Evaluation and use of the Pd | SrCe0.95Yb0.05O3| Pd electrochemical reactor for equilibrium-limited hydrogenation reactions

The current — overpotential characteristics of the H₂ - Pd - SCY interphase have been studied at atmospheric total pressure and temparatures between 400 – 550 °C in the single chamber reactor — cell: Pd | SCY | Pd. The results of I−η measurements indicate that the apparent anodic and cathodic charge tranfer coefficients are equal to: α_a=α_c=0.5. The present results are compared to those obtained with the single — chamber reactor cell: Ag | SCY | Ag. A solid state proton (H⁺) conducting reactor — cell with Pd electrodes was tested for the ammonia synthesis from its elements at atmospheric pressure. At 570 °C, over 75% of the ectrochemically supplied hydrogen was converted into NH₃. The thermodynamic requirement for a high pressure process was eliminated. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Structural,magnetic and XPS studies of Sn0.95Co0.05O2-0.05 and Sn0.95Fe0.05O2-0.05 nanoparticles

Structural, microstructural, X-ray photoemission spectra (XPS) and magnetic properties of transition metal ion [5 mol% of Co (SC5) and Fe (SF5)]-doped SnO₂ nanoparticles have been studied. The SC5 and SF5 nanoparticles were synthesized by a chemical route using polyvinyl alcohol as surfactant. The doped SnO₂ crystallites were found to exhibit a tetragonal rutile structure and the average grains size was measured by the Scherer relation of X-ray diffraction. Transmission electron micrographs showed that the average grain size of SC5 is smaller than SF5. SC5 nanoparticles showed strong ferromagnetic behaviour but SF5 exhibited an F-centre exchange (FCE) mechanism. Temperature-dependent magnetization showed the values of phase transition temperature. XPS confirmed the presence of Sn–O–Co and Sn–O–Fe bonds in these SC5 and SF5 nanoparticles. The oxidation states of Sn, Co and Fe were found to be +4, +2 and +2, respectively, while the core level XPS peaks of Sn 3d, O 1s, Co 2p and Fe 2p were analyzed.     

Structural transitions in La 0.95 Ba 0.05 Mn 0.98 57 Fe 0.02 O 3 under heat treatment

Structural transitions in polycrystalline Ba-doped lanthanum manganite La_0.95Ba_0.05Mn_0.98Fe_0.02O_3?+?δ have been investigated under different cooling conditions after vacuum annealing (fast and slow cooling) by Mössbauer spectroscopy and X-ray diffraction (XRD) analysis. A rhombohedral structure of the synthesized La_0.95Ba_0.05Mn_0.98Fe_0.02O_3?+?δ sample transfers into a mixture of the orthorhombic PnmaI, PnmaII* and PnmaII phases (common space group Pnma) with a stoichiometric oxygen composition under vacuum annealing. The further vacuum annealing leads to fluctuations in a partial relation of the orthorhombic phases on fast cooling. This unusual behavior of the structural transitions are discussed.     

Structural and electrical properties of SrZr0.95Y0.05O3/SrTiO3 superlattices

Superlattice thin films of a perovskite-type oxide proton conductor SrZr_0.95Y_0.05O₃/SrTiO₃ were fabricated and their structural and electrical properties were investigated. X-ray and electron diffraction analysis reveals that the thin films were epitaxially grown on MgO (001) substrate. High-resolution transmission electron microscopy observation shows that the multilayered structure is uniform and that the interfaces between the different layers are of low roughness. Misfit dislocations are found at the interface, having Burgers vectors in direction a[100]. From the local elemental analysis, the interdiffusion of Zr and Ti between layers was not observed, while Mg impurities diffused from the substrate are observed. The in-plane electrical conductivity of the thin films was measured by impedance spectroscopy. The conductivity of the superlattices shows a higher value than a single SrZr_0.95Y_0.05O₃ film. The activation energies of the epitaxial layers show relatively higher value than the corresponding single crystal.     

