Y2O3稳定ZrO2薄膜的结构和光学特性

用电子束蒸发法制备出四种不同Y2O3含量的Y2O3稳定ZrO2（YSZ）薄膜,用X射线衍射和透射光谱测定薄膜的结构和光学性能.结果表明：随着Y2O3含量的增加,ZrO2薄膜从单斜相向高温相（四方相和立方相）转变,获得了结构稳定的YSZ薄膜；YSZ薄膜的晶粒尺寸都比ZrO2薄膜的大,但随着Y2O3加入量的增加,晶粒尺寸有减小的趋势,薄膜表面也趋向光滑平整.所有YSZ薄膜的透射谱线都与ZrO2薄膜相似,在可见光和红外光区都有较高的透过率.Y2O3的加入还可以改变薄膜的折射率,在一定范围内可得到所需的任意折射率.     

三氧化二铝含量对Ni／Zr0.4Ce0.6O2—Al2O3催化剂的CH4—CO2重整反应性能影响

采用水热合成法．制备了不同Al2O3含量的Ni／Zr0.4Ce0.6O2-Al2O3催化剂。采用X-射线衍射(XRD)和扩展X光吸收精细结构(EXAFS),对催化剂样品进行结构表征;考察了Al2O3的加入对催化剂结构和CH4-CO2重整反应活性的影响。结构表征和活性测试表明,催化剂中存在的主要晶相是Zr0.4Ce0.6O2.Al2O3的加入,使催化剂颗粒度变小,镍的分散度提高。并使反应活性有明显改进,而过量Al2O3的加入,却容易导致积炭．     

ZrO2,Nb2O5助剂改性Au/α-Fe2O3催化剂的光谱研究

通过并流共沉淀方法,制备了一系列添加助剂ZrO2和Nb2O5的Auα-Fe2O3催化剂,并用紫外-可见漫反射光谱,X射线光电子能谱,透射电镜和X射线荧光元素分析对其进行了表征.结果表明ZrO2和Nb2Os之间存在着较强的协同作用;两种助剂的同时添加促进了Au,ZrO2和Nb2O5在Au/α-Fe2O3催化剂表面的富集,有效地阻止了纳米微粒的团聚.经甲醇重整气氛下的催化性能评价,在200℃时,AuFZ的活性达到平衡转化率99.9%;经50 h的稳定性测试,其稳定性远远高于未加助剂的Au/α-Fe2O3样品.这表明ZrO2和Nb2O5双助剂的添加有效地改善了Au/α-Fe2O3催化剂的性能.     

催化精馏专用填料型固体酸SO42-/ZrO2-Al2O3-Al的研究

为了研制催化精馏专用催化剂 ,采用铝阳极氧化法制备了Al2 O3 Al一体型载体 ,并将活性固体超强酸SO42 -/ZrO2 引入到Al2 O3 Al上 ,得到一种新型催化精馏专用填料式固体酸SO42 -/ZrO2 Al2 O3 Al催化剂 .利用XRD、SEM、BET、XPS、NH3 TPD等手段对其进行了表征 .结果表明 ,所制得的阳极氧化铝膜厚为 5 6 μm ,SO42 -/ZrO2 Al2 O3 Al固体酸具有比表面积大、酸强度适中的特点 .XRD结果表明 ,ZrO2 在Al2 O3 Al上处于高度分散状态 .将该固体酸用于乙酸 /乙醇酯化反应中 ,显示出较高的催化活性 ,且稳定性较好     

含贵金属的BaZrO3 储存NOx 催化剂结构及性能研究

用溶胶 凝胶法制备了钙钛矿型BaZrO3催化剂 ,再用等量浸渍法制备了Rh/BaZrO3样品 ,并制备了Rh/BaZrO3/γ Al2 O3和Pt/BaZrO3/γ Al2 O3催化剂 .对它们的NOx 储存量 (NSC)及其抗硫性能进行了测试 ,并用X射线衍射 (XRD)、X光电子能谱 (XPS)和傅里叶变换红外光谱 (FT IR)等方法研究了它们的结构及其对性能的影响 .结果表明 ,BaZrO3催化剂具有良好的储氮及抗硫性能 ,直接添加贵金属到BaZrO3中会使NSC降低 ,而混合γ Al2 O3后添加Pt或Rh可以大大提高NSC ,上述两种方式引入贵金属都能改善催化剂的抗硫性能 .     

