Surface and grain-boundary energies as well as surface mass transport in polycrystalline yttrium oxide

The sessile drop technique has been used to measure the temperature dependence of the contact angle, θ, of the liquid metals Ag and Cu in contact with polycrystalline yttrium oxide (yttria, Y₂O₃) at the temperature range 1,333–1,773 K in Ar/4%H₂ atmosphere. Combination of the experimental results with literature data taken for nonwetted and nonreactive oxide/liquid metal systems permit the calculation of the surface energy of Y₂O₃ as γ_sv (J/m²) = 2.278–0.391 × 10⁻³ T. For the same atmospheric conditions, thermal etching experiments on the grain boundaries intersecting the surface of the polycrystalline ceramic allow to determine the groove angles, ψ, with respect to temperature and time as well as the grain-boundary energy of Y₂O₃ as γ_ss (J/m²) = 1.785–0.306 × 10⁻³ T. Grain-boundary grooving studies on polished surfaces of Y₂O₃ annealed in Ar/4%H₂ atmosphere between 1,553 K and 1,873 K have shown that surface diffusion is the dominant mechanism for the mass transport. The surface diffusion coefficient can be expressed according to the equation D _s (m²/s) = 1.22 × 10⁻³ exp(−343554/RT).     

Hydrothermal synthesis of CeO2 nano-octahedrons

CeO₂ nano-octahedrons were synthesized with a facile hydrothermal synthesis process where Ce(NO₃)₃·6H₂O and urea were used as a cerium resource and mineralizer respectively and no surfactant or template was applied. The effects of synthesis parameters such as reaction temperature, reaction time, as well as the dosages of Ce (NO₃)₃·6H₂O and urea were studied. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analysis were conducted to characterize the crystalline and morphology of the obtained CeO₂ powders. The optimal reaction condition to prepare the CeO₂ of the desired fluorite structure was established. The possible mechanism of synthesis of CeO₂ with a nano-octahedron morphology was illustrated.     

Infrared to visible upconversion luminescence in Er/Yb co-doped CeO2 inverse opal

Infrared to visible upconversion luminescence has been investigated in Er³⁺/Yb³⁺ co-doped CeO₂ inverse opal. Under the excitation of 980 nm diode lasers, visible emissions centered at 525, 547, 561, 660 and 680 nm are observed, which are assigned to the Er³⁺ transitions of ²H_11/2 → ⁴I_15/2 (525 nm), ⁴S_3/2 → ⁴I_15/2 (547, 561 nm), ⁴F_9/2 → ⁴I_15/2 (660 and 680 nm), respectively. The effect of photonic band gap on the upconversion luminescence intensity was also obtained. Additionally, the upconversion luminescence mechanism was studied. The dependence of Er³⁺ upconversion emission intensity on pump power reveals that it is a two-photon excitation process.     

Hydrothermal synthesis of monodisperse CeO2 nanocubes

Monodisperse CeO₂ nanocubes have been fabricated via an acrylamide-assisted hydrothermal route. NH₃ and acrylic acid from the hydrolysis of acrylamide act as OH⁻ provider and capping reagent, respectively. The structure and morphology of the products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), field-emission scanning electron microscopy (FE-SEM) and Fourier transformed infrared (FT-IR). The products have a cubic morphology with a mean size of 200 nm. The possible formation mechanism has been discussed based on the experimental results.     

Novel synthesis of nanocrystalline CeO2 by mechanochemical and water-in-oil microemulsion methods

Nanocrystalline cerium dioxide (CeO₂) had been synthesized by two different methods which were mechanochemical and water-in-oil microemulsion. Effects of synthesis conditions on properties of nanocrystalline cerium dioxide were investigated. X-ray diffraction (XRD) was used to characterize the phase and crystallite size of synthesized cerium dioxide nanoparticles. XRD results showed that face centered cubic CeO₂ nanoparticles with crystallite size in nanometer scale were formed. The crystallinity increased with increasing annealing temperature. The average specific surface area of the particles was probed using gas adsorption-desorption measurements. The average particles size was calculated from the specific surface area and was determined to be 5.2 nm for microemulsion samples and 6.9 nm for mechanochemical samples. These results showed that properties of synthesized cerium dioxide could be tailored by adjusting the synthesis conditions.     

Microstructure of YBCO bulk superconductors with CeO2 addition

The refinement of Y₂BaCuO₅ (Y211) particles by CeO₂ in the single-grain YBa₂Cu₃O₇/Y₂BaCuO₅ (Y123/Y211) bulk superconductors of nominal composition Y_1.5Ba₂Cu₃O_x prepared by top-seeded melt-growth process with Y₂O₃ addition has been studied by polarised light microscopy. It is shown that cerium is active in the Y211 particle refinement when it is solved in the peritectic melt, L_p. Observed growth of Y211 particles during sintering stage is ascribed to higher amount of melt induced by CeO₂ reaction with Y123 phase producing barium cerate and CuO.     

