Influence of silver addition on microstructures and transport properties of La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript>:Ag<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> composites

In order to obtain high temperature coefficient of resistance (TCR) value of La_0.67Ca_0.33MnO₃:Ag _x (LCMO:Ag _x ) composites, samples with different Ag contents (x?=?0, 0.1, 0.2, 0.25, 0.3, and 0.5) were prepared by sol–gel method. X-ray diffraction analyses indicated that all samples had orthorhombic perovskite structures. As x increased, lattice parameters (a, b, c) and cell volumes underwent slight expansions. Interestingly, the addition of Ag dramatically affected TCR and magneto-resistance (MR) values. Elevated TCR value up to 53.46%·K^?1 at 277 K was observed for LCMO:Ag _x composites with added Ag at the composition of x?=?0.1. Meanwhile, MR value at 263 K reached 71% at the magnetic field of 1 T for samples with Ag composition of x?=?0.25. The increase in Mn⁴⁺/Mn³⁺ ratio and improvement in crystallization caused by added Ag was found responsible for the elevated values of TCR, MR, and T_p. These findings may have practical use in high-performance magneto-resistive manganites.     

Investigation of Magnetic,Magnetocaloric, and Critical Properties of La<Subscript>0.5</Subscript>Ba<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> Manganite

We present an extensive study of the magnetic properties of a novel La_0.5Ba_0.5MnO₃ perovskite material prepared by the hydrothermal method. The explored sample was structurally studied by the x-ray diffraction (XRD) method which confirms the formation of a pure cubic phase of a perovskite structure with Pm3m space group. The magnetic properties were probed by employing temperature M (T) and external magnetic field M (μ_oH) dependence of magnetization measurements. A magnetic phase transition from ferromagnetic to paramagnetic phase occurs at 339 K in this sample. The maximum magnetic entropy change (\(\left | {{\Delta } S}_{M}^{\max } \right |\)) took a value of 1.4 J kg^??1 K^??1 at the applied magnetic field of 4.0 T for the explored sample and has also been found to occur at Curie temperature (T_C). This large entropy change might be instigated from the abrupt reduction of magnetization at T_C. The magnetocaloric effect (MCE) is maximum at T_C as represented by M (μ_oH) isotherms. The relative cooling power (RCP) is 243.2 J kg^??1 at μ_oH =?4.0 T. Moreover, the critical properties near T_C have been probed from magnetic data. The critical exponents δ, β, and γ with values 3.82, 0.42, and 1.2 are close to the values predicted by the 3D Ising model. Additionally, the authenticity of the critical exponents has been confirmed by the scaling equation of state and all data fall on two separate branches, one for T < T_C and the other for T > T_C, signifying that the critical exponents obtained in this work are accurate.     

Inducement of Itinerant Electron Transport in Charge-Ordered Pr<Subscript>0.6</Subscript>Ca<Subscript>0.4</Subscript>MnO<Subscript>3</Subscript> by Ba Doping

The effects of Ba ²⁺ doping on the electrical and magnetic properties of charge-ordered Pr_0.6Ca_0.4MnO₃ were investigated through electrical resistivity and AC susceptibility measurements. X-ray diffraction data analysis showed an increase in unit cell volume with increasing Ba ²⁺ content indicating the possibility of substituting Ba ²⁺ for the Ca-site. Electrical resistivity measurements showed insulating behavior and a resistivity anomaly at around 220 K. This anomaly is attributed to the existence of charge ordering transition temperature, \(T^{\mathrm {R}}_{\text {CO}}\) for the x = 0 sample. The Ba-substituted samples exhibited metallic to insulator transition (MI) behavior, with transition temperature, T _MI, increasing from ～98 K (x = 0.1) to ～122 K (x = 0.3). AC susceptibility measurements showed ferromagnetic to paramagnetic (FM-PM) transition for Ba-substituted samples with FM-PM transition temperature, T _c, increasing from ～121 K (x = 0.1) to ～170 K (x = 0.3), while for x = 0, an antiferromagnetic to paramagnetic transition behavior with transition temperature, T _N, ～170 K was observed. In addition, inverse susceptibility versus T plot showed a deviation from the Curie–Weiss behavior above T _c, indicating the existence of the Griffiths phase with deviation temperature, T _G, increasing from 160 K (x = 0.1) to 206 K (x = 0.3). Magnetoresistance, MR, behavior indicates intrinsic MR mechanism for x = 0.1 which changed to extrinsic MR for x > 0.2 as a result of Ba substitution. The weakening of charge ordering and inducement of ferromagnetic metallic (FMM) state as well as increase in both T _c and T _MI are suggested to be related to the increase of tolerance factor, τ, and increase of e _g ?electron bandwidth as average ionic radius at A-site, <r _A> increased with Ba substitution. The substitution may have reduced MnO₆ octahedral distortion and changed the Mn–O–Mn angle which, in turn, promotes itinerancy of charge carrier and enhanced double exchange mechanism. On the other hand, increase in A-site disorder, which is indicated by the increase in σ ² is suggested to be responsible for the widening of the difference between T _c and T _MI.     

