High temperature resistivity characteristics of nonstoichiometric V2O3

The resistivity anomaly encountered in stoichiometric V₂O₃ is gradually suppressed with increasing density of cation vacancies. These observations are discussed in terms of related findings reported in the literature. Research supported by NSF-MRL Grant DMR 77-23798.     

Dielectric properties of NaF-B2O3 glasses doped with certain transition metal ions

Dielectric constant ε, loss tan δ, a.c. conductivity Σ and dielectric breakdown strength of NaF-B₂O₃ glasses doped with certain transition metal ions (viz. Cu²⁺, VO²⁺, Ti⁴⁺ and Mn⁴⁺) are studied in the frequency range 10²-10⁷ Hz and in the temperature range 30–250°C. The values of ε, tan δ, Σ_a.c. are found to be the highest for Cu²⁺ doped glasses and the lowest for Mn⁴⁺ doped glasses. Activation energy for a.c. conduction and the value of dielectric breakdown strength are found to be the lowest for Cu²⁺ doped glasses and the highest for Mn⁴⁺ doped glasses. With the help of infrared spectra, increase in the values of ε and tan δ of these glasses with frequency and temperature are identified with space charge polarization. An attempt has been made to explain a.c. conduction phenomenon on the basis of quantum mechanical tunneling model (QMT)/carrier barrier hopping model.     

NH4Zr2V3O12 proton conductor

NH₄Zr₂V₃O₁₂, a new proton conductor, has been synthesized by flux, melt and hydrothermal methods. The crystals were subjected to X-ray diffraction, differential thermal analysis, infrared spectroscopy and impedance measurements.     

Acoustic investigations on PbO-Al2O3-B2O3 glasses doped with certain rare earth ions

Elastic moduli (Y, η), Poisson’s ratio (σ), microhardness (H) and some thermodynamical parameters such as Debye temperature (θ_D), diffusion constant (D _i),latent heat of melting (ΔH _m) etc of PbO-Al₂O₃-B₂O₃ glasses doped with rare earth ions viz. Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Er³⁺ and Yb³⁺, are studied as functions of temperatures (in the temperature range 30–200°C) by ultrasonic techniques. All these parameters are found to increase with increasing atomic numberZ of the rare earth ions and found to decrease with increasing temperature of measurement. From these results (together with IR spectra of these glasses), an attempt is made to throw some light on the mechanical strength of these glasses.     

Synthesis and characterization of β type solid solution in the binary system of Bi2O3-Eu2O3

We have investigated Bi₂O₃-Eu₂O₃ binary system by doping with Eu₂O₃ in the composition range from 1 to 10 mole% via solid state reactions and succeeded to stabilize β-Bi₂O₃ phase which is metastable when pure. Stability of β-Bi₂O₃ polymorph was influenced by heat treatment temperature. Tetragonal type solid solution was obtained in 3–6 mole% addition range when annealed at 750°C and the range was 2–7 mole% when annealed at 800°C. We have also carried out investigations on lattice parameters, microstructural properties and elemental compositions of this β type solid solution for each doping ratio. Lattice parameters increased with amount of Eu₂O₃ addition. Our experimental observations strongly suggested that oxygen deficiency type non-stoichiometry is present in doped β type solid solutions.     

Relaxation studies on V2O5-TeO2 glasses using heterogeneous conductor model

The dielectric modulus spectra of glasses in the system V₂O₅-TeO₂ have been studied as a function of frequency in the temperature range 230 to 330K. A heterogeneous conductor model developed recently with the assumption of a sinusoidally varying local conductivity in the conducting phase has been successfully applied to analyse the data in this glass system. The Kohlrausch-Williams-Watts (KWW) stretched exponential function has also been used to fit the measured modulus spectra. The exponentβ is found to be correlated to the conductivity fluctuation in the conducting phase as assumed in the heterogeneous model.     

