Mn离子取代M型钡铁氧体的研究

本文对Mn离子取代M型钡铁氧体BaFe_12-xMn_xO₁₉作了较系统的研究。主要结论如下:(1)在我们的实验条件下,Mn的取代量x可达4,其中约有0.1—0.3的Mn²⁺存在,其余Mn为三价。(2)Mn离子主要进入12k和2a晶位。(3)BaFe_12-xMn_xO₁₉的各向异性常数K₁₉,居里温度T_c和饱和磁化强度σ_s均随x的增加而下降。(4)Mn引起BaFe_12-xMn_xO₁₉的非共线自旋结构。(5)Mn³⁺在12k和2a晶位中的平均零场劈裂因子D^h比尖晶石中八面体B位上的Mn³⁺之D^c值小近一个数量级。 关键词：     

Y1-xPrxBa2Cu3O7+δ的红外反射谱

测量了温度范围为4.2—300K的Y_1-xPr_xBa₂Cu₃O_7+δ(x=0,0.1,0.2,0.4,0.5,0.61.0)的红外反射谱,发现在低温下Ba模有双模行为,随着x值增大双模强度反转,在YBa₂Cu₃O_7+δ中已被判定为Y模的位于194cm^-1的反射峰的位置与Pr的含量无关,即用Pr部份或全部替代Y时此峰不发生频移。建议Pr在Y_1-xPr_xBa₂Cu₃O_7+δ,中是正4价,Pr的替代使原来可移动的空穴被定域在Pr的周围,使超导电性受到压制。 关键词：     

Y_3Fe_(5-x)Mn_xO_(12)的磁结构和磁性能

对多晶Y_3Fe_(5-x)Mn_xO_(12)(x=0.05和0.09),得到300K下的中子衍射曲线。发现当x=0.05时,Mn~(3+)离子占据16a和24d位置的几率分别为0.72和0.28;当x=0.09时,Mn~(3+)离子全部占据16a位置;还得到两种组分16a和24d位置各自的磁矩值。 在外磁场(800—10KOe)下测量Y_3Fe_(5-x)Mn_xO_(12)(x=0—0.11)的磁化曲线,温度范围是1.5—300K。得到饱和磁矩值;并利用趋近饱和定律确定1.5K下的磁晶各向异性常数k_1值,发现|K_1|值随含锰量增加而减小。     

Y1-xCaxBa2Cu3-xMxO7-δ (M=Fe,Ni)体系的超导电性

本文报道,通过对Y_1-xCa_xBa₂Cu_3-xMxO_7-δ(M=Fe,Ni)体系样品的晶体结构、氧含量、正常态电阻率与温度的关系,以及超导转变温度等测量,并与YBa₂Cu_3-xMxO_7-δ(M=Fe,Ni)体系进行比较,发现Y_1-xCa_xBa₂Cu_3-xFe_xO_7-δ体系的T_c显著地高于相应x值的YBa₂Cu_3-xFe_xO_7-δ体系,而Y_1-xCa_xBa₂Cu_3-xNi_xO_7-δ体系则相反,T_c低于仅Ni替代的体系,表明Ca和Fe同时替代时两者引起的载流子浓度(n_H)变化相互补偿,抑制了仅Fe替代时引起的n_H和T_c急剧下降;而作Ca和Ni同时替代时主要的不是两者引起载流子浓度变化的相互补偿,Ca和Ni替代效应之间的关联较弱。作者认为,对Y_1-xCa_xBa₂Cu_3-xFe_xO_7-δ体系属于CuO₂平面外的元素替代,这时载流子浓度是决定Tc的主要因素;而对Y_1-xCa_xBa₂Cu_3-xNi_xO_7-δ体系,由于Ni²⁺离子主要占据Cu(Ⅱ)位,它导致磁拆对效应,Ni²⁺离子的拆对效应是引起T_c下降的直接原因。 关键词：     

