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。     

纳米氧化钛陶瓷的烧结

将醇盐水解制备的纳米氧化钛粉体（～13nm）在500～800℃下煅烧,用XRD研究氧化钛相变过程中粉体的热稳定性,发现在加入0．4wt％的金红石相作为晶种后;晶粒生长受到较好的控制,同时分别在30、57和200MPa下对纳米氧化钛样品进行热压烧结,用密度仪、压汞仪和SEM对烧结前后的样品进行表征后表明,700℃的热压烧结样品已开始致密化,200MPa、800℃热压烧结样品的相对密度为97．2％,此时3～15nm的小气孔仍难以消除,这些小气孔的存在是纳米氧化钛陶瓷在较高的压力下难以完全致密的主要原因．     

溶胶-凝胶法制备CaCu_3Ti_4O_(12)粉体及其电性能

利用溶胶-凝胶法制备CaCu3Ti4O12粉体,采用差热分析、X射线衍射、扫描电子显微镜等技术进行表征,并探讨CaCu3Ti4O12粉体的烧结特性及电性能。结果表明,干凝胶经750℃低温煅烧可获得粒径分布较窄、平均粒径为80～100 nm的CaCu3Ti4O12粉体。CaCu3Ti4O12陶瓷在1 000℃时实现致密烧结,比固相反应法制备的粉体烧结温度降低100～200℃,具有较宽的烧结温区。溶胶-凝胶法制备的陶瓷经1 050℃烧结2 h,获得优良的电性能,相对介电常数为20 190,介电损耗为0.022,非线性系数为4.530。     

燃烧法合成铪酸钇粉体及其透明陶瓷的制备

以硝酸钇(Y(NO₃)₃)和氯化铪(HfCl₄)为原料, 乙二胺四乙酸(EDTA)作为燃剂, 采用燃烧法制备了粒径为50nm左右的纯相铪酸钇粉体. 粉体经1200℃煅烧后高能球磨15h, 然后在200MPa条件下进行冷等静压成型, 素坯尺寸为20mm×2.5mm, 最后采用真空烧结(1850℃保温6h), 制备出可见光波段直线透过率为50%的铪酸钇透明陶瓷. 研究了真空烧结温度对样品透过率和显微结构的影响, 当烧结温度高于1850℃时, 温度对于透过率影响不是很明显; 随着烧结温度的升高, 样品的晶粒尺寸增大.     

SPS烧结制备TiB2/TiC复合材料

采用金属钛粉和碳化硼为初始粉料,利用SPS放电等离子烧结技术制备了致密的纳米结构TiB2/TiC复合材料.并借助XRD、SEM考察了复合材料的相组成和显微结构,利用压痕法和小样品力学性能测试方法(MSP)测定了室温显微硬度、断裂韧性和MSP强度.研究结果表明:利用一步法直接升温至1550℃并保温6 min制备的复合材料,其晶粒尺寸大于1μm,MSP强度为833 MPa.而采用两步法升温至1550℃,然后迅速降低保温温度至1450℃,并保温6 min条件下使金属钛粉和碳化硼同步完成反应、烧结、致密化,生成晶粒细小的TiB2/TiC复合材料,晶粒尺寸大约为200 nm,并且所制备的复合材料力学性能更好,MSP强度达到1095 MPa.     

低温制备高致密度细晶W-10％TiC复合材料

采用高能球磨结合真空热压的手段制备了W-10％（质量分数）TiC复合材料。采用扫描电镜、透射电镜和x射线衍射等对复合粉体及复合材料进行表征。结果表明，通过高能球磨得到了粒径均匀，平均粒径约为100nm的纳米复合粉体，粉体经过1700℃真空热压烧结后致密度达到99．1％，并且保持细晶结构（平均晶粒尺寸为0．8gm）。热压和高能球磨导致的机械活化以及引入的Fe、Ni等杂质是复合材料低温烧结达到高致密度的重要原因。     

固相反应法合成碳化硼纳米粉体

以六方氮化硼和炭黑(或石墨)为原料, 采用固相反应法合成了碳化硼粉体. 碳源、反应气氛和温度对粉体合成产生重要影响. 以炭黑为碳源, 在1900℃真空下保温5 h, 得到了平均粒径约为100 nm的碳化硼纳米粉体. 与商业粉体相比, 合成的粉体具有较好的烧结活性. 在2000℃/30 MPa/1 h条件下烧结, 样品的相对密度达到97.9%(商业粉体样品为93.1%), 这可归结于合成的粉体具有细小的粒径、低的氧含量和一定程度的孪晶结构.     

