Synthesis of β-Si3N4 by Chemical Vapor Deposition

Beta-type CVD-Si₃N₄ plates (up to 1.1 mm thick) have been prepared by adding TiCl₄ vapor to the system SiCl₄-NH₃-H₂ at deposition temperatures of 1350° to 1450°C, while α-type or amorphous CVD-Si₃N₄ was obtained without TiCl₄ vapor at the same deposition temperature. Three to four wt % 777V was included in the β-type CVD-Si₃N₄ matrix. The density, preferred orientation, and lattice parameters of β-type CVD-Si₃N₄ were examined.     

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.     

Novel Deposition of Columnar Y3Al5O12 Coatings by Electrostatic Spray-Assisted Vapor Deposition

A novel and cost-effective electrostatic spray-assisted vapor deposition (ESAVD) was used to deposit Y₃Al₅O₁₂ (YAG) coatings. Polycrystalline single-phase Y₃Al₅O₁₂ coatings were synthesized using the ESAVD method in an open atmosphere at 650°C, and then annealed at 700°–900°C for 1 h. The ESAVD process involves the decomposition and chemical reactions of charged aerosol in vapor phase. The low-temperature coating deposition characteristics of the ESAVD process using a suitable sol precursor decreases the reaction and crystallization temperatures for forming Y₃Al₅O₁₂ coatings. The microstructure of the Y₃Al₅O₁₂ coating prepared using the ESAVD method is columnar and such strain-resistance microstructure could be useful for thermal barrier coating applications.     

Additive-Assisted Nitridation to Synthesize Si3N4 Nanomaterials at a Low Temperature

Starting from Si powder, NaN₃ and different additives such as N -aminothiourea, iodine, or both, Si₃N₄ nanomaterials were synthesized through the nitridation of silicon powder in autoclaves at 60°–190°C. As the additive was only N -aminothiourea, β-Si₃N₄ nanorods and α-Si₃N₄ nanoparticles were prepared at 170°C. If the additive was only iodine, α-Si₃N₄ dendrites with β-Si₃N₄ nanorods were obtained at 190°C. However, when both N -aminothiourea and iodine were added to the system of Si and NaN₃, the products composed of β-Si₃N₄ nanorods and α, β-Si₃N₄ nanoparticles could be prepared at 60°C.     

Nd2O3-Doped Sialons with ZrO2/ZrN Additions Formed by Sintering and Hot Isostatic Pressing

β-sialon and Nd₂O₃-doped α-sialon materials of varying composition were prepared by sintering at 1775° and 1825°C and by glass-encapsulated hot isostatic pressing at 1700°C. Composites were also prepared by adding 2–20 wt% ZrO₂ (3 mol% Nd₂O₃) or 2–20 wt% ZrN to the β-sialon and α-sialon matrix, respectively. Neodymium was found to be a fairly poor α-sialon stabilizer even within the α-phase solid solution area, and addition of ZrN further inhibited the formation of the α-sialon phase. A decrease in Vickers hardness and an increase in toughness with increasing content of ZrO₂(Nd₂O₃) or ZrN were seen in both the HIPed β-sialon/ZrO₂(Nd₂O₃) composites and the HIPed Nd₂O₃-stabiIized α-sialons with ZrN additions.     

Synthesis, Characterization, and Consolidation of Si3N4 Obtained from Ammonolysis of SiCl4

Thermal decomposition of silicon diimide, Si(NH)₂, in vacuum resulted in very-high-purity, fine-particle-size, amorphous Si₃N₄ powders. The amorphous powder was isothermally aged at 50° to 100° intervals from 1000° to 1500°C for phase identification. Examination of ir spectra and X-ray diffraction patterns indicated a slow and gradual transition from an amorphous material to a crystalline α-phase occurring at 1200°C for >4 h and/or 1300° to 1400°C for 2 h. As the temperature was increased to ≥1450°C for 2 h, the crystalline β-phase was observed. Phase nucleation and crystallite morphology in this system were studied by electron microscopy and electron diffraction combined with TG as functions of temperature for the inorganic polymer starting materials. Powders prepared in this manner with 4 wt% Mg₃N₂ added as a sintering aid were hot-pressed to high-density fine-grained bodies with uniform microstructures. The optimum hot-pressing condition was 1650°C for 1 h. Silicon concentration steadily increased as the hot-pressing temperature or time was increased. A method for chemical etching for high-density fine-grained Si₃N₄ is described. Electrical measurements between room temperature and ∼500°C indicated dielectric constant and tan δ values of 8.3±0.03 and 0.65±0.05×10⁻², respectively.     

