The Role of Cerium Orthosilicate in the Densification of Si3N4

The existence of compounds between Si₃N₄-CeO₂ and Si₃N₄-Ce₂O₃ was investigated for firing temperatures of 1600° to 1700°C. The two new monoclinic compounds found were Ce₂O₃·2Si₃N₄ with lattice parameters a = 16.288, b = 4.848, and c =7.853 Å and β=91.54° and Ce₄Si₂O₇N₂ with lattice parameters a = 10.360, b = 10.865, and c =3.974 Å and β=90.33°. Cerium orthosilicate (Ce 4.67 (SiO₄)₃O) is present during firing as a glassy intermediate phase which promotes sintering and densification and then reacts with silicon nitride to form cerium silicon oxynitrde (CeSiO₂N).     

Sinterability of β-Calcium Orthophosphate Powder Prepared by Spray-Pyrolysis

Mixed solutions of Ca(NO₃)₂ and (NH₄)₂HPO₄ with Ca/P = 1.50 were spray-pyrolyzed at 600°C to produce β-calcium orthophosphate (β-Ca₃(PO₄)₂) powder; the spray-pyrolyzed powder was ground and then calcined at 600°C for 1 h. The best crystalline β-Ca₃(PO₄)₂ powder was obtained from the solution with 1.80 mol.L^–1 Ca(NO₃)₂, 1.20 mol.L^–1 (NH₄)₂HPO₄. The resulting powder was composed of primary particles with sizes of <0.5 μm. Dense β-Ca₃(PO₄)₂ ceramics with a relative density of 96.1% could be fabricated by firing this compressed powder at 1070°C for 5 h.     

Near-Net-Shaped Calcium Hydroxyapatite by the Oxidation of Machinable, Calcium-Bearing Precursors (the Volume Identical Metal Oxidation, or VIMOX, Process)

A novel VIMOX (volume identical metal oxidation) route to near-net-shaped calcium hydroxyapatite, Ca₁₀(PO₄)₆(OH)₂, is demonstrated: the oxidation of machinable Ca—Ca₂P₂O₇ precursors. Mechanically alloyed mixtures of Ca and β-Ca₂P₂O₇ were compacted into disk- and bar-shaped preforms. The latter preforms could be machined into cylinders using a metalworking lathe (200 rpm, hardened steel tooling). After oxidation at 600°C in O₂, and then postoxidation annealing in H₂O/O₂ mixtures at 850°C and 1150°C, phase-pure hydroxyapatite was obtained. Because of offsetting volume changes from calcium oxidation and hydroxyapatite formation, porous hydroxyapatite bodies were produced that retained the shapes and dimensions (within 1%) of the machined precursors.     

The Al2O3-Nd2O3 Phase Diagram

A tentative phase diagram for the system Al₂0₃-Nd₂O₃ is presented. Three compounds were obtained: a β -A1₂O₃-type compound, the perovskite NdAlO₃, and Nd₄Al₂O₉. The perovskite melts congruently (mp 2090°C), and the two other compounds exhibit incongruent melting behavior: β -Nd/Al₂O₃, mp 1900°C; Nd₄Al₂O₉, mp 1905°C. Two eutectics exist with the following compositions and melting points: 80 mol% Al₂O₃, 1750°C; 23 mol% Al₂O₃,1800°C. Nd₄Al₂O9 decomposes in the solid state at 1780°C.     

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.     

Physical Stabilization of the β→γ Transformation in Dicalcium Silicate

It has been shown that the monoclinic β -phase of dicalcium silicate (Ca₂SiO₄) can be stabilized against transformation to the orthorhombic γ -phase by physical rather than chemical factors. Stabilization was studied in different types of microstructures fabricated under various processing conditions such as different powder or grain sizes, chemical additives, cooling kinetics, or high-temperature annealing treatments. The observations can be explained in terms of a critical particle size effect controlling nucleation of the transformation. Rapid quenching through the high-temperature hexagonal ( α ) to orthorhombic ( a' _H) transformation at 1425°C, which is accompanied by a −4.7% volume decrease, causes periodic fracture of β -twins due to accumulated strains. Chemical doping with K₂O or Al₂O₃ promotes the formation of amorphous phases which mold themselves around β -Ca₂SiO₄ grains. Annealing treatments cause crystallization of the glass and subsequent transformation to the γ -phase.     