AlN粉末特性对AlN-BN复合陶瓷致密化的影响

以比表面积分别为4.26和17.4 m2/g两种AlN粉末为原料,添加5%Y2O3作为烧结助剂制备AlN-15BN陶瓷(质量分数,%),研究了AlN粉末特性对复合陶瓷致密化过程的影响。结果表明,AlN粉末比表面积对复合陶瓷致密化有重要影响,比表面积高的AlN粉末所制备的复合陶瓷致密化过程主要发生在1500~1650℃,1650℃烧结3 h后,复合材料的相对密度达95.6%,继续升高温度,对材料的密度影响不大;而低比表面积的AlN粉末所制备的复合陶瓷的致密化过程主要发生在1650~1850℃,1850℃烧结3 h,复合陶瓷的相对密度为86.4%。即高比表面积的AlN粉末有利于获得相对密度高的AlN-BN复合材料。     

氧化锆纳米粉体烧结性能研究

为了研究纳米氧化锆粉体的烧结性能,以4种不同粒度的氧化锆粉体为原料,在热分析仪上测试了室温～1000℃范围内坯体的形变量和热膨胀性能.采用1450℃恒温1～6 h的烧结工艺,制备了氧化锆陶瓷,并进行了性能表征.结果表明:粉料1次粒子粒径越小,其初始烧结温度越低;粉料的团聚粒径越小,分布越窄,坯体的烧结致密化越容易.     

聚合物前驱体法制备(Ce,Cu)-SnO2纳米粉体及其烧结行为

采用聚合物前驱体法制备了CeO2-CuO-doped SnO2纳米粉体,并研究了掺杂SnO2纳米粉体的无压烧结行为.结果表明乙二醇、柠檬酸与金属离子的摩尔比为631时制得的掺杂SnO2粉体为分散良好的球形颗粒,大小为～15nm,粒度分布范围窄;CuO掺杂可显著提高SnO2的烧结性能,CeO2-CuO复合掺杂可进一步降低SnO2陶瓷的致密化温度;1.0%CeO2-1.5%CuO-doped SnO2可在1050℃烧结致密,相对密度达96%以上;两步法(先升温到1050℃保温15min,然后降到980℃烧结5h)烧结的1.0%CeO2-1.5%CuO-doped SnO2陶瓷相对密度为96.1%,其晶粒＜800nm.     

Constitutive modeling of alumina sintering: grain-size effect on dominant densification mechanism

In the present work, alumina powders with the initial grain sizes of 0.9 and 7.0 μm, respectively, were sintered at different temperatures. Constitutive laws for densification were employed to model the sintering process of alumina ceramics. Based on the constitutive laws employed and the experimental results obtained, the dominant densification mechanism was identified and the effect of grain size on dominant densification mechanism was discussed. The activation energy for densification was also evaluated. In the investigated sintering temperature range, interface reaction was identified as the controlling process in sintering of alumina powders with the initial grain size of 0.9 μm, while grain-boundary diffusion was identified as the dominant process in sintering of alumina powders with the initial grain size of 7.0 μm. The activation energies for densification of the finer and coarser grain size alumina ceramics were determined as 342 and 384 kJ mol⁻¹, respectively, which provided a strong support on the densification mechanism investigation.     

Al_2O_3/B_4C的致密化机制

初始晶粒尺寸为0.33μm和7.0μm的Al2O3/14%B4C粉末在不同温度烧结,并模拟计算陶瓷粉末烧结过程。通过对比实验结果和计算结果,找出影响材料致密化的机制,讨论晶粒尺寸对扩散机制的影响,并估算出致密化激活能。在实验烧结温度范围内,界面反应被认为是影响Al2O3/B4C粉末致密化过程的主要因素。Al2O3/14%B4C陶瓷的致密化激活能是1820±60KJ.mol-1,这结果很大程度上支持界面反应致密化机制。     

球磨转速对Nd:YAG透明陶瓷的显微结构及光学性能的影响

以高纯商业Y₂O₃、α-Al₂O₃和Nd₂O₃粉体为原料, 以TEOS(正硅酸乙酯)和MgO为烧结助剂, 采用固相反应和真空烧结技术制备了1.0at%Nd:YAG透明陶瓷。系统研究了球磨转速(球磨时间10 h)对混合粉体的尺寸以及对陶瓷样品致密化行为、显微结构和光学性能的影响。结果表明: 通过球磨过程可以充分细化原料粉体的颗粒; 随着球磨转速的提高, 陶瓷烧结时样品中的气孔能更好地排除。但是球磨转速过高时, 陶瓷烧结体中存在少量的富铝第二相会降低样品的光学透过率。当球磨转速为130 r/min时, 真空烧结(1760℃×50 h)所得Nd:YAG透明陶瓷的微结构均匀致密, 几乎没有晶界和晶内气孔存在, 样品在1064 nm处的直线透过率高达83%。     

Liquid-phase sintering in the glass-cordierite system: particle size effect

The effect of particle sizes of glass and ceramic filler on the densification kinetics of glassfilled ceramics has been studied using borosilicate glass-cordierite as the model system. Within the particle size range investigated, the densification is found to be significantly enhanced by increasing the cordierite size, reducing the glass size and increasing the green density. These results are attributed to both the increased driving force of densification by reducing the glass particle size and the decreased glass redistribution distance by either increasing the green density of compacts or increasing the particle size ratio between the cordierite and glass powders. In addition, a large cordierite-to-glass size ratio gives a dense, uniform microstructure of sintered body as a result of forming a homogeneous close packing of the low-melting glass phase around the refractory cordierite particles.     

