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.     

Effect of H2O Vapor on the Internal Friction of Binary Alkali Silicate Glasses

Internal friction and shear modulus of Na, K, and Li disiticate glasses were measured by a torsional pendulum as a function of H₂O vapor treatment at T=300°C. H₂O produced changes in the acoustic spectra (between—100° and 400°C and f=0.5 Hz) similar to the mixed-alkali effect which appears upon introduction of a second alkali to a single-alkali glass. An Na₂O·2SiO₂ glass free from the common nonbridging oxygen relaxation was produced .     

Fabrication of Silicon Carbide Whisker/Alumina Composite by Thermal-Gradient Chemical Vapor Infiltration

SiC( w )/Al₂O₃ composites were made from an AlCl₃-H₂-CO₂ mixture by a thermal-gradient chemical vapor infiltration (CVI) method. Al₂O₃ was deposited from the reaction of AlCl₃ and H₂O, which was produced from the oxidation of H₂ by CO₂. The densification rate was measured at various reactant compositions and total pressures. When the reaction rate or total pressure increased, the rate-controling step shifted from H₂O production to AlCl₃ diffusion, which led to premature pore closing. To obtain dense composites in a short infiltration time, the diffusion rate of AlCl₃ had to be increased by decreasing the total pressure.     

Partition of Hydrogen in the Modified Chemical Vapor Deposition Process

In the modified chemical vapor deposition (MCVD) process for making glass fibers, most of the hydrogen coming into the reaction from hydrogen-bearing impurities in the starting materials is not incorporated in the glass. It is instead mostly converted to HCl, which is not absorbed by the newly formed silica particles, and passes out the exhaust stack. The residual partial pressure of H₂O formed in equilibrium with HCl in the presence of O₂ and Cl₂ accounts quantitatively for the OH appearing in the glass when the known solubility of H₂O in silica is considered. The H₂O/HCl equilibrium is quenched at a temperature below that of the reaction zone at a value for which the rate of reaction approximates the transit time across the deposition zone. Quantitative agreement is obtained for published OH concentrations produced by SiHCl₃ doping.     

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.     

Effect of Heat-Treatment on the Constitution and Mechanical Properties of Some Hydrated Aluminous Cements

The compound compositions of four aluminous cements were determined on anhydrous as well as hydrated specimens which had been heat-treated at temperatures between room temperature and 1400° C. Phases were identified by X-ray diffraction and differential thermal analysis. Specimens were also tested for transverse strength, dynamic modulus of elasticity, and thermal length change. A study of the dehydration characteristics of CaO - Al₂O₈ - 10H₂O₃ 3CaO.Al₂O₃. 6H₂O, and Al₂O₃. 3H₂O was included. The data indicated that CaO. Al₂O₃ 10H₂O was the primary crystalline hydrate formed in the cements at room temperature. At 50° C., 3 CaO Al₂O₃-6H₂O and Al₂O₃. 3H₂O were formed as by-products of the dehydration of CaO.Al₂O₃.10H₂O. When heated alone in an open system, CaO.Al₂O₃.10H₂O did not convert to 3CaO. Al₂O₃. 6H₂O and A1₂O₃. 3H₂O. A correlation between the mechanical properties and compound compositions was noted.     

Thermal Analysis of Some Barium and Strontium Titanyl Oxalates

The thermal decompositions of BaTiO(c₂O₄)₂.- 4H₂O, BaTiO(OH)₂C₂O₄.2H₂O, SrTiO(C₂O₄)₂.- 4H₂O, and SrTiO(OH)₂C₂O₄.H₂O were investigated using TGA, DTA, and effluent gas analysis. The stoichiometry of the decompositions is discussed and it is proposed that a reduced state of titanium is formed as an intermediate.     

