氧化物陶瓷闪烧机理及其应用研究进展

闪烧是近些年广受关注的一种电场辅助烧结技术。本文介绍了闪烧的起源与发展, 并对闪烧的基本特征进行了分析。在闪烧孕育与引发过程的研究方面, 发现了孕育阶段的非线性电导特征和电化学黑化现象, 提出了氧空位主导的缺陷机制; 在闪烧阶段的快速致密化研究方面, 提出了电场作用导致的缺陷产生和运动会在粉体颗粒间产生库仑力, 有利于烧结前期的致密化过程, 同时发现闪烧致密化过程中还伴随着金属阳离子的快速运动; 在闪烧阶段的晶粒生长和微结构演变方面, 发现了试样温度沿电流方向呈非对称分布, 试样中间位置的晶界迁移率明显提高, 提出电化学缺陷对微观结构有重大影响。基于上述研究成果, 本团队利用电场作用下出现的低温快速传质现象, 发展了陶瓷闪焊技术, 实现了同种陶瓷/陶瓷、陶瓷/金属, 甚至异种陶瓷/陶瓷之间的快速连接; 发展了陶瓷闪烧合成技术, 不仅实现了典型氧化物陶瓷的快速合成, 而且实现了高熵陶瓷和具有共晶形貌的氧化物陶瓷的快速合成; 发展了氧化物陶瓷的电塑性成形技术, 初步实现了氧化锆陶瓷低温低应力下的快速拉伸和弯曲变形。本文最后总结了闪烧机理研究面临的挑战, 并从焦耳热效应和非焦耳热效应两方面展望了闪烧的发展方向, 期望对闪烧技术在国内的发展有所裨益。     

空气中无压烧结Al2O3/SiC陶瓷的微观结构及性能

研究了Al2O3/SiC陶瓷在空气中的烧结行为,实现了该体系在空气中的致密化烧结,1600℃添加10%(体积分数,下同)SiC的试样致密度达到97.6%,维氏硬度达到14.45GPa.探讨了烧结温度与SiC含量对Al2O3/SiC陶瓷微观结构和致密度、硬度等性能的影响,高温下烧结可得到较致密的陶瓷,但SiC含量超过30%的试样会产生"夹心"现象.探索了粉末埋烧对陶瓷致密度的影响,表明埋烧的方法可以降低低SiC含量试样的气孔率,起到抑制氧化的作用.     

AlN陶瓷的高压烧结研究

以自蔓延高温合成的AlN粉体为原料,用六面顶压机在高压(3.1～5.0GPa)下实现了未添加烧结助剂的AlN陶瓷体的烧结.研究了烧结工艺参数对AlN烧结性能的影响.用XRD、SEM对AlN高压烧结体进行了表征.研究表明:高压烧结能够有效降低AlN陶瓷的烧结温度并缩短烧结时间,烧结体的结构致密.在5.0GPa/1300℃条件下高压烧结50min的AlN陶瓷的相对密度达94.9%.在5.0GPa/1700℃/125min条件下制备的AlN陶瓷晶格常数比其粉体减小了约0.09%.     

Zn_2SnO_4掺杂对SrTiO_3陶瓷烧结温度和储能性能的影响

采用固相反应法制备了SrTiO_3+xmol%Zn_2SnO_4(x=1,2,5,10)陶瓷,研究了Zn_2SnO_4掺杂对SrTiO_3陶瓷烧结温度和储能性能的影响。结果表明,Zn_2SnO_4掺杂可将SrTiO_3陶瓷的最佳烧结温度从1 400℃降低至1 200℃。随着掺杂量的增加,SrTiO_3陶瓷的室温介电常数逐渐减小,击穿电场和储能密度呈现先增大而后减小的趋势。当Zn_2SnO_4掺杂量为2 mol%时,样品具有最大的击穿电场250 kV/cm和最高的储能密度1.06 J/cm~3。相较于未经掺杂的SrTiO_3陶瓷,储能密度提高了1.8倍。深入研究表明,由于烧结温度降低,SrTiO_3陶瓷的平均晶粒尺寸从5.5μm降低至0.8μm左右,从而增加了晶界的相对含量,提高了材料的绝缘性能,进而增强了SrTiO_3陶瓷的击穿电场,最终导致了SrTiO_3陶瓷储能密度的提高。     