The heterostructured AAO/CeO2 nanosystem fabricated by electrodeposition for charge storage and hydrophobicity

Tilted cathode was adopted to prepare porous anodic alumina membrane (PAAM) during the second aluminum anodic oxidation (AAO). A heterostructured AAO/CeO₂ nanosystem was fabricated by filling CeO₂ into the PAAM by electrochemical deposition. The larger the intersection angle of the cathode, the more the charge storage of the fabricated system. A lower potential scan rate is beneficial to the electrochemical charge storage of the system. With the cathode intersection angle increasing, the hydrophobicity of the AAO/CeO₂ system is greatly improved. As the 40° is the optimum angle, the charge storage and hydrophobicity of the system increase with the increasing cathode intersection angle up to 40°. The AAO/CeO₂ system could be utilized in both charge storage and self-cleaning.     

Nano-sized CeO2 with extra-high surface area and its activity for CO oxidation

Using Cerium chloride octahydrate as a precursor and dodecyl sodium sulfate as a template, nano-sized CeO₂ with extra-high surface area were synthesized by a surfactant-templated method. The highest surface area of the synthesized CeO₂ was 457 m² g⁻¹. Combined with XRD, TEM and BET results, it was found that when the calcination temperature was lower than 600 °C, the particle size of CeO₂ hardly changed while the surface area declined due to the co-action of the sintering and agglomeration of the particles. However, with a high calcination temperature (above 600 °C), the sintering was the mainly reason to the decline of the BET surface area and the rapid growth of the particles size. Moreover, by the test for CO oxidation, it was found that the reactivity of the CeO₂ sample remarkably increased with decreasing particle size, which was due to the fact that smaller particles provided more structural defects.     

Interaction mediated by size differences between Y2BaCuO5 and CeO2 particles in melt-textured YBCO superconductors

The Refining of Y₂BaCuO₅ (Y211) is crucial in the fabrication of YBa₂Cu₃O_x (Y123) bulk superconductors with a high critical current density (J_c) for power engineering applications.In this work, the influence of an addition of Y211 and CeO₂ of different sizes on the Y211 refinement and superconducting properties of melt-textured Y123 superconductors is investigated. Nano-size Y211 and nano-size CeO₂ were prepared by attrition-milling (250 rpm and 2 h). Using mixed powders consisting of 85 wt.% Y123, 15 wt.% Y211, and 1 wt.% CeO₂, Y123 quasi-single crystals were fabricated via a top seed melt-textured growth process. The interaction between Y211 and CeO₂ of different particle sizes was examined in terms of the size, uniformity and density of the Y211 particles that existed in the melt-textured samples. The reaction between the nano-size Y211 and the nano-size CeO₂ was more violent due to the more frequent collisions compared to the other reactions (micro-size Y211/nano-size CeO₂ or micro-size Y211/micro-size CeO₂), resulting in the most effective for refinement of Y211 particles and the best J_c value of 4.2 × 10⁴ (A/cm²) (at 77 K and a zero-field).     

大比表面积、高孔隙率多孔仿生CeO2-CuO光催化剂

以富含多孔结构的纤维素为诱导体,采用浸渍法制备仿生CeO_2-CuO催化材料,通过X射线衍射(XRD)、场发射扫描电子显微镜(SEM)、透射电子显微镜(TEM)、氮气吸附-脱附(N2adsorption-desorption)、紫外-可见漫反射光谱(UV-vis)等分析手段对产物的结构和形貌进行了表征。在可见光条件下,以亚甲基蓝溶液为模拟废水,测试其TOC(Total organic carbon)去除率,并对光催化降解机理进行探讨。实验结果表明所制备的材料颗粒均匀,平均颗粒尺寸在10nm左右,并且含有丰富的介孔结构,其孔径集中分布于5~10nm。由紫外-可见漫反射吸收光谱可知,材料对可见光的吸收程度高于块状氧化铈,从而具有更高的可见光催化活性,光照2.5h后对亚甲基蓝的TOC去除率为90%。     

Characteristics of stacked CuInS2 and CuGaS2 layers as determined by the growth sequence

CuInS₂ and CuGaS₂ thin films have been prepared sequentially from elemental evaporation sources onto conventional soda lime glass substrates heated at 350 °C during the deposition process. The gradient in the structure and composition of the stacked layers has been investigated for the two possible growth sequences. Structural depth profiling and crystallographic phase analysis were performed by grazing incidence X-ray diffraction. The atomic distribution in the films depth was analyzed by X-ray photoelectron spectroscopy combined with sputter etching. Formation of the quaternary compound CuIn_1 − xGa_xS₂, with a high Ga content x > 0.80, has been detected with different distribution depending on the growth sequence.     

