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     

Structural modulation and physical properties of cobalt-doped layered La_2M_5As_3O_2(M=Cu,Ni) compounds

We investigate the structural variation and physical properties of layered La_2M_5As_3O_2(M=Cu,Ni) compound upon Co doping. It is found that the substitution of Co ion just induces the monotonous change of lattice constants without observing the anomalous kink in superconducting La_2(Cu~(1-x)Nix)_5 As_3O_2 solid-solutions. Meanwhile, this doping barely changes As–As bond length in [M_5As_3]~(2-) subunit(±2%), being significantly smaller than 7% shrinkage of that in La_2(Cu~(1-x)Nix)_5 As_3 O_2. Therefore, the doping dependence of crystal structure exhibits similar trend with Ba~(1-x)K_xFe_2 As_2 without the interference of As1–As 2 bonding, implying that the Co substitution for Cu/Ni is hole-doped. In terms of physical property, La2(Cu1-xCox)~5As_3O_2 turns into itinerant ferromagnetic metal, while La2(Ni1-x Cox)5 As3 O2 shows paramagnetism and suppressed structural phase transition upon Co-doping. The distinct structural variation and absence of superconductivity provide important clues to understand the effect of As–As bond in [M_5 As_3]~(2-) subunit.     

多铁材料Bi1-xCaxFeO3的介电、铁磁特性和高温磁相变

采用溶胶凝胶法制备Bi_1-xCa_xFeO₃ (x=0, 0.05, 0.1, 0.15, 0.2)陶瓷样品. X衍射图谱表明所有样品的主衍射峰均与纯相BiFeO₃相符合且具有良好的晶体结构. 随着x的增大, Bi_1-xCa_xFeO₃样品的主衍射峰由双峰(104)与(110) 逐渐重叠为单峰(110), 当x ≥0.15时, 样品呈现正方晶系结构; 扫描电镜形貌分析可知, 晶粒由原来的0.5 μm逐渐增大到2 μm. Bi_1-xCa_xFeO₃样品介电常数和介电损耗随着x 的增加先增大而后减小. 当f=1 kHz, Bi_0.9Ca_0.1FeO₃ 的介电常数达到最大值, 是BiFeO₃的7.5倍, 而Bi_0.8Ca_0.2FeO₃的介电常数达到最小值, 仅仅是BiFeO₃的十分之一. Bi_1-xCa_xFeO₃样品所呈现的介电特性是由偶极子取向极化和空间电荷限制电流两种极化机理共同作用的结果. 随着Ca²⁺ 的引入, BiFeO₃ 样品的铁磁性显著提高. X射线光电子能谱图表明Fe²⁺和Fe³⁺ 共存于Bi_1-xCa_xFeO₃ 样品中, Fe²⁺/Fe³⁺比例随着Ca²⁺ 掺杂量的增加而增大, 证明Ca²⁺掺杂增加了Fe²⁺的含量, 增强BiFeO₃的铁磁特性. 从M-T曲线观察到BiFeO₃样品在878 K附近发生铁磁相变, 示差扫描量热法测试再次证明BiFeO₃ 在878 K发生相变. Ca²⁺掺杂使BiFeO₃样品的T_N略有变化而T_M基本不变, 其主要原因是Fe-O-Fe反铁磁超交换作用的强弱和磁结构相对稳定.     