Polymorphism and Thermodynamic Stability of Zn7Sb2O12

The composition Zn_2.33Sb_0.67O₄ (or Zn₇Sb₂O₁₂) exists in two polymorphic forms. The thermodynamically stable, low-temperature orthorhombic β form transforms to the high-temperature cubic α-polymorph with a spinel structure at 1225°±25°C. The transformation is fully reversible but slower in the α→β direction and therefore, it is easy to preserve the high-temperature α-polymorph to lower temperatures where it is kinetically stable but thermodynamically metastable. It is also possible to synthesize the α-polymorph directly at low temperatures, e.g., 900°C. This synthesis, of a phase that is thermodynamically stable only at high temperatures, but which has sufficient kinetic stability to exist metastably at low temperatures, represents an example of Ostwald's law of successive reactions in which the first phase to crystallize from a reaction mixture is not necessarily the equilibrium phase of lowest free energy. The crystal structure of the α-polymorph has been confirmed by Rietveld refinement of X-ray powder diffraction data to be an inverse spinel, (Zn)[Sb_2/3Zn_4/3]O₄, in which octahedral sites contain a disordered, random mixture of Zn and Sb and tetrahedral sites are fully occupied by Zn.     

Melting Properties of Bi2O3-ZnO-Nb2O5-Based Dielectric Ceramics

Cubic-pyrochlore-structure α-phase and low-symmetry-structure ß-phase are the basic phases of dielectric ceramics that are based on Bi₂O₃-ZnO-Nb₂O₅ (BZN). In this paper, the melting behaviors of the α-phase and the ß-phase have been explored using differential thermal analysis and X-ray diffractometry. The results show that BZN-based α-phase is a congruent compound; its congruent melting point is 1190°C. BZN-based ß-phase is an incongruent compound that dissociates to form α-phase and a liquid phase, with an absorption of heat, at its incongruent melting point (peritectic temperature) of 1100°C. Upon cooling, the α-phase reacts with the liquid phase to form the ß-phase via peritectic reaction. Upon quenching, the BZN-based cubic-fluorite phase precipitates from the liquid phase.     

Microstructure and Mechanical Properties of the in situβ-Si3N4/α'-SiAlON Composite

The in situ β-Si₃N₄/α'-SiAlON composite was studied along the Si₃N₄–Y₂O₃: 9 AlN composition line. This two phase composite was fully densified at 1780°C by hot pressing Densification curves and phase developments of the β-Si₃N₄/α'-SiAlON composite were found to vary with composition. Because of the cooperative formation of α'-Si AlON and β-Si₃N₄ during its phase development, this composite had equiaxed α'-SiAlON (∼0.2 μm) and elongated β-Si₃N₄ fine grains. The optimum mechanical properties of this two-phase composite were in the sample with 30–40%α', which had a flexural strength of 1100 MPa at 25°C 800 MPa at 1400°C in air, and a fracture toughness 6 Mpa·m^1/2. α'-SiAlON grains were equiaxed under a sintering condition at 1780°C or lower temperatures. Morphologies of the α°-SiAlON grains were affected by the sintering conditions.     

Microstructure and Humidity-Sensitive Characteristics of α-Fe2O3 Ceramic Sensor

The microstructure and humidity-sensitive characteristics of α -Fe₂O₃ porous ceramic were investigated. Microporous α -Fe₂O₃ powders were obtained by controlling the topotactic decomposition reaction of α -FeOOH. Water vapor adsorption thermogravimetrical experiments were carried out in the relative humidity (rh) range 0% to 95% on the α -Fe₂O₃ powder and the 900°C sintered compact. The microstructure was investigated by SEM, TEM, Hg intrusion, and N₂ adsorption porosimetry techniques. The humidity sensitivity was investigated by the impedance measurements technique in 0% to 95% rh on the compacts sintered at 50°C steps in the 850° to 1100°C range. Humidity response was found to be affected by the microstructure, i.e., the characteristics of the precursor powders and sintering temperatures.     

Microstructural Observations on Hot-Pressed Si3N4

The development of microstructure in hot-pressed Si_aN₄ was studiehd for a typical Si₃N₄ powder with and without BeSiN₂ as a densification aid. The effect of hot-pressing temperature on density, α- to β-Si₃N₄ conversion and specific surface area showed that BeSiN₂ appears to increase the mobility of the system by enhancing densification, α- to β-Si₃N₄ transformation, and grain growth at temperatures between 1450° and 1800°. These processes appear to occur in the presence of a liquid phase.     

The Join Ca2SiO4-CaMgSiO4

New data obtained on the join Ca₂SiO₄-CaMgSiO₄ established a limit of crystalline solubility of Mg in α-Ca₂SiO₄ corresponding to the composition Ca_1.90Mg_0.10SiO₄ at 1575°C. The α-α'Ca₂SiO₄ inversion temperature is lowered from 1447° to 1400°C by Mg substitution in the lattice. α'-Ca₂SiO₄ takes Mg into its lattice up to the composition Ca_1.94Mg_0.06SiO₄ at 1400°C and to Ca_1.96Mg_0.04SiO₄ at 900°C. A new phase (T) reported previously by Gutt, with the approximate composition Ca_1.70Mg_0.30SiO₄, was stable between 979° and 1381°C, and should be stable at liquidus temperatures in multicomponent systems involving CaO–MgO–SiO₂.     