BaCoxZn2-xFe16O27六角铁氧体电子结构与介电特性的第一性原理研究

提出了W型六角铁氧体BaCo_xZn_2-xFe₁₆O₂₇的晶体结构模型,并通过基于密度泛函理论框架下Hubbard参数U修正的广义梯度近似密度泛函理论方法研究了该材料的基态电子结构、磁性和静电介电性特性.Co和Zn共掺杂引起BaFe₁₈O₂₇的导电性从半金属转换到半导体.BaCo_xZn_2-xFe₁₆O₂₇的能隙随x增加而增加,品格常数和原胞磁矩随之而变小.介电常数计算表明,BaCo_xZn_2-xFe₁₆O₂₇的静电介电常数随x增加而增加,在6.2—7.2范围而且显示各向异性.Bom电荷计算分析表明Co和Zn本身极化对材料的介电常数和其各向异性影响不大.     

Y2O3·Cr2O3复合氧化物热力学性质的研究

在1182—1386K温度范围内,用固体电解质氧浓差电池:Mo|Cr,Y₂O₃,Y₂O₃·Cr₂O₃|ZrO₂(+MgO)|Cr,Cr₂O₃|Mo测定了复合氧化物Y₂O₃·Cr₂O₃的热力学性质。对于反应Y_{2关键词：}     

Er2AlFe16－xMnx化合物的磁性及反常热膨胀

通过X射线衍射及磁测量手段研究了Er₂AlFe_16-xMn_x(x=1，2，3，4，6，8)化合物的结构和磁性. 研究结果表明Er₂AlFe_16-xMn_x化合物具有六角相的Th₂Ni₁₇型结构. 采用X射线热膨胀测定法在103—654K的温度范围内测量了Er₂AlFe_16-xMn_x(x=1，2，3，4)化合物的热膨胀性质，发现这些化合物在低温下存在热膨胀反常现象，在居里点附近具有负膨胀性质. 对自发磁致伸缩的研究结果表明Er₂AlFe_16-xMn_x化合物中存在着较强的各向异性的自发磁致伸缩，低温下自旋重取向的出现使得化合物的自发体磁致伸缩有所增强. 磁测量结果表明Mn的替代导致Er₂AlFe_16-xMn_x化合物的居里温度及自发磁化强度急剧下降，并且使得化合物的磁晶各向异性发生显著改变. 关键词： 2AlFe_16-xMn_x化合物')" href="#">Er₂AlFe_16-xMn_x化合物 反常热膨胀 自发磁致伸缩     

Y3-xBixFe5O12的晶体生长

本文讨论了Y₂O₃-Fe₂O₃-Bi₂O₃-PbO·0.2B₂O₃赝四元系相图的得出与运用;用Bi₂O₃-PbO-B₂O₃做助熔剂,获得了磁性石榴石Y_3-xBi_xFe₅O₁₂单晶(0≤x≤1.2);还论述了Bi-YIG晶体内Bi含量与助熔剂熔液成份的关系。 关键词：     

R2Fe17-xAlx化合物中R-T交换耦合常量的计算

讨论了利用分子场近似结合中子衍射或X射线衍射的实验结果计算R₂Fe₁₇型稀土过渡族化合物中稀土磁矩与过渡族磁矩之间交换耦合常量的方法,并据此计算了R₂Fe_17-xAl_x(R=Tb,Dy,Ho,Er,Gd,x=7或8)化合物中稀土磁矩与过渡族磁矩之间的交换耦合常量.计算结果与实验值符合较好. 关键词： 2Fe_17-xAl_x化合物')" href="#">R₂Fe_17-xAl_x化合物 交换耦合常量     

