Giant magneto-caloric effect around room temperature at moderate low field variation in La0.7(Ca1−xSrx)0.3MnO3 perovskites

Among the perovskite manganites, a series of La_1?xCa_xMnO₃ has the largest magneto-caloric effect (MCE) (|ΔS_m|_max=3.2–6.7 J/kg K at ΔH=13.5 kOe), but the Curie temperatures, T_C, are quite low (165–270 K). The system of LaSrMnO₃ has quite high T_C but its MCE is not so large. The manganites La_0.7(Ca_1?xSr_x)_0.3MnO₃ (x=0, 0.05, 0.10, 0.15, 0.20, 0.25) have been prepared by solid state reaction technique with an expectation of large MCE at room temperature region. The samples are of single phase with orthorhombic structure. The lattice parameters as well as the volume of unit cell are continuously increased with the increase of x due to large Sr²⁺ ions substituted for smaller Ca²⁺ ions. The field-cooled (FC) and zero-field-cooled (ZFC) thermomagnetic measurements at low field and low temperatures indicate that there is a spin-glass like (or cluster glass) state occurred. The Curie temperature T_C increases continuously from 258 K (for x=0) to 293 K (for x=0.25). A large MCE of 5 J/kg K has been observed around 293 K at the magnetic field change ΔH=13.5 kOe for the sample x=0.25. The studied samples can be considered as giant magneto-caloric materials, which is an excellent candidate for magnetic refrigeration at room temperature region.     

Defect equilibria and partial molar properties of (La,Sr)(Co,Fe)O3−δ

The oxygen nonstoichiometry δ of La_1−xSr_xCo_1−yFe_yO_3−δ (x = 0.6 and y = 0.2, 0.4) was investigated by thermogravimetry in the range 703 ≤ T/°C ≤ 903 and 1E−5 < pO₂/atm < 1. The oxygen deficit increases with increasing T and decreasing pO₂. Electronic conductivities σ were measured as a function of pO₂ in the range 1E−5 < pO₂/atm < 1 at 700 ≤ T/°C ≤ 900. At constant T, a p-type pO₂-dependence of σ is observed. Oxygen nonstoichiometry data are analyzed with regard to the enthalpy and entropy of oxidation ΔH_ox^θ and ΔS_ox^θ, as well as to the partial molar enthalpy and entropy of oxygen with respect to the standard state of oxygen (pO₂^θ = 1 atm), (h_O − H_O^θ) and (s_O − S_O^θ), respectively. For 2.67 ≤ (3 − δ) ≤ 2.79, (h_O − H_O^θ) decreases with increasing δ, while (s_O − S_O^θ) is constant within the limits of error. Defect chemical modelling was performed by an ideal solution model under consideration of three different valence states for B-site ions (Co or Fe). The dependence of σ on δ is modelled, using calculated defect concentrations as functions of δ. Deviations from the ideal behaviour suggest an immobilization of n-type charge carriers by oxygen vacancies.     

Magnetic properties and magnetocaloric effects in Gd1−xHoxNiIn intermetallic compounds

Magnetic properties and magnetocaloric effects (MCEs) of the intermetallic Gd_1?xHo_xNiIn (x=0?1) compounds have been evaluated by magnetization and heat capacity measurements. The Curie temperature T_C can be tuned from near 100 K to 20 K by substituting Ho for Gd atoms. In addition, all the compounds with Ho atoms undergo two successive magnetic transitions with the decrease of temperature: a paramagnetic (PM) to ferromagnetic (FM) transition around T_C and a spin-reorientation (SR) transition around 7?9 K. It is found that both transitions contribute to the magnetic entropy change (ΔS_M). For a field change of 5 T, the maximum values of ?ΔS_M for Gd_0.4Ho_0.6NiIn are 6 J/kg K at T_t=9 K and 10 J/kg K at T_C=52 K, respectively. These two ?ΔS_M peaks overlap partly and result in a wide working temperature range of MCE, and thus leading to the largest RC value of 443 J/kg in the Gd_1?xHo_xNiIn system.     

