Effect of SiC on Interfacial Reaction and Sintering Mechanism of TiB2

Compacts of TiB₂ with densities approaching 100% are difficult to obtain using pressureless sintering. The addition of SiC was very effective in improving the sinterability of TiB₂. The oxygen content of the raw TiB₂ powder used in this research was 1.5 wt%. X-ray photoelectron spectroscopy showed that the powder surface consisted mainly of TiO₂ and B₂O₃. Using vacuum sintering at 1700°C under 13–0.013 Pa, TiB₂ samples containing 2.5 wt% SiC achieved 96% of their theoretical density, and a density of 99% was achieved by HIPing. TEM observations revealed that SiC reacts to form an amorphous phase. TEM-EELS analysis indicated that the amorphous phase includes Si, O, and Ti, and X-ray diffraction showed the reaction to be TiO₂+ SiC → SiO₂+ TiC. Therefore, the improved sinterability of TiB₂ resulted from the SiO₂ liquid phase that was formed during sintering when the raw TiB₂ powder had 1.5 wt% oxygen.     

Microstructural Characterization of Superplastic SiO2-doped TZP with a Small Amount of Oxide Addition

The microstructures of 5 wt% SiO₂-doped TZP, 5 wt% (SiO₂+ 2 wt% MgO)-doped TZP, and 5 wt% (SiO₂+ 2 wt% Al₂O₃)-doped TZP are characterized by high-resolution electron microscopy, energy-dispersive X-ray spectroscopy, and electron energy loss spectroscopy. An amorphous phase is formed at multiple grain junctions but not along the grain-boundary faces in these three materials. A small addition of MgO and Al₂O₃ into the SiO₂ phase results in a marked reduction in tensile ductility of SiO₂-doped TZP. This reduction seems to correlate with segregation of magnesium or aluminum ions at grain boundaries and a resultant change in the chemical bonding state.     

Spherulitic Growth of Apatite in a MgO─CaO─SiO2─P2O5 Glass

Differential thermal analysis, X-ray diffraction, scanning electron microscopy with energy dispersive X-ray analysis, and transmission electron microscopy were used to study the crystallization of a glass with a composition of 11.2 wt% MgO, 40.5 wt% CaO, 33.3 wt% SiO₂, and 15 wt% P₂O₅. A two-phase "composite," which was composed of apatite and an intermediate phase (H-phase), was formed under appropriate heat-treatment conditions. The spherulitic morphology of apatite phase transformed from "open sheaf" into ellipsoidal as samples were heated to a higher temperature. These phenomena were due to the intermediate H-phase becoming unstable at this temperature so that the retardation effect on the apatite dendritic growth disappeared.     

Effect of B2O3 Addition on the Thermal Properties and Structure of Bulk and Powdered Barium Phosphate Glasses

The glass transition temperature increases and the thermal expansion coefficient and density decrease with increasing B₂O₃ concentration in a series of (100− x )(50BaO–50P₂O₅)− x B₂O₃ where x =0–10 mol% for bulk samples. According to Raman spectroscopy, the bulk BaO–P₂O₅–B₂O₃ (BaP–B) glasses consist of metaphosphate Q ² units with ring-type metaborate, diborate, and PO₄–BO₄ groups. X-ray photoelectron spectroscopy results reveal qualitatively that P–O–B bonds are formed at the surface of BaP–B glass samples ground in laboratory air over 6 mol% B₂O₃ only. The P–O–B bonds are related to the suppression of the crystallization of powdered BaP–B glasses with >6 mol% B₂O₃ during differential thermal analysis.     

Crystallization of MgO-Al2O3-SiO2-ZrO2 Glasses

The crystallization of MgO-Al₂O₃-SiO₂-ZrO₂ glasses at 1000°C was studied. Isothermal heat treatments of a cordierite-based glass (2MgO.2Al₂O₃.5SiO₂= Mg₂Al₄Si₅O₁₈) with 7 wt% ZrO₂ produced surface crystallization of α-cordierite and tetragonal ZrO₂ ( t -ZrO₂). These phases advanced into the glass by cocrystallization of t -ZrO₂ rods in an α-cordierite matrix with a well-defined orientation relation. The t -ZrO₂ rods were unstable with respect to diffusional breakup (a Rayleigh instability) and decomposed into rows of aligned ellipsoidal and spheroidal particles. The t -ZrO₂ was very resistant to transformation to monoclinic symmetry. With a similar glass containing 15 wt% ZrO₂, surface crystallization of α-cordierite and t -ZrO₂ was accompanied by internal crystallization of t -ZrO₂ dendrites. Transformation of the dendrites to mono-clinic symmetry was observed under some conditions.     

