Dy,Co共掺杂对BiFeO3陶瓷磁特性和磁相变温度Tc的影响

采用快速液相烧结法制备BiFeO₃和Bi_0.95Dy_0.05Fe_1-xCo_xO₃ (x=0, 0.05, 0.1, 0.15)陶瓷样品. 实验结果表明: 所有样品的主衍射峰与纯相BiFeO₃相符合且具有良好的晶体结构, 随着Co³⁺掺杂量的增大, Bi_0.95Dy_0.05Fe_1-xCo_xO₃样品的主 衍射峰由双峰(104)与(110)逐渐重叠为单峰(110), 当掺杂量x>0.05时, 样品呈现正方晶系结构; SEM形貌分析可知: Dy³⁺, Co³⁺共掺杂使BiFeO₃晶粒尺度由原来的3—5 μ减小到约1 μ. 室温下, BiFeO₃样品表现出较弱的铁磁性, 随着Dy³⁺和Co³⁺掺杂, BiFeO₃样品的铁磁性显著提高. 在外加磁场为30 kOe的作用下, Bi_0.95Dy_0.05Fe_1-xCo_xO₃ (x=0.05, 0.1, 0.15)的M_r分别为0.43, 0.489, 0.973 emu/g; M_S分别为0.77, 1.65, 3.08 emu/g. BiFeO₃和Bi_0.95Dy_0.05Fe_1-xCo_xO₃样品磁矩M随着温度T的升高而逐渐减小, Dy掺杂使BiFeO₃样品的T_N由644 K升高到648 K, 而T_C基本没有变化. Dy和Co共掺杂导致BiFeO₃样品磁相变温度T_C由870 K降低到780 K, 其T_C变化主要取决于Fe-O-Fe反铁磁超交换作用的强弱和磁结构的相对稳定性. 关键词： 铁磁电材料 磁滞回线 磁相变温度     

Ti1－xCrxO2±δ体系的相关系、晶体结构和磁性能研究

采用溶胶凝胶法制备了Ti_1-xCr_xO_2±δ体系系列样品.利用扫描电子显微镜(SEM)，X射线光电子能谱(XPS)，粉末X射线衍射分析(XRD)方法研究了Ti_1-xCr_xO_2±δ系列样品的颗粒尺寸、形貌、组分化学态、相关系和固溶区范围；并利用超导量子干涉磁强计对样品的磁性能进行了研究.采用Rietveld结构精修的方法研究了Cr的不同掺杂量对TiO₂晶体结构的影响，研究表明，1000℃烧结的样品的固溶区范围是x=0—0.03，为金红石单相；随着Cr掺杂量的增加，金红石相晶胞参数规律性地减小；当x>0.03，为金红石相和CrO₂相两相共存.综合XRD和磁性测量结果，500℃烧结的样品的固溶区范围是x=0—0.02，为锐钛矿单相；随着Cr掺杂量的增加，锐钛矿相晶胞参数规律性地减小；当x≥0.04，为锐钛矿相和绿铬矿相(Cr₂O₃)两相共存.XPS实验结果表明，500℃和1000℃退火的样品中Cr都是以Cr⁺³和Cr⁺⁶两种化学态存在，1000℃烧结的样品中可能有更多的Cr³⁺转化为Cr⁶⁺.根据M-H和M-T曲线的测试结果发现，本文500℃烧结的Ti_1-xCr_xO_2±δ体系样品当x=0—0.02时，为室温铁磁性.当x≥0.04时，由铁磁相和顺磁相所组成，在低温下有较强的铁磁性；室温下主要是顺磁相，铁磁相只占据很小的体积分数. 关键词： 1-xCr_xO_2±δ体系')" href="#">Ti_1-xCr_xO_2±δ体系 相关系 固溶区 磁性能     

