Infrared Absorption Due to H2O and D2O in a Fluorozirconate Glass

A comparative study of infrared absorption due to H₂O and D₂O impurities in a fluorozirconate glass (53ZrF₄·20BaF₂·4LaF₃·3AlF₃·20NaF) was carried out. The H₂O and D₂O were introduced into the glass by reaction of the surface at 260°C with H₂O and D₂O vapor entrained in a stream of N₂. Reaction with H₂O produced IR absorption bands at 2.9 μm (O–H stretch) and 6.1 μm (H₂O bend). Reaction with D₂O produced bands at 3.9 μm (O–D stretch) and 8.3 μm (D₂O bend). The ratios of the corresponding D₂O/H₂O peak frequencies are 0.74 for both the stretching and bending vibrations, in good agreement with the value of 0.727 predicted from the difference in the OH and OD reduced masses.     

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.     

Mechanochemical Changes of Weinschenkite-Type RPO4·2H2O (R = Dy, Y, Er, or Yb) by Grinding and Thermal Reactions of the Ground Specimens

It is reported that, on mechanochemical treatment, weinschenkite-type RPO₄·2H₂O (R = Dy, Y, or Er) gradually transforms into rhabdophane-type RPO₄· nH₂O (n = 0.5 to 1) and weinschenkite-type YbPO₄·2H₂O into xenotime-type YbPO₄, at room temperature in air. Rhabdophane-type YPO₄·0.8H₂O and ErPO₄·0.9H₂O obtained by grinding weinschenkite-type RPO₄·2H₂O (R=Y or Er) are new. The new rhabdophane-type YPO₄·0.8H₂O and ErPO₄·0.9H₂O gradually transform to xenotime-type YPO₄ and ErPO₄ when heated above 900°C (R = Y) and 700°C (R = Er) in air.     

Formation and Transformation of WO3 Prepared from Alkoxide

Amorphous WO₃ or WO₃ or H₂O is formed by hydrolysis of tungsten ethoxide. The temperature of hydrolysis influences the crystallization of WO₃·H₂O. Tungsten hydrate (WO₃·H₂O) has an orthorhombic unit cell with a=0.5235 nm, b = 1.0688 nm, and c=0.5123 nm. Orthorhombic WO₃ crystallizes at 350° to 500°Cfrom amorphous WO₃. Cubic WO₃ is formed at 200° to 310°C with dehydration of WO₃·H₂O. WO₃ transformations are examined by high-temperature X-ray diffraction. The kinetics of formation of the cubic modification have been studied by measuring the weight decrease with a thermobalcnce. Formation isotherms can be interpreted in terms of the first-order equation –In (1–f)=kt; activation energies are 110 and 80 kJ mol⁻¹ for initial and final stages, respectively.     

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.     

The System MgO─P2O5─H2O at 25°C

The phase diagram for the ternary system MgO─P₂O₅─H₂O at 25°C has been constructed. The magnesium phosphates represented are Mg(H₂PO₄)₂· n H₂O ( n = 4, 2, 0), MgHPO₄·3H₂O, and Mg₃(PO₄)₂· m H₂O ( m = 8, 22). Because of the large differences in the solubilities of these compounds, the technique which involves plotting the mole fractions of MgO and P₂O₅ as their 10th roots has been employed. With the exception of MgHPO₄·3H₂O, the magnesium phosphates are incongruently soluble. Because incongruency is associated with a peritectic-like reaction, the phase Mg₂(PO₄)₃· 8H₂O persists metastably for an extended period.     

High-Temperature Stability of Alumina in Argon and Argon/Water-Vapor Environments

The high-temperature stability of alumina (Al₂O₃) in argon and argon/water-vapor (Ar/H₂O) environments has been investigated. Samples were exposed at temperatures of 1300°C–1700°C for 10 h. The microstructure, flexural strength, and volume all showed significant changes in the Ar/H₂O environment at 1700°C. Samples also became whiter, because of the oxidation of graphite impurities that had diffused from the hot-processing dies. In the Ar/H₂O environment at 1700°C, grain-boundary etching occurred and was much more severe than in the pure-argon environment, which was very likely caused by the enhanced formation of gaseous Al(OH)₃ and Al(OH)₂ along grain boundaries. In addition, in the Ar/H₂O environment, substantial grain growth occurred in the surface vicinity. This grain growth, together with grain-boundary etching, led to a decrease in flexural strength.     

Effect of Water Content on Transport in Na2O·3SiO2 Glass

Na₂O·₃SiO₂ glasses of high water content were prepared under high-pressure, hydrothermal conditions. The sodium diffusion coefficient, DNa , in these glasses measured at 100°C depended strongly on H₂O content. With increasing H₂O content, DNa . at 100°C decreased initially to a minimum at 3∼4 wt% H,O and then increased. This behavior of DNa . Was similar to that of dc conductivity.     

