Effects of Pr substitution on the hydrogenating process and magnetocaloric properties of La_(1-x)Pr_xFe_(11.4)Si_(1.6)H_y hydrides

In this paper, we study the effects of Pr substitution on the hydrogenating process and magnetocaloric properties of La_(1-x)Pr_xFe_(11.4)Si_(1.6)H_y hydrides. The powder x-ray diffraction patterns of the La_(1-x)Pr_xFe_(11.4)Si_(1.6) and its hydrides show that each of the alloys is crystallized into the single phase of cubic Na Zn_(13)-type structure. There are hydrogen-absorbing plateaus under 0.4938 MPa and 0.4882 MPa in the absorbing curves for the La_(0.8)Pr_(0.2)Fe_(11.4)Si_(1.6) and La_(0.6)Pr_(0.4)Fe_(11.4)Si_(1.6) compounds. The releasing processes lag behind the absorbing process, which is obviously different from the coincidence between absorbing and releasing curves of the La Fe_(11.4)Si_(1.6) compound. The remnant hydrogen content for La_(0.6)Pr_(0.4)Fe_(11.4)Si_(1.6) is significantly more than that for La_(0.8)Pr_(0.2)Fe_(11.4)Si_(1.6) after hydrogen desorption, indicating that more substitutions of Pr for La are beneficial to retaining more hydrogen atoms in the alloys. The values of maximum magnetic entropy change are 14.91 J/kg·K and 17.995 J/kg·K for La_(0.8)Pr_(0.2)Fe_(11.4)Si_(1.6)H_(0.13) and La_(0.6)Pr_(0.4)Fe_(11.4)Si_(1.6)H_(0.87),respectively.     

Microstructure and magnetocaloric properties in melt-spun and high-pressure hydrogenated La0.5Pr0.5Fe11.4Si1.6 ribbons

The effects of wheel speeds and high-pressure hydrogen treatment on phase evolution, microstructure, and magnetocaloric properties in La_0.5Pr_0.5Fe_11.4Si_1.6 melt-spun ribbons are studied in this work. The results reveal that the increase of wheel speed is beneficial to the formation of cubic NaZn₁₃-type phase and the grain refinement. The optimized wheel speed for microstructural and magnetocaloric properties is 30 m/s. The largest entropy change of 18.1 J/kg·K at 190 K under a magnetic field change of 0 T-5 T is obtained in La_0.5Pr_0.5Fe_11.4Si_1.6 ribbons melt-spun at 30 m/s. After a high-pressure hydrogen treatment of 50 MPa, the Curie temperature of the ribbons prepared at 30 m/s is adjusted to about 314 K and the large -ΔS_M of 17.9 J/kg·K under a magnetic field change of 0 T-5 T is achieved at room temperature with almost none hysteresis loss. The small thermal and magnetic hysteresis and the large -ΔS_M make the La_0.5Pr_0.5Fe_11.4Si_1.6 hydride ribbons appropriate for magnetic refrigerant applications around room temperature.     

La3Co29-xFexSi4B10的择优占位、电子结构和晶格振动性质的理论研究

分别用第一性原理及原子间相互作用势对初始模型进行几何优化, 所得稳定结构的晶格参数均与实验值符合较好. 通过第一性原理密度泛函理论, 计算了稳定结构La₃Co_29-xFe_xSi₄B₁₀化合物择优占位情况, 计算结果表明, Fe原子最择优替代Co 原子的2c晶位, 择优占位顺序为2c > 8j1 > 8i2 > 8j2 > 8i3 > 16k > 8i1, 这与实验结果非常符合. Fe原子每次只替代不同晶位的一个Co原子时, La₃Co_29-xFe_xSi₄B₁₀ 体系的晶格常数几乎不变, 磁矩却发生了有趣的变化. 当Fe原子沿着择优顺序依次替代不同晶位的所有Co原子时, 随着La₃Co_29-xFe_xSi₄B₁₀体系中Fe原子含量的增多, 其电子态密度整体向左移动. Fe原子完全替代Co时, 与未掺杂时相比体系的总磁矩增加. 最后, 利用原子间相互作用势进一步预测了La₃Co_29-xFe_xSi₄B₁₀体系的晶格振动及热力学性质. 在低频部分, 振动模式主要由质量较大的Co, Fe和La元素作贡献; 随着掺杂原子Fe的增多, 体系的截止频率先减小后增多, 中频部分由Si元素引起的振动模式减少; B-B强相互作用引起了高频部分的振动模式. 基于声子态密度预测了不同数量Fe掺杂后体系的比热、熵和德拜温度的变化, 当Fe 含量大于Co时, 德拜温度明显升高.     

