CaO–MgO–SiO2 glass ceramics: Transferred arc plasma (TAP) synthesis and microstructural characterization

In this paper, synthesis of CaO–MgO–SiO₂ glass ceramic using transferred arc plasma (TAP) processing method is illustrated. Homogeneous mixture of 51.6% SiO₂, 35.6% CaO and 12.8% MgO prepared by dry mixing in a ball mill was kept in the anode well (which is the melting bed) of the 10 kW transferred arc plasma torch. It was melted in plasma at an operating power of 5 kW (by varying the processing time for 3, 5 and 8 min). The melt was cooled to solidify by applying forced air on it. The resulting samples were characterized for microstructure and phase composition. The phases were identified by scanning electron microscopy (SEM), using the back-scattered electron (BSE) image mode and X-ray diffraction (XRD) and energy dispersive X-ray analysis (EDX). The microstructure was examined using optical microscopy (OM) and scanning electron microscopy. The micro-hardness, density and porosity measurements for the synthesized samples were carried out. Differential thermal analysis (DTA) was performed to study the thermal evolution. The results show the formation of diopside phase in the transferred arc plasma melted CaO–MgO–SiO₂ glass ceramic system achieved with in a quite considerable short time of plasma processing. The method indicated that TAP technique could be a promising, time saving and one-step manufacturing process for the production of functional bulk glass ceramics.     

Combustion synthesis and photoluminescence of Eu, Dy-doped La2Zr2O7 nanocrystals

A facile and energy saving sol-gel combustion method has been used to prepare La₂Zr₂O₇ nanocrystallines. The pyrochlore La₂Zr₂O₇ nanocrystals have been obtained at a relatively low temperature with the grain size ranging from 45 to 70 nm. Eu³⁺ and Dy³⁺ have been introduced into the La₂Zr₂O₇ crystal structure, respectively, and the intense photoluminescence was observed. The relative intensity of electric dipole transition and magnetic dipole transition is considered for luminescence emission both of Eu³⁺ and Dy³⁺. The dependence of luminescence intensity on dopant concentration and the effect of Dy³⁺ co-doping on Eu³⁺ luminescence are also discussed.     

Superacid Catalyst SO42-/ZrO2-La2O3 Prepared by Ultrasonic Co-precipitation and Low Temperature Aging

低温陈化超声波共沉淀法制得SO₄^2-/ZrO^2-La₂O₃前驱体, 经H₂SO₄处理, 在不同温度下焙烧得到纳米晶催化剂SO₄^2-/ZrO^2-La₂O₃;用Hammett指示剂法测定其酸性. 用XRD、BET、TEM、IR和XPS对样品进行表征,其催化活性用醋酸和甘油的酯化反应进行了评价. 结果表明经超声波搅拌和低温(-15 ºC)陈化,650 ºC焙烧4 h得到的固体超强酸表现出较高催化活性.     

Conductivity behaviour of a cubic/tetragonal phase stabilized nanocrystalline La2O3-ZrO2

La₂O₃ doped nanocrystalline zirconia (ZrO₂) was prepared by chemical co-precipitation method for the 3, 5, 8, 10, 15, 20 and 30 mol.% concentrations of La₂O₃. Structural studies were performed using X-ray diffraction (XRD). All the as-synthesized samples were found to be in monoclinic phase. As-synthesized samples were given heat treatment at higher temperatures for tetragonal/cubic structural phase stabilization. Sintering the samples at temperature 1173 K stabilized the tetragonal and cubic phases. A slight shift in the 100% peak of the cubic phase was observed towards the low diffraction angle indicating the substitution of the bigger La³⁺ ion into the ZrO₂ lattice. Grain sizes were found to lie between 10 and 13 nm. Electrical conductivity studies were performed on the cubic phase stabilized La₂O₃-ZrO₂ by complex impedance spectroscopy. The conductivity increases up to the dopant concentration 10 mol.% and then decreases with further increase in La₂O₃ concentration. Initial increase in conductivity is correlated to the stabilization of the cubic phase and the subsequent decrease in the conductivity with the dopant content is interpreted on the basis of the oxygen-ion movement model. Electrical conductivity has contributions from grain and grain boundary regions. But the grain boundary conductivity is slightly higher than the corresponding grain conductivity. Higher grain boundary conductivity shows higher diffusion coefficient for the atoms on the surface of the ZrO₂ grains. The possible mechanism of the oxygen ion conduction in the La₂O₃ stabilized zirconia (LSZ) is reported. The Barton, Nakajima and Namikawa (BNN) relation has been applied to the conductivity data and found that the d.c. and a.c. conductions have been correlated to each other by the same mechanism.     