模拟核芯FCM燃料的振荡烧结行为研究

全陶瓷微封装弥散(FCM)燃料以其较好的固有安全性而成为核能领域研究的重点。针对SiC基体难以烧结的问题,本研究利用振荡烧结具有加速传质和降低烧结温度的优势,开展了模拟核芯FCM燃料振荡烧结行为研究,重点考察了振荡烧结温度、振荡时间与振荡压力等参数对基体致密化行为的影响,并与热压烧结结果进行了对比。结果表明,振荡烧结温度、保温时间以及中值压力对基体致密化有重要影响,而振荡压力的振幅对基体致密化影响不大。相比于热压烧结,振荡烧结可以提高材料的致密度,振荡烧结试样的致密度更高, 1850℃振荡烧结试样的致密度为99.99%;振荡烧结试样的晶粒尺寸更小,1850℃振荡烧结试样的晶粒尺寸为(284±4)nm,比同等温度下热压烧结试样的晶粒尺寸减小～27%;振荡烧结试样的硬度更高, 1850℃振荡烧结试样的硬度为(26.7±0.4) GPa。借助改进的热压烧结本构方程,计算得到试样在致密度为90%时的应力指数n=1,活化能Q=430 kJ/mol,致密化的主导机制为晶界扩散协调的晶界滑移。     

空心阴极等离子烧结AlN陶瓷

将空心阴极效应运用于AlN陶瓷的烧结,选用自蔓延高温合成的AlN粉体为原料,用Y2O3-CaO-Li2O作为烧结助剂,制备出了致密度高,导热性能好的AlN陶瓷.在添加5.5wt％的Y2O3-CaO-Li2O(Y2O3:Li2O:CaO=44:6:5wt％)作为烧结助剂,在1700℃,保温3h的烧结条件下,获得相对密度为98.89％,热导率为93.8 W/(m·K)AlN烧结体.烧结体的断口SEM照片显示烧结试样的晶粒生长发育完善,晶粒轮廓清晰呈尖锐的多面体形状,晶粒大小均匀,气孔和晶界相少,断裂模式为穿晶断裂.TEM表明:晶界相少,且大部分都缩至三角晶界,AlN颗粒与颗粒接触紧密.     

ZrB2颗粒增韧B4C陶瓷的原位合成

采用机械混合法无压烧结原位合成ZrB2/B4C陶瓷复合材料,研究了ZrB2含量对复相陶瓷主要性能的影响,分析了复相陶瓷的增韧机理.结果表明,当ZrB2的体积分数为16%时,相对密度最大约为94%,维氏硬度为39.5 GPa,抗折强度为320 MPa,断裂韧性为3.10 MPa·m1/2.由B4C基体和ZrB2颗粒热膨胀系数不匹配引起的裂纹偏转是ZrB2/B4C复相陶瓷增韧的主要原因.     

利用电瓷废料原位合成莫来石陶瓷

为探讨能否用纯电瓷废料合成莫来石陶瓷,本文对比了以电瓷废料细粉为原料,再添加部分Al_2O_3细粉和以纯电瓷废料细粉为原料合成莫来石陶瓷。探讨了原料配比和烧结温度对合成的莫来石陶瓷的结构和性能的影响。采用X射线衍射(XRD)、扫描电镜(SEM)分别研究了莫来石的物相组成与显微结构。研究表明:随着烧成温度升高,莫来石的含量增加,体积密度增大;由于原料采用电瓷废料细粉,烧结活性较大,有利于烧结的进行,并提高烧结密度;采用纯电瓷废料合成的莫来石陶瓷的体积密度和耐压强度最高,气孔率最小,综合性能最优。     

微波和常规烧结制备纳米Al_2O_3/3Y-TZP陶瓷

采用共沉淀法制备Al2O3/3Y-TZP纳米粉体,粉体压制后通过微波和常规烧结制备Al2O3/3Y-TZP陶瓷,并研究两种烧结方法对Al2O3/3Y-TZP陶瓷相对密度、抗弯强度、断裂韧性和断口形貌等的影响。结果表明,共沉淀法制得的Al2O3/3Y-TZP纳米粉体晶粒细小、均匀,近似球形,尺寸为40~60nm;随烧结温度的升高,两种烧结方法制备的陶瓷试样相对密度、抗弯强度和断裂韧性均先升高后降低;与常规烧结相比,Al2O3/3Y-TZP陶瓷的微波烧结温度明显降低,时间显著缩短,且晶粒更细小,相对密度、抗弯强度和断裂韧性显著提高。     

