溶胶凝胶法制备超细负热膨胀性ZrW2O8粉体

以溶胶凝胶法制备负热膨胀材料ZrW2O8粉体并与固相法制备的粉体相比较.对其前驱体进行热重-差热分析(TG-DSC)、以X射线粉末衍射(XRD)、透射电镜(TEM)、扫描电子显微镜(SEM)分别对粉体进行物相分析和形貌观测.结果表明溶胶凝胶法比固相法合成温度低,于610℃合成单一立方结构ZrW2O8粉体,并且粉体颗粒比固相法小,为100nm;ZrW2O8粉体有很好的负热膨胀特性,以高温X射线衍射分析,在室温约500℃范围内,溶胶凝胶法制备的粉体的热膨胀系数为-5.93×10-6/K;比固相法(-6.31×10-6/K)的略低.     

柠檬酸溶胶-凝胶法合成负热膨胀性ZrW_2O_8粉体及其性质研究

以柠檬酸为螯合剂,采用溶胶-凝胶法制备负热膨胀性Zr W2O8粉体,对其前驱体进行热重-差热分析,以X射线粉末衍射、扫描电子显微镜对产物结构及形貌进行表征,结果表明所得粉体为单一α-Zr W2O8相,具有无规则形状。随着柠檬酸量的增加,颗粒有明显聚集长大的趋势,且形貌向片层状发展。变温X射线粉末衍射分析表明,所得Zr W2O8粉体具有很好的负热膨胀特性,在室温~500℃时,平均热膨胀系数为-6.14×10-6/℃。     

PVP对溶胶凝胶法制备负热膨胀ZrW_2O_8粉体形貌及性能的影响

以PVP为添加剂,采用溶胶凝胶法制备ZrW_2O_8粉体,研究添加剂对粉体形貌的影响及其负热膨胀特性。对其前驱体进行热重-差热分析(TG-DSC),以X射线粉末衍射(XRD),扫描电子显微镜(SEM)对产物结构及形貌进行表征。结果表明所得粉体为单一立方α-ZrW_2O_8相。加入PVP后,可以有效地改变粉体的形貌,随着加入量的增大,粉体的形貌从无规则的团聚体转变为长棒状、扇形及短棒颗粒。原位X射线粉末衍射分析表明,所得ZrW_2O_8粉体具有良好的负热膨胀特性。     

固相法制备超细ZrW2O8粉体及其负热膨胀特性的研究

以化学合成的ZrO2和WO3为原料,以固相法制备具有负热膨胀特性的超细立方相ZrW2O8粉体.对其前驱体进行差热分析(DSC),以X射线粉末衍射(XRD)、扫描电子显微镜(SEM)及透射电子显微镜(TEM)对产物结构及形貌进行表征.结果表明:通过化学方法合成出单斜相和四方相混合的纳米级ZrO2粉体,纯单斜相的纳米级WO3粉体,以其为原料能够制备出超细立方相ZrW2O8粉体.同时考察不同研磨时间对其粒径的影响.变温X射线粉末衍射分析表明:所得ZrW2O8粉体具有很好的负热膨胀特性,在20～600℃范围内的平均热膨胀系数为-6.82×10-6K-1.     

ZrW2O8 / ZrO2 可控热膨胀复合材料的制备

采用分步加热固相法成功制备了纯度较高的各向同性负热膨胀材料ZrW₂O₈ 。将ZrW₂O₈ 与ZrO₂ 按一定比例混合, 在1200 ℃烧结24 h 制备了热膨胀系数可控的ZrW₂O₈ / ZrO₂ 复合材料。研究结果表明, 通过改变ZrW₂O₈ 的体积分数, ZrW₂O₈ / ZrO₂ 复合材料的热膨胀系数可以控制为负、正或零。当ZrW₂O₈ 的体积分数为37 %时, 复合材料的热膨胀系数接近零。为了得到致密的ZrW₂O₈ / ZrO₂ 复合陶瓷, 采用Al₂O₃ 作为烧结剂, 取得了较好的效果。0. 35 wt % Al₂O₃ 的加入可以在不影响复合材料热膨胀性能的前提下, 显著提高复合材料的致密度。      

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。      

共沉淀法合成负热膨胀材料ZrW2O8

ZrW2O8是极具应用前景的各向同性负热膨胀材料.用共沉淀法合成了ZrW2O8,经X射线衍射、红外-拉曼光谱分析证明用共沉淀法合成的ZrW2O8纯度高.经高温X射线衍射测定,ZrW2O8在298～973K温度区间线膨胀系数αl=-7.0×10-6K-1, α-ZrW2O8(空间群P213)相到β-ZrW2O8(空间群Pa3)的转变温度在443K与446K之间.对ZrW2O8前驱体进行了热重-差热分析(TG-DTA).     

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。     

负热膨胀材料ZrW2O8及其复合材料研究进展

ZrW2O8是一种优良的各向同性负热膨胀材料。本文对ZrW2O8的晶体结构、负热膨胀特性和制备方法作了简要介绍,着重论述了以Cu／ZrW2O8、ZrO2／ZrW2O8和聚酰亚胺（Polyimide）/ZrW2O8为代表的ZrW2O8复合材料的研究现状。     

溶胶-凝胶法合成亚微米α-ZrW2O8的研究

以分析纯氯氧化锆、钨酸铵、氨水和浓硝酸为原材料,采用溶胶-凝胶法合成前驱体,通过后热处理生成α-ZrW2O8.所合成的前驱体为无定形,其在650℃晶型转变完全,但是其转变产物不是ZrW2O8,而是单斜的WO3和ZrO2以及WO3·0.5H2O和W2O6(H2O).温度和时间参数对所合成的前驱体转变过程影响较大.实验结果表明:低于600℃的热处理温度前驱体无法转变成ZrW2O8粉末.前驱体在600℃保温10～18h,随着保温时间的延长,其转变成ZrW2O8的量也相应增加.但在600℃保温时间超过18h,或者热处理温度高于600℃,都使生成的ZrW2O8粉末发生分解.溶胶-凝胶法合成的ZrW2O8粉末颗粒经SEM分析发现,平均粒径在0.1～0.2μm.     

