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At least 19 records

Water mediated growth of oriented single crystalline SrCO3 nanorod arrays on strontium compounds

Abstract Morphology-controlled strontianite nanostructures have attracted interest in various fields, such as electrocatalyst and photocatalysts. Basic additives in aqueous strontium solutions is commonly used in controlling strontianite nanostructures. Here, we show that trace water also serves an important role in forming and structuring vertically oriented strontianite nanorod arrays on strontium compounds. Using in situ Raman spectroscopy, we monitored the structural evolution from hydrated strontium to strontianite nanorods, demonstrating the epitaxial growth by vapor–liquid–solid mechanism. Water molecules cause not only the exsolution of Sr liquid droplets on the surface but also the uptake of airborne CO 2 followed by its ionization to CO 3 2− . The existence of intermediate SrHO + –OCO 2 2− phase indicates the interaction of CO 3 2− with SrOH + in Sr(OH) x (H 2 O) y cluster to orient strontianite crystals. X-ray diffraction simulation and transmission electron microscopy identify the preferred-orientation plane of the 1D nanostructures as the (002) plane, i.e., the growth along the c-axis. The anisotropic growth habit is found to be affected by the kinetics of carbonation. This study paves the way for designing and developing 1D architecture of alkaline earth metal carbonates by a simple method without external additives at room temperature.

36 MATERIALS SCIENCE↗

Electrochemical cells for direct oxide reduction, and related methods

A method of direct oxide reduction includes forming a molten salt electrolyte in an electrochemical cell, disposing at least one metal oxide in the electrochemical cell, disposing a counter electrode comprising a material selected from the group consisting of osmium, ruthenium, rhodium, iridium, palladium, platinum, silver, gold, lithium iridate, lithium ruthenate, a lithium rhodate, a lithium tin oxygen compound, a lithium manganese compound, strontium ruthenium ternary compounds, calcium iridate, strontium iridate, calcium platinate, strontium platinate, magnesium ruthenate, magnesium iridate, sodium ruthenate, sodium iridate, potassium iridate, and potassium ruthenate in the electrochemical cell, and applying a current between the counter electrode and the at least one metal oxide to reduce the at least one metal oxide. Related methods of direct oxide reduction and related electrochemical cells are also disclosed.

Tripathy, Prabhat K.↗

(2,2'-Bipyridyl-κ 2 N , N ')bis(η 5 -pentamethylcyclopentadienyl)barium

In the title compound, [Ba(C 10 H 15 )2(C 10 H 8 N 2 )], the Ba—N distances are 2.798 (3) and 2.886 (3) Å, and the Cp ring centroid distances to Ba 2+ are 2.7291 (7) and 2.7192 (9) Å. The angle between the N atoms in the bypyridine ligand and the metal ion is 56.80 (8) and the N—C—C—N torsion angle in the bipyridine ligand is 1.7 (4)°. The bipyridine ligand is almost planar, the dihedral angle formed by the intersection of the planes defined by the pyridyl rings being 3.04 (19)°, and the angle between the plane defined by the Ba 2+ ion and the two bipyridyl N atoms and the plane defined by the 12 atoms of the bipyridine ligand is 10.2 (3)°. The average Ba—N and Ba—centroid distances are 0.16 and 0.14 Å longer, respectively, than the equivalent distances in the isotypic strontium compound. This difference is in accord with the difference between the ionic radii of 0.16 Å suggested by Shannon.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preparation of Fine Single Crystals of Rutheno-Cuprates by the Self-Flux Method with Alumina Boats