纳米(Y0.95Eu0.05)2O3及其SiO2气凝胶介孔组装体的制备与光致发光

采用尿素溶胶法合成（Ｙ０．９５Ｅｕ０．０５）２Ｏ３纳米粉,用超临界干燥技术制备了ｎ－（Ｙ０．９５Ｅｕ０．０５）２Ｏ３／ＳｉＯ２气凝胶介孔组装体。结果表明,当Ｙ＾３＋：Ｅｕ＾３＋＝２０：１,均相反应时间为４ｈ,且经６８０℃、４ｈ灼烧热处理后得到的ｎ－（Ｙ０．９５Ｅｕ０．０５）２Ｏ３中,光致发光强度最大（发光峰位于６１２ｎｍ）,以Ｓｉ与２Ｙ摩尔比为１：７的ｎ－（Ｙ０．９５Ｅｕ０．０５）２Ｏ３／ＳｉＯ２气凝胶介孔组装体,经同样条件热６１６ｎｍ）。对产生上述发光强度减弱和峰位红移现象进行讨论。     

Multiferroic and resistive switching behaviors in BiFe0.95Cr0.05O3 thin films deposited on Pt/Ti/SiO2/Si substrates

Multiferroic and resistive switching properties of single-phase polycrystalline perovskite BiFe_0.95Cr_0.05O₃ (BFCO) thin films grown on Pt/Ti/SiO₂/Si substrates by radio-frequency magnetron sputtering were investigated. The BFCO film shows ferroelectric and magnetic properties simultaneously at room temperature, and also exhibits a good piezoelectric property with remanent effective piezoelectric coefficient d _33,f ～55±4 pm/V. An obviously resistive switching behavior was observed in the BFCO thin film at room temperature, which was discussed by the filamentary conduction mechanism associated with the redistribution of oxygen vacancies.     

μSR and Mössbauer studies on semiconducting YBa2(Cu0.95Fe0.05)3O6+δ

μSR and⁵⁷Fe Mössbauer spectroscopy were used to study the magnetic properties of powders ofsemiconducting YBa, (Cu_0.95Fe_0.05)₃O_6+δ using the same sample in the temperature range from 4–300 K. TF and ZF μSR were performed at the BOOM facility at KEK using the pulsed surface beam.     

Structural refinement,optical and ferroelectric properties of microcrystalline Ba(Zr0.05Ti0.95)O3 perovskite

For this study, a microcrystalline Ba(Zr_0.05Ti_0.95)O₃ (BZT) powder was prepared by a high energy ball milling method followed by calcination at 1100 °C for 4 h. The calcined powder was structurally characterized by X-ray diffraction and Rietveld refinement data, which showed that this material has a perovskite-type tetragonal structure with a space group of (P4mmm). The micro-Raman spectrum revealed local lattice distortions due to distorted octahedral [TiO₆] clusters. The temperature and frequency-dependent dielectric study of the BZT ceramic showed normal phase transition behavior. The ferroelectric property was studied by a P–E hysteresis loop. Optical band gap was investigated by ultraviolet–visible (UV–vis) absorption spectroscopy at room temperature. The UV–vis spectrum indicated that the BZT powder has an optical band gap of 3.15 eV.     

Depoling of porous Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3 ferroelectric ceramics under shock wave load

Poled Pb_0.99(Zr_0.95Ti_0.05)_0.98Nb_0.02O₃ ferroelectric ceramics in different porosity depoled under shock wave load. Porosity and material dielectric characteristic effects on the depoling current evolution were discussed. The results showed that under open circuit condition, the dielectric constant of all samples exhibited obvious increase, but as the porosity increased, the dielectric constant decreased. As a result of lower dielectric constant of porous samples during depoling process, the charge-releasing rate is faster than that of dense sample.     

The influence of grain structures on the electrical conductivity of a BaZr0.95Y0.05O3 proton conductor

The grain structure and the electrical conductivity of a Y-doped BaZrO₃ perovskite type proton conductor were investigated in terms of preparation method. Powders of Y-doped BaZrO₃ were prepared using two methods and were sintered at various temperatures and durations. In this study, grain structures showed no effect in regard to the two preparation methods. The samples which were sintered for a relatively long period showed broad grain diameter distributions (GDD). It was also revealed that most of grain boundaries were assigned as random and this trend was not affected by sintering condition. The bulk and grain boundary conductivities of the sample sintered for long period were significantly lower than those of other samples by more than three orders of magnitude. However, this was not related to differences of grain structure and grain boundary characteristics.     

