(1-x)K0.48Na0.52NbO3-xBi0.45Nd0.05(Na0.92Li0.08)0.5ZrO3无铅压电陶瓷相结构及压电性能

为了在获得较高压电性能的同时又不大大降低陶瓷的居里温度(T_C), 设计和制备了Bi_0.45Nd_0.05(Na_0.92Li_0.08)_0.5ZrO₃改性的K_0.48Na_0.52NbO₃系无铅压电陶瓷((1-x)KNN-xBNNLZ), 研究了BNNLZ含量对KNN基无铅压电陶瓷相结构和电学性能的影响。研究结果表明, 所有陶瓷样品均具有较高的居里温度T_C(>300℃)。随着BNNLZ含量的增加, 陶瓷的正交-四方相变温度(T_O-T)不断向低温方向移动, 而三方-正交相变温度(T_R-O)不断向高温方向移动, 最终在陶瓷中形成了三方-四方(R-T)共存相, R-T共存相处于0.05<x<0.07范围。BNNLZ的加入引起陶瓷相结构的演化改变导致压电常数(d₃₃ )、介电常数(ε_r )、剩余极化强度 (P_r )和机电耦合系数(k_p )都先增大后减小, 当x=0.06时陶瓷具有最佳压电性能: d₃₃=313 pC/N, k_p=42%, P_r=25.48 μC/cm², ε_r=1353, tanδ=2.5%, T_C=327℃。     

Study of Superconducting State Parameters of Binary Metallic Glasses by Pseudopotential Method

The theoretical calculation of the superconducting state properties (SSP) viz electron–phonon coupling strength λ, Coulomb pseudopotential μ ^*, transition temperature T _C , isotope effect exponent α and effective interaction strength N _O V of 50 binary metallic glasses of simple, non-simple, and transition metals have been carried out using a well-recognized model potential. We have employed here five different types of local field correction functions proposed by Hartree (H), Taylor (T), Ichimaru–Utsumi (IU), Farid et al. (F), and Sarkar et al. (S) to study the exchange and correlation effects on the present investigations. Instead of using Vegard’s law, a pseudo-alloy-atom model (PAA) in the present investigation is proposed and found successful. The present results of the SSP are found to be in qualitative agreement with other such earlier reported data wherever they exist, which confirms the superconducting phase in the metallic glasses.     

Polar nanodomains and relaxor behaviour in (1 − x)Pb(Mg1/3Nb2/3)O3–xPbTiO3 crystals with x = 0.3–0.5

Phase transitions and dielectric properties of the (1 − x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ crystals with x = 0.3–0.5 are studied. The solid solutions in this composition range are shown to be relaxor ferroelectrics. The crystals with low x demonstrate a diffused maximum in the temperature dependences of the dielectric permittivity at T_m. T_m varies with frequency according to the Vogel–Fulcher law. The polarizing microscopy investigations reveal a first-order phase transition from the relaxor phase to the low-temperature ferroelectric phase at T_C, which is several degrees below T_m. The permittivity peak in the crystals with x = 0.5 is sharp, and T_m is equal to T_C and does not depend on frequency, as is typical of the transition from a ferroelectric to an ordinary paraelectric phase. Nevertheless, the relaxor, but not the paraelectric, phase is observed at T > T_m. This conclusion is confirmed by the observation of the temperature behaviour of complex dielectric permittivity at T > T_m, which is typical of relaxors and related to the existence of polar nanodomains.     

Orientation-dependent mobilities from analyses of two-dimensional TiN(111) island decay kinetics

We present a method for the determination of orientation-dependent mobilities Γ_eff(φ) based upon analyses of the detachment-limited coarsening/decay kinetics of equilibrium-shaped two-dimensional islands. An exact analytical expression relating the orientation-dependence of Γ_eff(φ) to that of the anisotropic step energies β(φ) is derived. This provides relative values of Γ_eff(φ) to within an orientation-independent scale factor that is proportional to the decay rate of the island area. Using in situ high temperature (T = 1550–1700 K) low-energy electron microscopy measurements of two-dimensional TiN island coarsening/decay kinetics on TiN(111) terraces for which β(φ) values are known [Phys. Rev. B 67 (2003) 35409], we demonstrate the applicability of our analytic formulation for the determination of absolute Γ_eff(φ) values.     