缺氧条件下准一维自旋梯状结构化合物(Sr1-xCax)14Cu24O41-δ的磁化率特性研究

在空气环境中采用固相反应方法制备出三种A位Ca掺杂自旋梯状结构化合物(Sr_1-xCa_x)₁₄Cu₂₄O_41-δ样品(x＝0,0.25,0.43)能量损失谱(EDS)分析表明,该体系Ca掺杂样品均严重缺氧(分别对应的缺氧含量δ＝7.64,6.99,6.67).X射线衍射(XRD)结果显示,所有样品均为单相,并且晶格常数a,b,c的值随着缺氧含量δ的增加而增大.1T直流磁场下的磁化率-温度曲线及其拟合结果表明,对无Ca掺杂样品Sr₁₄Cu₂₄O_41-δ(δ＝7.64),氧含量减少导致自旋链上空穴数的减少,自旋链上自由自旋的Cu离子数目增大,而参与二聚化的Cu离子数目略有减小;而对Ca掺杂样品(Sr_1-xCa_x)₁₄Cu₂₄O_41-δ,随着Ca含量的增加,样品中氧缺失量降低,但Ca掺杂引起空穴减少的程度更强. 关键词： 自旋梯状结构化合物 氧缺位 晶体结构 磁化率     

Co(S1-xSex)2系统中的铁磁量子相变

针对Co(S_1-xSe_x)₂系统在x=0.11附近发生的铁磁金属到顺磁金属相变,制备了一系列不同Se替代浓度的多晶样品.通过对其结构和电阻率-温度ρ(T)关系的系统观测,结果发现,样品铁磁相变温度T_C随着Se替代浓度x值的增加,以(1-x)^1/2关系单调下降,其二级铁磁相变转变为一级相变 关键词： 量子相变 自旋量子涨落 1-xSe_x)₂')" href="#">Co(S_1-xSe_x)₂     

钙钛矿锰氧化物(La1-xGdx)4/3Sr5/3Mn2O7 (x=0, 0.025) 磁性和输运性质研究

采用传统的高温固相烧结法制备了双层钙钛矿锰氧化物(La_1-xGd_x)_4/3Sr_5/3Mn₂ O₇ (x=0, 0.025)多晶样品. 通过X射线衍射仪研究发现样品为Sr₃Ti₂O₇型四方结构, 空间群为I4/mmm; 磁性测量表明, Gd³⁺掺杂后的样品(La_0.975Gd_0.025)_4/3Sr_5/3Mn₂O₇的三维磁有序转变温度(T_C1^3D)、磁化强度(M)均降低, 这是由于Gd³⁺的掺杂引起晶格的畸变, 从而使得晶格常数发生改变, 减弱了铁磁耦合而导致的; 通过电子自旋共振谱测量发现, 在T_C^3D<T<300 K温度范围内, 两样品在顺磁的基体上均有短程的铁磁团簇存在, 出现了相分离现象. 电性测量表明: 两样品分别在T_C1^3D (La_4/3Sr_5/3Mn₂O₇ 样品的三维磁有序转变温度, T_C0^3D)<T<300 K温度范围内均以三维变程跳跃的方式导电, 分析得出Gd³⁺的掺杂使得载流子局域长度的减小. 这表明载流子需要吸收更多的能量才能克服晶格的束缚进行跳跃, 因此(La_0.975Gd_0.025)_4/3Sr_5/3Mn₂ O₇ 样品的电阻较高.     

Sr掺杂钙钛矿型氧化物Y1-xSrxCoO3的溶胶-凝胶制备及电阻率温度关系研究

采用溶胶-凝胶方法成功制备了Sr的替代化合物Y_1-xSr_xCoO₃ (x=0, 0.01, 0.05, 0.10, 0.15, 0.20), 系统地研究了20–720 K温度范围内Y_1-xSr_xCoO₃的电阻率温度关系. 研究表明, 随着Sr的替代含量的增加, Y_1-xSr_xCoO₃的电阻率迅速地降低, 这主要是由于载流子浓度的增加引起. 样品x=0和0.01在低于330和260 K的温度范围内, 电阻率与温度之间满足指数关系lnρ∝1/T, 获得导电激活能分别为0.2950和0.1461 eV. 然而, 实验显示lnρ∝1/T关系仅成立于重掺杂样品的高温区; 在低温区莫特定律lnρ∝T^-1/4成立, 且表明重掺杂引入势垒, 导致大量局域态的形成. 根据莫特T^-1/4定律拟合实验数据, 评估了局域态密度N(E_F), 它随着掺杂量的增加而增加. 关键词： 热电材料 溶胶-凝胶 3')" href="#">YCoO₃     