Synthesis, structure and exchange bias in Cr2O3/CrO2/Cr2O5 particles

We report on the synthesis, structure and magnetic properties of a novel exchange bias system with Cr₂O₃/CrO₂/Cr₂O₅ interfaces. Chromium oxide particles with mixed chromium valences were prepared by sintering CrO₃ in air. X-ray diffraction patterns show that CrO₃ lost its oxygen gradually with increasing temperature and time through Cr₃O₈, Cr₂O₅, CrO₂, and finally Cr₂O₃ at temperatures above 760 K. X-ray photoelectron spectra indicate a low CrO₂ content and a binding energy of 579.3 eV for Cr 2p_3/2 photoelectrons in Cr₂O₅. Chromium dioxide was found to stably coexist with Cr₂O₃ and Cr₂O₅ in the particles. Magnetic measurements show hysteresis loop shifts in the sample, indicating an exchange bias induced by antiferromagnetic Cr₂O₃/Cr₂O₅ in ferromagnetic CrO₂. An exchange bias of 9 mT at 5 K and a coercivity of 26.3 mT were observed in the chromium oxide particles containing CrO₂.     

碳纤维颗粒增强CeO2/PMMA/PVDF超疏水复合涂层及其耐磨性能

提高耐磨性能是推动仿生超疏水表面走向实际应用的关键挑战之一。设计了二氧化铈微米粒子增强PMMA/PVDF超疏水复合涂层配方,获得了水珠接触角达152°、水珠滚动角为5°的超疏水复合涂层。该涂层经过落砂磨损试验后接触角下降为103°、滚动角增大为20°。采用碳纤维颗粒对CeO2/PMMA/PVDF超疏水复合涂层进行增强,优化配方的接触角达153°、滚动角达到5°。经过相同落砂磨损试验后,增强后的复合涂层水珠接触角能在一定程度磨损后达到140°左右。可见,CeO2/PMMA/PVDF复合涂层具有良好的超疏水性能,碳纤维颗粒增强是提高该涂层耐磨性能的有效方法。     

CeO2掺杂制备Ba0.9Ca0.1Ti1-xSnxO3压电陶瓷的结构及电性能

采用传统的陶瓷烧结技术,通过添加0.15%(摩尔分数)CeO2,在1120℃烧结2h,成功制备了新型无铅压电陶瓷Ba0.9 Ca0.1 Ti1-x Snx O3,并且检测了陶瓷样品的微结构和电性能.XRD显示所有陶瓷样品均具有纯的钙钛矿结构,在室温下为典型的四方相,SEM显示适量添加锡离子可以提高陶瓷致密性.在室温下,锡离子改性的BaTiO3基压电陶瓷在x=0.02处显示了优异的压电、介电和铁电性能(d33=276 pC/N,kp=46%,εr=3678,tanδ=2.4%,Pr=18.2μC/cm2,EC=1.12 kV/mm).这些优异的检测结果证实适当添加锡离子能改善BaT iO3基压电陶瓷的电性能.     

Surface characteristics of parylene-C films in an inductively coupled O2/CF4 gas plasma

In this article, we report the results obtained from a study carried out on the inductively coupled plasma (ICP) etching of poly-monochloro-para-xylylene (parylene-C) thin films using an O₂/CF₄ gas mixture. The effects of adding CF₄ to the O₂ plasma on the etch rates were investigated. As the CF₄ gas fraction increases up to approximately 16%, the polymer etch rate increases in the range of 277-373 nm/min. In this work, the atomic force microscopy (AFM) analysis indicated that the surface roughness was reduced by the addition of CF₄ to the O₂ plasma. Contact angle measurements showed that the surface energy decreases with increasing CF₄ fraction. At the same time, X-ray photoelectron spectroscopy (XPS) demonstrated the increase in the relative F atomic content on the surface.     

A new method for surface modification of TiO2/Al2O3 nanocomposites with enhanced anti-friction properties

In this paper, the TiO₂/Al₂O₃ composite nanoparticles were prepared by a hydrothermal method and in situ modified with acrylic acid. It was found that the mean particle size of modified TiO₂/Al₂O₃ composite nanoparticles was about 80 nm with a uniform distribution by the particle size analysis. The modified TiO₂/Al₂O₃ composite nanoparticles can disperse in lubricating oil homogenously for several weeks. The dispersion stabilization of modified TiO₂/Al₂O₃ composite nanoparticles in lubricating oil was significantly improved in comparison with the as-prepared nanoparticles, which was due to the introduction of grafted polymers by surface modification. The formation of covalent bands was identified by Fourier transform infrared spectrum. Under an optimized concentration of 0.1 wt%, the averaged friction coefficient was reduced by 14.75%, when the modified TiO₂/Al₂O₃ composite nanoparticles were used as lubricating oil additivities.     

