利用主烧结曲线预测TiO2陶瓷无压烧结显微组织演变

纳米金红石TiO2粉末在高温热膨胀仪中进行恒速无压烧结,升温速率为2℃/min和5℃/min,热膨胀仪自动记录烧结收缩量,根据全期烧结模型,建立TiO2主烧结曲线;利用阿基米德法测量烧结体的相对密度,利用扫描电镜观察烧结体在不同温度的显微组织演变.结果表明:利用主烧结曲线得到的相对密度和Archimedes法实测的密度吻合,证明了主烧结曲线对烧结路径不敏感,烧结体的相对密度仅是时间和温度的函数.烧结体的显微组织是烧结温度和时间的函数,烧结体的相对密度和显微组织有关联,主烧结曲线理论可以用来预测和控制烧结体的相对密度、显微组织和陶瓷性能.     

比表面积对TiO2陶瓷烧结初期致密化行为的影响

将比表面积分别为30 m2/g和1 m2/g的纳米(50 nln)和微米(2 μm)金红石TiO2陶瓷坯体在高温热膨胀仪中自室温至1200℃进行恒速无压烧结,升温速率为1℃/min,3℃/min和5℃/min,热膨胀仪自动记录烧结收缩.为阐明比表面对无压烧结初期致密化行为的影响,研究了氧化钛陶瓷的烧结收缩行为.同时,利用Arrhenius曲线研究了纳米和微米氧化钛陶瓷的烧结激活能.结果表明:随烧结温度的增加,比表面积的增加加速了致密化速率;纳米和微米氧化钛的烧结激活能分别为115±10 kJ/mol和302±15 kJ/mol;对于纳米氧化钛,当烧结体的瞬时相对密度为70～80%时,出现最大致密化速率,而对于微米氧化钛陶瓷,最大致密化速率出现在相对密度为75～85%.     

微米级α-Al2O3陶瓷恒速无压主烧结曲线的建立

主烧结曲线对于预测陶瓷的烧结行为非常有用,以主烧结曲线理论为基础,对微米级α-Al2O3,的恒速无压烧结行为进行了研究.根据Hansen提出的全期烧结模型,结合低升温速率条件下热膨胀仪记录的烧结数据建立了α-Al2O3(平均粒径为2.5μm)的主烧结曲线,并由此得到其烧结过程中的表观激活能为1148kJ/mol.为验证所建主烧结曲线的正确性,对同批次坯体样品进行不同路径的烧结,用Archimedes法实测烧结体密度,所测结果与主烧结曲线预测的结果相一致,从而证明了所建主烧结曲线的正确性.因此微米级α-Al2O3主烧结曲线对烧结路径不敏感,烧结体的相对密度仅是时间和温度的函数,可以预测烧结收缩率和最终相对密度,反之,可以根据目标相对密度制定相应的烧结制度.     

TiO2对烧成镁钙砖烧结性能的影响

研究了两种晶型的TiO2(锐钛矿型和金红石型)作为添加剂对烧成镁钙砖烧结性的影响.结果表明,两种晶型的TiO2都能显著促进镁钙砖的烧结,其中以锐钛矿晶型为添加剂的效果好于金红石型的.XRD分析结果表明,TiO2与CaO反应生成了CaTiO3,这是加入TiO2使镁钙砖烧结性变好的主要原因.     

CMS和纳米TiO2对氧化铝陶瓷烧结的影响

选用CaO-MgO-SiO2(CMS)和纳米TiO2两种添加剂及其复合来降低氧化铝陶瓷的烧结温度、改善其烧结性能.讨论了烧结助剂配比和掺量、烧结温度对氧化铝陶瓷的相对密度、抗弯强度的影响,利用扫描电子显微镜观察了氧化铝陶瓷的显微结构.研究结果发现:CMS/TiO2质量比为1/1,(CMS+TiO2)质量分数为6%,烧结温度为1450 ℃时,氧化铝陶瓷相对密度为93.07 %,晶粒细小均匀、排列紧密、平均粒径3 μm,抗弯强度达到362.87 MPa.     

低温烧结氧化铝陶瓷的动力学研究

用CaO-MgO-SiO2玻璃(CMS-G)和TiO2为烧结助剂,在1450℃下实现了氧化铝陶瓷的致密烧结.探讨了CMS-G和TiO2质量百分含量对氧化铝陶瓷烧结性能、显微结构以及其烧结动力学的影响.结果表明:CMS-G和TiO2可有效促进氧化铝陶瓷的致密化,当CMS-G含量为3%、TiO2含量为1%时,氧化铝陶瓷的相对密度达到98.25%;液相烧结激活能为113.4kJ/mol,表明扩散控制了烧结过程.     