冲击波加载下孔隙率对Pb_(0.99)(Zr_(0.95)Ti_(0.05))_(0.98)Nb_(0.02)O_3铁电陶瓷去极化性能的影响

制备了四种不同孔隙率的Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3铁电陶瓷,并研究了冲击波作用下孔隙率对陶瓷去极化性能的影响.研究表明:短路负载条件下陶瓷的放电波形不随孔隙的加入而改变,均为方波.多孔陶瓷的放电脉冲幅度较低,脉冲宽度较长.释放的电荷量随着孔隙率的增加而减小,与静态电滞回线测试结果一致.多孔陶瓷具有较低的冲击阻抗,改善了与封装介质的阻抗匹配.用Lysne模型拟合了材料在高电阻负载条件下的放电行为,并指出高电阻负载条件下材料的介电常数是静态介电常数的4—5倍,而且材料的介电常数随孔隙率的增加而减小.冲击波通过样品以后,电路的放电时间常数随着孔隙率的增大而增大.随着电阻的增大,样品负载电压增高,材料铁电-反铁电相变受到抑制,电流上升沿变缓,致密陶瓷出现了击穿现象.     

Preparation of cytocompatible luminescent and magnetic nanohybrids based on ZnO, Zn0.95Ni0.05O and core@shell ZnO@Fe2O3 polymer grafted nanoparticles for biomedical imaging

ZnO, Zn_0.95Ni_0.05O and core@shell ZnO@??-Fe₂O₃ nanoparticles (NPs) have been prepared by forced hydrolysis in polyol medium and then coated via the ??grafting from?? approach with poly(sodium-4-styrenesulfonate) and poly(sodium-4-styrenesulfonate?Cco?Csodium methacrylate) in the case of ZnO. The surface-initiated atom transfer radical polymerization occurred from the surface-functionalized NPs with ??-bromoisobutyric acid as initiator. The polymer chains were grown from the surface to yield hybrid NPs with a 1?C3-nm thick organic shell. FT-IR, TGA and electron microscopy evidenced the presence of a polymer layer on the surface of NPs. Magnetic and optical properties of bare and coated NPs have been measured. Eventually, the weak cytotoxicity of coated NPs on human endothelial cell allows considering their potentialities as new tools for nanomedicine and biomedical imaging.     

Influences of Al doping concentration on structural,electrical and optical properties of Zn0.95Ni0.05O powders

Nanocrystalline Zn_0.95−xNi_0.05Al_xO (x = 0.01, 0.02, 0.05 and 0.10) diluted magnetic semiconductors have been synthesized by an auto-combustion method. X-ray diffraction measurements indicate that all Al-doped Zn_0.95Ni_0.05O samples have the pure wurtzite structure. Transmission electron microscope analyses show that the as-synthesized powders are of the size 40–45 nm. High-resolution transmission electron microscope, energy dispersive spectrometer and X-ray photoemission spectroscope analyses indicate that Ni²⁺ and Al³⁺ uniformly substitute Zn²⁺ in the wurtzite structure without forming any secondary phases. The Al doping concentration dependences of cell parameters (a and c), resistance and the ratio of green emission to UV emission have the similar trends.     

Dielectric and piezoelectric properties of the Ba0.92Ca0.08Ti0.95Zr0.05O3 thin films grown on different substrate

Lead free Ba_0.92Ca_0.08Ti_0.95Zr_0.05O₃ (BCZT) thin films were deposited on Pt/Ti/SiO₂/Si and LaNiO₃(LNO)/Pt/Ti/SiO₂/Si substrates by a sol–gel processing technique, respectively. The effects of substrate on structure, dielectric and piezoelectric properties were investigated in detail. The BCZT thin films deposited on LNO/Pt/Ti/SiO₂/Si substrates exhibit (100) orientation, larger grain size and higher dielectric tunability (64%). The BCZT thin films deposited on Pt/Ti/SiO₂/Si exhibit (110) orientation, higher Curie temperature (75 °C), better piezoelectric property (d₃₃ of 50 pm/V) and lower dielectric loss (0.02). The differences in dielectric and piezoelectric properties in the two kinds of oriented BCZT films should be attributed to the difference of structure, in-plane stress and polarization rotation in orientation engineered BCZT films.     

Oxygen vacancy control of electrical,optical, and magnetic properties of Fe0.05Ti0.95O2 epitaxial films

High-quality Fe-doped TiO₂ films are epitaxially grown on MgF₂ substrates by pulsed laser deposition. The x-ray diffraction and Raman spectra prove that they are of pure rutile phase. High-resolution transmission electron microscopy (TEM) further demonstrates that the epitaxial relationship between rutile-phased TiO₂ and MgF₂ substrates is 110 TiO₂₂. The room temperature ferromagnetism is detected by alternative gradient magnetometer. By increasing the ambient oxygen pressure, magnetization shows that it decreases monotonically while absorption edge shows a red shift. The transport property measurement demonstrates a strong correlation between magnetization and carrier concentration. The influence of ambient oxygen pressure on magnetization can be well explained by a modified bound magnetization polarization model.     

