Phase, structural, and magnetocaloric properties of high temperature annealed LaFe11.6Si1.4BX

The phase relation, microstructural, hysteresis, Curie temperature, and magnetocaloric effects of LaFe_11.6Si_1.4B_x (x = 0.1, 0.2, 0.3, 0.4, and 0.5) prepared by arc-melting and then annealed at 1373 K (1.5 h) + 1523 K (5 h) were investigated. It was found that the main phase is NaZn₁₃-type phase, the impurity phases include α-Fe, Fe₂B, and small amount of La₅Si₃. The boron atom can dissolve into the crystal lattice of LaFe_11.6Si_1.4B_x to form interstitial solid solution, but the content of solid solution is not up to x = 0.5. For LaFe_11.6Si_1.4B_x (x = 0.1, 0.3, and 0.5) compounds, the Curie temperature T_C increases from 190.6 to 198.3 K with the increasing of B content from x = 0.1 to 0.5. The first order magnetic transition behavior becomes weaker and magnetic entropy change ΔS_M (T, H) drops with the increasing of B content, respectively. However, ΔS_M (T, H) still remains a large value, 11.18 J/kg K, when x reaches to 0.5 at 0-2 T. An attractive feature is that both thermal and magnetic hysteresis can be reduced remarkably by introducing B. The maximum magnetic hysteresis loss near T_C drops from 22.52 to 4.95 J/kg when the content of B increases from x = 0.1 to 0.5.     

The studies of phase relation, microstructure, magnetic transition, magnetocaloric effect in (Gd1−xErx)5Si1.7Ge2.3 compounds

The phase relation, microstructure, Curie temperatures (T_C), magnetic transition, and magnetocaloric effect of (Gd_1−xEr_x)₅Si_1.7Ge_2.3 (x = 0, 0.05, 0.1, 0.15, and 0.2) compounds prepared by arc-melting and then annealing at 1523 K (3 h) using purity Gd (99.9 wt.%) are investigated. The results of XRD patterns and SEM show that the main phases in those samples are mono-clinic Gd₅Si₂Ge₂ type structure. With increase of Er content from x = 0 to 0.2, the values of magnetic transition temperatures (T_C) decrease linearly from 228.7 K to 135.3 K. But the (Gd_1−xEr_x)₅Si_1.7Ge_2.3 compounds display large magnetic entropy near their transition temperatures in a magnetic field of 0-2 T. The maximum magnetic entropy change in (Gd_1−xEr_x)₅Si_1.7Ge_2.3 compounds are 24.56, 14.56, 16.84, 14.20, and 13.22 J/kg K⁻¹ with x = 0, 0.05, 0.1, 0.15, and 0.2, respectively.     

Magnetocaloric effect in the Ce2Fe17−xMnx helical magnets

The Ce₂Fe_17−xMn_x (x = 0-2) compounds demonstrate a complex temperature dependence of the magnetocaloric effect MCE, which is inverse in a narrow temperature interval just below Néel temperature T_N and normal at higher or lower temperatures. The normal MCE exhibits two peaks in the vicinity of temperatures of ferromagnetic ordering Θ_T and T_N for compositions x = 0-0.35, 1.3-2 or one peak near T_N for antiferromagnets with x = 0.5-1. The maximal change of the peak entropy −S_M is about 3 J/kg K in a field of 5 T for the compounds with x = 0-0.5 at T ∼230 K close to T_N. The drastic decrease of the MCE, by half, in the Ce₂Fe_17−xMn_x system is traceable to a decrease of the spontaneous magnetization and the helical type of magnetic states in the compounds.     

