Microstructural Evolution of Titanium Carbide–Chromium Carbide (TiC–Cr3C2) Composites Produced via Combustion Synthesis

A microstructural analysis of compounds produced by combustion synthesis coupled with hot pressing, for reactions between titanium, chromium, and carbon, was conducted. The reactions were aimed to produce composites of Cr₃C₂ and TiC at three different volume fractions of each carbide (25/75, 50/50, and 75/25). Large amounts of chromium and carbon were found to be in solution in the B1 rock-salt structure of TiC. The materials with 25 and 50 vol% of Cr₃C₂ consisted of 100% (Ti,Cr)C_ss solid solution, while the composition with 75 vol% Cr₃C₂ was formed by Cr₃C₂+ (Ti,Cr)C_ss. Some precipitation of Cr₃C₂ was achieved by annealing, but a minimum of 20 wt% was always in solution. The 50 vol% Cr₃C₂–50 vol% TiC composition was the most affected by the heat treatments. Discontinuous and general precipitation were observed, depending on the annealing conditions. A TTT-type diagram was plotted for this material.     

Reaction Mechanism in Alumina/Chromia (Al2O3–Cr2O3) Solid Solutions Obtained by Coprecipitation

The aim of this work is to study the structural characteristics and properties of the solid solution (Al,Cr)₂O₃. XRD analysis, ²⁷Al MAS-NMR measurements, and microstructural characterization were used to determine the relationship between color and crystallochemical properties of the compounds formed. In particular, to determine more accurately the mechanism of solid solution formation above the miscibility gap of the system, the marker technique was used. In order to define the behavior of the system for temperatures below the miscibility gap at 1 bar pressure, the composition Al₂O₃:Cr₂O₃ 1:1 was studied with high-temperature XRD.     

Vibrational Spectroscopic Study of Structural Evolution in the Coprecipitated Precursors to La2Sn2O7 and La2Ti2O7

Structural evolution in the X-ray amorphous precursors to La₂Sn₂O₇ and La₂Ti₂O₇ is examined using IR and Raman spectroscopy. These precursors are prepared by rapid coprecipitation from mixed aqueous solutions of the corresponding metal chlorides. Rapid coprecipitation from an SnCl²⁻₆ and La³⁺-containing aqueous solution yields microcrystalline particles of SnO₂· n H₂O and La(OH)₃, which instantaneously interconnect to form an ultimate, complex colloid particle. The Ti(OH)²⁺₂ and La³⁺ in the other solution system coprecipitate into a different, complex colloid (an unidentified phase), which is definitely not a mixed dispersion of single-component colloids. A comparative examination of the vibrational spectra of the coprecipitates heated to various temperatures indicates that the SnO₂ and anatase phases develop in the respective precursors before crystallization of the desired double oxides. Crystallization itself can be attributed to a solid-state reaction among the various microcrystallites of each single-metal oxide in a gel particle of the precursor.     

Hydrothermal Synthesis of Nanosized CoAl2O4 on ZnAl2O4 Seed Crystallites

ZnAl₂O₄-seeded CoAl₂O₄, with a core-shell structure, has been prepared under hydrothermal conditions when the Co²⁺ salt solution is substituted by 10% Zn²⁺ as a precursor. The ZnAl₂O₄ seed is generated during the synthesis process. The seeding process can decrease the synthesis temperature from 245° to 230°C and the particle size from 67 to 20 nm. The process can economize the consumption of Co²⁺ and control the particle size effectively.     

Preparation of Porous Cr3C2 Grains with Cr2O3

Porous Cr₃C₂ grains (∼300 to 500 μm) with ∼10 wt% of Cr₂O₃ were prepared by heating a mixture of MgCr₂O₄ grains and graphite powder at 1450° to 1650°C for 2 h in an Al₂O₃ crucible covered by an Al₂O₃ lid with a hole in the center. The porous Cr₃C₂ grains exhibited a three-dimensional network skeleton structure. The mean open pore diameter and the specific surface area of the porous grains formed at 1600°C for 2 h were ∼3.5 (μm and ∼6.7 m²/g, respectively. The present work investigated the morphology and the formation conditions of the porous Cr₃C₂ grains, and this paper will discuss the formation mechanism of those grains in terms of chemical thermodynamics.     

Cation Self-Diffusion in Cr2O3

Self-diffusion of ⁵¹Cr was measured both parallel to and perpendicular to the c axis in single crystals of Cr₂O₃ as a function of oxygen partial pressure at 1490° and 1570°C. The oxygen-partial-pressure dependence of the diffusivity indicates that cation self-diffusion occurs by a vacancy mechanism. The values of the self diffusion coefficients determined in this experiment are about 10⁴ times smaller than those previously reported in this temperature range .     

