Preparation and Characterization of Single-Phase β-SiAlON

A simple method for the preparation of monophasic β-SiAlON using nitridation of Si and AIN with an oxygen partial pressure of 10 ^-4 atm is described. The effect of the AIN/Si ratio in the initial mixture on the formation of β-SiAlON is discussed. The likely mechanism of the formation of β-SiAlON is outlined.     

Mechanism of Grain Growth of β-SiAlON

The mechanism for grain growth of β-SiAlON has been investigated by annealing high-density β-SiAlON–YAG materials at 1650°C. An observed decrease in grain growth with increasing weight fraction of liquid confirms a diffusion-controlled growth mechanism in the system. The grain-growth mechanism is further characterized by the development of large elongated grains in addition to smaller grains. After prolonged heating, an equilibrium maximum grain size is developed causing a homogenization of the microstructure.     

The Mechanical Properties of β-SiAlON Ceramics Joined Using Composite β-SiAlON-Glass Adhesives

The mechanical properties of β-SiAlON ceramics joined using β-SiAlON-glass-forming adhesives consisting of mixed Si³N⁴, Y²O³, Al²O³, and SiO² powders are described. Use of adhesives with a β-SiAlON:glass ratio of 60:40 gave an optimum joint strength of 650 MPa in four-point bending mode, i.e., 85% of that of unbonded material, when joining was carried out at 1600°C for 10 min, under an applied uniaxial pressure of 2 MPa. Bonding pressures in excess of 2 MPa caused excessive compressive creep distortion during the joining operation. The strengths of postjoined HIPed material and HIPed, unbonded material, differed by only 4%, i.e., 975 and 1010 MPa, respectively, which indicates that HIPing reduces the size of critical defects in the joint. Fracture toughness of the joint also improved upon HIPing.     

Elucidation of the Formation Mechanism of β-SiAlON from a Zeolite

β-SiAlON was synthesized from Y-type zeolite and its formation mechanism was determined using magic-angle spinning nuclear magnetic resonance (NMR) spectroscopy and powder X-ray diffraction (XRD). Y-type zeolite and carbon powders were mixed for 36 h, fired at 1050° to 1450°C for 0–2 h in flowing gas (0.5 L/min N₂), then heat treated at 700°C for 2 h in air to remove residual carbon. The resulting product was, according to XRD analysis, mono-phase β-SiAlON; but minor amounts of unreacted SiO₂ and SiC (possibly amorphous) were detected in the NMR spectra. It was found that β-SiAlONs with higher and lower Z values are formed by different reaction pathways.     

Thermomechanical Properties of β-Sialon Synthesized from Kaolin

β-Sialon powder was synthesized by the simultaneous reduction and nitridation of Hadong kaolin at 1350°C in an N₂–H₂ atmosphere, using graphite as a reducing agent. The average particle size of β-sialon powder was about 4.5 μm. The synthesized β-sialon powder was pressureless sintered from 1450° to 1850°C under a N₂ atmosphere. The relative density, modulus of rupture, fracture toughness, and microhardness of β-sialon ceramics sintered at 1800°C for 1 h were 92%, 248 MPa, 2.8 MN/m^3/2, and 13.3 GN/m², respectively. The critical temperature difference (ΔT_c) in water-quench thermal-shock behavior was about 375°C for the synthesized β-sialon ceramics.     

Fracture Strength and Microstructure of β-SiAlON with Hafnia Addition

The influence of HfO₂ addition on the fracture strength and microstructure of ß-SiAlON ceramics sintered from Si₃N₄ and Al₂O₃ powders was investigated. The strength was increased by the addition of HfO₂, from ∼500 MPa to 700 MPa, and was almost constant from ambient temperature to 1300°C. Monoclinic HfO₂ grains that were distributed in the SiAlON grain boundaries had a flat shape (∼20 nm thick) and were surrounded by an amorphous phase. The aluminum concentration in ß-SiAlON in the samples with an Al₂O₃ starting composition of 15 wt% was decreased by the addition of HfO₂. The amount of secondary phases was very small at grain boundaries between the SiAlON grains; amorphous phases were observed infrequently at the triple points but were very small (∼20 nm). The effects of HfO₂ addition on the mechanism of the microstructure development and fracture strength are discussed.     

