Fabrication of Mullite and Mullite-Matrix Composites by Transient Viscous Sintering of Composite Powders

Mullite was fabricated by a process referred to as transient viscous sintering (TVS). Composite particles which consisted of inner cores of α-alumina and outer coatings of amorphous silica were used. Powder compacts prepared with these particles were viscously sintered to almost full density at relatively low temperatures (∼1300°C). Compacts were subsequently converted to dense, fine-grained mullite at higher temperatures (∼1500°C) by reaction between the alumina and silica. The TVS process was also used to fabricate mullite/zirconia/alumina, mullite/silicon carbide particle, and mullite/silicon carbide whisker composites. Densification was enhanced compared with other recent studies of sintering of mullite-based composites. This was attributed to three factors: viscous flow of the amorphous silica coating on the particles, avoidance of mullite formation until higher temperatures, and increased threshold concentration for the development of percolation networks.     

Effects of Complex Precursors on Alkoxide-Derived Cordierite Powder

Preparation of chemically homogeneous cordierite powders of submicrometer size was investigated using alkoxide precursors, synthesized from Mg metal, Al(OBu^s)₃, and partially prehydrolyzed Si(OEt)₄. The amount of partial prehydrolysis water in precursor synthesis was changed to study the effects on the hydrolysis products. In the hydrolysis of the diluted solution of the precursor, product morphology was quite sensitive to the precursor, and different morphologies such as gelation, gel precipitation, and powder precipitation were observed. A redispersable powder of submicrometer size was obtained only from the precursor synthesized at a H₂O/Si(OEt)₄ ratio of 1.2. Differences were also observed in minor crystalline phases among calcined hydrolysis products. The alkoxide precursors were characterized using Raman spectroscopy, gas chromatography, and NMR spectroscopy. The differences in hydrolysis products are most likely due to differences in hydrolysis and condensation of different chemical species in precursors.     

Preparation of Mullite Cordierite Composite Powders by the Sol-Gel Method: Its Characteristics and Sintering

Mullite/cordierite composite powders containing different proportions of cordierite were prepared by the sol-gel method using boehmite, colloidal silica, and Mg(NO₃)₂·6H₂O. Mullite and cordierite sols were prepared separately and mixed to form the composite sol. Mullitization temperature depends on the cordierite content in the composite. Also, α-cordierite crystallizes at a lower temperature in a mullite-rich (MC20) composite. The XRD patterns of the powders calcined at 1450°C for 12 h showed that mullite and cordierite exist as two different phases, and no additional phases were observed. The IR absorbance spectra of composites showed characteristic peak corresponding to both mullite and cordierite. The sintered density of the powders increases with temperature up to 1450°C and decreases beyound the melting point of cordierite (1455°C). The microstructure of MC30 sintered at 1440°C for 3 h consisted of acicular grains, whereas in MC40 and MC50 equiaxed grain morphology was observed under similar sintering conditions. The flexural strength and Vickers hardness decreases with the increase of cordierite content in the composite. Dielectric constant and thermal expansion showed a similar behavior.     

Sintering of the Mechanochemically Activated Powders of Hexagonal Boron Nitride

Pressureless sintering of hexagonal boron nitride (BN) was performed using a powder activated by mechano-chemical treatments. Physical properties of the sintered BN bodies depend on the type of starting powder and the conditions of the treatments. The BN body, which was obtained at 2000°C using an appropriate activated powder, was 99 wt% pure and was excellent in mechanical and physical properties, in spite of its low density (1.64 g/cm³).     

Sm2O3掺杂对纳米莫来石前驱粉体微观结构和烧结性能的影响

为了改善纳米莫来石粉体烧结性能,以硫酸铝和硅酸钠为主要合成原料,添加不同含量Sm2O3,采用共沉淀工艺制备莫来石前驱粉体,经过煅烧得到莫来石纳米粉体,研究了Sm2O3掺杂量对莫来石粉体微观结构和烧结性能的影响.研究表明:当Sm2O3的加入量为4wt%时,合成温度可由传统的1300 ℃左右降低至1000 ℃,晶粒尺寸约为39 nm,比表面积达到95.265 m2/g.说明适当掺杂Sm3+对于合成纳米莫来石具有改善微观结构,促进烧结,促进莫来石晶相形成的作用.     