First-principles calculations on surface hydroxyl impurities in BaF2

OH⁻ impurities located near the (1 1 1) BaF₂ surface have been studied by using density functional theory (DFT) with hybrid exchange potentials, namely DFT-B3PW. Twenty surface OH⁻ configurations were studied, and the hydroxyls located on the first surface layer are the energetically most favorable configurations. For the (1 1 1) BaF₂ surface atomic layers, the surface hydroxyls lead to a remarkable XY-translation and a dilating effect in the Z-direction, overcoming the surface shrinking effect in the perfect slab. Bond population analysis shows that the surface effect strengthens the covalency of surface OH⁻ impurities. The studies on band structures and density of states (DOS) of the surface OH⁻-impurity systems demonstrate that there are two defect levels induced by OH⁻ impurities. The O p_x and p_y orbitals form two superposed occupied O bands, located above the valence bands (VB), and the H s orbitals do the major contribution to an empty H band, located below the conduction bands (CB). Because of the surface effect, the O bands move downward, toward the VB with respect to these bands in the bulk case, and this leads to narrowing of the VB → O gap and widening of the O → H gap which corresponds to the first optical absorption.     

Synthesis of ordered mesoporous CuO/CeO2 composite via co-nanocasting replication method and its improved reactivity towards hydrogen

Ordered mesoporous CuO/CeO₂ composites with cubic Ia3d or 2-D hexagonal p6mm structure have been synthesized by a co-nanocasting-replication method using mesoporous silica KIT-6 or SBA-15 as hard template. XRD, TEM, N₂-adsorption and H₂-TPR techniques were used for the structural analysis and catalytic activity characterization. The results indicated that the high surface area mesoporous CuO/CeO₂ composites with different amounts of CuO addition were well-crystallized and exhibited much improved reactivity towards hydrogen than pure mesoporous CeO₂, and the CuO/CeO₂ composite with 20 wt.% CuO addition possessed the highest reactivity towards hydrogen. The enhanced H₂-TPR property could be attributed to the synergetic catalytic effects between copper oxide and cerium oxide.     

UV Raman spectroscopic study on the surface phase of ZrO2 modified with Nd2O3

The Nd₂O₃ modified ZrO₂ was synthesized using two methods of co-precipitation (Nd-ZrO₂) and wet impregnation (Nd/ZrO₂). The surface and bulk crystalline phases of Nd₂O₃ modified ZrO₂ were investigated by using UV Raman spectroscopy, visible Raman spectroscopy, and X-ray diffraction (XRD). It is observed that the tetragonal phase in the surface region of Nd-ZrO₂ was not effectively stabilized by Nd₂O₃, as Nd₂O₃ is mainly present in the bulk of Nd-ZrO₂. However, in Nd/ZrO₂, it is found that with the impregnation of 0.5 mol% Nd₂O₃ on ZrO₂, the surface tetragonal phase of Nd/ZrO₂ can be stabilized even after calcination at 700 °C. The UV Raman results indicate that a disordered structure, or intermediate structure, which is involved in the transition from the tetragonal to the cubic phase, is formed at the surface region of Nd/ZrO₂. The formation of the aforementioned intermediate structure inhibits the phase transition from tetragonal to monoclinic in the surface region of Nd/ZrO₂. Furthermore, it is observed that the mixed tetragonal and monoclinic phases in the surface region of ZrO₂ which has been impregnated with Nd₂O₃ can also be stabilized after calcination at 700 °C. This work provides a simple method for controlling the surface phase of ZrO₂ at high temperatures.     

Epitaxial and polycrystalline CuInS2 thin films: A comparison of opto-electronic properties

Epitaxial and polycrystalline thin CuInS₂ (CIS) layers were grown by means of molecular beam epitaxy (MBE) on single crystalline silicon substrates of 4 inch diameter. Photoluminescence (PL) studies were performed to investigate the opto-electronic properties of these layers. For the epitaxial CIS, low-energy-hydrogen implantation leads to the passivation of deep defects and several donor-acceptor (DA) pair recombinations (from 1.034 eV to 1.439 eV) and two free-to-bound (FB) transitions (at 1.436 eV and 1.485 eV) become observable at low temperatures (5 to 100 K). Excitonic luminescence is completely absent for all investigated epitaxial CIS layers. This contrasts sharply with the PL of the polycrystalline films which is dominated by excitonic luminescence (1.527 eV). Also a donor-to-valence band transition at 1.465 eV (BF-1) and one donor-acceptor recombination at 1.435 eV (DA-1) were observed, while luminescence from deep levels is not present at all. Based on these data, a refined defect model for CuInS₂ with two donor and two acceptor states is presented. Under comparable growth conditions, the electronic quality of polycrystalline CIS is superior to epitaxially grown material.