Microstructure evaluation of 3YSZ sintered by Two-Step Flash Sintering

Flash Sintering (FS) is an energy-efficient sintering technique, which allows a considerable reduction in processing time and temperature. However, a recurring problem of flash sintered samples is the microstructural heterogeneity, which occurs mostly on samples with a high surface-to-volume ratio (e.g., cylindrical samples). Thus, aiming to obtain homogeneous microstructures and smaller grain sizes, this work evaluated the application of Two-Step Flash Sintering (TSFS) in 3YSZ and compared them with samples sintered by FS. The TSFS experiments consisted of applying a first step of current density with greater magnitude (100 mA mm^-2 and 200 mA mm^-2) followed by the second step with smaller magnitude (50 mA mm^-2 and 75 mA mm^-2). In the FS experiments, a single step of current density was used (100 mA mm^-2 and 200 mA mm^-2). The Results showed that TSFS significantly reduced the microstructural heterogeneity compared to FS, promoting smaller and more homogeneous grain sizes in different regions of the samples.     

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.     

Seasonal Variation of Microstructure and Sintered Strength of Dry-Pressed Alumina

An origin was investigated for the variation of the density and the fracture strength of sintered alumina with the manufacturing season. Direct observation using immersion microscopy was utilized to examine the microstructures of granules, green bodies, and sintered samples for two specific cases: samples made in summer and others made in winter. This method revealed a seasonal difference in the pore structure of both green and sintered bodies. The variation of the density and the fracture strength with the manufacturing season was ascribed to the different concentrations of large pore defects in sintered bodies, which were developed from the green body structures. Formation of large pore defects resulted from void spaces at the center and at the boundary of granules in the green bodies. High temperature and humidity contributed to an increase in the deformability of granules, reducing defect sizes in summer and thus improving fracture strength.     

Coating of Small Alumina Crucibles with Magnesia using a Two-Step Drain Casting Technique

A new technique of coating ceramic ware using two-step drain casting is described in which small alumina crucibles are drain cast followed by drain casting a magnesia coat in the same mold. Cosintering at 1500°C resulted in ware defects unless heating schedules embodying arrests at lower temperatures were used.     

High-Strength Porous Alumina Ceramics by the Pulse Electric Current Sintering Technique

High-strength porous alumina has been fabricated with a microstructure control using the pulse electric current sintering (PECS) technique. During sintering the discharge, which is assumed to take place in the voids between the particles, is thought to promote the bridging of particles by neck growth in the initial stages of sintering, leaving high porosity. The effect of dopants (MgO, 200 ppm; TiO₂, 1000 ppm) and of secondary inclusions (3 vol% 3Y-TZP) on the constrained densification and the improvement in the mechanical behavior of porous alumina ceramics has been reported. The porosity of the fabricated porous alumina was controllable between 30% and 50% depending on the sintering temperature. The flexural strength of alumina having 30% and 42% porosity showed impressive values of 250 and 177 MPa, respectively. The dominance of the preferential neck growth of grains over densification significantly improved the mechanical properties of porous alumina, besides leaving high porosity.     

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.     

Liquid Phase Sintering of Alumina, I. Microstructure Evolution and Densification

The microstructure evolution and densification of alumina containing 10 vol% calcium aluminosilicate glass and 0.5 wt% magnesium oxide sintered at 1600°C were quantified by measuring the evolution of pore-size distribution, the redistribution of liquid phase, and the fraction of closed and open pores. The densification stopped at a limiting relative density during the final stage of sintering, and the small and large pores were filled simultaneously by glass during sintering. In addition, the results indicate that the pressure build-up of the trapped gases in pores causes a significantly negative contribution to the driving force, and consequently the observed reduction in densification during the final stage of liquid phase sintering.     

真空烧结氧化铝的实验研究

以150nm Al2O3粉为原材料,用真空烧结的方法来烧结Al2O3陶瓷。实验发现:在真空条件下烧结时,氧化铝与石墨间会发生还原反应,使真空烧结得到的样品质量明显小于常压烧结样品的质量;而且,真空烧结样品的颜色由白色变成了灰色。其原因是在真空条件下烧结时,烧结气氛为还原性气氛,在样品表面产生氧空位。氧空位捕获电子,产生带有一个电子氧空位的F+色心。     

Strength of Partly Sintered Alumina Compacts

Pressed compacts of sized alumina powders were studied to determine the dependence of strength of compacts as sintering begins and proceeds through the initial stage. By carefully controlling the time and temperature of heat treatment in a helium atmosphere, it was determined that the strength-controlling feature of these porous compacts is the area of the interparticle boundaries. Under isothermal conditions the strength was approximately proportional to time of sintering to the 2/7 power as described by theory. From these relations, it is possible to develop the semi-empirical relation between strength and porosity that predicted zero strength at a porosity equivalent to the unfired condition of the powder compact. Although not a confirmation of the grain boundary sintering model, the strength and porosity data are more consistent with the grain boundary diffusion model for initial sintering of alumina than with bulk diffusion models.     

1300℃烧成的75氧化铝瓷的研究

以实验为依据，理论为指导，系统研究了75氧化铝瓷的配料、工艺对烧结性能和产品结构、性状的影响，分析探讨了影响产生的原因、机理。研究表明，在合理配方、优化工艺条件下，75瓷的烧结温度可降至1300℃，产品性能达到或超过同类瓷性能，且具良好的工艺性和经济性。     

Determination of Biaxial Compressive Strength of a Sintered Alumina Ceramic

The compressive strength of commercial high-density alumina was measured in several compressive biaxial stress states. The compressive strength was only slightly affected by the magnitude of the intermediate principal stress. The average value of the compressive strengths measured in all stress states, excluding the equibiaxial and the near-uniaxial compressive stress states, was 528 ksi. The average of the coefficients of variation was 3%. The tensile strength measured for the material indicates that the ratio of compressive strength to tensile strength is ∼ 18.     

