Enhanced multiferroic properties in La and Ce co-doped BiFeO3 nanoparticles

Room temperature multiferroic properties of BiFeO₃ (BFO), Bi_0.9La_0.1FeO₃ ((La)BFO) and Bi_0.9La_0.075Ce_0.025FeO₃ ((La,Ce)BFO) nanoparticles have been reported in this paper. XRD (X-ray diffraction) analyses of the nanoparticles show a decrease in the lattice constants and cell volume with the substitution of La and Ce. It is evident from the SEM (scanning electron microscope) micrographs that the (La,Ce) co-doped sample possesses dense microstructure made of smaller particles. Raman study accounts for the weakening of the strong hybridization between Bi-O by the substitution of La and Ce ions. This is also accompanied by an increase in the remanent magnetization, dielectric constant, and ferroelectric polarization. BFO nanoparticles show exchange bias effect under an applied magnetic field while the (La)BFO and (La,Ce)BFO samples show no trace of such effect. Ac-conductivity of (La,Ce) co-doped sample is observed to be several orders lesser in magnitude than bulk BFO ceramics. These results are interpreted by means of the subtle change in the structure, suppression of the spin cycloid and reduction of oxygen vacancies in the doped samples.     

Enhanced alignment and magnetic properties of die-upset nano-crystal Nd2Fe14B magnets with Nb addition

It is difficult to obtain the crystallographic alignment for stoichiometric Nd₂Fe₁₄B alloys by applying the melt-spun and subsequent hot-pressing and hot-deformation techniques. However, the enhanced alignment and magnetic properties of die-upset nano-crystal Nd₂Fe₁₄B magnets have been obtained by Nb addition in the present paper. The magnetic properties studies show that Nb addition leads to the remarkable increase of remanence B_r and intrinsic coercivity H_ci, which is due to the improvement of c-axis texture and refinement of microstructure. Microstructure studies using transmission electron microscopy (TEM) and X-ray diffraction (XRD) reveal that Nb atoms are enriched at grain boundary and the NbFeB phase is observed with increasing Nb content. Since some Fe atoms in the Nd₂Fe₁₄B phase participate in the formation of NbFeB phase, the excessive Nd atoms may be enriched at grain boundary, which may improve the physical property of grain boundary and provide a mass transport pass for preferential growth of oriented Nd₂Fe₁₄B grains, thus leading to the enhanced alignment and magnetic properties.     

Luminescence characteristics and optimization of (La,Gd)Sr2(Al,B)O5:Ce phosphor for white light emitting diodes

Luminescence properties of (La,Gd)Sr₂(Al,B)O₅:Ce phosphors were investigated by changing the content of Gd and B substituent. The Gd or B substitution was confirmed to improve the emission intensity. The emission peak of LaSr₂AlO₅:Ce was shifted to the longer wavelength due to the enlargement of crystal-field splitting for Ce³⁺ activators as the result of the unit-cell volume reduction when the Gd and B atoms are substituted. In the B-substituted samples, in addition to the cell volume reduction, the change in the lattice covalency due to the large electronegativity difference between B³⁺ and Al³⁺ has additionally contributed to shift the emission peak. The crystallite sizes of phosphors were enlarged using small amount of Gd and B atoms. Also, the absorption for the 4f→5d absorption of Ce³⁺ ions in UV/visible spectrum was greatly enhanced by the substitution of both Gd and B. Therefore, it was concluded that the enhancement of the emission intensity via the substitution is due to the increase in the crystallinity and the light-absorption ability. Finally, the optimized sample La_0.89Ce_0.01Gd_0.1Sr₂Al_0.9B_0.1O₅ had about 368% improved emission intensity compared with La_0.99Ce_0.01Sr₂AlO₅.     

Superconducting—normal phase boundaries of (La,Th)Ce systems

The dependence of the superconducting transition temperature T_c on Ce impurity concentration n is reported for various ($\text{La, Th}$)Ce systems. These results document for the first time the evolution of the superconducting— normal phase boundary (T_c vs n curve) as an impurity undergoes magnetic- nonmagnetic transition which for Ce impurities in ($\text{La, Th}$)Ce systems proceeds with increasing Th concentration. Observed for only the second time, re-entrant T_c vs n curves are reported for two La-rich La, Th host compositions.     

Hyperfine interaction of Ce and La in 3-d ferromagnets

NMR/ON measurements on¹⁴¹CeFe show the sign of the hyperfine field of CeFe to be negative. For the¹⁴¹Ce nucleus a g-factor of ¦g_N¦=0.311±0.011 is found. With this g-value a hyperfine field of H_hf=?41±2 T for CeFe is derived. Low temperature nuclear orientation experiments on¹⁴¹CeCo and¹⁴⁰LaFe yield ¦H_hf¦=30±3 T and ¦H_hf¦=46±5 T respectively. The valence of cerium impurities in Fe, Co and Ni is discussed.     

