Pressureless sintering of negative thermal expansion ZrW2O8/Zr2WP2O12 composites

Negative thermal expansion material ZrW₂O₈/Zr₂WP₂O₁₂ composite was prepared by liquid phase sintering. The apparent density of ZrW₂O₈ without any sintering additive was about 3.7 g/cm³, corresponding to about 73% of its theoretical density. However, the relative density of the samples, sintered with more than 5 mol% P₂O₅ was about 90%. The identified phases were mainly ZrW₂O₈ with small amounts of WO₃, ZrO₂ and Zr₂WP₂O₁₂ by XRD. The intensity of Zr₂WP₂O₁₂ peaks increased with increasing P₂O₅ content. It was surmised that the melting of ZrO₂-P₂O₅ resulted in liquid phase formation, which is then converted to Zr₂WP₂O₁₂ on the final stage of sintering. Therefore, Zr₂WP₂O₁₂ phase was observed at the gap between the ZrW₂O₈ grains and at the triple junctions. The ceramics sintered with 20 mol% P₂O₅ showed a negative thermal expansion coefficient of − 4.0 × 10^− 6 °C^− 1.     

ZrO2-膨化石墨/焦炭复合材料的结构和制备

运用两种不同技法制备了ZrO2纳米粒子改性的膨化石墨/焦炭复合材料,应用XRD、SEM和TEM对所得ZrO2改性炭材料进行了表征.技法1:在ZrO(NO3)2及NH4OH溶液中反复交替地浸渍低密度膨化石墨/焦炭块体,随后在1200℃氮氛中热处理,以使在炭块自由表面沉积ZrO2纳米粒子的薄层.技法2:将可膨胀石墨、酚醛树脂粉和ZrOC2 O4-改性的纤维素纤维混合物封装于一容器中,使之经受900℃热激震,随后在氮氛中1200℃热处理,获得改性复合材料.结果表明:复合材料中ZrO2纳米粒子呈现三种尺寸:6nm～30nm为单独的纳米粒子和小微粒;200nm～1000nm为长树突状结构物;1μm～40μm为形如纤维素前驱体的杆状物.     

Pressureless sintering ZrB2-SiC ceramics at low temperatures

ZrB₂-SiC ceramics are prepared by pressureless sintering using ZrB₂ powders and liquid polycarbosilane (LPCS) precursors. The LPCS can effectively reduce the sintering temperature. The phases of the sintered ceramics are characterized by X-ray diffraction, and their morphologies are observed by scanning electron microscopy. From these results, it is learned that LPCS can provide free carbon and silicon at high temperatures. Therefore, the oxides on the ZrB₂ surface can be removed by free carbon, and the densification process can be promoted by silicon. These coupled effects make it possible to pressureless sinter the ZB₂-SiC ceramics at low temperatures.     

化学共沉淀法合成低热膨胀ZrW2O8/ZrO2复合材料

采用化学共沉淀法合成前驱体,前驱体经1150℃烧结得到ZrW2O8/ZrO2复合材料.对ZrW2O8/ZrO2前驱体进行傅里叶变换红外光谱、热重-差示扫描量热分析;通过X射线衍射仪(XRD)、扫描电镜(SEM)、能谱仪(EDS)和热膨胀仪对合成样品的晶体结构、断面形貌和热膨胀性能进行表征.研究结果表明:合成的复合材料的组元为α-ZrW2O8和m-zrO2相,化学均匀性良好且易烧结;随着ZrW2O8质量分数增加,复合材料的热膨胀系数减小,其中26%ZrW2O8/ZrO2复合材料在30～600℃的平均热膨胀系数为-0.5649×10-6K-1,近似为0.     

Nano ZrO2 Particulate-reinforced Lead-Free Solder Composite

A lead-free solder composite was prepared by adding ZrO2 nanopowders in eutectic Sn-Ag alloy. Microstrucrural features and microhardness properties of those solders with different ZrO2 nanopowder fraction were examined. Results indicate that the addition of ZrO2 nanopowders reduced the size of β-Sn grains and restrained the formation of bulk Ag3Sn intermetallic compounds （IMCs） due to the adsorption effect of the ZrO2 particles. The Vicker＇s hardness of the obtained lead-free solder composites fits well with the HalI-Petch relationship. The refinement of β-Sn grains favors to improve the microhardness of composite solders.     

Control of thermoelectric properties in ZrO2/CoSb3 nano‐dispersed composites

Nano‐dispersed ZrO₂/CoSb₃ composites of various composition were prepared by uniaxial hot pressing of nano‐sized powders of thermoelectric CoSb₃ intermixed with ceramic nano‐powders. The phase purity, the microstructure, and the temperature dependent transport parameters of the composites were investigated. Non‐dispersed samples from nano‐sized CoSb₃ powders show higher electrical conductivity compared to melt‐grown material which is attributed to the presence of a small excess of metallic Sb, but they exhibit lower thermal conductivity due to the fine‐grained structure. Addition of 5 at.‐% ZrO₂ enhances the ratio of electrical to thermal conductivity, whereas hardly affects the Seebeck coefficient. In this manner the nano‐dispersion method provides an effective approach to improving the material´s thermoelectric performance.     