Superconducting state parameters of ternary metallic glasses

The well-known empty core (EMC) model potential of Ashcroft was used to study the theoretical investigation of the superconducting state parameters (SSP) viz. electron-phonon coupling strength λ, Coulomb pseudopotential µ*, transition temperature T _C, isotope effect exponent α and effective interaction strength N _O V of some ternary metallic glasses. Most recent local field correction function due to Sarkar et al is used to study the screening influence on the aforesaid properties. Quadratic T _C equations have been proposed and found successful. Also, the present findings are found to be in qualitative agreement with other such earlier reported data, which confirms the superconducting phase in the ternary superconductors. The pseudo-alloy-atom (PAA) model was applied for the first time instead of Vegard’s law.     

Magnetic and electrical characterization of heavily boron-doped diamond

For a heavily boron-doped diamond (BDD) film, temperature variations of the electrical conductivity σ and magnetic susceptibility χ are reported. The room temperature σ 143 (Ω-cm)⁻¹ corresponds to a carrier concentration 10³ ppm, and its temperature variation yields an activation energy E_a 28 meV from 140 to 300 K and E_a0.88 meV from 40 to 80 K. It is argued that larger boron doping leads to lower magnitudes of E_a. The χ vs. T data (1.8–350 K) fits the Curie–Weiss law, with the concentration of paramagnetic species 120 ppm and a diamagnetic susceptibility −0.4×10⁻⁶ emu/g Oe. The results obtained from the measurements of σ and χ are discussed and compared.     

CdGeAs2晶体的热膨胀行为研究

采用WinTA 100热膨胀仪研究了四方黄铜矿CdGeAs₂晶体在320~620 K温度范围内的热膨胀行为, 探索了CdGeAs₂晶体热膨胀各向异性的物理机制。测定晶体a轴和c轴方向的热膨胀系数α_a和α_c发现, α_a>>α_c>0, 表现出强烈的各向异性热膨胀特性。利用最小二乘法, 拟合出CdGeAs₂晶体的晶格常数(a, c)与温度(T)的函数关系式, 与文献报道值吻合。分别计算出不同温度下的四方畸变因子δ=2-c/a, Cd-As 键长(l_Cd-As)和 Ge-As 键长(l_Ge-As)以及相应的热膨胀系数α_Cd-As和α_Ge-As。结果表明, a、c、δ、l_Cd-As、l_Ge-As和α_Cd-As均随着温度的升高而增大, c/a和α_Ge-As则随着温度的升高而减小。当T=360 K时,α_Cd-As是α_Ge-As的6.36倍, 是造成CdGeAs₂晶体强烈热膨胀各向异性的主要原因。     

Effect of ferroic domain pattern changes on the Raman spectra of some ferroic crystals

The influence of changes in the pattern of ferroic domain structure on the Raman spectra of β-LiNH₄SO₄ and (NH₄)₃H(SO₄)₂ single crystals were studied. It was shown that the Raman spectra of β-LiNH₄SO₄ passed from the ferroelastic phase differ from those of “as-grown” crystal and those of the crystal, which was in the paraelectric phase. Significant changes could be observed in the Raman bands related to triply degenerated ν₃ and ν₄ vibrations of the SO₄ tetrahedron. Detailed temperature studies of the Raman spectra of β-LiNH₄SO₄ close to the paraelectric–ferroelectric phase transition, exhibit anomaly of some internal vibrations of SO₄ in the temperature range where a regular large-scale structure is observed. Different types of evolution of the ferroelastic domain structure and temperature behaviour of the donor and acceptor vibrations were shown while heating and cooling the (NH₄)₃H(SO₄)₂ crystal. Different values of temperature hysteresis were found in temperature studies of the ferroelastic domain structure (ΔT_S  3–5 K) and in Raman spectra studies (ΔT_S  12 K). No changes were observed in the pattern of ferroelastic domain structure at the temperature T_II–III  265 K, at which C2/c → P2/n structural phase transition takes place. On the other hand, at T_III–IV  135 K additional domains with W′-type of domain wall orientation were found.     

Powder X-ray diffraction, infrared and conductivity studies of AgSbMP3O12 (M = Al, Ga, Fe and Cr)

New Nasicon type of compounds of composition AgSbMP₃O₁₂ (M = Al, Ga, Fe and Cr) are synthesized by solid-state method. All the compounds crystallize in the hexagonal lattice with space group . The infrared spectra of these compounds show characteristic bands due to PO₄ group. The frequency independent conductivity of these compounds shows Arrhenius type behavior and the activation energy for conduction is in the range 0.40–0.55 eV. Frequency independent conductivity (σ_dc) studies and frequency dependent (σ_ac) impedance measurements correlate well. The Cole–Cole plots do not show any spikes on the lower frequency side indicating negligible electrode effects. The activation energies obtained from the plots of log σ_dcT versus 1/T, log σ_ac(0) versus 1/T and log τ versus 1/T are approximately the same. The peak width at half height for electric modulus (M″) plot is 1.24 decades for all samples, which is close to 1.14 decades observed for Debye solid. The height of electric modulus (M″) obtained from the experimental plots are close to that of M″ (max) = C₀/2C indicating the Debye nature of the samples.     