Stabilization of a very high-k crystalline ZrO2 phase by post deposition annealing of atomic layer deposited ZrO2/La2O3 dielectrics on germanium

The impact of the ZrO₂/La₂O₃ film thickness ratio and the post deposition annealing in the temperature range between 400 °C and 600 °C on the electrical properties of ultrathin ZrO₂/La₂O₃ high-k dielectrics grown by atomic layer deposition on (1 0 0) germanium is investigated. As-deposited stacks have a relative dielectric constant of 24 which is increased to a value of 35 after annealing at 500 °C due to the stabilization of tetragonal/cubic ZrO₂ phases. This effect depends on the absolute thickness of ZrO₂ within the dielectric stack and is limited due to possible interfacial reactions at the oxide/Ge interface. We show that adequate processing leads to very high-k dielectrics with EOT values below 1 nm, leakage current densities in the range of 0.01 A/cm², and interface trap densities in the range of 2-5 × 10¹² eV⁻¹ cm⁻².     

Er3+及Er3+/Yb3+掺杂ZrO2-Al2O3的制备及发光性质

采用共沉淀法制备了纳米晶ZrO₂-Al₂O₃∶Er³⁺发光粉体.所制备的粉体室温下具有Er3+离子特征荧光发射,主发射在绿光,其中位于547 nm、560 nm的绿光最强,并得出稀土离子与基质之间有能量传递.对不同煅烧温度下的样品研究表明:因不同温度下所制得的样品晶相不同.研究了纳米晶ZrO2-Al2O3∶Er3+及ZrO₂-Al₂O₃∶Er³⁺/Yb³⁺的上转换发光,并分析了上转换的跃迁机制.发现ZrO₂-Al₂O₃∶Er³⁺的绿光为双光子过程,而ZrO₂-Al₂O₃∶Er³⁺、Yb³⁺的上转换光谱中,红光和绿光也为双光子过程,而极弱的蓝光为三光子过程.讨论了Er³⁺的浓度猝灭现象.最适宜掺杂浓度的原子分数为2%（Er³⁺/Zr⁴⁺）.     

Stability of La2O3 and GeO2 passivated Ge surfaces during ALD of ZrO2 high-k dielectric

La₂O₃ grown by atomic layer deposition (ALD) and thermally grown GeO₂ are used to establish effective electrical surface passivations on n-type (1 0 0)-Ge substrates for high-k ZrO₂ dielectrics, grown by ALD at 250 °C substrate temperature. The electrical characterization of MOS capacitors indicates an impact of the Ge-surface passivation on the interfacial trap density and the frequency dependent capacitance in the inversion regime. Lower interface trap densities can be obtained for GeO₂ based passivation even though a chemical decomposition of the oxidation states occur during the ALD of ZrO₂. As a consequence the formation of a ZrGeO_x compound inside the ZrO₂ matrix and a decline of the interfacial GeO₂ are observed. The La₂O₃ passivation provides a stable amorphous lanthanum germanate phase at the Ge interface but also traces of Zr germanate are indicated by X-ray-Photoelectron-Spectroscopy and Transmission-Electron-Microscopy.     

