Cu1-xHxZr2(PO4)3中Cu2+的EPR谱和局域结构研究

本文采用Cu²⁺斜方对称电子顺磁共振（EPR）参量的高阶微扰公式计算了晶体Cu_1-xH_xZr₂（PO₄）₃中Cu²⁺的EPR参量（g因子和超精细结构常数A因子）．计算结果表明，晶体Cu_1-xH_xZr₂（PO₄）₃中[CuO₆]^10-基团的Cu-O键长分别为R_||≈0.241 nm，R_⊥≈0.215 nm，平面键角τ≈80.1°；由于对称性降低，中心金属离子基态²A_1g（θ）和²A_1g（ε）有一定程度混合，混合系数α≈0.995．所得EPR谱图的理论计算值与实验数据符合得很好．     

A contribution to the invar problem by hyperfine field distribution analyses

The Mössbauer spectra of Invar type Fe₆₅(Ni_1-xMn_x)₃₅ alloys (0 x 0.3) were analyzed to yield hyperfine field distribution (P(H)) curve. The P(H) curves of the alloy with x = 0, that is the “classical” Invar alloy, at 4.2 K is character ized by a relatively sharp main peak at 350 kOe and a weak low field component around 50 kOe. With increasing x, the low field component grows and the high field main peak spreads toward a low field. By raising temperature, the main peak exhibits a remarkable broadening as well as a decrease in the average internal field and a growth of the low field component has not been detected. On the basis of these observations, models of the Invar alloy so far proposed are discussed.     

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     

Dielectric and piezoelectric properties of(110) oriented Pb(Zr_(1-x)Ti_x)O_3 thin films

A phenomenological Landau–Devonshire theory is developed to investigate the ferroelectric, dielectric, and piezoelectric properties of(110) oriented Pb(Zr_(1-x)Ti_x)O_3(x = 0.4, 0.5, 0.6, and 0.7) thin films. At room temperature, the tetragonal a_1 phase, the orthorhombic a_2c phase, the triclinic γ_1 phase, and the triclinic γ_2 phase are stable. The appearance of the negative polarization component P_2 in the a_2c phase and the γ_1 phase is attributed to the nonlinear coupling terms in the thermodynamic potential. The γ phase of the Pb(Zr_(1-x)Ti_x)O_3 thin films has better dielectric and piezoelectric properties than the a_2c phase and the a_1 phase. The largest dielectric and piezoelectric coefficients are obtained in the Pb(Zr_(0.5)Ti_(0.5))O_3 thin film. The piezoelectric coefficient of 110–150 pm/V is obtained in the(110) oriented Pb(Zr_(0.5)Ti_(0.5))O_3 thin film, and the Pb(Zr_(0.3)Ti_(0.7))O_3 thin film has the remnant polarization and relative dielectric constant of 50 μC/cm~2 and 100, respectively,which are in agreement with the experimental measurements reported in the literature.     

Abnormal variation of magnetic properties with Ce content in(PrNdCe)_2Fe_(14)B sintered magnets prepared by dual alloy method

Resource-saving(PrNdCe)_2Fe_(14)B sintered magnets with nominal composition(PrNd)_(15-x)Ce_xFe_(77)B_8(x=0–10)were prepared using a dual alloy method by mixing(PrNd)_5Ce_(10)Fe_(77)B_8 with(PrNd)_(15)Fe_(77)B_8 powders. For Ce atomic percent of 1% and 2%, coercivity decreases dramatically. With further increase of Ce atomic percent, the coercivity increases, peaks at 6.38 kOe in(PrNd)_(11)Ce_4Fe_(77)B_8, and then declines gradually. The abnormal dependence of coercivity is likely related to the inhomogeneity of rare earth chemical composition in the intergranular phase, where Pr Nd concentration is strongly dependent on the additive amount of(PrNd)_5Ce_(10)Fe_(77)B_8 powders. In addition, for Ce atomic percent of 8%,7%, and 6% the coercivity is higher than that of magnets prepared by the conventional method, which shows the advantage of the dual alloy method in preparing high abundant rare earth magnets.     

Itinerant magnetism in TiMxBe2-x (M = Cu, Fe)

Magnetization and Mössbauer studies of TiCu_xFe_yBe_2-x-y (x = 0, 0.03, 0.4, y = 0, 0.02) show that TiBe₂ is an enhanced paramagnet, 0.02 Fe or 0.03 Cu reduce the susceptibility. On the other hand, TiCu_0.4Be_1.6 is ferromagnetic (T_c = 20 K) and 0.02 Fe reduces the magnetization and Curie point (T_c = 16 K). The magnetic properties of all samples are extremely sensitive to sample preparation and heat treatments.

The Mössbauer studies show that the itinerant magnetism resides on the Ti site, all Ti sites have the same local spin density irrespective of local environment.     

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.     

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.     