Large magnetic entropy change near room temperature in La0.7(Ca0.27Ag0.03)MnO3 perovskite

In this paper, the magnetic properties and magnetocaloric effect (MCE) of La_0.7(Ca_1−xAg_x)_0.3MnO₃ (x = 0, 0.1, 0.2, 0.7, and 1) powder samples are reported. Our polycrystalline compounds were synthesized using the solid state reaction method at high temperature. Magnetization measurements versus temperature showed that all our samples exhibited a paramagnetic to ferromagnetic transition with decreasing temperature. The Curie temperature, T_C, has been found to increase from ∼250 K for x = 0-270 K for x = 1. Ag doping weakens the first order phase transition, and at higher Ag doping, the phase transition is of second order. For the La_0.7(Ca_0.27Ag_0.03)MnO₃ composition, the maxima of the magnetic entropy changes from the applied magnetic field (ΔS_M) at 2 and 5 T are about 4.5 and 7.75 J/kg K, respectively, at the Curie temperature of ∼263 K. The relative cooling power (RCP) values without hysteresis loss are about 102 and 271 J/kg for the applied fields of 2 and 5 T, respectively. Due to the large ΔS_M, large RCP, and high Curie temperature, La_0.7(Ca_0.27Ag_0.03)MnO₃ is promising for application in potential magnetic refrigeration near room temperature.     

1:13 phase formation mechanism and first-order magnetic transition strengthening characteristics in (La,Ce)Fe<Subscript>13–<Emphasis Type="Italic">x</Emphasis></Subscript>Si<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> alloys

The effects of the introduction of Ce to La_1?x Ce _x Fe_11.5Si_1.5 alloys on 1:13 phase formation mechanism, the first-order magnetic phase transition strengthening characteristics, and magnetocaloric property were studied, respectively. The results show that the formation mechanisms of 1:13 and LaFeSi phases in La_1?x Ce _x Fe_11.5Si_1.5 alloys are the same as those of Ce₂Fe₁₇ and CeFe₂ phases in Ce–Fe binary system, respectively. The substitution of Ce in 1:13 phase which is limited can make the first-order magnetic phase transition characteristics strengthen, which can make thermal and magnetic hysteresis increase, the temperature interval of temperature-induced phase transition decrease, and the critical magnetic field of field-induced magnetic phase transition (H _C) increase, respectively. Owing to the lattice shrink of 1:13 phase with the increase in Ce content, the Curie temperatures (T _C) show a linear decrease. The maximum change in magnetic entropy gradually increases due to the decrease in temperature interval of temperature-induced phase transition, but the relative cooling capacities are all about 80 J·kg^?1 at magnetic field of 2 T.     

Magnetic behaviour and experimental study of the magnetocaloric effect in the pseudobinary Laves phase Er1−xDyxCo2

We have investigated the crystal structure, the bulk magnetization characteristics and the magnetocaloric properties of Er_1−xDy_xCo₂ compounds. X-ray diffraction (XRD) analyses confirm that all these Laves phase type compounds crystallize in the cubic MgCu₂-type structure. First, the magnetization behaviour and the magnetic transition are analyzed in terms of Landau theory. Then, a direct correlation was pointed out between the character of the magnetic transition and the behaviour of the cell parameter versus x. Substitution of Dy to Er enhances markedly the Curie temperature T_C from 35 to 142 K, while ΔS the corresponding change of isothermal entropy decreases significantly. The refrigerant capacity of the Er_1−xDy_xCo₂ compounds is discussed and our experimental data are compared with the corresponding theoretical results reported in the literature [de Oliveira, von Ranke, J. Magn. Magn. Mater. 264 (2003) 55].     

Structural, magnetic and dielectric properties of La2−xCaxNiO4+δ (x = 0, 0.1, 0.2, 0.3)

The synthesis, structural, magnetic and dielectric properties of a new type of high permittivity materials La_2−xCa_xNiO_4+δ (x = 0, 0.1, 0.2, 0.3) (abbreviated as LCNs) were reported. The samples were prepared through conventional solid state reaction route. Detailed structural information was retrieved by Rietveld refinement; normalized bond length and bond valence was calculated to investigate the compression/dilation effect of bonds and atoms in unit cell. It can be found all samples belong to K₂NiF₄ structure with space group I4/mmm. Doping of Ca in La₂NiO_4+δ shrinks the unit cell and makes the structure tend to become instable. Three types of (La, Ca)-O bonds, and two kinds of Ni-O bonds exist in LCNs. Along c axis there are alternately compressed (La,Ca)O₉ dodecahedra and lengthened NiO₆ octahedra. Room temperature magnetic measurements show that the materials are paramagnetic and Ca doping can improve the spontaneous magnetization. Furthermore, all samples have colossal values of the dielectric constant (?) at frequencies lower than 1 kHz. Interestingly, La_1.8Ca_0.2NiO_4+δ maintains its high permittivity at frequencies up to 1 MHz while La_1.7Ca_0.3NiO_4+δ has the lowest dielectric loss (tan δ). Calcium doping can effectively enhance ? and inhibit tan δ. The distortion of (La,Ca)O₉ dodecahedra can well explain their dielectric properties.     