Effect of Cu and Ga additions on the anisotropy of R2Fe14B/α-Fe nanocomposite die-upset magnets (R=Pr,Nd)

Fully dense nanocomposite magnets containing hard R₂Fe₁₄B and soft α-Fe phases were produced from both melt-spun and mechanically milled alloys by hot pressing and subsequent die upsetting. Although R-lean R–Fe–B alloys that do not contain the grain-boundary R-rich phase are known not to be susceptible to texture development by means of die upsetting, we found that small additions of Cu make the texturing possible. The resulting microstructure of oriented platelet grains is similar to that of the R-rich die-upset magnets. Properties of the Cu-containing R₂Fe₁₄B/α-Fe die-upset magnets can be further improved by adding Ga. The anisotropic Pr₁₂Fe₈₀Cu₁Ga₁B₆ magnet made from mechanically milled alloy and containing 17.2 wt% α-Fe had a remanence of 13 kG and a maximum energy product of 23.4 MG Oe. The Pr_11.25Fe_80.75Cu₁Ga₁B₆ magnet made from melt-spun alloy and containing 16.2 wt% α-Fe had a maximum energy product of 19.9 MG Oe. The low coercivity of 3–4 kOe typical for the Cu-containing R₂Fe₁₄B/α-Fe die-upset magnets is due to the relatively coarse α-Fe grains. The latter grains are too large for intergranular exchange interaction, but, nevertheless, they are well coupled with the R₂Fe₁₄B grains by a long-range magnetostatic interaction.     

Effects of La3+ doping on the optical characteristics and color tunability of (Mg,Mn)(Y,Ce, La)4Si3O13 phosphors

The doping effects of La³⁺ ions on the photoluminescence properties and color tunability of (Mg, Mn)(Y, Ce, La)₄Si₃O₁₃ phosphors have been elaborated in this study. On increasing the La³⁺ concentration in the host, tunability of excitation wavelength is achieved first, which in turn leads to the blue shift in the wavelength of Ce³⁺ emission. The high-energy emission shift of Ce³⁺ ions results from the change in the crystal field around Ce³⁺ ions. With the incorporation of La³⁺ ions, the chromaticity coordinates shift towards white-light region showing the tunable characteristics. Moreover, the correlated color temperature (CCT) change from warm white to cool white light region with different concentration of La³⁺ ions. The variation of different excitation wavelength tunes the emission thus augmenting the probability of (Mg, Mn)(Y, Ce, La)₄Si₃O₁₃ phosphors for potential application in optical devices.     

Effect of Ce impurities on superconductivity and nuclear spin-lattice relaxation in La1−cCecAl2

In the superconducting state of La_1?cCe_cAl₂ alloys ¹³⁹La spin-lattice relaxation times T_1s for relatively high c were found to agree with theory based on weak exchange coupling between conduction electrons and paramagnetic impurities. But for a dilute specimen the measured values of T_1s are significantly longer than expected. These results are tentatively attributed to the existence of a localized impurity band within the superconducting energy gap.     

Electronic and magnetic properties of layered LnFePO (Ln=La and Ce)

Effects of the replacement of La with Ce on the electronic and magnetic properties of a layered superconductor LaFePO (T_c=∼5 K) were studied. Polycrystalline samples of CeFePO, prepared by a solid-state reaction, showed metallic conduction down to 2 K without exhibiting superconducting transition, although the resistivity decreased largely at temperatures below 30 K. Further, they showed an apparent positive magnetoresistance (MR) below ∼2 K, superposed on a negative MR. Temperature dependence of magnetic susceptibility is decomposed to a temperature-sensitive Curie-Weiss component presumably due to the Ce³⁺ ions with a magnetic moment of 1.98μ_B and a less temperature-sensitive component attributable to itinerant electrons. The magnetic interaction between Ce³⁺ ions and itinerant electrons in CeFePO likely suppresses the superconducting transition observed in LaFePO.     