Crystallization Behavior of a High-Zinc-Content Li2O-ZnO0-SiO2 Glass-Ceramic and the Effect of K2O Additions

The crystallization behavior of an Li₂O-Zn0-SiO₂ glass with a ZnO content of −28.5 wt% and nucleated with P₂O₅ was investigated by infrared spectroscopy, X-ray diffraction, and scanning electron microscopy. A three-stage process, consisting of the nucleation, crystallization, and transformation of Li₃Zn_0.5Si0₄ and the emergence of a silica phase, occurs during heat treatment of this system. A small addition of K₂O varies the sequence of crystallization and the phase composition of the resulting glass-ceramic.     

Crystallization of MgO-CaO-SiO2-P2O5 Glass

The crystallization behavior of a glass with a composition of 40 wt% 3CaO · P₂O₅−60 wt% CaO · MgO · 2SiO₂ was investigated. The primary crystalline phase was apatite with a dendritic form and ellipsoidal shape. β-(3CaO · P₂O₅) and CaO · MgO · 2SiO₂ were crystallized as samples heated to 990°C, and a three-layer structure was obtained. The development and morphology of this construction were explained by both the surface crystallization of the apatite and CaO · MgO · 2SiO₂ and the bulk crystallization of apatite and the CaO · MgO · 2SiO₂-β-(3CaO · P₂O₅) composite.     

Quaternary System Al2O3–CaO–MgO–SiO2: II Study of the Crystallization Volume of MgAl2O4

Solid-state compatibility and melting relations of MgAl₂O₄ in the quaternary system Al₂O₃–CaO–MgO–SiO₂ were studied by firing and quenching selected samples located in the 65 wt% MgAl₂O₄, plane followed by microstructural and energy dispersive X-ray analysis. A projection of the liquidus surface of the primary crystallization volume of MgAl₂O₄ was constructed from CaO, SiO₂ and exceeding Al₂O₃, not involved in stoichiometric MgAl₂O₄ formation; those three amounts were recalculated to 100 wt%. The temperature and character of six invariant points, where four solids co-exist with a liquid phase, were defined. One maximum point was localized and the positions of the isotherms were tentatively established. The effect of CaO, SiO₂, and Al₂O₃ impurities on the high temperature behavior of spinel materials was also discussed.     

Crystallization Kinetics and Properties of Nonstoichiometric Cordierite-Based Thick-Film Dielectrics

Dielectric thick films based on a nonstoichiometric cordierite (2.4MgO·2Al₂O₃·5SiO₂, containing 3 wt% B₂O₃, 3 wt% P₂O₅, and 3 wt% PbO) were investigated, in regard to their microstructure, crystallization kinetics, and properties. A stable glass-ceramic thick-film microstructure that was formed on a 96% alumina substrate was observed after firing at a temperature of 915°C for 30 min in a nitrogen atmosphere. No µ-cordierite was observed in the X-ray diffraction (XRD) patterns of the thick film. The crystallization kinetics were studied via quantitative XRD analysis using the Avrami equation, and the rate constant increased as the temperature increased. The decreasing tendency of the Avrami parameter, relative to temperature, suggested a change in growth directionality during crystallization. The activation energy for crystallization of the thick film was determined to be ~83 kcal/mol (~350 kJ/mol). The coefficient of thermal expansion (CTE) and the dielectric constant of the glass phase were evaluated using the bulk-sample data. For the case of a 3-wt%-PbO sample fired at 950°C for 30 min in a nitrogen atmosphere, the remaining glass was estimated, using the parallel mixing rule, to have a dielectric constant of 15.3 at 1 MHz. The dielectric constant of the remaining glass was dependent on the PbO content and the heat-treatment temperature. The estimated CTE of the remaining glass for the 3-wt%-PbO sample was 19 × 10^-6/°C.     

