La_(2/3)Ca_(1/3)Mn_(1-x)Fe_xO_3化合物铁掺杂效应的Mssbauer谱研究

利用固相反应方法制备了名义成分为La2 / 3Ca1 / 3Mn1 -xFexO3(0 .0 1≤x≤ 0 .2 0 )的一系列样品 .在整个掺杂范围内晶体结构没有明显变化 .在室温下测量了各样品的M ssbauer谱 ,拟合结果表明 +3价高自旋态的铁离子占据锰的八面体晶位 ,随Fe掺杂量的增加 ,铁离子的 3d电子出现局域化趋势 ,并伴随Fe O配位体畸变程度的增强 .本文对此进行了讨论 .     

La2/3(Ca1-xMgx)1/3MnO3(0≤x≤60%)系统中不寻常的超大磁电阻

用溶胶-凝胶法并经过1450℃后处理而制备出名义组分为La2/3(Ca1-xMgx)1/3MnO3 (0≤x≤60%)多晶样品.磁化测量表明,除磁转变温度因Mg掺杂而稍有降低外,磁性质整体上和不含Mg样品无本质上的差别.未加磁场下阻温关系测量表明,即使Mg含量高达60%,实验上仍观察到绝缘体到金属的转变.特别有意义的结果是,适当的Mg掺杂可明显提高转变温度附近的磁电阻效应,例如,在Mg掺杂量为30～40%的样品中,1T磁场下观察到的磁电阻甚至比不含Mg样品在5T磁场下得到的值还要大.     

Y替代La2/3Ca1/3MnO3体系的结构与输运行为

系统研究了(La1-xYx)2/3Ca1/3MnO3(0.0≤x≤0.3)体系的结构和输运行为.结果表明，实验样品具有很好的单相结构，随Y掺杂浓度的增加，金属—绝缘体（M—I）转变温度T-MI向低温区移动，对应的峰值电阻率ρp升高，对x=0.3样品，较未替代样品（x=0.0）增幅达8个数量级.在外加磁场下，材料表现出很强的磁电阻效应.同时，从实验结果出发，直接给出了输运特性与晶体结构之间的关联，并从双交换模型和可变程跃迁理论出发，对实验结果进行了初步讨论. 关键词： La2/3Ca1/3MnO3锰氧化物 Y替代 晶体结构 输运行为     

Fe掺杂量对双层复合结构BaTi1-zFezO3+δ-Tb1-xDyxFe2-y中磁电耦合的影响

采用溶胶凝胶方法制备了Fe掺杂钛酸钡多晶系列陶瓷BaTi_1-zFe_zO_3+δ(0.005≤z≤0.02) (BTFO).X射线衍射实验显示,所制备的BTFO的结构仍然为四方相钙钛矿.差热分析表明,该BTFO样品的铁电-顺电转变温度及相变潜热随掺杂量z的增加而下降.将该BTFO极化后与Tb_1-xDy_xF 关键词： 磁电耦合 掺杂效应 掺杂钛酸钡     

Sr1-xYxCoO3的磁性和电输运性质

采用传统的固相反应法制备了A位Y掺杂的多晶钙钛矿氧化物Sr1-xYxCoO3(x-0～0.30),系统研究了Y掺杂对体系结构、磁性和电输运性质的影响.X射线衍射结果表明室温下体系经过六方对称到立方对称再到四方对称的结构相变,x=0样品为六方结构,空间群为P63/mmc,0.05≤x≤0.15样品为立方对称结构,空间群为Pm3 m,x≥0.20样品为四方对称结构,空间群为I4/mmm,x=0.20时具有最大矫顽场Hc=4.6kOe.体系在外加磁场为1kOe下表现出如下磁性特征:x=0时Jc=163K,随着掺杂量的增加,转变温度呈现上升趋势,同时反铁磁性也随之增强.所有组分均表现出半导体特征,并且观察到复杂的磁电阻(MR)与温度变化关系:所有组分均表现出+MR与-MR共存的特征,当掺杂量为x=0.1时,在T=370K下表现出测量最大磁电阻的绝对值︱MR︳约为17%.Sr1-xYxCoO3样品遵循可变程传到模型,在150K≤T≤400K温度范围内ln(ρ)与T-1/4呈线性关系.     

