chlorocarbonate phase.     

Kinetics of the Reaction of UC2 and Nitrogen from 1500° to 1700°C

The kinetics of the reaction of UC₂ spheres with nitrogen was studied from 1500° to 1700°C. A metallographic method was used to determine the time-dependent conversion of UC₂ to U(C,N) and free C. The conversion appeared to be controlled by the diffusion of solid carbon in solution to sites where it could precipitate as free carbon. These sites were the surface of the sphere and particles of free carbon that existed within the original UC₂. An increased distribution of these internal sites decreased the distance for carbon diffusion and resulted in an increased rate of reaction. The UC₂ appeared to undergo a very rapid initial reaction that resulted in the uptake of 1 to 5 at.% nitrogen in the UC₂ at these temperatures.     

Phase Relations in the System MgO-V2O3-VO2 at 1200°C

Phase relations in the quasi-ternary system MgO-V₂O₃-VO₂ at 1200°C were studied using the quenching technique under controlled O₂ atmospheres. A new phase of a type z VO _y Mg_{2− x} V_{1+ x} O₄ (0< x <1, y ≥1.5, z >0) was found with a compositional region along the MgV₂O₄-Mg₂VO₄ join. Equilibrium P _{O 2} observed for Mg_{2− x} V_{1+ x} O₄ is quite different from that for V _n O_{2 n -1} with an equal ratio of V³⁺/V⁴⁺, corresponding to the V³⁺ stabilities in two types of compounds. Thus, the phase relations in the ternary system were constructed on a conventional triaxial diagram as a function of P _O2.     

Phase Compatibilities in the System Y2O3-BaO-CuO at 950°C

We report the compatibility relationships between compounds, including the newly discovered superconducting Y₁Ba₂Cu₃O_x phase, in the Y₂O₃-BaO-CuO system at 950°C. In addition to the previously reported ternary compounds, there is a new compound with a composition Y_lBa₃Cu₂O_x. The new compound is a perovskite 'space group P4mm) with lattice parameters a =4.078 Å (0.4078 nm) and c =4.01 Å (0.401 nm). There are also at least two structurally distinguishable binary phases between barium oxide and the known BaCuO₂, but they appear to be hygroscopic and are beyond our current capabilities of analysis.     

Phase Equilibria in the System CaO-MgO-B2O3 at 900°C

Phase equilibria in the system CaO-MgO-B₂O₃ were investigated at 900°C using X-ray powder diffraction techniques. With the exception of MgO-B₂O₃, the binary phases reported previously were confirmed, but no ternary phases were found. Solid solution effects were investigated for the binary phases by comparison of patterns, whereas for CaO and MgO, accurate lattice parameters were compared. No solid solutions were detected. As a result, the isothermal equilibrium diagram at 900°C reduces to three phase triangles. X-ray powder diffraction data for the calcium berates are included.     

Activity–Composition Relations in FeCr2O4–FeAl2O4 and MnCr2O4–MnAl2O4 Solid Solutions at 1500° and 1600°C

Activity–composition relations of FeCr₂O₄–FeAl₂O₄ and MnCr₂O₄–MnAl₂O₄ solid solutions were derived from activity–composition relations of Cr₂O₃–Al₂O₃ solid solutions and directions of conjugation lines between coexisting spinel and sesquioxide phases in the systems FeO–Cr₂O₃–Al₂O₃ and MnO–Cr₂O₃–Al₂O₃. Moderate positive deviations from ideality were observed.     

Preparation of Ti3SiC2 by Electron-Beam-Ignited Solid-State Reaction

This paper describes a novel way to prepare the ternary phase Ti₃SiC₂ in a single-step procedure that we call electron-beam-ignited solid-state reaction (EBI-SSR). The preparation route is discussed by means of an isothermal section of the Ti-Si-C phase diagram. Properties such as the Vickers hardness and the electrical resistivity of the resulting samples are presented. Our property data compare well to those that have been published. The main advantages of this preparation method are the controllability of process parameters such as heating rates, temperatures, and times, as well as the short duration of the overall sample preparation. However, a disadvantage is the presence of second phases (typically in amounts of <8%) that must be reduced via further optimization of the process.     

Synthesis of Ti3SiC2 Powders: Reaction Mechanism

Titanium silicon carbide (Ti₃SiC₂) and Ti₃SiC₂-based composite powders were synthesized by isothermal treatment in an inert atmosphere as a function of initial compositions (mixtures). A high content of TiC was obtained in the final product when the initial mixtures contained free carbon. The use of TiC as a reagent was unsuccessful in obtaining Ti₃SiC₂. High Ti₃SiC₂ conversion was found for the initial mixtures containing SiC as the main source for silicon and carbon. An initial mixture with a large excess of silicon, 3Ti/1.5SiC/0.5C, was needed to obtain high-purity Ti₃SiC₂. A reaction mechanism, where Ti₃SiC₂ nucleates on Ti₅Si₃C crystals and grows by long-range diffusion of Ti and C, is proposed. The reaction mechanism was proposed to be based on silicon loss during the formation of Ti₃SiC₂.     

Subsolidus Phase Equilibria in the System Na2O-Bi2O3-TiO2 at 1000°C

Subsolidus phase relations in the system Na₂O-Bi₂O₃-TiO₂ at 1000°C were investigated by solid-state reaction techniques and X-ray diffraction methods. Five ternary compounds were observed in the system: Na_0.5Bi_4.5Ti₄O₁₅; Na_0.5Bi_0.5TiO₃; a cubic pyrochlore solid solution composed of xNa₂O.25Bi₂O₃.(75−;x) TiO₂ where x is 2.5 to 3.75; a new compound Na_0.5Bi_8.5Ti₇O₂₇ indexed with the orthorhombic cell of a = 5.45, b = 5.42, and c = 36.8 Å; and an unidentified phase with the probable composition NaBiTi₆O₁₄.     

Subsolidus Phase Relationships in the System Fe2O3–Al2O3–TiO2 between 1000° and 1300°C

Subsolidus phase equilibria in the system Fe₂O₃–Al₂O₃–TiO₂ were investigated between 1000° and 1300°C. Quenched samples were examined using powder X-ray diffraction and electron probe microanalytical methods. The main features of the phase relations were: (a) the presence of an M₃O₅ solid solution series between end members Fe₂TiO₅ and Al₂TiO₅, (b) a miscibility gap along the Fe₂O₃–Al₂O₃ binary, (c) an α-M₂O₃( ss ) ternary solid-solution region based on mutual solubility between Fe₂O₃, Al₂O₃, and TiO₂, and (d) an extensive three-phase region characterized by the assemblage M₃O₅+α-M₂O₃( ss ) + Cor( ss ). A comparison of results with previously established phase relations for the Fe₂O₃–Al₂O₃–TiO₂ system shows considerable discrepancy.