Cu添加对La0.7Ce0.3Fe11.54-xCuxMn0.16Si1.3合金及其氢化物磁性能的影响

La(Fe, Si)₁₃系合金是具有一级相变大磁热效应的磁制冷合金,被认为是极具应用前景的磁热效应材料之一。本文采用高频感应悬浮炉制备了添加不同Cu元素比例的La_0.7Ce_0.3Fe_11.54-xCu_xMn_0.16Si_1.3(x=0, 0.05, 0.1, 0.15)合金。并利用粉末XRD衍射仪,扫描电镜(SEM)对合金的相组成、微观组织结构进行了研究,采用多功能振动样品磁强计VersaLab对合金的磁性能进行了分析。添加Cu元素后,合金的居里温度提高,但氢化后添加Cu的合金居里温度反而偏低。随着Cu元素提高磁热性能下降,但La_0.7Ce_0.3Fe_11.44Cu_0.1Mn_0.16Si_1.3H_1.68合金的最大等温磁熵变仍高达8.5 J/kg.K(0 ~ 2 T),相对制冷能力RCP提高(118 J/kg),磁滞明显降低。     

The effect of high-temperature annealing on LaFe_(11.5)Si_(1.5) and the magneto-caloric properties of La_(1-x)Ce_xFe_(11.5)Si_(1.5) compounds

The powder X-ray diffraction patterns of LaFe11.5Si1.5 compounds annealed at different high temperatures from 1323 K (5 h) to 1623 K (2 h) show that a large amount of 1:13 phase begins to form in LaFe11.5Si1.5 compound annealed at 1423 K (5 h). In the temperature range from 1423 to 1523 K, α-Fe and LaFeSi phases rapidly decrease to form 1:13 phase. LaFeSi phase is rarely observed, and the most amount of 1:13 phase is obtained in the compound annealed at 1523 K (5 h). With the annealing temperature increasin...     

Electrochemical hydrogen storage properties of non-stoichiometric La0.7Mg0.3−xCaxNi2.8Co0.5 (x = 0-0.10) electrode alloys

The microstructure and electrochemical hydrogen storage characteristics of La_0.7Mg_0.3−xCa_xNi_2.8Co_0.5 (x = 0, 0.05 and 0.10) alloys prepared by arc-melting and subsequent powder sintering method are investigated. The electrochemical measurement results show that the cycle stability after 100 charge/discharge cycles first increases from 46.4% (x = 0) to 54.3% (x = 0.05), then decreases to 43.2% (x = 0.10), and the high rate dischargeability increases from 64.5% (x = 0) to 68.5% (x = 0.10) at the discharge current density of 1200 mA/g. The electrochemical impedance spectroscopy analysis indicates that the electrochemical kinetics of the alloy electrodes is improved by increasing Ca. The entire results exhibit that a suitable content of Ca (x = 0.05) can improve the overall electrochemical hydrogen storage characteristics of the alloys.     

Correlating structure with ferromagnetism in melt-spun Gd100−xFex

X-ray diffraction and transmission electron microscopy measurements of melt-spun Gd_100−xFe_x (0 ≤ x ≤ 40) and inert-gas condensed/compacted samples (3.8 ≤ x ≤ 12.7) reveal a structure of crystalline hcp-Gd grains surrounded by a non-crystalline Gd1−xeffFexeff phase, where x_eff > x is the effective iron concentration within the amorphous region. The two-phase structure is responsible for an unusual dependence of the coercivity on temperature in which non-zero coercivity is observed above the hcp-Gd T_c with a peak near 320 K. The coercivity decreases as the hcp-Gd grains order, then increases with decreasing temperature. This behavior is explained by the presence of magnetically correlated Fe-rich regions.     