陈化温度和Fe/Zr配比对SO42-/Fe2O3-ZrO2固体超强酸结构与性能的影响

用低温陈化法制备了SO42 -/Fe2 O3 ZrO2 (简称SFZ)固体超强酸催化剂 ,用红外光谱 (IR)和X光衍射(XRD)对其结构进行了表征 ,并考察了它对合成癸二酸二正丁酯的催化性能 .IR谱显示 ,低温陈化的SFZ样品在10 70cm-1处吸收峰远强于常温陈化样品 .XRD分析则显示 ,在焙烧温度为 6 5 0℃、Fe/Zr为 2∶1时 ,低温陈化的样品出现了亚稳态的ZrO2 四方晶相 .该样品在催化酯化反应中使产率达 90 %以上 ,高于常温陈化样品的 30 % .研究结果表明 :在其他条件不变时 ,低温陈化所出现的亚稳态的ZrO2 四方晶相是表面酸性和催化活性增加的微观原因     

不同沉积参量下ZrO2薄膜的微结构和激光损伤阈值

ZrO2采用X射线衍射(XRD)技术分析了不同充氧条件和沉积温度对ZrO2溥膜组成结构的影响,并对不同工艺下制备的薄膜的表面粗糙度和激光损伤阈值进行了测量。结果发现随着氧压的升高,ZrO2溥膜将由单斜相多晶态逐渐转变为非晶态结构,而随着基片温度的增加,溥膜将由非晶态逐渐转变为单斜相多晶态。同时发现随着氧压升高晶粒尺寸减小,而随着沉积温度增加,晶粒尺寸增大。氧压增加时工艺对表面粗糙度有一定程度的改善,而沉积温度升高,工艺对表面粗糙度的改善不明显。晶粒尺寸大小变化与表面粗糙度变化存在对应关系。激光损伤测量表明,氧压条件和沉积温度对ZrO2薄膜的抗激光损伤能力有着较大影响。     

由组分可控的LB膜前驱物法制备Y2O3稳定立方相ZrO2的超薄陶瓷膜

由有机LB膜技术发展了一种制备组分、厚度可控的无机超薄陶瓷膜的方法 .以Zr、Y的 β 二酮络合物的作为“表面离子”代替传统的亚相离子 ,沉积它们与花生酸的混合LB膜 .并将它作为前驱物 ,经臭氧处理和热处理 ,成功制得了Y2 O3 稳定的立方相ZrO2 超薄膜 (YSZ) .用X射线衍射 (XRD)、X射线光电子能谱 (XPS)等手段研究了YSZ薄膜的相结构和其组成 .结果表明 ,超薄陶瓷膜中Zr与Y的含量比率控制得很好 ,且形成Y2 O3 稳定的立方相ZrO2 .说明这种方法可以成功地用来制备组分和膜厚均可控的纳米陶瓷膜 .     

烧绿石型富氧相Ce_2Zr_2O_8与缺氧相Nd_2Zr_2O_7的振动光谱及XPS对比研究

采用石墨还原法成功制备了富氧相Ce2Zr2O8,选用缺氧相Nd2Zr2O7替代其前驱体CeZrO3.5+δ进行结构对比分析,利用X射线衍射(XRD)、拉曼光谱(Raman)、红外光谱(IR)及X射线光电子能谱(XPS)对样品体、表晶体结构进行表征。XRD结果表明,Ce2Zr2O8相具有典型烧绿石结构特征,表征Ce/Zr阳离子有序排列的超结构峰非常明显,但其Zr—O配位体由前驱体中的[ZrO6]八面体转变为[ZrO8]立方体,[ZrO8]配位体形成大大降低了Ce2Zr2O8的结构稳定性。Raman和IR结果表明,Ce2Zr2O8相的振动光谱谱带比其前驱体替代物Nd2Zr2O7显著增多,说明氧离子的富集导致Ce2Zr2O8相中某些振动简并峰消除简并,该结果进一步证实了其结构对称性较前驱体更低。XPS结果表明,Ce2Zr2O8相表面Ce(Ⅳ)特征峰(916.3eV)非常明显,没有Ce(Ⅲ)特征峰(885eV)出现,说明该相前驱体中的Ce3+已被完全氧化成Ce4+;Ce2Zr2O8相中Zr(3d)结合能与萤石相Gd1.2U0.8Zr2O7+y接近证实其表面形成了与体相一致的[ZrO8]配体;O(1s)低位结合能升高表明Ce2Zr2O8体相氧种介于晶格氧和吸附氧之间,高位氧峰出现说明其表面含有吸附氧,吸附氧与Ce2Zr2O8体相结合强度介于CeO2和Nd2Zr2O7之间。     