Sintering Behavior and Electrical Properties of Nanosized Doped-ZnO Powders Produced by Metallorganic Polymeric Processing

Homogeneous and nanosized (28 nm crystallite size) doped-ZnO ceramic powders were obtained by a metallorganic polymeric method. Calcining and granulating resulted in green compacts with uniform powder packing and a narrow pore-size distribution (pore size 19 nm). Dense ceramic bodies (>99% of theoretical) were fabricated by normal liquid-phase sintering at 850° and 940°C for 1–5 h. Apparently, the low pore-coordination number allowed a uniform filling of the small pores by the liquid formed in the early stages of sintering, and, consequently, high shrinkage and rapid densification occurred in a short temperature interval (825°–850°C). At these sintering temperatures, limited grain growth occurred, and the grain size was maintained at <1 μm. Ceramics so-fabricated showed a nonlinear coefficient, α, of ≥70, and a breakdown voltage, V _b (1 mA/cm²), of ≥1500 V/mm. The high electrical performance of the doped-ZnO dense ceramics was attributed to liquid-phase recession on cooling, which enhanced the ZnO-ZnO direct contacts and the potential barrier effect.     

Sintering of Industrial Mullites in the Presence of Magnesia as a Sintering Aid

The sinterability of two industrial mullite powders, in the presence of MgO as a sintering aid, was investigated. A glassy phase, which was generated during preparation, was present in both powders; this glassy phase had a strong influence on sintering, depending on its content, composition, and spatial distribution. MgO promoted sintering in the presence of a liquid phase, both in the as-received materials and in samples washed with HF, in which most of the pre-existing glassy phase was eliminated. Investigations using transmission electron microscopy, coupled with energy-dispersive spectroscopy, as well as dilatometric measurements and X-ray diffraction data, on washed and unwashed materials and on quenched and slow-cooled samples allowed a better understanding of the influence of MgO and the glassy phase on the sintering behavior and the formation of new phases. Most of the phases, in fact, can be explained by using the MgO–Al₂O₃–SiO₂ phase diagram, even in such complex systems.     

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.     

纳米ZrO_2－Al_2O_3复合粉末注浆成型与烧结行为研究

平均粒径为２０ｎｍ的ＺｒＯ_２添加５～１５ｖｏｌ％的粒径为２００ｎｍ的Ａｌ_２Ｏ_３粉末注浆成型与烧结特性表现出与普通微米及亚微米级粉末不同的特性：浆料具有较低的含固量，粘度为５厘泊时为５５ｗｔ％；浆料呈微弱触变性：生坯具有较低相对密度，仅为理论值的３５．５％；少量Ａｌ_２Ｏ_３（５～１０ｖｏｌ％）促进复合材料的烧结，但也伴随着Ａｌ_２Ｏ_３晶粒异常长大。上述现象归因于纳米粉末具有非常高的比表面，粉末表面吸附大量紧吸附水不能被石膏模所排除，而粉末巨大的表面能促进了烧结过程中的质点扩散。     

Sintering of Lithium Zinc Ferrites with Alkoxide-Derived Borosilicate Liquid Phase

Lithium zinc ferrites (Li_0.3Zn_0.4Mn_0.05Fe_2.25O₄) of > 97% theoretical density were prepared with alkoxide-derived borosilicate sintering additive. A sol-gel technique was used to incorporate the borosilicate phase prior to sintering. The effects of borosilicate composition and additive quantity on microstructural development and densification are reported. Direct current resistivity, dynamic hysteresis, and microwave property data are discussed in terms of processing parameters and resultant microstructures. The microstructure of the sintered ferrites was analyzed using SEM and TEM. Heterogeneities including regions of liquid-phase coalescence and intragranularly included glass phase were observed in some cases. These microstructural features were shown to have deleterious effects on microwave magnetic properties when compared to those of commercial ferrites of the same nominal composition sintered with Bi₂O₃ additive.     