Dielectric properties of LiF-B2O3 glasses doped with certain rare earth ions

Dielectric constantɛ, loss tanδ and a.c. conductivityσ of LiF-B₂O₃: Ln³⁺ (where Ln=Ce, Pr, Nd and Tb) glasses are studied as functions of frequency (in the range 10²–10⁶ Hz) and temperature (range 30–200°C). The dielectric breakdown strength of these glasses was also determined at room temperature in an air medium. The rate of increase ofɛ and tanδ with temperature decreases with decrease in the ionic radius of RE³⁺ ion whereas the dielectric breakdown strength, the activation energy for a.c. conduction in the high temperature region decreases with increase in the ionic radius of RE³⁺ ion. An attempt has been made to explain the a.c. conduction in these glasses on the basis of quantum mechanical tunnelling (QMT) model.     

Promotional effects of carbon nanotubes on V2O5/TiO2 for NOX removal

A series of V₂O₅/TiO₂-carbon nanotube (CNT) catalysts were synthesized by sol-gel method, and their activities for NO_X removal were compared. A catalytic promotional effect was observed by adding CNTs to V₂O₅/TiO₂. The catalyst V₂O₅/TiO₂-CNTs (10 wt.%) showed an NO_X removal efficiency of 89% at 300 °C under a GHSV of 22,500 h⁻¹. Based on X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, NH₃-temperature-programmed desorption, temperature-programmed reduction, Brunauer-Emmett-Teller surface area measurements, differential scanning calorimetry, and thermogravimetric analysis, the increased acidity and reducibility, which could promote NH₃ adsorption and oxidation of NO to NO₂, respectively, contributed to this promotion.     

Preparation and Properties of Al2O3-doping LiNi1/3Co1/3Mn1/3O2 Cathode Materials

LiNi_1/3Co_1/3-xMn_1/3O₂ doped with Al₂O₃ (x = 0%, 2.5%, 5%, 10%) was synthesized by co-precipitation of Ni, Co, and Mn acetates. The influence of Al₂O₃ doping on structure and electrochemical performances of LiNi_1/3Co_1/3Mn_1/3O₂ was studied using X-ray diffraction (XRD) analysis, scanning electron microscopy, charge/discharge tester, and electrochemical workstation. It was found that the materials achieved the best electrochemical properties when x was 5%. The first discharge capacity was 156.3 mAh · g^?1(0.1 C, 2.0–4.8 V), which was close to the un-doped sample (156.8 mAh · g^?1). After 20 cycles, the capacity retention ratios at the C-ratios of 0.1C, 0.2C, and 0.5 C were 96.1%, 94.9%, and 89.4%, respectively, while the capacity retention ratios of the un-doped samples were only 92.6% (0.1 C), 91.8% (0.2 C), and 88.7% (0.5C). The alternating current impedance shows that the charge transfer in the electrode interface was the easiest when x was 5%.     

Electronic and Magnetic Properties of Superconducting Sr4V2Fe2As2O6 Versus Sr4Sc2Fe2As2O6

First principles of FLAPW-GGA calculations have been performed with the purpose to understand the peculiarities of band structure and Fermi surface topology for recently discovered 37 K superconductor: Sr₄V₂Fe₂As₂O₆—in comparison with isostructural phase Sr₄Sc₂Fe₂As₂O₆. Our main finding is that the replacement of Sc with V leads to drastic transformation of electronic, magnetic and conductive properties of these materials: as against non-magnetic Sr₄Sc₂Fe₂As₂O₆ which is formed from non-magnetic conducting [Fe₂As₂] and insulating [Sr₄Sc₂O₆] blocks, Sr₄V₂Fe₂As₂O₆ consists of non-magnetic conducting [Fe₂As₂] blocks and [Sr₄V₂O₆] blocks which exhibit magnetic half-metallic properties.     

Adhesion Properties of Milled CuO-CeO2/γ-Al2O3 on Metallic Substrate for Automotive Catalytic Converter

Adhesion properties of CuO-CeO₂/γ-Al₂O₃ layers on FeCrAl metallic substrate was investigated, where the hybrid preparation method between suspension and sol-gel is further combined with the mechanical milling process of the slurry. Poor coating adhesion was observed when the slurry is vigorously stirred, where the milled powders are agglomerated, and the stirring process hardly reduces the particle size. The combined method was found to significantly improve the adhesion property between the milled CuO-CeO₂ catalytic layer and the γ-Al₂O₃ washcoat, compared with the vigorous stirring of the slurry. The so-called “over-milling” phenomenon was also exhibited, where the elongated large particles are observed after sintering of the longer-milled powders, leading to the lowered adhesion quality.     