在永磁体强磁场中Mn1.2Fe0.8P1-xSix系列化合物热磁发电研究

研究了处于永磁体强磁场中Mn_1.2Fe_0.8P_1-xSi_x 系列化合物的热磁发电性能, 采用高性能球磨和固相烧结合成方法制备了Mn_1.2Fe_0.8P_1-xSi_x 系列化合物, 并对该系列化合物的物相结构、磁性和热磁发电性能进行了测量. 结果表明: Mn_1.2Fe_0.8P_0.37Si_0.63和Mn_1.2Fe_0.8P_0.35Si_0.65化合物是具有Fe₂P型六角结构的一级相变软磁性材料, 两者居里温度分别为334 K和348 K, 处于工业余热温区. 根据一级相变磁性材料在居里温度磁化强度发生突变这一特性, 研制热磁发电演示装置, 测量了Mn_1.2Fe_0.8P_0.37Si_0.63和Mn_1.2Fe_0.8P_0.35Si_0.65这两种材料铁磁相变产生感应电流大小与线圈匝数、热磁发电材料质量、表面积、表面上温度梯度的关系. 研究结果表明, Mn_1.2Fe_0.8P_1-xSi_x系列化合物具有很好的热磁发电性能, 有望成为热磁发电候选材料.     

Observation of hydrogen induced intermediate borides in PrFeB based alloys by Mössbauer effect spectroscopy

In the present work, a quantitative analysis of the phase compositions by Mössbauer effect spectroscopy of solid and conventional hydrogen disproportionated Pr_13.7Fe_80.3B_6.0 and Pr_13.7Fe_63.5Co_16.7Zr_0.1B_6.0 alloys was carried out. Significant amounts of intermediate borides t-Fe₃B and Pr(Fe, Co)₁₂B₆ were detected after solid hydrogen disproportionation treatment in Pr_13.7Fe_80.3B_6.0 and Pr_13.7Fe_63.5Co_16.7Zr_0.1B_6.0 alloys, respectively. After conventional hydrogenation–disproportionation–desorption–recombination treatment these phases were not detected and in no case residual Pr₂Fe₁₄B-phase was found. It was observed that the amount of intermediate borides after disproportionation can be correlated with the degree of texture after recombination at various temperatures.     

Spin-dependent valence-band density of states of 3d ferromagnets

Spin-resolved X-ray photoelectron spectroscopy (SRXPS) and high resolution X-ray photoelectron spectroscopy (HRXPS) studies of the valence bands of ferromagnetic Fe, Co, Co₆₆Fe₄Ni₁B₁₄Si₁₅ and Ni are reported. The SRXPS and HRXPS spectra are compared with theoretical densities of states (DOS) that are corrected for photoelectric cross section variations within the valence band. Agreement between theory and experiment is very good for ferromagnetic Fe and Co₆₆Fe₄Ni₁B₁₄Si₁₅. For Co metal, experiment agrees poorly with theory incorporating a 1.5 eV exchange splitting. Agreement is improved if a reduced Co exchange splitting of 1.2 eV is adopted theoretically. The reduced exchange splitting is attributed to valence electron correlation in Co metal. Ferromagnetic Ni shows poor agreement between experiment and theory. The SRXPS Ni spectra demonstrate that most of the disagreement concerns the ↑-spin channel.     