退火对ZrO2薄膜微结构及激光损伤阈值的影响

利用电子束蒸发方法在Yb∶YAG晶体和熔融石英衬底上沉积单层ZrO2薄膜，分别在673 K和1 073 K的温度下经过12 h退火以后，通过X射线衍射（XRD）分析了薄膜晶相，计算了薄膜的晶粒尺寸;利用表面热透镜技术获得了薄膜的吸收；测量了退火后薄膜的激光损伤阈值。实验结果表明:两种衬底上的薄膜结构受到退火温度和衬底表面结构的影响，高温退火有利于单斜相的形成，含单斜相的ZrO2薄膜具有较高的激光损伤阈值，而由于衬底的吸收，Yb∶YAG晶体上薄膜的损伤阈值远小于石英衬底上薄膜的损伤阈值。     

紫外拉曼光谱研究钇掺杂的氧化锆体系表面相变

本文用紫外拉曼 ,近可见拉曼光谱和XRD检测了不同焙烧温度下Y2 O3-ZrO2 的相变过程。紫外拉曼光谱对样品表面相变极其灵敏 ,而近可见拉曼光谱和XRD提供的主要是体相和表面的混合信息。在紫外拉曼谱图中 ,只观察到单斜相的谱峰 ,没有明显的四方晶相的信号 ,这表明样品的表面主要是单斜晶相。然而 ,XRD和近可见拉曼光谱的结果显示Y2 O3-ZrO2 体相是四方晶相。焙烧温度超过 40 0°时 ,紫外拉曼 ,近可见拉曼和XRD晶之间明显不同的结果表明Y2 O3-ZrO2 在表面区四方相很易转变为单斜相 ,体相中的四方相由于钇的添加而稳定存在。根据紫外拉曼和XRD结果 ,当升高温度时 ,在样品的表面形成一单斜相层 ,体相钇稳定的四方相 ,且由于Y2 O3的存在抑制了单斜相进一步向体相发展。     

Er-Y共掺杂ZrO2的Raman光谱和Er3+的荧光光谱

采用柠檬酸溶胶凝胶法制备Er-Y共掺杂的具有单斜、四方和立方结构的ZrO2基复合氧化物．用XRD和Raman对复合氧化物结构和不同晶相环境中Er3+的荧光光谱进行了表征．结果表明，掺杂Er3+在三种不同晶相Y-ZrO2中表现出不同的荧光特征．随着基体ZrO2由单斜相逐渐向四方和立方相转变，其荧光谱峰位置对称性提高，峰分裂数减少，谱带逐步向单峰转变．在632.8 nm激发下的Raman图谱有Er3+的荧光干扰，在514.5 nm下则以荧光光谱为主体，不能获得Raman信号，在325 nm激发下无荧光干扰．XRD和紫外Raman二种方法对物相表征结果的差别是由于样品体相和表面不一致，表层容易生成比内层结构对称性更低的物相造成的．     

The structure and phase composition of stabilized zirconia-based nanosystems exposed to shock-wave treatment

The special features of the structure and phase composition of nanocrystalline zirconia-based powders subjected to shock-wave treatment are studied. The investigations show that zirconia with small amounts of yttria and/or alumina is in nanocrystalline and quasi-amorphous states representing a nonequilibrium solid solution of ZrO2 (Y, Al) and that an increase in the monoclinic phase abundance is associated with a reduction in the critical size of tetragonal crystallites due to an accumulation of lattice microdistortions. The monoclinic phase in powders with yttria and alumina additions is not formed even with shock compression at pressures up to 20 GPa. This is attributed to the fact that the resultant lattice microdistortion level is inadequate to destabilize the nanocrystalline tetragonal phase. Relaxation of microdistortions on annealing causes the critical size of tetragonal crystallites to increase. As this takes place, the monoclinic phase is converted into the tetragonal one.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 61–70, September, 2004.     

Synthesis of zirconium dioxide by ultrasound assisted precipitation: effect of calcination temperature

Nanostructured zirconium dioxide was synthesized from zirconyl nitrate using both conventional and ultrasound assisted precipitation in alkaline medium. The synthesized samples were calcinated at temperatures ranging from 400°C to 900°C in steps of 100°C. The ZrO(2) specimens were characterized using X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The thermal characteristics of the samples were studied via Differential Scanning Calorimetry-Thermo-Gravimetry Analysis (DSC-TGA). The influence of the calcination temperature on the phase transformation process from monoclinic to tetragonal to cubic zirconia and its consequent effect on the crystallite size and % crystallinity of the synthesized ZrO(2) was studied and interpreted. It was observed that the ultrasound assisted technique helped to hasten to the phase transformation and also at some point resulted in phase stabilization of the synthesized zirconia.     