Observation of broadband infrared luminescence in a novel Bi-doped P2O5-B2O3-Al2O3 glass

A novel Bi-doped P₂O₅-B₂O₃-Al₂O₃ glass was investigated, and strong broadband NIR (near infrared) luminescence was observed when the sample was excited by 445 nm, 532 nm, 808 nm and 980 nm lasers, respectively. The max FWHM with 312 nm, the lifetime with 580 μs and the σ_emτ product with 5.3 × 10^− 24 cm² s were obtained which indicates that this glass is a promising material for broadband optical amplifier and tunable laser. The effect of the introduction of B₂O₃ on the glass structure and Bi-ions illuminant mechanism were discussed and analyzed. It is suggested that the introduction of B₂O₃ makes the glass structure closer, and the broadband NIR emission derives from Bi⁰:²D_3/2 → ⁴S_3/2 and Bi⁺:³P₁ → ³P₀ transitions.     

Single-Step Synthesis of Sr4V2O6Fe2As2: The Blocking Layer Based Potential Future Superconductor

We report synthesis, structural details and transport measurements on Sr₄V₂O₆Fe₂As₂. Namely, the stoichiometric amounts of V₂O₅+1/2×SrO₂+7/2×Sr+2×FeAs are weighed mixed, ground thoroughly and palletized in rectangular form in a glove box in high purity Ar atmosphere. The pellet is further sealed in an evacuated (10^?5 torr) quartz tube and put for heat treatments at 750 and 1150°C in a single step for 12 and 36 hours respectively. Finally the quartz ampoule is allowed to cool naturally to room temperature. The as-synthesized sample is black in color. The compound crystallized in P4/nmm space group with lattice parameters a=b=3.925 Å and c=15.870 Å. Also seen are some small impurity lines. The compound did not exhibit superconductivity but instead a spin density wave (SDW) like metallic step at around 175 K is seen in R(T) measurements. Principally in [FeAs]^?1{Sr₄V₂O₆}^C[FeAs]^?1 the net value of blocking layer charge C must be either less or more than 2, to let it be electron or hole type superconductor respectively. Efforts are under way to achieve superconductivity in the studied system.     

Evidence for supercooling across a vortex-matter phase transition: studies on CeRU2 and Bi2Sr2CaCu2O8

We present DC magnetization data indicating a first-order phase transition in the vortex state of CeRu₂, with the higher entropy phase exhibiting enhanced pinning. Minor hysteresis loops show evidence of supercooling of the higher entropy phase as the phase boundary is crossed both isothermally as well as at constant field. These features are shown to be absent across the Bragg-glass to vortex-glass transition in Bi₂Sr₂CaCu₂O₈. The supercooling is more persistent in the constant field case.     

Spectroscopic and transport studies of Cu2+ ion doped in (40 —x)Li2O—xLiF—60Bi2O3 glasses

The preparation of (40-x)Li₂O-xLiF-60Bi₂O₃ glassy system and spectroscopic and transport studies of this system are reported. IR results show that this glass consists of [BiO₃] units and indicate formation of Bi-F bonds with the addition of LiF. From the ESR spectra of Cu²⁺ ion, the effectiveg values are found to vary slightly with increasing concentration of fluorine ion. The optical absorption peak corresponding to Cu²⁺ increased linearly with increasing concentration of LiF between 620 nm and 728 nm except at 2.5 mole% of LiF where its value is 729 nm. This peculiar behaviour is attributed to the varying structural coordination of fluorine as the concentration of lithium fluoride is increased. The ionic conductivity measurements indicate that the conduction is due to adiabatic hopping of polarons and the activation energies are found to be temperature and concentration dependent     

Effect of Ni-modified α-Al2O3 prepared by sol–gel and solvothermal methods on the characteristics and catalytic properties of Pd/α-Al2O3 catalysts