Studies in Lithium Oxide Systems: XIII, Li,O.Al2O3.2SiO2-Li2O.Al2O3.2GeO2

Complete solid solubility was demonstrated to occur between LiAlGeO₄ and the low temperature form of Li AlSiO₂ (a-eucryptite). Hydrother-mal preparation was necessary for the silicate-rich compositions. Under atmospheric pressure, about 65 mole % LiAlGeO₄ entered the β-eucryβ-tite phase at 1150°C, but solid solutions containing more than 25 mole % LiAlGeO4 exsolved if held at lower temperatures. Directional thermal expansion data were obtained by X-ray diffraction methods on both α- and β-eucryptite and their solid solutions. Substitution of Ge⁴⁺ for Si⁴⁺ produced no significant difference in the thermal expansion coefficients in the α and β phases. An increase in the lattice parameters in the a and c directions took place as expected when Ge⁴⁺ (0.53 A) was substituted for Si⁴⁺ (0.39 A).     

Solvothermal Synthesis of Si3N4 Nanomaterials at a Low Temperature

Silicon nitride nanowires or nanorods have been synthesized from SiCl₄, NaN₃, and metallic Mg at temperatures ranging from 200° to 300°C. X-ray powder diffraction patterns indicated that the as-obtained products were mainly β-Si₃N₄. Scanning electron microscope and high-resolution transmission electronic microscopy showed that the samples mostly consisted of Si₃N₄ nanowires or nanorods. As metallic iron powder was used, α-Si₃N₄ was mainly formed at 250°C.     

Spark Plasma Sintered Silicon Nitride Ceramics with High Thermal Conductivity Using MgSiN2 as Additives

Silicon nitride ceramics were prepared by spark plasma sintering (SPS) at temperatures of 1450°–1600°C for 3–12 min, using α-Si₃N₄ powders as raw materials and MgSiN₂ as sintering additives. Almost full density of the sample was achieved after sintering at 1450°C for 6 min, while there was about 80 wt%α-Si₃N₄ phase left in the sintered material. α-Si₃N₄ was completely transformed to β-Si₃N₄ after sintering at 1500°C for 12 min. The thermal conductivity of sintered materials increased with increasing sintering temperature or holding time. Thermal conductivity of 100 W·(m·K)⁻¹ was achieved after sintering at 1600°C for 12 min. The results imply that SPS is an effective and fast method to fabricate β-Si₃N₄ ceramics with high thermal conductivity when appropriate additives are used.     

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.     

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.     

Formation of Frozen α-Agl in Twin-Roller-Quenched Agl─Ag2 O─MxOy (MxOy= WO3, V2O5) Glasses at Ambient Temperature

Superionic conductor α-AgI, which is stable only above 147°C, was successfully frozen at ambient temperature in AgI─Ag₂O─M_xO_y (M_xO_y= WO₃, V₂O₅) glass matrices by a twin-roller-quenching technique. The system with WO₃, provided the larger composition regions where α-AgI was frozen at ambient temperature, compared to the system with V₂O₅. The matrix glasses with higher glass-transition temperatures had a stronger effect in depressing the α–β transformation of AgI. The α-AgI-frozen samples exhibited extremely large conductivities of 3 × 10⁻²-5 × 10⁻²S.cm⁻¹at 25°C.     

Reactions in the System Li2O–MgO–Al2O3–SiO2: I, The Cordierite-Spodumene Join

Phase equilibria along the nonbinary join between cordierite (2MgO · 2Al₂O₃· 5SiO₂) and spodumene (Li₂O · Al₂O₃· 4SiO₂) were investigated in the temperature range 800° to 1550°C. using the quench technique on fourteen compositions. The phase diagram at high temperatures is characterized by a very small region of solid solution on the cordierite side, appreciable solid solution on the spodumene side, and regions of three and four phases toward the center of the system, including liquid, α-cordierite, mullite, spinel, corundum, and β-spodumene and its solid solutions. The liquidus has a flat minimum between 40 and 50% cordierite at 1347°, and rises on one side to the congruent melting point of β-spodumene (1421°) and on the other side to the temperature of complete melting of cordierite (1530°). The lowest temperature at which liquid appears is 1325°. At low temperatures a complete series of metastable solid solutions exists between μ-cordierite and β-spodumene. The significance of the data in the preparation of thermal-shock-resisting bodies is discussed.     

Solid Solubility and Polymorphism in the System Sr2SiO4-Sr2GeO4-Ba2GeO4-Ba2SiO4

The reciprocal salt pair Sr₂SiO₄-Sr₂GeO₄-Ba₂GeO₄-Ba₂SiO₄ was investigated using X-ray powder diffraction and DTA. Unlimited solubility in the low-K₂SO₄ structure type (α') occurs throughout the system above 85°C. The nonlinear changes of some lattice constants of the solid solutions are discussed. A stable monoclinic low-temperature (β) form of Sr₂SiO₄ was found which converts reversibly to the high-temperature α'-modification at 85°C. The enthalpy of the β-α' transition is 51 cal/mol. In the reciprocal salt pair the β-form solid solutions occur in a very narrow region below 85°C.