Sintering Kinetics at Isothermal Shrinkage: Effect of Specific Surface Area on the Initial Sintering Stage of Fine Zirconia Powder

The isothermal shrinkage behaviors of fine zirconia powders (containing 2.8–2.9 mol% Y₂O₃) with specific surface areas of about 6 and 16 m²/g were investigated to clarify the effect of specific surface area on the initial sintering stage. The shrinkage of powder compact was measured under constant temperatures in the range of 1000°–1100°C. The increase in specific surface area enhanced the densification rate with increasing temperature. The values of activation energy ( Q ) and frequency-factor term (β₀) of diffusion at initial sintering were estimated by applying the sintering-rate equation to the isothermal shrinkage data. The Q of diffusion changes little but the β₀ increases with the increase in specific surface area. It is therefore concluded that the increase in the specific surface area of fine zirconia powder enhances the shrinkage rate because of an increase in the β₀ at the initial stage of sintering.     

Preparation of High-Silica Glasses from Colloidal Gels: II, Sintering

The sintering of dried colloidal SiO₂ gels, whose preparation and properties are reported in Part I, is described. The effects of various sintering parameters were studied and the conditions for achievement of the best optical quality include the use of: a pretreatment of the SiO₂ at ∼925°C, moderate heating rate (∼400°C/h), He+CI₂ atmosphere, 1500° to 1600°C sintering temperature, and 1 to 4 h sintering time. Dynamic sintering kinetic studies (heating rate=400°C/h) show that this SiO₂ sinters to nearly theoretical density by about 1380°C. However, optical transparency is achieved by removal of minor residual porosity at above 1500°C. Isothermal sintering data fit to a model assuming interconnecting cylinders of SiO₂ predict the proper activation energy for the viscosity if initial stages of sintering are considered. Residual porosity in sintered glasses is related to large interstices in the unsintered gel.     

Mechanism of Alumina-Enhanced Sintering of Fine Zirconia Powder: Influence of Alumina Concentration on the Initial Stage Sintering

The isothermal shrinkage behavior of 2.9 mol% Y₂O₃-doped ZrO₂ powders with 0–1 mass% Al₂O₃ was investigated to clarify the effect of Al₂O₃ concentration on the initial sintering stage. The shrinkage of the powder compact was measured at constant temperatures in the range of 950°–1050°C. The Al₂O₃ addition increased the densification rate with increasing temperature. The values of apparent activation energy ( nQ ) and apparent frequency-factor term (β₀ ⁿ ), where n is the order depending on the diffusion mechanism, were estimated at the initial sintering stage by applying a sintering-rate equation to the isothermal shrinkage data. The diffusion mechanism changed from grain-boundary diffusion (GBD) to volume diffusion (VD) by Al₂O₃ addition and both nQ and β₀ ⁿ increased with increasing Al₂O₃ concentration. The kinetic analysis of the sintering mechanism suggested that the increase of densification rate by Al₂O₃ addition largely depends on the increase of β₀ ⁿ , that is, the increases of n with GBD→VD change and β₀ with an increase in Al₂O₃ content, although the nQ also increases with Al₂O₃ addition. This enhanced sintering mechanism is reasonably interpreted by the segregated dissolution of Al₂O₃ at ZrO₂ grain boundaries.     

Some Roles of MgO and TiO2 in Densification of a Sinterable Alumina

Sinterability of undoped, MgO-doped, and TiO₂-doped Al₂O₃ has been examined by applying reported sintering equations. The order of sinterability was MgO-doped ∼ undoped≪ TiO₂-doped Al₂O₃ in the initial and intermediate stages of sintering, but a relative sintered density at 1600°C for 1 h occurred in the order undoped < TiO₂-doped < MgO-doped AI₂O₃. The dispersion of thermal grooving angles increased in the order MgO-doped < undoped < TiO₂-doped Al₂O₃, The change of sinterability by the dopants is explained in terms of mobility of mass transfer estimated from a densification rate in the initial- and intermediate-stage sintering and of dispersed driving forces of densification and grain growth qualitatively evaluated from the width of the dispersion of thermal grooving angles.     

Densification of Alumina and Silica in the Presence of a Liquid Phase

Alumina and silica powders were sintered at 1250° to 1460°C in the presence of liquid phases containing CaO, A1₂O₃, and SiO₂. The data were analyzed using the equation D = K log t +C and the Arrhenius equation. The activation energy for sintering decreases with increasing amounts of liquid phase.     