La0.4Ca0.6MnO3系统中Mn位Fe和Cr掺杂效应的比较性研究

利用固相反应法制备了Mn位Fe³⁺和Cr³⁺掺杂的系列锰氧化物La_0.4Ca_0.6(Mn_1-x(y)B_x(y))O₃ (B=Fe³⁺ (0≤x≤0.1); Cr³⁺ (0≤y≤0.1)) 多晶样品,研究了掺杂对样品输运性质的影响.实验结果表明两种离子具有截 关键词： 锰氧化物 反铁磁 磁电阻效应     

Bi0.5Ca0.5Mn1-xCoxO3体系中的电荷有序和相分离

利用固相反应法制备了Bi_0.5Ca_0.5Mn_1-xCo_xO₃(0≤x≤0.12)系列多晶样品.研究了Co掺杂对Bi_0.5Ca_0.5MnO₃电荷有序的影响.结果表明,Co掺杂导致电荷有序相逐渐融化、铁磁相互作用的增强;当x≥0.08时,电荷有序转变峰完全消失,但残留的反铁磁电荷有 关键词： 钙钛矿锰氧化物 电荷有序 团簇玻璃 相分离     

(1-x)(K0.5Na0.5)NbO3-xSrTiO3陶瓷的弛豫铁电性能

通过对（1-x）（K_0.5Na_0.5）NbO₃-xSrTiO₃（0≤x≤0.15）陶瓷的相组成、晶体结构和介电性能的研究发现,该陶瓷为单一的钙钛矿结构相.当x含量较小（x＜0.1）时为正交相结构,x≥0.1时转变为四方相结构.随着SrTiO₃掺杂量的增加,样品的致密度增加,样品由正常铁电相逐渐向弥散铁电相转变,且相 关键词： 弛豫铁电体 0.5Na_0.5）NbO₃铁电陶瓷')" href="#">（K_0.5Na_0.5）NbO₃铁电陶瓷 3掺杂')" href="#">SrTiO₃掺杂 相变温度     

(La1-xYx)2/3Ca1/3MnO3体系的正电子湮没研究

为研究超大磁阻材料的掺杂效应,我们测量了(La1-xYx)2/3Ca1/3MnO3系列样品的正电子寿命谱,并结合X射线衍射和电阻温度关系的测量结果,系统地研究了Y掺杂引起的样品局域电子结构和空位型缺陷的变化,并提出了局域电荷转移的观点,解释正电子体寿命的变化.     

相分离体系Nd1-xSrxCoO3的亚铁磁行为

研究了Nd1-xSrxCoO3(0.1≤x≤0.5)系列多晶样品在低温时的亚铁磁行为.通过传统的固相反应法合成了Nd1-xSrxCoO3多晶样品,应用物理性质测试系统对样品进行了直流磁化强度、磁滞回线的测试.磁化强度的研究表明,随掺杂量增加,团簇的数目和尺寸都在增加,铁磁性增强.同时,多晶样品在低温时形成亚铁磁序.磁滞回线的研究表明,Nd离子与Co离子之间存在磁性耦合.由于Co与Nd的反平行排列,Nd1-xSrxCoO3体系低温时出现亚铁磁序.     

Colossal room-temperature magnetoresistance of La1/3Nd1/3Sr1/3MnO3 single crystals

Replacement of one half of the neodymium ions by lanthanum in Nd_2/3Sr_1/3MnO₃ is shown to result in a considerable increase in the Curie temperature. The single-crystal La_1/3Nd_1/3Sr_1/3MnO₃, whose Curie point lies at 315 K, has been found to exhibit a record-high magnetoresistance of 27% in a weak magnetic field of 8.4 kOe in the temperature range above room temperature.     

Exchange interaction between ferromagnetic and antiferromagnetic phases in La1/3Nd1/3Ca1/3MnO3

Magnetization measurements of a La_1/3Nd_1/3Ca_1/3MnO₃ perovskite at magnetic field up to 6 T have revealed an anomalous behaviour – above 130 K the material exhibits a loop displacement about a field of 2 T. We assume that this is the result of an exchange interaction between ferromagnetic and antiferromagnetic phases in a magnetically inhomogeneous compound. At about 115 K a transition from a semiconducting to a metallic-like state has been observed.     