Frequency dependent electrical conductivity and dielectric relaxation behavior in amorphous (90V2O5–10Bi2O3) oxide semiconductors doped with SrTiO3

We report on the experimental results of frequency dependent a.c. conductivity and dielectric constant of SrTiO₃ doped 90V₂O₅–10Bi₂O₃ semiconducting oxide glasses for wide ranges of frequency (500–10⁴ Hz) and temperature (80–400 K). These glasses show very large dielectric constants (10²–10⁴) compared with that of the pure base glass (≈10²) without SrTiO₃ and exhibit Debye-type dielectric relaxation behavior. The increase in dielectric constant is considered to be due to the formation of microcrystals of SrTiO₃ and TiO₂ in the glass matrix. These glasses are n-type semiconductors as observed from the measurements of the thermoelectric power. Unlike many vanadate glasses, Long's overlapping large polaron tunnelling (OLPT) model is found to be most appropriate for fitting the experimental conductivity data, while for the undoped V₂O₅–Bi₂O₃ glasses, correlated barrier hopping conduction mechanism is valid. This is due to the change of glass network structure caused by doping base glass with SrTiO₃. The power law behavior (σ_ac=A(ω^s) with s<1) is, however, followed by both the doped and undoped glassy systems. The model parameters calculated are reasonable and consistent with the change of concentrations (x).     

Dielectric properties, ac conductivity and thermal behaviour of flux grown cadmium titanate crystals

The dependence of loss tangent (tan δ) and both real and imaginary parts of the dielectric constant (′ and ″) on temperature in the range 298–923 K and frequency in the range 10³–10⁶ Hz for flux grown CdTiO₃ single crystals is reported. The ln σ_ac versus T plots suggest the conduction mechanism to be ionic hopping conduction. From ln σ_ac versus frequency curves, it can be seen that the slope decreases with the rise in temperature, suggesting that the ionic hopping conduction diminishes with the rise in temperature. The activation energy at various fixed frequencies is calculated from the slope of the graph between ln σ_ac versus 1/T (×10³ K⁻¹). Thermal behaviour of flux grown CdTiO₃ crystals using thermoanalytical techniques including TG, DTA and DTG is discussed. Thermal analysis suggests decomposition of CdTiO₃ in the temperature interval of 1386–1693 K leading to the formation of TiO₂ as the final product. Results obtained on application of TG based models viz. Horowitz–Metzger, Coats–Redfern and Piloyan–Novikova are reported. The results of kinetics of thermal decomposition suggest contracting cylinder model as the one that is relevant to the decomposition of CdTiO₃. The kinetic parameters viz. the order of reaction, activation energy, frequency factor, and entropy of activation using the above mentioned models are computed.     

Bi过量以及冷却方式对BiFeO3-BaTiO3陶瓷的相结构及电学性能的影响

采用传统固相烧结法制备了0.7BiFeO₃-0.3BaTiO₃-xBi₂O₃(0≤x≤0.05)无铅压电陶瓷, 研究了Bi补偿量x和冷却方式对其相结构、微观形貌和综合电学性能的影响。结果表明：所有样品均为菱方相(R)和伪立方相(PC)两相共存, 0≤x≤0.01样品为纯的钙钛矿结构, 且x=0.01样品的两相比例C_R/C_PC接近1; x>0.01样品中出现富Bi杂相Bi₂₅FeO₄₀。与冷却方式相比, 优化Bi补偿量更有利于提升BFBT-xBi₂O₃陶瓷的压电性能。随着x增大, d₃₃先增大后减小, 在x=0.01时获得最优值。由于较小的晶粒、较合适的C_R/C_PC以及较大的残余应变, 水冷BFBT-0.01Bi₂O₃陶瓷获得了最优的压电性能(d_33水冷=141 pC/N、k_p=27%)和高T_C=507℃。研究结果表明, BFBT基陶瓷有希望成为兼具高压电性能和高T_C的无铅压电材料体系之一。     