层状钙钛矿La1.3Sr1.7Mn2-xCuxO7的磁性及电特性

通过固相反应烧结法成功制备了层状钙钛矿La_1.3Sr_1.7Mn_2-xCu_xO₇多晶,主要研究了其磁电特性.结果表明,样品为Sr₃Ti₂O₇型钙钛矿结构.随着温度的降低,其磁性经历了一个很复杂的转变过程.当x=0时,在T^*=231K出现二维短程铁磁有序,在< 关键词： 层状钙钛矿 磁性 电特性     

Ni2O3掺杂对新固相源顶部籽晶熔渗生长法制备单畴GdBCO超导块材超导性能的影响

本文通过在新固相源中添加Ni₂O₃的方法, 采用顶部籽晶熔渗生长工艺(TSIG)制备出组分为(1-x) (Gd₂O₃+1.2BaCuO₂)+x Ni₂O₃、直径为20 mm的单畴GdBCO 超导块材(其中x = 0, 0.02, 0.06, 0.10, 0.14, 0.18, 0.30, 0.50 wt%), 并研究了Ni₂O₃的掺杂量x对样品的表面生长形貌、微观结构、临界温度T_c、磁悬浮力以及俘获磁通密度的影响. 研究结果表明, 当Ni₂O₃的掺杂量x在0–0.50 wt%的范围内时, 均可制备出单畴性良好的样品, 且Ni₂O₃的掺杂对样品中Gd211粒子的分布和粒径没有明显的影响. 在Ni₂O₃的掺杂量x从0增加到0.50 wt%的过程中, 样品的临界温度T_c呈现下降的趋势, 从x=0时的92.5 K下降到x=0.50 wt%时的86.5 K, 这是由于Ni^{3 +}替代GdBCO晶体中Cu^{2 +}所致; 样品磁悬浮力和俘获磁通密度均呈现先增大后减小的变化规律, x=0.14 wt%时, 磁悬浮力达到最大值34.2 N, x=0.10 wt%时, 俘获磁通密度达到最大值0.354 T. 样品磁悬浮力和俘获磁通密度的变化规律与Ni₂O₃的掺杂量x有密切关系, 只有当掺杂量x合适时, Ni³⁺对Cu^{2 +}的替代既不会造成T_c的明显下降, 但又能产生适量的Ni^{3 +}/Cu²⁺ 晶格畸变, 从而达到提高样品磁通钉扎能力和超导性能的效果.     

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     

Co掺杂对铁磁金属La0.8Sr0.2MnO3磁电阻影响机理

通过对La_0.8Sr_0.2Mn_1-yCo_yO₃(y≤02)饱和磁矩和输运的测量,研究了Co对La_0.8Sr_0.2MnO₃的磁电阻影响机制.结果表明,在La_0.8Sr_0.2Mn_1-yCo_yO₃（y≤02）中Co³⁺离子是低自旋态.由于Mn³⁺—O—Co³⁺—O—Mn³⁺类型的磁交换与Mn³⁺-Mn⁴⁺离子间双交换作用相比较弱,Curie温度T_C附近的磁电阻随着Co掺杂量的增加而降低.与此相反,由于Co²⁺离子与e_g巡游电子的反铁磁交换耦合作用,低温区间的磁电阻随着Co掺杂量的增加而升高. 关键词： 低自旋 磁电阻 磁交换作用     

层状钙钛矿La1.3Sr1.7Mn2-xCuxO7的磁性及电特性

通过固相反应烧结法成功制备了层状钙钛矿La_1.3Sr_1.7Mn_2-xCu_xO₇多晶，主要研究了其磁电特性.结果表明，样品为Sr₃Ti₂O₇型钙钛矿结构.随着温度的降低，其磁性经历了一个很复杂的转变过程.当x=0时，在T^*=231K出现二维短程铁磁有序，在<     

