Studies on 4CaOAl2.O3.13H2O and the Related Natural Mineral Hydrocalumite

Single-crystal X-ray and electron-diffraction studies show the existence in one polymorph of 4CaO.Al₂O₃. 13H₂O of a hexagonal structural element with α= 5.74 a.u., c = 7.92 a. u. and atomic contents Ca₂(OH)₇- 3H₂O. These structural elements are stacked in a complex way and there are probably two or more poly-types as in SiC or ZnS. Hydrocalumite is closely related to 4CaO.A1₂O₃.13H₂O, from which it is derived by substitution of CO₃^2-for 20H^-+ 3H₂O once in every eight structural elements; similar substitutions explain the existence of compounds of the types 3CaO Al₂O₃.Ca Y ₂- xH₂O and 3CaO Al₂O₃ Ca Y xH₂O. On dehydration, 4CaO.Al₂O₃.13H₂O first loses molecular water and undergoes stacking changes and shrinkage along c. At 150° to 250°C., Ca(OH)₂ and 4CaO.3Al₂O₃.3H₂O are formed and, by 1000°C., CaO and 12CaO.7Al₂O₈. The dehydration of hydrocalumite follows a similar course, but no 4CaO.3Al₂O₃.3H₂O is formed.     

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.     

Homogeneous Precipitation of TiO2 Ultrafine Powders from Aqueous TiOCl2 Solution

Crystalline TiO₂ powders were prepared by the homogeneous precipitation method simply by heating and stirring an aqueous TiOCl₂ solution with a Ti⁴⁺ concentration of 0.5 M at room temperature to 100°C under a pressure of 1 atm. TiO₂ precipitates with pure rutile phase having spherical shapes 200-400 nm in diameter formed between room temperature and 65°C, whereas TiO₂ precipitates with anatase phase started to form at temperatures >65°C. Precipitates with pure anatase phase having irregular shapes 2-5 µm in size formed at 100°C. Possibly because of the crystallization of an unstable intermediate product, TiO(OH)₂, to TiO₂ x H₂O during precipitation, crystalline and ultrafine TiO₂ precipitates were formed in aqueous TiOCl₂ solution without hydrolyzing directly to Ti(OH)₄. Also, formation of a stable TiO₂ rutile phase between room temperature and 65°C was likely to occur slowly under these conditions, although TiO₂ with rutile phase formed thermodynamically at higher temperatures.     

Solubilities of Ar, N2, CO2, and He in Glasses at Pressures to 10 Kbars

Glasses containing up to several percent of Ar, N₂, and CO₂ were prepared at 2000 to 150,000 psi and up to 950°C and retained under ambient conditions. The solubilities are presented as a function of pressure, temperature, and composition of glass. Solubilities of O, He, and H₂O were also investigated in various glass compositions, especially K₂O–4SiO₂ and B₂O₃. The evolution of the gases at atmospheric pressure was followed by electron microscopy and density measurements.     

Studies in Lithium Oxide Systems: IX, Li2o-Al2O3-TiO2

Compatible phases in the system Li₂O-Al₂O₃-TiO₂ at various temperature levels were determined mainly by solid-state reactions for the portion of the ternary system bounded by Li₂O Al₂O₂, Li₂O.TiO₂, Al₂O, and TiO₂. The existence of a ternary compound, Li₂O.Al₂O₃.4TiO₂, and nine joins was established. The ternary compound has a lower limit of stability at 1090°± 15°C. and dissociates and recombines rapidly at 1380°± 15°C.     

Effects of Trace O2 Levels on the Nitriding Kinetics of High-Purity Silicon Powders

The effects of trace O₂ levels on the nitridation of compacts made from silane-derived Si powders were studied in N₂ atmospheres, with oxygen levels of either 5 ppm or 10 ppb (approximately). The nitriding kinetics were studied by thermogravimetric analysis as a function of temperature (1100–1200°C) and heating rate (5°C/min and 100°C/min). Reducing the O₂ level in the nitriding gas enhanced conversion to Si₃N₄ at lower temperatures, reduced the composition variations within the samples, and decreased the α/β ratios. The results suggest that nucleation and rapid growth of Si₃N₄ at relatively low temperatures are possible only when the oxygen partial pressure in the system is below the threshold value for passive oxidation.     

Low-Temperature Atomic Layer-Deposited TiO2 Films with Low Photoactivity

Atomic layer deposition (ALD) has been successfully utilized for the conformal and uniform deposition of ultrathin titanium dioxide (TiO₂) films on high-density polyethylene (HDPE) particles. The deposition was carried out by alternating reactions of titanium tetraisopropoxide and H₂O₂ (50 wt% in H₂O) at 77°C in a fluidized bed reactor. X-ray photoelectron spectroscopy confirmed the deposition of TiO₂ and scanning transmission electron microscopy showed the conformal TiO₂ films deposited on polymer particle surfaces. The TiO₂ ALD process yielded a growth rate of 0.15 nm/cycle at 77°C. The results of inductively coupled plasma atomic emission spectroscopy suggested that there was a nucleation period, which showed the reaction mechanism of TiO₂ ALD on HDPE particles without chemical functional groups. TiO₂ ALD films deposited at such a low temperature had an amorphous structure and showed a much weaker photoactivity intensity than common pigment-grade anatase TiO₂ particles.     