In the present study, Ni-modified α-Al₂O₃ with Ni/Al ratios of 0.3 and 0.5 were prepared by sol–gel and solvothermal method and then were impregnated with 0.3 wt.% Pd. Due to different crystallization mechanism of the two preparation methods used, addition of nickel during preparation of α-Al₂O₃ resulted in various species such as NiAl₂O₄, mixed phases between NiAl₂O₄ and α-Al₂O₃, and mixed phases between NiAl₂O₄ and NiO. As revealed by NH₃-temperature programmed desorption, formation of NiAl₂O₄ drastically reduced acidity of alumina, hence lower amounts of coke deposited during acetylene hydrogenation was found for the Ni-modified α-Al₂O₃ supported catalysts. For any given method, ethylene selectivity was improved in the order of Pd/Ni–Al₂O₃-0.5 > Pd/Ni–Al₂O₃-0.3 > Pd/Ni–Al₂O₃-0  Pd/α–Al₂O₃-commercial. When comparing the samples prepared by different techniques, the sol–gel-made samples showed better performances than the solvothermal-derived ones.     

Fe2O3掺杂MgTiO3-CaTiO3微波陶瓷的介电性能研究

采用固相法制备0.93MgTiO3-0.07CaTiO3-xFe_2O_3(摩尔分数x=0.01~0.025)微波介质陶瓷材料,研究添加Fe_2O_3后,体系的晶体结构、显微结构和微波介电性能之间的变化规律。利用XRD、SEM、网络分析仪对样品的相组成、微观结构、介电性能进行测试分析。研究表明:该复合陶瓷样品的致密度、介电常数和Q·f值随Fe_2O_3含量的增加先增大后减小。当x(Fe_2O_3)为0.015,在1290℃烧结4h时,获得最优的介电性能:εr=21.32,Q·f=37448GHz,τf=0.577×10-6/℃。     

Structural and optical properties of spray pyrolytically prepared Fe2O3 thin films

Fe₂O₃ thin film was prepared using aqueous solution of FeCl₃ by spray pyrolysis. The substrate temperature was 450°C. The lattice parametersa andc for different concentrations were calculated from X-ray diffraction study. Hexagonal structure of the Fe₂O₃ thin film was confirmed. Band gap values of Fe₂O₃ prepared from different concentrations were determined from optical transmission data.     

Epitaxial growth and relaxation of γ-Al2O3 on silicon

0.5-10 nm-thick single crystal γ-Al₂O₃ films was epitaxially grown, at high temperature, on Si(001) and Si(111) substrates using electron-beam evaporation techniques. Reflection High Energy Electron Diffraction studies showed that the Al₂O₃ films grow pseudomorphically on Si (100) up to thickness of 2 nm. For higher thicknesses, a cubic to hexagonal surface phase transition occurs. Epitaxial growth and relaxation were also observed for Si(111). The film surfaces are smooth and the oxide-Si interfaces are atomically abrupt without interfacial layers.     

La2O3、Nd2O3、Y2O3对高岭石高温相变动力学的影响

利用综合热分析技术、X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)和扫描电镜(SEM)研究了La_2O_3、Nd_2O_3、Y_2O_3对高岭石高温条件下转变成莫来石过程的作用,并采用Kissinger方程、Ozawa方程以及JMA修正方程(Ⅰ)和(Ⅱ)分析了La_2O_3、Nd_2O_3、Y_2O_3对高岭石高温相变动力学的影响。结果表明:3种稀土氧化物的掺入对高岭石的相变动力学参数产生了影响,相变活化能和频率因子与未掺入稀土氧化物的高岭石相比有所降低,析晶方式则未发生变化,均属于体积晶化。对比掺入3种稀土氧化物的高岭石相变活化能和频率因子可以看出,Y_2O_3对于高岭石高温条件下相变的促进作用最为明显,相变活化能最低。稀土氧化物对于高岭石高温相变产物影响不大,主晶相为莫来石相,次晶相为方石英相,但稀土氧化物的掺入使得方石英相的结晶度明显提高。