Zr(OH)4的热分解及ZrO2的相变过程

利用TG-TDG-DTA热分析技术研究了由Zr（OH）4热分解制备ZrO2的脱水过程,并结合X射线粉末衍射技术研究了ZrO2的相变过程．发现在82℃的吸热峰对应Zr（OH）4的脱水,而435℃附近出现的放热峰则为四方ZrO2向单斜ZrO2的晶相转变．采用外推法确定了Zr（OH）4脱水过程遵循三维扩散机理,其函数方程为g（α）=[{1／（1-α）}^1/3-1]^2．以实验获得的动力学参数ln A和E为基础,用最小二乘法对ln A和E进行线性拟合,得到动力学补偿效应表达式为ln A=0．437E-20．69．     

Electroconduction and linear expansion of solid electrolytes Ce1? x Sm x O2?δ ( x = 0.10?0.30)

A complex investigation of solid electrolytes Ce_1−x Sm _x O_2−δ (x = 0.10−0.30) is performed in a broad temperature interval by methods of x-ray diffraction analysis, electroconduction, dilatometry, differential scanning calorimetry, and thermogravimetry. Ceramic technology is used for the synthesis. The density of the obtained specimens is no lower than 95%. The dilatometry measurements reveal the presence of singularities in the curves obtained at temperatures in the region of 180–230°C, which may be ascribed to a phase transition of the type order-disorder of hypothetical phase Ce₇SmO_15.5. The electroconduction and dilatometry methods also point to the presence of singularities in the temperature dependences in the temperature interval extending from 800 to 870°C. Original Russian Text ? E.G. Vaganov, V.P. Gorelov, N.M. Bogdanovich, I.V. Korzun, V.A. Kazantsev, 2007, published in Elektrokhimiya, 2007, Vol. 43, No. 6, pp. 695–698. Based on the report delivered at the 8th International Meeting on Fundamental Problems of Solid-State Ionics, Chernogolovka (Russia), 2006.     

Influence of the support on the state of nickel in the Ni/SiO2, Ni/ZrO2, and Ni/SO4/ZrO2 oxide systems studied by diffuse-reflectance IR spectroscopy

The Ni/SiO₂, Ni/ZrO₂, and Ni/SO₄/ZrO₂ systems were studied by diffuse-reflectance IR spectroscopy using CO as a probe molecule. The Ni/SiO₂ and Ni/ZrO₂ systems are similar in properties, and the state of nickel in the Ni/ZrO₂ system is determined by the specific surface area. In the Ni/SO₄/ZrO₂ system, the surface sulfur compounds affect substantially the state of nickel: Ni^δ+ species with a partial positive charge are formed due to the strong electron-acceptor properties of the sulfur compounds. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 409–413, March, 1998.     

Oxo-Bridged Zr Dimers as Well-defined Models of Oxygen Vacancies on ZrO2

While ZrO₂ is known to have a large effect on the activity and selectivity of the Cu/ZrO₂ catalyst for methanol synthesis, its role in this process is poorly understood. Surface defects such as oxygen vacancies could play a role in the strong metal-support interaction (SMSI) between Cu and ZrO₂. However, due to the complexity of the surfaces, the exact molecular nature of this interaction is not at present known. Here, we make well-defined models of both reduced and coordinatively unsaturated surface oxygen vacancies on ZrO₂ using the molecular precursor [Cp₂ZrCl]₂(μ²-O) ( 1 ). Complex 1 can be reduced to form a complex ( 2 ) containing one Zr(III) center and a bridging hydride ligand (according to EPR and IR spectroscopy) derived from C−H activation of either thf or the Cp ring. Complex 2 reacts with CO₂ to largely produce CO, suggesting that surface defects with similar structures probably do not play a role in the industrial catalyst. Halide abstraction from complex 1 results in the Lewis acidic species 3 , which has similar Lewis acid properties to acidic defects on the ZrO₂ surface. Similarities of both of these model species to real surface oxygen vacancies and their role in the catalytic reaction are discussed.     

Optimisation of the plasma electrolytic oxidation process efficiency on aluminium

Plasma electrolytic oxidation (PEO) is a surface treatment technology enabling fabrication of adherent thick (50–150 µm) coatings on light metal alloys with significantly enhanced hardness, wear and corrosion resistance compared with other conventional treatments. The technology has the potential to play a significant role in the transport sector for replacement of steel with light‐weight materials of improved durability. A main limitation of PEO lies in its relatively high cost, associated with high energy consumption and low coating efficiency. The present work explores possible routes to improve the process efficiency. It is shown that a combination of conventional pre‐anodising with sequential PEO treatment reduces specific energy consumption up to five times because of an increase of the coating growth rate, up to 10 µm/min, compared with existing PEO processes. A further approach to improved coating efficiency involves PEO in electrolytes with suspended fine or nanoparticles, which results in the formation of thicker coatings in reduced time as a result of the incorporation of the particles from the electrolyte into the coating. Additionally, melting of the coating material during the micro‐arc discharge process leads to formation of stabilised high‐temperature phases, such as tetragonal and cubic zirconia, which provide significantly improved microhardness of the coating material and give a potential for thermal barrier applications. Copyright © 2009 John Wiley & Sons, Ltd.     