Prediction of Magnetocaloric Effect by a Phenomenological Model and Critical Behavior for La<Subscript>0.78</Subscript>Dy<Subscript>0.02</Subscript>Ca<Subscript>0.2</Subscript>MnO<Subscript>3</Subscript> Compound

The La_0.78Dy_0.02Ca_0.2MnO₃ (LDCMO) compound prepared via high-energy ball-milling (BM) presents a ferromagnetic-to-paramagnetic transition (FM-PM) and undergoes a second-order phase transition (SOFT). Based on a phenomenological model, magnetocaloric properties of the LDCMO compound have been studied. Thanks to this model, we can predict the values of the magnetic entropy change ΔS, the full width at half-maximum δ T _FWHM, the relative cooling power (RCP), and the magnetic specific heat change ΔC _p for our compound. The significant results under 2 T indicate that our compound could be considered as a candidate for use in magnetic refrigeration at low temperatures. In order to further understand the FM-PM transition, the associated critical behavior has been investigated by magnetization isotherms. The critical exponents estimated by the modified Arrott plot, the Kouvel–Fisher plot, and the critical isotherm technique are very close to those corresponding to the 3D-Ising standard model (β = 0.312 ± 0.07, γ = 1.28 ± 0.02, and δ = 4.80).Those results revealed a long-range ferromagnetic interaction between spins.     

Phenomenological Model of Magnetocaloric Effect in La<Subscript>0.7</Subscript>Ca<Subscript>0.2</Subscript>Ba<Subscript>0.1</Subscript>MnO<Subscript>3</Subscript> Manganite Around Room Temperature

In this work, we studied in detail the magnetic and magnetocaloric properties of the La_0.7Ca_0.2Ba_0.1MnO₃ compound according to the phenomenological model. Based on this model, the magnetocaloric parameters such as the maximum of the magnetic entropy change ΔS _M and the relative cooling power (RCP) have been determined from the magnetization data as a function of temperature at several magnetic fields. The theoretical predictions are found to closely agree with the experimental measurements, which make our sample a suitable candidate for refrigeration near room temperature. In addition, field dependences of \({{\Delta } S}_{\mathrm {M}}^{\max }\) and RCP can be expressed by the power laws \({\Delta S}_{\mathrm {M}}^{\max }\approx a\)(μ ₀ H) ⁿ and RCP ≈b(μ ₀ H) ^m , where a and b are coefficients and n and m are the field exponents, respectively. Moreover, phenomenological universal curves of entropy change confirm the second-order phase transition.     