Final Sintering of Cr2O3

The effect of oxygen activity on the sintering of high-purity Cr₂O₃ is shown. Theoretical density was approached at the equilibrium O₂ partial pressure needed to maintain the Cr₂O₃ phase ( P _o2=2×10⁻¹² atm). The presence of N₂ in the atmosphere during sintering did not prevent final sintering. The addition of 0.1 wt% MgO at this equilibrium pressure effectively controlled the grain growth and further increased the sintered density to very near the theoretical value. The solute segregation of MgO at the grain boundaries, followed by nucleation of spherulites of magnesium chromite spinel on the boundaries, accounted for the grain-growth control. It is speculated that these isolated spherulites locked the grain boundaries together, changing the fracture mode of the sintered oxide from inter-to intragranular and also that larger MgO additions produced a more continuous spinel formation at the boundaries, resulting in decreased sintered density. Weight loss, which was also monitored as a function of O₂ activity, correlated with the changing predominant volatile species in the Cr-O system.     

Aluminum Titanate Formation by Solid-State Reaction of Fine Al2O3 and TiO2 Powders

The formation of Al₂TiO₅ has been studied in equimolar Al₂O₃-TiO₂ powder mixtures of ∼1μm particle sizes and moderate purity (∼99.8 wt%) at temperatures around 1300°C, where the free energy of formation is very small. Micro-structural development and reaction kinetics indicate that different mechanisms operate depending on the advancement of the reaction. The rapid initial reaction stage is interpreted as the nucleation-growth of Al₂TiO₅ cells in a virtually non-reacting matrix. The final reaction stage corresponds to the slow diffusion-controlled elimination of Al₂O₃ and TiO₂ dispersoids trapped during the growth of the initial Al₂TiO₅ cells.     

Cation Tracer Diffusion in Cr2O3 and Cr2O3-0.09 wt% Y2O3

The cation diffusivities in the lattice and along dislocations and grain boundaries have been measured on sintered polycrysals of Cr₂O₃; and Cr₂Cr₂O₃-0.09 wt% Y₂O₃ at1100°C and at the pO₂ corresponding to that of Cr/Cr₂O₃ equilibrium at that temperature. Results for lattice and dislocation diffusivities in pure Cr₂O₃ are in good agreement with previous work. The present results indicate that yttrium additions have negligible effect on lattice and dislocation diffusion. However, grain-boundary diffusion in pure Cr₂O₃ is significantly slower than grain-boundary diffusion in Cr₂O₃-0.09 wt% Y₂O₃. The results are discussed in terms of their implications for the reactive-element effect in high-temperature oxidation of chromium-containing alloys.     

Aluminum Titanate Formation by Solid-State Reaction of Coarse Al2O3 and TiO2 Powders

Reaction kinetics in a coarse equimolar powder mixture were slow enough to allow for the different stages to be identified, notably in the lower and higher temperature ranges, respectively. In the former ( T ≤ 1600 K), Al₂TiO₅ nucleation was hindered by the strain energy contribution to the overall driving force. The setting up of metastable layer sequences Al₂TiO₅/TiO₂/Al₂O₃ was found to occur generally during subsequent growth. The high Al mobility in the TiO₂ provided a rapid aluminum transport from the metastable Al₂O₃/TiO₂ interface to the TiO₂/Al₂TiO₅ front. At temperatures above ∼1700 K the Al₂O₃/TiO₂ interface was very rapidly sealed off by Al₂TiO₅ formation. Reactant transport across the Al₂TiO₅ was slow because of the low mobilities in the product phase. Therefore, much lower product growth velocities were observed at higher temperatures than at lower temperatures.     

Formation of Nanometric TiB2 from TiO2

Titanium diboride can be produced by ball-milling a mixture of TiO₂, B₂O₃, and Mg metal for between 10 and 15 h. The reaction was found to be completed during the milling with no evidence of residual Mg. The unwanted phase, MgO, was readily removed by leaching in acid. The leached powder obtained after 15 h milling had a particle size of <200 nm and was highly faceted. The particle size decreased to ∼50 nm after 100 h milling and seemed to be relatively monodisperse. Scherrer calculation of the crystallite size showed that the product particles were probably single crystal.     