Solubility of Magnesia in Polycrystalline Alumina at High Temperatures

High-purity Al₂O₃ compacts were doped with 0–350 ppm (by weight) of MgO using a liquid immersion technique and equilibrated at temperatures between 1700° and 2000°C under hydrogen. The solubility limits of MgO in Al₂O₃ at temperatures of 1720° and 1880°C were very low, ∼75 and 175 ppm, respectively. Variation of MgO solubility with temperature could be represented by the equation, ln Mg/Al = 3.80–2.63 × 10⁴/ T . The small MgO solubilities were understood by the high enthalpy (326 kJ/mol) of solution. The results of this study suggested that previous investigations on sintering and grain-growth mechanisms in MgO-doped Al₂O₃ were probably not done in single-phase Al₂O₃ solid solutions. However, the conclusions on sintering and grain-growth mechanisms in prior research work in MgO-doped A₂O₃ may be correct. The effects of SiO₂ impurity and grain size on MgO solubility are discussed. Previous grain-growth experiments in MgO-doped Al₂O₃ are described that demonstrate the clearest evidence for grain-boundary mobility controlled by a solid-solution mechanism.     

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.     

Densification and Thermal Conductivity of AIN Doped with Y2O3, CaO, and Li2O

Small amounts of Li₂O result in sintering in the AIN-Y₂O₃-CaO and AIN-CaO systems at firing temperatures <1600°C. The effect is ascribed to reduction of the liquidus temperature. Furthermore, Li₂O is removed by volatization at temperatures from 1300° to 1600°C, and its content decreases several ppm from the initial 0.3 wt%. Li₂O-doped AIN specimens containing Y₂O₃ and CaO additives are well densified by firing at 1600°C for 6 h, and their thermal conductivity is 135 W^.m^−1.K⁻¹.The effect of Li₂O addition on sintering and thermal conductivity also is discussed through thermo-dynamic considerations.     

Densification and Mechanical Behavior of HfC and HfB2 Fabricated by Spark Plasma Sintering

Hafnium diboride (HfB₂)- and hafnium carbide (HfC)-based materials containing MoSi₂ as sintering aid in the volumetric range 1%–9% were densified by spark plasma sintering at temperatures between 1750° and 1950°C. Fully dense samples were obtained with an initial MoSi₂ content of 3 and 9 vol% at 1750°–1800°C. When the doping level was reduced, it was necessary to raise the sintering temperature in order to obtain samples with densities higher than 97%. Undoped powders had to be sintered at 2100°–2200°C. For doped materials, fine microstructures were obtained when the thermal treatment was lower than 1850°C. Silicon carbide formation was observed in both carbide- and boride-based materials. Nanoindentation hardness values were in the range of 25–28 GPa and were independent of the starting composition. The nanoindentation Young's modulus and the fracture toughness of the HfB₂-based materials were higher than those of the HfC-based materials. The flexural strength of the HfB₂-based material with 9 vol% of MoSi₂ was higher at 1500°C than at room temperature.     

Sintering of Al2O3–TiC Composite in the Presence of Liquid Phase

The results obtained from the sintering of Al₂O₃–50TiC (in weight percent) composite in the temperature range from 1650° to 1800°C with addition of Y₂O₃ are presented. Densification is accelerated by the formation of liquid at temperatures above 1750°C, and 99% of theoretical density can be achieved by vacuum sintering at 1800°C for 15 min. The liquid presented at the sintering temperature is crystallized to YAG (Y₃Al₅O₁₂) during cooling.     

Suppression of Rhombohedral-Phase Appearance and Low-Temperature Sintering of Scandia-Doped Cubic-Zirconia

Inhibition of cubic-rhombohedral phase transformation and low-temperature sintering at 1000°C were achieved for 10-mol%-Sc₂O₃-doped cubic-ZrO₂ by the presence of 1 mol% Bi₂O₃. The powders of 1-mol%-Bi₂O₃–10-mol%-Sc₂O₃-doped ZrO₂ were prepared using a hydrolysis and homogeneous precipitation technique. No trace of rhombohedral-ZrO₂ phase could be detected, even after sintering at 1000°–1400°C. The average grain size of the ZrO₂ sintered at 1200°C was >2 μm because of grain growth in the presence of Bi³⁺. Cubic, stabilized Bi-Sc-doped ZrO₂ sintered at 1200°C had sufficient conductivity at 1000°C (0.33 S/cm) to be used as an electrolyte for a solid-oxide fuel cell (SOFC) and at 800°C (0.12 S/cm) for an intermediate-temperature SOFC.     