Ferromagnetic order and spin-glass behavior in multi-metallic compound Ni1.125Co0.375[Fe(CN)6] · 6.8H2O

Multi-metallic Prussian blue compound Ni_1.125Co_0.375[Fe(CN)₆] · 6.8H₂O has been synthesized. The Mössbauer spectroscopy at room temperature and IR spectra study revealed that the metal ions are bonded through cyanide ligand and the presence of low spin Fe^III(S = 1/2) and high spin Fe^III(S = 5/2) ions, as showed in these structure: Fe^III(S = 1/2)-CN-(Co^II/Ni^II)(96%) and Fe^III(S = 5/2)-NC-(Co^II/Ni^II) (4%). The Curie constant of C = 3.00 cm³ K mol⁻¹ and Weiss paramagnetic Curie temperature of θ = 16.43 K were observed in fitting according to Curie–Weiss law. These results indicate that there existed a ferromagnetic exchange interaction in the complexes. The observed value of coercive field (H_c) and remanent magnetization (M_r) at 4 K for the compound are 497 Oe and 1.03 Nβ. The presence of spin-glass behaviours in the compound is ascribed mainly to domain mobility or domain growth under different cooling conditions.     

Structure and magnetic properties of the intermetallic La2Co17−xMox (x=0.5, 1, 1.5, 2) and La2Co16−yFeyMo (y=0, 1, 2, 3, 4, 6) compounds

The effect of Mo and Fe atoms on the crystal structure and magnetic properties of the intermetallic La₂Co_17−xMo_x (x=0.5, 1, 1.5, 2), and La₂Co_16−yFe_yMo (y=0, 1, 2, 3, 4, 6) compounds have been studied by X-ray diffractometry, magnetic measurements and Mössbauer spectroscopy. All samples belong to the rhombohedral Th₂Zn₁₇-type structure and their lattice parameters a and c increase both with Mo and Fe content. From the La–Co–Mo samples only the one with x=0.5 presents planar anisotropy, whereas from the La–Co–Fe–Mo samples only the y=1 has uniaxial anisotropy. The magnetization M_S and the Curie temperature T_C decrease upon Mo substitution, whereas the anisotropy field H_A does not change significantly. In the Fe-substituted compounds M_S increases, but the Curie temperature increases slightly for 0⩽y⩽4 but decreases in y=6. The low temperature M–T curve shows that the samples La₂Co_16.5Mo_0.5, and La₂Co₁₀Fe₆Mo present a spin reorientation transitions at 70 and 260 K, respectively. Mössbauer samples were obtained for all Fe-containing samples in the temperature range 20–300 K. Above 260 K a jump in the values of the hyperfine fields and quadrupole splitting parameters is observed which can be associated to the spin reorientation.     

Effect of Ge4+ and Mg2+ doping on superconductivity,fluctuation induced conductivity and interplanar coupling of TlSr2CaCu2O7−δ superconductors

Substitution of Ge⁴⁺ in place of Cu in Tl_0.85Cr_0.15Sr₂CaCu_2?xGe_xO_7?δ (x = 0–0.6) showed initial increase in zero critical temperature value, T_{c zero} from 98 K (x = 0) to 100 K (x = 0.1) and in the range of 85–86 K for x = 0.2–0.3. The slow decrease in T_{c zero} is unexpected as tetravalent Ge⁴⁺ substitution is expected to strongly reduce hole concentration in the samples and suppress T_{c zero}. Excess conductivity analyses of resistance versus temperature data based on Asmalazov–Larkin (AL) theory revealed that the substitution induced 2D-to-3D transition of fluctuation induced conductivity with the highest transition temperature, T_2D–3D observed at x = 0.1. FTIR spectroscopy analysis indicates Ge⁴⁺ substitution cause reduction in CuO₂/GeO₂ interplanar distance while our calculation based on Lawrence–Doniach model revealed highest superconducting coherence length, ξ_c(0) and interplanar coupling, J at x = 0.3. On the other hand, substitution of divalent Mg²⁺ for Ca²⁺ in (Tl_0.5Pb_0.5)(Sr_1.8Yb_0.2)(Ca_1?yMg_y)Cu₂O₇ (y = 0–1.0), which is not expected to directly vary hole concentration, surprisingly caused T_{c zero} to increase from 89.6 K (y = 0) to an optimum value of 95.9 K (y = 0.6) before decreasing with further increase in y. Excess conductivity analyses showed 2D-to-3D transition of fluctuation induced conductivity for all samples where the highest T_2D–3D was at y = 0.4. Similar calculation revealed highest values of ξ_c(0) and J also at y = 0.4. FTIR analysis of the samples indicates inequivalent Cu(1)O(2)Pb/Tl lengths and possible tilting of CuO₂ plane as a result of Mg²⁺ substitution. The increased ξ_c(0) and J as a result of the Ge⁴⁺ and Mg²⁺ substitutions are suggested to contributed to sustenance of superconductivity above 80 K in the samples.     

