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The temperature dependence of the thermal conductivity k(T) of the AsxS100-x glass system was studied down to 1.8 K in a wide range of various (x = 20, 28.6, 40, 45, and 50) compositions. Universal glass anomalies in k(T) were revealed. The temperature dependence k(T) ∼ T2 onset at the lowest temperatures and plateau below 15 K were detected. The plateau formation is sample quality sensitive and composition-dependent. It was experimentally found that even with a slow cooling rate, several samples were cracked. Depending on the sample damage, the additional internal scattering process leads to the k(T) plateau suppression. The observed k(T) temperature dependence is similar to the glassy ceramics-like behavior. [ABSTRACT FROM AUTHOR]

An experimental study of the magnetocaloric effect in tetraaquabis(hydrogen maleato)nickel(II), [Ni(C4H3O4)2(H2O)4] powder sample is presented. The magnetocaloric properties of the studied sample were investigated using specific heat and magnetization measurements in magnetic fields up to 9 T in the temperature range from 0.4 to 50 K. A large conventional magnetocaloric effect was found at a temperature of about 3.5 K, where −ΔSM = 8.5 Jkg−1K−1 and 11.2 Jkg−1K−1 for a magnetic field of 5 T and 7 T, respectively. Assuming a substantial role of the crystal field, the temperature dependence of the magnetic specific heat in a zero magnetic field was compared with an S = 1 model with single-ion anisotropy parameters D and E (axial and rhombic). The best agreement was found for the parameters D/kB = −7.82 K and E/kB = −2.15 K. On the other hand, the experimental temperature dependence of −ΔSM shows higher values compared to the theoretical prediction for the mentioned model, indicating the presence of additional factors in the system, such as an exchange interaction between magnetic ions. The first exchange pathway can be realized through maleic rings between the nearest Ni(II) ions. The second exchange pathway can be realized through water molecules approximately along the a crystallographic axis. Broken-symmetry DFT calculations performed using the computational package ORCA provided the values of ferromagnetic exchange interactions, J1/kB = 1.50 K and J2/kB = 1.44 K (using B3LYP functional). The presence of such ferromagnetic correlations in the studied system may explain the enhanced magnetocaloric effect compared with the model of an anisotropic spin-1 paramagnet. [ABSTRACT FROM AUTHOR]

An experimental study of the rotational magnetocaloric effect in Ni(en)(H2O)4SO4∙2H2O (en = ethylenediamine) single crystal is presented. The study was carried out at temperatures above 2 K and was associated with adiabatic crystal rotation between the easy plane and hard axis in magnetic fields up to 7 T. The magnetocaloric properties of the studied system were investigated by isothermal magnetization measurement. The experimental observations were completed with ab initio calculations of the anisotropy parameters. A large rotational magnetic entropy change ≈12 Jkg−1K−1 and ≈16.9 Jkg−1K−1 was achieved in 5 T and 7 T, respectively. The present study suggests a possible application of this material in low-temperature refrigeration since the adiabatic rotation of the single crystal in 7 T led to a cooldown of the sample from the initial temperature of 4.2 K down to 0.34 K. Finally, theoretical calculations show that S = 1 Ni(II)-based systems with easy-plane anisotropy can have better rotational magnetocaloric properties than costly materials containing rare-earth elements in their chemical structures. [ABSTRACT FROM AUTHOR]

The phase content and sequence, the crystal structure, and the magnetic properties of perovskite solid solutions of the (1-y)BiFeO3-yBiZn0.5Ti0.5O3 series (0.05 ≤ y ≤ 0.90) synthesized under high pressure have been studied. Two perovskite phases, namely the rhombohedral R3c and the tetragonal P4mm, which correspond to the structural types of the end members, BiFeO3 and BiZn0.5Ti0.5O3, respectively, were revealed in the as-synthesized samples. The rhombohedral and the tetragonal phases were found to coexist in the compositional range of 0.30 ≤ y ≤ 0.90. Magnetic properties of the BiFe1-y[Zn0.5Ti0.5]yO3 ceramics with y < 0.30 were measured as a function of temperature. The obtained compositional variations of the normalized unit-cell volume and the Néel temperature of the BiFe1-y[Zn0.5Ti0.5]yO3 perovskites in the range of their rhombohedral phase were compared with the respective dependences for the BiFe1-yB3+ yO3 perovskites (where B3+ = Ga, Co, Mn, Cr, and Sc). The role of the high-pressure synthesis in the formation of the antiferromagnetic states different from the modulated cycloidal one characteristic of the parent BiFeO3 is discussed. [ABSTRACT FROM AUTHOR]