Sintering and Microstructure Modification of Mullite/Zirconia Composites Derived from Silica-Coated Alumina Powders

This paper addresses the densification and microstructure development during firing of mullite/zirconia composites made from silica-coated-alumina (SCA) microcomposite powders. Densification occurs in two stages: in the presence of a silica–alumina mixture and after conversion to mullite. The first stage of densification occurs through transient viscous phase sintering (TVS). This is best promoted by rapid heating, which delays the crystallization of silica to higher temperatures. A further sintering stage is observed following mullitization. The introduction of seeds promotes solid-state sintering, most probably due to refinement of the mullite matrix. For seed concentrations up to about 1% the sintering kinetics depend on seed concentration. This suggests that nucleation still remains the rate-controlling mullitization step. Above this concentration the reaction becomes growth controlled. Introduction of seeds also promotes direct mullitization without transient zircon formation that was observed in a previous study of the same process without seeding. Seeding also promotes the development of elongated grains by way of a solid-state recrystallization process.     

Spark Plasma Sintering of Alumina

A systematic study of various spark plasma sintering (SPS) parameters, namely temperature, holding time, heating rate, pressure, and pulse sequence, was conducted to investigate their effect on the densification, grain-growth kinetics, hardness, and fracture toughness of a commercially available submicrometer-sized Al₂O₃ powder. The obtained experimental data clearly show that the SPS process enhances both densification and grain growth. Thus, Al₂O₃ could be fully densified at a much lower temperature (1150°C), within a much shorter time (minutes), than in more conventional sintering processes. It is suggested that the densification is enhanced in the initial part of the sintering cycle by a local spark-discharge process in the vicinity of contacting particles, and that both grain-boundary diffusion and grain-boundary migration are enhanced by the electrical field originating from the pulsed direct current used for heating the sample. Both the diffusion and the migration that promote the grain growth were found to be strongly dependent on temperature, implying that it is possible to retain the original fine-grained structure in fully densified bodies by avoiding a too high sintering temperature. Hardness values in the range 21–22 GPa and fracture toughness values of 3.5 ± 0.5 MPa·m^1/2 were found for the compacts containing submicrometer-sized Al₂O₃ grains.     

Initial Stages of Sintering of Alumina by Thermo-Optical Measurements

The behavior of nanostructured and submicrometer α-Al₂O₃ powders during the initial stages of field-assisted sintering technique (FAST), conventional, and microwave sintering was investigated using the laser-flash technique for thermo-optical measurements (TOM). An enhanced neck formation due to surface diffusion at very early stages of sintering was found in FAST samples. No significant difference due to heating rate has been found in these various samples.     

Characterization of Creep Cavitation in Sintered Alumina by Small-Angle Neutron Scattering

Small-angle neutron scattering experiments were performed on compression-crept alumina. The results suggest that grain-boundary cavities, on the order of 100 nm in diameter, probably are present initially. For compression strains up to 8%, the average cavity size changes very little. However, the cavity density approximately triples, and it appears that the cavities become elongated in the direction of the compression axis .     

Influence of Various Consolidation Techniques on the Green Microstructure and Sintering Behavior of Alumina Powders

Submicrometer alumina powders, of both standard and narrow particle-size distributions, were consolidated by dry-pressing and colloidal-forming techniques. The resulting green compacts were characterized in terms of pore-size distribution, green density, shrinkage behavior, and sintered density. The interrelationships between powder characteristics, green compact microstructure, and sintering behavior are discussed. There are distinct differences between the characteristics of compacts that were directly consolidated from powder suspensions and those that were dry pressed. Dense microstructures can be achieved at low temperatures using narrow-sized, well-dispersed powders with colloidal-forming techniques.     

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.     

两步烧结法制备纳米氧化钇稳定的四方氧化锆陶瓷

采用共沉淀法制备纳米氧化钇稳定的四方氧化锆（yttria stabilized tetragonal zirconia,3Y-TZP）粉体。利用X射线衍射、N2吸附–脱附等温线,透射电子显微镜对3Y-TZP粉体的物理性能和化学性能进行表征。研究了纳米3Y-TZP粉体的烧结曲线,分析了3Y-TZP素坯在烧结过程中的致密化行为和显微结构,探讨了两步烧结工艺对3Y-TZP纳米陶瓷微观结构的影响。结果表明：采用共沉淀法,在600℃煅烧2h后,可获得晶粒尺寸为13nm、晶型发育良好、团聚较少的纳米3Y-TZP粉体;采用两步烧结法,将素坯升温至1200℃保温1min后,再降温到1050℃保温35h,可获得相对密度大于98%,晶粒尺寸约为100nm的3Y-TZP陶瓷。两步烧结法通过控制煅烧温度和保温时间,利用晶界扩散及其迁移动力学之间的差异,使晶粒生长受到抑制,样品烧结致密化得以维持,实现在晶粒无显著生长前提下完成致密化。     

Microstructure of Sintered Mullite-Zirconia Composites

Fused mullite, pure and with 10 to 25 vol% ZrO₂ added, was milled in an attritor and sintered in air at temperatures near 1600°C to a dense fine-grained ceramic. The ZrO₂ promoted densification and retarded grain growth of the mullite phase. Transmission electron microscopy showed that compositions containing ZrO₂ were substantially free of glass, whereas pure mullite bodies contained a glassy phase. The ZrO₂ formed inter granular, isolated particles .