Magnetocaloric properties of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>K<Emphasis Type="Italic">x</Emphasis>MnO<Subscript>3</Subscript> manganites

A technology for obtaining single-phase ceramic samples of La_{1 − x} K _x MnO₃ manganites, as well as the dependence of their structure parameters on the potassium content, is described. The magnetocaloric effect in the samples has been measured by two direct methods, the classical method and the magnetic field modulation method, and has been calculated from the specific heat data. The values of the magnetocaloric effect obtained by these methods are significantly different. The observed discrepancies have been explained. Correlation between the doping level and the value of the effect has been found. It has been shown that the magnetic-field dependence of variation of the magnetic entropy near T _C in weak fields corresponds to theoretical calculations and that the value of the magnetocaloric effect in high magnetic fields can be predicted using this dependence.     

Thermal and magnetic properties of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript>

The thermodynamic and magnetic properties of the La_{1 − x} Pb _x MnO₃ (0.24 ≤ x ≤ 0.40) solid solution system were investigated in the temperature range of 4.2–340 K. All objects were ferromagnetics with Curie temperature T _C ≈ 320–340 K, which slowly increased with x. The M(T) behavior in the magnetic ordering region indicated a nonuniform ground state, due possibly to the competition of ferromagnetic and antiferromagnetic interactions. The increase in the saturation magnetic moment with x can be described by a simple model of the binary bonds in La_{1 − x} Pb _x MnO₃.     

Spin-glass like behaviors in La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Tb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> perovskite

A series of samples of La_1−x Tb _x MnO₃ (0⩽x⩽0.15) are prepared. The static and dynamic magnetizations of La_1−x Tb _x MnO₃ have been investigated. The results indicate that the spins with the short-range order are frozen into random direction at low enough temperatures which leads to the samples exhibiting the spin-glass like behavior. It is considered that the spin-glass like behavior originates from the competition between ferromagnetic double exchange among Mn³⁺ and Mn²⁺ and antiferromagnetic superexchange among Mn³⁺ and Mn³⁺, as well as Tb³⁺ and Tb³⁺.     

Magnetic ordering in La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript>x</Subscript>MnO<Subscript>3−<Emphasis Type="Italic">x</Emphasis>/2</Subscript> anion-deficient manganites

The structural, magnetic, and electrotransport properties of La_1?xSr_xMnO_{3? x/2}(0≤x≤0.30) manganites with perovskite structure are investigated experimentally as a function of oxygen deficiency. In the solid solutions La_1?xSr_xMnO₃, a change in the type of symmetry of the unit cell is observed at x=0.125. Samples with x≤0.125 are characterized by an O′-orthorhombic unit cell, whereas samples with x>0.125 are characterized by a rhombohedral unit cell. The structural properties of the anion-deficient solid solutions La_1?xSr_xMnO_3?x/2 are analogous to those of the stoichiometric system. It is assumed that, as the oxygen content decreases, La_{1? x}Sr_xMnO_3?x/2 anion-deficient solid solutions experience a series of successive magnetic phase transformations in the ground state: from an A-type (x=0) antiferromagnet to a cluster spin-glass-type inhomogeneous magnetic state (0.175>x≤0.30) through a two-phase (antiferromagnetic and ferromagnetic) state (0>x≤0.175). The anion-deficient solid solution with x=0.175 has the maximal value of the ferromagnetic component. As the oxygen deficiency increases, the resistivity of La_{1? x}Sr_xMnO_3?x/2 samples first decreases (up to a value of x=0.175), acquiring an activation character, and then increases (up to a value of x=0.30). In this case, none of the anion-deficient solid solutions exhibits a metal-semiconductor transition in the whole range of concentrations considered. A peak of magnetoresistance at a temperature below the point of magnetic ordering is observed only in the sample with x=0.175. The results of experiments carried out with a series of La_1?xSr_xMnO_3?x/2 anion-deficient solid solutions are summarized in the concentration diagrams of the spontaneous magnetic moment and the critical temperature of magnetic phase transitions. Hypothetical magnetic phase states are pointed out. The experimental results obtained can be interpreted in terms of the phase-separation model and the competition between ferromagnetic and antiferromagnetic indirect superex-change interactions. It is assumed that Mn³⁺-O-Mn³⁺ indirect superexchange interactions in the orbitally disordered phase are positive in the case of octahedral coordination of manganese ions and are negative when the coordination of at least one Mn³⁺ ion is pentahedral.     