Magnetic,magnetocaloric properties,and critical behavior in a layered perovskite La<Subscript>1.4</Subscript>(Sr<Subscript>0.95</Subscript>Ca<Subscript>0.05</Subscript>)<Subscript>1.6</Subscript>Mn<Subscript>2</Subscript>O<Subscript>7</Subscript>

We report the results of magnetic, magnetocaloric properties, and critical behavior investigation of the double-layered perovskite manganite La_1.4(Sr_0.95Ca_0.05)_1.6Mn₂O₇. The compounds exhibits a paramagnetic (PM) to ferromagnetic (FM) transition at the Curie temperature T _C = 248 K, a Neel transition at T _N = 180 K, and a spin glass behavior below 150 K. To probe the magnetic interactions responsible for the magnetic transitions, we performed a critical exponent analysis in the vicinity of the FM–PM transition range. Magnetic entropy change (??S _M) was estimated from isothermal magnetization data. The critical exponents β and γ, determined by analyzing the Arrott plots, are found to be T _C = 248 K, β = 0.594, γ = 1.048, and δ = 2.764. These values for the critical exponents are close to the mean-field values. In order to estimate the spontaneous magnetization M _S(T) at a given temperature, we use a process based on the analysis, in the mean-field theory, of the magnetic entropy change (??S _M) versus the magnetization data. An excellent agreement is found between the spontaneous magnetization determined from the entropy change [(??S _M) vs. M ²] and the classical extrapolation from the Arrott curves (µ₀H/M vs. M ²), thus confirming that the magnetic entropy is a valid approach to estimate the spontaneous magnetization in this system and in other compounds as well.     

Ferromagnetism in Fe-doped BaTiO<Subscript>3</Subscript> Ceramics

Polycrystalline samples of BaTi_1?xFe_xO₃ (x = 0.00–0.30) are prepared by solid-state reaction method and their structural and magnetic properties are studied. Detailed investigation of XRD patterns reveal the coexistence of tetragonal (space group P4mm) and hexagonal phases (space group P6 ₃/mmc) for x ≥ 0.1. Magnetic measurements reveal room-temperature ferromagnetism in x = 0.15–0.3 samples, and their ferromagnetic transition temperature increases from 397 K for x = 0.15 to 464 K for x = 0.3. The initial magnetization curves for x = 0.15–0.3 are analyzed in terms of bound magnetic polaron (BMP) model. The analysis of susceptibility data in the paramagnetic region by Curie-Weiss law confirms the ferromagnetic transition for x ≥ 0.15 and the effective magnetic moment systematically increases with increase in Fe concentration.     

Magnetic and Electrical Properties Induced by the Substitution of Divalent by Monovalent in the La<Subscript>0.6</Subscript>Ca<Subscript>0.4</Subscript>MnO<Subscript>3</Subscript> Compound

The La_0.6Ca_0.4?x Ag _x MnO₃ samples with x = 0 and 0.10 were prepared by sol–gel methods. Structural and electrical measurements were performed to examine the effect of the silver substitution in the calcium sites on the physical properties. Magnetization versus temperature studies have shown that all samples exhibit a magnetic transition from ferromagnetic to paramagnetic phase when temperature is increased. The second transition in the resistivity in the La_0.6Ca_0.4MnO₃ compound can be attributed to an abnormality characteristic of charge ordering (CO) effect. The electrical resistivity was described by a phenomenological percolation model. Ten percent of Ag substitution in the Ca site exhibits a magnetoresistance value about 75 % near room temperature at the applied magnetic field of 8 T.     

Strain-Induced First-Order Magnetic Phase Transition in Epitaxial Sm<Subscript>0.35</Subscript>Pr<Subscript>0.15</Subscript>Sr<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> Thin Film

Epitaxial Sm_0.35Pr_0.15Sr_0.5MnO₃ thin films were deposited on LaAlO₃ (LAO, (001)), SrTiO₃ (STO, (001)), and (La_0.18Sr_0.82)(Al_0.59Ta_0.41)O₃ (LSAT, (001)) single-crystalline substrates by using pulsed laser deposition technique. In order to examine the strain effect on electronic and magnetic properties, films were studied by X-ray diffraction, electrical resistivity, and dc magnetization measurements. The film grown on LAO substrate is under compressive strain, and it undergoes ferromagnetic → paramagnetic transition at Curie temperature (T _C) of ～ 165 K and metal → insulator transition at ～ 107 K. The films grown on STO and LSAT substrates are under tensile strain and have T _C of ～ 120 and 130 K, respectively, and show metal → insulator transition at ～ 145 and 137 K, respectively. At T < T _C, the zerofield and fieldcooled magnetization curves of all the films show a huge bifurcation. In the case of films on STO and LSAT substrates, hysteresis is also observed in fieldcooled cooling and warming magnetization vs. temperature measurement protocols at low magnetic field. All the signatures of the firstorder magnetic phase transition are absent in the case of film on LAO substrate. The occurrence and absence of firstorder magnetic phase transition in films on LAO, STO, and LSAT substrates, respectively, have been well explained through the substrateinduced film lattice strain.     