Giant magnetoimpedance in glass-covered amorphous microwires at microwave frequencies

In this work, results on the giant magnetoimpedance (GMI) of a glass-covered amorphous microwires with nominal compositions Co_70.4Fe_4.6Si₁₅B₁₀ and Fe_77.5Si_7.5B₁₅ are presented. The impedance Z=R+iX has been investigated as function of frequency (up to 1.8 GHz) and magnetic field (up to ±400 Oe), using a HP4396B impedance analyzer and an appropriate coaxial microwave cavity. The effects of the thermal treatments (Joule heating, from 20 mA up to 100 mA for 10 min) for anisotropy induction and, as a consequence, for GMI effect have been investigated.     

Dynamical effects in magnetic and transport properties of phase separated La0.5Ca0.5Mn0.95Fe0.05O3

We have measured transport and magnetic properties of polycrystalline La_0.5Ca_0.5Mn_0.95Fe_0.05O₃, a phase separated manganite with ferromagnetic ground state. Cooling rate dependences and time relaxation were found; the coexistence of ferromagnetic and charge ordered regions determines a dynamics which influences physical properties. We show that a dynamical contribution to the resistivity can account for the observed cooling rate dependence and ageing effects on this phase separated manganite.     

The condition for the occurence of zero coercive field in amorphous ribbon carrying an ac current

A zero coercive field H_c has been obtained by passing an ac current with appropriate phase, frequency and amplitude through an amorphous Co_70.3Fe_4.7Si₁₅B₁₀ ribbon. The phenomenon is explained in terms of the model for magnetization of amorphous ribbons carrying dc current. The condition for the occurence of H_c=0 has been derived and the evidence provided that the strength of pinning centres responsible for H_c increases at elevated currents. Some applications of the phenomenon are briefly discussed.     

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.     

Effect of Ti and C additions on structural and magnetic properties of (Pr,Nd)–Fe–B nanocrystalline magnetic materials

Effects of titanium carbide (TiC) addition on structural and magnetic properties of isotropic (Pr,Nd)–Fe-B nanocrystalline magnetic materials have been investigated. In this work, we investigate the effect of TiC addition on a (Pr,Nd)-poor and B-rich composition, as well as on a B-poor and (Nd,Pr)-rich composition. Rapidly solidified (Pr,Nd)–Fe–B alloys were prepared by melt-spinning. The compositions studied were (Pr_1−xNd_x)₄Fe₇₈B₁₈ (x=0, 0.5, and 1) with addition of 3 at% TiC. Unlike the (Pr_xNd_1−x)_9.5Fe_84.5B₆ materials that present excellent values for coercive field and energy product, the (Pr,Nd)-poor and B-rich composition alloys with TiC addition present lower values. Rietveld analysis of X-ray data and Mössbauer spectroscopy revealed that samples are predominantly composed of Fe₃B and -Fe. For the RE-rich compositions (Pr_xNd_1−x)_9.5Fe_84.5B₆ (x=0.1, 0.25, 0.5, 0.75, and 1) with the addition of 3 at% TiC, the highest coercive field and energy product (8.4 kOe and 14.4 MGOe, respectively) were obtained for the composition Pr_9.5Fe_84.5B₆.     

Effects of torsion stress on the domain wall unpinning AC field in amorphous FeCoBSi wires

The unpinning or propagation field, h_p, where domain walls are unpinned and start their displacement under the AC magnetic field of as-cast amorphous wires of nominal composition (Co₉₄Fe₆)_72.5B₁₅Si_12.5, was determined for each torsion angle between –90° (counterclockwise) and +150° (clockwise) at a constant frequency of 1 kHz. A plot of h_p as a function of torsion angle showed a sharp minimum at a torsion angle of +120. The results are interpreted in terms of the counterbalance effect of the torsion against the intrinsic helical anisotropy induced during the wire fabrication.     