Al2TiO5添加量对MgO-Al2TiO5复合陶瓷烧结及抗热震性的影响

以纳米MgO粉为原料,选用以纳米Al2O3粉和纳米TiO2粉经1500℃保温3 h烧结制备的Al2TiO5为添加剂,采用固相烧结法经1500℃保温3 h制备了Al2TiO5质量分数分别为0、5%、10%和20%的MgO-Al2TiO5复合陶瓷,并采用XRD、SEM和EDS等研究了Al2TiO5添加量对MgO-Al2TiO5复合陶瓷烧结性能及抗热震性能的影响。结果表明:添加Al2TiO5有利于促进复合陶瓷的烧结,其体积密度和线收缩率随Al2TiO5添加量的增加而增大,当Al2TiO5添加量为20%(w)时,其体积密度和线收缩率分别为3.68 g·cm-3和22.07%;当Al2TiO5添加量为10%(w)时,其抗热震性能最佳。Al2TiO5位于方镁石晶粒交界处,抑制方镁石晶粒生长,阻碍裂纹扩展,使MgO-Al2TiO5复合陶瓷的抗热震性能得到改善。     

液相烧结氧化铝陶瓷及其烧结动力学分析

研究了CuO TiO2复相添加剂对Al2O3陶瓷烧结性能、显微结构的影响以及添加剂形成液相时Al2O3陶瓷的烧结动力学.结果显示:添加剂的加入明显地促进了Al2O3陶瓷的烧结致密度.添加剂含量对致密有明显影响,含量越高,烧结速率越快.当添加剂(CuO TiO2)为2%(质量分数),CuO/TiO2质量比为1/2时,Al2O3样品致密度最高.添加剂的存在使Al2O3晶粒发生较快生长,晶粒形貌为等轴状.通过等温烧结动力学,确定掺杂Al2O3陶瓷烧结激活能为25.2kJ/mol,表明可能是氧离子和铝离子在液相中的扩散作用控制了烧结过程.     

气氛对氧化铬材料烧结的影响

以Cr2O3微粉为主要原料,TiO2微粉为烧结助剂,聚乙烯醇为结合剂,经制浆、喷雾造粒、机压和等静压二次成型后,分别在空气(氧分压为2.1×104Pa)、工业氮气(氧分压为1×103Pa)、纯氮气(氧分压为10 Pa)和高纯氮气(氧分压为0.1 Pa)中以及埋炭(氧分压为2.3×10-12Pa)条件下,于1 500℃保温3 h烧成制备了氧化铬试样,研究了烧成气氛的氧分压对氧化铬材料烧结的影响。结果表明:氧分压在0.1～2.1×104Pa之间,氧分压对添加有3%(w)烧结助剂TiO2的氧化铬材料烧结影响显著,随着氧分压的降低,试样的体积密度增加,显气孔率下降;但未添加烧结助剂TiO2时,即使在0.1 Pa这一较低氧分压下,氧化铬材料也未能实现致密化烧结;而在埋炭造成的极低氧分压下,无论是否添加烧结助剂TiO2,均能使氧化铬材料烧结致密。     

纳米TiO2添加剂对Al2O3陶瓷微观结构与烧结性能的影响

用微米级和纳米级两种不同的TiO2作为烧结助剂,研究其对Al2O3陶瓷微观结构和烧结性能的影响.结果表明:纳米TiO2能更好的提高Al2O3陶瓷的烧结活性,降低烧结温度.当TiO2含量为2%时,在1 580℃烧结试样的显气孔率为0.54%;在1 650℃烧结试样的显气孔率为0.16%.纳米TiO2的加入改变了Al2O3陶瓷的微观结构,更有利于Al2O3陶瓷的烧结.     

Construction and validation of master sintering curve for TiO2 for pressureless sintering

Abstract

One of the ultimate objectives for sintering research is to predict densification results under different thermal profiles for a given processing method. This paper studies the construction and validation of the master sintering curve (MSC) for rutile TiO₂ for pressureless sintering. The MSC was constructed using dilatometry data at two heating rates and was then validated using isothermal holds at three different temperatures. The scanning electron microscopy (SEM) observation shows that the partially sintered samples have the same density under different heating procedures, which demonstrates that the assumptions of the model are reliable. The concept of the MSC could be used to predict the sintering shrinkage and final density and calculate the activation energy. A value of 105 kJ mol^-1 for TiO₂ was obtained. The MSC could be applied to predict the sintering profile to prepare ceramics with required density and a minimum of grain growth.     

氧化锆层状复合陶瓷成型和烧结特性

由不同成型方法,单面或双面加压,制备了氧化锆层状复合陶瓷,研究了制备方法和工艺参数,如：加压压力、时间,对生坯密度的影响.探讨了生坯密度与烧结收缩之间的相关性.研究结果表明：选取成型压力在250 MPa左右,双向加压方式,可以获得沿x,y,z轴方向收缩较一致的层状陶瓷制品.引入评价不同方向的烧结收缩变化参数k（=a/b,a和b分别为沿x,y和z方向的烧结收缩率）,kxy,kz,当kxy=kz=1时,表示烧结过程基本完成,坯体中颗粒已达到致密化状态;当kxy-1/kz^2=0或接近于0时,表示沿x,y轴和z轴方向的烧结收缩基本无差别,是一种最佳的层状陶瓷烧结状态.     

