Densification as an exothermic process revealed by rapid high temperature consolidation of BaTiO3 nanopowder

Abstract

Densification is an exothermic process according to the classical sintering theories; however, it has never been explored experimentally. In the present work, such heat release was successfully detected from nanosized BaTiO₃ nanopowder compact, which was rapidly consolidated by spark plasma sintering. A reduction of total power consumption was observed immediately when rapid densification occurred. The effects of the deviation of overall electric resistance on total power consumption were analysed. The temperature at which a falling inflection point of the power supply was observed can be used as an indicator of the minimum temperature required for densification. This would be of help for defining the ‘kinetic window’ for processing of nanoceramics in sintering practice.     

Synthesis, spark plasma sintering and electrical conduction mechanism in BaTiO3-Cu composites

BaTiO₃-Cu composite powders were prepared via an alkoxide-mediated synthesis approach. As-synthesized BaTiO₃ nanoparticles were as small as 40 nm and coated partially larger Cu particles of approximately 1 μm in size. Thermogravimetric analysis (TGA) and dilatometry revealed a gradual increase in weight loss and retarded shrinkage with the increase of Cu addition. BaTiO₃-Cu composites were successfully densified by spark plasma sintering (SPS). The microstructures show an average grain-size for BaTiO₃ of around 100 nm and a crystallite size of about 1 μm for the Cu inclusions. The AC conductivity of the BaTiO₃-Cu composites increased with increasing Cu content or with temperature. The dominant electrical conduction mechanism in SPSed BaTiO₃-Cu composites changed from migration of oxygen vacancies to band conduction of trapped electrons in oxygen vacancies with the increase of Cu content.     

Parameters investigation during simultaneous synthesis and densification WC–Ni composites by field-activated combustion

The field-activated, and pressure-assisted combustion synthesis (FAPACS) process, which combines the simultaneous synthesis and densification of materials, was utilized to produce WC–Ni composites from powdered reactants, mixtures of tungsten, carbon and nickel. These reactants were subjected to high DC currents and uniaxial pressures. Under these conditions, a reaction is initiated by field activation and completed within a short period of time. Several experimental parameters, such as pulse current, power-controlled mode, temperature-increasing rate, maximum temperature and pressure during FAPACS on the relative densities of products were studied. Finally, the material with nearly complete density was fabricated. The percentage of the total shrinkage occurring before and during the synthesis reaction and addition densification was measured. The relative density of the end product and Vickers microhardness measurement (at 50 kg force) on the dense sample is 99.2% and 1424 kg mm⁻², respectively.     

Tooling Design and Compaction Analysis on P/M Copper Bushes

The successful production of P/M (powder metallurgy) components depends to a large extent on the tooling used for powder compaction. While designing the tool, the complexities arise from the interaction of the parameters such as powder characteristics, expected green density, the size and geometry of the product, and to whom the properties of the tool materials during compaction should be addressed. Floating type of compaction tooling set (die, punches, and core rod) was designed and fabricated. Pure electrolytic copper powder was compacted in the above-mentioned tool to obtain P/M copper bushes. Compaction pressure-density relationship and their influence on green strength are analyzed.     

Cu-Cr粉体致密化及颗粒流变三维数值模拟分析

利用MSC.Marc有限元软件对Cu-Cr粉体致密化及颗粒流变行为进行了三维数值模拟。分析了不同颗粒排列方式压制载荷下Cu-Cr颗粒致密化、颗粒与节点的流动规律。首次再现了Cu-Cr颗粒在致密化过程中的三维流变行为。结果表明,六角形排列的Cu-Cr颗粒不仅流动性高,而且均匀性也好于方形排列的Cu-Cr颗粒。温粉冷模比温粉温模(恒温环境)在100℃条件下的致密度高0.36%,在800℃条件下高2.87%。六角形排列的Cu-Cr颗粒致密度在摩擦系数为0.1时最高为95.6859%,方形排列的Cu-Cr颗粒致密度在摩擦系数为0.5时最高为97.5343%。无摩擦理想状态下的Cu-Cr颗粒致密化并没有达到最大致密度。     

钢混凝土组合桁架的纵向剪切力

钢混凝土组合桁架中钢和混凝土界面的纵向剪切分布一般是高度非均匀,在桁架节点出现峰值。对两个钢混凝土组合桁架梁的性能进行试验研究,所获试验结果对ANSYS软件包的非线性三维数值有限元模型进行校准。对30多个空腹板简支桁架中跨剪切变量进行研究,包括不同的荷载-滑移关系。在弹性阶段,尤其重要的是连接点受疲劳荷载导致塑性区的塑性重分配,使桁架节点连接处出现独特的剪切流峰值。数值结果与欧洲规范4进行比较,详细探讨了桁架节点剪切连接的增浓作用的影响。最后,对实际设计提出建议。     