Ca~(2+)掺杂对SmFeO_3的介电、铁磁特性及磁相变温度的影响

采用固相反应法制备Sm_(1-x)Ca_xFeO_3(x=0,0.1,0.2,0.3)样品,研究Ca~(2+)掺杂对SmFeO_3介电性能、铁磁性及磁相变温度的影响.X射线衍射图谱分析表明:所有样品的主衍射峰与SmFe03相符合且具有良好的晶体结构.随着x的增加,SmFeO_3样品的晶粒尺寸由原来的0.5μm逐渐增大到2μm.当f=1 kHz时,Sm_(1-x)Ca_xFeO_3(x=0.1,0.2,0.3)样品的ε_r分别是SmFe03的5倍、3倍和2.6倍,而tgσ增大一个数量级.在3T磁场作用下,SmFe03样品的M-H呈线性,随着x的增加,M-H逐渐趋向饱和,Sm_(1-x)Ca_xFeO_3(x=0.1,0.2,0.3)样品的M_r分别是SmFeO_3的20倍、31倍和68倍.X射线光电子能谱分析表明:Fe~(2+)和Fe3+共存于Sm_(1-x)Ca_xFeO_3样品中,Fe~(2+)/Fe~(3+)比例随着x的增加而增大,证明Ca~(2+)掺杂增加了Fe~(2+)的含量,形成Fe~(2+)—O~(2-)—Fe~(3+)超交换作用,增强SmFe03的铁磁特性.测量了Sm_(1-x)Ca_xFeO_3样品在外加磁场为1000 Oe(1 Oe=79.5775 A/m)的M-T变化关系,观测到其自旋重组温度(T_(SR))和尼尔温度(T_N)分别为438 K和687 K,发现SmFe03样品的T_(SR)和T_N均随着x的增加向低温方向移动,当x=0.3时,自旋重组现象消失.这主要是SmFeO_3样品磁结构的稳定性和Fe~(3+)—O~(2-)—Fe~(3+)及Sm~(3+)—O~(2-)—Fe~(3+)超交换三者共同作用的结果.     

钙钛矿锰氧化物(La_(1-x)Eu_x)_(4/3)Sr_(5/3)Mn_2O_7(x=0,0.15)的磁性和电性研究

通过传统固相反应法制备了钙钛矿锰氧化物(La1-xEux)4/3Sr5/3Mn2O7(x=0,0.15)多晶样品,并且对其磁性和电性进行了研究.磁性测量表明:随着温度的降低,样品经历了一个复杂的转变过程,在温度为T*时经历二维短程铁磁有序转变,在温度为TC时进入三维长程铁磁态.随着Eu的掺杂,T*和TC减小,并且样品(La0.85Eu0.15)4/3Sr5/3Mn2O7在低温区表现出自旋玻璃行为.电性质测量表明:在母体La4/3Sr5/3Mn2O7中La位掺杂Eu后电阻率明显变大,金属绝缘转变温度TMI降低,磁电阻峰值增大.这些影响归因于较小的Eu3+离子替代La3+离子导致平均离子半径减小,晶格发生畸变.此外,较小的Eu3+离子优先占据层间岩盐层的R-site,使La3+,Sr3+,Eu3+离子在(La0.85Eu0.15)4/3Sr5/3Mn2O7中的分布更加有序,所以x=0.15的样品的ρ-T曲线只有一个峰.     

Invar effects of laves phase untermetallic compounds

The magnetovolume effects in Laves phase compounds such as AFe₂ and ACo₂ are received. In particular, Invar like behaviour which is found in (Zr_1-xNb_x)Fe₂ and Zr(Fe_1-xCo_x)₂ systems is reported. Comparing the present results with the classical Invar such as Fe-Ni and Fe-Pt alloys, it is proposed that so-called Invar anomalies should be classified into two type, i.e. the giant spontaneous volume magnetostriction, which is the essential characteristic of the Invar effect and the other anomalies which are observed in Fe-Ni and Zr(Fe_1-xCo_x)₂ systems but not in Fe-Pt and (Zr_1-xNb_x)Fe₂ systems.     

Co含量对Fe3Si合金磁学性能的影响

采用基于密度泛函理论（DFT）的赝势平面波法,对过渡金属Co掺杂Fe₃Si进行几何结构优化,计算Co含量对Fe₃Si合金磁学性质的影响.研究表明：Fe_3-xCo_xSi的磁性主要来源于过渡金属元素Fe和Co,并且相对于A、C位的Fe和Co原子,B位Fe的原子磁矩较大;在0≤x≤0.75范围内,随着Co含量的增大,Fe_3-xCo_xSi的总磁矩缓慢减小,在0.75≤x≤1.5时,其总磁矩迅速地增大;A、C位Fe原子的磁矩和合金总磁矩的变化趋势相同,Co原子的磁矩随着Co含量的增大缓慢地增大,原子的磁矩变化与自旋向上和向下方向的电荷转移有关.     