Sintering and characterization of alkaline-earth-doped and zirconium-defficient Na3Zr2Si2PO12

The sintering behavior of Na₃Zr₂Si₂PO₁₂, Na_3.08Zr_1.96X_0.04Si₂PO₁₂ (X = Mg, Ca, Sr, Ba), Na₃Zr_1.5 Si₂PO₁₂, and Na₃Zr_1.3Si₂PO₁₂ was studied between 900 and 1300°C. Microstructural examination indicated that liquid-phase sintering had occurred and that free ZrO₂ was present in all of the samples. X-ray diffraction indicated that the NASICON and ZrO₂ were monoclinic and that doping the Na₃Zr₂Si₂PO₁₂ with 0.02 mole% alkaline-earth ions (compared to the ZrO₂ content) did not significantly increase the unit-cell volume.     

电解等离子体法制备Al2O3陶瓷层及其特性研究

利用电弧喷铝并重熔后进行电解等离子体处理(EPP)的方法在Q235钢基体上制备出呈冶金结 合的Al₂O₃陶瓷层.利用XRD，SEM和EDS等手段对陶瓷层的成分和显 微组织进行了分析， 测定了陶瓷层的耐蚀性能和耐磨性能.实验结果表明，陶瓷层主要由α-Al₂O3，γ-Al₂O₃，θ-Al₂O₃以及一 些非晶相组成，组织致密，耐蚀性能和耐磨性能良好. 关键词： 电解等离子体处理 陶瓷层 复合技术 生长机理     

Preparation and properties of composite ceramic coating containing Al2O3–ZrO2–Y2O3 on AZ91D magnesium alloy by plasma electrolytic oxidation

A composite ceramic coating containing Al₂O₃–ZrO₂–Y₂O₃ was successfully prepared on AZ91D magnesium alloy by plasma electrolytic oxidation (PEO) technique in an alkaline aluminate electrolyte. The morphology, elemental and phase composition, corrosion behavior and thermal stability of the uncoated and coated samples were studied by environmental scanning electron microscopy (ESEM), energy dispersive X-ray spectrometer (EDS), X-ray diffractometer (XRD), electrochemical corrosion test, high temperature oxidation test and thermal shock test. The results showed that the composite ceramic coating was composed of Al₂O₃, c-ZrO₂, t-ZrO₂, Y₂O₃ and some magnesium compounds, such as MgO, MgF₂ and MgAl₂O₄. After PEO treatment, the corrosion potential of AZ91D alloy was increased and the corrosion current density was significantly reduced. Besides, the coated magnesium alloys also showed excellent high temperature oxidation resistance and thermal shock resistance at 500 °C environment.     

Double-ceramic-layer thermal barrier coatings based on La2(Zr0.7Ce0.3)2O7/La2Ce2O7 deposited by electron beam-physical vapor deposition

Double-ceramic-layer (DCL) thermal barrier coatings (TBCs) of La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3) and La₂Ce₂O₇ (LC) were deposited by electron beam-physical vapor deposition (EB-PVD). The composition, interdiffusion, surface and cross-sectional morphologies, cyclic oxidation behavior of DCL coating were studied. Energy dispersive spectroscopy and X-ray diffraction analyses indicate that both LZ7C3 and LC coatings are effectively fabricated by a single LZ7C3 ingot with properly controlling the deposition energy. The chemical compatibility of LC coating and thermally grown oxide (TGO) layer is unstable. LaAlO₃ is formed due to the chemical reaction between LC and Al₂O₃ which is the main composition of TGO layer. Additionally, the thermal cycling behavior of DCL coating is influenced by the interdiffusion of Zr and Ce between LZ7C3 and LC coatings. The failure of DCL coating is a result of the sintering of LZ7C3 coating surface, the chemical incompatibility of LC coating and TGO layer and the abnormal oxidation of bond coat. Since no single material that has been studied so far satisfies all the requirements for high temperature applications, DCL coating is an important development direction of TBCs.     