渤中凹陷深层砂砾岩气藏油气充注与储层致密化

渤海湾盆地渤中凹陷砂砾岩储层致密化成因及其与晚期油气侵位的关系一直没有得到合理地解释。为此,以渤中凹陷西南部地区古近系砂砾岩气藏为研究对象,利用物性、热史、包裹体等分析资料,确定油气首次成藏时间、划分油气充注期次、恢复成藏期储层物性,进而模拟压实作用对储层的影响,并结合包裹体、铸体、扫描电镜、X射线衍射等实验手段明确油气侵位关系,分析石英加大、黏土矿物转化、碳酸盐胶结等关键致密化作用发生的序列,探究储层致密化作用机理及其与油气充注的关系。研究结果表明:①该区深层砂砾岩油气充注至少可分为3期,早期包裹体为重质油,晚期包裹体气油比高;②首次油气充注期为距今5Ma,储层埋深介于2500～2800m,以中孔、中渗储层为主,储集物性较好,成藏后盆地快速沉降、充填,上覆地层增加厚度超过1 000 m;③首次油气充注后砂砾岩进入成岩快速演化期,埋深介于2 500～3 200 m,是砂砾岩快速压实阶段,石英加大在油气充注后经历了两期强烈发育,减孔作用明显,压实减孔作用是储层致密化的重要机制;④埋深介于2 500～3 500 m为该区黏土矿物快速转化区间,花状及丝发状伊利石极其发育,对渗透率的大小产生了决定性的影响;⑤铁方解石及铁白云石沉淀于石英加大之后,使储层进一步致密化,以残余孔隙为主。结论认为,该区古近系砂砾岩气藏具有先成藏后致密的特点,尽管油气充注对储层成岩具有抑制作用,但后者仍然会导致储层的致密化。     

Densification mechanism and microstructure characteristics of nano- and micro- crystalline alumina by high-pressure and low temperature sintering

Fully dense ceramics with retarded grain growth can be attained effectively at relatively low temperatures using a high-pressure sintering method. However, there is a paucity of in-depth research on the densification mechanism, grain growth process, grain boundary characterization, and residual stress. Using a strong, reliable die made from a carbon-fiber-reinforced carbon (C_f/C) composite for spark plasma sintering, two kinds of commercially pure α-Al₂O₃ powders, with average particle sizes of 220 nm and 3 μm, were sintered at relatively low temperatures and under high pressures of up to 200 MPa. The sintering densification temperature and the starting threshold temperature of grain growth (T_sg) were determined by the applied pressure and the surface energy relative to grain size, as they were both observed to increase with grain size and to decrease with applied pressure. Densification with limited grain coarsening occurred under an applied pressure of 200 MPa at 1050 °C for the 220 nm Al₂O₃ powder and 1400 °C for the 3 μm Al₂O₃ powder. The grain boundary energy, residual stress, and dislocation density of the ceramics sintered under high pressure and low temperature were higher than those of the samples sintered without additional pressure. Plastic deformation occurring at the contact area of the adjacent particles was proved to be the dominant mechanism for sintering under high pressure, and a mathematical model based on the plasticity mechanics and close packing of equal spheres was established. Based on the mathematical model, the predicted relative density of an Al₂O₃ compact can reach ～80 % via the plastic deformation mechanism, which fits well with experimental observations. The densification kinetics were investigated from the sintering parameters, i.e., the holding temperature, dwell time, and applied pressure. Diffusion, grain boundary sliding, and dislocation motion were assistant mechanisms in the final stage of sintering, as indicated by the stress exponent and the microstructural evolution. During the sintering of the 220 nm alumina at 1125 °C and 100 MPa, the deformation tends to increase defects and vacancies generation, both of which accelerate lattice diffusion and thus enhance grain growth.     

Induction plasma spheroidization of ZrB2-SiC powders for plasma-spray coating

To improve the microstructure and properties of ZrB₂-SiC (ZrB₂-30?vol%SiC, Z7S3) coatings, a facile synthesis route involving induction plasma spheroidization (IPS) has been proposed, and the morphologies, particle size distributions, and phase compositions of the feedstock powders were analysed by scanning electron microscopy and focused ion beam techniques. The obtained results showed that the surfaces of the produced powders contained eutectic-like and granular zones. Owing to the existence of a temperature gradient, the internal microstructure of the IPS-treated powder exhibited a three-layered structure consisting of a ′surface shell′, a ′transition layer′, and a ′porous core′. Additionally, the properties of the IPS-treated samples were compared with those of the spray-dried (SD) powders. The former exhibited good plastic deformation properties, and their single splats contained flattened structures, while the single splats of the SD powder melted only partially retaining some of their original characteristics.     

Sintering behavior of BaCe0.7Zr0.1Y0.2O3-δ electrolyte at 1150 °C with the utilization of CuO and Bi2O3 as sintering aids and its electrical performance

BaCe_0.7Zr_0.1Y_0.2O_3-δ (BCZY) is one of the promising electrolytic candidate for solid oxide fuel cell (SOFC) due to its good proton conductivity and better stability. Herein, the effect of dual sintering aids such as CuO-Bi₂O₃ upon the sinterability at low temperature, improved electrochemical properties, and thermo-chemical changes about proton-conducting BaCe_0.7Zr_0.1Y_0.2O_3-δ electrolyte were investigated in detail. FESEM micrographs and shrinkage curves revealed significant improvement in sinterability and densifications of BCZY electrolyte. The dense pellets were sintered with CuO-Bi₂O₃ (2–3 mol %) as sintering aids at a temperature of 1150 °C for 5 h. The perfectly uniform distribution of sintering aids increased the linear shrinkage of BCZY from 5% till 19–21%. The crystallite size and grain growth within the structure was enhanced due to the formation of the melting phase of Bi₂O₃ and Cu²⁺ incorporation in the perovskite structure. The elevated and improved electrochemical measurement for BCZY with 2 mol% of CuO-Bi₂O₃ as sintering aid categorized it well suited for solid oxide fuel cells.