Effect of Nitrate Salts as Sintering Additives during the Ball-Milling Process of Silicon Nitride Powders

A chemical adsorption method in a Si₃N₄ slurry that contained a nitrate solution was studied during ball milling, with particular interest in increasing the oxide layer in the Si₃N₄ powder and improving the distribution homogeneity of the sintering additives. The nitrate salts Al(NO₃)₃·9H₂O and Y(NO₃)₃·6H₂O were selected as sintering additives. The following characterization techniques were used: oxygen–nitrogen analysis, X-ray photoelectron spectroscopy, high-resolution electron microscopy (coupled with energy-dispersive X-ray spectroscopy), and X-ray imaging (using wavelength-dispersive X-ray spectroscopy). The thickness of the amorphous layer and the oxygen content of the Si₃N₄ powder were greater for samples that were milled with nitrate additives, which were heat-treated at 600°C, than those of powders that were milled with oxide additives. The chemical composition of the oxygen-containing layer—that is, the amorphous layer that formed and/or changed on the Si₃N₄ surface—was similar to Si₂N₂O in heat-treated Si₃N₄ powder with nitrate additives, whereas the composition of heat-treated Si₃N₄ powder with oxide additives was similar to SiO₂. Furthermore, a homogeneous distribution of the additives was achieved via the incorporation of aluminum and yttrium into the amorphous layer on the Si₃N₄ surface. The metal ratio (Y:Al) of the adsorbates was somewhat higher than that of the additives.     

Influence of Molybdenum Silicide Additions on High-Temperature Oxidation Resistance of Silicon Nitride Materials

The influence of additions of molybdenum disilicide (MoSi₂) on the microstructure and the mechanical properties of a silicon nitride (Si₃N₄) material, with neodymium oxide (Nd₂O₃) and aluminum nitride (AIN) as sintering aids, was studied. The composites, containing 5, 10, and 17.6 wt% MoSi₂, were fabricated by hot pressing. All materials exhibited a similar phase composition, detected by X-ray diffractometry. Up to MoSi₂ additions of 10 wt%, mechanical properties such as strength, fracture toughness, or creep at 1400°C were not affected significantly, in comparison to that of monolithic Si₃N₄. The oxidation resistance of the composites, in terms of weight gain, degraded. After 1000 h of oxidation at 1400° and 1450°C in air, a greater weight gain (by a factor of approximately three) was obtained, in comparison to that of the material without MoSi₂. Nevertheless, after 1000 h of oxidation, the degradation in strength of the composites was considerably less severe than that of the material without MoSi₂. An additional layer was formed, caused by processes at the surface of the Si₃N₄ material, preventing the formation of pores, cracks, or glassy-phase-rich areas, which are common features of oxidation damage in Si₃N₄ materials. This surface layer, containing Mo₅Si₃ and silicon oxynitride (Si₂ON₂), was the result of reactions between MoSi₂, Si₃N₄, and the oxygen penetrating by diffusion into the material during the hightemperature treatment.     

Crystallization in 70Ga2S3.30La2S3(mol%) Glasses as a Function of Oxide/Hydroxide Concentration

The crystallization of 70Ga₂S₃^.30La₂S₃(mol%) glasses has been studied using X-ray diffraction and transmission electron microscopy. Two of the glasses were prepared from raw materials with nominally different oxide concentrations. The third was prepared from raw materials aged in an oxygen-depleted, argon-flushed glove box for more than 1 yr. Their oxide/hydroxide impurity content was qualitatively ranked using Fourier transform infrared spectroscopy. The lowest oxide content composition (≤0.5 wt%, supplied information) devitrified readily close to the glass transition temperature, T _g, forming crystallites of a new (GLS) phase with a monoclinic Bravais lattice and a lathlike internal structure. Ga₂S₃was observed in small quantities between the laths. Samples prepared from nonaged, high oxide (1–3 wt%) content precursors produced the most stable glass. On crystallization, these samples exhibited spherulites composed of intergrown laths of melilite-structured La_3.33Ga₆S₁₄and the new monoclinic GLS phase. Whiskers of Ga₂S₃were found in the residual glass between crystallites. Samples prepared from aged raw materials produced spherulites of La_3.33Ga₆S₁₄on crystallization with no identifiable regions of the new GLS phase.     