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.     

Kinetics of Crystallization of Stoichiometric SiO2 Glass in H2O Atmospheres

Crystallization rates were measured in vacuum, dry nitrogen, and water-saturated nitrogen atmospheres from 1300° to 1540°C. In all cases the observed rates were linear. Three reactions appeared to contribute to crystallization: the intrinsic crystallization, the impurity effect of H₂O vapor, and furnace contamination. Enhancement of crystallization by both water vapor and furnace contamination is attributed to the breaking of silicon—oxygen bonds of the glass structure. Competitive adsorption mechanisms were proposed to characterize the adsorption of water and impurity species. The activation energy for apparent intrinsic crystallization was 134 kcal/mole; the activation energy for crystallization in H₂O vapor was 77 kcal/mole.     

Synthesis of Mesoporous Needle-Shaped Ytterbium Oxide Crystals by Solvothermal Treatment of Ytterbium Chloride

The reaction of rare-earth (RE; Y, Er, and Yb) chloride hydrates in 1,4-butanediol at 300°C for 2 h gave mixtures of RE(OH)₂Cl and RE₂O₃· x H₂O, and the products were composed of irregularly shaped particles. A prolonged reaction (10 h) yielded a mixture of RE(OH)₂Cl and RE₂O₃· x H₂O for Er or Y, but phase-pure RE₂O₃· x H₂O was obtained for Yb. The product for Yb comprised needle-shaped single crystals of Yb₂O₃· x H₂O with a width of 0.2–0.6 μm and a length of 5–15 μm. The Yb₂O₃· x H₂O phase decomposed to Yb₂O₃ at 350°–500°C, preserving the needle-shaped morphology; this was maintained even after calcination at 1100°C. Single crystals of Yb₂O₃ obtained by the calcination of Yb₂O₃· x H₂O at 500°C had very small voids and the voids were enlarged to 35 Å in diameter by calcination at 800°C.     

Synthesis of Titanate Derivatives Using Ion-Exchange Reaction

Two types of titanate derivatives, layered hydrous titanium dioxide (H₂Ti₄O₉· n H₂O) and potassium octatitanate (K₂Ti₈O₁₇) with a tunnellike structure, were synthesized using an ion-exchange reaction. Fibrous potassium tetratitanate (K₂Ti₄O₉· n H₂O) was prepared by calcination of a mixture of K₂CO₃ and TiO₂ with a molar ratio of 2.8 at 1050°C for 3 h, followed by boiling-water treatment of the calcined products for 10 h. The material then was transformed to layered H₂Ti₄O₉· n H₂O through an exchange of K⁺ ions with H⁺ ions using HCl. K₂Ti₈O₁₇ was formed by a thermal treatment of KHTi₄O₉· n H₂O. Pure KHTi₄O₉· n H₂O phase was effectively produced by a treatment of K₂Ti₄O₉ with 0.005 M HCl solution for 30 min. Thermal treatment at 250°–500°C for 3 h resulted in formation of only K₂Ti₈O₁₇.     

Synthesis of ZrO2 and Y2O3-Doped ZrO2 Thin Films Using Self-Assembled Monolayers

Undoped or Y₂O₃-doped ZrO₂ thin films were deposited on self-assembled monolayers (SAMs) with either sulfonate or methyl terminal functionalities on single-crystal silicon substrates. The undoped films were formed by enhanced hydrolysis of zirconium sulfate (Zr(SO₄)·4H₄O) solutions in the presence of HCl at 70°C. Typically, these films were a mixture of two phases: nanocrystalline tetragonal- ( t -) ZrO₂ and an amorphous basic zirconium sulfate. However, films with little or no amorphous material could be produced. The mechanism of film formation and the growth kinetics have been explained through a coagulation model involving homogeneous nucleation, particle adhesion, and aggregation onto the substrate. Annealing of these films at 500°C led to complete crystallization to t -ZrO₂. Amorphous Y₂O₃-containing ZrO₂ films were prepared from a precursor solution containing zirconium sulfate, yttrium sulfate (Y₂(SO₄)₃8·H₂O), and urea (NH₂CONH₂) at pH 2.2–3.0 at 80°C. These films also were fully crystalline after annealing at 500°C.     