CO2 Decomposition by Oxide Ceramics Intercalated in Layered Compound

Iron oxide polymers intercalated and/or loaded within täniolite have been studied as a CO₂ decomposition medium. Fe²⁺ was exchanged for Li⁺ in täniolite, oxidized by air-bubbling at 60°–70°C. The basic d -spacing (13.75 Å in the Li⁺ form) was expanded to give 14.86 Å in the Fe²⁺ form. Oxidation by air in the form of suspension gave a 15.3-Å phase, which was ascribed to formation of magnetite within the interlayer. The interlayer distance of the intercalated phase remained the same upon heating at 300°C. The magnetite–intercalated täniolite was heated to activate in a H₂ and/or H₂O steam. CO₂ decomposition reactivity at 300°C has been evidenced by evolution of CO gas. The high reactivity for CO₂ decomposition is ascribed to the highly dispersed iron oxide ceramics within the interlayer of täniolite Li[(Mg₂Li)(Si₄O₁₀)]F₂ n H₂O.     

Studies in Lithium Oxide Systems: II, Li2O Al2O3–Al2 O 3

Solid-state reactions between Li₂O and Al₂ O₃ were studied in the region between Li₂O.Al₂ O ₃ and Al₂ O ₃. The compound Li₂ O Al₂ O ₃ melts at 1610°± 15°C. and undergoes a rapid reversible inversion between 1200° and 1300°C. Vaporization of Li₂ O from compositions in the system proceeds at an appreciable rate at 1400°C, as shown by fluorescence. Lithium spinel, Li₂ O -5Al₂O₃, was the only other compound observed. The effect of Li₂ O on the sintering of alumina was investigated.     

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.     

X-Ray Study of the Solid Solution of TiO, Fe2O3, and G, O3 in Mullite (3A12O3a2Si02)

A study of the solid solution of TiO₂, Fe₂O₃, and Cr₂0₃ in mullite was made by measuring the changes in lattice parameters and unit-cell volume. Synthetic mullite (3O₃-2SiO₂) was reacted with up to 12 weight % of the oxides at temperatures ranging from 1000° to 17000C. The approximate minimum temperature required for the formation of solid solution was 12000C. for Fe₂0₃ and 1400°C. for Cr₂O₃ and TiO₃. The maximum amount of solid solution found was 2 to 4% TiO₂ at 1600°C., 10 to 12% Fe₂O_s at 1300°C., and 8 to 10% Cr_ZO₃ at 1600OC. Lattice parameters and unit-cell volumes for each solid solution series increased with increasing amounts of foreign oxide. There was good agreement between the calculated and observed increase in cell dimensions for the iron oxide series. Except in the case of titania, there was good agreement between X-ray data and petrographic observations.     

Phase Relations in the System UO2-UO3– Y2O3

The phase relations in the system U02-U03-Yz03, particularly in the Y203-rich region, were examined by X-ray and chemical analyses of reacted powders heated at temperatures up to 1700°C in H₂, CO₂-CO₂ and air. Four phases were identified in the system at temperatures between 1000° and 1700°C: U308, face-centered cubic solid solution, body-centered cubic solid solution, and a rhombohedral phase of composition (U,Y)₇O₂ ranging from 52.5 to 75 mole % Y₂O₃. The rhombohedral phase oxidized to a second rhombohedral phase with a nominal composition (U,Y), at temperatures below 1000°C. This phase transformed to a face-centered cubic phase after heating in air above 1000° C. The solubility of UO, in the body-centered cubic phase is about 14 mole % between 1000° and 1700°C but decreases to zero as the uranium approaches the hexavalent oxidation state. The solubility of Yz03 in the face-centered cubic solid solution ranges from 0 to 50 mole % Y2O3 under reducing conditions and from 33 to 60 mole % Y2O3 under oxidizing conditions at 1000°C. At temperatures above 1000° C, the face-centered cubic solid solution is limited by a filled fluorite lattice of composition (U,Y)O₂. For low-yttria content, oxidation at low temperatures (<300°C) permits additional oxygen to be retained in the structure to a composition approaching (U,Y)O_2.25 A tentative ternary phase diagram for the system UO₂-UO₃-Y₂O₃ is presented and the change in lattice parameter and in cell volume for the solid-solution phases is correlated with the composition.     

Preparation of Lead Zirconate Titanate (Pb(Zr0.52Ti0.48)O3) by Homogeneous Precipitation and Calcination

Preparation of phase-pure PZT (Pb(Zr_0.52Ti_0.48)O₃) powders was achieved, in the presence of urea (CH₄N₂O), by homogeneous precipitation. Aqueous solutions of PbCl₂, ZrOCl₂·8H₂O, and TiCl₄ were used as the starting materials in the synthesis of phase-pure PZT powders. Phase evolution behavior of precursor powders was studied by powder X-ray diffraction (XRD) in air, over the temperature range of 90° to 750°C. The morphology of the formed powders was studied by scanning electron microscopy (SEM). Semiquantitative chemical analyses of the samples were performed by energy-dispersive X-ray spectroscopy (EDXS).     

