脱氧La0.5Ca0.5MnO3样品的铁磁-反铁磁转变和电阻率变化

研究了氧空位对La_0.5Ca_0.5MnO₃ （LCMO）多晶块材的电输运和磁性质的影响. 随着氧空位的增加, 样品在高温段的电阻率一直增加, 并满足绝热小极化子模型, 而低温段的电阻率先下降后上升, 并出现明显的dR/dT>0的行为, 直至最后变为绝缘的. 氧空位的增加抑止了反铁磁相的出现, 使得脱氧的LCMO样品不发生反铁磁转变, 进一步增加氧空位则会抑制铁磁相. 关键词： 0.5Ca_0.5MnO₃')" href="#">La_0.5Ca_0.5MnO₃ 反铁磁相变 铁磁相变 脱氧     

Na0.25K0.25Bi0.5TiO3无铅压电陶瓷的介电特性研究

用固相反应法制备了Na_0.25K_0.25Bi_0.5TiO₃ (NKBT50)陶瓷，研究了该陶瓷在室温至400℃温度范围内的介电性能.发现该陶瓷的介电温谱与烧结气氛、极化状态有关.在空气中烧结的未极化样品在70℃附近存在介电和损耗峰，而极化后及在氧气氛中烧结的样品并不存在该介电、损耗峰.分析认为70℃的介电和损耗峰与氧空位形成的缺陷偶极子的极化弛豫有关.热激电流显示，陶瓷的去极化温度为225℃，与此相对应的介电、损耗峰也 关键词： 介电性能 氧空位 极化弛豫 钛酸铋钠钾     

Glassy-ferromagnetic behavior in Eu0.5Sr0.5CoO3

Polycrystalline perovskite cobalt oxide Eu_0.5Sr_0.5CoO₃ was prepared by the conventional solid-state reaction method. X-ray powder patterns indicated the prepared samples are pure, cubic perovskite structure (Pm3?m), and with no evidence of any secondary phases. The dc magnetization and ac susceptibility measurements were carried out to investigate the magnetic properties of the sample, and which indicated that cluster-glasses properties are suppressed with the increasing of the coercive field. We denied the possibility of spin-glasses and the existence of the Hopkinson effect in Eu_0.5Sr_0.5CoO₃ through the temperature-dependent ac susceptibility measurements, and explained the magnetic behavior of Eu_0.5Sr_0.5CoO₃ with the competition between magnetic anisotropy and the external magnetic field.     

Preparation of LiNi0.5Mn0.5O2 cathode materials by urea hydrolysis coprecipitation

Layered LiNi_0.5Mn_0.5O₂ has been successfully synthesized via urea hydrolysis coprecipitation method. Well-crystallized LiNi_0.5Mn_0.5O₂ was obtained after calcinations of coprecipitation precursors and lithium salts at 450 °C for 3 h and following 900 °C for 10 h in air. Both the precursors and LiNi_0.5Mn_0.5O₂ powders show an agglomerated secondary structure with crystalline particles inside. The quasi-spherical morphology of the precursors was maintained during the calcinations. The first charge and discharge capacities of as-prepared LiNi_0.5Mn_0.5O₂ were 200 and 165mAh/g respectively. The discharge capacity of about 160mAh/g was retained after 10cycles for as-prepared samples.     

0.5NdAlO3-0.5CaTiO3电子结构及光学性质的第一性原理计算

采用基于第一性原理密度泛函理论的平面波赝势方法,对0.5NdAlO₃-0.5CaTiO₃晶体进行结构优化,并对其能带结构,态密度和光学性质进行了理论计算.结构优化后晶格参数与实验数据相符合,误差小于1%;能带计算结果表明0.5NdAlO₃-0.5CaTiO₃为间接带隙,带隙值为0.52eV;费米面附近的能带由Nd-4f,O-2p,Nd-4p,Al-3p,Ti-4d层的电子态密度确定.同时也计算了该结构的介电函数,反射率和复折射率等光学性质.     

First-principle study of electronic structure and stability of Sn0.5Sb0.5O2

A theoretical study on Sb-doped SnO₂ has been carried out by means of periodic density functional theory (DFT) at generalized gradient approximation (GGA) level. Stability and conductivity analyses were performed based on the formation energy and electronic structures. The results show that Sn_0.5Sb_0.5O₂ solid solution is stable because the formation energy of Sn_0.5Sb_0.5O₂ is −0.06 eV. The calculated energy band structure and density of states showed that the band gap of SnO₂ narrowed due to the presence of the Sb impurity energy levels in the bottom of the conduction band, namely there is Sb 5s distribution of electronic states from the Fermi level to the bottom of conduction band after the doping of antimony. The studies provide a theoretical basis to the development and application of Sn_1−xSb_xO₂ solid solution electrode.     