Ce3+和Mn2+掺杂的Ba9(Y2-xScx)(SiO4)6光谱特性和温度特性研究

采用高温固相法制备了Ba₉(Y_2-xSc_x)(SiO₄)₆:Ce³⁺,Mn²⁺(x=0,0.5,1.0,1.5,2.0)样品。在该体系中,当Sc³⁺含量从x=0逐渐增加至x=2时,Ce³⁺的蓝光发射强度提高了1.7倍;同时,Mn²⁺的红光发射强度提高了1.9倍,显示了优良的红光特性。样品的发射光谱和漫反射光谱表明,Ce³⁺、Mn²⁺发射强度的增加与Ce³⁺吸收能力和Ce³⁺向Mn²⁺能量传递的提升有直接关系。研究了样品Ba₉Sc₂(SiO₄)₆:Ce³⁺,Mn²⁺的热稳定性。随着温度的升高,Mn²⁺的红光发射呈现先升后降的态势。当温度从室温升至488 K时,Mn²⁺发射强度仅下降至室温时的84%,表现出优良的热稳定性。高亮的红光发射和优良的热稳定性表明该荧光材料可为紫外基白光LED提供良好的红色光源。     

Magnetic and transport properties of double distorted perovskites CaCuMn6O12 and CaCu2Mn5O12

Magnetic and transport properties of double distorted perovskites CaCuMn₆O₁₂ and CaCu₂Mn₅O₁₂ are studied in a range 2–300 K. The leading role in magnetism of these compounds belongs to antiferromagnetic exchange interaction of Cu²⁺ in square coordination with Mn³⁺/Mn⁴⁺ in octahedral coordination. The values of saturation magnetization indicate that Mn³⁺ ions in square coordination are coupled ferromagnetically with Mn³⁺/Mn⁴⁺ in octahedral coordination. The colossal magnetoresistance in the pellet samples is due assumingly to intergranular spin-polarized tunneling of current carriers.     

Magnetic properties of the mixed spinel Co1+xSnxFe2−2xO4

The structural and magnetic properties of the mixed spinel Co_1+xSn_xFe_2?2xO₄ system for 0.1≤x≤0.5 have been studied by means of X‐ray diffraction, magnetization, a.c. susceptibility and Mössbauer effect measurements. X‐ray intensity calculations indicate that Sn⁴⁺ ions occupy only octahedral (B) sites replacing Fe³⁺ ions and the added Co²⁺ ions substitute for A‐site Fe³⁺ ions. The lattice constants are determined and the applicability of Vegard's law has been tested. The Mössbauer spectra at 300 K have been fitted with two sextets in the ferrimagnetic state corresponding to Fe³⁺ at tetrahedral (A) and octahedral (B) sites for x≤0.4. The Mössbauer intensity data show that Sn possesses a preference for the B‐site of the spinel. As expected, the hyperfine field and Curie temperature determined from a.c. susceptibility decreases with increasing Sn content. The variation of the saturation magnetic moment per formula unit measured at 77 and 300 K with Sn content is satisfactorily explained on the basis of Néel's collinear spin ordering model for x=0.1–0.4.     

Magnetic properties of transition metal substituted La0.85Ag0.15Mn1−yMyO3 compounds (M=Co, Cr and Al)

In this paper we report a systematic study of Mn-site substitution by M=Co, Cr and Al in La_0.85Ag_0.15MnO₃ series to understand the magnetic interactions between Mn and other transition metals. The long-range ferromagnetic (FM) ordering of the parent compound was significantly affected by Mn-site substitution. The measured magnetic properties of Co-doped samples have been explained on the basis of FM interactions in Mn³⁺-O-Mn⁴⁺, Co²⁺-O-Mn⁴⁺, Co³⁺-O-Mn⁴⁺ networks and simultaneous antiferromagnetic (AFM) interactions in Mn⁴⁺-O-Mn⁴⁺, Co²⁺-O-Mn³⁺ networks. The magnetic properties of Cr-doped compounds could be understood on the basis of double exchange FM interactions in Mn³⁺-O²⁻-Mn⁴⁺ networks and competing AFM in Cr³⁺-O-Mn⁴⁺, Mn⁴⁺-O-Mn⁴⁺, Cr³⁺-O-Mn³⁺ networks. However, it is found that the doping of Al ions play a role of magnetic dilution, without contributing any other competing magnetic interaction. The field variations of magnetization of all the above three series could be analysed by fitting to Brillouin function model and the effective spin contribution for FM has been determined. The measured saturation magnetization has been explained quantitatively.     