We investigate the single crystal growth of rutheno-cuprates, which are known to be magnetic superconductors. We attempted the single crystal growth of two systems, RuSr{sub 2}GdCu{sub 2}O{sub 8−δ} (RuGd-1212) and RuSr{sub 2}(Gd,Ce){sub 2}Cu{sub 2}O{sub 10−δ} (RuGd-1222), by the self-flux method with alumina boats. Fine cubic crystals of RuGd-1212 with a side length of approximately 5 μ m were obtained by slow cooling from 1350 to 940 {sup ∘}C. Plate-like RuGd-1222 crystals with a smooth plane were obtained at the surface of the precursor pellet. RuGd-1222 was more stable at high temperatures than RuGd-1212 and was also superconductive, but its superconductivity weakened as the cooling rate decreased. This weakening was induced by decomposition. Therefore, high-quality RuGd-1222 single crystals were difficult to obtain, and we failed to extract only the smooth planar crystal part. As a modified synthesis technique, we mixed a precursor containing Ru–Sr–Gd–Ce flux with RuGd-1222 powders and gradually cooled the mixture from 1350 to 1090 {sup ∘}C. A plate-like RuGd-1222 sample with a smooth surface and a size of 70 × 30μm{sup 2} was obtained from the side surface of the precursor pellet. By this technique, we could separate the planar crystal part. Semiquantitative composition analysis confirmed this planar crystal as a RuGd-1222 phase. The X-ray diffraction peak suggested the (0014) plane, implying that the plate-like precipitates are c-axis-oriented RuGd-1222 single crystals.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Critical Current Density and AC Susceptibility of Bi{sub 1.6}Pb{sub 0.4}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10} Superconductor with Ni{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} Nanomaterial

The juxtaposition of superconductivity and magnetism is an interesting research topic due to the exclusivity nature of both phenomena. In this paper, we report the effect of nanosized (~ 5 nm) nickel zinc ferrite Ni{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} (NZFO) on Bi{sub 1.6}Pb{sub 0.4}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10} (Bi-2223) superconductor. Bi-2223 powders were prepared using the co-precipitation method. Samples with starting formula Bi{sub 1.6}Pb{sub 0.4}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10}(Ni{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4}){sub x} for x = 0 to 0.1 wt% have been prepared. The structure, microstructure, electrical resistance, and AC susceptibility were determined. The transport critical current density, J{sub ct}, was measured using the 1 μV/cm criterion. The non-added sample sintered for 48 h showed the highest zero resistance temperature, T{sub c-zero} (105 K) and J{sub ct} of 1.83 A cm{sup −2} at 40 K. The x = 0.02 wt% sample sintered for 48 h (T{sub c-zero} = 103 K) showed the highest J{sub ct} of 5.30 A cm{sup −2} at 40 K. The peak temperature of the imaginary part of the complex susceptibility, T{sub p}, increased with sintering time and nanoparticle addition, indicating full flux penetration occurred at higher temperatures and improved intergrain coupling. NZFO nanoparticle did not suppress the transition temperature but it improved the transport critical current density by more than five times indicating it enhanced flux pinning and connectivity between grains in the Bi-2223 phase.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effect of Hydrostatic Pressure on Eu{sub 3−x}Sr{sub x}Bi{sub 2}S{sub 4−y}Se{sub y}F{sub 4} (x = 1 and 2 and y = 1.5 and 2) Superconductors