Study of Magnetic Entropy Change in Nd<Subscript>0.67</Subscript>Ba<Subscript>0.33</Subscript>Mn<Subscript>0.98</Subscript>Fe<Subscript>0.02</Subscript>O<Subscript>3</Subscript> by Means of Theoretical Models

Magnetic entropy change (?ΔS _M ) of Nd_0.67 Ba_0.33Mn_0.98Fe_0.02O₃ perovskite have been analyzed by means of theoretical models. An excellent agreement has been found between the (ΔS_M) values estimated by Landau theory and those obtained using the classical Maxwell relation. In order to estimate the spontaneous magnetization M _{s pont}(T), we used the mean-field theory to analyses the (ΔS_M) vs. M ² data. The obtained M _{s pont}(T) values are in good agreement with those found from the classical extrapolation from the Arrott plots(H/M vs. M ²), confirming that the magnetic entropy is a valid approach to estimate the spontaneous magnetization in our system. At a relatively low magnetic field, a phenomenological model has been used to estimate the values of the magnetic entropy change. The results are in good agreement with those obtained from the experimental data using Maxwell relation.     

Electron Spin Resonance Study of Polycrystalline La<Subscript>0.4</Subscript>Bi<Subscript>0.1</Subscript>Ca<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript>

We have inspected the magnetic properties of polycrystalline La_0.4Bi_0.1Ca_0.5MnO₃ using electron spin resonance (ESR) in the temperature range 150–280 K. The temperature dependence of magnetization indicates that the Curie temperature is T _C= 225 K. ESR spectra revealed that the sample is not completely paramagnetic above its Curie temperature through the presence of ferromagnetic interactions in the temperature range 225–270 K which can be attributed to the presence of Griffiths phase in this temperature range. The sample becomes completely paramagnetic above 270 K. The presence of Griffiths phase can be attributed to the disorder induced by the 6 s ² lone pair electrons of Bi³⁺ ions.     

Influence of Na Addition on Magnetic and Magnetocaloric Effects of La<Subscript>0.67</Subscript>Pb<Subscript>0.13</Subscript>Na<Subscript>0.2</Subscript>MnO<Subscript>3</Subscript> Ceramics

Structural, magnetic, magnetocaloric, and electrical properties are reported for mixed-valence manganite La_0.67Pb_0.13Na_0.2MnO₃. X-ray diffraction reveals that the sample crystallizes in the rhombohedric structure with the R-3c space group. The magnetic properties of the polycrystalline La_0.67Pb_0.13Na_0.2MnO₃ compound are discussed in detail, based on the susceptibility, magnetization, and isotherm. The sample presents a ferromagnetic property with T _C= 275 K and a Griffiths phase at T _G= 325 K which gives the existence of ferromagnetic clusters in the paramagnetic domain. A large deviation is usually observed between field cooled (FC) and zero field cooled (ZFC). M(T) is a low temperature below the blocking temperature. At 40 K, a spin-glass or a cluster-glass state is seen to arise from a ferromagnetic state. This is caused by the competition between the antiferromagnetic and ferromagnetic interactions. The electrical properties show the presence of a metal–semiconductor transition at T _M?Sc. To understand the dependence of disorder with the transport mechanism, we used the phenomenological equation for resistivity under a percolation approach, which is dependent on the phase segregation of a paramagnetic semiconductor and ferromagnetic metallic regions.     

