Influence of Yttria–Alumina Content on Sintering Behavior and Microstructure of Silicon Nitride Ceramics

The present study investigates the influence of the content of Y₂O₃–Al₂O₃ sintering additive on the sintering behavior and microstructure of Si₃N₄ ceramics. The Y₂O₃:Al₂O₃ ratio was fixed at 5:2, and sintering was conducted at temperatures of 1300°–1900°C. Increased sintering-additive content enhanced densification via particle rearrangement; however, phase transformation and grain growth were unaffected by additive content. After phase transformation was almost complete, a substantial decrease in density was identified, which resulted from the impingement of rodlike β-Si₃N₄ grain growth. Phase transformation and grain growth were concluded to occur through a solution–reprecipitation mechanism that was controlled by the interfacial reaction.     

Pulsed Electric Current Sintering of Silicon Nitride

Pulsed electric current sintering (PECS) has been used to densify α-Si₃N₄ powder doped with oxide additives of Y₂O₃ and Al₂O₃. A full density (>99%) was achieved with virtually no transformation to β-phase, resulting in a microstructure with fine equiaxed grains. With further holding at the sintering temperature, the α-to-β phase transformation took place, concurrent with an exaggerated grain growth of a limited number of elongated β-grains in a fine-grained matrix, leading to a distinct bimodal grain size distribution. The average grain size was found to obey a cubic growth law, indicating that the growth is diffusion-controlled. In contrast, the densification by hot pressing was accompanied by a significant degree of the phase transformation, and the subsequent grain growth gave a broad normal size distribution. The apparent activation energy for the phase transformation was as high as 1000 kJ/mol for PECS, almost twice the value for hot pressing (∼500 kJ/mol), thereby causing the retention of α-phase during the densification by PECS.     

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.     

Experimental Design Applied to Silicon Carbide Sintering

Silicon carbide is a promising structural ceramic used as abrasives and applied in metallurgical components, due to its low density, high hardness, and excellent mechanical properties. The composition and content of the additive can control liquid-phase sintering of SiC. Compositions based on the SiO₂–Al₂O₃–RE₂O₃ system (RE = rare earth) have been largely used to promote silicon carbide densification, but most studies are not systematically presented. The aim of this work is to study the effect of several oxide additives in the SiO₂–Al₂O₃–Y₂O₃ system on the densification of silicon carbide using experimental design. This technique seems to be effective in optimizing the values of maximum density with minimum weight loss.     

Role of Carbon in the Sintering of Boron-Doped Silicon Carbide

The effect of carbon on the sintering of boron-doped SiC was studied. The free carbon present in the green compact was found to react with the SiO₂ covering the surfaces of the SiC particles; however, even if no carbon was added, the surface SiO₂ reacted with the SiC itself at a slightly higher temperature. This latter reaction was associated with the onset of substantial pore growth in the shrinking green body, which, as the pores continued to grow at higher temperatures, prevented complete densification. Therefore, the reaction of the SiC with the SiO₂ may have led to the fracture of interparticle contacts, resulting in the onset of coarsening. Thus, the role of the carbon was to prevent reaction between the SiC and the surface SiO₂, by removing the SiO₂ at a temperature below that at which this reaction could occur.     

Effect of Sintering Atmosphere on Grain Shape and Grain Growth in Liquid-Phase-Sintered Silicon Carbide

We investigated the effects of the sintering atmosphere on the interface structure and grain-growth behavior in 10-vol%-YAG-added SiC. When α-SiC was liquid-phase-sintered in an Ar atmosphere, the grain/matrix interface was faceted, and abnormal grain growth occurred, regardless of the presence of α-seed grains. In contrast, when the same sample was sintered in N₂, the grain interface was defaceted (rough), and no abnormal grain growth occurred, even with an addition of α-seed grains. X-ray diffraction analysis of this sample showed the formation of a 3C (β-SiC) phase, together with a 6H (α-SiC) phase. These results suggest that the nitrogen dissolved in the liquid matrix made the grain interface rough and induced normal grain growth by an α→β reverse phase transformation. Apparently, the growth behavior of SiC grains in a liquid matrix depends on the structure of the grain interface: abnormal growth for a faceted interface and normal growth for a rough interface.     

Fabrication of Dense Nanostructured Silicon Carbide Ceramics through Two-Step Sintering

SiC powder compacts were prepared with Al₂O₃, Y₂O₃, and CaO powders. By two-step sintering, fully dense nanostructured SiC ceramics with a grain sizes of ∼40 nm were obtained. The grain size–density trajectories are compared with those of conventional sintering processes.     

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.     