SiC含量对机械合金化-热压制备B4C-SiC复合陶瓷的影响

以B₄C、SiC粗粉为原料, 采用机械合金化辅助热压烧结工艺, 在不添加任何助烧剂的情况下于1950℃制备出致密的B₄C-SiC复合陶瓷。通过对烧结样品进行相对密度、维氏硬度、抗弯强度和断裂韧性测试, 研究SiC含量对复合陶瓷力学性能的影响; 结合XRD、SEM和TEM对样品进行组分和微观结构分析, 研究其微观结构与力学性能之间的关系。结果表明: 复合陶瓷的相对密度和断裂韧性随SiC含量的增加而增大, 当SiC含量为50wt%时获得最大值为96.1%和4.6 MPa•m^1/2; 复合陶瓷的硬度和抗弯强度随SiC含量的增加呈先增大后减小的趋势, 在SiC含量为20wt%时获得最大值25.5 GPa和480 MPa。SiC相均匀分布在B₄C基体中使得复合陶瓷具有较高的强度; B₄C与SiC之间好的界面相容性以及SiC的高断裂韧性是该B₄C基复合陶瓷韧性得到显著提高的原因。     

Temperature gradient and microstructure evolution in AC flash sintering of 3 mol% yttria-stabilized zirconia

Systematic statistical analysis of the microstructural changes in 3?mol% yttria-stabilized zirconia was performed after flash sintering by alternating current (AC). The micrographs in the gauge section of the specimen were identical to those from DC flash sintered samples while no evident electrode effect was present for AC flash sintered samples. However, finite element modeling revealed a temperature gradient from the surface to the volume of the sintered body. Microstructure gradients, across the width of gauge section, were revealed for the AC flash sintered sample. Classical grain growth models due to Joule heating were insufficient in justifying the microstructural evolution under the simulated temperature distribution. Bimodal grain diameter distributions in flash sintered samples were observed. Therefore, it is proposed that faster grain growth mechanisms activated on a fraction of the grains by electric field/current occurred during flash sintering, and is responsible for the instantaneous grain growth.     

Fabrication of hydrothermal ageing resistant of 3 mol % yttria-stabilised tetragonal zirconia polycrystalline via microwave sintering

The influence of microwave sintering on the densification, mechanical performances, microstructure evolution and hydrothermal ageing behaviour of pure 3 mol % yttria-stabilised tetragonal zirconia polycrystalline (3Y-TZP) ceramics was compared with conventional sintered samples. Green bodies were sintered via conventional pressure-less and microwave sintering method between 1200 °C to 1400 °C with dwelling time and firing rate at 120 min, 10 °C/min and 1 min, 20 °C/min. Result showed that reduced processing temperature and holding time is possible with microwave sintering technique for fabricating good resistant zirconia sample with bulk density, Young's modulus, and Vicker's hardness that are comparable to samples sintered with conventional method. However, the microwave sintered samples suffered from hydrothermal ageing where their average grain size is above critical size. The enhancement of hydrothermal ageing resistance of the sintered samples is associated with the decreasing grain size of the sintered samples instead of sintering method.     

Effects of sintering conditions on the microstructure and mechanical properties of SiC prepared using powders recovered from kerf loss sludge

The effects of sintering conditions on the microstructure and mechanical properties of the sintered SiC prepared using the SiC powder recovered from the kerf loss sludge were investigated. The recovered SiC powders were consolidated by spark plasma sintering (SPS) and conventional sintering methods. The effects of sintering temperature, time and methods (SPS and conventional sintering) on the phase, grain size and density of SiC were systematically studied. The Vickers hardness of spark plasma-sintered (SPSed) samples was higher than that of conventional sintered samples due to small grain size. When holding time was increased from 10 to 30 min, the grain size and relative density of SPSed samples were also increased, which lead to the almost constant Vickers hardness by competing effects of grain size and relative density. When holding time was over 30 min, no appreciable change of the relative density and grain size were observed, which can lead to similar values of Vickers hardness. SPS process can be used to make SiC with high density and hardness at relatively low temperature compared with the conventional sintering process.     

Effect of laser irradiation on superconducting properties of bulk MgB<Subscript>2</Subscript> sintered at different temperatures

The surfaces of MgB₂ bulk samples produced by a pellet/closed tube method at two different sintering temperatures of 650 and 850?°C, after hot pressing at 200?°C, were irradiated with the same irradiation dose by using an Nd:YVO₄ laser in order to study the possible potentiality of laser irradiation to improve pinning performances and critical current density of MgB₂ superconductor. The measurements showed that the magnetic field dependence of the critical current density values of irradiated sample sintered at 650?°C slightly increased with a narrowing in superconducting transition region as compared to the reference sample sintered at same temperature. However, irradiated sample sintered at 850?°C showed a decrease in pinning performance and similar critical temperature values as compared to the corresponding reference sample. From these results it can be said that the same laser irradiation dose affects superconducting properties of bulk MgB₂ in different ways depending on sintering temperature of the superconductor.     