(Fe1-xCox)3BO5纳米棒磁性的研究

本文采用高温有机溶剂法制备了(Fe_1-xCo_x)₃BO₅纳米棒, 通过控制反应物中乙酰丙酮钴的含量合成了不同Co含量的(Fe_1-xCo_x)₃BO₅. 利用高分辨透射电子显微镜(HRTEM)、超导量子干涉磁强计(SQUID)对其形貌和磁性能进行了表征. 高分辨透射电子显微镜结果表明制备出的纳米(Fe_1-xCo_x)₃BO₅为多晶棒状, 且具有多折孪晶结构; 磁性测量的结果表明,(Fe_1-xCo_x)₃BO₅纳米棒在室温下表现出铁磁性, 随着Co含量的增加, 纳米棒的铁磁性逐渐增加, 该纳米棒有望用来研究生物大分子的机械性能.     

Raman phonon anomalies in Sr(Fe1-xCox)2As2

Phonon anomalies have been reported in iron-pnictide superconductors indicating a diverse interplay between different orders in the materials.Here,we report Raman scattering measurements on Sr(Fe_1-xCo_x)₂As₂(x=0 and x=0.04)single crystals in the B;symmetry with respect to a 1 Fe unit cell.Upon cooling,we observe a larger split(13 cm;)of Eg Raman phonon modes pertaining to in-plane Fe and As displacements as the crystals undergo the tetragonal-toorthorhombic structural phase transition,although a considerable split(9 cm;)has been reported in BaFe_1-xCo_x)₂As₂.Furthermore,the splitting of E;phonon modes is strongly reduced upon doping.We perform an order-parameter analysis revealing a similar doping dependence of E;phonon splitting as reported in other compounds of the 122 family,indicating these phonon anomalies widely exist in 122 iron-based superconductors and might share the same mechanisms.     

Large magnetocaloric effect in van der Waals crystal CrBr3

We study the magnetocaloric effect (MCE) in van der Waals (vdW) crystal CrBr₃. Bulk CrBr₃ exhibits a second-order paramagnetic-ferromagnetic phase transition with T_C = 33 K. The maximum magnetic entropy change −ΔS_M near T_C is about 7.2 J·kg⁻¹·K⁻¹ with the maximum adiabatic temperature change ΔT^max_ad = 2.37 K and the relative cooling power RCP= 191.5 J·kg⁻¹ at μ₀H = 5 T, all of which are remarkably larger than those in CrI₃. These results suggest that the vdW crystal CrBr₃ is a promising candidate for the low-dimensional magnetic refrigeration in low temperature region.     

Oxygen permeability of La2Cu(Co)O4+δ solid solutions

Formation of the La₂Cu_1−xCo_xO_4+δ solid solutions with orthorhombic K₂NiF₄-type structure was found to be in the range of 0≤x≤0.30 at temperatures above 1270 K. Incorporating cobalt into the copper sublattice of lanthanum cuprate leads to increasing oxygen hyperstoichiometry and decreasing electrical conductivity. Thermal expansion coefficients of the La₂Cu_1−xCo_xO_4+δ (x=0.02–0.30) ceramics at 470–1100 K were calculated from the dilatometric data to vary in the range (12.2–13.2)×10⁻⁶ K⁻¹. Studying the dependence of oxygen permeation fluxes through La₂Cu(Co)O_4+δ on the membrane thickness demonstrated that the oxygen transport at the thickness values below 1 mm is limited by both surface exchange rate and bulk ionic conductivity. Oxygen permeability of the La₂Cu_1−xCo_xO_4+δ solid solutions was ascertained to increase with cobalt concentration at x=0.02–0.10 and to decrease with further dopant additions, indicating a participation of interstitial oxygen in the ionic transport.     