Mechanical-Alloying-Assisted Synthesis of Ti3SiC2 Powder

Mechanical alloying (MA) has been used to synthesize Ti₃SiC₂ powder from the elemental Ti, Si, and C powders. The MA formation conditions of Ti₃SiC₂ were strongly affected by the ball size for the conditions used. MA using large balls (20.6 mm in diameter) enhanced the formation of Ti₃SiC₂, probably via an MA-triggered combustion reaction, but the Ti₃SiC₂ phase was not synthesized only by the MA process using small balls (12.7 mm in diameter). Fine powders containing 95.8 vol% Ti₃SiC₂ can be obtained by annealing the mechanically alloyed powder at relatively low temperatures.     

Thermodynamic Modeling of the Isomorphous Phase Diagrams in the Al2O3–Cr2O3 and V2O3–Cr2O3 Systems

The phase diagrams in the Al₂O₃–Cr₂O₃ and V₂O₃–Cr₂O₃ systems have been assessed by thermodynamic modeling with existing data from the literature. While the regular and subregular solution models were used in the Al₂O₃–Cr₂O₃ system to represent the Gibbs free energies of the liquid and solid phases, respectively, the regular solution model was applied to both phases in the V₂O₃–Cr₂O₃ system. By using the liquidus, solidus, and/or miscibility gap data, the interaction parameters of the liquid and solid phases were optimized through a multiple linear regression method. The phase diagrams calculated from these models are in good agreement with experimental data. Also, the solid miscibility gap and chemical spinodal in the V₂O₃–Cr₂O₃ system were estimated.     

Densification of Cr2O3-ZrO2 Ceramics by Sintering

Cr₂O₃ and ZrO₂ were mixed in various ratios and pressed to form compacts, which were then sintered in carbon powder. Compacts with >30 wt% Cr₂O₃ were sintered to densities >98% of true density at 1500°C. This method of sintering in carbon powder can be used to prepare very dense Cr₂O₃-ZrO₂ ceramics at a relatively low temperature, (∼1500°C) without additives.     

Oxidation/Vaporization Kinetics of Cr2O3

The weight loss of Cr₂O₃ in oxidizing environments (Po₂= 1 to 10⁻³ atm) at 1200°C was measured. Both hot-pressed and sintered Cr₂O₃ pellets were investigated in O₂/Ar gas mixtures, and the dependence of the weight loss on the O₂ partial pressure, the gas flow rate, and the total pressure was determined independently. The experimentally determined O₂ partial pressure dependence (rate ∝ PO₂^3/4) corresponds to that expected for the reaction Cr₂O₃(s)+3/2O₂⇌2CrO₃(g). The flow rate and total pressure dependencies show that mass transport through a gaseous boundary layer is the rate-controlling step in the oxidation/vaporization of Cr₂O₃. Evaporation coefficients for the loss of CrO₃(g) under the experimental conditions were <0.01.     

Novel Synthesis of SrBi2Nb2O9 Powders From Hydroxide Precursors

Simple hydroxide precursors were used for the first time for the synthesis of a typical Aurivillius compound (SrBi₂Nb₂O₉ (SBN)) at a low temperature. This method is very advantageous because it circumvents the use of SrCO₃ in the case of conventional ceramics as well in the coprecipitation methods, thereby lowering the formation of the product phase. Commercially purchased strontium hydroxide is mixed thoroughly with freshly precipitated bismuth and niobium hydroxides in a stoichiometric ratio and heated at different temperatures ranging from 100°C to 750°C for 12 h. The sequence of the reaction and evolution of the product phase was monitored by X-ray diffraction (XRD) studies by recording the XRD for samples calcined at different temperatures. The incipient SBN phase begins to form at temperatures as low as 400°C, and phase formation was complete only at 650°C as revealed by the XRD observations. The differential thermal/thermogravimetric analyses) also corroborate this result. The morphology and average particle size of these powders were investigated by transmission electron microscopy studies.     

Sublimation of Cr2O3 at High Temperatures

The sublimation of chromic oxide, Cr₂O₃, has been observed in vacuum by the Langmuir technique using induction and solar heating. Extensive sublimation did not yield any new phases on the basis of X-ray powder studies, and condensates of Cr₂O₃ were always obtained. Flash vaporization and flow experiments in CO or O₂ atmospheres and in vacuum indicated no appreciable differences in rates of sublimation. Weight-loss experiments showed that the rate of sublimation was slightly higher than predicted for decomposition to the elements and suggested that small amounts of complex molecules, e.g. CrO and CrO₂, were also present in the equilibrium vapor.