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.     

The cryogenic thermal expansion and mechanical properties of plasma modified ZrW2O8 reinforced epoxy

In this article, epoxy resin reinforced by negative thermal expansion material, ZrW₂O₈, was fabricated. The surface modification of ZrW₂O₈ particles was performed via plasma enhanced chemical vapor deposition (PECVD) process. As a result, a thin film was uniformly deposited on the surfaces of the ZrW₂O₈ particles, leading to an improvement of compatibility and dispersion of ZrW₂O₈ fillers inside epoxy matrix. Moreover, the coefficients of thermal expansion (CTEs) of the composite material containing 0-40 vol.% fillers were studied under cryogenic temperatures. The results showed a significant reduction in thermal expansion with increasing ZrW₂O₈ content. The cryogenic mechanical properties of ZrW₂O₈/epoxy composites were also investigated, showing the properties were improved by adding ZrW₂O₈ to certain content. In addition, the mechanical strength and modulus of the composite were observed significantly higher at cryogenic temperature than that at room temperature because of the thermal shrink effect and the frozen epoxy matrix.     

Cf-ZrW2O8/9621复合材料制备及碳纤维和ZrW2O8含量对其热膨胀的影响

热膨胀是影响复合材料性能和使用寿命的主要因素之一。为研究具有低/负热膨胀的复合材料,本文以碳纤维粉、ZrW₂O₈颗粒和环氧树脂为原料,采用模压法制备了C_f-ZrW₂O₈/9621环氧树脂基复合材料,研究了碳纤维粉和ZrW₂O₈颗粒含量对复合材料热膨胀行为的影响规律,并分析了不同温度区间内C_f-ZrW₂O₈/9621环氧树脂基复合材料热膨胀的变化规律。研究结果表明：在30～200℃范围内,当ZrW₂O₈颗粒含量不变时,随着碳纤维粉含量的增加复合材料的平均热膨胀系数逐渐降低,其中碳纤维粉含量增加到12%时,复合材料的平均热膨胀系数最低,为29.9×10^-6/℃,降低了约60%;当碳纤维粉含量不变时,ZrW₂O₈颗粒含量逐渐增加到12%时,复合材料的平均热膨胀系数呈现...     

Hydration of ZrW2O8 nanopowders under ambient conditions

We report hydration of ZrW₂O₈ under ambient conditions, and its effect on the negative coefficient of thermal expansion (CTE) of ZrW₂O₈. On storing under ambient conditions for six months, about 66% of the outer annular volume was hydrated to ZrW₂O₈·0.35H₂O, while after one year of storage the sample was hydrated to ZrW₂O₈·0.72H₂O. The CTE was determined by in-situ high temperature X-ray diffraction (XRD) measurements in the temperature range from 25 to 200 °C. XPS and TGA were used to characterize the nature of bonding of the water in the ZrW₂O₈ structure. The negative CTE behavior of partially hydrated ZrW₂O₈·0.35H₂O remained intact, while on further hydration to ZrW₂O₈·0.72H₂O, negative CTE was not observed. The bonding of the water molecules to the ZrW₂O₈ structure were stronger than those of adsorbed water molecules but weaker than those of the structural hydroxyl ions.     

Preparation and properties of negative thermal expansion Zr2WP2O12 ceramics

Using solid-state reaction method, Zr₂WP₂O₁₂ powder was synthesized for this study. The optimum heating condition was 1200 °C for 4 h. The obtained powder was compacted and sintered. The relative density of the Zr₂WP₂O₁₂ ceramics with no sintering additive was 60%. That of samples sintered with more than 0.5 mass% MgO was about 97%. The average grain size (D₅₀), as estimated from the polished surface of a sample sintered at 1200 °C for 4 h was about 1 μm. The obtained ceramics showed a negative thermal expansion coefficient of about −3.4 × 10⁻⁶ °C⁻¹. Young's modulus, Poisson's ratio, three-point bending strength, Vickers microhardness, and fracture toughness of the obtained ceramics were, respectively, 74 GPa, 0.25, 113 ± 13 MPa, 4.4 GPa and 2.3 MPa m^1/2.     

ZrW_(2)O_(8)-Cf/E51低/负热膨胀复合材料制备及超声时间对其热膨胀和力学性能的影响EI北大核心

为了制备低膨胀、高强、轻质复合材料,采用模压法制备了ZrW_(2)O_(8)-Cf/E51复合材料,并研究了超声时间对其微观组织、热膨胀行为和极限抗拉强度的影响。结果表明:在制备过程中颗粒团聚后容易受到纤维单丝阻挡并在纤维束表面聚集。在20 min之内,延长超声时间会减少ZrW_(2)O_(8)颗粒团聚。随着颗粒团聚的减少,复合材料断口会由平面状、无纤维拔出变为台阶状、有纤维拔出。在碳纤维和ZrW_(2)O_(8)颗粒的综合作用下,ZrW_(2)O_(8)-Cf/E51复合材料在热膨胀过程中膨胀量dL/L0会出现增大、减小和缓慢上升三个阶段,平均热膨胀系数也会出现相应的三个阶段。超声时间从5 min延长到20 min,ZrW_(2)O_(8)-Cf/E51复合材料的平均热膨胀系数降低了约130%,极限抗拉强度提高了约8%。