Sintering of Platelike Bismuth Titanate Powder Compacts with Preferred Orientation

The sintering of platelike Bi₄Ti₃O₁₂ powder particles was investigated. Special emphasis was given to the role of particle orientation in the green sheet on densification and microstructure development. Compacts were made by tape-casting and dry-pressing. During the initial stage of sintering, the particles rearranged and formed colonies with the development of face-to-face contacts. Pores between particles in a colony disappeared during colony formation, and the volume of pores between colonies decreased on further heating. Grain growth started when the sintered density reached about 90% of theoretical density. The growth of well-oriented grains increased the degree of orientation. Thus, highly oriented sintered bodies with high densities were prepared by heating at 1150°C.     

Calculating the Thermal Conductivity of Heated Powder Compacts

This work is devoted to the theoretical understanding of the microstructure and thermal conductivity relationships of compacted ceramic powders in the initial, nondensifying stage of sintering. A model based on surface diffusion of vacancies for the growth of the neck between particles is combined with numerical fully three-dimensional code calculations, which solve for the effective heat conductivity coefficient of lightly sintered particles. The predictions of the model are in agreement with experimental observations. The approach presented can be applied to solve a series of related problems, like dielectric properties, with arbitrary microstructure and multicomponent composite of the powders.     

Effect of Internal Lubricants on Defects in Compacts Made from Spray-Dried Powders

The role of internal lubricants in the closure of large intergranular pores during dry-pressing was investigated. Alumina was spray-dried with and without an internal lubricant to yield granules with similar characteristics other than lubricant effects. Green and sintered microstructures were evaluated at different compaction pressures. The defects were quantified by evaluating the fracture surface of ∼90% dense sintered compacts. The samples that contained an internal lubricant had higher green densities and fewer defects at comparable compaction pressures. The internal lubricant did not cause any significant reduction in green strength or increase in springback.     

Shear and Densification of Glass Powder Compacts

Sinter-forging types of experiments were carried out on powder compacts of glass. The shear and densification strains were measured simultaneously during the forging process. This information was analyzed to obtain the shear viscosity of the glass and the intrinsic sintering pressure, both as a function of density. The viscosity of the porous glass changed nonlinearly with density and was empirically fitted to an exponential function. The sintering pressure was found to increase with density; it was 100 kPa at ρ= 0.55 and 250 kPa at ρ= 0.90. In this range the sintering pressure could be adequately described in terms of a simple geometrical model. However, when the density approached 95%, the sintering pressure appeared to assume an uncertain value. The measurements were also used to calculate the viscous bulk modulus of the porous glass; these estimates agreed well with theoretical prediction.     

Initial Sintering of Submicrometer Titania Anatase Powder

Measurements of surface area reduction of TiO₂ anatase powder (of initially 100 m²· g⁻¹) were carried out for various partial pressures of water and oxygen at 823 K. The kinetic equation obtained for the experimental rates has the formulation r = k[P _H2O]^1/α [ P _O2]^1/β where α and β are equal to 2 and -12, respectively. A mechanistic model involving six consecutive elementary steps was developed, in which hydroxyl species play a dominant role. No geometrical assumption is required. The general expression of the deduced theoretical rates has the same form as previously given. The comparison between the experimental and the predicted rates points out that the rate-limiting step is the surface diffusion of hydroxyl species. This model can easily be used for any other compounds, for particle growth, and for porosity elimination.     

Fracture Toughness of Spray-Dried Powder Compacts

The strengths and fracture toughness values were measured for alumina powder compacts containing two different binder systems. Diametral compression was used to measure both the tensile strength and the fracture toughness (through-thickness notch). This methodology was very useful in linking processing parameters, such as binder choice and compaction stress, to the quality of the green bodies. Observations of the compact structure before and after fracture showed that the binders segregated to the region between the spray-dried granules. The presence of the excess binder in this region was linked to both the failure mode and the creation of secondary cracks.     

Mathematical Simulation of Sintering of an Ultrafine Powder

A pointwise mathematical model of sintering of a compact of an ultrafine metal powder in the thermal explosion mode is developed. A condition for occurrence of this reaction mode is found. The model is verified by results on the delay and temperature of the beginning of Ptblack powder sintering.     

Sintering of Spherical Glass Powder under a Uniaxial Stress

The sintering of spherical borosilicate glass powder (particle size 5 to 10 μm) under a uniaxial stress was studied at 800°C. The experiments allowed the measurement of the kinetics of densification and creep, the viscosities for creep and bulk deformation, and the sintering stress which was found to increase with density. The data show excellent qualitative agreement with Scherer's theory of viscous sintering. In addition, the quantitative comparison between theory and experiment shows good agreement; the measured viscosity of the bulk glass was ∽1×10⁹ P (∽1×10⁸ Pa·s) compared to ∽3×10⁹ P (∽3 Pa·s) obtained by fitting the data with Scherer's theory.     