第一性原理模拟U在Gd2Zr2O7烧绿石中的固溶

采用第一性原理密度泛函理论模拟U在Gd₂Zr₂O₇烧绿石中的固溶,在低浓度U掺杂时,Gd₂Zr₂O₇烧绿石保持烧绿石结构;随着U掺杂浓度增加,Gd₂(Zr_{2-y}U_y)O₇和(Gd_{2-y}U_y)Zr₂O₇体系的晶格常数发生线性变化．计算结果表明,由于总能较低,U原子更偏向于替代无序换位后Gd₂Zr₂O₇晶格中B位的Gd原子．     

Permeation barrier properties of an Al2O3/ZrO2 multilayer deposited by remote plasma atomic layer deposition

We report the permeation barrier properties of Al₂O₃/ZrO₂ multi-layers deposited by remote plasma atomic layer deposition. Electrical Ca degradation tests were performed to derive the water vapor transmission rate (WVTR) of Al₂O₃, ZrO₂ and Al₂O₃/ZrO₂ multi-layers at 50 °C and 50% relative humidity (RH). Al₂O₃/ZrO₂ multi-layers exhibit better barrier properties than Al₂O₃ and ZrO₂ layers, and when more individual layers were deposited in the same total thickness, the WVTR value was reduced further, indicating a better barrier property. The WVTR of the Al₂O₃ and ZrO₂ layers were 9.5 × 10⁻³ and 1.6 × 10⁻² g/m² day, respectively, but when deposited alternatively with 1 cycle of each layer, the WVTR decreased to 9.9 × 10⁻⁴ g/m² day. X-ray diffraction results indicated that ZrO₂ has a monoclinic structure but Al₂O₃ and Al₂O₃/ZrO₂ multi-layers show an amorphous structure. Cross sectional Al₂O₃/ZrO₂ multi-layer structures and the formation of a ZrAl_xO_y phase are observed by transmission electron microscopy (TEM). X-ray photoelectron spectrometry (XPS) results indicate that Al₂O₃ and ZrO₂ contain 33.7% and 37.8%, respectively, Al–OH and Zr–OH bonding. However, the ZrAl_xO_y phase contained 30.5% Al–OH and Zr–OH bonding. The results of transmittance measurement indicate that overall, Al₂O₃, ZrO₂ and Al₂O₃/ZrO₂ multi-layers show high transmittance greater than 80% in the visible region.     

High temperature ferromagnetism in cubic Mn-doped ZrO2 thin films

Theory has predicted that high temperature ferromagnetism (FM) should be found in cubic fake-diamonds, Mn-doped ZrO₂. Experimentally, it is shown that Mn-doped ZrO₂ ceramics are not ferromagnetic, but the nanosized Mn-doped ZrO₂ thin films grown on LaAlO₃ substrates can be ferromagnets with T_C above 400 K. The largest saturated magnetic moment (M_s) is huge as of about 230 emu/cm³ for the Mn_0.05Zr_0.95O₂ films, and it decreases as the Mn content increases. The intrinsic FM is strongly associated with the cubic structure of Mn-doped ZrO₂, and the Mn–Mn interactions via oxygen intermediates are important. No electrical conductivity is observed. Mn-doped ZrO₂ thin films can be truly considered as excellent candidates for spintronic applications.     

Microstructure and electrical properties of Ba0.5Sr0.5TiO3 thin films prepared on copper foils with La2O3 buffer layers

Ba_0.5Sr_0.5TiO₃ (BST) thin films were deposited on copper foils via sol-gel method with La₂O₃ as a buffer layer. The films were processed in almost inert atmosphere so that the substrate oxidation was avoided while allowing the perovskite film phase to crystallize. The existence of a La₂O₃ buffer layer between the BST thin film and Cu foil improved the dielectric constant and reduced the leakage current density of the BST thin film. Meanwhile, the BST thin film exhibited ferroelectric character at room temperature, which was contrast to the para-electric behavior of the film without the buffer layer. Effects of La₂O₃ buffer layer on the crystallizability and microstructure of BST thin films were also investigated.     