Superconductivity of LiTi2O4 and related systems

New experimental results are reported on spinel LiTi₂O₄, and the related mixed valent systems Li_1+x Ti_2–x O₄ and Li_1–x Mg _x Ti₂O₄ characterized by distinct Ti³⁺/Ti⁴⁺ ratios (<1 in the former and >1 in the latter). Specific heat data and transport properties show the high quality of the samples prepared by new routes. It is emphasized that, as far the specific heat data are concerned, the stoichiometric compound (withT _c =12.4 K) satisfies BCS predictions in the weak coupling limit. Conversely, the mechanism of superconductivity is shown to be more complex when off-stoichiometric compouds are considered, due to the vicinity of metal-insulator transition. It is to be noted that the disappearance of sizable superconductivity occurs for 0.12<x<0.18, but the insulator features are only reached forx=1/3.     

Magnetic Phase Transitions in Substituted Spinels of Zn1−x Cu χ Cr2 Se4; 0.0 ≤ x ≤ 0.3

Magnetic and crystallographic properties have been studied by neutron powder diffraction and measurements of magnetization and magnetization hysteresis-loops for substituted spinels of Zn_1?xCu_xCr₂Se₄ with 0.0≤x≤0.3. It is found that the Zn_0.85Cu_0.15Cr₂Se₄ spinel has two magnetic phase transitions at 23.0 K (Néel temperature; T _N) and 410 K (Curie temperature; T _C) and that the Zn_0.70Cu_0.30Cr₂Se₄ spinel has magnetic transitions at 24.5 K (T _N) and 415 K (T _C) on heating. The low-temperature magnetic phase transition is from a spiral antiferromagnet to a ferromagnet, and the high-temperature magnetic phase transition is from a ferromagnet to a paramagnet, while ZnCr₂Se₄ shows a magnetic phase transition only from a spiral antiferromagnet to a paramagnet at about 21.0 K. From neutron powder diffraction, it is also found that the spinels of Zn_1?x Cu _x Cr₂Se₄; 0.0 ≤ x ≤ 0.3. show satellite-like magnetic reflection having indexes (h ± Q, k, l) with Q = 0.470 below T _N and short-range order of spins (spin glass-like) above T _N. The incommensurate antiferromagnetic phase below T _N results from a spiral long-range order of the spins of Cr³⁺. The intermediate ferromagnetic phase between T _N and T _C is related not to the spiral spin order but to double-exchange magnetic interaction among Cr³⁺ and Cr⁴⁺ mediated by current carriers, positive holes, which is made by the substitution of Zn²⁺ ions with Cu¹⁺ ions in Zn_1?x Cu _x Cr₂Se₄.     

Neutron-powder-diffraction study of structural and magnetic structure of La0.7Sr0.3Mn1−xTixO3 (x=0, 0.10, 0.20, and 0.30)

Neutron-diffraction and magnetic measurements have been used in order to study the structure and magnetic changes of La_0.7Sr_0.3Mn_1−xTi_xO₃ (x=0, 0.10, 0.20, and 0.30) perovskites. Magnetic measurements show that our samples exhibit a ferromagnetic–paramagnetic transition with decreasing temperature. Effects of Ti doping on the magnetic and nuclear structures are studied here by neutron-powder-diffraction for La_0.7Sr_0.3Mn_1−xTi_xO₃ (x=0.10, 0.20, and 0.30). Our analysis indicates that the three representative samples, with x=0.10, 0.20, and 0.30, have a hexagonal system of R3¯c space group, and that the magnetic moments order ferromagnetically into the (1 0 1) crystallographic planes, i.e. the magnetic moments of the Mn ion are in the ac plane, with no component along the b-axis. There is no crystalline structure changes when the Ti doping level increases.     