Phase Relations in the Pseudobinary System Na2TiSi4O11-Na2Ti2Si2O9

The quenching technique was used to study subliquidus and subsolidus phase relations in the pseudobinary system Na₂ Ti₂Si₂ O₁₁-Na₂ Ti₂ Si₂ O₉. Both narsarukite (Na₂TiSi₄O₁₁) and lorenzenite (Na₂Ti₂Si₂O₉) melt incongruently. Narsarsukite melts at 911°±°C to SiO₂+liquid, with the liquidus at 1016°C. Lorenzenite melts at 910°±5°C to Na₂ Ti₆ O₁₃+liquid; Na₂ Ti₆ O₁₃ reacts with liquid to form TiO₂ and is thus consumed by 985°±5°C. The liquidus occurs at 1252°C.     

Phase Equilibrium in the System PbO-TiO2–ZrO2

Phase equilibrium relations in the system PbO–TiO₂–ZrO₂ were studied by quenching in the range where the PbO content is 50 mole % and more. Isotherms were examined at 1100°, 1200°, and 1300°C and tie lines were determined between the liquid and solid solution in equilibrium. The incongruent melting point of PbZrO₃ was 1570°C and the equilibrium between liquid, PbO-type solid, and PbZrO₃ is peritectic. Pb(Zr,Ti)O₃ solid solutions containing more than 14 mole % PbZrO₃ decomposed to liquid, ZrO₂, and Pb(Zr,Ti)O₃ and the decomposition temperature rises from 1340° to 1570°C with increasing PbZrO₃ content. The system PbTiO₃–PbZrO₃ should not be treated as a binary, but as a section of the ternary system.     

Stability of SrFeO3-Based Materials in H2O/CO2-Containing Atmospheres at High Temperatures and Pressures

The chemical stability of SrFeO₃-based perovskites in H₂O- and CO₂-containing atmospheres at high temperatures and pressures has been examined. The extent of reaction as a function of p CO₂, p H₂O, temperature, and time has been determined. Either strontium carbonate or Sr(OH)₂·H₂O was observed on sample surfaces after exposure. Observation of two different reaction-rate behaviors could be explained by the formation of different products. The stability of the perovskite has been found to increase when the activity of Sr is decreased. Chemical stability in H₂O/CO₂ is important to understand in order to use these membrane materials for syngas production.     

Formation of BaTiO3 from BaCO3 and TiO2 in Air and in CO2

The formation of BaTiO₃ from equimolar BaCO₃ and TiO₂ (rutile) mixtures was studied in air and in CO₂. A small amount of BaTiO₃ is formed first directly from BaCO₃ and TiO₂ at the surface of contact. From then on it is a diffusion-controlled reaction, and both BaTiO₃ and Ba₂TiO₄ are produced, with Ba₂TiO₄ being formed in much larger amounts. In 1 atmosphere of CO₂, the intermediate Ba₂TiO₄ was suppressed up to a temperature of about 1100°C. in agreement with thermodynamic calculations. Ba₂TiO₄ reacts fast with 1 atmosphere of CO₂ below about 1100°C. to produce BaTiO₃and BaCO₃     

Chemical Vapor Deposition of Polycrystalline Al2O3

Polycrystalline Al₂O₃ was chemically vapor-deposited onto sintered Al₂O₃ substrates by reaction of AlCl₃ with (1) H₂O, (2) CO:H₂, and (3) O₂ at 1000° and 1500°C and 0.5 and 5.0 torr. Although the thermodynamics of all these reactions predict the formation of solid Al₂O₃, the deposition rate of the first reaction was considerably greater than that of the second. The third reaction was so slow that no measurable deposit was formed in 6 h at 1500°C. Formation of dense deposits of α-Al₂O₃ was favored by increasing temperature and decreasing pressure. Microstructural examination of the dense deposits showed long columnar grains, the largest of which extended through the deposit from the substrate to the surface.     

Use of Stabilized ZrO2 to Measure O2 Permeation

The rate of permeation of CaO-stabilized ZrO₂ (CSZ) by O₂ gas was measured from 640° to 1200°C with the CSZ tubing used simultaneously as the sample and the O₂ pressure detector. The apparent permeation rate depended significantly on the O₂ pressure at the low-pressure side. The rate measured by this method was orders of magnitude smaller than that measured under steady-state conditions, except when the O₂ partial pressure was high (>10⁻⁴ atm), in which case the agreement was good. The difference between steady-state permeability and non-steady-state permeability is related to the deviation in stoichiometry in a sample or detector. The transient response (measured under variable pressure difference) may be very different from steady-state permeation (measured under constant differential pressures across the membranes). To apply CSZ to typical O₂ gas permeability measurements, the O₂ pressure must be kept above ∼ 10^−3.5 atm. In this range, the permeability of CSZ may be regarded as a temperature-dependent material property which is governed by the electron-hole mobility. At lower O₂ pressures the permeation rate is a more complex function of the pressure difference and level.     

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.