高居里温度BaTiO3-(Bi0.5Na0.5)TiO3无铅正温度系数电阻陶瓷的制备

用传统的固相反应烧结法制备了(1-xmol%)BaTiO₃-xmol%(Bi_0.5Na_0.5)TiO₃(BBNTx)高温无铅正温度系数电阻( positive temperature coefficient of resistivity, PTCR)陶瓷。X射线衍射表明所有的BBNTx陶瓷形成了单一的四方钙钛矿结构。SEM分析结果显示随着BNT含量的增加, 陶瓷晶粒尺寸减小。空气中烧结的0.2mol% Nb掺杂的BBNT1陶瓷, 室温电阻率为~10² Ω·cm, 电阻突跳为~4.5个数量级, 居里温度为~150℃。氮气中烧结的0.3mol% Nb掺杂的BBNTx(10≤x≤60)陶瓷, 同样具有明显的PTCR效应, 居里温度在180~235℃之间。随着BNT含量的增加, 材料的室温电阻率增大, 同时陶瓷的电阻突跳比下降。     

A theory of suppressed nitrogen solubility in Fe–Z–N ternary alloy systems in the relatively high range of concentration of Z (Z=Si or C)

It was shown in earlier work that, for the FeZ_zN_x in the relatively low range of z, the solubility pattern of N as a function of temperature T and nitrogen partial pressure p(N₂) can be interpreted in terms of decreased number θ of available interstitial sites for occupation by N atoms per Fe atom in the Fe lattice in proportion to increased z under the assumption of negligible interaction between two interstitial constituents, N and Z (Z=Si or C). In the present work, solubility reduction of N in ternary FeZ_zN_x with increasing z in the relatively high range of z were analysed on the basis of statistical thermodynamics. The present analysis for molten FeSi_zN_x in the relatively high range of z showed that a correction to the θ versus z relation for the relatively high range of z was desirable taking into account overlapping of blocked interstitial sites for occupation of N atoms in order to reproduce the observed equilibrium pressure–temperature–composition (PTC) relation for this system while the interaction between N and Si remains negligible. On the other hand, for the simulation of equilibrium PTC relation for austenitic FeC_zN_x alloy over the entire range of z analysed, significant N–C interaction was important in addition to the blockage effect for the available interstitial sites for occupation of N atoms.     

Optical absorption and emission properties of Er doped mixed alkali borosilicate glasses

This paper presents the optical absorption and luminescence properties of Er³⁺ doped mixed alkali borosilicate glasses: 59.5SiO₂ · 20B₂O₃ · xLi₂O · (20 − x)Na₂O · 0.5Er₂O₃ and 59.5SiO₂ · 20B₂O₃ · xLi₂O · (20 − x)K₂O · 0.5Er₂O₃, with x = 0, 4, 8, 12, 16 and 20 mol%. The variations of Judd–Ofelt intensity parameters (Ω₂, Ω₄, and Ω₆), hypersensitive transition intensities, total radiative transition probability (A_T), radiative lifetimes (τ_R), integrated absorption cross-sections (Σ) and stimulated emission cross-sections (σ_p) as a function of x are discussed in detail. The changes in Ω₂ and intensities of hypersensitive transitions are attributed to optical basicity changes in the host glass matrix, which leads to variations in the covalency of the Er–O bond. The luminescence properties are reported for certain transitions, and the emission cross-section is high at x = 8–12 in the case of lithium sodium glass, whereas in lithium potassium glass it is high at x = 8.     

Strong magnetoelastic effect in Pr1−xCaxMnO3

Manganese oxides with distorted perovskite structure have attracted much attention during the last decade due to their colossal magnetoresistance (CMR), and the strong correlations among the various degrees of freedom involved. In particular, Pr_1−xCa_xMnO₃ compounds present in a wide Ca-doping range a charge ordering phenomenon, consisting of real space ordering of Mn³⁺ and Mn⁴⁺ in alternate lattice sites below a certain temperature T_CO. This ordering brings about a lattice distortion and a large hardening of the sound velocity below T_CO. Tomioka et al. have observed that an applied magnetic field can melt this charge ordered state and induce a transition from an insulating to a metallic state. In order to study the effects of this charge order melting, ultrasonic longitudinal sound velocity measurements were performed on polycrystalline Pr_1−xCa_xMnO₃ (x=0.35 and 0.5) as a function of magnetic field and temperature. Interesting anomalies were found related to the melting of the charge ordered phase into a metal-like state even at low temperatures.     