Gadolinium oxymolybdate, Gd2MoO6 (monoclinic, C2/c) was prepared via nonconventional mechanochemical/thermal process from powdered oxide precursors (Gd2O3 and (NH4)2MoO4). The effect of mechanical activation via high-energy ball milling on the reactivity of the stoichiometric Gd2O3 + (NH4)2MoO4 mixture was studied by thermal analysis (TG-DSC) and Fourier-transform infrared spectroscopy. While thermal treatment of nonactivated mixture leads only to decomposition of (NH4)2MoO4 and formation of Gd2O3-MoO3 system, mechanical activation provides enough energy for a chemical reaction between both reactants. The product with an average crystallite size of approximately 1 μm shows a well-faceted morphology. The investigation of magnetic properties revealed antiferromagnetic coupling, which is attributed to exchange interactions. [ABSTRACT FROM AUTHOR]

The comprehensive study reported herein provides compelling evidence that anion templates are the main driving force in the formation of two novel nanoscale lanthanide hydroxide clusters, {Gd38(ClO4)6} ( 1) and {Gd48Cl2(NO3)} ( 2), characterized by single-crystal X-ray crystallography, infrared spectroscopy, and magnetic measurements. {Gd38(ClO4)6}, encapsulating six ClO4− ions, features a cage core composed of twelve vertex-sharing {Gd4} tetrahedrons and one Gd⋅⋅⋅Gd pillar. When Cl− and NO3− were incorporated in the reaction instead of ClO4−, {Gd48Cl2(NO3)} is obtained with a barrel shape constituted by twelve vertex-sharing {Gd4} tetrahedrons and six {Gd5} pyramids. What is more, the cage-like {Gd38} can be dynamically converted into the barrel-shaped {Gd48} upon Cl− and NO3− stimulus. To our knowledge, it is the first time that the linear M-O-M′ fashion and the unique μ8-ClO4− mode have been crystallized in pure lanthanide complex, and complex 2 represents the largest gadolinium cluster. Both of the complexes display large magnetocaloric effect in units of J kg−1 K−1 and mJ cm−3 K−1 on account of the weak antiferromagnetic exchange, the high NGd/ MW ratio (magnetic density), and the relatively compact crystal lattice (mass density). [ABSTRACT FROM AUTHOR]

Two kinds of inorganic gadolinium(III)-hydroxy 'ladders', [2× n] and [3× n], were successfully trapped in succinate (suc) coordination polymers, [Gd2(OH)2(suc)2(H2O)] n ⋅ 2 n H2O ( 1) and [Gd6(OH)8(suc)5(H2O)2] n ⋅4 n H2O ( 2), respectively. Such coordination polymers could be regarded as alternating inorganic-organic hybrid materials with relatively high density. Magnetic and heat capacity studies reveal a large cryogenic magnetocaloric effect (MCE) in both compounds, namely (Δ H=70 kG) 42.8 J kg−1 K−1 for complex 1 and 48.0 J kg−1 K−1 for complex 2. The effect of the high density is evident, which gives very large volumetric MCEs up to 120 and 144 mJ cm−3 K−1 for complexes 1 and 2, respectively. [ABSTRACT FROM AUTHOR]

Quantum Heisenberg chain and square lattices are important paradigms of a low-dimensional magnetism. Their ground states are determined by the strength of quantum fluctuations. Correspondingly, the ground state of a rectangular lattice interpolates between the spin liquid and the ordered collinear Néel state with the partially reduced order parameter. The diversity of additional exchange interactions offers variety of quantum models derived from the aforementioned paradigms. Besides the spatial anisotropy of the exchange coupling, controlling the lattice dimensionality and ground-state properties, the spin anisotropy (intrinsic or induced by the magnetic field) represents another important effect disturbing a rotational symmetry of the spin system. The S = 1/2 easy-axis and easy-plane XXZ models on the square lattice even for extremely weak spin anisotropies undergo Heisenberg-Ising and Heisenberg-XY crossovers, respectively, acting as precursors to the onset of the finite-temperature phase transitions within the two-dimensional Ising universality class (for the easy axis anisotropy) and a topological Berezinskii–Kosterlitz–Thouless phase transition (for the easy-plane anisotropy). Experimental realizations of the S = 1/2 two-dimensional XXZ models in bulk quantum magnets appeared only recently. Partial solutions of the problems associated with their experimental identifications are discussed and some possibilities of future investigations in quantum magnets on the square and rectangular lattice are outlined. [ABSTRACT FROM AUTHOR]