ZrO2 and Cu/ZrO2 Sol-Gel Synthesis in Presence of Microwave Irradiation

The sol-gel technique with a microwave irradiation was used to synthesize ZrO₂ and Cu/ZrO₂ solids at various pH values and hydrolysis catalysts. Microwave irradiation induces ZrO₂ tetragonal phase formation at almost any pH. The copper was bonded through oxygen bonds to the zirconia lattice. The introduction of copper favored the support acidity.     

Anodic treatment of steel 40Kh in a 35-% sulfuric acid electrolyte containing chloride ions

Anodic dissolution of steel 40Kh in a sulfuric acid electrolyte containing Cl^– ions is studied by analyzing the experimental dependence of anodic current on the specimen potential. The dependences of the critical passivation current, anodic current at –0.15 to 0.55 V (Ag/AgCl), and passivation current on the concentration of Cl^– ions (c) are determined. The maximum value of c for the passivation at 0.55–1.6 V (Ag/AgCl) is refined. The dependence of the specimens steady-state potential on c is determined and its decrease is related to an abrupt increase in the anodic current at the passivation potentials.Translated from Elektrokhimiya, Vol. 41, No. 3, 2005, pp. 371–374.Original Russian Text Copyright © 2005 by Ivashkin.     

Preparation of high surface area ZrO2 and ZrO2-Y2O3 from the alkoxide

In order to obtain a catalyst support with a high surface area, ZrO₂ and ZrO₂-Y₂O₃ were prepared by the hydrolytic decomposition of the corresponding isopropoxide dissolved in benzene. The hydrolysis was carried out at 80°C using an excess amount of distilled water in flowing dry nitrogen. The precipitates thus obtained were dried at 100°C followed by calcination at 500°C in air or nitrogen for 1 h. The specific surface areas for both of the ZrO₂ and ZrO₂-Y₂O₃ increased with increasing amount of water added for hydrolysis, and the surface areas for ZrO₂-Y₂O₃ increased with increasing yttrium content. A ZrO₂ having a surface area of 130 m²/g was produced, and a stabilized tetragonal ZrO₂ with 15 mol% Y³⁺ having a surface area of 200 m²/g was produced. Furthermore, despite the difference in the ZrO₂ and ZrO₂-Y₂O₃ crystal structures, the lattice-strain of ZrO₂ has been unequivocally related to the surface area.     

Liquid crystal alignment on a ZrO2 thin film as a function of ion beam incident angle

Nematic liquid crystal alignment capabilities and electro-optical performance characteristics have first been embodied in a ZrO₂ layer using ion-beam irradiation. The study demonstrates that liquid crystal layers can be aligned homogeneously as a function of the incident angle of the ion beam device, which causes a uniform dense plasma. X-ray photoelectron spectroscopy indicated that full oxidation of the ZrO₂ thin-film surfaces was produced by ion irradiation, shifting the Zr 3d spectra to lower binding energies. In addition, the electro-optical performance characteristics of twisted nematic cells on a ZrO₂ thin-film layer after ion beam irradiation showed similar characteristics to those of a rubbed polyimide cell.     

SAXS study of polymer adsorption on porous ZrO2

The small‐angle X‐ray scattering method (SAXS) has been used for the analysis of polymer adsorption on porous ZrO₂. Particular attention has been paid to the adsorption of polyacrylic acid (PAA) and polyacrylamide (PAM) on the surface of porous ZrO₂. It has been established that the SAXS method determines whether the polymer has penetrated the carrier's pores, and that polymers of low molecular weight create a thin transition layer on the surface of ZrO₂ (understood in the context of a change in the electron density). The creation of this layer is clearly reflected in the run of SAXS curves (Porod's plot). Ruland–Vonk's method has been used to determine the thickness of the transition layer. The results are consistent with those obtained when the viscosity method was used. Copyright © 2003 John Wiley & Sons, Ltd.     