Spinel-type solid solutions involving Mn and Ti:Crystal chemistry, magnetic and electrochemical properties

This study reports the structural and magnetic properties of spinel systems Li₄Mn_5−xTi_xO₁₂ (“4-5-12” series) and LiNi_0.5Mn_1.5−xTi_xO₄ (“LNMTO” series), both based on Mn⁴⁺ substitution by Ti⁴⁺. Intermediate compositions covering the whole range of compositions (0≤x≤5 and 0≤x≤1.5, respectively) were prepared by solid state reaction. The 4-5-12 system forms a continuous spinel solid solution, whereas the spinel phase range in LNMTO stops before the end member “LiNi_0.5Ti_1.5O₄”, which is multi-phased with a major hexagonal phase component. Cell parameters and (Mn,Ti)-O distances increase monotonically with titanium content in both series. In the LNMTO series, the end member LiNi_0.5Mn_1.5O₄ is known to form a superstructure with Ni/Mn cation ordering. Neutron diffraction and Raman spectroscopy show that this order is lost when Ti is substituted, even at low level (x=0.15). The LNMTO crystal chemistry is also complicated by the presence of partial cation inversion, and the presence of a secondary rocksalt-type phase that modifies the spinel stoichiometry. Magnetic properties are characterized by a competition between ferromagnetic and antiferromagnetic interactions; no magnetic ordering is achieved, in agreement with B-site cation frustration and disorder. Electrochemical measurements show that the Ti^3+/4+ and Mn^3+/4+ redox couples behave independently in the 4-5-12 series, and that titanium decreases the high-potential electrochemical redox activity of LNMTO because of its blocking character for electron transfer to and from the nickel sites in the spinel structure.     

Synthesis and electrochemical performances of Li4Ti4.95Al0.05O12/C as anode material for lithium-ion batteries

Spinel compounds Li₄Ti_5−xAl_xO₁₂/C (x=0, 0.05) were synthesized via solid state reaction in an Ar atmosphere, and the electrochemical properties were investigated by means of electronic conductivity, cyclic voltammetry, and charge-discharge tests at different discharge voltage ranges (0-2.5 V and 1-2.5 V). The results indicated that Al³⁺ doping of the compound did not affect the spinel structure but considerably improved the initial capacity and cycling performance, implying the spinel structure of Li₄Ti₅O₁₂ was more stable when Ti⁴⁺ was substituted by Al³⁺, and Al³⁺ doping was beneficial to the reversible intercalation and deintercalation of Li⁺. Al³⁺ doping improved the reversible capacity and cycling performance effectively especially when it was discharged to 0 V.     

Magnetic behavior in the incommensurate phase ∼LaCrS3:: effect of the partial substitution of Cr by Ti on the magnetic properties

Dilution of the magnetic interactions between Cr³⁺ ions by Ti³⁺ ions was observed in the CrS₂ layer of the misfit-layer compound ∼LaCrS₃. Pure ∼LaCrS₃ has complex magnetic properties which are reminiscent of spin glass behavior. This magnetic behavior comes from both the modulated character of the structure and the magnetic frustration of the planar-antiferromagnetic-triangular network of Cr³⁺ ions. Thus, there is a large hysteresis between the zero field cooled and the field cooled magnetic susceptibility curves below the transition temperature (≈75 K). Formation of a solid solution ∼LaCr_1−xTi_xS₃ by the addition of Ti³⁺ ions results in the decrease of transition temperature up to a doping level of x≈0.5, where the transition is no longer observed. The magnetic behavior of the phase with x≈0.5 is similar to that of several random exchange antiferromagnetic compounds.     

Electronic structure studies of Mg0.95Mn0.05Fe2−2xTi2xO4 (0x0.8)

The electronic structure of Mg_0.95Mn_0.05Fe_2−2xTi_2xO₄ (0x0.8) compound is investigated using near edge X-ray absorption fine structure, (NEXAFS) spectroscopy measurements, carried out at O K, Fe and Ti L_3,2-edges at room temperature. The O K-edge spectra indicate that the Fe 3d orbitals have been considerably modified and a new spectral feature start dominating in the pre-edge region at higher Ti doping. The Fe 2p NEXAFS spectra exhibit a mixed valent Fe²⁺/Fe³⁺ states apart from the conversion of Fe³⁺ to Fe²⁺ with the substitution of Ti ions. The Ti L_3,2-edge spectra indicate that Ti ions remain unchanged at 4+ state. These variations in the host electronic structure due to Ti substitution are consistent with the dielectric and transport properties of the material.