Effects of Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> doping on the microstructure and electrical properties of (Ba,Ca)(Zr,Ti)O<Subscript>3</Subscript> lead-free ceramics

Lead-free ceramics (Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃?x wt.%Cr₂O₃ (BCZT-xCr) were prepared via the conventional solid-state reaction method. The microstructure and electrical properties of BCZT-xCr samples were systematically studied. XRD and Raman results showed that all samples possessed a single phased perovskite structure and were close to the morphotropic phase boundary (MPB). With the increase of the Cr content, the rhombohedral-tetragonal phase transition temperature (T _R-T) increases slightly, and the Curie temperature (T _C) shifts towards the low temperature side. XPS analysis reveals that Cr³⁺ and Cr^{5 +} ions co-existed in Cr-doped BCZT ceramics, indicating the different impact on the electrical properties from Cr ions as “acceptor” or “donor”. For the x = 0.1 sample, relative high piezoelectric constants d ₃₃ (～316 pC/N) as well as high Q _m (～554) and low tanδ (～0.8%) were obtained. In addition, the AC conductivity was also investigated. Hopping charge was considered as the main conduction mechanism at low temperature. As the temperature increases, small polarons and oxygen vacancies conduction played important roles.     

Phase relations in the Ag<Subscript>8</Subscript>SnS<Subscript>6</Subscript>-Ag<Subscript>2</Subscript>SnS<Subscript>3</Subscript>-AgBr system and crystal structure of Ag<Subscript>6</Subscript>SnS<Subscript>4</Subscript>Br<Subscript>2</Subscript>

The T-x phase diagram of the Ag-Sn-S-Br system has been studied in the composition region Ag₈SnS₆-Ag₂SnS₃-AgBr, and a compound of composition Ag₆SnS₄Br₂ has been identified. Ag₆SnS₄Br₂ has a new structure, closely related to that of Ag₆GeS₄Br₂: sp. gr. Pnma, a = 6.67050(10), b = 7.82095(9), c = 23.1404(3) Å, Z = 4, R _B = 0.0519, R _wp = 0.0782, χ² = 1.36.     

The enhanced interface effect induced by thermal pressure in Nd<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> ceramics

Polycrystalline ceramics Nd_0.7Sr_0.3MnO _y prepared by solid-state reaction were treated under high pressure of 9 GPa and temperature of 1000 K. The electrical transport behaviour of samples were investigated by a variable temperature system and a peculiar transport character was found at low temperature of 120 K, the I–V showed an obvious step-shape behaviour with the increase in the measurement voltages; at much lower temperature of 12.3 K, the I–V curves exhibited a notable symmetric hysteresis at a critical voltage of 4.5 V, although a linear I–V behaviour at 293 K. On the other hand, the R–T measurement revealed that the resistivity peak (resistivity at T _{M I} ) disappeared gradually and is replaced by a resistivity platform with the increase in the load currents, surprisingly, the resistivity platform broadened with continuous increase in the load currents but weakened when an external magnetic field was applied. All of these phenomena were not observed for the un-treated sample. The particle attenuated and the enhanced interface effect which resulted from the violent thermal-pressure treatment was responsible for the unique electromagnetic transport.     

High-temperature heat capacity and vibrational spectra of Eu<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Eu₂Sn₂O₇ compound has been prepared by solid-state reaction (by sequentially firing a stoichiometric mixture of Eu₂O₃ and SnO₂ in air at 1273 and 1473 K) and its heat capacity has been determined by differential scanning calorimetry in the temperature range 370–1000 K. The heat capacity data have been used to evaluate the thermodynamic properties of europium stannate: enthalpy increment H°(T)–H°(370 K), entropy change S°(T)–S°(370 K), and reduced Gibbs energy Ф°(T). Raman spectra of Eu₂Sn₂O₇ polycrystals with the pyrochlore structure have been measured in the range 200–1200 cm^–1.     