掺Sr铬酸镧粉体的合成及低温烧结行为研究

通过溶胶-凝胶法制备了La_1-xSr_xCrO₃纳米粉体并实现了低温致密烧结, 用X射线衍射仪、透射电镜、差示扫描量热分析仪和扫描电镜对粉体和烧结体进行分析. 结果表明: 粉体的平均直径<50nm, 当x=0, 0.1时, 粉体为单一的La_1-xSr_xCrO₃, x=0.3时存在第二相SrCrO₄. Sr掺杂使铬酸镧晶格产生畸变, 随Sr含量的增加, 晶格常数逐渐变小. 铬酸镧纳米粉体的烧结分为两个阶段, 1200℃以前的缓慢放热和1350℃左右的较快放热, 分别对应烧结的初期和中期. 依据DSC分析结果制订了烧结工艺, 并在1380℃烧结得到相对密度91％的铬酸镧烧结体.     

Densification,microstructure, and properties of W-Mo-Cu alloys prepared with nano-sized Cu powders via large electric current sintering

This study rapidly fabricated a novel W-Mo-Cu alloy by large current electric field sintering at a relatively low temperature, and the effects of the powder size of Cu on the densification, microstructure, and properties were comprehensively investigated. The particle size of Cu did not influence the phase type but significantly affected the densification, microstructure, and properties. XRD and TEM results showed that the alloy contained three new phases aside from W, Mo, and Cu phases, i.e., Mo-W ordered phase, Mo-Cu solid solution, and Cu_0.4W_0.6 intermetallic compound. Copper powders with smaller sizes were beneficial to improving the distributional homogeneity of elements and the sintering densification. Therefore, the alloy prepared with 100 nm Cu powders had a denser and more homogeneous microstructure and better comprehensive properties than that prepared with 5 μm Cu powders. Overall, the W-Mo-Cu alloy prepared with 100 nm Cu powders at 980 °C proposed the best comprehensive properties, and its relative density can reach 98% approximately.     

The sintering of combustion-synthesized titanium diboride

A comparative study of the sinterability of combustion-synthesized titanium diboride was conducted over the temperature range of 1800 to 2100° C. During the initia! sintering stage, the densification rate was slightly higher in the combustion-synthesized than in the commercially obtained titanium diboride. For sintering times of > 30 min, however, the shrinkage rates for both types of powders were the same. The activation energy for the late sintering stage was 774 ± 46 kJ mol^–1, consistent with 8 volume diffusion mechanism, end was the same for both combustion-synthesized and commercial powders. The microstructures of sintered specimens with initial particle size below 1O µm exhibited a grain size ranging from 5 to over 40 µm after 30 min of sintering. The addition of 5 wt% NbB₂ to the combustion-synthesized resulted in enhanced shrinkage during the initial sintering stage, but did not affect later stage kinetics. Various amounts of additives of CrB₂, NiB and TiC had no effect on early and late stage sintering kinetics, with the exception of 50 wt% TiC which appreciably inhibited densification.     

SDC电解质致密化研究

以共沉淀-喷雾干燥法制备的Ce0.8 Sm0.2 O1.9(SDC)粉体为原料,模压成型后高温烧结获得SDC电解质陶瓷片.研究模压成型过程中加压时间、压力大小以及烧结温度对烧结体致密度的影响,利用XRD和SEM分别对不同烧结温度获得的烧结体结构和表面形貌进行分析.研究表明,压力30MPa、加压时间30min后获得的坯体,随着烧结温度的升高,烧结体致密度呈上升趋势,烧结温度达到1450℃时进入烧结后期,烧结体具有较高的致密度.此外,通过测定烧结过程中坯体收缩率,对SDC电解质陶瓷片的烧结动力学进行了研究,从而确定SDC电解质致密化的烧结温度为1300～1500℃.     

Densification and microstructure development during the sintering of submicrometre magnesium oxide particles prepared by a vapour-phase oxidation process

The densification behaviour and microstructure development of MgO compacts fired from room temperature up to 1700°C at a heating rate of 10°C min^–1 were examined. Starting materials were seven kinds of MgO powder with primary particle sizes ranging from 11–261 nm; these powders were produced by a vapour-phase oxidation process. The original powders contained agglomerates, due to the spontaneous coagulation of primary particles, which ranged in size from 100–500 nm. The MgO compacts densified during firing by three types of sintering: sintering within agglomerates; sintering between agglomerates and grains; and rearrangement of agglomerates and grains. The MgO compact with the lowest primary particle size (11 nm) densified by the first and second types of sintering, but the effects of these two types of sintering decreased when the primary particle size became 44 nm; here the rearrangement of agglomerates and grains primarily contributed to densification of the compact. All three types of densification became less complete with further increases in primary particle size up to 261 nm. The relative densities of the MgO compacts with smaller primary particle sizes (11–44 nm) became 96–98% when the compacts were fired up to 1700°C.