Critical properties of superconducting Ba1−xKxFe2As2

Magnetisation and magneto-resistance measurements have been carried out on superconducting Ba_1?xK_xFe₂As₂ samples with x = 0.40 and 0.50. From high field magnetization hysteresis measurements carried out in fields up to 16 T at 4.2 K and 20 K, the critical current density has been evaluated using the Bean critical state model. The J_C determined from the high field data is >10⁴ A/cm² at 4.2 K and 5 T. The superconducting transitions were also measured resistively in increasing applied magnetic fields up to 12 T. From the variation of the T_C onset with applied field, dH_C2/dT at T_C was obtained to be ?7.708 T/K and ?5.57 T/K in the samples with x = 0.40 and 0.50.     

Electrical,magnetic and magnetocaloric properties of polycrystalline Pr0.63A0.07Sr0.3MnO3 (A=Pr,Sm and Bi)

We studied the effects of the partial substitution (10%) of praseodymium by samarium and bismuth, on the structural, magnetic, magnetocaloric and electrical properties of the Pr_0.63A_0.07Sr_0.3MnO₃ (A=Pr, Sm and Bi) manganites prepared using the solid state reaction. Refinement of the X-ray diffraction patterns shows that all our samples are single phase and crystallize in the orthorhombic structure with Pnma space group. Magnetic studies indicate that all the samples exhibit a ferromagnetic–paramagnetic transition with increasing temperature. Curie temperature T_C decreases by substitution. M(H) curves indicate the presence of some antiferromagnetic domains in the substituted samples testifying the phase-separated nature of these samples. The magnetic entropy curves –ΔS(T) show a maximum in vicinity of T_C. Important values of maximum of −ΔS are recorded for our compounds. For the parent compound, we found 4.59 J/kg K for an applied magnetic field of 2 T at T_C=266 K which raises the possibility of using this compound as a magnetic refrigerant. The temperature dependence of the electrical resistivity ρ(T) indicates that all compounds exhibit a metal-insulator transition with increasing temperature. Electrical study suggests the presence of a correlation between electrical and magnetic properties.     

Antiferromagnetic phase transition in garnet-type AgCa2Mn2V3O12 and NaPb2Mn2V3O12

Ferrimagnetism has been extensively studied in garnets, whereas it is rare to find the antiferromagnet. Present work will demonstrate antiferromagnetism in the two Mn–V-garnets. Antiferromagnetic phase transition in AgCa₂Mn₂V₃O₁₂ and NaPb₂Mn₂V₃O₁₂ has been found, where the magnetic Mn²⁺ ions locate only on octahedral A site. The heat capacity shows sharp peak due to antiferromagnetic order with the Néel temperature T_N=23.8 K for AgCa₂Mn₂V₃O₁₂ and T_N=14.2 K for NaPb₂Mn₂V₃O₁₂. The magnetic entropy change over a temperature range 0–50 K is 13.9 J K^?1 mol-Mn²⁺-ions^?1 for AgCa₂Mn₂V₃O₁₂ and 13.6 J K^?1 mol-Mn²⁺-ions^?1 for NaPb₂Mn₂V₃O₁₂, which are in good agreement with calculated value of Mn²⁺ ion with spin S=5/2. The magnetic susceptibility shows the Curie–Weiss behavior over the range 29–350 K. The effective magnetic moment μ_eff and the Weiss constant θ are μ_eff=6.20 μ_B Mn²⁺-ion^?1 and θ=?34.1 K (antiferromagnetic sign) for AgCa₂Mn₂V₃O₁₂ and μ_eff=6.02 μ_B Mn²⁺-ion^?1 and θ=?20.8 K for NaPb₂Mn₂V₃O₁₂.     