Electrochemical performance of mixed ionic–electronic conducting oxides as anodes for solid oxide fuel cell

Mixed ionic–electronic conducting (MIEC) oxides, SrFeCo_0.5O_x, SrCo_0.8Fe_0.2O_3−δ and La_0.6Sr_0.4Fe_0.8Co_0.2O_3−δ have been synthesized and prepared on yttria-stabilized zirconia as anodes for solid oxide fuel cells. Power output measurements show that the anodes composed of such kinds of oxides exhibit modest electrochemical activities to both H₂ and CH₄ fuels, giving maximum power densities of around 0.1 W/cm² at 950°C. Polarization and AC impedance measurements found that large activation overpotentials and ohmic resistance drops were the main causes for the relative inferior performance to the Ni-YSZ anode. While interlayered with an Ni-YSZ anode, a significant improvement in the electrochemical performance was observed. In particular, for the SrFeCo_0.5O_x oxide interlayered Ni-YSZ anode, the maximum power output reaches 0.25 W/cm² on CH₄, exceeding those of both SrFeCo_0.5O_x and the Ni-YSZ, as anodes alone. A synergetic effect of SrFeCo_0.5O_x and the Ni-YSZ has been observed. Future work is needed to examine the long-term stability of MIEC oxide electrodes under a very reducing environment.     

STRUCTURE AND MAGNETIC PROPERTIES OF LaCo13-BASED ALLOYS

The structure and magnetic properties of two series of LaCois-based alloys, LaCo_13-xFe_x(0≤x≤6) and La_1-xR_x(Co, Fe)₁₃ (x=0.1,0.2; R=Y, Ge, Pr, Nd Sm, Gd, Tb, Dy, Ho, Er, and Yb), are studied by X-ray diffraction and magnetic mea- surements. In the above-mentioned composotions, all the samples display a structure of NaZn₁₃ type (space group: Fm3c). In LaCo_13-xFe_x system, as the iron content increases, its Curie temperature decreases, while thc magnetic moment per 3d atom increases. This may be explained by a rigid band model. In the other alloy system, the Curie temperature goes through a maxium at R=Gd, and this reflects the influ- ence of R - T interaction. It is also observed that saturation magnetization varies with R and gets lower when R is a heavy rare earth element. The contribution of R is close to that of a free-ion moment. La_0.9Pr_0.1Co₉Fe₄ has the largest value 29μ_B/f.u.     

The effect of key process parameters on crystallographic texture and magnetic properties of PrFeB HD sintered magnets produced using high-energy milling

A combination of hydrogen decrepitation and planetary ball milling has been used to produce sintered Pr₁₆Fe₇₆B₈ magnets. The effects of key process parameters and texture have been studied. The alignment degree (cos Θ) has been investigated by X-ray pole figure analysis using the (0 0 4) reflection. Magnets prepared from the alloy decrepitated for 3.6 ks and milled for 1.8 ks exhibited a low degree of crystal alignment (0.71±0.02) due to polycrystalline particles. Increasing the milling time to 4.5ks has led to an improvement in cos Θ to 0.84±0.02. This has been ascribed to the smaller particle size with a narrower size distribution as well as a more favorable particle shape for orientation. Superior alignment degree (cos Θ=0.88±0.02) has been achieved for the sintered magnet from the alloy decrepitated for 120 s and milled for 5.4 ks. This particular processing condition has led to a magnet with (BH)_max=250±5 kJ m⁻³, value found in magnets produced using roller ball milling, with the advantage of a reduced milling time (about 90%).     

Dielectric loss of half-doped manganite La_(0.5)Ca_(0.5)MnO_3

The dielectric loss tanδ of half-doped manganite La 0.5 Ca 0.5 MnO 3 is investigated using Green's function technique. The La 0.5 Ca 0.5 MnO 3 is described by the Kondo-lattice model in the double exchange limit, taking into account the Jahn-Teller distortion and the super-exchange interaction between the localized electrons. It is found that the intensity of tanδ decreases with increasing | ε JT |, V, and U. It is also observed that the transition temperature T P rises as | ε JT | and U increase. It is worth noting that T P remains unchanged and the strength of tanδ increases with increasing g. The calculated dielectric loss results are explained theoretically, and these behaviors are in qualitative agreement with the experimental results.     