Phase Transformations of Plasma-Sprayed Zirconia–Ceria Thermal Barrier Coatings

Phase constituents and transformations of plasma-sprayed thermal barrier coatings (TBCs) with CeO₂-stabilized ZrO₂ (CSZ; 16–26 wt% CeO₂) have been investigated using X-ray diffractometry (XRD), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS). The as-coated CSZ coatings with 16 and 18 wt% CeO₂ consisted only of the nonequilibrium tetragonal ( t ') phase. A mixture of the t ' and the nonequilibrium cubic ( c ') phases was observed for the as-coated CSZ coatings containing 20–26 wt% CeO₂. During 65 min cyclic oxidation at 1135°C (45 min hold time) in air, the t ' or the mixture of the t ' and the c ' phases decomposed to the equilibrium tetragonal ( t ) and the equilibrium cubic ( c ) phases. Some of the t phase transformed to the monoclinic ( m ) phase on cooling. More m phase was observed to develop in the CSZ coating containing 16 wt% CeO₂ than in the other coatings. More m phase was observed on the top surface than on the bottom surface of the CSZ coating. Spalling of the plasma-sprayed CSZ coating during thermal cycling occurred after 230 cycles for the CSZ coating containing 16 wt% CeO₂, whereas the lifetime of the CSZ coatings with 18–26 wt% CeO₂ ranged between 320 and 340 cycles.     

Compatibility Relations of A1203 in the System Zr02-Al203-Si02-CaO

Compatibility relations of Al₂0₃ in the quaternary system Zr02-Al₂0₃-Si0₂-CaO were studied by firing and quenching followed by microscopy and energy-dispersive X-ray examination. A projection of the boundary surface of the primary crystallization volume of Al₂0₃ was constructed in terms of the CaO, Si0₂, and Zr0₂ contents of the mixtures recalculated to 100 wt%. Two invariant points, where four solids coexist with a liquid phase, are defined, and the positions of the isotherms were established.     

Effects of B2O3 Addition on the Dielectric and Ferroelectric Properties of Ba0.7Sr0.3TiO3 Ceramics

The effects of B₂O₃ addition on the sintering behavior and the dielectric and ferroelectric properties of Ba_0.7Sr_0.3TiO₃ (BST) ceramics were investigated. The dielectric and ferroelectric properties of a BST sample with 0.5 wt% B₂O₃ sintered at <1150°C were as good as those of undoped BST sintered at 1350°C, and the dielectric loss was better. When >1.0 wt% B₂O₃ was added to BST, the overdoped B₂O₃ did not form a liquid phase or volatilize; it remained in the samples and formed a secondary phase that lowered the sintering behavior and the dielectric and ferroelectric properties of the BST.     

Li2O─SiO2─Al2O3─MeIIO Glass-Ceramic Systems for Tile Glaze Applications

In order to verify the possibility of using glass-ceramic materials as tile coatings, the devitrification processes of three industrial formulations belonging to the Li₂O─Al₂O₃─SiO₂ glass-ceramic system were investigated by differential thermal analysis, X-ray diffractometry, scanning electron microscopy, and IR spectroscopy. Compositional variations were made by addition of large amounts of MgO or CaO or PbO (ZnO) oxides as well as through smaller additions of other oxides. In these systems the surface crystallization contributes appreciably to the bulk crystallization mechanism. All the systems investigated show a high tendency toward crystallization even at very high heating rates, developing a very close network of interlocked crystals of synthetic β-spodumene-silica solid solutions (LiAlSi₄O₁₀). The results of this research are expected to establish the conditions under which these glass-ceramic systems can be practically used as tile glazes.     

DTA and X-Ray Analysis Study of Nucleation and Crystallization of MgO-Al2O3-SiO2 Glasses Containing ZrO2, TiO2, and CeO2

Crystallization sequences of glasses with compositions in the tridymite primary phase field of the MgO-Al₂O₃-SiO₂ system were studied by DTA, X-ray diffraction, and other techniques. Crystallization was catalyzed by the addition of 7 wt% of either ZrO₂ or TiO₂. Up to 10 wt% CeO₂ was also added to some glasses. Metastable solid solutions with the high-quartz structure exhibiting varying lattice parameters commonly occurred at low temperatures, transforming into a high cordierite at higher temperatures. Depending on the composition and heat treatment, other phases also appeared, e.g. Ce₂Ti₂O₄ (Si₂O₇). The rate of crystallization was markedly dependent on the catalyst. Colloidal precipitation of the catalyst accompanied by bulk crystallization of the glass was observed with ZrO₂, but no crystalline TiO₂ was detected. In the presence of CeO₂, TiO₂ was a more effective catalyst than ZrO₂. Although CeO₂ lowered the melting temperatures of the glass-ceramics, it increased the stability of the glasses and inhibited volume nucleation, causing coarse structures to form on crystallization.     