Effects of Mg substitution on the structural and magnetic properties of Co_(0.5)Ni_(0.5-x)Mg_xFe_2O_4 nanoparticle ferrites

In this study, nanocrystalline Co–Ni–Mg ferrite powders with composition Co_(0.5)Ni_(0.5-x)Mg_xFe_2O_4 are successfully synthesized by the co-precipitation method. A systematic investigation on the structural, morphological and magnetic properties of un-doped and Mg-doped Co–Ni ferrite nanoparticles is carried out. The prepared samples are characterized using x-ray diffraction(XRD) analysis, Fourier transform infrared spectroscopy(FTIR), field emission scanning electron microscopy(FESEM), and vibrating sample magnetometry(VSM). The XRD analyses of the synthesized samples confirm the formation of single-phase cubic spinel structures with crystallite sizes in a range of ~ 32 nm to ~ 36 nm. The lattice constant increases with increasing Mg content. FESEM images show that the synthesized samples are homogeneous with a uniformly distributed grain. The results of IR spectroscopy analysis indicate the formation of functional groups of spinel ferrite in the co-precipitation process. By increasing Mg2+substitution, room temperature magnetic measurement shows that maximum magnetization and coercivity increase from ~ 57.35 emu/g to~ 61.49 emu/g and ~ 603.26 Oe to~ 684.11 Oe(1 Oe = 79.5775 A·m-1), respectively. The higher values of magnetization Ms and Mr suggest that the optimum composition is Co_(0.5)N_(i0.4)Mg_(0.1)Fe_2O_4 that can be applied to high-density recording media and microwave devices.     

Magnetic properties of xFe2O3(1−x)[B2O3 · PbO] glasses

The magnetic measurements performed on xFe₂O₃(1-x)[B₂O₃ · PbO] glasses show that for x 5 mol.% Fe₂O₃ the thermal variation of reciprocal susceptibility obeys a Curie behaviour. For higher iron content, at T 50 K, a nonlinear variation, typical for systems with random distribution of exchange interactions is observed. At greater temperatures than 50 K a Curie-Weiss behaviour is shown. The composition dependence of the Curie constants is analysed in correlation with the number of Fe³⁺ and Fe²⁺ ions as determined from Mössbauer effect measurements. A comparison with the data obtained in case of xFe₂O₃(1-x)[3B₂O₃ · PbO] glasses is made.     

Evolution of structure and physical properties in Al-substituted Ba-hexaferrites

The investigations of the crystal and magnetic structures of the Ba Fe12-xAlx O19(x = 0.1–1.2) solid solutions have been performed with powder neutron diffractometry. Magnetic properties of the Ba Fe12-xAlx O19(x = 0.1–1.2) solid solutions have been measured by vibration sample magnetometry at different temperatures under different magnetic fields.The atomic coordinates and lattice parameters have been Rietveld refined. The invar effect is observed in low temperature range(from 4.2 K to 150 K). It is explained by the thermal oscillation anharmonicity of atoms. The increase of microstress with decreasing temperature is found from Rietveld refinement. The Curie temperature and the change of total magnetic moment per formula unit are found for all compositions of the Ba Fe12-xAlx O19(x = 0.1–1.2) solid solutions. The magnetic structure model is proposed. The most likely reasons and the mechanism of magnetic structure formation are discussed.     

Mixed electronic and ionic conductivity of LaCo(M)O3 (M=Ga, Cr, Fe or Ni).: V. Oxygen permeability of Mg-doped La(Ga, Co)O3−δ perovskites

The LaGa_1−x−yCo_xMg_yO_3−δ solid solutions with rhombohedrally-distorted perovskite structure were ascertained to form in the concentration range of 0≤y≤0.10 at x=0.60 and 0≤y≤0.20 at x=0.35–0.40. Increasing cobalt content results in increasing electrical conductivity and thermal expansion of the perovskites. Thermal expansion coefficients of the LaGa_1−x−yCo_xMg_yO_3−δ ceramics were calculated from the dilatometric data to vary in the range of 12.4–19.8×10⁻⁶ K⁻¹ at 300–1100 K. Doping La(Ga,Co)O_3−δ solid solutions with magnesium leads to increasing oxygen nonstoichiometry, electronic and oxygen ionic conductivity. Oxygen permeation fluxes through LaGa_1−x−yCo_xMg_yO_3−δ membranes were found to be limited by the bulk ionic conduction and to increase with magnesium concentration, being essentially independent of cobalt content.     

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.     