The thermopower of transition-metal double-perovskites: A sensitive probe of their electronic structures around the Fermi level

We report on a comparative study of S(T) for a series of transition-metal double-perovskites A₂BB′O₆ (A – Ca, Sr, Ba, and B, B′ = transition metal ions), some of them known to have half-metallic ground states. For Sr₂BB′O₆ with BB′ = CrMo, CrW, CrRe, FeMo, and FeRe (ferrimagnetic with high Curie temperatures), S(T) is metallic, for B′ = Mo and W it is n-type and for B′ =  Re, p-type. For A₂FeMoO₆ (A = Ca, Sr, Ba), the crystallographic differences (monoclinic, tetragonal and cubic space-groups, respectively) are accompanied by prominent differences in their (metallic) S(T). For the insulating Sr₂MnReO₆ and Ba₂MnReO₆, the onset of ferromagnetic order below T_c ∼ 120 K is marked by a steep drop of S(T) accompanied by only a slight change in the slope of ln ρ versus 1/T^1/2. Significant conclusions were drawn from the experimental results without the need for elaborate models.     

Comparative study of the magnetic and electrical properties of Pr1−xBaxMnO3−δ manganites depending on the preparation conditions

Magnetization, electrical resistivity and magnetoresistance of Pr_0.50Ba_0.50MnO_3−δ manganites with perovskite structure have been investigated as a function of preparation conditions. It was found that the as-prepared samples (prepared in air) show T_C=110 K (first order phase transition), whereas for those annealed in flowing argon the T_C value increases up to 340 K without change of cubic symmetry (second order phase transition). Ferromagnet–paramagnet transition is accompanied by both a metal–insulator transition and a magnetoresistance peak. The X-ray study has revealed that the samples annealed in argon have broad peaks apparently due to microstrains and crystal structure defects. The argon-treated samples improve the magnetization after subsequent annealing in air at T⩽1000°C. T_C of argon-treated samples is stable with respect to annealing in air up to 1300°C where it becomes again 110 K. In contrast, a treatment in vacuum destroys the ferromagnetic order. Auger-spectroscopy has not revealed any additional ions except Pr, Ba, Mn and O for all the samples. External pressure enhances the Curie point of the sample prepared in air at a rate of 43 K/GPa. We have observed that the samples Pr_1−xBa_xMnO_3−δ, x⩾0.30, exhibited the above-mentioned effect of increasing T_C after treatment in flowing argon without changes of the phase state, whereas the samples x<0.30 decomposed into different phases. The dramatic increase of T_C after argon treatment is supposed to result from microstrains and crystal structure defects in the sample.     

New ternary ThCr2Si2-type iron–selenide superconducting materials: Synthesis,properties and simulations

Very recently, the first ThCr₂Si₂-type ternary superconductor K_0.8Fe₂Se₂ with enhanced T_C ～ 31 K has been discovered. This finding has stimulated much activity in search for related materials and triggered intense studies of their properties. Indeed, very soon superconductivity (T_C ～ 28–32 K) was also found in the series of related ternary systems (so-called 122 phases) such as Cs_xFe_2?ySe₂, Rb_xFe_2?ySe₂, (TlK)_xFe_ySe₂, and (TlRb)_xFe_ySe₂, which formed a new group of superconducting iron-based materials without toxic As. In this paper the recent progress in synthesis of 122-like iron–selenide systems and in experimental research of their properties is reviewed. Available theoretical data on electronic, magnetic, and elastic properties of this newest group of superconducting materials are also discussed.     