Hydrodechlorination of 4-Chlorophenol on Pd-Fe Catalysts on Mesoporous ZrO2SiO2 Support

A mesoporous support based on silica and zirconia (ZS) was used to prepare monometallic 1 wt% Pd/ZS, 10 wt% Fe/ZS, and bimetallic FePd/ZS catalysts. The catalysts were characterized by TPR-H₂, XRD, SEM-EDS, TEM, AAS, and DRIFT spectroscopy of adsorbed CO after H₂ reduction in situ and tested in hydrodechlorination of environmental pollutant 4-chlorophelol in aqueous solution at 30 °C. The bimetallic catalyst demonstrated an excellent activity, selectivity to phenol and stability in 10 consecutive runs. FePd/ZS has exceptional reducibility due to the high dispersion of palladium and strong interaction between FeOx and palladium, confirmed by TPR-H₂, DRIFT spectroscopy, XRD, and TEM. Its reduction occurs during short-time treatment with hydrogen in an aqueous solution at RT. The Pd/ZS was more resistant to reduction but can be activated by aqueous phenol solution and H₂. The study by DRIFT spectroscopy of CO adsorbed on Pd/ZS reduced in harsh (H₂, 330 °C), medium (H₂, 200 °C) and mild conditions (H₂ + aqueous solution of phenol) helped to identify the reasons of the reducing action of phenol solution. It was found that phenol provided fast transformation of Pd⁺ to Pd⁰. Pd/ZS also can serve as an active and stable catalyst for 4-PhCl transformation to phenol after proper reduction.     

阳极氧化物纳米孔道和TiO2纳米管形成机理的研究进展

自组织有序的TiO2纳米管和多孔型阳极氧化膜(PAO)因其潜在的应用价值而倍受关注.阀金属的阳极氧化研究了80多年,但是六棱柱元胞结构和多孔纳米管的形成机理至今尚不清楚.本文不是简单地综述PAO的形成机理,而是从更宽的视角综述了致密型阳极氧化膜与PAO的本质联系和形貌差异.对比两种膜的形貌差异和生长过程有助于孔洞形成本质的认识.简要综述了PAO的传统"场致助溶(FAD)"理论和局限性,重点综述了PAO形成机理的最新研究进展,包括粘性流动模型、阻挡层击穿模型、氧气气泡成孔模型、等电场强度模型等.在充分对比分析最新成果的基础上,对PAO机理研究的发展趋势进行了展望:采用超声氧化、真空或高压条件下氧化以及对电解液中添加碳酸钠或还原剂等方法,对揭示孔洞形成和自组织的本质将会有很大帮助;从电流和阳极氧化效率角度入手,是探究传统FAD理论的物理本质的有效途径.     

负载型纳米ZrO2-Al2O3复合载体中ZrO2的负载量对Ni基催化剂性能的影响

采用真空浸渍法在负载型纳米ZrO2-Al2O3复合载体上负载NiO,并用X射线衍射考察了NiO在复合载体上的分散周值.结果表明,该分散阈值与ZrO2-Al2O3复合载体中ZrO2的负载量有关,当ZrO2的负载量为0.60 g/g时,NiO的分散阈值达到最高值0.315 g/g.热重-微分热重和程序升温脱附结果表明,NiO在不同ZrO2负载量的复合载体表面形成不同的相互作用和分布状态,复合载体中ZrO2的负载量影响催化剂表面活性中心的种类和对CO2的吸附.同时考察了不同ZrO2负载量的复合载体Ni基催化剂在CO2重整CH4反应中的活性和稳定性.     

Ag/ZrO2-NT/Zr hybrid material: A new platform for SERS measurements

In this paper, we present recent results of our attempts to produce nanoporous zirconia, as well as our investigations of a hybrid material consisting of nanoporous zirconia loaded with Ag-nanoparticles, Ag-n/ZrO₂-NT/Zr, which could be used as an active SERS substrate. The Zr-based hybrid material, as our investigations have shown, is an active and stable substrate in SERS investigations aimed at detecting various organic molecules: mercaptobenzoic acid, pyridine and two different dyes – rodhanine derivatives. The SERS spectra for the probe molecules adsorbed on silver nanoparticles on a ZrO₂-NT/Zr platform display characteristic intensity ratios different from those measured on previously studied nanoporous substrates based on Ti and Al, which ensure a different (alternative) interaction between the investigated adsorbate and adsorbent. In order to characterize our new substrate we used high-resolution SEM and surface analytical techniques: XPS (X-ray photoelectron spectroscopy) and SERS (surface enhanced Raman spectroscopy).     