Grain-Boundary Phase Crystallization of Silicon Nitride with Material Loss During Heat Treatment

An analysis was made of the Si₃N₄· Y₂O₃ crystallization process from a compacted Si₃N₄ powder (composition: 5 wt% Y₂O₃ and 2 wt% Al₂O₃) during heat treatment in various powder beds. X-ray diffraction was used to measure the degree of cyrstallization, which was correlated with weight loss. Crystallization and weight loss were affected significantly by the SiO₂ content in the packing powder. Crystallization correlated strongly with the weight loss. The dominant loss was attributed to SiO volatilization from the Y-Si-Al-O-N liquid. The crystallization mechanism with the loss of material was interpreted using a solubility—supersolubility diagram at constant temperature.     

Measurement of Phase Abundance in Magnesia-Partially-Stabilized Zirconia by Rietveld Analysis of X-ray Diffraction Data

The relative abundance of the cubic ( c ), tetragonal ( t ), monoclinic ( m ), and orthorhombic ( o ) polymorphs of ZrO₂, and the δ phase, Mg₂Zr₅O₁₂, present in samples of 3.4-wt%-magnesia-partially-stabilized zirconia have been determined by Rietveld analysis of X-ray powder diffraction data. The samples studied correspond to the as-fired (AF), and subetectoid-aged maximum-strength (MS) and thermalshock (TS) states, with their surfaces in the ground or polished condition. The polymorph abundances of the bulk and near-surface regions are discussed in relation to the type of surface treatment. Grinding produces significant quantities of both m - and o -ZrO₂ in the near-surface regions of all samples. The m content increases from about 5 wt% in the bulk, to 10, 24, and 33 wt% in AF, MS, and TS material, respectively, while the o content increases from trace amounts to about 11 wt% in all samples. The m and o phases both increase at the expense of t -ZrO₂, and the transformation is accompanied by significant lattice distortion and/or crystal size reduction. Thus, measurement of only the 'ground-surface-monoclinic' content does not give an accurate indication of the total amount of transformable t -ZrO₂ in ceramics of this kind. Polishing removes some of the ground-surface m -ZrO₂ in MS and TS, and all of the m -ZrO₂ in AF material. The o -ZrO₂ produced by grinding also declines substantially in AF and MS, but is not removed by polishing of TS. As a result, the bulk composition cannot be guaranteed, in the general case, to be accessible by X-ray analysis of polished surfaces.     

Crystallization of Titanosilicate Glasses for Nuclear Waste Immobilization

The effects of different cooling and reheating rates on the phase constitutions of Na₂O–Al₂O₃–TiO₂–SiO₂ glass-ceramics containing up to 20 wt% of simulated nuclear fuel recycle waste have been studied using X-ray diffraction, differential thermal analysis, and scanning and transmission electron microscopy. The metastable formation of a perovskite-structured phase (nominally CaTiO₃, but containing ionic substituents) was observed in samples with up to 15 wt% of simulated waste after cooling from the melt at rates between 0.25 and 50°C/min. When the partially devitrified glass was reheated to 1050°C, incomplete conversion of this phase to sphene (nominally CaTiSiO₅) occurred by reaction with the silica-rich glass matrix. The conversion was completed by heating further to 1150°C. Waste loadings ⋝10 wt% produced crystallization of powellite (nominally CaMoO₄) in addition to sphene and perovskite, whereas metastable perrierite (a rare-earth titanosilicate) was also crystallized at waste loadings ⋝15 wt%. New data on elemental partitioning between the crystalline and vitreous phases confirmed earlier results obtained in different atmospheres and with simplified waste compositions and were largely in accord with crystal-chemical predictions.