Effect of calcination temperature on the structure and hydroxylation activity of Ni0.5Cu0.5Fe2O4 nanoparticles

Nanocrystalline Ni_0.5Cu_0.5Fe₂O₄ was synthesized by sol-gel method with varying calcination temperature over the range of 500-1000. The powders obtained were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). In addition, thermal analysis (TG-DTG-DTA) of the precursor was carried out. The study reveals the simultaneous decomposition and ferritization process at rather low temperature (280-350). For the crystalline structure investigated, single cubic spinel is gained when the precursor was decomposed at 800-1000, whereas separated crystal CuO formed when calcination temperature is below 800. The increase of calcination temperature favors the appearance of Fe_B³⁺, Cu_A²⁺ and O on the spinel surface. The hydroxylation activity is relative to the amount of Cu_B²⁺ species on the spinel surface. The lattice oxygen species on the spinel surface are favorable for the deep oxidation of phenol.     

Site occupation of doping La3+ cations and phase transition in Na0.5Bi0.5TiO3–BaTiO3 solid solution

The effects of La doping on the ferroelectric properties of 0.92Na0.5Bi0.5TiO3-0.08BaTiO3(NBT-BT) solid solution have been studied both experimentally and theoretically.The experimental results show that an abnormal ferro-toantiferroelectric phase transition is induced by La doping in NBT-BT.The first-principles calculations indicate that La3+ cations selectively substitute for the A site in NBT-BT as donors.Furthermore,the computed binding energy reveals that La cations is most likely to substitute Ba 2+or Na+,not Bi3+,at A site as donors in NBT-BT,as supported by our Raman spectra.The ferro-to-antiferroelectric phase transition of La-doped NBT-BT is believed to originate from the lattice aberrance and redistribution of valence electrons,thus strengthening the bonding of A-O,enhancing the hybridization between the A cation d orbital and O 2p orbital,and resulting in the deflection of the polar direction of NBT-BT lattice.     

Influence of epitaxial growth on phase competition in Pr0.5Sr0.5MnO3 films

A series of Pr_0.5Sr_0.5MnO₃ (PSMO) films with various thickness were epitaxially grown on substrates of (0 0 1)-oriented (LaAlO₃)_0.3(SrAl_0.5Ta_0.5O₃)_0.7 (LSAT), LaAlO₃ (LAO) and SrTiO₃ (STO), and (0 1 1)-oriented STO using pulse laser deposition. Influence of epitaxial growth on phase competition was investigated. A ferromagnetic metal to antiferromagnetic insulator (FMM-AFI) transition upon cooling is present in both largely compressed situations deposited on LAO (0 0 1) and tensile cases deposited on STO (0 0 1) but absent in little strained films grown on LSAT (0 0 1), indicating that the antiferromagnetic insulating state is favored by strains. On the other hand, the 400 nm films deposited on (0 1 1)-oriented STO as well as LAO substrates show FMM-AFI transition. These results reveal that both the orientation of epitaxial growth and substrate-induced strain affect the FMM-AFI transition.     

阳离子空位和吸附氧的协同作用对Na0.5Bi0.5TiO3(100)表面磁性影响的第一性原理研究

The combination effect of cation vacancies and O₂ adsorption on ferromagnetism of Na_0.5Bi_0.5TiO₃(100) surface is studied by using density functional theory.An ideal Na_0.5Bi_0.5TiO₃(100) surface is non-magnetic and the cation vacancy could induce the magnetism.By comparing the formation energies for Na,Bi and Ti vacancy,the Na vacancy is more stable than the others.Therefore,we focus on the configuration and electric structure for the system of O₂ molecule adsorption on the Na_0.5Bi_0.5TiO₃(100) surface with a Na vacancy.Among the five physisorption configurations we considered,the most likely adsorption position is Na vacancy.The O₂ adsorption enhances the magnetism of the system.The contribution of spin polarization is mainly from the O 2p orbitals.The characteristics of exchange coupling are also calculated,which show that the ferromagnetic coupling is favorable.Compared with the previous calculation results,our calculations could explain the room-temperature ferromagnetism of Na_0.5Bi_0.5TiO₃ nanocrytalline powders more reasonably,because of taking into account adsorbed oxygen and cation vacancies.Moreover,our results also show that adsorption of O₂ molecule as well as introduction of cation vacancies may be a promising approach to improve multiferroic materials.     