In-field Conductivity Fluctuations in Ba<Subscript>0.72</Subscript>K<Subscript>0.28</Subscript>Fe<Subscript>2</Subscript>As<Subscript>2</Subscript> Single Crystals

Fluctuations in the conductivity of Ba_0.72K_0.28Fe₂As₂ single crystal are studied systematically by resistance measurements as a function of temperature and magnetic field. A clear Maki?Thompson and Aslamakov?Larkin (MT–AL) two- to three-dimensional (2D–3D) crossover is found on the excess conductivity (Δσ) curves as the temperature approaches the superconducting critical temperature, T _c. 3D fluctuations in superconductivity are realized near T _c that are well fitted to experimental data by the 3D Aslamazov–Larkin theory. The Maki–Thompson model shows a 2D conductivity fluctuation above the 2D-3D temperature transition, T ₀, which depends on magnetic field. Results show that the 2D-3D dimensional crossover moves to lower temperature with increasing magnetic field. The values of the transition temperature and the crossover in the reduced temperature, ln(ε ₀), as functions of magnetic field were used to determine the coherence length and the lifetime, τ _φ , of the fluctuational pairs at the temperature of 35 K. Analysis of the Ba_0.72K_0.28Fe₂As₂ single crystal gives a value of 3.76 × 10^??12 s for the τ _φ in the absence of magnetic field and it decreases to 2.4 × 10^??12 s in magnetic field of 13 T.     

Effect of Al Substitution in Structural and Magnetic Properties of MnCr<Subscript>2</Subscript>O<Subscript>4</Subscript>

Single-phase samples of Mn(Cr_1?x Al _x )₂O₄ (x = 0 – 0.30) with cubic spinel structure were prepared and the lattice constant is found to decrease from a = 8.4396 Å for x = 0 to a = 8.3801 Å for x = 0.30. The substitution of Al at Cr site is confirmed from the blue shift of Raman modes. Magnetization measurements and analysis show all the prepared samples exhibit ferrimagnetic transition with transition temperature in the range of 46 K for x = 0 to 33 K for x = 0.30. The saturation magnetization (M _s ) and the estimated anisotropy constant (K) show an anomalous behavior up to x = 0.10 and beyond that they decrease monotonously. They are explained by considering different site preferences of Al ³⁺ ions as the doping concentration is increased. The theoretical and experimental effective magnetic moment of the samples is found to be comparable and it decreases with increase in Al concentration.     

Metamagnetic Transition and Magnetocaloric Effect in La<Subscript>0.45</Subscript>Dy<Subscript>0.05</Subscript>Ca<Subscript>0.5</Subscript>Mn<Subscript>0.9</Subscript>V<Subscript>0.1</Subscript>O<Subscript>3</Subscript> Compound

La_0.45Dy_0.05Ca_0.5Mn_0.9V_0.1O₃, prepared by solid-state route, was characterized using x-ray diffraction at room temperature. The Rietveld refinement shows that the sample crystallizes in orthorhombic structure with Pbnm space group. A secondary phase LaVO₄ has been also detected. The temperature dependence of the magnetization was investigated to determine the characteristics of the magnetic transition. The sample exhibits a paramagnetic-ferromagnetic transition (PM-FM) at T _C = 81 ± 0.7 K when temperature decreases. The study of the inverse of susceptibility reveals the presence of ferromagnetic clusters in the paramagnetic region. A metamagnetic transition was observed from the M(H) curves and the magnetic entropy change was calculated from magnetization curves at different temperatures in order to evaluate the magnetocaloric effect.     

Synthesis and High-Temperature Heat Capacity of Dy<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript> and Ho<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Dy₂Ge₂O₇ and Ho₂Ge₂O₇ pyrogermanates have been prepared by solid-state reactions in several sequential firing steps in the temperature range 1237–1473 K using stoichiometric mixtures of Dy₂O₃ (or Ho₂O₃) and GeO₂. The heat capacity of the synthesized germanates has been determined as a function of temperature by differential scanning calorimetry in the range 350–1000 K. The experimentally determined C _p (T) curves of the dysprosium and holmium germanates have no anomalies and are well represented by the Maier–Kelley equation. The experimental C _p (T) data have been used to evaluate the thermodynamic functions of the Dy₂Ge₂O₇ and Ho₂Ge₂O₇ pyrogermanates: enthalpy increment H°(T)–H°(350 K), entropy change S°(T)–S°(350 K), and reduced Gibbs energy Ф°(T).