Magnetic phase transitions in Nd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Emphasis Type="Italic">x</Emphasis>MnO<Subscript>3</Subscript> manganites

The magnetic properties of manganites of the Nd_1?xCa_xMnO₃ system with x≤0.15 have been studied. It is shown that, in the 0.06≤x≤0.1 interval, the results can be interpreted using a model according to which the concentrational transition from a weakly ferromagnetic (WFM) state (x=0) to a ferromagnetic (FM) state (x>0.15) proceeds via a mixture of the exchange-coupled FM and WFM phases. In the vicinity of T=9 K, samples with 0.06≤x≤0.1 exhibit a spontaneous magnetic phase transition involving reorientation of the magnetization vectors of the WFM and the exchange-coupled FM phases. In the temperature interval between 5 and 20 K, a sample with the composition Nd^0.92Ca^0.08MnO^2.98 exhibits metamagnetic behavior. Magnetic phase diagrams in the H?T and T?x coordinates are presented. The appearance of the spin-reorientation transitions is explained in terms of the magnetic analog of the Jahn-Teller effect with allowance for the fact that, according to the neutron diffraction data, the magnetic moments of neodymium ions in the FM phase are parallel to the magnetic moments of manganese ions.     

Magnetothermal properties of Gd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Y<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript>2</Subscript> compounds

The heat capacity of pseudobinary intermetallic compounds Gd_1−x Y _x Ni₂ (0≤x≤1) has been studied. The magnetic contribution to the total heat capacity is isolated with the use of the data obtained for the paramagnetic analogs Lu_1−y Y _y Ni₂ possessing the same molar masses as the gadolinium compounds. It has been found that the difference between the entropies of the Gd_1−x Y _x Ni₂ (x<0.8) compounds and the corresponding paramagnetic Lu_1−y Y _y Ni₂ analogs reaches larger values than those expected from the calculations performed under the assumption that only Gd ions contribute to the magnetic part of the total entropy. The existence of an additional contribution of magnetic nature to the entropy of the Gd_1−x Y _x Ni₂ compounds, as well as the large values of the γ coefficient in the linear-in-temperature term of the heat capacity, is assigned to the spin fluctuations induced by the f—d exchange in the subsystem of Ni 3d electrons.     

Heat capacity and magnetocaloric properties of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>K<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> manganites

The magnetocaloric effect and the heat capacity of La_{1 − x} K _x MnO₃ (x = 0.1, 0.15, 0.175) ceramic samples have been studied at temperatures in the range 77–350 K and in magnetic fields of up to 27 kOe. The technique for preparing the samples has been described. The heat capacity anomalies related to the ferromagnetic-paramagnetic magnetic phase transition have been revealed and interpreted. It has been demonstrated that the change in the magnetic entropy ΔS calculated from the data on the heat capacity C _p and direct measurements of the magnetocaloric effect ΔT reaches values that are of practical interest.     

Structure and Curie temperature of Y<Subscript>2</Subscript>Fe<Subscript>17−<Emphasis Type="Italic">x</Emphasis></Subscript>Cr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

The structures of Y₂Fe_17−x Cr _x are simulated by theab initio potentials. The site preference of Cr atom in Y₂Fe₁₇ is evaluated and the order is determined as 4f, 12j, which is close to the experimental result. Based on the site preference behavior, the calculated parameters and the atom sites of Y-Fe-Cr system are studied. The result corresponds well to observed data. Further, the DOS of the relaxed structures are calculated and the variation in Curie temperature is explained qualitatively by the spin-fluctuation theory.     

High-temperature study of SrFe<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Mo<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>3−<Emphasis Type="Italic">z</Emphasis></Subscript> perovskites

The structure of high-temperature SrFe_{1 − x} Mo _x O_{3 − z} (0 ≤ x ≤ 0.5) phases was studied. Such studies are necessary to understand the mechanism of oxygen transport in membrane materials used for high-temperature oxygen separation.     