Shaped crystal growth and scintillating properties of Yb:(Gd,Lu)3Ga5O12 solid solutions

Shaped single crystals of (Lu_xGd_1−x)₃Ga₅O₁₂ (0.0x1.0) and (Yb_0.05Lu_xGd_0.95−x)₃Ga₅O₁₂ (0.0x0.9) were grown by the modified micro-pulling-down method. Continuous solid solutions with garnet structure and a linear compositional dependency of crystal lattice parameter in the system Yb:(Gd,Lu)₃Ga₅O₁₂ are formed. Measured optical absorption spectra of the samples show 4f–4f transitions related to Gd³⁺ ion at 275 and 310 nm, and also an onset of charge transfer transitions from oxygen ligands to Gd³⁺ or Yb³⁺ cations below 240 nm. A complete absence of Yb³⁺ charge transfer luminescence under X-ray excitation in any of the investigated samples was explained by the overlapping of charge transfer absorption of Yb³⁺ by that of Gd³⁺ ions. For specific composition of Lu_1.5Gd_1.5Ga₅O₁₂ an intense defect-host lattice-related emission, which achieve of about 40% integrated intensity compared with Bi₄Ge₃O₁₂, was found.     

Intercalation thermodynamics and chemical diffusion of oxygen in the solid solution YBa2Cu3−xCoxO6+δ

The equilibrium oxygen content as a function of the temperature and oxygen pressure was measured for the solid solution YBa₂Cu_3−xCo_xO_6+δ, where x=0, 0.2, 0.4, 0.6, 0.8, by using coulometric titration in the temperature range 600–850°C and oxygen pressures between 10⁻⁵ and 1.0 atm. The change in the partial molar enthalpy and entropy of the intercalated oxygen was determined at different oxygen and cobalt contents. The oxygen chemical diffusion was studied by thermogravimetric relaxation in the oxygen-controlled atmosphere. The thermodynamic data were employed to determine how the chemical diffusion coefficient, the thermodynamic factor and the random-diffusion coefficient depend on oxygen content in specimens with different cobalt concentration. The oxygen intercalation thermodynamics and diffusivity results provide evidence of ordering phenomena on a microscopic scale in the basal plane of the tetragonal solid solution YBa₂Cu_3−xCo_xO_6+δ. A model for the oxygen diffusion is suggested to explain the large difference between the random and tracer diffusion coefficients in YBa₂Cu₃O_6+δ     

哈斯勒合金Ni-Fe-Mn-In的马氏体相变与磁特性研究

利用电弧炉制备了Ni_50-xFe_xMn₃₇In₁₃(x=1, 3, 5) 多晶样品, 通过结构和磁性测量, 系统分析了Ni_50-xFe_xMn₃₇In₁₃(x=1, 3, 5)样品的晶体结构和马氏体相变. 结果表明, 三样品在室温下呈现出了不同的晶体结构. 同时, 随着Fe含量的增加, 样品的马氏体相变温度急剧下降, 而铁磁性却逐渐增强. 研究了Fe3和Fe5样品在反马氏体相变过程中的磁电阻和磁卡效应. 在外加3 T的磁场下, 两样品在反马氏体相变区域所表现出的磁电阻效应分别约为-46%和-15%, 而等温熵变则约为6 J·kg^{-1·K-1和9.5 J}·kg^{-1·K-1. 然而, 伴随非常宽的相变温跨和较小的磁滞损失, Fe3样品在反马氏体相变区域的净制冷量达到96 J}·kg^-1.     

PrNi$lt;sub$gt;2$lt;/sub$gt;的磁和磁热性能研究

在一些磁性材料内, 磁性离子间交换作用和磁性离子的自旋涨落对材料磁性有影响. 本文根据磁比热实验值确定了晶场参数后, 利用包含自旋涨落的交换作用有效场H_m= n₀ (1 + γ T + β e^{ω T})M, 计算了PrNi₂晶体晶场能级的Zeeman劈裂. 在温度为3.8 K ≤T≤ 30 K范围内, 计算了该晶体多晶磁矩随外磁场的变化, 以及外磁场H=5000 Oe时磁化率倒数随温度的变化, 计算结果和实验值符合较好. 当外磁场在0–50000 Oe时, 计算的该晶体的磁熵变与已有文献的理论结果相似. 计算结果说明, 提出的包含自旋涨落的交换作用有效场不仅适合亚铁磁性晶体, 而且也适合顺磁性晶体. 关键词： 2')" href="#">PrNi₂ 磁比热 交换作用有效场 磁矩 磁熵变