We have investigated the effect of pressure on Se-doped Eu{sub 2}SrBi{sub 2}S{sub 4}F{sub 4} and EuSr{sub 2}Bi{sub 2}S{sub 4}F{sub 4} at S sites. We report the electrical resistivity measurements under hydrostatic pressure (P) ~ 3 GPa and ~ 2.5 GPa on Eu{sub 2}SrBi{sub 2}S{sub 4−y}Se{sub y}F{sub 4} [dT{sub c}/dP ~ 1.68 K/GPa (x = 2)] and EuSr{sub 2}Bi{sub 2}S{sub 4−x}Se{sub x}F{sub 4} [dT{sub c}/dP ~ 1.57 K/GPa (x = 1.5) and 1.74 K/GPa (x = 2)] respectively. Pressure-induced superconductivity has been observed in EuSr{sub 2}Bi{sub 2}S{sub 2.5}Se{sub 1.5}F{sub 4} with T{sub c} of 2.42 K at 0.12 GPa and the T{sub c} increases with further application of P up to 3 GPa (dT{sub c}/dP ~ 1.12 K/GPa) and maximum T{sub c} of ~ 8 K is observed for EuSr{sub 2}Bi{sub 2}S{sub 2}Se{sub 2}F{sub 4.} These results corroborate the behavior of this material under high pressure magnetization studies. Further, the metallic nature is observed for EuSr{sub 2}Bi{sub 2}S{sub 2.5}Se{sub 1.5}F{sub 4}, EuSr{sub 2}Bi{sub 2}S{sub 2}Se{sub 2}F{sub 4}, and Eu{sub 2}SrBi{sub 2}S{sub 2}Se{sub 2}F{sub 4} compositions and it is slightly suppressed with the application of pressure. Pressure effect on upper critical field H{sub c2}(0) is estimated from magnetic field–dependent ρ(T) measurements and it is found to be higher for all compositions than parent compound. The field-dependent thermal activation energy (μ{sub 0}/k{sub B}) is calculated from Arrhenius plot using ρ(T) and designates a robust flux pinning potential which might be co-existing with applied magnetic field and pressure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Robust Half-Metallicity in Quaternary Heusler Compounds KSrNZ (Z = O, S, and Se)

The first principle calculations based on density functional theory using full potential linearized augmented plane wave method was performed on the quaternary Heusler alloys KSrNZ (Z = O, S, and Se). Studies on structural properties showed that quaternary Heusler alloys KSrNZ (Z = O, S, and Se) were stable in Y{sub I}-type structure. Furthermore, values of formation energies confirmed that these alloys may be synthesized experimentally. Verification of electronic properties resulted that KSrNO, KSrNS, and KSrNSe compounds were half-metals at equilibrium lattice constants with majority band gaps of 4.61, 3.82, and 3.51 eV, respectively. KSrNZ (Z = O, S, and Se) compounds maintained half-metallic behavior in relatively wide ranges of lattice constant under uniform strain distortion. This indicates that these compounds are promising materials for future spintronic applications. Furthermore, the origin of half-metallic characteristic was verified using electronic density of states. Calculations of magnetic properties showed that the total magnetic moments of KSrNZ (Z = O, S, and Se) were obtained equal to 2 μ{sub B} satisfying the famous Slater-Pauling rule (M{sub tot}= 12-Z{sub tot}).

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Sodium citrate (Na{sub 3}Cit)-assisted hydrothermal synthesis of uniform spindle-like SrMoO{sub 4}:Eu{sup 3+} phosphors

Graphical abstract: A facile hydrothermal method for the synthesis of uniform spindle-like SrMoO{sub 4}:Eu{sup 3+} phosphors with the assistance of sodium citrate (Na{sub 3}Cit). - Highlights: • Well-crystallized spindle-like SrMoO{sub 4}:Eu{sup 3+} phosphors have been synthesized. • The influence of the reaction temperature and reaction time were clearly shown. • The dosage of Na{sub 3}Cit has a strong effect on the spindle-like SrMoO{sub 4}:Eu{sup 3+} phosphors. • The growth mechanism for the formation of final samples was proposed. - Abstract: Highly uniform spindle-like SrMoO{sub 4}:Eu{sup 3+} phosphors have been prepared by a facile hydrothermal method using sodium citrate (Na{sub 3}Cit) as the chelating reagent. X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectrum (EDS), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), Fourier transform-infrared spectroscopy (FT-IR) and photoluminescence spectra (PL) were used to characterize the resulting samples. The dosage of sodium citrate, reaction temperature and reaction time play key roles in the formation of the final samples. The possible formation mechanism for SrMoO{sub 4}:Eu{sup 3+} phosphors has been proposed. Upon excitation by ultraviolet radiation, the as-synthesized SrMoO{sub 4}:Eu{sup 3+} phosphors show the characteristic {sup 5}D{sub 0}–{sup 7}F{sub J} (J = 1, 2, 3, 4) emission lines with red emission {sup 5}D{sub 0}–{sup 7}F{sub 2} (613 nm) as the most prominent group.