Phase Formation in the System Na2O · Al2O3-CaO · A12O3-Al2O3 at 1200°C in Air

Phase relations in the system Na₂O_· Al₂O₃-CaO· Al₂O₃-Al₂O₃ at 1200°C in air were determined using the quenching method and high-temperature X-ray diffraction. The compound 2Na₂O · 3CaO · 5Al₂O₃, known from the literature, was reformulated as Na₂O · CaO · 2Al₂O₃. A new compound with the probable composition Na₂O · 3CaO · 8Al₂O₃ was found. Cell parameters of both compounds were determined. The compound Na₂O · CaO-2Al₂O₃ is tetragonal with a = 1.04348(24) and c = 0.72539(31) nm; it forms solid solutions with Na₂O · Al₂O₃ up to 38 mol% Na₂O at 1200°C. The compound Na₂O · 3CaO · 8Al₂O₃ is hexagonal with) a = 0.98436(4) and c = 0.69415(4) nm. The compound CaO · 6Al₂O₃ is not initially formed from oxide components at 1200°C but behaves as an equilibrium phase when it is formed separately at higher temperatures. The very slow transformation kinetics between β and β "-Al₂O₃ make it very difficult to determine equilibrium phase relations in the high-Al₂O₃ part of the diagram. Conclusions as to lifetime processes in high-pressure sodium discharge lamps can be drawn from the phase diagram.     

Synthesis and Structure Refinement of Zinc-Doped β-Tricalcium Phosphate Powders

Zinc substituted β-tricalcium phosphate [β-Ca₃(PO₄)₂] was formed by substituting a zinc precursor in calcium-deficient apatite through aqueous precipitation technique. Heat treatment at 1000°C led to the formation of well crystalline β-Ca₃(PO₄). Refinement technique was used to determine the influence of incorporated zinc in the β-Ca₃(PO₄) structure. The structural data for all the four different zinc substituted β-Ca₃(PO₄) ranging from 0–9 mol% of zinc investigated in the present study confirmed the rhombohedral structure of β-Ca₃(PO₄) in the hexagonal setting (space group R 3 c ). The incorporation of lower sized Zn²⁺ (0.745 Å for sixfold coordination with O) at the higher sized Ca²⁺ (1.00 Å for sixfold coordination with O) site in the β-Ca₃(PO₄) structure led to the contraction of unit cell parameters. The added zinc prefers to occupy the Ca(5) site of β-Ca₃(PO₄) structure.     

Crystallization Behavior of CaO–P2O5 Glass with TiO2, SiO2, and Al2O3 Additions

TiO₂ above 4 mol% is an effective nucleating agent for CaO–P₂O₅ glass which also contains substantial SiO₂ and Al₂O₃ additions. Glass ceramics can be made from this glass using a single slow heating ramp with no need for a nucleating heat treatment step. Powder of this composition crystallizes rapidly to β-Ca₂P₂O₇, whereas bulk glass crystallizes from diphasic nuclei consisting of a central cubic Ca-P-Ti-Si-Al oxide phase surrounded by impure AlPO₄ dendrites. Metastable calcium phosphate grows on the AlPO₄ dendrites and later transforms to β-Ca₂P₂O₇.     

High-Temperature Transmission Electron Microscopy and X-Ray Powder Diffraction Studies of Polymorphic Phase Transitions in Ba4Nb2O9

Polymorphic phase transitions in Ba₄Nb₂O₉ were studied by thermal analyses, high-temperature transmission electron microscopy and X-ray powder diffractometry. Two stable polymorphs were isolated, low-temperature α-modification and high-temperature γ-modification, with the endothermic phase transition at 1176°C. The α→γ transformation is accompanied by the formation of a 120° domain structure, which is a consequence of hexagonal→orthorhombic unit cell reconstruction. Reheating the presintered γ-Ba₄Nb₂O₉ results in the formation of a metastable γ'-modification (formerly known as β-polymorph) in the temperature range between 360° and 585°C, before the γ→α transformation at 800°C. Above ∼490°C Ba₄Nb₂O₉ becomes moderately sensitive to a loss of BaO. In air the surface of Ba₄Nb₂O₉ grains decomposes to nanocrystalline Ba₅Nb₄O₁₅ and BaO, which instantly reacts with atmospheric CO₂ to form BaCO₃. Surface reaction delays γ→α transformation up to 866°C in air. In vacuum the loss of BaO is even more enhanced and consequently the formation of minor Ba₃Nb₂O₈ phase is observed above 1150°C.     