Preparation of Monodisperse, Spherical Alumina Powders from Alkoxides

Monodisperse, spherical alumina powders were prepared by the controlled hydrolysis of aluminum alkoxide in a dilute solution consisting of octanoi and acetonitrile. The reagent concentration influenced the particle size, size distribution, morphology, and state of agglomeration. The addition of acetonitrile and octanol affected both particle shape and the state of agglomeration and prevented gelation during hydrolysis. Sub-micrometer-sized alumina particles grew to 10 μm with increased concentration of hydroxypropylcellulose dispersant. As-prepared amorphous powders crystal-lized to γ-alumina at 1000°C and converted to α-alumina at 1150°C without intermediate phases. The particle morphology was retained after crystallization to γ-alumina.     

碳酸氢铵沉淀法制备纳米氧化铝粉体的性能与表征

以Al(NO3)3.9H2O、NH4HCO3为原料,采用化学沉淀法制备了NH4Al(OH)2CO3和AlO(OH)前驱体。通过X射线衍射、透射电镜和热膨胀仪研究发现:由NH4Al(OH)2CO3热处理得到的Al2O3粉体具有较高的结晶温度和α相变温度;其粒径较小,分散良好,具有较好的烧结活性;非晶态、亚稳相和稳定的α相氧化铝的烧结曲线上分别具有不同数量的拐点,亚稳相氧化铝烧结过程中的α相变产生大量的气孔,阻碍了烧结体的致密化。     

硼酸对熔融石英烧结及其晶化的影响

本文通过XRD、SEM等分析,从显微结构方面研究了硼酸对熔融石英烧结及其晶化的影响.结果表明硼酸在本实验范围内促进烧结,而且当硼酸含量小于0.5wt%时,随硼酸含量的增加,效果越明显;当硼酸含量为0.5wt%至1.0wt%时,变化不大;当硼酸含量大于1.0wt%时,烧结的驱动力大大提高,促进烧结的效果也更加明显.研究还发现,添加硼酸同时也促进了熔融石英的晶化,而且随硼酸含量的增加,晶化越严重,其结晶度成指数增长.当硼酸含量小于1.0wt%时,结晶相为低温方石英相;当硼酸含量高于1.0wt%时,结晶相以低温方石英相为主,同时还生成新的结晶相(BSi)O_2和Si_(30.72)B_(1.28)O_(64).     

Flame Spray Pyrolysis of Precursors as a Route to Nano-mullite Powder: Powder Characterization and Sintering Behavior

The flame spray pyrolysis of alcohol-soluble precursors allows the synthesis of mullite-composition nanopowders (average size of ∼60–100 nm) that, when annealed carefully, provide processable nano-mullite powders. The powders have been characterized using several spectroscopic and microscopy methods, including thermal gravimetric analysis, differential thermal analysis, diffuse reflectance infrared Fourier transform spectroscopy, and transmission electron microscopy. Preliminary studies on the pressureless-sintering behavior of these powders are presented. Without additives or any efforts to optimize the process, powder compacts could be sintered to relative densities of >90%, with grain sizes of <500 nm at 1600°C.     

Alkoxide-Hydroxide Route to Syntheltize BaTiO3-Based Powders

When preparing homogeneous, fine barium titanate powders, the major difficulty is to avoid the spontaneous self-condensation between the Ti-OH groups. In the usual way of preparing fine barium titanate powders, chelating agents (citrate, oxalate) or simply unidentate ligands (alkoxy or carboxyl groups) are used to complex titanium atoms. Another way is to mix barium and titanium precursors in a strongly basic medium. The condensation between the Ti(OH)^2-₆Ba²⁺ species directly gives the perovskite compound. Using an alkoxide-hydroxide route, a homogeneous Ba-Ti solution was prepared that completely advanced by condensation between the Ti(OH)^2-₆Ba²⁺ species and led to a controlled-stoichiometry powder. Concerning pure barium titanate, dried powders exhibited the cubic perovskite structure, and a direct sintering at 1150°C, without calcination, led to highly dense BaTiO₃ bodies with fine-grained uniform microstructure (1 μm) that exhibited a high permittivity value at room temperature ( K = 5400). The alkoxide-hydroxide method was also used to prepare dense alkaline-earth perovskite ceramics with complex compositions.     