The System CaO-Al2O3-H2O

Phase equilibria have been determined in the system CaO-Al₂O₃-H₂O in the temperature range 100° to 1000°C. under water pressures of up to 3000 atmospheres. Only three hydrated phases are formed stably in the system: Ca(OH)₂, 3CaO·Al₂O₃·6H₂O, and 4CaO·3Al₂O₃-3H₂O. Pressure-temperature curves delineating the equilibrium decomposition of each of these phases have been determined, and some ther-mochemical data have been deduced therefrom. It has been established that both the compounds CaO·Al₂O₃ and 3CaO·Al₂O₃ have a minimum temperature of stability which is above 1000°C. The relevance of the new data to some aspects of cement chemistry is discussed.     

Preparation of BaTi4O9 from Oxalates

A barium titanate precursor with a barium:titanium ratio of 1:4 was prepared by controlled coprecipitation of mixed barium and titanium species with an ammonium oxalate aqueous solution at pH 7. The results of thermal analysis and IR measurement show that the obtained precursor is a mixture of BaC₂O₄·0.5H₂O and TiO(OH)₂·1.5H₂O in a molar ratio of 1:4. Crystallized BaTi₄O₉ was obtained by the thermal decomposition of a precipitate precursor at 1300°C for 2 h in air. The dimensions of the powder calcined at 1000°C are between 100 and 300 nm. The grain dimensions of the sintered sample for 2 h at 1300°C are of the order of 10 to 30 μm. Dielectric properties of disk-shaped sintered specimens in the microwave frequency region were measured using the TE₀₁₁ mode. Excellent microwave characteristics for BaTi₄O₉—ɛ= 38 ± 0.5, Q = 3800–4000 at 6–7 GHz and τ _f = 11 ± 0.7 ppm/°C—were found.     

Solubility of Water Vapor in Alkali Borate Melts

The solubility of water vapor at 750° to 1050°C was determined for alkali borate melts containing 0 to 40 mole % Li₂O, Na₂O, or K₂O. In all cases the solubility in these melts is linearly proportional to the square root of the H₂O partial pressure. At p H₂O = 1 atm and T = 900°C, o.5 to 2.2 mole % H₂O are dissolved in the melts in equilibrium. In the potassium borate melts a minimum of solubility was observed at about 25 mole % K₂O; in the sodium borate melts the minimum was at 35 to 40 mole % Na₂O. In the lithium borate melts a minimum of solubility was not reached in the range of compositions investigated. These results are discussed in terms of a concept for the acid-base properties of melts and glasses in which the position of the solubility minimum corresponds to the "neutral point" of an acidity-basicity scale. Some corroborating qualitative observations concerning the evaporation of components from the glass melts and the chemical resistivity of the corresponding solid glasses are discussed.     

High-Temperature Oxidation of Boron Nitride: II, Boron Nitride Layers in Composites

The oxidation of BN composite interphases was examined with a series of model materials. Oxidation was examined in both low-water-vapor (∼20 ppm H₂O/O₂) environments at 900°C and high-water-vapor (1% and 10% H₂O/O₂) environments at 700° and 800°C. The low-water-vapor case was explored with layered BN/SiC materials. This case was dominated by borosilicate glass formation, and the 20 ppm water vapor gradually removed the boron from the glass, leaving a larger amount of SiO₂ than would be expected from simple SiC oxidation. Layered SiC/BN/SiC materials were also used to study low-water-vapor oxidation effects within the composite. The high-water-vapor case was explored with SiC/BN/SiC minicomposites, and it was dominated by volatilization of BN as HBO₂( g ), H₃BO₃( g ), and H₃B₃O₆( g ). A model for recession of the BN fiber coating was developed based on the gas-phase diffusion of these species out of the annular region around the SiC fiber and concurrent sealing of this annular region by oxidation.     

Wetting in an Electronic Packaging Ceramic System: II, Wetting of Alumina by a Silicate Glass Melt under Controlled pO2 Conditions

The wetting of polycrystalline alumina by a colored, calciamagnesia aluminosilicae glass was found to be dependent on temperatutre between 1300° and 1500°C, but independent of gas atmosphere effects. Neither the oxygen partial pressure, oveer the range of 10^-6 to 10^-10 Pa, the gas buffer system (Co/CO₂ or H₂/H₂O), nor pre-equilibration of the substrate surface with the atmosphere at tge exoperimental temperature before solid-liuid interface formation affected the stable contact angle. An initial drop in contact angle the stable contact angle. An initial drop in contact angle occurring within the first hour is attributed to repaid dissolution of alumina and the formation of a stable glass/alumina interface. The contact angle after an 8-h isothermal hold decreased from 1300° to 1500°C. The solid-liquid interfacial energy, μM_S1, controls the wetting behavior. Changes in μM_s1 are attributed to he breakup of the silica network as temperature increases.     

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.     

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.