Synthesis of spherical LiNi1/3Co1/3Mn1/3O2 cathode materials for Li-ion batteries

Spherical LiNi_1/3Co_1/3Mn_1/3O₂ was successfully prepared by controlled crystallization. The preparation started with the spherical coprecipitate of Ni_1/3Co_1/3Mn_1/3CO₃ from NiSO₄, CoSO₄, MnSO₄, NH₄HCO₃, and NH₃·H₂O, followed by pyrolysis of Ni_1/3Co_1/3Mn_1/3CO₃ at 600°C for 3 h. The X-ray diffraction analysis showed that the homogeneous cubic (Ni_1/3Co_1/3Mn_1/3)₃O₄ was obtained after the pyrolysis. Spherical LiNi_1/3Co_1/3Mn_1/3O₂ was obtained by sintering of the mixture of as-obtained (Ni_1/3Co_1/3Mn_1/3)₃O₄ and LiOH·H₂O at 900°C for 6 h in air. As-prepared spherical LiNi_1/3Co_1/3Mn_1/3O₂ presented initial discharge capacity of 162.9 mA h g⁻¹ and capacity retention of 98% at 50th cycle.     

Characterization of Na-substituted LiNi1/3Co1/3Mn1/3O2 cathode materials for lithium-ion battery

Highly crystalline layered Li_1?xNa_xNi_1/3Co_1/3Mn_1/3O₂ (x?=?0, 0.001, 0.01, 0.03, 0.05) materials are synthesized by molten salts method and characterized by scanning electron microscopy, inductively coupled plasma (ICP), X-ray diffraction, Rietveld refinement, and electrochemical measurement, respectively. ICP, SEM, and EDS results show that Na ions are incorporated in LiNi_1/3Co_1/3Mn_1/3O₂. Rietveld refinement results show that suitable Na substitution leads to stable layered structure by full Na occupying in Li layer and further attributes to low cation mixing. Electrochemical studies demonstrate that the Na-substituted LiNi_1/3Co_1/3Mn_1/3O₂ shows improved rate capability and cycling performance compared to that of pure LiNi_1/3Co_1/3Mn_1/3O₂.     

Physical properties of BaMg1/3Nb2/3O3-BaCo1/3Nb2/3O3 solid solutions

Structural, electric and magnetic properties of Ba₃Mg_1−xCo_xNb₂O₉ based dielectric ceramic compounds have been studied. The samples, prepared by a solid state reaction method, were characterised by X-ray powder diffraction (XRPD), electron microscopy (SEM), dielectric (ε(T)) and magnetic measurements (χ⁻¹(T)). The XRPD analyses showed that the crystal structure of these compounds does change by the increase of substitution degree, passing from a superstructure hexagonal-type, (no. 164), space group (SG) to a simple structure cubic-type, (no. 221), SG. However, the evolution of the elementary unit cell lattice parameter can be followed and it exhibit a linear increasing tendency with increase in the substitution, indicating the existence of a solid solution through out the investigated range of substitution (0-1). The microstructure analysis shows a variation in the grain size and also the porosity of the samples with the degree of substitution. The results are in good agreement with that of dielectric measurements, which also showed that the dielectric constant (ε) increases with the increase of cobalt content. The magnetic characterization of cobalt substituted samples showed an antiferromagnetic type super-exchange interaction between these magnetic ions. At the same time, the values of effective magnetic momentum (μ_eff) are close to the value that corresponds to Co²⁺ free ions. The study highlights the possibility of modelling these materials by substitutions, in order to improve properties of negative-positive-zero (NPO) type dielectric applications.     

ZrO2 coating of LiNi1/3Co1/3Mn1/3O2 cathode materials for Li-ion batteries

ZrO₂-coated LiNi_1/3Co_1/3Mn_1/3O₂ materials were prepared by hydroxide precipitation. The structure and electrochemical properties of the ZrO₂-coated LiNi_1/3Co_1/3Mn_1/3O₂ were investigated using X-ray diffraction, scanning electron microscope, and charge–discharge tests, indicating that the lattice structure of LiNi_1/3Co_1/3Mn_1/3O₂ were unchanged after the coating but the cycling stability was improved. As the coating amount increased from 0.0 to 0.5 mol.%, the initial capacity of the coated LiNi_1/3Co_1/3Mn_1/3O₂ decreased slightly; however, the cycling stability increased remarkably over the cut-off voltages of 2.5~4.3 V and the capacity retention reached 99.5% after 30 cycles at the coating amount of 0.5 mol.%. ZrO₂ coating also improved the cycling stability of LiNi_1/3Co_1/3Mn_1/3O₂ over wider cut-off voltage of 2.5~4.6 V.     