Transport properties and magnetoresistance in La0.8Te0.2MnO3/ZrO2 composites

The transport properties and magnetoresistance of electron-doped manganate / insulator composites (La_0.8Te_0.2MnO₃)_{1 - x}/(ZrO₂)_x (x=0, 0.3, and 0.5) are investigated. It is found that the metal-insulator transition temperature of this system shifts to a lower value as the ZrO₂ content increases. The introduction of ZrO₂ enhances both the domain scattering and electron relative scattering in the metal transport region. In the adiabatic small polaron hopping transport region, the thermal activation energy seems invariable regardless of the ZrO₂ content. The application of a magnetic field promotes the charge transportation capabilities of the composites, and the magnetoresistance is enhanced with an increase of the ZrO₂ content. This could be attributed to the more remarkable modification effect of magnetic field on ordering degree in the composites than in pure La_0.8Te_0.2MnO₃.     

Experimental and Theoretical Study of Hydrogen Atom Abstraction from C2H6 and C4H10 by Zirconium Oxide Clusters Anions

使用配有团簇产生和化学反应源的飞行时间质谱装置,研究了锆氧阴离子团簇Zr_xOy^-与乙烷和丁烷的反应. 在反应中发现了Zr₂O₅H^-和Zr₃O₇H^-产物. 用密度泛函理论研究了乙烷在Zr₂O₅^-上的反应通道,发现乙烷脱氢反应可以发生,从而证明观察到的产物是源于脱氢反应. 该工作揭示了锆氧负离子团簇与烷烃反应中的新通道.     

La2O3对Yb:Y2O3透明陶瓷光谱性能的影响

研究了La₂O₃对Yb：Y₂O₃透明陶瓷光谱性能的影响，添加适量La₂O₃以后，Yb：Y₂O₃透明陶瓷的吸收峰和发射峰的位置不变，但由于La³⁺的离子半径大于Y³⁺的离子半径，在Y₂O₃中引入La³⁺离子后，导致Y₂O₃晶格常数变大，晶场强度变弱，同时降低了Y₂O₃晶体的有序度，致使发射峰强度有所下降，发射截面变小.过量的La₂O₃（x=0.16）造成Yb³⁺激活离子发射强度明显下降；其荧光寿命在添加La₂O₃后总体增大45%—60%. 关键词： 氧化镧 氧化钇 透明陶瓷 光谱性能     

Possible anisotropy gap in La1.35Sr1.65Mn2O7 and La1.5Sr0.5NiO4 detected through specific heat and magnetization measurements

Magnetization and specific heat measurements, as a function of temperature, were performed on single crystals of La_1.35Sr_1.65Mn₂O₇ and La_1.5Sr_0.5NiO₄, under different applied magnetic fields (H). The specific heat in La_1.35Sr_1.65Mn₂O₇ was decreased for H=9 T parallel to the crystal c axis, compared with H=0, possibly due to a suppression of spin-wave excitations (magnons) in that ferromagnetic bilayer structure. On the other hand, the applied magnetic field had no effect in the specific heat of the antiferromagnetic La_1.5Sr_0.5NiO₄. For H=9 T and below the temperature of 4 K the specific heat data, for each crystal, was well fitted by an exponential decay law. This allowed the calculation of energy gaps around 1 meV for both compounds, in close agreement with Δ=2μ_BH for an expected energy gap in the magnon spectrum. Detailed magnetization measurements showed monotonic variations below 4 K and a steep increase close to 2 K. Both magnetization and specific heat measurements suggest the existence of an anisotropy gap in the energy spectrum of La_1.35Sr_1.65Mn₂O₇ and La_1.5Sr_0.5NiO₄.