La1-xCaxMnO3的巨磁电阻效应

通过测量La_2/3Ca_1/3MnO₃，La_0.6Ca_0.4MnO₃单相多晶样品的磁电阻、电阻与温度的依赖关系，发现在La_1-xCa_xMnO₃体系中随x的变化，其磁电阻峰和电阻峰都发生了位移．作者认为体系中Mn⁴⁺含量是受Ca含量调制的，正是Mn⁴⁺含量的变化，导致磁性 关键词：     

ESR study of Fe3+ and Mn2+ ions on trigonal sites in ilmenite structure MgTiO3

Electron spin resonance has been observed for Fe³⁺ and Mn²⁺ ions occupying sites with trigonal symmetry in undoped and doped Verneuil-grown crystals of the ilmenite type compound MgTiO₃. At 300 K, the fine structure parameters in the spin Hamiltonian are (in 10^?4cm^?1) D = +844 (± 1), (a? F) = +118 (± 1), a = 69 (± 7) for Fe³⁺ and D = +164 (± 1), (a ? F) = +10.2 (± l), a = 7.0 (± 1) for Mn²⁺. These values are compared with literature data for Fe³⁺ and Mn²⁺ in other oxides, especially Al₂o₃, with particular reference to the recent “superposition” theory of the effect of a trigonal distortion. From the orientation of the axes of cubic pseudosymmetry of the spin Hamiltonian, and with the assumption that a has the same sign for both ions, it is proposed that Fe³⁺ and Mn²⁺ occupy the same octahedral site, namely the Mg²⁺ site. Anomalous line splittings observed for one sample were attributed to twinning on (0001) or {1120} planes.     

Mössbauer effect study of Ni1−xCuxMnyFe2−yO4 system

The Mössbauer effect technique has been employed for the study of magnetic properties of spinel series Ni_1?xCu_xMn_yFe_2?yO₄ with 0.0≤x≤1.0, and y=0.6. The substitution of Mn³⁺ and Cu²⁺ ions results in a slight decrease of the hyperfine field at B‐ as well as A‐sites. The area ratio of Fe³⁺ ions at the A‐ and B‐site at 77 K indicates that Cu²⁺, Ni²⁺ and Mn³⁺ ions occupy the octahedral sites in an evidence for complete inverse spinel in this system. The temperature dependence of the hyperfine parameters has been studied for composition with x=0.5 where Nèel point T_N and Debye temperature θ_D are found to be 650 and 679 K, respectively. The temperature dependence of the sublattice magnetization σ(T) obeys a one‐third‐power law in the range 0.5N<0.99.     

Charge ordering and structural transitions in Pr0.5Sr0.41Ca0.09MnO3

The structural and magnetic transitions in Pr_0.5Sr_0.41Ca_0.09MnO₃ have been investigated by neutron diffraction and electron microscopy. Two structural transitions, Imma to I4/mcm and I4/mcm to Pmmn, are observed by decreasing the temperature. Two magnetic transitions, from a paramagnetic insulating to a ferromagnetic metallic and from a ferromagnetic metallic to an antiferromagnetic insulating states at T_C=250 K and T_N=180 K, respectively, are also observed. The structures of these three forms have been determined from neutron powder diffraction data. The first important result concerns the low temperature antiferromagnetic CE type and charge ordered structure, which has been refined in the Pmmn space group, without any constraint. This structure is completely long range ordered, with two Mn-sites, Mn³⁺ in tetragonally elongated octahedra, and Mn⁴⁺, off-centered in nearly regular octahedra. The second important point concerns the abrupt character of the structural transition from the I4/mcm to the Pmmn structure, without any appearance of incommensurability. The magnetic and transport properties of this compound are compared with those of Pr_0.5Sr_0.5MnO₃.     