Dispersion and Slip Casting of Hydroxyapatite

The dispersibility in deionized water of hydroxyapatite (HA) synthesized by a high-temperature (1000°C) solid-state reaction between tricalcium phosphate and calcium hydroxide was investigated as a function of the pH of the medium and the quantity of two dispersing agents (A = inorganic, B = organic) added to the slips. Although pH modification had a negligible effect on dispersibility, both of the dispersing agents produced a good dispersion at considerably higher concentrations (>2 wt% of HA). At optimum amounts (2–4 wt%) of the dispersing agents, the slips showed near-Newtonian flow behavior up to 45 wt% solids loading and non-Newtonian behavior at >50 wt%. By the optimal addition of dispersing agents and conditioning by ball milling, 60–67 wt% (32–39 vol%) solids-loaded HA slips could be cast into plaster molds to produce 50%–58% dense green bodies, which, in turn, sintered to 90%–94% density in the temperature range 1300°–1400°C. The sintered HA exhibited a three-point flexural strength of 40–60 MPa and a homogeneous microstructure, with interspersed microporosities.     

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。     

烧结温度对氮化硅陶瓷球显微结构和力学性能的影响

以α-Si3N4粉为原料,纳米级Y2O3和Al2O3为烧结助剂,采用气压烧结工艺制备氮化硅陶瓷球,研究了烧结温度对陶瓷球显微结构及力学性能的影响.结果表明,随着烧结温度的升高,陶瓷球的维氏硬度和压碎强度先提高后降低,断裂韧性不断提高.烧结温度为1780℃的陶瓷球综合力学性能最佳,其相对密度达到了99％,维氏硬度、断裂韧...     

Gas Pressure Sintering of Silicon Nitride Powder Coated with Al2O3 and TiO2

Gas pressure sintering kinetics of silicon nitride powder coated with 10 wt% (9:1) Al₂O₃ and TiO₂ have been studied at 1850°C with a pressure schedule of 0.3 MPa in the first stage and 1 MPa in the second stage. The rates have been analyzed with a liquid-phase sintering model. Diffusion-controlled intermediate-stage kinetics have been observed. The role of second-step pressurization with nitrogen and argon has been determined by monitoring the kinetics. Pressurization at an earlier stage (∼90% relative density) reduces the densification rate but produces a denser material at the final stage. Although final density is greater, a porous surface layer forms on samples sintered with argon pressurization at the second stage. No such porous layer is formed in the case of pressurization with nitrogen. The mechanism of the intermediate-stage kinetics has been discussed with respect to the nature of the product analyzed by XRD after sintering.     

Effect of Hot-Pressing Temperature on Densification and Mechanical Properties of Titanium Diboride with Silicon Nitride as a Sintering Aid

The effect of hot-pressing temperature on the densification behavior and mechanical properties of titanium diboride (TiB₂) was investigated. TiB₂ specimens were hot-pressed for 1 h at temperatures in the range of 1500°–1800°C, with an addition of 2.5 wt% of silicon nitride (Si₃N₄) as a sintering aid. The density increased markedly at temperatures in the range of 1500°–1600°C and remained constant thereafter. The formation of a eutectic liquid at 1550°C was attributed to the steep increase in density. The hot-pressing temperature also improved the mechanical properties, such as the flexural strength, Vickers hardness, and fracture toughness of the specimens. Similar to the density, the mechanical properties improved remarkably at ∼1550°C, so that optimum properties were obtainable at temperatures as low as 1600°C.     

Effect of Sintering Additive Composition on the Processing and Thermal Conductivity of Sintered Reaction-Bonded Si3N4

Two compositions of the Y₂O₃–MgO (YM) and Yb₂O₃–MgO (YbM) systems were chosen to study the effect of the sintering additive composition on the processing and thermal conductivity of sintered reaction-bonded silicon nitride (SRBSN). The nitridation, postdensification, microstructural evolution, and thermal conductivity of SRBSN were found to depend strongly on the sintering additive composition. The RBSN materials with YbM exhibited a poor sinterability, whereas those with YM exhibited an excellent sinterability. However, the SRBSN materials with YbM showed a higher thermal conductivity than those with YM. This was associated primarily with the isolated distribution and lower amount of secondary phase and the higher percentage of large grains in the former materials.     

Microstructural Evolution in Liquid-Phase-Sintered SiC: Part III, Effect of Nitrogen-Gas Sintering Atmosphere

Effects of N₂ sintering atmosphere and the starting SiC powder on the microstructural evolution of liquid-phase-sintered (LPS) SiC were studied. It was found that, for the β-SiC starting powder case, there was complete suppression of the β→α phase transformation, which otherwise goes to completion in Ar atmosphere. It was also found that the microstructures were equiaxed and that the coarsening was severely retarded, which was in contrast with the Ar-atmosphere case. Chemical analyses of the specimens sintered in N₂ atmosphere revealed the presence of significant amounts of nitrogen, which was believed to reside mostly in the intergranular phase. It was argued that the presence of nitrogen in the LPS SiC helped stabilize the β-SiC phase, thereby preventing the β→α phase transformation and the attendant formation of elongated grains. To investigate the coarsening retardation, internal friction measurements were performed on LPS SiC specimens sintered in either Ar or N₂ atmosphere. For specimens sintered in N₂ atmosphere, a remarkable shift of the grain-boundary sliding relaxation peak toward higher temperatures and very high activation energy values were observed, possibly due to the incorporation of nitrogen into the structure of the intergranular liquid phase. The highly refractory and viscous nature of the intergranular phase was deemed responsible for retarding the solution–reprecipitation coarsening in these materials. Parallel experiments with specimens sintered using α-SiC starting powders further reinforce these arguments. Thus, processing of LPS SiC in N₂ atmosphere open the possibility of tailoring their microstructures for room-temperature mechanical properties and for making high-temperature materials that are highly resistant to coarsening and creep.     