Characterization of β-Silicon Carbide Powders Synthesized by the Carbothermal Reduction of Silicon Carbide Precursors

Boron-doped and nondoped ultrafine β-silicon carbide (β-SiC) powders were synthesized via the carbothermal reduction of SiC precursors at temperatures of 1773–1973 K. Although the reaction rate of carbothermal reduction was generally higher when a boron-doped precursor was used, the reaction rate for the boron-doped precursor was reduced considerably at 1873 K. For boron-doped and nondoped precursors, the reaction rates were almost the same. Powder characterization via transmission electron microscopy indicated that the suppression of the reaction rate for boron-doped precursor at 1873 K was due to the formation of a special coexistent system with two types of particle agglomerates. As expected, boron doping inhibited the particle growth in the synthesis of SiC powder.     

Properties and Microstructure of Molybdenum Disilicide–β';-SiAlON Particulate Ceramic Composites

Particulate ceramic composites that were composed of a combustion-synthesized β';-SiAlON matrix and dispersed MoSi₂ particles were hot pressed at 1600°C in a nitrogen atmosphere. The physical and mechanical properties of the composites that contained 15, 30, and 45 vol% MoSi₂ were evaluated. The average four-point bend strength, fracture toughness, and Vickers hardness of the composites were in the ranges of 500-600 MPa, 3-4 MP·am^1/2, and 11-13 GPa, respectively. The measured mechanical strength and hardness were very similar to the values that were predicted from the rule of mixtures. The fracture toughness of the combustion-synthesized β';-SiAlON (2.5 MPa·m^1/2) was apparently enhanced by the MoSi₂ particles that were added. The increase in the fracture toughness was predominately attributed to the residual thermal stress that was induced by the thermal expansion mismatch between the MoSi₂ particles and the β';-SiAlON matrix. The composites showed improved electrical conductivity and oxidation resistance over monolithic β';-SiAlON. High-resolution transmission electron microscopy examination of the composites indicated that the MoSi₂ was chemically well compatible with the β';-SiAlON.     

Diffusion Bonding of Silicon Nitride Using a Superplastic β-SiAlON Interlayer

A superplastic β-SiAlON was used as an interlayer to diffusionally bond a hot-pressed silicon nitride to itself. The bonding was conducted in a graphite furnace under a constant uniaxial load of 5 MPa at temperatures varying from 1500° to 1650°C for 2 h, followed by annealing at temperatures in the range of 1600° to 1750^oC for 2 h. The bonds were evaluated using the four-point-bend method at both room temperature and high temperatures. The results indicate that strong, void-free joints can be produced with the superplastic β-SiAlON interlayer, with bond strengths ranging from 438 to 682 MPa, and that the Si₃N₄ joints are heat resistant, being able to retain their strength up to 1000°C (635 MPa), and therefore have potential for high-temperature applications.     

α-β Sialon Ceramics Made from Different Silicon Nitride Powders

The present work is concerned with the sintering of an α-β sialon ceramic using five different silicon nitride powders from a single source. The parameters varied in the silicon nitride were the amount of "free' silicon, iron content, α:β ratio, and grain size as measured by BET surface. The sintering atmosphere was varied by use of protective powder beds with passive (boron nitride) and active (SiO-generating) properties. Five sintering temperatures between 1600° and 1800°C were used. Microstructural characterization as well as density, hardness, and fracture toughness measurements were carried out. The sintering conditions were found to be critical for obtaining fully dense materials and low weight change. The optimum sintering temperature was 1750°C. The silicon nitride powder with a high content of free silicon resulted in a material which was more susceptible to the sintering atmosphere conditions. An α-β sialon made from a silicon nitride powder with a high β-α phase ratio resulted in a higher β-α ratio in the sintered material.     

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.     

Early-Stage Thermal Oxidation of Carbothermal β-Sialon Powder

Early-stage thermal oxidation (below 1100°C) of carbothermally synthesized β-sialon powder was monitored by X-ray powder diffraction, solid-state ²⁹Si and ²⁷Al MAS NMR spectroscopy, and thermogravimetry. No crystalline oxidation products were detected by XRD but ²⁹Si and ²⁷Al MAS NMR indicated the early formation of amorphous silica, followed by the formation of an amorphous aluminosilicate with an atomic environment similar to that of mullite. The initial oxidation was described by a linear kinetic law with an activation energy of 170 kJmol⁻¹, suggesting the rate-limiting step to be due to dissolution of O₂ in an amorphous silica surface layer on the β-sialon particles.     

Friction Coefficient of (α+β)-SiAlON Composite against a Steel and Dense Silicon Nitride Tribopair

The friction characteristics of hot-pressed (α+β)-SiAlON, versus those of bearing steel and dense Si₃N₄ under dry sliding conditions, are reported. The coefficient of friction decreases as the alpha-SiAlON content increases and is double that of a metal-ceramic pair, in comparison to that of a ceramic-ceramic pair.     