Anomalous magnetotransport phenomena in θ-(BEDT-TTF)2I3

Anomalous magnetotransport phenomena have been observed in θ-(BEDT-TTF)₂I₃ crystals at temperatures below 15 K. The magnetoresistance M : (1) is a linear function of the magnetic field H, (2) is not affected by the angle between the electric current and the magnetic field, (3) but depends on the magnetic field orientation with respect to the crystal axis. Magnetoresistance is expressed as M = (aH²_a + bH²_b + cH²_c)₀^-3/2/H in terms of H = (H_a, H_b, H_c), the zero field resistivity ₀, and parameters a, b, and c which are independent of temperature and magnetic field. We have found that b a > c. Magnetoresistance up to 40 is observed for H = 7T along the b-axis at T = 1.5K.     

Magnetic properties and domain structure of polycrystalline DyFe3

Magnetization σ vs. temperature T was measured from 80 to 700 K in polycrystalline DyFe₃ in a magnetic field H = 10 kOe. From σ = f(T), the Curie temperature was determined. Also, σ was measured vs. H from 0 to 70 kOe at 4.2 K. Magnetization at saturation σ₀ at 4.2 K and the magnetic moment of DyFe₃ were also determined. First observations of domain structure in DyFe₃ are reported. The mean domain with is determined in its dependence on the grain size . The magnetocrystalline anisotropy constant of polycrystalline DyFe₃ is determined as K₁ = -1.2×10⁷ erg/cm³.     

Magnetic dynamics of two-dimensional itinerant ferromagnet Fe_3GeTe_2

Among the layered two-dimensional ferromagnetic materials(2 D FMs),due to a relatively high T_C,the van der Waals(vdW) Fe_3 GeTe_2(FGT) crystal is of great importance for investigating its distinct magnetic properties.Here,we have carried out static and dynamic magnetization measurements of the FGT crystal with a Curie temperature TC ≈ 204 K.The M-H hysteresis loops with in-plane and out-of-plane orientations show that FGT has a strong perpendicular magnetic anisotropy with the easy axis along its c-axis.Moreover,we have calculated the uniaxial magnetic anisotropy constant(K_1)from the SQUID measurements.The dynamic magnetic properties of FGT have been probed by utilizing the high sensitivity electron-spin-resonance(ESR) spectrometer at cryogenic temperatures.Based on an approximation of single magnetic domain mode,the K_1 and the effective damping constant(α_(eff)) have also been determined from the out-of-plane angular dependence of ferromagnetic resonance(FMR) spectra obtained at the temperature range of 185 K to T_C.We have found large magnetic damping with the effective damping constant α_(eff) ～ 0.58 along with a broad linewidth(ΔH_(pp) 1000 Oe at 9.48 GHz,H ‖ c-axis).Our results provide useful dynamics information for the development of FGT-based spintronic devices.     

Field-induced parameters of re-entrant magnets and concentrated spin glasses

We have used electron spin resonance measurements to derive the temperature and frequency dependences of the field-induced magnetization [M(T, f)] and anisotropy field [H_an (T)] in a number of amorphous alloys belonging to the series (Fe_pNi_1−p)₇₅P₁₆B₆Al₃. In re-entrant (p > p_c, the critical concentration for ferromagnetism) alloys at hi gh frequencies (f = 35 GHz, field ≈ 12 kOe) M reduces as T^3/2 at high T and as T below ≈ 40 K, the deviation from T^3/2 becoming more marked as p → p⁺_c. For p close to p_c, lowering the frequency first causes the T term to increase and ultimately ( ≈ 4 GHz) changes the variation of M with T to that discovered previously for concentrated spin glasses, namely M is constant at low T and drops linearly at high temperatures. For the re-entrants, the results are interpreted on the basis of a model which invokes an energy gap in the spin-wave spectrum, introduces a non-zero density of states of the gap energy and takes into consideration a low-q cut-off in the spin-wave integral in thelow-T (T) regime.In the concentrated spin glasses [M (0) - M (T)]/ M (0) is well represented by the function [exp (Δ / T) - 1]^-1, where Δ has values close to the corresponding Curie-Weiss temperatures θ_p but much larger than the respective spin glass transition temperatures T_SG. The temperature dependence of H_an is largely given by the function (1 - T/T^*), where T^* is equal to the zero-field freezing temperature for the re-entrants and T_SG for the spin glasses, respectively.     