TiO2 coating of LiNi1/3Co1/3Mn1/3O2 cathode materials for Li-ion batteries

TiO₂-coated LiNi_1/3Co_1/3Mn_1/3O₂ materials were prepared by the hydrolyzation of Ti(OBu)₄. The impact of TiO₂ coating on the structure and electrochemical properties of LiNi_1/3Co_1/3Mn_1/3O₂ was investigated using X-ray diffraction, scanning electron microscope, and charge–discharge tests. The results indicated that TiO₂ coating did not affect the lattice of LiNi_1/3Co_1/3Mn_1/3O₂, but exhibited obvious effects on its discharge capacity and cycling stability. As coated TiO₂ increased from 0.0 to 2.0 mol%, the initial capacity of samples decreased slightly, but the cycling stability over 2.5∼4.3 V increased remarkably. The capacity retention reached 99.5% at the 50th cycle at a coating amount of 2.0 mol%.     

Luminescence properties of K1/2Bi1/2TiO3:Pr3+ and Na1/2Bi1/2TiO3:Pr3+

The luminescence properties of K(1/2)Bi(1/2)TiO(3):Pr(3+) and Na(1/2)Bi(1/2)TiO(3):Pr(3+) powders are investigated in the temperature range 10-600 K. The experimental data are interpreted on the basis of metal-to-metal charge transfer processes and by considering Bi(3+)-to-Pr(3+) sensitization effects.     

Giant dielectric relaxation in SrTiO3-SrMg1/3Nb2/3O3 and SrTiO3-SrSc1/2Ta1/2O3 solid solutions

Ceramic samples of (1−x)SrTiO₃-xSrMg_1/3Nb_2/3O₃ and (1−x)SrTiO₃-xSrSc_1/2Ta_1/2O₃ were prepared, and their dielectric properties were studied at x=0.005–0.15 and 0.01–0.1, respectively, at frequencies 10 Hz–1 MHz and at temperatures 4.2–350 K. A giant dielectric relaxation was observed in the temperature range 150–300 K, and not so strong but well-developed relaxation was found in the temperature range 20–90 K. The activation energy U and the relaxation time τ₀ were determined to be 0.21–0.3 eV and from 10⁻¹¹ to 10⁻¹² s for the high-temperature relaxation and 0.01–0.02 eV and 10⁻⁸–10⁻¹⁰ s for the low-temperature relaxation, respectively. The additional local charge compensation of the heterovalent impurities Mg²⁺ and Nb⁵⁺ (or Sc³⁺ and Ta⁵⁺) by free charge carriers or the host ion vacancies is suggested to be the underlying physical mechanism of the relaxation phenomena. On the basis of this mechanism, the Maxwell-Wagner model and the model of reorienting dipole centers Mg²⁺ (or Sc³⁺) associated with the oxygen vacancy are proposed to explain the high-temperature relaxation with some arguments in favor of the latter model. The polaron-like model with the Nb⁵⁺-Ti³⁺ center is suggested as the origin of the low-temperature relaxation. The reasons for the absence of ferroelectric phase transitions in the solid solutions under study are also discussed. From Fizika Tverdogo Tela, Vol. 44, No. 11, 2002, pp. 1948–1957. Original English Text Copyright ? 2002 by Lemanov, Sotnikov, Smirnova, Weihnacht. This article was submitted by the authors in English.     

E-T phase diagrams of a solid solution of the multicomponent PbZn1/3Nb2/3O3-PbMg1/3Nb2/3O3-PbNi1/3Nb2/3O3-PbTiO3 system near the morphotropic phase boundary

The specific features of the dielectric and pyroelectric responses of a solid solution in the barium-doped multicomponent yPbZn_1/3Nb_2/3O₃-mPbMg_1/3Nb_2/3O₃-nPbNi_1/3Nb_2/3O₃-xPbTiO₃ system of the composition y = 0.0982, m = 0.4541, n = 0.1477, and x = 0.3 near the morphotropic phase boundary have been investigated. It has been assumed that the maxima revealed in the dependences of the reversible permittivity on the electric field strength with both the forward and backward changes in the field (E ₌) are associated with the induced phase transition. Based on the experimental results, the E-T phase diagrams are constructed in the temperature range from ?100 to 150°C for different temperature-field regimes: (i) variation in the electric field E ₌ at a fixed temperature of the sample and (ii) variation in the temperature of the sample at a constant value of E ₌. It has been found that there is a singular point in the E-T phase diagram and that, in the vicinity of this point, the dielectric and pyroelectric responses of the studied ceramics exhibit specific features.