Hydration of Sodium β- and β'-Aluminas

The enthalpy and entropy for the hydration of sodium β - and β '-aluminas have been determined by measuring the infrared absorbance of single-crystal samples following equilibration at elevated temperatures in water vapor pressures ranging from 3 to 70 kPa. The equilibrium water concentrations can be varied continuously and reversibly up to saturation concentrations of about 0.9H₂O-Na_1.2AI₁₁O_17.1 for the β-phase and 0.4H₂O.Na_1.67Mg_.67Al_10.33O₁₇ for the β'-phase. The hydration reactions are exothermic; Δ H =−56 ± 2 for sodium β '-aIumina and ΔH =−67 ± 2 kJ/mol for sodium β-alumina. The entropies of hydration are about −143 ± 6 J/(mol-K) for both sodium β - and β '-aIuminas.     

Oxidation Kinetics of Hot-Pressed and Sintered α-SiC

The oxidation kinetics of sintered α- and hot-pressed SiC were investigated over the temperature range 1200° to 1500°C. Oxide thicknesses were measured by ellipsometry, interferometry, and profilometry. The two materials behaved similarly, exhibiting parabolic behavior for short times (up to 100 min) followed by decreasing rates for longer times. The oxidation rates for the sintered material were lower than for the hot-pressed material at all temperatures studied. Apparent activation energies varied with temperature, from 134 to 389 kJ/mol for the sintered alpha material and from 155 to 498 kJ/mol for the hot-pressed variety. Platinum-marker experiments indicated that new oxide is formed at the silicon carbide/ oxide interface. It is proposed that the diffusion of oxidant through the growing oxide film is the rate-controlling process. The details of the oxidation kinetics were complicated by the partial crystallization of the oxide film at higher temperatures, leading to complex paths for transport of oxidant through the film so that the apparent activation energies are difficult to interpret.     

Photoluminescence of Cerium-Doped α-SiAlON Materials

Cerium-doped α-SiAlON (M _x Si_{12−( m + n )}Al _{m + n} O _n N_{16– n} ) materials have been prepared by gas-pressure sintering and post-hot-isostatic-press (HIP) annealing, using four powder mixtures of α-Si₃N₄, AlN, and either (i) CeO₂, (ii) CeO₂+ Y-α-SiAlON seed, (iii) CeO₂+ Y₂O₃, or (iv) CeO₂+ CaO. Cerium-containing CeAl(Si_{6– z} Al _z )(N_{10– z} O _z ) (JEM) phase, rather than Ce-α-SiAlON phase, forms in the sample with only CeO₂, whereas a single-phase α-SiAlON generates in samples with dual doping (CeO₂+ Y₂O₃ and CeO₂+ CaO). On ultraviolet-light excitation, JEM gives one broad emission band with maximum at 465 nm and a shoulder at 498 nm; α-SiAlON shows an intense and broad emission band that peaks at 500 nm. The unusual long-wavelength emissions in JEM and α-SiAlON are due to increases in the nephelauxetic effect and the ligand-field splitting of the 5 d band, because the coordination of Ce³⁺ in JEM and α-SiAlON is nitrogen enriched.     

Kinetics of Dissolution and Crystallization in a β-Spodumene Glass-Ceramic

The kinetics of partial melting in a β-spodumene glass-ceramic was measured by holding fully crystallized material above the solidus but below the liquidus temperature. The kinetics was apparently limited by the rate of diffusion of silica in the crystalline phase. The measured lattice diffusivity of silica was 8×10⁻¹⁰ exp(-251 kJ mol⁻¹ /RT ) m² s⁻¹ with a possible error of ±60 kJ mol⁻¹ in the activation energy. The partially molten samples were heat-treated below the solidus to obtain the kinetics of crystallization, which was found to be interface-reaction-controlled.     

Synthesis of Sinterable β-SiC Powders by a Solid Combustion Method

A solid combustion method for obtaining sinterable β-SiC powders from Si and C mixtures is described. The method is similar to the thermal explosion method in which a proper preheating of the reactive mixture enables a substantial increase in the temperature of the mixture, due to the heat of reaction, in a short time. The characteristics of the powders obtained by the method are given. Both a high chemical purity of the powders, which is due to the high temperature of synthesis, and an adequate BET surface area of the powders, obtained after vibratory milling, enable these powders to be used for producing sintered SiC materials.     

Synthesis of α-SiAlON Seed Crystals

Single-phase seed crystals of Ca- and Y-α-SiAlONs have been synthesized for tailoring microstructure of α-SiAlON ceramics. The influence of composition, sintering temperature, and nitrogen pressure on the size and morphology of seeds has been explored. Guidelines for α-SiAlON seed preparation and morphology control are provided.