Theory of the giant magnetoresistance in La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>A<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript>

To clarify the origin of the giant magnetoresistance (GMR) observed in La_1?x A _x MnO₃ (A²⁺=Sr²⁺, Pb²⁺, Ba²⁺ and Ca²⁺), we have investigated theoretically the electrical resistivity ρ of carriers in the background of Mn spins which interact with each other through the double exchange interaction. It has been found that extraordinarily large pin fluctuations caused by the instability of the ferromagnetic state are responsible for the transport anomalies including the GMR.     

Magnetic and magnetoresistive properties of Gd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Se selenides

Gd _x Mn_1–x Se (0 ≤ х ≤ 0.15) solid solutions are synthesized on the basis of manganese monoselenide. Their magnetic and electrical properties are studied in the temperature range of 80–900 K in magnetic fields up to 10 kOe. An FCC lattice with the Fm3m space group and antiferromagnetic ordering of the magnetic moments of manganese ions is found. A monotonic reduction in the Néel temperature and an increase in the effective magnetic moment along with the gadolinium concentration are observed. Anomalies in the temperature dependence of electrical resistivity and a shift in the temperatures of anomalies in a magnetic field are found.     

The magnetic properties of nanosized La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> (0.5 ≤ <Emphasis Type="Italic">x</Emphasis> ≤ 0.8)

Magnetic properties of La_1−x Ca _x MnO₃ (0.5 ≤ x ≤ 0.8) samples with an equivalent average particle size ~50 nm prepared by a sol–gel method were investigated. The charge ordering (CO) transition that is observed in the bulks disappears and the ferromagnetic (FM) transition occurs in all the prepared samples. For all the samples, the spontaneous magnetization (M _S) value is much lower than the corresponding theoretic value, which shows that the majority of the sample is antiferromagnetic (AFM). However, the M _S value is much larger than the corresponding value reported by some other groups. The invisible of CO transition and the large M _S value can be attributed to the good connection among the adjacent particles. Moreover, the exchange bias (EB) phenomenon is observed except the x = 0.5 sample. With x increasing, the M _S value decreases and the EB field increases, which can be understood by considering the coexistence of FM phase with Mn³⁺–Mn⁴⁺ spin clusters in the shell and the AFM phase in the core of the nanoparticles.     

Physical properties of Fe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Dy<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Si crystals

The results of experimental investigation of magnetic and electric properties of Fe_1?x Dy _x Si crystals are reported. It is shown that the magnitude and position of the anomaly observed in the temperature dependences of magnetization are controlled to a considerable extent by the external magnetic field. It is found that the introduction of Dy ions leads to a weak magnetoresistive effect.     

Transport properties and ferromagnetism of Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>S sulfides

We have studied the resistivity and thermoelectromotive force (thermo emf) in a temperature range of T = 80–1000 K, the magnetic susceptibility and magnetization in a temperature range of T = 4.2–300 K at an external magnetic field of up to 70 kOe, and the structural characteristics of Co _x Mn_1?x S sulfides (0 ≤ x ≤ 0.4). Anomalies in the transport properties of these compounds have been found in the temperature intervals ΔT ₁ = 200–270 K and ΔT ₂ = 530–670 K and at T ₃ ～ T _N. The temperature dependences of the magnetic susceptibility, magnetization, and resistivity, as well as the current-voltage characteristics, exhibit hysteresis. In the domain of magnetic ordering at temperatures below the Néel temperature (T _N), the antiferromagnetic Co _x Mn_1?x S sulfides possess a spontaneous magnetic moment that is explained using a model of the orbital ordering of electrons in the t _2g bands. The influence of the cobalt-ion-induced charge ordering on the transport and magnetic properties of sulfides has been studied. The calculated values of the temperatures corresponding to the maxima of charge susceptibility, which are related to a competition between the on-site Coulomb interaction of holes in various subbands and their weak hybridization, agree well with the experimental data.     

Low temperature features of the local structure of Sm<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Y<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>S

The particular features of the local electronic and local crystal structures of the mixed-valence compound Sm_{1 ? x} Y _x S are studied by the XAFS spectroscopy methods in the temperature range 20–300 K for the yttrium concentration x = 0.17, 0.25, 0.33, and 0.45. The temperature behavior of the valence of Sm, as well as of the lengths and the Debye-Waller factors of the bonds Sm-S, Sm-Sm(Y), Y-S, and Y-Sm(Y), has been determined. The violation of the Vegard law has been observed. A model for the estimation of the energy width of the 4f level and of its position with respect to the Fermi level is proposed.     