Luminescence of Mn ions in ordered and disordered LiAl5O8

The phosphorescence and excitation spectra of Mn ions in the ordered and disordered phases of LiAl₅O₈ have been measured. In both phases Mn²⁺ ions substitute for Al³⁺ ions in two different tetrahedral sites of the LiAl₅O₈ lattice. In both sites in the ordered phase, sharp zero-phonon transitions have been observed in the low temperature phosphorescence and excitation spectra - these transitions were considerably broadened in the disordered phase due to crystal field inhomogeneity in that phase. The deviation from neutrality caused by the Mn²⁺ ions in the ordered phase is largely compensated by Mn⁴⁺ ions occupying octahedral Al³⁺ sites. On disordering, a large proportion of Mn⁴⁺ is reduced to Mn²⁺, while the remainder takes up a site with a higher proportion of Li⁺ ions as next nearest neighbours. This leads to an increase in the ionicity of the Mn⁴⁺ site in the disordered phase and hence to a larger value of the Racah parameter B.     

Magnetocaloric effect in polycrystalline La0.65Ba0.3M0.05MnO3 (M=Na, Ag, K) manganites

The effects of monovalent doping on the crystallographic, magnetic and magnetocaloric properties of La_0.65Ba_0.3M_0.05MnO₃ (M=Na, Ag, K) powder samples, elaborated using the solid state reaction method at high temperature, have been investigated. In our three samples the Mn⁴⁺ amount remains constant equal to 40%. The Rietveld refinement of the X-ray powder diffraction shows that all our synthesized samples are single phase and crystallize in the distorted rhombohedral system with R3¯c space group. All our studied samples undergo a paramagnetic–ferromagnetic transition with decreasing temperature. Using the Arrott plot, the second-order transition Curie temperature T_C for M=Na, Ag and K is found to be 310, 300 and 290 K, respectively. The magnetic entropy change, deduced from isothermal magnetization curves, exhibits a maximum |ΔS_M^Max| of about 2.65, 2.82 and 2.66 J/kg K for M=Na, Ag and K, respectively, in a magnetic applied field change of 5 T. Although these values are modest, the magnetocaloric effect extends over a large temperature range leading to an important value of the relative cooling power (RCP). The RCP values exhibit a nearly linear dependence with the magnetic applied field. The refrigeration capacity in a magnetic applied field of 1 T is found to be 28.8, 27.8 and 25.6 J/kg for M=Na, Ag and K compounds.     

Co2+-Ti4+和Cu2+-Nb5+离子取代BaFe12O19单晶体中Fe3+离子的研究

本文对用Co²⁺-Ti⁴⁺和Cu²⁺-Nb⁵⁺离子取代BaFe₁₂O₁₉单晶体中Fe³⁺离子进行了研究,以Bi₂O₃作为助熔剂生长出了BaFe_12-2xCo_x²⁺Ti_x⁴⁺O₁₉(x=0;0.04;0.09;0.13;0.27和0.68)以及BaFe_12-x[Nb_1/3⁵⁺Cu_2/3²⁺]_xO₁₉(x=0;0.28;0.44和0.60)这两系列的单晶体,测定了100—300K温度范围内样品的磁化强度σ与单轴各向异性常数K₁,我们发现,对Co²⁺-Ti⁴⁺取代的样品,当x≤0.09时,其σ与K₁随x的增加而缓慢增加;当x>0.09时,其σ与K₁随x的增加而迅速降低,至x=1.1时,K₁变为零,对Nb⁵⁺-Cu²⁺取代的样品,其σ值在整个成份范围内基本保持不变,且有缓慢增加趋势;而K₁值则随x增加而单调下降,提出了取代离子在M型六角铁氧体中可能的分布模型来解释我们的结果。 关键词：