Oxidation of HIPed TiC Ceramics in Dry O2, Wet O2, and H2O Atmospheres

Isothermal oxidation of dense TiC ceramics, fabricated by hot-isostatic pressing at 1630°C and 195 MPa, was performed in Ar/O₂ (dry oxidation), Ar/O₂/H₂O (wet oxidation), and Ar/H₂O (H₂O oxidation) at 900°–1200°C. The weight change measurements of the TiC specimen showed that the dry, wet, and H₂O oxidation at 850°–1000°C is represented by a one-dimensional parabolic rate equation, while the oxidation in the three atmospheres at 1100° and 1200°C proceeds linearly. Cross-sectional observation showed that the dry oxidation produces a lamellar TiO₂ scale consisting of many thin layers, about 5 μm thick, containing many pores and large cracks, while H₂O-containing oxidation decreases pores in number and diminishes cracks in scales. Gas evolution of CO₂ and H₂ with weight change measurement was simultaneously followed by heating the TiC to 1400°C in the three atmospheres. Cracking in the TiO₂ scale accompanied CO₂ evolution, and the H₂O-containing oxidation produced a small amount of H₂. A piece of single crystal TiC was oxidized in ¹⁶O₂/H₂¹⁸O to reveal the contribution of O from H₂O to the oxidation of TiC by secondary ion mass spectrometry.     

Equilibrium in the System CaSO4.2H2O-CaSO4.½H2O-H2O

Using a simple geometric model, the conditions of equilibrium for topotactical dehydration of gypsum to the hemihydrate in liquid H₂O were determined. The calculated equilibrium temperature agrees with the experimentally determined temperature at which the rate of topotactical dehydration of gypsum single crystals approaches zero.     

Studies in Lithium Oxide Systems: XIII, Li,O.Al2O3.2SiO2-Li2O.Al2O3.2GeO2

Complete solid solubility was demonstrated to occur between LiAlGeO₄ and the low temperature form of Li AlSiO₂ (a-eucryptite). Hydrother-mal preparation was necessary for the silicate-rich compositions. Under atmospheric pressure, about 65 mole % LiAlGeO₄ entered the β-eucryβ-tite phase at 1150°C, but solid solutions containing more than 25 mole % LiAlGeO4 exsolved if held at lower temperatures. Directional thermal expansion data were obtained by X-ray diffraction methods on both α- and β-eucryptite and their solid solutions. Substitution of Ge⁴⁺ for Si⁴⁺ produced no significant difference in the thermal expansion coefficients in the α and β phases. An increase in the lattice parameters in the a and c directions took place as expected when Ge⁴⁺ (0.53 A) was substituted for Si⁴⁺ (0.39 A).     

Kinetics of CeO2 Surface Area Reduction in a Mixture of HCI, H2O, and O2

Surface area reduction of a cerium dioxide powder is studied at 900 K in a HCI, H₂O, and O₂ atmosphere. The rate of surface area decrease is determined as a function of the surface chloride content and of the partial pressure of hydrogen chloride. It is shown that particle growth occurs due to the surface diffusion of cerium and hydroxyl ions, which results from hydrogen chloride adsorption. Adsorbed chloride ions react to give gaseous chlorine. The rate-determining step of the process of initial coarsening is hydrogen chloride fixation at the surface of cerium dioxide particles.     

Strength of Hot Isostatically Pressed Si3N4 After Heat Treatment in Ar-O2 and H2-H2O

The effects of heat treatment in Ar-O₂ and H₂-H₂O atmospheres on the flexural strength of hot isostatically pressed Si₃N₄ were investigated. Increases in room-temperature strength, to values significantly above that of the aspolished material, were observed when the Si₃N₄ was exposed at 1400°C to (1) H₂ with water vapor pressure ( P _H2O) greater than 1 × 10⁻⁴ MPa or (2) Ar with oxygen partial pressure ( P _O2) of between 7 × 10⁻⁶ and 1.5 × 10⁻⁵ MPa. However, the strength of the material was degraded when the P _H2O in H₂ was lower than 1 × 10⁻⁴ MPa, and essentially unaffected when the P _O2 in Ar was higher than 1.5 × 10⁻⁵ MPa. We suggest that the observed strength increases are the result of strength-limiting surface flaws being healed by a Y₂Si₂O₇ layer formed during exposure.     

High-Pressure Synthesis of Perovskites Pb(Li1/4Nb3/4)O3 and Pb(Li1/4Ta3/4)O3

Complex perovskite-type compounds with the general formula Pb(B⁺_1/4B⁵⁺_3/4)O₃, where B⁺= Li⁺ and B⁵⁺= Nb⁵⁺ or Ta⁵⁺, were synthesized using a high-pressure technique and studied by X-ray powder diffraction. The X-ray patterns were indexed on the basis of a cubic cell with a ₀= 4.071 Å for Pb(Li_1/4 Nb_3/4)O₃ and a ₀= 4.052 Å for Pb(Li_1/4Ta_3/4)O₃. Electrical properties of the new perovskites were also studied.     