Electrical Properties of Sputter-deposited ZrO2-based Pt/ZrO2/Si Capacitors

Pt/ZrO2/Si sandwich structures where ZrO2 is deposited by radio frequency （r.f.） magnetron sputtering using a Zr target in an atmosphere of O2/Ar gas mixture, were fabricated and the effects of the O2/Ar flow ratio in the reactive sputtering process, the annealing temperature, the ZrO2 film thickness on the structure, the surface roughness of ZrO2 films and the electric properties of Pt/ZrO2/Si metal-oxide-semiconductor （MOS） capacitors were investigated. The optimum process parameters of the Pt/ZrO2/Si capacitor based on reactively sputtered-ZrO2 determined in such a way as the capacitance is maximized and the leakage current, the oxide charge, and the interface trap density are minimized that is the O2/Ar flow ratio of 1.5, the annealing temperature of 800℃, and the film thickness of 10 nm. Also the conduction mechanism in the Pt/ZrO2/Si capacitor has been discussed.     

载银ZrO2无机抗菌剂的制备及性能研究

以ZrO2为载体、银离子为抗菌成分制备无机抗菌材料,并对所制备的抗菌材料的抗菌性能及安全性能进行了分析检测,结果表明:在银盐的掺入量为1%～3%,烧结温度为600～1000℃时,所制备的样品对大肠杆菌及金黄葡萄球菌的MIC值均小于75×10-6;对大、小白鼠的急性经口毒性的LD50＞10000mg/kg,急性经皮肤毒性的LD50＞3000mg/kg.     

单分散PSMMA@ZrO2核壳胶体颗粒及ZrO2中空颗粒的制备与表征

采用乙腈与乙醇混合溶剂法制备出单分散的PSMMA@ZrO2核壳胶体颗粒,并通过TEM、SEM等表征手段对乙腈相对含量以及催化剂选择等参数的影响进行研究,结果表明室温下乙腈相对体积含量为20%时,采用去离子水为催化剂可制得高质量的单分散核壳胶体颗粒.通过高温煅烧得到ZrO2中空球,XRD结果表明二氧化锆转化为单斜相.漫反射光谱结果表明ZrO2核壳颗粒与中空颗粒在测量光谱区间内均具有较高的反射率.     

Pt/MoO3/ZrO2催化剂的制备及三效催化性能的研究

采用浸渍法制备了MoOz/ZrO2,用低温氮吸附-脱附法和NH3-程序升温脱附法(TPD)分别对其比表面积和酸碱性进行了表征.结果表明,MoO3/ZrO2具有106.8m2/g的比表面积和超强酸的性能.用等体积浸渍法制备了Pt/MoO3/ZrO2催化剂,在汽车尾气模拟气中考察了其对C3H8、CO和NO的催化活性.与传统三效催化剂Pt/La2O3/Al2O3相比较,Pt/MoO3/ZrO2具有更好的低温起燃性能和更宽的空燃比窗口,并显著地改善了C3H8在富氧状态下的转化效率.通过XRD、H2-TPR对催化剂进行了表征,结果表明,Pt在催化剂载体上具有高度的分散性和优异的氧化还原性能.     

Sc2W3O12/ZrO2可控热膨胀复合材料的制备

采用固相法成功制备了纯度较高的各向异性负热膨胀材料Sc₂W₃O₁₂。将ZrO₂与Sc₂W₃O₁₂按一定体积比混合, 在1200 ℃烧结10 h制备Sc₂W₃O₁₂/ZrO₂复合材料。通过XRD、SEM、EDS和热膨胀仪对合成样品的晶体结构、断面形貌和热膨胀性能进行表征。结果表明: 样品组元为正交相Sc₂W₃O₁₂和单斜相ZrO₂; 在 30~600 ℃内, Sc₂W₃O₁₂/ZrO₂复合材料的热膨胀系数皆线性一致, 并且通过改变Sc₂W₃O₁₂的体积分数, 其热膨胀系数可以控制为正、负或零, 其中60%Sc₂W₃O₁₂/ZrO₂复合材料在30~600 ℃的平均热膨胀系数为0.026×10^-6 ℃^-1, 近似为0。     

氧化锆增韧HA/ZrO2功能梯度涂层的TEM分析

利用净能量控制的PRAXAIR4500型等离子喷涂系统,在钛合金基体上制备出HA/ZrO2功能梯度涂层,采用HTEM、XRD、SEM等对涂层过渡层ZrO2相的结构特征进行分析.结果表明:(1)富锆的过渡层存在ZrO2 3种晶型,主要以四方氧化锆为主,含有少量的立方氧化锆及微量的单斜氧化锆和CaZrO3,单斜氧化锆的出现说明材料内发生了四方氧化锆向单斜氧化锆马氏体相变,这种马氏体相变有利于提高HA材料的韧性;(2)生物活性功能涂层的富锆过渡层致密,与钛合金基体结合紧密,纯羟基磷灰石的表面层具有典型的多孔结构特征,整个涂层沿垂直基体方向从过渡层致密结构向表面层多孔结构过渡;涂层的这种结构特征有利于改善功能梯度涂层的综合性能,提高涂层与基体的结合强度,其结合强度达到48.6MPa.     