Determining crystallization kinetic parameters of Li2O–Al2O3–SiO2 glass from derivative differential thermal analysis curves

The kinetic parameters such as crystallization activation energy, E, and the frequency factor, ν, of Li₂O–Al₂O₃–SiO₂ glass were determined by a new non-isothermal method. The method is described by the equation

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, where β is the heating rate and T_f is the inflection-point temperature of differential thermal analysis (DTA). The value of T_f is determined as the maximum peak temperature on derivative differential thermal analysis (DDTA) curves. Values of E and ν of Li₂O–Al₂O₃–SiO₂ glass were also determined by two existing non-isothermal methods, namely the Kissinger plot and the Ozawa plot, and compared with those determined by isothermal method. Values of E and ν determined by the proposed equation were 332 kJ/mol and 1.4×10¹³ s⁻¹, respectively. They are excellent agreement with the isothermal analysis results, 336 kJ/mol and 1.8×10¹³ s⁻¹, respectively. In contrast, both the Kissinger equation and the Ozawa equation give much higher values of E and ν.     

残余应力对SrRuO3薄膜磁学及电输运性能的影响

采用射频磁控溅射法在单晶SrTiO₃ (STO)衬底和硅(Si)衬底上制备出不同取向的SrRuO₃ (SRO)薄膜, 对薄膜的残余应力进行了分析, 并研究了应力对不同取向SRO薄膜磁学性能与电输运特性的影响。根据X射线衍射(XRD)结果分析可知, Si基SRO薄膜为多晶单轴取向薄膜, 且应力来源主要为热失配拉应力; STO基SRO薄膜为外延薄膜, 其应力主要为热失配压应力和外延压应力; 磁学性能测试表明, (001)取向SRO薄膜比(110)取向薄膜拥有更高的居里温度T_C; 压应力提高了(001)取向SRO薄膜的T_C, 却降低了(110)取向薄膜的T_C。电阻性能测试表明, 对于在同种类型衬底上沉积的SRO薄膜, (001)取向的薄膜的剩余表面电阻比(RRR)高于(110)取向的薄膜。另外, 拉应力引起了薄膜微结构的无序度增加, 弱化了表面电阻率的温度依赖性, 提高了金属绝缘体转变温度(T_MI)。     

Study of Screening Dependence Superconducting State Parameters of Cu<Subscript><Emphasis Type="Italic">C</Emphasis></Subscript>Zr<Subscript>100−<Emphasis Type="Italic">C</Emphasis></Subscript> Binary Metallic Glasses by a Pseudopotential

The screening dependence theoretical investigations of the superconducting state parameters (SSP) viz. electron–phonon coupling strength λ, Coulomb pseudopotential μ ^*, transition temperature T _C , isotope effect exponent α and effective interaction strength N _O V of ten binary Cu _C Zr_100−C (C=25, 30, 33, 35, 40, 45, 50, 55, 57 and 60) metallic glasses have been reported using Ashcroft’s empty core (EMC) model potential. Five local field correction functions proposed by Hartree (H), Taylor (T), Ichimaru–Utsumi (IU), Farid et al. (F), and Sarkar et al. (S) are used in the present investigation to study the screening influence on the aforesaid properties. It is observed that the electron–phonon coupling strength λ and the transition temperature T _C are quite sensitive to the selection of the local field correction functions, whereas the Coulomb pseudopotential μ ^*, isotope effect exponent α and effective interaction strength N _O V show weak dependences on the local field correction functions. The values of T _C obtained from the H-local field correction function are in qualitative agreement with available theoretical or experimental data and show almost linear nature with the concentration C of Cu element. A linear T _C equation is proposed by fitting the present outcomes for the H-local field correction function, which is in conformity with other results for the experimental data. Also, the present results are in qualitative agreement with other such earlier reported data, which confirms the superconducting phase in the metallic glasses.     

SiO2对掺钕铝酸盐玻璃结构及光谱性质的影响

实验通过高温熔融法制备了不同SiO₂ 浓度的掺钕钙铝酸盐玻璃。采用拉曼光谱法分析玻璃结构变化, 发现随着SiO₂含量的增加, [AlO₄]网格中非桥氧逐渐转移至Si⁴⁺离子周围, 玻璃主体Al-O网络中非桥氧减少, 聚合度提高。实验测试了玻璃的吸收光谱和荧光光谱, 并运用Judd-Ofelt理论计算Nd³⁺离子⁴F_3/2→⁴I_11/2跃迁的J-O参数Ω, 自发辐射几率A_rad, 荧光分支比β, 受激发射截面σ_e, 辐射寿命τ_rad等。结果显示: 随着SiO₂浓度的增加, 钕离子周围环境结构对称性提高, 荧光发射峰半高宽变窄, 同时受激发射截面逐渐增大。研究结果表明含有低浓度SiO₂的掺钕钙铝酸盐激光玻璃有望用于超短脉冲激光领域。