稀土含量对速凝工艺制备(Nd,Dy)-(Fe,Al)-B合金结构和磁性能的影响

采用双合金法制备了不同稀土含量的(Nd,Dy)-(Fe,Al)-B合金系列,研究了稀土含量的多寡对薄带和最终烧结磁体的微观结构和磁性能的影响.研究结果表明,适量的稀土含量(～3145%)不仅能改善速凝带主相(Nd,Dy)₂Fe₁₄B的单相性,还有利于富稀土(Nd,Dy)相在晶界的均匀分布.当主相薄带的稀土含量在接近2∶14∶1相稀土含量时,磁体的内禀矫顽力和磁能积显著提高.当稀土含量较少时,对速凝薄带的合适时效热处理将能有效地提高最终烧结NdFeB磁体的磁特性. 关键词： 双相烧结 速凝技术 微观结构 磁性能     

The coercive field of sintered and melt-spun NdFeB magnets

The magnetic hysteresis loops have been investigated in the temperature range between 4.2 and 575 K for aligned sintered permanent magnets of nominal composition Nd₁₅Fe₇₇B₈ and for isotropic melt-spun ribbons of composition Nd₁₅Fe₇₆B₉. The measured temperature and field dependence of the coercive field is analysed within the framework of theoretical results for nucleation fields of the ideal Nd₂Fe₁₄B matrix and, of disturbed surface regions of Nd₂Fe₁₄B grains. Furthermore the pinning of domain walls at thin soft magnetic grain boundary phases is considered for the high temperature range. It is concluded that for both types of NdFeB magnets the relevant magnetic hardening mechanisms at lower temperatures are nucleation processes in magnetically inhomogeneous regions whereas at higher temperatures the pinning of domain walls at grain boundaries predominates. The critical temperature where the change of nucleation hardening to pinning hardening occurs depends sensitivity on the crystal anisotropy, the grain boundary microstructure and the macroscopic grain- and multi phase arrangements.     

Magnetic properties of As-spun MmxFe92−xB8 ribbons

X-ray phase analysis and magnetic measurements have been made on melt-spun Mm_xFe_92−xB₈ alloys (10 < x < 23.5, Mm - Mishmetal). The existence of a Mm₂Fe₁₄B phase have been confirmed. The alloys investigated exhibit hard magnetic properties with (BH)_max and _iH_c up to 9.1 MGOe and 10.5 kOe, respectively.     

Near stabilization of the Ce moment upon dilution in (Ce,La)Al3

Susceptibility measurements taken for 1.5 ≤ T ≤ 17 K on the system Ce_xLa_1?xAl₃ indicate that the Ce moment is nearly stabilized on dilution. Evidence for this is the fact that the fractional occupancy of the 4f¹ configuration and the spin correlation time both increase as x → 0. Crystalline electric fields influence the susceptibility of these valence fluctuation systems.     

Valence instability of Ce and La impurities in YNi2

Measurements of resistivity and lattice constants are reported for the Y_0.98RE_0.02Ni₂ series of alloys. Both the Ce and the La alloys show strong anomalies in volume and resistivity increment, especially at low temperatures. This is the first indication for a valence instability on an impurity of La.     

Research on La–Co-substituted strontium ferrite magnets for high intrinsic coercive force

M-type strontium ferrites with substitution of Sr²⁺ by rare-earth La³⁺, and a little amount of Fe³⁺ by Co²⁺ according to the formula Sr_1−xLa_xFe_12−xCo_xO₁₉, are prepared by the ceramic process. Effects of the substituted amount of La³⁺ and Co²⁺ on structure and magnetic properties of Sr_1−xLa_xFe_12−xCo_xO₁₉ compounds have systematically been investigated by X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and B–H hysteresis curve measurements. In our results, the suitable amount of La³⁺–Co²⁺ substitution may remarkably increase saturation magnetization. Intrinsic coercive force (H_cj) of Sr ferrite magnets is evidently increased without significant decrease in residual flux density (B_r) by La³⁺–Co²⁺ substitution.     

Effect of substitution of Zr on the magnetic properties of R2Co17 (R = Ce and Sm)

The ternary systems Ce₂Co_17?xZr_x and Sm₂Co_17?xZr_x have been studied to ascertain the effect of Zr substitution on the magnetic properties. X-ray diffraction experiments show that single phase materials can be obtained only in the range of x ≤ 1 and that Zr stabilizes the hexagonal Th₂Ni₁₇ structure. The unit cell volume is found to increase by substitution of Zr. The Curie temperature T_c decreases monotonically with increasing x at an approximate rate of 100 and 90 deg/atom for the Ce and Sm systems, respectively. The saturation magnetic moments also decrease monotonically with increasing x for both the systems. The rate of decrease is larger than that expected as a simple dilution. The anisotropy fields H_A are significantly increased by Zr substitutions for both the systems, reaching 70 and 200 kOe at 77 K in the cases of Ce₂Co₁₆Zr₁ and Sm₂Co₁₆Zr₁, respectively. Among all the substituents studied until now, Zr seems to be the most effective for permanent magnet applications. Crystallographic and magnetic characteristics indicate that Zr replaces Co when the ternaries are formed.     