Sintering of Si3N4 with the Addition of Rare-Earth Oxides

The effect of rare-earth oxide additives on the densification of silicon nitride by pressureless sintering at 1600° to 1700°C and by gas pressure sintering under 10 MPa of N₂ at 1800° to 2000°C was studied. When a single-component oxide, such as CeO₂, Nd₂O₃, La₂O₃, Sm₂O₃, or Y₂O₃, was used as an additive, the sintering temperature required to reach approximate theoretical density became higher as the melting temperature of the oxide increased. When a mixed oxide additive, such as Y₂O₃–Ln₂O₃ (Ln=Ce, Nd, La, Sm), was used, higher densification was achieved below 2000°C because of a lower liquid formation temperature. The sinterability of silicon nitride ceramics with the addition of rare-earth oxides is discussed in relation to the additive compositions.     

Microwave Dielectric Properties of Li2TiO3 Ceramics Doped with ZnO–B2O3 Frit

A type of new low sintering temperature ceramic, Li₂TiO₃ ceramic, has been found. Although it is difficult for the Li₂TiO₃ compound to be sintered compactly at temperatures above 1000°C for the volatilization of Li₂O, dense Li₂TiO₃ ceramics were obtained by conventional solid-state reaction method at the sintering temperature of 900°C with the addition of ZnO–B₂O₃ frit. The sintering behavior and microwave dielectric properties of Li₂TiO₃ ceramics with less ZnO–B₂O₃ frit (≤3.0 wt%) doping were investigated. The addition of ZnO–B₂O₃ frit can lower the sintering temperature of the Li₂TiO₃ ceramics, but it does not apparently degrade the microwave dielectric properties of the Li₂TiO₃ ceramics. Typically, the good microwave dielectric properties of ɛ_r=23.06, Q × f =32 275 GHz, τ_f = 35.79 ppm/°C were obtained for 2.5 wt% ZnO–B₂O₃ frit-doped Li₂TiO₃ ceramics sintered at 900°C for 2 h. The porosity was 0.08%. The Li₂TiO₃ ceramic system may be a promising candidate for low-temperature cofired ceramics applications.     

Low-Temperature, Single Step, Reactive Sintering of Lead Magnesium Niobate Using Mg(OH)2-Coated Nb2O5 Powders

A low-temperature, single step, reactive sintering method for Pb(Mg_1/3Nb_2/3)O₃ (PMN) and PMN–PbTiO₃ (PMN–PT) processing was developed based on the coating of Mg(OH)₂ on Nb₂O₅. This method simplified the processing of PMN and PMN–PT to a single step of heat-treatment and decreased the sintering temperature to 1000°C. It was found that the pyrochlore phase formation reaction at 500°C reduced the particle size to 130 nm. The overlap of the pyrochlor-perovskite phase transformation between 700° and 900°C and the densification process between 800° and 1000°C improved the sintering process. These two factors were the major reasons of the low temperature sintering.     

Processing and Properties of TiB2 with MoSi2 Sinter-additive: A First Report

The densification of non-oxide ceramics like titanium boride (TiB₂) has always been a major challenge. The use of metallic binders to obtain a high density in liquid phase-sintered borides is investigated and reported. However, a non-metallic sintering additive needs to be used to obtain dense borides for high-temperature applications. This contribution, for the first time, reports the sintering, microstructure, and properties of TiB₂ materials densified using a MoSi₂ sinter-additive. The densification experiments were carried out using a hot-pressing and pressureless sintering route. The binderless densification of monolithic TiB₂ to 98% theoretical density with 2–5 μm grain size was achieved by hot pressing at 1800°C for 1 h in vacuum. The addition of 10–20 wt% MoSi₂ enables us to achieve 97%–99%ρ_th in the composites at 1700°C under similar hot-pressing conditions. The densification mechanism is dominated by liquid-phase sintering in the presence of TiSi₂. In the pressureless sintering route, a maximum of 90%ρ_th is achieved after sintering at 1900°C for 2 h in an (Ar+H₂) atmosphere. The hot-pressed TiB₂–10 wt% MoSi₂ composites exhibit high Vickers hardness (∼26–27 GPa) and modest indentation toughness (∼4–5 MPa·m^1/2).     

Preparation of High-Density Si3N4 by a Gas-Pressure Sintering Process

Si₃N₄ compacts, containing ≅7 wt% of both BeSiN₂ and SiO₂ as densification aids, can be reproducibly sintered to relative densities >99% by a gas-pressure sintering process. Nearly all densification takes place via liquid-phase sintering of transformed β-Si₃N₄ grains at T =1800° to 2000°C. Compacts with high density are produced by first sintering to the closed-pore stage (≅92% relative density) in 2.1 MPa (20 atm) of N₂ pressure at 2000°C and then increasing the N₂ pressure to 7.1 MPa (70 atm) where rapid densification proceeds at T = 1800° to 2000°C. The experimental density results are interpreted in terms of theoretical arguments concerning the growth (coalescence) of gas-filled pores and gas solubility effects. Complex chemical reactions apparently occur at high temperatures and are probably responsible for incomplete understanding of some of the experimental data.     