Phase states in the Y<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> solid solution system

The room-temperature stability region of the tetragonal phase in the Y_{1 − x} Ca _x MnO₃ solid solution system has been found for the first time. The concentration boundaries between this phase and the orthorhombic (x > 0.5) and hexagonal (x < 0.25) phases are sensitive to the sample preparation conditions. The coexistence of the hexagonal and tetragonal phases in the range 0.15 < x < 0.25 indicates that these phases undergo a first-order reconstructive phase transition. Preliminary measurements of magnetic ordering effects for compositions with x = 0.3, 0.5, and 0.7 have been performed.     

Magnetic Properties of a Layered Cobaltite Sr<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Y<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>CoO<Subscript>3–δ</Subscript> (<Emphasis Type="Italic">x</Emphasis> = 0.1)

The structure, the magnetic and magnetotransport properties of perovskite Sr_0.9Y_0.1CoO_2.63 have been studied. The sample is shown to have a two-phase structure. The main phase has a tetragonally distorted unit cell and is described by space group I4/mmm. The broadening of the reflections with indices corresponding to doubling unit cell parameter c indicates the absence of the rigorous translation symmetry along axis c. The existence of the broadened superstructure reflection observed in the diffraction pattern at small angles at temperature lower than 400 K is explained by the existence of the monoclinic phase whose content is significantly lower than that of the tetragonal phase, but is dominant in the Sr_0.8Y_0.2CoO_3–δ composition. The spontaneous magnetization appears as the monoclinic phase forms. The magnetic structure is mainly G-type antiferromagnetic with magnetic moments 1.5μ_B in the layers of CoO₆ octahedra and 2μ_B in the anion-deficit CoO_{4 + γ} layers. The conduction of the Sr_0.9Y_0.1CoO_2.63 composition has a semiconducting character. The magnetoresistance is 57% in a field of 14 T at a temperature of 5 K and strongly decreases with the temperature increase.     

Features of properties of microinhomogeneous PdMn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript>1− <Emphasis Type="Italic">x</Emphasis></Subscript> alloys

Complex investigation of the properties of PdMn _x Fe_{1? x} ternary alloys with interacting magnetic and structural order parameters has been performed. It is shown that the complex structural and magnetic state near the transition from the atomically ordered PdFe ferromagnet to the intermetallic antiferromagnetic PdMn compound leads to unusual features not only in magnetic and lattice characteristics but also in electronic properties.     

Magnetic properties of single crystals of the Cr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>S solid solutions (0 ≤ <Emphasis Type="Italic">x</Emphasis> < 0.3)

The Cr _x Mn_{1 − x} S single crystals have been synthesized based on manganese monosulfide as a result of cation substitution, and their magnetic properties have been studied. It has been established that the Cr _x Mn_{1 − x} S solid solutions with a face-centered cubic NaCl structure are formed in the concentration region 0 ≤ x < 0.3. The unit cell parameter of the solid solution decreases as the degree of substitution increases due to the variation in the ionic radius of cations. These substances are antiferromagnets. An increase in the degree of cation substitution in the Cr _x Mn_{1 − x} S solid solutions is accompanied by a decrease in the number of 3d electrons in the d shell of manganese monosulfide and causes a decrease in the magnetic transition temperature from 149 K (x = 0) to 96 K (x = 0.29), which differs from previously known results.     

Dielectric properties and specific heat of Bi<Subscript>1–<Emphasis Type="Italic">x</Emphasis> </Subscript>Sm<Subscript> <Emphasis Type="Italic">x</Emphasis> </Subscript>FeO<Subscript>3</Subscript> multiferroics

The specific heat and dielectric permittivity of Bi_1–xSm_xFeO₃ (x = 0–0.30) multiferroics have been studied in the temperature range of 300–800 K. A slight substitution of bismuth with samarium is established to cause a considerable shift in the antiferromagnetic phase transition temperature and to an increase in the specific heat over a wide temperature range. Other anomalies typical of phase transitions have been found in the temperature dependences of the specific heat and dielectric permittivity for the compounds with x = 0.10 and 0.15 at T ≈ 735 and 495 K, respectively. The results of the studies of the specific heat have been discussed together with the data of the structural investigations.