Prediction and control of microstructure evolution for sub-microscale α-Al2O3 during low-heating-rate sintering based on the master sintering curve theory

The master sintering curve (MSC) can sometimes be used for analyzing the shrinkage behaviour of ceramics. Densification of α-Al₂O₃ with the mean particle size of 350 nm was continuously recorded during heating at 0.5, 2 and 5 °C/min. A MSC was successfully constructed using dilatometry data with the help of combined-stage sintering model. The validity of the MSC has been verified by a few experimental runs. The microstructural evolution with densification during different heating-rate sintering was explored. The sintered microstructure is a function of the time–temperature sintering conditions, and it is verified that there exists a link between sintered density and microstructure. The MSC can be used to predict and control microstructure evolution during sintering of α-Al₂O₃ ceramics.     

合成和烧结工艺对PZT95/5陶瓷致密化影响的研究

以Pb3O4、ZrO2和TiO2为原料，Nb2O5为掺杂剂，利用固相法制备钙钛矿型PZT95／5陶瓷。采用正交实验优化合成和烧结工艺．综合分析了合成温度、合成时间、烧结温度、烧结保温时间、升温速率和烧结气氛对陶瓷体致密化影响的规律性变化。结果表明：其中合成温度和烧结温度是影响陶瓷致密化的重要因素。     

Analysis of Nanocrystalline and Microcrystalline ZnO Sintering Using Master Sintering Curves

Master sintering curves were constructed for dry-pressed compacts composed of either a nanocrystalline or a microcrystalline ZnO powder using constant heating rate dilatometry data and an experimentally determined apparent activation energy for densification of 268±25 and 296±21 kJ/mol, respectively. The calculated activation energies for densification are consistent with one another, and with values reported in the literature for ZnO densification by grain boundary diffusion. Grain boundary diffusion appears to be the single dominant mechanism controlling intermediate-stage densification in both the nanocrystalline and the microcrystalline ZnO during sintering from 65% to 90% of the theoretical density (TD). Based on both the consistency of the calculated activation energy as a function of density and the narrow dispersion of the sintering data about the master sintering curve (MSC) for the nanocrystalline ZnO, there is no evidence of either significantly enhanced surface diffusion or grain growth during sintering relative to the microcrystalline ZnO. The MSC constructed for the nanocrystalline ZnO was used to design time–temperature profiles to successfully achieve four different target sintered densities on the MSC, demonstrating the applicability of the MSC theory to nanocrystalline ceramic sintering. The most significant difference in sintering behavior between the two ZnO powders is the enhanced densification in the nanocrystalline ZnO powder at shorter times and lower temperatures. This difference is attributed to a scaling (i.e., particle size) effect.     

An oscillatory pressure sintering of zirconia powder: Rapid densification with limited grain growth

A novel oscillatory pressure sintering (OPS) process is reported to prepare high‐quality ceramics. The oscillatory pressure was applied at three stages (initial, intermediate, and final) during sintering process of zirconia ceramics for the first time. The microstructure of the samples prepared by OPS develops in a more homogeneous manner, leading to a higher final density, a smaller average grain size, and a narrower distribution of grain sizes compared with the samples prepared by conventional pressureless sintering (PS) and hot‐pressing (HP) processes. Remarkably, the OPS samples was obtained at relatively lower heating temperature and less soaking time for 1300°C and 0.5 hours than the samples prepared by other two techniques at 1450°C and 1 hour. The current results suggest that OPS is an effective technique for preparing high‐quality zirconia ceramics with low heating temperature and short sintering time, thus, it obviously reduces cost.     

高压烧结高纯微晶氧化铝陶瓷

以商业生产的高纯纳米α-Al2O3粉(99.9%,质量分数)、分析纯Mg(NO3)2为原料,以两面顶压机高压烧结,制备了纯Al2O3陶瓷及微量MgO掺杂的Al2O3陶瓷,并进行了密度测试与显微结构分析.与常压烧结相比,高压烧结可显著降低高纯Al2O3陶瓷的烧结温度,提高传质速率,大幅度缩短烧结时间,达到快速、低温烧结的效果.与常压烧结明显不同,在高压烧结时,MgO对高纯AlO3陶瓷的烧结致密化几乎没有影响.在4.5GPa,100 ℃高压烧结30 min,制备的纯Al2O3陶瓷的相对密度为97.65%,微量MgO掺杂的Al2O3陶瓷的相对密度达97.93%、平均晶粒尺寸约为4 μm.     

选择性激光烧结用复合尼龙粉的制备与性能

采用溶剂沉析法制备了低熔点复合尼龙12基料,对其改性处理后获得适合于选择性激光烧结用的复合尼龙粉末。通过正交实验的方法对复合尼龙粉末的烧结工艺进行研究,得到优化的烧结工艺参数,探讨了烧结工艺参数对成型件烧结成型性能的影响,对复合尼龙粉及其烧结成型件进行了SEM分析,发现尼龙12烧结件的烧结精度和力学性能都得到了很大的改善。