Sintering Behavior of Fine Aluminum Nitride Powder Synthesized from Aluminum Polynuclear Complexes

The sintering behavior of fine AIN powder synthesized from an aluminum polynuclear complex was investigated. The focus of this work was to investigate the densification behavior of the AIN powder with different particle sizes (specific surface area: 3.2–22.8 m²/g). The AIN powder was synthesized from basic aluminum chloride and glucose mixed in a water solution. This powder was divided into two groups: one with 2 wt% Y₂O₃ added as the sintering aid and the other without such an additive. The AIN powder investigated possessed favorable densification potential. The density of the AIN powder with a surface area of 16.6 m²/g and without additives attained theoretical density at 1700°C. Adding Y₂O₃ further decreased the sintering temperature required for full densification to 1600°C. It is speculated that low-temperature sintering of our fine AIN powder with Y₂O₃ proceeds in two steps: in the initial stage, sintering proceeds predominantly through interdiffusion between yttrium aluminates formed on the AIN powder surface; in the second stage, the densification may occur by the interdiffusion between solid phases formed by a reaction between the yttrium aluminates and AIN. To investigate the effect of oxygen on sintering, the content of oxygen in AIN powder was varied while the particle size was kept constant. In this study, the difference in surface oxygen content scarcely affected the sintering behavior of fine AIN powder.     

基于注射成型并三步烧结法制备透明氧化铝陶瓷

本文采用注射成型制备氧化铝坯体,并用三步烧结法获得了完全致密的透明氧化陶瓷.研究了直线透光率与烧结方法,微观结构的关系.结果表明基于注射成型并采用三步烧结方法制备的氧化铝陶瓷没有晶粒异常长大,总透光率和直线透光率分别达到了71％和50.8％.用三步烧结法制备的氧化铝陶瓷直线透光率比一步法制备的氧化铝陶瓷要高25.8％.     

Nitridation Kinetics and Thermodynamics of Silicon Powder Compacts

The nitridation kinetics of Si powder compacts were studied by measuring the flow rate dependence of N₂ and N₂–H₂ gas mixtures during slow heating of Si compacts while simultaneously monitoring the oxygen partial pressure of the egress gas. The reaction was found to occur in two distinct stages. In pure nitrogen the initial stage was interpreted in terms of devitrification of the native silica layer, catalyzed by Fe impurities, and the exposure of the underlying Si. The reaction sequence at that point has been unequivocally shown to be followed by the formation of oxynitride according to as evidenced by a large increase in the oxygen partial pressure simultaneously with the onset of the initial stage. In the absence of hydrogen, both reactions are rapidly suppressed as the oxygen liberated competes with the nitrogen for the exposed silicon surface and reoxidizes it. However, in the presence of hydrogen, the oxygen liberated reacts with the hydrogen and prevents the reoxidation of the Si. The net reaction in this case is and/or with the second reaction being thermodynamically favored. The main nitridation reaction occurring between 1300° and 1400°C appears to be diffusion controlled and depends on the nature of the passivating layer that forms during the initial stage.     

烧结助剂对氮化硅陶瓷显微结构和性能的影响

氮化硅中氮原子和硅原子的自扩散系数很低，致密化所必需的扩散速度和烧结驱动力都很小，在烧结过程中需采用烧结助剂。烧结助剂是影响氮化硅陶瓷的显微结构和性能的关键因素之一。有效的烧结助剂不但可以改善氮化硅陶瓷的显微结构，而且可以提高氮化硅陶瓷的高温性能和抗氧化性能。     

Binder Evolution from Powder Compacts: Thermal Profile for Injection-Molded Articles

Binder evolution information generated using thermal analysis techniques is used along with microstructural information to define a thermal cycle for debinderizing injection-molded articles. In addition, the roles of binder chemistry, powder morphology, binder loading, article size, heating rate, and environmental conditions in determining a satisfactory thermal cycle are investigated. Major binder evolution events and types of defects generated are identified. An improved binder removal cycle is developed from this evaluation for organics elimination of a honeycomb structure.     