氮化硅/羟基磷灰石复合材料的制备研究

主要用超声分散结合滴定工艺制备了氮化硅／羟基磷灰石(Si3N4/HAp)复合粉体，并经冷压成型、冷等静压成型及无压烧结制备了氮化硅／羟基磷灰石复合材料。X射线衍射(XRD)及扫描电镜(SEM)研究发现，氮化硅的加入促进了羟基磷灰石的分解，细化了晶粒，可降低羟基磷灰石的烧结温度。     

Transparent Hydroxyapatite Ceramics through Gelcasting and Low-Temperature Sintering

Transparent hydroxyapatite (HAP) was prepared by sintering gel-cast powder compacts at 1000°C for 2 h; the resultant HAP material was studied using X-ray diffractometry, transmission electron microscopy, scanning electron microscopy, and microhardness measurement. Nanoscale HAP crystallites were prepared using a precipitation method that involved calcium nitrate and ammonium dihydrogen orthophosphate solutions; the preparation was conducted at a temperature of 0°C. The precipitate was gel-cast and sintered at 1000°C in the form of a transparent ceramic that had a uniform grain size of 250 μm. The maximum Vickers microhardness obtained for a sample sintered at 1000°C was 6.57 GPa. The sintering behavior of gel-cast samples prepared from high-temperature-precipitated HAP was compared with that of material prepared at 0°C.     

Consolidation of Nanostructured β-SiC by Spark Plasma Sintering

Nanostructured β-SiC, with crystallite size in the range of 5–20 nm in agglomerates of 50–150 nm, was formed by reactive high-energy ball milling and consolidated to a relative density of 98% by sintering at 1700°C without the use of additives. X-ray line broadening analysis gave a crystallite size of 25 nm, while transmission electron microscopy observations showed the crystallite size to be in the range of 30–50 nm. Evidence demonstrating the role of a disorder–order transformation in the densification process is provided by changes in the diffraction peak patterns and in the integral width with temperature.     

Fabrication and Microstructure Characterization of Ti3SiC2 Synthesized from Ti/Si/2TiC Powders Using the Pulse Discharge Sintering (PDS) Technique

Ti/Si/2TiC powders were prepared using a mixture method (M) and a mechanical alloying (MA) method to fabricate Ti₃SiC₂ at 1200°–1400°C using a pulse discharge sintering (PDS) technique. The results showed that the Ti₃SiC₂ samples with <5 wt% TiC could be rapidly synthesized from the M powders; however, the TiC content was always >18 wt% in the MA samples. Further sintering of the M powder showed that the purity of Ti₃SiC₂ could be improved to >97 wt% at 1250°–1300°C, which is ∼200°–300°C lower than that of sintered Ti/Si/C and Ti/SiC/C powders using the hot isostatic pressing (HIPing) technique. The microstructure of Ti₃SiC₂ also could be controlled using three types of powders, i.e., fine, coarse, or duplex-grained, within the sintering temperature range. In comparison with Ti/Si/C and Ti/SiC/C mixture powders, it has been suggested that high-purity Ti₃SiC₂ could be rapidly synthesized by sintering the Ti/Si/TiC powder mixture at relatively lower temperature using the PDS technique.     

Crack-Healing Behavior of Liquid-Phase-Sintered Silicon Carbide Ceramics

Crack-healing behavior of liquid-phase-sintered (LPS) SiC ceramics has been studied as functions of heat-treatment temperature and crack size. Results showed that heat treatment in air could significantly increase the indentation strength. The heat-treatment temperature has a profound influence on the extent of crack healing and the degree of strength recovery. The optimum heat-treatment temperature depends on the softening temperature of an intergranular phase in each material. After heat treatment at the optimum temperature in air, the crack morphology almost entirely disappeared and the indentation strength recovered to the value of the smooth specimens at room temperature for the investigated crack sizes up to ∼200 μm. In addition, a simple heat treatment of SiC ceramics sintered with Al₂O₃–Y₂O₃–CaO at 1100°C for 1 h in air resulted in even further improvement of the strength, to a value of 1054 MPa (∼150% of the value of the unindented strength). Crack closure and rebonding of the crack wake due to oxidation of cracked surfaces were suggested as a dominant healing mechanism operating in LPS-SiC ceramics.