Li2O烧结助剂对固体氧化物燃料电池LSGM电解质烧结特性及离子电导率的影响

本工作研究了Li₂O作为烧结助剂对固体氧化物燃料电池La_0.8Sr_0.2Ga_0.8Mg_0.2O_3-δ (LSGM)电解质烧结行为的影响规律, 系统表征了烧结助剂含量和烧结温度对LSGM烧结体的致密度、微观组织结构、相组成以及离子电导率的影响。研究结果表明, Li₂O烧结助剂不仅可显著降低LSGM电解质的完全致密化烧结温度, 还可以消除电解质粉体中原有的LaSrGa₃O₇杂相, 并且抑制常规烧结过程中易于产生的MgO杂相, 从而获得较高离子电导率的LSGM块体。当Li元素添加量为摩尔分数1%时, 在1400 ℃烧结4 h 获得的LSGM烧结体, 其体密度达到理论密度的99% 且为单一的钙钛矿结构。烧结体的离子电导率在800 ℃测试温度下达到最大值0.17 S/cm, 相比未添加烧结助剂的试样提升20%以上。上述结果表明, 通过添加适量的Li₂O作为烧结助剂对制备用于中温固体氧化物燃料电池(IT-SOFCs)高离子电导率的电解质具有重要意义。     

无铅压电陶瓷KNN常压烧结及其电学性能

用常压烧结法制备K_0.5Na_0.5NbO₃陶瓷。研究烧结温度与陶瓷密度和电学性能的关系。研究表明在1065℃~1120℃范围内, 温度对陶瓷的密度有显著影响。当烧结温度为1100℃时, 密度达到4.35 g/cm³ (占理论密度的95%); 1100℃烧结的陶瓷表现出最好的电学性能, 压电常数最大118 pC/N, 相对介电常数最大达538, 介电损耗最小仅4.7%, 剩余极化强度为15.37 μC/cm², 矫顽场为13.16 kV/cm。陶瓷样品在206℃从正交结构转变到四方结构, 居里温度为410℃。     

Studies on sintering behaviour of Al2O3–ZrO2 oxide composites processed by extended arc thermal plasma and conventional heating

Al₂O₃–ZrO₂ composites were sintered using low cost extended arc thermal plasma reactor and conventional heating. Composites prepared in a wide range of composition were studied in terms of their density, shrinkage, hardness, structure, microstructure and dielectric response. Experimental parameter such as sintering time, sintering temperature and plasma power were optimized to achieve higher sintered end product. Highly dense sintered products were obtained by plasma heating route within short sintering time compared with conventional sintered method. Interesting development pertaining to structure and phase evolution, structure and dielectric response are analyzed. It is found that compositional variation in this composite produces structural phase separation at different sintering conditions, which is more in plasma heating product than conventional heated product. Plasma sintered product always shows less dielectric constant as compared to conventional sintered sample.     

Cu-Al梯度功能材料性能研究

为解决大电流设备铜铝线接头电冲击、烧毁等问题,运用粉末叠层的方法制备了Cu-Al梯度功能材料试样。研究发现620℃烧结的7层试样具有较高的平均硬度和较低的电阻率,可用作铜铝导线的接头;试样的铜铝混合区烧结后有θ(CuAl2)生成,显著提高了局部区域的硬度;540℃烧结的试样电阻率最小;提高烧结温度,出现液相烧结,烧结进行更充分,θ(CuAl2)增加,平均硬度提高,电阻率也随之增加。     

不同烧结工艺对K0.5Na0.5NbO3陶瓷微结构的影响

采用普通烧结方法和热压烧结方法制备了K0.5Na0.5NbO3(KNN)无铅压电陶瓷.着重研究了两种烧结工艺对陶瓷的微观结构、晶粒形貌及致密度的影响.研究结果表明,两种烧结方法制备的陶瓷样品都具有单一的正交钙钛矿结构,与普通烧结工艺相比,利用热压烧结工艺制备的样品呈现较高的相对密度(大于98%)、较小的晶粒尺寸(0.6μm左右)及较低的介电损耗(1 kHz,tanδ≤2.8%).实验中发现对于热压烧结的样品,通过改变后期退火温度,样品的晶粒尺寸,致密度可以有规律地变化.