Stress and Moisture-Sorption in Ozone-Annealed Films of Zirconium Oxide Obtained from Sol-Gel

The stress development in zirconium oxide films prepared by sol-gel and annealed under ozone-enriched oxygen has been investigated. The organic compounds are mostly oxidized at 200°C with ozone and the stress rises up to higher values than the stress in films annealed with pure oxygen between 200 to 400°C. During exposure to humid air of films annealed at 150°C under pure or ozone-enriched oxygen chemical transformations of organic compounds have been observed. The moisture-induced stress change during film exposure to the ambient air also has been investigated. The competition between hydration of ZrO₂, H-bound formation, surface ionization and capillary condensation mechanisms is discussed.     

Surface characteristics of anodic oxide films fabricated in acid and neutral electrolytes on Ti–10V–2Fe–3Al alloy

Anodic oxide films were fabricated on Ti–10V–2Fe–3Al alloy in acid (H₂SO₄/H₃PO₄) and neutral environmental friendly (C₄H₄O₆Na₂) electrolytes. The morphology, roughness, crystalline structure of the anodic oxide film were characterized by using scanning electron microscopy, atomic force microscopy, Raman spectroscopy and electrochemical impedance spectroscopy (EIS). The results showed that the oxide film fabricated in H₂SO₄/H₃PO₄ electrolyte had a porous structure and the thickness of the film was 3.5 µm. The oxide film fabricated in C₄H₄O₆Na₂ electrolyte presented a nonporous structure that sustained the evident microstructure of the substrate, and the thickness of the film was 6.0 µm. The surface average roughness values of the two types of films were 245 nm and 166 nm, respectively. The phase of the anodic oxide films consisted mainly of anatase and rutile. EIS results showed that the film fabricated in C₄H₄O₆Na₂ electrolyte had higher impedance of the outer layer, while the film fabricated in H₂SO₄/H₃PO₄ electrolyte had higher impedance of the inner layer. Moreover, we attempt to explain the differences in the anodizing kinetics, structure and electrochemical impedance of anodic oxide films by the different films growth processes in the two types of electrolytes. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of Copper on Solid Electrolytes (Ce0.8Sm0.2)1 ? xCuxO2 ? δ and Composite Cathodes Based on La0.8Sr0.2MnO3

The phase composition and electroconduction in air of solid electrolytes (Ce_0.8Sm_0.2)_{1 − x} Cu_xO_{2 − δ} (CSCu), where x = 0, 2, 5, 10, and 20 mol % and which are synthesized using the ceramic technology, are studied. Adding an additive of CuO lowers the CSCu sintering temperature by 100– 200°C and leads to the formation of single-phase solid solutions of a fluorite type up to x = 10 mol %. The electroconductivity of the CSCu electrolytes remains practically invariant upon adding up to 5 mol % Cu and equals 0.089–0.095 and 0.017–0.021 S cm⁻¹ at 800 and 600°C. The sintering, adhesion, and electroconductance of composite cathodes based on La_0.8Sr_0.2MnO₃ with 40% CSCu and their electrochemical behavior in air in the temperature interval 900–1000°C on carrying electrolyte Zr^0.9Y_0.1O_1.95 with a CSCu sublayer containing 2 mol % Cu are studied.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 656–661.Original Russian Text Copyright © 2005 by Bogdanovich, Gorelov, Balakireva, Dem’yanenko.     

Phase Transitions,Thermal Desorption of Gases,and Electroconduction in BaCeO<Subscript>3</Subscript>, a Base for High-Temperature Protonic Conductors

Investigations of phase transitions in barium cerate are carried out by methods of dilatometry and differential scanning calorimetry. Thermal desorption of gases and temperature dependences of electroconduction in dry and humid air are studied. Barium cerate exhibits complex polymorphism, undergoing a number of structural conversions at 300– 1300 K. The peaks in the spectra of thermal desorption of CO₂ and H₂O correlate with variations in the crystal lattice. Structural changes in BaCeO₃ affect activation energies for the carrier transport and the shares of partial conductivities.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 620–626.Original Russian Text Copyright © 2005 by Kuz’min, Gorelov, Vaganov, Korzun, Kazantsev, Aksenova, Khromushin.     

Anodic oxidation of foil copper on fiber-glass plastic in sulfate-chloride electrolyte

The effect of the conditions of galvanostatic anodizing of copper foil at fiber-glass plastic on growth kinetic parameters of Cu₂O films is studied. It is shown that the anodic treatment current density in the sulfate-chloride electrolyte features a logarithmic dependence on the electric field strength in the anodic Cu₂O film, which is probably caused by the presence of either a p-n-transition, or an inversion layer of electronic conductivity at the Cu/Cu₂O interface. It is found that the dependence of the film thickness on the formation time at different current densities is nonlinear.