Conventional and Microwave-Induced Sintering Mechanisms for Reaction-Bonded Aluminum Oxide with Zirconium Oxide Additions

Powder compacts consisting of Al, Al₂O₃, and ZrO₂ were heated by microwave radiation. Tracing the phase evolution during reaction bonding revealed the reaction mechanism. In the case of conventional heating, the compacts expanded slightly at temperatures of <700°C due to Al surface oxidation and expanded sharply at temperatures greater than 700°C as oxidation proceeded from the surface to the interior. Then, the compacts shrank at 1550°C due to sintering. For the case of microwave heating, the compacts expanded at temperatures of <550°C due to the formation of Al₃Zr. This Al₃Zr formation was caused by the preferential heating of ZrO₂ relative to Al and Al₂O₃ by microwave radiation. Then, Al₃Zr was oxidized to form Al₂O₃ and ZrO₂ at temperatures of >1000°C. Finally, the compacts shrank at 1550°C due to sintering, similarly to conventional sintering.     

Double Precursor Solution Coating Approach for Low-Temperature Sintering of [Pb(Mg1/3Nb2/3)O3]0.63[PbTiO3]0.37 Solids

Lead-based piezoelectric ceramics typically require sintering temperatures higher than 1000°C at which significant lead loss can occur. Here, we report a double precursor solution coating (PSC) method for fabricating low-temperature sinterable polycrystalline [Pb(Mg_1/3Nb_2/3)O₃]_0.63-[PbTiO₃]_0.37 (PMN–PT) ceramics. In this method, submicrometer crystalline PMN powder was first obtained by dispersing Mg(OH)₂-coated Nb₂O₅ particles in a lead acetate/ethylene glycol solution (first PSC), followed by calcination at 800°C. The crystalline PMN powder was subsequently suspended in a PT precursor solution containing lead acetate and titanium isopropoxide in ethylene glycol to form the PMN–PT precursor powder (second PSC) that could be sintered at a temperature as low as 900°C. The resultant d ₃₃ for samples sintered at 900°, 1000°, and 1100°C for 2 h were 600, 620, and 700 pm/V, respectively, comparable with the known value. We attributed the low sintering temperature to the reactive sintering nature of the present PMN–PT precursor powder. The reaction between the nanosize PT and the submicrometer-size PMN occurred roughly in the same temperature range as the densification, 850°–900°C, thereby significantly accelerating the sintering process. The present PSC technique is very general and should be readily applicable to other multicomponent systems.     

Sintering of Nanophase γ-Al2O3 Powder

The sintering of ultrafine γ-Al₂O₃ powder (particle size ∼10–20 nm) prepared by an inert gas condensation technique was investigated in air at a constant heating rate of 10°C/min. Qualitatively, the kinetics followed those of transition aluminas prepared by other methods. Measurable shrinkage commenced at ∼ 1000°C and showed a region of rapid sintering between ∼1125° and 1175°C followed by a transition to a much reduced sintering rate at higher temperatures. Starting from an initial density of ∼0.60 relative to the theoretical value, the powder compact reached a relative density of 0.82 after sintering to 1350°C. Compared to compacts prepared from the as-received powder, dispersion of the powder in water prior to compaction produced a drastic change in the microstructural evolution and a significant reduction in the densification rate during sintering. The incorporation of a step involving the rapid heating of the loose powder to ∼1300°C prior to compaction (which resulted in the transformation to α-Al₂O₃) provided a method for significantly increasing the density during sintering.     

Electric-Field Effects on Sintering and Reaction to Form Aluminum Titanate from Binary Alumina–Titania Sol–Gel Powders

The field-activated sintering technique (FAST) was applied to simultaneously sinter and react sol–gel amorphous powders to form Al₂TiO₅. Densities close to theoretical and conversion to Al₂TiO₅ (to 92.5%) have been achieved using FAST at 1050°–1200°C for 10 min. Conventional sintering of the same powders at 1300°C for 2 h resulted in 88.9% Al₂TiO₅ and ∼75% of theoretical density. The enhanced sintering and compound formation using FAST have been explained by the synergistic effects of precursor reactivity, nanosized powders, and electric-field effects.