Suggested Chemistry of Zinc Oxychloride Cements

Solutions of ZnCl₂ were prepared from ZnCl₂· n H₂O and by reaction of zinc metal with HCl. Specific gravities and pH values were determined as a function of composition. A ternary phase, 4ZnO·ZnCl₂·5H₂O, was precipitated when the ZnCl₂ solutions were diluted to a pH of 5.48 ± 0.05. Mixtures of ZnO with ZnCl, and HCI solutions were equilibrated in sealed containers and analyzed by X-ray diffraction. The resulting phase diagram shows 2 ternary phases, 4ZnO·ZnCl₂·5H₂O (4·1·5) and ZnO·ZnCl₂·2H₂O (1.1.2), both of which are soluble to the extent of < 1 wt% in ZnCl₂ solutions. Thermogravimetric data indicate that the 1.1.2 phase loses half the constituent H₂O at ∼230°C and the remainder, with ZnCl₂, at higher temperatures. The 4.1.5 phase dissociates to ZnO and 1.1.2 at ∼160°C. The system ZnCl₂-H₂O is not binary, but is a section through the ternary system ZnO-HCl-H₂O, with the solubility curve of the 4.1.5 phase intersecting the ZnCl₂-H₂O section in dilute solutions.     

Effect of Surface Moisture on Dielectric Behavior of Ultrafine BaTiO3 Particulates

The effects of adsorbed H₂O on the dielectric properties of ultrafine BaTiO₃ particulates of varying particle size and environmental history were determined. The dielectric behavior depends strongly on surface hydration. No particle size dependence of dielectric constant was found for dehydroxylated surfaces in ultrafine particulate (unsintered) BaTiO₃ materials. For equivalent particle sizes, the ac conductivity is sensitive to surface morphology. Reactions with H₂O vapor appear to account for the variations in dielectric properties. Surface dehydration was effectively accomplished by washing as-received powders in isopropanol.     

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.     

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.     

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.     

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.     

Mass Spectrometric Studies of the Nitridation of Silicon

The nitridation of silicon was examined by analyzing the nitriding atmosphere with a mass spectrometer. Silicon monoxide vapor was found throughout the entire temperature range of the process in amounts of the order of 10⁻³ of the volume of the nitriding agent. Controversial results obtained in previous investigations of nitridation kinetics are explained in terms of the SiO vapor and the O₂ partial pressure of the system. The effects of H₂ and H₂O on nitridation are also discussed.     

The System Alumina-Gallia-Water

A study of the system Al₂O₃–Ga₂O₃–H₂O has resulted in the determination of equilibrium diagrams for the systems Al₂O₃–Ga₂O₃ and Al₂O₃.-H₂O–Ga₂O₃.H₂O. Extensive solid solution characterizes the α -Al₂O₃ and β -Ga₂O₃ structures at high temperatures, but it is shown that below 810°C. a compound, GaAlO₃, and a new series of (Al, Ga)₂O₃ structures are stable. Among the hydrates, a complete series of diaspore solid solutions extends from Al₂O₃.H₂O to Ga₂O₃.H₂O. Boehmite solid solutions extend to approximately the composition 70Al₂O₃.H₂O, 30Ga₂O₃.H₂O.     

Infrared Spectra of a Water-Containing Glass

Infrared absorption was measured on an NajO-K₂O-ZnO-Al₂O₃-SiO₂ glass with up to ∼11 wt% water. Fundamental and overtone-combination bands were observed at 1.41, 1.91, 2.22, 2.87, and 6.1 μm. Molar absorptivities were determined for the hydrated glass for H₂O and OH levels using the molar absorptivity calculated for the 2.22-μm band in the as-melted glass. By this procedure the concentration of molecular water and OH groups could be determined separately. These results show that the OH content of the hydrated glass, as determined from the 2.22-μm band, is constant at >7 wt% H₂O; additional H₂O is attributed to molecular water only. Good agreement was found between these data and H₂O/OH molecular ratios obtained from NMR.     

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.     

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.     

Water Sorption-Desorption Characteristics of Proton-Conducting Antimonic Acids with Cubic and Monoclinic Structures

Protonic conductivities of cubic and monoclinic antimonic acids are known to depend on water vapor pressure. Their water sorption-desorption characteristics are compared and discussed with the water sorption isotherms and the desorption spectra of H₂¹⁶O, D₂O, and H₂¹⁸O. The cubic antimonic acid contains more water than the monoclinic acid, which can be attributed to the existence of micropores in the cubic (pyrochlore type) structure.     

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.