Synthesis, thermal stability and properties of [(Fe1−xCox)72Mo4B24]94Dy6 bulk metallic glasses

A series of [(Fe_1−xCo_x)₇₂Mo₄B₂₄]₉₄Dy₆ (x = 0.1, 0.2, 0.3, 0.4 and 0.5 at.%) bulk metallic glasses (BMGs) in rod geometries with critical diameter up to 3 mm were fabricated by copper mold casting method. This alloy system exhibited good thermal stability with high glass transition temperature (T_g) 860 K and crystallization temperature (T_x) 945 K. The addition of Co was found to be effective in adjusting the alloy composition deeper to eutectic, leading to lower liquidus temperature (T_l). The [(Fe_0.8Co_0.2)₇₂Mo₄B₂₄]₉₄Dy₆ alloy showed the largest supercooled liquid region (ΔT_x = T_x − T_g = 92 K), reduced glass transition temperature (T_rg = T_g/T_l = 0.622) and gamma parameter (γ = T_x/(T_g + T_l) = 0.424) among the present system. Maximum compressive fracture strength of 3540 MPa and micro-Vickers hardness of 1185 kg/mm² was achieved, resulting from the strong bonding structure among the alloy constituents. The alloy system possessed soft magnetic properties with high saturation magnetization of 56.61-61.78 A m²/kg and coercivity in the range of 222-264.2 A/m, which might be suitable for application in power electronics devices.     

Influence of interstitial and substitutional atoms on the crystal structure of La(FeSi)13

The influence of interstitial hydrogen or carbon on the crystal structure of LaFe_11.5Si_1.5H_δ (δ = 0, 1.2, and 2) and LaFe_11.5Si_1.5C_δ (δ = 0, 0.1, 0.2, 0.3, 0.4, and 0.5) has been investigated based on the Rietveld analyses of powder X-ray diffraction spectra. Effects of Ce substitution for La are also studied for comparison. The incorporation of interstitial atoms causes a lattice expansion of the compounds while leaves the structural symmetry unchanged. Accompanying the lattice expansion, Fe-Fe bond exhibits a concomitant variation. Four of the five Fe-Fe bonds show a tendency to expansion. The largest elongation occurs for the shortest inter-cluster bond, and the relative change is as large as ∼2.53% as δ increases from 0 to 2 for LaFe_11.5Si_1.5H_δ. In contrast, the longest Fe-Fe bond shrinks considerably (−0.97%). Similarly effects on Fe-Fe bonds are produced by the paramagnetic to ferromagnetic transition, though the bond variation is smaller. Increase in Ce content produces, fascinatingly, essentially the same effects as the decrease of interstitial content, though Ce occupies different crystallographic sites than those occupied by interstitial atoms. Influence of interstitial atoms on magnetic behaviors may be dominated by the change of the shortest Fe-Fe bond.     

Near room temperature magnetic entropy changes in as-cast Gd100−xMnx (x = 0, 5, 10, 15, and 20 at.%) alloys

A series of Gd_100−xMn_x (x = 0, 5, 10, 15, and 20 at.%) alloys were prepared by arc-melting. The Curie temperature (T_C) associated with the ferromagnetic-paramagnetic transitions, derived from M-T curves, show decrease in T_C for as-cast alloys (∼279 K) as compared to as-cast Gd (∼292 K). No appreciable decrease in the |ΔS_M|_max values ∼4.6 J/kg K (0-2 T) and ∼8.6 J/kg K (0-5 T) were observed upon alloying Gd with Mn up to x ≤ 15 at.%. Refrigerant capacity (q) showed negligible variation ∼195 J/kg (0-2 T) and ∼450 J/kg (0-5 T) with increasing Mn (up to x ≤ 15 at.%) content. Similar values of |ΔS_M|_max and q coupled with ∼13 K decrease in T_C for as-cast Gd_100−xMn_x (0 ≤ x ≤ 15) alloys as compared to Gd, suggests expansion of working temperature region of Gd upon alloying with Mn up to 15 at.%. Low cost, adjustable T_C, favorable magnetocaloric properties make Gd_100−xMn_x alloys potential candidates as second-order transition based magnetic refrigerants for near room temperature air-conditioning and magnetic refrigeration.     