Porous Glass-Ceramic in the CαO–TiO2–P2O5 System

A porous glass-ceramic in the CaO–TiO₂—P₂O₅ system has been prepared by crystallization and subsequent chemical leaching of the corresponding glass. By applying a two-step heat treatment to 45CaO · 25TiO₂· 30P₂O₅ glasses containing a few mol% of Na₂O, volume crystallization results in the formation of dense glass-ceramics composed of CaTi₄(PO₄)₆ and β-Ca₃(PO₄)₂ phases. By leaching the resultant glass ceramics with HCI, β-Ca₃(PO₄)₂ is selectively dissolved out, leaving a crystalline CaTi₄(PO₄)₆ skeleton. The surface area and mean pore radius of the porous glass-ceramics were approximately 40 m²/g and 13 nm, respectively.     

Crystallization of Li2O · Al2O3· 6SiO2 Glasses Containing Niobium Pentoxide as Nucleating Dopant

Niobium pentoxide (T form, orthorhombic system) was utilized to promote devitrification in Li₂O · Al₂O₃· 6SiO₂ glasses. Two or more mole percentage of this nucleating dopant enhanced crystallization in these glasses. Glasses containing 4.0 and 8.0 mol% T-Nb₂O₅ exhibited a high tendency to form dispersed TT-Nb₂O₅ (monoclinic system) precipitates during the glass quenching process. The crystallization process in glasses containing 2.0 or 4.0 mol% T-Nb₂O₅ occurred as microphase separation, followed by the formation of dispersed TT-Nb₂O₅ crystalline precipitates (760°C), followed by β-quartz solid-solution ( ss ) formation (850° to 900°C) heterogeneously nucleated from the precipitates. β-quartz( ss ) transformed to β-spodumene( ss ), along with a polymorphic transition from the TT-Nb₂O₅ to M-Nb₂O₅ (tetragonal system) crystalline phase.     

Sintering Silicon Nitride Ceramics in Air

Silicon nitride (Si₃N₄) ceramics, prepared with Y₂O₃ and Al₂O₃ sintering additives, have been densified in air at temperatures of up to 1750°C using a conventional MoSi₂ element furnace. At the highest sintering temperatures, densities in excess of 98% of theoretical have been achieved for materials prepared with a combined sintering addition of 12 wt% Y₂O₃ and 3 wt% Al₂O₃. Densification is accompanied by a small weight gain (typically <1–2 wt%), because of limited passive oxidation of the sample. Complete α- to β-Si₃N₄ transformation can be achieved at temperatures above 1650°C, although a low volume fraction of Si₂N₂O is also observed to form below 1750°C. Partial crystallization of the residual grain-boundary glassy phase was also apparent, with β-Y₂Si₂O₇ being noted in the majority of samples. The microstructures of the sintered materials exhibited typical β-Si₃N₄ elongated grain morphologies, indicating potential for low-cost processing of in situ toughened Si₃N₄-based ceramics.     

Wet-Chemical Routes Leading to Scandia Nanopowders

Two wet-chemical routes have been used to synthesize Sc₂O₃ nanopowders from nitrate solutions employing ammonia water (AW) and ammonium hydrogen carbonate (AHC) as the precipitants. The precursors and the resultant oxides are characterized by elemental analysis, X-ray diffractometry, differential thermal analysis/thermogravimetry, high-resolution scanning electron microscopy, and Brunauer-Emmett-Teller analysis. Crystalline γ-ScOOH· n H₂O ( n ≈ 0.5) is the only phase obtained by the AW method. This phase dehydrates to Sc₂O₃ at ∼400°C, yielding hard aggregated nanocrystalline Sc₂O₃ powders. Three types of precursors have been synthesized by the AHC method, depending on the AHC/Sc³⁺ molar ratio ( R ): amorphous basic carbonate [Sc(OH)CO₃·H₂O] at R ≤ 3, crystalline double carbonate [(NH₄)Sc(CO₃)₂·H₂O] at R ≥ 4, and a mixture of the two phases at 3 < R < 4. Among these precursors, only the basic carbonate shows spherical particle morphology, ultrafine particle size (∼50 nm), and weak agglomeration. Sc₂O₃ nanopowders (∼28 nm) with high surface area (∼49 m²/g) have been prepared by calcining the basic carbonate at 700°C for 2 h.     