Polymorphic phase transition and thermal stability in squaric acid (H2C4O4)

Phase transformations in squaric acid (H₂C₄O₄) have been investigated by thermogravimetry and differential scanning calorimetry with different heating rates β. The mass loss in TG apparently begins at onset temperatures T_di=245±5 °C (β=5 °C min^?1), 262±5 °C (β=10 °C min^?1), and 275±5 °C (β=20 °C min^?1). A polymorphic phase transition was recognized as a weak endothermic peak in DSC around 101 °C (T_c⁺). Further heating with β=10 °C min^?1 in DSC revealed deviation of the baseline around 310 °C (T_i), and a large unusual exothermic peak around 355 °C (T_p), which are interpreted as an onset and a peak temperature of thermal decomposition, respectively. The activation energy of the thermal decomposition was obtained by employing relevant models. Thermal decomposition was recognized as a carbonization process, resulting in amorphous carbon.     

Magnetic properties of GdCo12B6 compound under high pressures

The effects of hydrostatic pressure up to 10 kbar on Curie temperature T_C, compensation temperature T_COMP and spontaneous magnetization M_S of ferrimagnetic GdCo₁₂B₆ compound have been studied. Two antiferromagnetically coupled sublattices that are carrying magnetization of typically 0.42 μ_B/Co atom and 7 μ_B/Gd cancel out at compensation temperature at about 50 K and magnetic ordering temperature T_C=163±2 K. The volume dependence of intrinsic magnetic properties of the GdCo₁₂B₆ compound has been determined by studying it under hydrostatic pressure. The observed increase of M_S with pressure (dM_S/dp=+0.005 μ_B kbar^?1 at 5 K) is attributed predominantly to the pressure induced decrease of Co magnetic moments. The crucial role of Co in this behavior is confirmed by the change of sign of the pressure slope at temperatures above T_COMP and by the fact that the estimated decrease of m_Co is also quite comparable with pressure induced decrease of M_S in YCo₁₂B₆ (dM_S/dp=?0.007 μ_B kbar^?1). The decrease of m_Co is also responsible for the increase of T_COMP with pressure (dT_COMP/dp=+0.06 K kbar^?1). The decrease of T_C with pressure (dT_C/dp=?0.55 K kbar^?1) is comparable to the decrease observed on RCo₁₂B₆ compounds with non-magnetic R and can be attributed to the volume dependence of Co–Co exchange interactions. The remarkable role of the hybridization as a consequence of small distances between Co and B atoms could be a background of this rather unexpected volume stability of magnetic properties.     

Thermodynamics and kinetics of CO and benzene adsorption on Pt(111) studied with pulsed molecular beams and microcalorimetry

The adsorption and desorption of the system CO/Pt(111) and C₆H₆/Pt(111) at 300 K has been investigated with a pulsed molecular beam method in combination with a microcalorimeter. For benzene the sticking probability has been measured in dependence of the coverage θ. For coverages θ > 0.8 transient adsorption is observed. From an analysis of the time-dependence of the molecular beam pulses the rate constant for desorption is determined to be 5.6 s^? 1. With a precursor-mediated kinetic adsorption model this allows to obtain also the hopping rate constant of 95.5 s^? 1. The measured adsorption enthalpies could be best described by (199 ? 77θ ? 51θ²) kJ/mol, in good agreement with the literature values. For CO on Pt(111) also transient adsorption has been observed for θ > 0.95 at 300 K. The kinetic analysis yields rate constants for desorption and hopping of 20 s^?1 and 51 s^?1, respectively. The heats of adsorption show a linear dependence on coverage (131 ? 38θ) kJ/mol between 0 ≤ θ ≤ 0.3, which is consistent with the desorption data from the literature. For higher coverage (up to θ = 0.9ML) a slope of ?63 kJ/mol describes the decrease of the differential heat of adsorption best. This result is only compatible with desorption experiments, if the pre-exponential factor decreases strongly at higher coverage. We found good agreement with recent quantum chemical calculations made for (θ = 0.5ML).     