A位等价与非等价取代对(K0.5Na0.5)NbO3陶瓷极化的影响

研究了在铌酸钾钠基陶瓷中,A位等价与非等价取代对陶瓷极化温度和极化电场的影响,结果表明:A位等价取代的陶瓷对极化温度和极化电场没有强烈依赖性,可以使极化足够充分,能有效提高铌酸钾钠基陶瓷的压电性能;相反,A位非等价取代的陶瓷对极化温度和极化电场敏感,容易击穿,极化不充分,限制了铌酸钾钠基陶瓷的压电性能. 关键词： 铌酸钾钠 极化 压电     

NbTi0.5Ni0.5O4 as anode compound material for SOFCs

NbTi_0.5Ni_0.5O₄ (NTNO) has been prepared using solid state synthesis and investigated as a potential anode material. The oxide form of NTNO has single phase rutile-type structure with tetragonal (P42/mnm) space group. The reduced form is a composite of nano-scaled particles of metallic Ni and Nb_1.33Ti_0.67O₄ phase. Reduced NTNO showed high electronic conductivity up to 280 S.cm^− 1 at 900 °C in reducing atmosphere, but suffers from low CTE equal to 3.78 10^− 6 K^− 1. Studies of NTNO as anode material were carried out in a three electrode - electrochemical half cell configuration under pure humidified H₂ at 900 °C using a 2 mm thick zirconia electrolyte and without any additional current collector material. The results show a reasonable series resistance (R_s) equal to 2.7 Ωcm² (about 50% higher than for metallic gold layers) indicating a good current collection performance for a 10 μm layer of material. The polarization resistance (R_p) was equal to 33 Ωcm² and is attributed to a poor density of three phase boundaries (TPB) and shortage of oxide ion conduction in the anode layer. The results show the potential of NTNO as an anode material, especially after optimization of the microstructure towards the increase of TPB length.     

Effects of A-site non-stoichiometry on the structural and electrical properties of 0.96K0.5Na0.5NbO3- 0.04LiSbO3 lead-free piezoelectric ceramics

Effects of A-site non-stoichiometry on the structural and electrical properties of 0.96K0.5+xNa0.5+xNbO3- 0.04LiSbO3 lead-free piezoelectric ceramics were examined for 0 ≤ x ≤ 0.02. The piezoelectric coefficients exhibited a maximum, d33 = 187 pC/N at x = 0.0075, coinciding with the maximum of the grain size and the apparent density at x = 0.0075. The apparent density and the piezoelectric coefficients decreased with increasing x at higher x which was likely due to the crystal geometrical distortion of 0.96K0.5+xNa0.5+xNbO3-0.04LiSbO3. In addition, super-large grains were found and this may be due to liquid phase sintering. Excess (K++Na+) attracted a sum of space charges to keep the charge neutral, resulting in charge leakage during the course of ceramic polarization, influencing the piezoelectric and ferroelectric properties. These findings are of importance for guiding the design of K0.5Na0.5NbO3-based lead-free ceramics with enhanced electrical properties.     

Synthesis of nanocrystalline Zn0.5Mn0.5Fe2O4 via in situ polymerization technique

Nanocrystalline Zn_0.5Mn_0.5Fe₂O₄ was synthesized through the pyrolysis of polyacrylate salt precursors prepared via in situ polymerization of the metal salts and acrylic acid. The pyrolysis behavior of the polymeric precursors was studied by use of thermal analysis. The as-obtained product was characterized by powder X-ray diffraction (XRD), transmission electron microscope (TEM), electron diffraction (ED) pattern, scanning electron microscopy (SEM) and electron dispersive X-ray (EDX) analysis. The results revealed that the particle size is in the range of 15–25 nm for Zn-Mn ferrites with good crystallinity. Magnetic properties of the sample at 300 K were measured using a vibrating sample magnetometer, which showed that the sample exhibited characteristics of superparamagnetism.     