Sintering Behavior of Fully Agglomerated Zirconia Compacts

Fully agglomerated superfine zirconia powders were prepared with the coprecipitation and spray-drying method. The compaction of such powders shows no fragmentation of the agglomerates. The sintering behavior of the compacts was studied and two sintering stages were identified: densification within agglomerates at temperatures not higher than 1250°C and the removal of interagglomerate pores at temperatures above 1600°C. The interagglomerate pores are difficult to remove, and sintering between agglomerates even at 1600°C is still insignificant. Heating of the compacts at temperatures above 1600°C leads only to grain growth and the entrapping of pores in large grains.     

Effect of Surface Impurities on the Microstructure Development during Sintering of Alumina

Microstructural evolution during sintering of alumina powder compacts prepared by cold isostatic pressing (CIP) was monitored. For CIP, rubber molds lubricated with silicone oil were used so that a very small amount of impurity was introduced to the surface of the powder compacts. During sintering at 1600°C, grain growth in the surface region was inhibited up to sintering for 1 h, but subsequently abnormal grain growth occurred. In the inner region, however, the grains grew uniformly without abnormal grain growth. Impurities that initially drag the boundary migration but form liquid at the end are suggested to cause abnormal grain growth.     

Creep and Densification During Sintering of Glass Powder Compacts

The simultaneous creep and densification of glass powder compacts was studied as a function of low applied uniaxial stress, temperature, and particle size. The creep rate can be expressed as the sum of the contribution from the applied stress that varies linearly with stress, and a contribution due to anisotropic densification that varies linearly with the densification rate. For a constant applied stress, the ratio of the creep rate to the densification rate is almost independent of both termperature and density. While these observations are consistent with the model of Scherer for the viscous sintering of glass, other observations show significant deviations from the model. Both the densification rate and the creep viscosity, which has an exponential dependence on porosity, show much stronger dependence on density compared with theoretical predictions.     

Novel Two-Step Sintering Process to Obtain a Bimodal Microstructure in Silicon Nitride

A two-step sintering process is described in which the first step suppresses densification while allowing the α-to-β phase transformation to proceed, and the second step, at higher temperatures, promotes densification and grain growth. This process allows one to obtain a bimodal microstructure in Si₃N₄ without using β-Si₃N₄ seed crystals. A carbothermal reduction process was used in the first step to modify the densification and transformation rates of the compacts consisting of Si₃N₄, Y₂O₃, Al₂O₃, and a carbon mixture. The carbothermal reduction process reduces the oxygen:nitrogen ratio of the Y-Si-Al-O-N glass that forms, which leads to the precipitation of crystalline oxynitride phases, in particular, the apatite phase. Precipitation of the apatite phase reduces the amount of liquid phase and retards the densification process up to 1750°C; however, the α-to-β phase transformation is not hindered. This results in the distribution of large β-nuclei in a porous fine-grained β-Si₃N₄ matrix. Above 1750°C, liquid formed by the melting of apatite resulted in a rapid increase in densification rates, and the larger β-nuclei also grew rapidly, which promoted the development of a bimodal microstructure.     

Compaction and Sintering Behavior of Bimodal Alumina Powder Suspensions by Pressure Filtration

The compaction behavior of fine alumina powders with different particle sizes or bimodal particle-size distributions that are undergoing pressure filtration was investigated. Three alumina powders—average particle sizes of 0.2—0.86 μm—were compacted to a solids fraction of 62—65 vol% from suspensions at pH 3, which was the pH level at which the suspensions showed their lowest viscosity. When the powders of different average sizes were mixed, the suspensions showed better flowability, and the lowest viscosity was obtained when the fraction of fines was ∼30 vol% and pH = 3. The mixed-sized powder suspensions were compacted to higher density than the suspensions of unmixed fine or coarse powders, and the maximum density was obtained for mixed suspensions that had the lowest viscosity, despite the different particle-size ratio. Maximum densities of 72.5% and 75.0% were attained when the size ratios were 2 and 5, respectively. The compacts that were pressure-filtered from mixed suspensions exhibited a single-peaked pore-size distribution and a homogeneous microstructure, whereas the pore-size distributions of dry-pressed compacts were double-peaked. The sintering behavior of the compacts that were pressure-filtrated from bimodal powders exhibited significantly better sinterability and much-less linear shrinkage than the coarser powders and the dry-pressed powder compacts.     

低温低膨胀系数高硬度无铅电子玻璃粉

叙述了低温低膨胀系数无铅电子玻璃粉研制过程。当Bi2O3的质量分数在60%,B2O3在10.7%,ZnO在21.3%,SiO2在5%,其它成分在3%时,可获得膨胀系数为(55～62)×10-7/℃,软化点为380～385℃,玻化温度在450±10℃,附着力优良的无铅玻璃粉。