Magnetic properties, magnetoresistance, and magnetic-field-induced phase transitions in Tb0.95Bi0.05MnO3 and Eu0.8Ce0.2Mn2O5 multiferroics

This paper reports on a study of the magnetic properties, magnetoresistance, and phase transitions in the semiconducting manganite multiferroics Tb_0.95Bi_0.05MnO₃ and Eu_0.8Ce_0.2Mn₂O₅ whose dielectric properties have been a subject of an earlier study. An analysis of these properties has led us to the conclusion that the above crystals at temperatures T ≥ 180 K undergo phase separation with the formation of a dynamic periodic alternation of quasi-2D layers of manganese ions in different valence states, i.e., charge-induced ferroelectricity. This state exhibits a giant permittivity and ferromagnetism in the layers containing Mn³⁺ and Mn⁴⁺ ions. At low temperatures (T < 100 K), the phase volume is occupied primarily by the dielectric phase. Studies of the magnetic properties and the effect of the magnetic field on the dielectric properties of crystals substantiate the scenario of the formation of a state with giant permittivity put forward by us. At low temperatures, Tb_0.95Bi_0.05MnO₃ exhibits features at the points of phase transitions in pure TbMnO₃. A ferromagnetic moment is observed to exist at all the temperatures covered. At the boundaries of the quasi-2D layers, magnetic-field-induced jumps of the electrical resistivity caused by metamagnetic transitions in the layers with Mn³⁺ and Mn⁴⁺ ions are observed. At temperatures T ≥ 180 K, the electrical resistivity undergoes a periodic variation in a magnetic field which is a manifestation of carrier self-organization. A high magnetic field is capable of shifting the phase transition from 180 K to higher temperatures and inducing additional phase transitions.     

退火温度对Ti0.95Fe0.05O2纳米颗粒结构和磁性的影响

采用溶胶-凝胶工艺制备了磁性Fe掺杂TiO2基稀磁半导体的纳米颗粒,在空气氛围中以不同温度对样品进行退火处理.通过差热/热重综合热分析仪(TG-DTA)、X射线衍射仪(XRD)、拉曼光谱(Raman)分析了纳米颗粒的结构和相变温度.研究发现:退火温度450℃和500℃时样品为锐钛矿结构,在600℃时既有锐钛矿相,又有金...     

Comparative studies on Zn0.95Co0.05O thin films on C- and R-sapphire substrates

Zn0.95Co0.05 O precipitate-free single crystal thin films were synthesized by a dual beam pulsed laser deposition method.The films form a wurtzite structure whose hexagonal axis is perpendicular or parallel to the plane of the surface depending on the C-plane (0001) or R-plane (11 ˉ 20) sapphire substrate.Based on the results of high-resolution transmission electron microscopy and x-ray diffraction,C-plane films show larger lattice mismatch.The films exhibit magnetic and semiconductor properties at room temperature.The coercivity of the film is about 8000 A/m at room temperature.They are soft magnetic materials with small remanent squareness S for both crystal orientations.There is no evidence to show that the anisotropy is fixed to the hexagonal axis (C-axis) for the wurtzite structure.     

Onset of resistive internal interfaces in SrTi0.95Nb0.05O3+δ materials on changing from reducing to oxidising conditions and on cooling

Impedance spectroscopy has been used to investigate the long-term drift of the electrical behaviour of SrTi_0.95Nb_0.05O_3+δ materials. The behavior of dense samples revealed the onset of resistive internal interfaces on cooling below about 950 °C in oxidizing conditions (typically air or N₂). Dense materials repond very slowly to step changes from reducing conditions to air; this was monitored by impedance spectroscopy to separate the contributions of the bulk and of internal interfaces. After an initial stage the resistance of internal interfaces increases slowly and almost linearly with time for up to three weeks. The changes in bulk resistance are smaller, and tend to level out after a smaller time interval, possibly because the reoxidation of the sample is very sluggish. Porous samples show relatively fast reoxidation, and thus a fast increase in bulk resistance. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.