Cement Formulations in the Calcium Phosphate H2O–H3PO4–H4P2O7 System

Despite numerous reports of calcium phosphate cement materials, a calcium cement that sets to form a matrix consisting of a pyrophosphate phase has not been reported. The formulation of such a material from the mixture of α-tricalcium phosphate (TCP), β-TCP, or tetracalcium phosphate with a solution containing pyro- and orthophosphoric acid is reported in this study. The effects of liquid and solid compositions on the setting times, compressive strengths and phase compositions of the resultant cements were investigated. It was found that cements could be produced that set to form up to 28 wt% dicalcium pyrophosphate, which appeared by comparison with Rietveld refinement and chemical methods to be entirely amorphous in nature. The solubilities of the different solid components were shown to have a marked effect on the composition of the cements. The strongest cement formulations exhibited compressive strengths comparable with those previously reported in the literature for brushite cements and set within clinically relevant time scales. This class of cement would appear to demonstrate potential as a bone replacement material.     

Phase Equilibria in the Systems NiO-Cr2,O3,-O2, MgO-Cr2O3−O2, and CdO-Cr2,O3,-O2, at High Oxygen Pressures

Phase equilibria were determined for the systems NiO-Cr₂O₃−O₂, MgO-Cr₂O₃,-O₂, and CdO-Cr₂O₃−O₂ from 450° to above 850° C and at oxygen pressures of from 2 to 3500 atm. Only two intermediate phases were found in the nickel system: NiCrO., (CrVO₄ structure) and the spinel NiCr₂O₄. The magnesium and cadmium systems are similar in that they have three analogous phases: the low-temperature α-MgCrO₄ and α-CdCrO₄ (both with the CrVO₄ structure), the high-temperature β-MgCrO₄ and β-CdCrO₄ (both with the α-MnMoO₄ structure), and the spinels MgCr₂O₄ and CdCr₂O₄. The cadmium system contains an additional phase, Cd₂CrO₅, which is primitive monoclinic.     

The Effects of Prehydration on the Liquid Hydration of 3CaO·Al2O3 with CaSO 4·2H2O

Liquid hydration and water-vapor hydration of 3CaO·Al₂O₃, were studied. Variable parameters were hydration time, temperature, relative humidity, and amount of gypsum. The hydration products (gel, ettringite, hexagonal hydrates, and 3CaO·Al₂O₃·6H₂O) were studied by electron microscopy, X-ray diffractometry, and thermal analysis. A reaction scheme is proposed. The degree of water-vapor hydration influenced the sequence of the subsequent liquid hydration which, however, was independent of the composition of the water-vapor hydration products. Below a critical degree of water-vapor hydration (≊3% combined water) the reaction with liquid water occurred as if no water-vapor hydration had taken place. Above this value the reaction gave hydration products suggesting a change of the 3CaO·Al²O³ reactivity. A possible correlation with the retardation of strength development of prehydrated cement is suggested.     

Conversion of CaO·Al2O3·10H2O to 3CaO·Al2O3·6H2O

The morphological changes accompanying the conversion of the hexagonal CaO·Al₂O₃·10H₂O phase to the cubic 3CaO·Al₂O₃·6H₂O phase were studied by scanning electron microscopy. The hydration and conversion reactions were monitored by X-ray diffraction analysis. From the micrographs, it was inferred that changes in the pore structure and the presence of large cubic crystals of questionable adhesive value were probably the principal factors responsible for the loss of strength in converted calcium aluminate cement pastes.     

Kinetics of Anatase TiO2 Surface Area Reduction in a Mixture of HCl, H2O, and O2: l, Experimental Study

Changes in the surface area of anatase TiO₂ were investigated at 690 K as a function of the gas composition in mixtures of hydrogen chloride, water vapor, and oxygen. The chlorine content on the catalyst support was not dependent on the annealing time, which indicates that the adsorption equilibrium is reached very quickly. The kinetics of surface area were obtained as a function of partial pressure of HCI (from 0.1 to 40 kPa), water vapor (from 0.05 to 10 kPa), and oxygen (from 0.4 to 20 kPa). A mathematical expression for the rate of surface area loss was obtained which includes the partial pressure of water and the chlorine content at the surface of anatase.     

Kinetics of Anatase TiO2 Surface Area Reduction in a Mixture of HCI, H2O, and O2: II, Quantitative Modeling

From the experimental rate for surface area reduction of anatase TiO₂, expressed versus the partial pressure in H₂O and the surface content of chloride ion, a kinetic model is proposed in which two parallel mechanisms are involved. Two ways of material transport appear to contribute to the surface area loss: in the vapor phase and at the surface of the oxide. The related rate-determining steps are attributed to the formation of the volatile compound Ti(OH)₂Cl₂ in the first case, and to the diffusion of hydroxyl ions in the second one. At high partial pressure of water, the rate is enhanced by surface interactions between water molecules and chlorine-containing species.     