Stabilization of ErFeAsO-based superconductor by hydrogen doping under high pressure

Here we report on the successful synthesis of ErFeAsO-based superconductor by hydrogen doping using high-pressure (HP) synthesis technique. The ErFeAsO_1?y target pellets were sandwiched between LaFeAsO_0.8H_0.8 pellets, which act as a hydrogen source. Hydrogen released from the hydrogen source soaks into the target pellets during HP synthesis and the target pellets crystallizes with the tetragonal crystal structure with the lattice constants a = 3.8219 Å and c = 8.2807 Å. The hydrogen doped sample ErFeAsO_1?y(H) thus obtained shows superconducting critical temperatures (T_c) of 44.5 K and 42.5 K determined by onsets of resistive and diamagnetic transitions, respectively.     

Giant magnetic refrigerant capacity in Ho3Al2 compound

Magnetic properties and magnetocaloric effects (MCEs) of the intermetallic Ho₃Al₂ compound are investigated by magnetization and heat capacity measurements. Two successive magnetic transitions, a spin-reorientation (SR) transition at T_SR=31 K followed by a ferromagnetic (FM) to paramagnetic (PM) transition at T_C=40 K, are observed. Both magnetic transitions contribute to the MCE and result in a large magnetic entropy change (ΔS_M) in a wide temperature range. The maximum values of ?ΔS_M and adiabatic temperature change (ΔT_ad) reach 18.7 J/kg K and 4.8 K for the field changes of 0–5 T, respectively. In particular, a giant value of refrigerant capacity (RC) is estimated to be 704 J/kg for a field change of 5 T, which is much higher than those of many potential refrigerant materials with similar transition temperatures.     

Ionic and electronic conductivities,stability and thermal expansion of La10 − x(Si,Al)6O26 ± δ solid electrolytes

Apatite-type La_10 − xSi_6 − yAl_yO_{27 − 3x/2 − y/2} (x = 0–0.33; y = 0.5–1.5) exhibit predominant oxygen ionic conductivity in a wide range of oxygen partial pressures. The conductivity of silicates containing 26.50–26.75 oxygen atoms per formula unit is comparable to that of gadolinia-doped ceria at 770–870 K. The average thermal expansion coefficients are (8.7–10.8) × 10^− 6 K^− 1 at 373–1273 K. At temperatures above 1100 K, silicon oxide volatilization from the surface layers of apatite ceramics and a moderate degradation of the ionic transport with time are observed under reducing conditions, thus limiting the operation temperature of Si-containing solid electrolytes.     

Growth of Sr2CrReO6 epitaxial thin films by pulsed laser deposition

We report the growth, structural, magnetic, and electrical transport properties of epitaxial Sr₂CrReO₆ thin films. We have succeeded in depositing films with a high crystallinity and a relatively large cationic order in a narrow window of growth parameters. The epitaxy relationship is Sr₂CrReO₆ (SCRO) (0 0 1) [1 0 0]∥SrTiO₃ (STO) (0 0 1) [1 1 0] as determined by high-resolution X-ray diffraction and scanning transmission electron microscopy (STEM). Typical values of saturation magnetization of M_S (300 K)=1 μ_B/f.u. and ρ (300 K)=2.8 mΩ cm have been obtained in good agreement with previous published results in sputtered epitaxial thin films. We estimate that the antisite defects concentration in our thin films is of the order of 14%, and the measured Curie temperature is T_C=481(2) K. We believe these materials be of interest as electrodes in spintronic devices.     

On the superconductivity and structural properties of YBa2Cu3 − xCdxO7 − y

A series of superconducting cuprates with the nominal composition YBa₂Cu_3 − xCd_xO_7 − yand the effect of Cd substitution on Cu sites in this compound is presented. X-ray powder diffraction patterns for these cadmium cuprates with reduced diamagnetism indicate an orthorhombic unit cell like-perovskite structure for (0 ≤ x ≤ 0.15), while for higher Cd concentration, i.e.x = 1.0 the material is polyphasic. The observed superconducting transition temperature of the samples is nearly the same ([formula] K), except for (x = 1.0) whereT_cdrops to 72 K and a transition from metallic to semiconducting behavior of the normal state of the resistivity is observed. Such a decrease inT_cfor higher Cd concentration could be attributed to the presence of the green phase in this composition.