Oxygen nonstoichiometry and electrical conductivity of the solid solutions La2−xSrxNiOy (0≤x≤0.5)

Oxygen nonstoichiometry and electrical resistance of a series La_2−xSr_xNiO_y solid solutions, where x=0.0, 0.2 and 0.5 in argon flows at oxygen partial pressures 1.5, 10.2, 49.2, 100 and 286 Pa within the temperature range of 20–1050°C were studied. Nickelate oxygen desorption/sorption spectra when heating–cooling at constant rate demonstrated strong dependence of cation composition of the samples. Unlike La_1.5Sr_0.5NiO_y compounds those of La₂NiO_y and La_1.8Sr_0.2NiO_y have weakly bonded oxygen, capable to exchange reversibly with the gas phase at the temperatures higher than 250°C. The equilibrium values of oxygen nonstoichiometry and specific resistance for the these nickelates were determined at 300–1050°C and p_O2=1.5–286 Pa as a functions of temperature versus oxygen partial pressure. All nickelate studied appear to be p-type conductors with metal electric conductivity at equilibrium states.     

Influence of misch metal content on microstructure and magnetic properties of R–Fe–B magnets sintered by dual alloy method

MM_(14)Fe_(79.9)B_(6.1)/Nd_(13.5)Fe_(80.5)B_6 magnets were fabricated by dual alloy method(MM, misch metal). Some magnets have two Curie temperatures. Curie temperatures T_(c1)corresponds to the main phase which contains more La Ce, and T_(c1) decreases from 276.5?C to 256.6?C with the content of MM increasing from 30.3 at.% to 50.6 at.%. The variation of Br with the increase of MM indicates the existence of inter-grain exchange coupling in the magnets. When MM/R ≤ 30.3 at.%,the magnetic properties can reach the level of the intrinsic coercivity Hcj≥ 7.11 kOe and the maximum energy product(BH)max≥ 41 MGOe. Compared with Nd, La and Ce are easier to diffuse to the grain boundaries in the sintering process,and this will cause the decrease of H_(cj) Due to the diffusion between the grains, the atomic ratio of La, Ce, Pr, and Nd in each grain is different and the percentage of Nd in all grains is higher than that in misch metal.     

稀土硼化物LaxCe1-xB6亚微米粉的制备及光吸收研究

以稀土氧化物La₂O₃和CeO₂为稀土源, 以NaBH₄为硼源在真空环境中通过固相反应成功制备出了分散性好的单相三元La_xCe_1-xB₆亚微米粉. 系统研究了掺杂元素La对CeB₆物相, 微观结构及光吸收性能的影响. 实验结果表明, La元素的掺杂没有改变CeB₆的物相和晶体结构, 而是无序替代了Ce原子晶位. 光吸收结果表明, 随着La掺杂量的增加La_xCe_1-xB₆分散液吸收谷波长从620 nm减小到610 nm出现了蓝移现象.     

凝胶浇注制备La0.8Sr0.2Cr0.5Fe0.5O3-δ-Zr0.84Y0.16O1.92非对称陶瓷透氧膜

要凝胶浇注制备多孔支撑体,并采用浆料涂膜和高温共烧技术制备非对称La_0.8Sr_0.2Cr_0.5Fe_0.5O_3-δ-Zr_0.84Y_0.16O_1.92（LSCF-YSZ）双相复合陶瓷透氧膜。结果显示,采用凝胶浇注制备技术,可获得结构均匀和高孔隙率的多孔支撑体;在多孔支撑体上,采用浆料涂膜和高温共烧技术制备的LSCF-YSZ非对称管状透氧膜,Air/He梯度下,950℃,氧渗透速率达到1.17×10^-8mol·cm^-2·s^-1;在850—950℃温度范围,膜的氧渗透表观活化能为163.7±0.4kJ/mol。