Mo-SiO2-C3H6催化反应体系的ESR动态表征

文章考察了Mo-SiO₂催化剂体系在丙烯歧化反应过程中的动态ESR波谱,发现在催化歧化反应过程中有两种Mo⁵⁺顺磁中心,一种为扰动八面体配位,g_||=1.89,g_⊥=1.94;另一种为扰动四棱锥配位,g_||=1.86,g_⊥=1.95。测得同位素^95,97Mo⁵⁺的各向异性超精细耦合常数A_||=90.3×10^-4cm^-1,A_⊥=44.8×10^-4cm^-1;观测到反应产生的积炭信号,g≈2.0O₂;氧阴离子自由基信号g₁=2.018,g₂=2.011,g₃=2.005。用LCAO-MO理论对上述Mo⁵⁺的ESR波谱进行计算,求得分子轨道系数,发现并总结出△g_||/△g_⊥与△g成直线关系,并建议用△g_||/△g_⊥=4(△E(B₂→E))/(△E(B₂→B₁)(β₁/ε)²之比值作为衡量C_4v扰动程度的尺度。     

Coercivity mechanism in nanophase (Nd–Pr)–Fe–B melt spun alloys

The nucleation mechanism to predict coercivity values in melt-spun exchange-coupled (Nd_1−xPr_x)_yFe_94−yB₆ alloys for various Nd:Pr ratios x, and Fe:RE ratios y, was tested using the dependence of the anisotropy constant K₁ on Pr content x for the minimum nucleation field H_N^min in the modified Brown's equation. Very good agreement was found between experimental data and theoretical values, confirming the predominance of the nucleation of reverse domains over the wall pinning process in the coercivity mechanism of melt spun REFeB alloys.     

Magnetic properties of TmFeO3 and TmGa0.13Fe0.87O3 orthoferrites

The magnetization σ_c has been observed to depend strongly on temperature and biasing field in the Γ₄-phase. Two families of σ_c (T) occur corresponding to the poly-domain (H < 200 Oe), and mono-domain (H > 200 Oe) states of the samples. This was proved by observation of domain structures in these samples. In addition to the maximum due to the second-order phase transition Γ₂-Γ₄, we have revealed a maximum in the susceptibility curves _Xc(T) at the high-temperature point of phase transition. The second maximum strongly depends on the biasing field value. Domain structure behaviour in that temperature range, and in various external fields, allowed us to suggest that there exists a relation between this maximum and the shifting processes of domain boundaries, which create a significant susceptibility along the c-axis.     

稠苯芳杂环及其烷基质子化学位移的计算

本文提出了予测稠苯芳杂环及其烷基链上质子化学位移的计算方法。 将稠苯芳杂环化合物用凯库勒式表示,计算式为为需考虑的苯环内的乙烯基效应。σ_mi,ci为各苯环的环流效应。σ_1,Hc为各芳杂环的屏蔽效应,对杂环上质子它就是该单独芳杂环上相应质子的δ值,对苯环上质子要将它分解为各结构因素的效应,即:σ_1,He=(1/2)^d-1δ_x=y(或σ_z)+σ_c-c·σ_m,H. σ_x-y与σ_z为杂原子或其基团的屏蔽效应,σ_c=c为存在于芳杂环中的乙烯基的效应,σ_m,Hc为芳杂环的环流效应,d为对不同质子所考虑的键数。有取代基时需考虑取代基的效应。计算环上烷基质子的公式为:δ=σ_p,CH3+ασ_c,CH3+βσ_t,CH3+σ_l,G σ_l,G为稠苯芳杂环基的某级效应。     

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.     

Cobalt substituted R---Fe(Co)---C alloys

The formation of tetragonal R₂(FeCo)₁₄C phase has been examined in as-cast and melt-spun R₁₄Fe_78−xCo_xC₈ alloys with cobalt substitutions (R = Y, Dy, Nd). The magnetic properties over a temperature range and the microstructure have been studied as a function of cobalt content. The Curie temperature is increased with Co content but the anisotropy K is decreased. High cobalt content leads to the formation of 1:5 phase. High corecivities have been developed in as-cast and melt-spun Dy₁₄Fe_78−xCo_xC₈ alloys with Co content at zero and 32 at %, respectively. As-cast Nd₁₆Fe_78−xCo_xC₈ alloys did not show any permanent magnetic properties although they had the 2:14:1 phase. However, melt-spun and powdered Nd---Fe---Co---C samples showed a coercivity with the highest value corresponding to a melt-spun Nd₁₄Fe₇₈C₈ sample. Microstructure studies showed that the high H_C in ribbons is due to the fine grain size which is in the range of 500–1000 Å.     

Reduced s-d model with antiferromagnetically coupled impurity spins

An antiferromagnetic equivalent-neighbour Heisenberg interaction H_i between impurity spins is added to the reduced s-d Hamiltonian H_r previously introduced by simplifying the Kondo s-d exchange Hamiltonian H_K. Asymptotic mean-field theory is developed for H_r + H_i, in the presence and absence of external magnetic field, and applied to (La_1−xCe_x)Al₂ alloys. Specific heat c_i(T) and zero-field susceptibility χ_i(0,T) curves for (La_1−xCe_x)Al₂ are depicted. The coupling constants of H_r + H_i and conduction bandwidth are adjusted so that T_c temperatures for x = 0.2, 0.1 are equal to the experimental values. c_i(T) exhibits a jump at T_c and is decreasing for T < T_c. χ_i(0,T) has a first order pole at T_c which corresponds to the maximum of experimental susceptibility and χ_i(0,0) > 0. These results improve those obtained earlier on the grounds of H_r theory.