Structural, magnetic and electrical properties of Bi1.4La0.6Sr2CaCu2−xMnxOy compounds

The Mn-doped compounds Bi_1.4La_0.6Sr₂CaCu₂O_y were prepared by sol-gel method. The structural variation was characterized systematically by X-ray diffraction (XRD), infrared (IR) spectra and Raman scattering spectra, respectively. The electrical and magnetic properties of the compounds were investigated by the temperature dependence of resistivity (R-T) and magnetic hysteresis loop (M (H)) measurements. Results indicate that the subtle change of lattice parameters has taken place in the compounds, which is attributed to CuO₂ planes canting and Mn valence alternation. In the condition of preserving Bi-2212 structure, Bi_1.4La_0.6Sr₂CaCu_2−xMn_xO_y compound has optimal resistivity and magnetism at x = 2%, which could provide a candidate as new barrier in Josephson junction in future.     

Preparation and characterization of La1−xKxFeO3 (x = 0-1) by self-propagating high-temperature synthesis for use as soot combustion catalyst

This paper proposes La_1−xK_xFeO₃ prepared by self-propagating high-temperature synthesis (SHS) as an alternative to platinum catalysts for promoting diesel soot combustion. The catalytic property of eleven products SHSed with different substitution ratios of potassium (x = 0-1) was experimentally evaluated using a thermobalance. In the mass loss curves of the product, T₅₀ was defined as the temperature at which the weight of the reference soot decreases to half its initial weight. The BET specific surface area of SHSed La_1−xK_xFeO₃ depended on x strongly. All the products showed good oxidation catalytic activity. Despite having the smallest surface area (0.11 m²/g) among the obtained products, La_0.9K_0.1FeO₃ (x = 0.1) was found to be the best catalyst with the lowest T₅₀ (442 °C). T₅₀ of La_1−xK_xFeO₃ decreased with increasing x for x > 0.2. The products with x = 0.6 and 0.8 were the second-best catalysts in terms of their T₅₀. Moreover, average apparent activation energy of La_0.9K_0.1FeO₃ (x = 0.1) calculated by Friedman method using TG was as much as 61 kJ/mol lower than that of Pt/Al₂O₃ catalyst. In conclusion, potassium-substituted SHSed La_1−xK_xFeO₃ can be used as an alternative to Pt/Al₂O₃ for soot combustion.     

Temperature and field induced strain in polycrystalline Ni50Mn35In15−xSix magnetic shape memory Heusler alloys

Magnetic shape memory properties of polycrystalline Ni₅₀Mn₃₅In_15−xSi_x were investigated. A reversible strain of more than 0.4% was observed for x = 0 at a magnetic field H = 5 T that was found to be associated with a field induced reverse martensitic transformation. The strains were found to increase with the substitution of In by Si and strains larger than 1% were observed for x = 2 at H = 5 T. Both the positive and negative strain changes were observed in the vicinity of martensitic transition temperatures. The strain in Ni₅₀Mn₃₅In_15−xSi_x was found to depend on silicon concentration, and on samples texture.     

Martensitic transformation and magnetic properties in high-Mn content Mn50Ni50−xInx ferromagnetic shape memory alloys

A series of Mn₅₀Ni_50−xIn_x (x = 9.75, 10, 10.25, 10.5 10.75, and 11) ferromagnetic shape memory alloys with Mn content as high as 50 at.% were prepared. The martensitic transformation (MT), magnetocaloric effect, and magnetoresistance in Mn₅₀Ni_50−xIn_x alloys were investigated. With x increasing from 9.75 to 11, the MT temperature decreased from 270 to 110 K and the Curie temperature of austenite remains relatively constant. Large positive magnetic entropy change and negative magnetoresistance were observed around MT temperatures in these alloys. Large magnetic entropy change and magnetoresistance would be ascribed to the temperature and magnetic field-induced MT in Mn₅₀Ni_50−xIn_x alloys.