The magnetic properties of the hybrid materials formed by coordination compounds and clay minerals represent one of the main challenges in material science. The investigation of the intercalation of tris (2,2′-bipyridine)nickel(II) cations [Ni(bpy) 3 ]2+ present in the solution with chloride anions into synthetic saponite (Sap) was carried out by direct exchange of the sodium ions by nickel(II) complex. The final intercalated [Ni(bpy) 3 ]2+ saponite complex was characterized by powder X-ray diffraction (XRD), infrared (IR) spectroscopy, carbon and thermal analysis, and for the first time also by magnetic measurements. The carbon analysis proved a full replacement of Na+ with [Ni(bpy) 3 ]2+ cations. Furthermore, significant increase of the d 001 value of the intercalated saponite confirmed the presence of the [Ni(bpy) 3 ]2+ in Sap interlayers. Only limited effect of the saponite layers on the ring C-H or skeletal vibrations of the [Ni(bpy) 3 ]2+ complex was observed. The thermal stability of the [Ni(bpy) 3 ]2+ increased after its intercalation into saponite. The magnetic properties of the [Ni(bpy) 3 ]2+ saponite complex revealed similar magnetic response as the starting compound [Ni(bpy) 3 ]Cl 2 · n H 2 O suggesting that the local surroundings of the Ni(II) atoms in [Ni(bpy) 3 ]2+ intercalated into saponite remained unchanged. • The intercalation of [Ni(bpy) 3 ]2+ complex into synthetic saponite was accomplished. • The increase of d-value confirmed its presence in the saponite interlayers. • Thermal stability of the complex increased after its intercalation. • Magnetic properties of [Ni(bpy) 3 ]2+ remained unchanged after intercalation into saponite. [ABSTRACT FROM AUTHOR]

Organo-metallic compounds Cu( en )(H 2 O) 2 SO 4 ( en =C 2 H 8 N 2 ) and Cu( tn )Cl 2 ( tn =C 3 H 10 N 2 ) representing S =1/2 quasi-two-dimensional Heisenberg antiferromagnets with an effective intra-layer exchange coupling J/ k B ≈3 K, have been examined by specific heat measurements at temperatures down to nominally 50 mK and magnetic fields up to 14 T. A comparative analysis of magnetic specific heat in zero magnetic field revealed nearly identical contribution of short-range magnetic correlations and significant differences were observed at lowest temperatures. A phase transition to long-range order was observed in Cu( en )(H 2 O) 2 SO 4 at T C =0.9 K while hidden in Cu( tn )Cl 2 . A response of both compounds to the application of magnetic field has rather universal features characteristic for a field-induced Berezinskii–Kosterlitz–Thouless transition theoretically predicted for ideal two-dimensional magnets. [ABSTRACT FROM AUTHOR]

The comprehensive study reported herein provides compelling evidence that anion templates are the main driving force in the formation of two novel nanoscale lanthanide hydroxide clusters, {Gd38(ClO4)6} (1) and {Gd48Cl2(NO3)} (2), characterized by single-crystal X-ray crystallography, infrared spectroscopy, and magnetic measurements. {Gd38(ClO4)6}, encapsulating six ClO4(-) ions, features a cage core composed of twelve vertex-sharing {Gd4} tetrahedrons and one Gd⋅⋅⋅Gd pillar. When Cl(-) and NO3(-) were incorporated in the reaction instead of ClO4(-), {Gd48Cl2(NO3)} is obtained with a barrel shape constituted by twelve vertex-sharing {Gd4} tetrahedrons and six {Gd5} pyramids. What is more, the cage-like {Gd38} can be dynamically converted into the barrel-shaped {Gd48} upon Cl(-) and NO3(-) stimulus. To our knowledge, it is the first time that the linear M-O-M' fashion and the unique μ8-ClO4(-) mode have been crystallized in pure lanthanide complex, and complex 2 represents the largest gadolinium cluster. Both of the complexes display large magnetocaloric effect in units of J kg(-1) K(-1) and mJ cm(-3) K(-1) on account of the weak antiferromagnetic exchange, the high N(Gd)/M(W) ratio (magnetic density), and the relatively compact crystal lattice (mass density)., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Two kinds of inorganic gadolinium(III)-hydroxy "ladders", [2×n] and [3×n], were successfully trapped in succinate (suc) coordination polymers, [Gd2(OH)2(suc)2(H2O)]n·2nH2O (1) and [Gd6(OH)8(suc)5(H2O)2 ]n·4n H2O (2), respectively. Such coordination polymers could be regarded as alternating inorganic-organic hybrid materials with relatively high density. Magnetic and heat capacity studies reveal a large cryogenic magnetocaloric effect (MCE) in both compounds, namely (ΔH=70 kG) 42.8 J kg(-1) K(-1) for complex 1 and 48.0 J kg(-1) K(-1) for complex 2. The effect of the high density is evident, which gives very large volumetric MCEs up to 120 and 144 mJ cm(-3) K(-1) for complexes 1 and 2, respectively., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)