纳米羟基磷灰石粉体的制备和低温烧结

对沉淀法制备纳米HAp粉体及低温烧结HAp材料进行了研究. 结果表明：陈化对于防止HAp在高温下分解有重要作用；在陈化前加入一定量的聚乙二醇，可以明显增大纳米HAp粉体的比表面积，降低烧结温度；在普通无压烧结条件下，可在950℃的低温下，获得相对密度达98%左右的HAp材料，致密化温度比商业用粉低数百度. 研究还表明：醇洗不能有效提高纳米HAp的烧结性能.     

Microstructural Characterization of Reactively Sintered Mullites

Mullite ceramics have been produced by reaction sintering of powders prepared using pseudoboehmite–colloidal silica and aluminum sulfate–colloidal silica mixtures. The microstructural development of these mullites was studied by a number of transmission electron microscopy based techniques including diffuse dark field, Fresnel fringe defocus imaging, and high-resolution transmission electron microscopy. This characterization procedure showed that mullite ceramics free from glassy phases at triple junctions and grain boundaries could be produced from both mixtures using suitable sintering temperatures and alumina/silica ratios. The wetting of grain boundaries by glass, occurring in the mullite ceramics from either incomplete reaction between alumina and silica components or release of silica from the mullite structure with increasing temperature, was found to depend on the prior thermal history of the ceramics.     

Sinterability of Calcined Freeze-Dried Alumina Powders

The sinterability of alumina powders derived from freezedried, calcined aluminum sulfate is highly variable. Sintered densities of similarly prepared powders can range from <40% of theoretical density to 99% of theoretical density. Our results suggest that this variation is a result of the sensitivity of freeze-dried powders to heating rate during calcination as well as calcination temperature, time, and atmosphere. Residual sulfur may also play a role in the sinterability.     

Characterization and Sintering of Lead Zirconate-Titanate Powders

Two techniques — conventional calcining of mixed oxides and molten salt synthesis—have been used to prepare lead zirconate-titanate powders for subsequent sintering experiments. Several characterization methods, including SEM microscopy and pressing behavior, were used to evaluate the primary particle size and agglomerate state of the powders. In the powders produced by conventional calcining of mixed oxides, the primary particle size was strongly dependent on calcining temperature. These powders also contained a large proportion of very strong agglomerates. The powders produced using molten salt synthesis had a primary particle size nearly independent of processing temperature. The agglomerates formed appeared to be quite friable. Subsequent sintering experiments showed that grain growth was more pronounced with the conventionally calcined powders. The ceramics produced from molten synthesized powders had a more uniform grain size which was nearly independent of powder processing conditions. The densities of these ceramics were, however, always lower than those produced from conventionally calcined powders.     

Precoarsening to Improve Microstructure and Sintering of Powder Compacts

MgO and Al₂O₃ were sintered by two types of processes: a conventional isothermal sintering and a two-step sintering consisting of an initial low-temperature precoarsening treatment before conventional isothermal sintering. The final microstructure from two-step sintering can be more uniform and finer than that of compacts sintered conventionally. A narrow-size-distribution alumina powder was sintered under constant-heating-rate conditions, with and without a precoarsening treatment, and the results were compared. The differences between two-step and conventional processing were clarified by experiments on precoarsened and as-received ZnO powders. These compacts were precoarsened at 450°C for 90 h with virtually no increase in the overall density. The resulting grain size was 1.7 times the starting one, but the standard deviation of the precoarsened powder size distribution was smaller than that of the asreceived powder. Precoarsened compacts sintered to nearly full density showed improved homogeneity. The sintering stress of the precoarsened ZnO was approximately 0.8 that of the as-received one. A computational model has been used with two components of coarsening to describe the differences in pore spacing evolution between the precoarsened and the as-received system. The benefit of two-step sintering is attributed to the increase in uniformity resulting from precoarsening. The increased uniformity decreases sintering damage and allows the system to stay in the open porosity state longer, delaying or inhibiting additional coarsening (grain growth) during the final stage of densification. Two-step sintering is especially useful for nonuniform powder systems with a wide size distribution and is a simple and convenient method of making more uniform ceramic bodies without resorting to specialized powders or complicated heat schedules.