立方(Ba0.5Sr0.5)TiO3高压诱导带隙变化的第一性原理研究

采用基于密度泛函理论(DFT)的第一性原理计算研究了 (Ba_0.5Sr_0.5)TiO₃ (BST) 晶体在高压下的电子结构及能带变化行为. 研究结果发现,随着压强的增加,BST能带间隙先增加,在压强为55 GPa时达到最大值,然后减小,这些有趣的结果将有助于开发与设计新的BST铁电器件. 进一步地,通过电子态密度和密度分布图的研究分析可知:在低压区域(055 GPa),则是出现的离域现象占主导(电子的离域作用超过键态的作用),从而使带隙减小. 关键词： 钛酸锶钡 第一性原理 高压 能带间隙     

Improving microwave dielectric properties of La2.98/3Sr0.01(Mg0.5Sn0.5)O3 ceramics with CuO additive

The microwave dielectric properties of CuO-doped La_2.98/3Sr_0.01(Mg_0.5Sn_0.5)O₃ ceramics were investigated with a view to their application in microwave devices. CuO-doped La_2.98/3Sr_0.01(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method. The X-ray diffraction patterns of CuO-doped La_2.98/3Sr_0.01(Mg_0.5Sn_0.5)O₃ ceramics exhibited no significant variation of phase with sintering temperature. By adding 0.75 wt.% CuO, a dielectric constant of 20.07, a quality factor (Q × f) of 63,000 GHz, and a temperature coefficient of resonant frequency τ_f (−77.0 ppm/°C) were obtained when La_2.98/3Sr_0.01(Mg_0.5Sn_0.5)O₃ ceramics were sintered at 1500 °C for 4 h.     

Magnetotransport properties of epitaxial Pr0.5Ca0.5MnO3 films grown by a solution technique

Epitaxial Pr_0.5Ca_0.5MnO₃ films have been synthesized on (0 0 1) SrTiO₃ substrate using a chemical solution deposition technique and two-step post-annealing process. The zero field resistivity of the films shows semiconducting behavior and a characteristic of charge ordering is observed at 230 K. The resistivity of the 10 nm film did not show any effect with the magnetic field. However, melting of charge ordering was observed for the 120 nm film at an applied magnetic field of 4 T. Large decrease in the resistivity of the 120 nm film (<100 K) resulted in magnetoresistance of nearly −100% at 75 K.     

Dielectric properties and relaxation behavior of [TMA]2Zn0.5Cu0.5Cl4 compound

The [TMA]₂Zn_0.5Cu_0.5Cl₄ hybrid material was prepared and its dielectric spectra were measured in the 10⁻¹ Hz-10⁶ Hz frequency range and 200-305 K temperature interval. The dielectric permittivity showed a ferroelectric-paraelectric phase transition at 293 K. Double relaxation peaks are observed in the imaginary part of the electrical modulus, suggesting the presence of grain and grain boundary in the sample. The frequency dependent conductivity was interpreted in term of Jonscher's law: σ(ω)=σ_dc+Aωⁿ. The temperature dependent of the dc conductivity (σ_dc) was well described by the Arrhenius equation: σ_dcT=σ_o×exp(−E_a/kT).     

Transverse laser induced thermoelectric voltage effect in tilted La0.5Sr0.5CoO3 thin films

The transverse laser induced thermoelectric voltage effect has been investigated in tilted La_0.5Sr_0.5CoO₃ thin films grown on vicinal cut LaAlO₃ (1 0 0) substrates when films are irradiated by pulse laser at room temperature. The detected voltage signals are demonstrated to originate from the transverse Seebeck effect as the linear dependence of voltage on tilted angle in the range of small tilted angle. The Seebeck coefficient anisotropy ΔS of 0.03 μV/K at room temperature is calculated and its distorted cubic structure is thought to be responsible for this. Films grown on a series of substrates with different tilted angles show the optimum angle of 19.8° for the maximum voltage. Film thickness dependence of voltage has also been studied.     

Microstructures and microwave dielectric properties of La1-xBx(Mg0.5Sn0.5)O3 ceramics

The microwave dielectric properties of La_1-xB_x(Mg_0.5Sn_0.5)O₃ ceramics were examined with a view to their exploitation for mobile communication. The La_1-xB_x(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the La_0.995B_0.005(Mg_0.5Sn_0.5)O₃ ceramics revealed no significant variation of phase with sintering temperatures. A maximum apparent density of 6.58 g/cm³, a dielectric constant (ε_r) of 19.8, a quality factor (Q × f) of 41,800 GHz, and a temperature coefficient of resonant frequency (τ_f) of −86 ppm/°C were obtained for La_0.995B_0.005(Mg_0.5Sn_0.5)O₃ ceramics that were sintered at 1500 °C for 4 h.