Phase Equilibria in the System Na2O – Nb2O5

Phase equilibria data, obtained both by differential thermal analysis and by quenching, are presented for the system Na₂O-Nb₂O₅. Five compounds corresponding to the formulas 3Na₂O.1Nb₂0₆, lNa₂O. 1Nb₂O₅, lNa₂O 4Nb₂O₆, lNa_zO.7Nb₂O₅, and lNa₂O. 10Nb₂O₆ have been found. The compound 3Na_z0.lNb₂O₅ melts congruently at 992°C. The compounds 1Na₂O. 4Nb₂O₆, lNa₂O.7Nb₂O, and 1Na₂O. 1Onb₂O₅ melt incongruently at 1265°, 1275°, and 1290°C., respectively. The well-known perovskite structure phase NaNbO₃ was found to melt congruently at 1412°C. The transition temperatures in NaNbO₅ were checked by thermal analysis and only the major structural changes at 368° and 640°C. could be detected. A new disordered form of NaNbO₃ could be preserved to room temperature by very rapid quenching.     

Analytical Electron Microscopic Studies of Doped Dicalcium Silicates

Dicalcium silicates having CaO/SiO₂ molar ratios of 1.8 to 2.2 were sintered at 1450°C for 90 min with or without small quantities of dopants (K₂O or Al₂O₃) and were air quenched. The microstructures of the fired samples were characterized using electron microscopy (SEM and TEM) and associated microanalytical techniques. There was no evidence for the existence of Ca_1.8SiO_3.8 or Ca_2.2SiO_4.2. Amorphous grain-boundary phases were observed between grains and as inclusions within the grains; the amounts decreased as CaO/SiO₂ ratios increased. The compositions of the amorphous phases were always rich in dopants and had a CaO/SiO₂ ratio close to that of wollastonite. High levels of Al₂O₃ were observed to enter the β-Ca₂SiO₄ grains under lime-rich conditions (CaO/SiO₂= 2.2) up to a saturation level of about 3.0 wt%. Some additional crystalline phases were observed to form depending on stoichiometry and dopant level.     

Effects of Temperature and Reagent Concentration on the Morphology of Chemically Vapor Deposited β-Ta2O5

Crystalline β-Ta₂O₅ coatings were deposited on hot-isostatically-pressed Si₃N₄ by reacting TaCl₅ with H₂ and CO₂ in the temperature range of 1000°–1300°C and at a pressure of 660 Pa. The Ta₂O₅ coatings generally consisted of wellcoalesced 2–3 μm grains, resulting in the formation of a nonporous coating morphology. However, the presence of microcracks on the as-deposited surface was consistently observed. The surface morphology, texture, and growth rate of the coatings were examined as a function of deposition parameters.     

Phase Stability Study on the Remelting Reaction in Ca2SiO4 Solid Solutions

A pseudobinary phase equilibrium diagram has been established for the P₂O₅-bearing Ca₂SiO₄-CaFe₄O₇ system to confirm the occurrence of remelting reaction in α-Ca₂SiO₄ solid solutions (C₂S(ss)). The reaction started at 1290°C immediately after the α-to-α'_H transition and finished at 1145°C. The reaction products were made up of about 1 wt% of liquid and 99 wt% of solid α'_H-C₂S(ss). The liquid exsolved at 1290°C was rich in Fe₂O₃, consisting of about 30 wt% of Ca₂SiO₄ and 70 wt% of CaFe₄O₇. The liquid coexisting with α-C₂S(ss) precipitated new α'-phase crystals in association with the remelting reaction.     

Ion Exchange in Alkali Layers of Potassium β -Ferrite ((1 + x)K2O · 11Fe2O3) Single Crystals

The potassium ions in potassium β-ferrite ((1 + x)K₂O ·11Fe₂O₃) crystals were exchanged with Na⁺, Rb⁺, Cs⁺, Ag⁺, NH₄⁺, and H₃O⁺ in molten nitrates or in concentrated H₂SO₄. On the other hand, spinel and hexagonal ferrites were formed by soaking the crystals in the melt of divalent salts. The crystals of K⁺, Rb⁺, and Cs⁺β-ferrites decomposed to form α-Fe₂O₃ at high temperatures of 800° to 1100°C. In addition, H₃O⁺, NH₄⁺, and Ag⁺β-ferrites decomposed to form α-Fe₂O₃ at relatively low temperatures of 350° to 650°C, in accordance with the stabilities of the inserted ions. The electrical properties of some β-ferrites were measured.     

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.