Chemical Processing of CaHPO4·2H2O:

The aim of this paper is to develop a robust chemical process to synthesize Na- and K-doped brushite (DCPD: dicalcium phosphate dihydrate, CaHPO₄·2H₂O), a potential starting material for bone substitutes. The powders were synthesized by using sodium phosphate and potassium phosphate and aqueous solutions containing calcium chloride at room temperature, followed by drying at 37°C. DCPD powders thus formed were found to contain 460 ppm K and 945 ppm Na. On calcination in air, these powders readily transformed into monetite (DCPA: dicalcium phosphate anhydrous, CaHPO₄) first, and then into Ca₂P₂O₇ (calcium pyrophosphate). Na- and K-doped DCPD powders were shown to completely transform, in less than 1 week, into poorly crystalline carbonated apatite on immersion in an acellular simulated/synthetic body fluid (SBF) solution at 37°C. The Tris (i.e., tris(hydroxymethyl)aminomethane) buffered SBF solution used in this study had a carbonate ion concentration of 27 m M equal to that of human plasma. DCPD powders of this study displayed a notable apatite-inducing ability. This finding suggests the use of these DCPD powders as the starting materials for potential bone substitutes, which can be easily manufactured in aqueous solutions friendly to living tissues, at temperatures between room temperature and 37°C.     

Studies in the System CaO-Al2O3-SiO2H2O: III, New Data on the Polymorphism of Ca2SiO2 and Its Stability in the System CaO-SiO2- H2O

The nature of the low-temperature inversions γ-α' and α'-β was investigated by various techniques: hydrothermal and "dry" quenching runs, differential thermal analysis at atmospheric and elevated nitrogen pressures, X-ray diffractometer patterns obtained at elevated temperatures, "static" pressure techniques, and infrared absorption spectrometry. A revised energy-temperature diagram is presented for Ca₂SiO₄, with the transition γ' to α' taking place at about 725°C. and the α'-β transition, although not reversible at an exact temperature, taking place at about 670° C. At low water pressures (2000 lb. per sq. in.) the inversion γ-α' was placed at 675°C. Attempts to extrapolate the value obtained at 2000 lb. per sq. in. to obtain a more accurate reversible inversion temperature at atmospheric pressure, although limited in accuracy by the reliability of heat-of-transition data, would indicate a temperature of about 725° C. at atmospheric pressure. Three new compounds, 8CaO.3SiO₂ -3H₂O (X), 6CaO 3SiO₂.H₂O (Y), and 9CaO-6SiO₂ H₂O (Z), were found to be stable above 700°C. at H₂O pressures greater than 7500 lb. per sq. in.     

Ractions of SiC with H2/H2O/Ar Mixtures at 1300°C

The reactions of a sintered α-SiC with 5% H₂/H₂O/Ar at 1300°C were studied. Thermomchemical modeling indicates that three reaction regions are expected, depending on the initial water vapor or equivalently oxygen content of the gas stream. A high oxygen content ( P (O₂) > 10⁻²² atm) leads to a SiO₂ formation. This generally forms as a protective film and limits consumption of the SiC (passive oxidation). An intermediate oxygen content (10⁻²² atm > P (O₂) > 10⁻²⁶ atm) leads to SiO and CO formation. These gaseous products can lead to rapid consumption of the SiC (active oxidation). Thermogravimetric studies in this intermediate region gave reaction rates which appear to be controlled by H₂O gas-phase transport to the sample and reacted microstructures showed extensive grain-boundary attack in this region. Finally, a very low oxygen content ( P (O₂) < 10⁻²⁶ atm) is thermochemically predicted to lead to selective removal of carbon and formation of free silicon. Experimentally low weight losses and iron silicides are observed in this region. The iron silicides are attributed to reaction of free silicon and iron impurities in the system.     

Structure Evolution from Pb(Mg1/3Nb2/3)O3 to La(Mg2/3Nb1/3)O3

The crystal structure of lanthanum-modified lead magnesium niobates having composition (Pb_{1− x} La _x ) (Mg_{(1+ x )/3}-Nb_{(2− x )/3})O₃ with X = 0 to 1 was investigated by X-ray powder diffraction. It was found that the fundamental reflections from perovskite structure remain in the whole range of composition. The superlattice reflections from the A(B'_1/2-B"_1/2)O₃ ordered structure are also well preserved for La content greater than 50 at.%; however, a series of extra peaks of mixing indices appears, with intensities gradually enhanced with the increase of La content. For the complete substitution of Pb by La, a splitting of some reflections can be observed in the diffraction pattern. The results indicate that the crystal structure evolves continuously with the La content, from disordered cubic perovskite of space group Pm 3 m for X = 0, to ordered cubic perovskite of space group Fm 3 m for X = 0.5, distorted cubic perovskite of space group Pa 3 for 0.5 < X < 0.9, and finally to a rhombohedral perovskite, possibly belonging to the space group R 3 , for X ≥ 0.9. In the evolution of structure, a linear reduction of the lattice constant of the perovskite cell from 4.048 to 3.964 Å was observed.