Absorptionsspektrum des Ce3+-Ions und Kristallfeld im La(Ce)Cl

The absorption spectrum of single crystals of La_(1?x)Ce _x Cl₃(x=0,05 ... 0,005) has been observed at low temperatures in the region of the 4f→4f infrared transitions. Values for the crystal-field parameters V ₂ ⁰ , V ₄ ⁰ , V ₆ ⁰ , V ₆ ⁶ and for the spin-orbit coupling constant of the ion in the crystalline environment are determined by fitting the observed splittings of the multiplet-components\({}^2F_{\tfrac{5}{2}} \) and\({}^2F_{\tfrac{7}{2}} \) in the crystal-field. The parameters are found to be consistent with values extrapolated from rare earth-ions with neighbouring atomic numbers in the same host-lattice. The only exception is the parameter V ₆ ⁶ , which is found to be smaller in La(Ce)Cl₃ than in other rare-earth-trichlorides (V ₆ ⁶ /V ₆ ⁰ =?6,23 in La(Ce)Cl₃, V ₆ ⁶ /V ₆ ⁰ ≈?10 in other trichlorides). The correct relation V ₆ ⁶ /V ₆ ⁰ in La(Ce)Cl₃ is obtained by fitting the parameters to the observed crystal-field-splitting of the\({}^2F_{\tfrac{5}{2}} \) — component and to the observed Zeeman-splitting-factors taken from the literature. The discrepancies between the two fitting procedures are explained by an effect of nonlinear shielding of the crystal-field.     

The magnetic entropy change in La0.8Ce0.2Fe11.4Si1.6Bx compounds prepared by copper-mold casting

The magnetocaloric effect (MCE) of La_0.8Ce_0.2Fe_11.4Si_1.6B_x (x=0.0-0.5) compounds, prepared by a copper-mold casting (CMC) method, has been investigated. Comparing with the conventional arc-melting (CAM) method, the relatively homogenous composition and microstructure were achieved in the precursor alloys prepared by the CMC method. As a result, the annealing time is dramatically shortened from several weeks for CAM alloys to 2 h for CMC alloys, suggesting that CMC method is a time-saving and energy-saving method for fabrication of MCE alloys. On the other hand, it is revealed that B addition gives rise to an enhancement of Curie temperature (T_C), a reduction of thermal lag and magnetic hysteresis and a broadening of working temperature span as well. Although the peak value of magnetic entropy change decreases with B content, various B-contained compounds hold close refrigerant capacities. Comprehensively considering magnetocaloric properties of the B-contained La_0.8Ce_0.2Fe_11.4Si_1.6B_x compounds, it can be concluded that the B-contained compounds prepared by CMC method are promising candidates of magnetocaloric materials in practical application.     

Die elektrischen Eigenschaften des Kondo-Supraleiters (La,Ce)Al2

In the ternary alloy (La, Ce)Al₂ the Kondo anomalies due to the Cerium impurities are studied in the normal and superconducting state. A vanishing of superconductivity in certain (La, Ce)Al₂ alloys below a second transition temperature has been observed for the narrow range of 0.6–0.7 at% Ce-additions. The transition back into the normal state has been observed by means of dc-conductivity and low frequency mutual inductance measurements down to 30 mK. Curves of the upper critical field versus temperature show a maximum at finite temperatures even for lower Ce-concentrations. The temperature dependence of the pair-breaking parameter has been deduced empirically from the upper critical field curves, assuming additive pair breaking theory. In contradiction to the theory no decrease of the pair-breaking parameter forT → 0 can be observed. Therefore the reentrance of superconductivity at ultra low temperatures cannot be expected.     

Mössbauer study of amorphous Fe2RE (RE=Ce,Er) alloys

Among amorphous Fe₂RE (RE=Er, Ce, Gd, La, Pr, Sm, Dy, Ho) alloys, Fe₂Ce exhibits a tendency toward short range order, while the other Fe₂RE compounds show clustering. However, we have almost no information about environments around Fe atoms. Using Mössbauer spectroscopy we have determined the quadrupole splitting distributionsP(QS) of two representative amorphous Fe₂RE (RE=Ce, Er) alloys, leading to local environments of Fe atoms. The analysis of the mixed magnetic dipole and quadrupole interactions in Fe₂Er shows two kinds of electrical field gradients (EFT) with the positive and negative signs in the sample, indicating a random packing of Fe atoms. Furthermore, the analyzed quadrupole splitting distributionP(QS) of Fe₂Er also supports random packing in this amorphous alloy. On the other hand, the amorphous Fe₂Ce alloy shows two kinds of distributions of quadrupole splitting; the major component indicating random packing and the minor component Ce-rich Ce-Fe clusters.