CuO/Al2O3、CuO/CeO2-Al2O3和CuO/La2O3-Al2O3催化剂中CuO物种被CO氧化的比较

用浸渍法制备了CuO/Al2O3 (Cu/Al)、CuO/CeO2- Al2O3 (Cu/CeAl)和CuO/La2O3-Al2O3(Cu/LaAl)催化剂. 通过原位XRD、Raman和H2-TPR方法， 对催化剂中的CuO物种以及CuO-Al2O3的固-固相反应进行了表征. 结果表明，对于Cu/Al催化剂，CuAl2O4存在于CuO与Al2O3层之间，CuO以高分散和晶相两种相态存在于催化剂的表层；对于Cu/CeAl催化剂，除了少量高分散和晶相的CuO存在于表层外，大部分CuO迁移到了CeO2的内层，     

ZYA系统的拉曼光谱研究

测试了６０ｗｔ％ＺｒＯ２（２．２５ｍｏｌ％Ｙ２Ｏ３）－４０ｗｔ％αＡｌ２Ｏ３（ＺＹＡ）粉末样品受高压前后的拉曼光谱，并由此证明了四方相ＺｒＯ２陶瓷基质的相变增韧机制。     

Influence of environment and grinding on the crystallisation mechanism of ZrO2 gel

The influence of grinding and surrounding atmosphere on the thermal transformations of zirconia gel has been studied. The XRD analysis of the products obtained by thermal decomposition of zirconia gel has shown that pure tetragonal phase is obtained if the gel decomposition is carried out under high vacuum or dry inert atmosphere, while monoclinic zirconia results from the decomposition of the zirconia gel under air or inert gas saturated with water vapour. A mechanism for the thermal crystallisation of zirconia gel has been proposed from the study of the variation of the crystal size of the monoclinic and tetragonal zirconia phases formed as a function of the temperature and the surrounding atmosphere.The thermal decomposition of ground zirconia leads to the formation of ZrO₂ with a percentage of tetragonal phase closed to 90% irrespectively of the surrounding atmosphere. The stabilisation of the tetragonal phase by grinding seems to be connected with the formation of tetragonal zirconia nuclei that cannot be observed by XRD. The crystallisation enthalpy measurements carried out by DSC support this conclusion.     

Stress driven phase transformation in ZrO2 film

Zirconia thin layers (250 nm) were deposited on stainless steel substrates using organo-metallic injection chemical vapour deposition (MOCVD) process with zirconium beta-diketonate as precursor at low oxygen pressure and 900 °C. Low roughness zirconia films were made up of a mixture of tetragonal and monoclinic phases depending on the process conditions. As the zirconia tetragonal phase is known to be stabilized by small grain size and/or internal compressive stresses, tensile and/or compressive external stress fields were applied at room temperature using a bending test device. Then, XRD measurements were used to determine tetragonal/monoclinic phase ratio and also residual stresses in the films before and after the tests. The film surface was observed at the various stages of the experiments by field electron gun-scanning electron microscopy (FEG-SEM).Under these stress fields, phase transformation occurs in the film, from tetragonal structure to a monoclinic one. Some preferential tetragonal planes give rise to monoclinic ones. The external stress field is also likely to redistribute the internal stresses within the films.     

Unusual structural phase transition in nanocrystalline zirconia

The present work is the first example demonstrating that a hydrous zirconia formed by precipitation can yield a nearly pure nanocrystalline monoclinic zirconia at a temperature as low as 320 °C. The X-ray diffraction pattern of the hydrous zirconia heated to 310 °C shows that diffraction peaks begin to emerge and reveals a just crystallized mixture of predominantly monoclinic zirconia (70%) with some tetragonal zirconia(30%). In other words, the hydrous zirconia formed in the present work yields the predominantly monoclinic structure coexisting with the tetragonal one as soon as crystallization starts at low temperature (310 °C). This is an important exception to the general principle that amorphous zirconia precursors first convert to the tetragonal structure of zirconia with increasing calcination temperature and then transform to the monoclinic one at a higher temperature (∼600 °C). At the crystallization temperature (310 °C), the monoclinic crystallite size is about 17 nm and the tetragonal one 28 nm. The monoclinic crystallite is much smaller than the tetragonal one with which it co-exists. This result is also not consistent with the traditional view that a critical particle size effect is responsible for the stability of the tetragonal and monoclinic structures. When the temperature (310 °C) is slightly raised to 320 °C, the XRD pattern shows a nearly pure monoclinic zirconia. The crystallite size of the monoclinic zirconia is around 15 nm, and it does not change appreciably as calcination temperature is increased from 320 to or above 400 °C. The unusual structural phase transition has been investigated by several complementary experimental tools: X-raydiffraction and surface analyses, and infrared and Raman spectroscopies. PACS 81.07.-b; 64.70.Nd; 82.80.-d; 78.67.-n; 81.05.Je