稳定剂对ZrO_2质定径水口基质烧成前后相组成和显微结构的影响

以ZrO2质定径水口基质为研究对象,在脱硅锆细粉中添加稳定剂,其中稳定剂的种类和加入量分别为2.8%MgO、2.1%MgO、2.2%MgO+1%Y2O3。借助XRD、SEM和EDS等检测手段,研究了稳定剂对ZrO2质定径水口基质烧成前后相组成和显微结构的影响。结果表明,试样经1630℃烧成,各试样立方相含量明显增加,单斜相含量明显减少,原料中稳定剂的种类和加入量的不同使得烧成后各试样立方相和单斜相的变化量也不相同;试样经1630℃烧成,稳定剂MgO与ZrO2形成固溶体,越靠近MgO颗粒的位置Mg2+与Zr4+的替换程度越明显,但稳定剂的扩散固溶远未达到均匀状态;以MgO+Y2O3为稳定剂的试样,烧成后立方相的增加量最多,固溶体的生成量最大,稳定化程度最高,且ZrO2颗粒的尺寸大小均匀,棱角分明,颗粒之间的结合非常紧密。     

Pressureless sintering of Al2O3-SiC whisker composites

High-density compacts, up to 88% theoretical density, of Al₂O₃-SiC whiskers were prepared by a pressure casting and impregnation technique. Starting with these green bodies, composites of Al₂O₃–20 vol% SiC whiskers were pressureless sintered to higher than 95% theoretical density. They were further densified by hot isostatic pressing up to 99% theoretical density, resulting in a rupture strength of 680 MPa and a fracture toughness of 4.70 Mpa m^1/2.     

Thermodynamic Assessment of the ZrO2—CeO2 and ZrO2—CeO1.5 Binary System

An optimal set of thermodynamic parameters of the ZrO2-CeO1.5 system has been obtained using phase diagram data by modern CALPHAD (CAL culation of PHAse Diagrams) technique.The liquid and other solid solution phases were regarded as substitutional solution.The ordered ZrCe2O7 phase was treated as a stoichiometric compound.The ZrO2-CeO2 system has been re-optimized with new reference state.A comparison between the ZrO2-CeO2 system and ZrO2-CeO1.5 system has been made through calculation.With the calculation, the experimental information is well reproduced and a good agreement is obtained.     

Rapid fabrication of in situ TiC particulates reinforced Fe-based composites by spark plasma sintering

TiC particulates reinforced Fe-based composites have been fabricated using ferrotitanium and carbon black powders with the combination of in situ and spark plasma sintering (SPS) technique. The sintering and densification behaviors were investigated. The results show that when the composite was sintered at 1150 °C for 5 min, the maximum relative density and hardness are 99.2% and 83.2 HRA, respectively. The phase evolution during sintering indicates that the in situ reaction occurs evidently between 850 °C and 1050 °C. The microstructure investigation demonstrates that with the rapid in situ SPS technique, fine TiC particulates with a size of ~ 1 μm are homogeneously distributed in the matrix.     

Pressureless sintering and mechanical properties of alumina-sialon composites

Compositions of Al₂O₃, Si₃N₄ and AlN were sintered to produce six different alumina-sialon composites. The composites reached the highest density at 1700 °C in a nitrogen atmosphere. Sialon acted as a binder, promoting the densification and suppressing the grain growth of alumina. The composites had a bending strength of 450 MPa at room temperature and maintained high strength over 300 MPa at 1400 °C. The composite with 30 wt % sialon had the maximum fracture toughness of 4.3 MPa·m^1/2 and exhibited good oxidation resistance even at 1400 °C. Mullite was formed in the oxidation layer and little degradation in strength was observed after oxidation.     

Al2O3/ZrO2层状复合陶瓷的显微结构特征与强韧化的关系

利用自带能谱的扫描电镜(SEM)和透射电镜(TEM)仪,对Al2O3/ZrO2层状复合陶瓷的显微结构特征及断口形貌进行深入分析研究.研究结果表明:表面压应力的作用细化了晶粒,提高了可相变四方相的含量,增加了相变增韧的效果;沿界面两端表现出2种不同的断裂机制:界面以外靠近表面部分,其断裂主要是穿晶断裂;在基体层的断裂则表现为沿晶和穿晶混合型断裂方式.该断裂行为与ZrO2层状陶瓷的相变增韧机制密切相关.