36 MATERIALS SCIENCE↗

The site occupation and valence of Mn ions in the crystal lattice of Sr{sub 4}Al{sub 14}O{sub 25} and its deep red emission for high color-rendering white light-emitting diodes

Highlights: • Different valences of Mn ions in Sr{sub 4}Al{sub 14}O{sub 25} were identified using XANES and EPR. • Red luminescence was attributed to Mn{sup 4+} occupying the center of AlO{sub 6} octahedron. • The Mn{sup 3+} incorporated in the center of AlO{sub 4} tetrahedron was non-luminescent. • The bond-valence theory was used to analyze the effective valences of cations. • A white LED device with CRI up to Ra 93.23 was packaged by using the red phosphor. - Abstract: The synthesis and component of red phosphor, Sr{sub 4}Al{sub 14}O{sub 25}: Mn, were optimized for application in white light-emitting diodes. The microstructure and morphology were investigated by the X-ray diffraction and scanning electron microscopy. Different valences of Mn ions in Sr{sub 4}Al{sub 14}O{sub 25} were discriminated using the electron paramagnetic resonance and X-ray absorption near-edge structure spectroscopy techniques. The bond-valence theory was used to analyze the effective valences of Sr{sup 2+} and Al{sup 3+} in Sr{sub 4}Al{sub 14}O{sub 25}. As a result, the strong covalence of Al{sup 3+} in the AlO{sub 4} tetrahedron other than in the AlO{sub 6} octahedron is disclosed. The deep red emission is attributed to Mn{sup 4+} occupying the center of AlO{sub 6} octahedron. The mechanism of energy transfer is mainly through dipole–dipole interaction, revealed by the analyses of critical distance and concentration quench. A high color rendering white LED prototype with color-rendering index up to Ra 93.23 packaged by using the red phosphor demonstrates its applicability.

36 MATERIALS SCIENCE↗

The formation and structure of mechano-synthesized nanocrystalline Sr{sub 3}Fe{sub 2}O{sub 6.4}: XRD Rietveld, Mössabuer and XPS analyses

Highlights: • The formation of mechano-synthesized nanocrystalline Sr{sub 3}Fe{sub 2}O{sub 7−δ} is investigated. • Pre-milling the reactants substantially lowers the formation temperature. • The core and surface structures were studied. • XRD and {sup 57}Fe Mössbauer spectroscopic analyses indicate the δ-value to be 0.60. • XPS shows a complex surface structure for the mechanosynthesized Sr{sub 3}Fe{sub 2}O{sub 7−δ} nanoparticles. - Abstract: The influence of ball milling and subsequent sintering of a 3:1 molar mixture of SrCO{sub 3} and α-Fe{sub 2}O{sub 3} on the formation of Sr{sub 3}Fe{sub 2}O{sub 7−δ} double perovskite is investigated with different analytical techniques. Milling the mixture for 110 h leads to the formation of SrCO{sub 3}-α-Fe{sub 2}O{sub 3} nanocomposites and the structural deformation of α-Fe{sub 2}O{sub 3} via the incorporation of Sr{sup 2+} ions. Subsequent sintering of the pre-milled reactants’ mixture has led to the partial formation of an SrFeO{sub 3} perovskite-related phase in the temperature range 400–600 °C. This was followed by the progressive development of an Sr{sub 3}Fe{sub 2}O{sub 7−δ} phase that continued to increase with increasing sintering temperature until a single-phased nanocrystalline Sr{sub 3}Fe{sub 2}O{sub 7−δ} phase was attained at 950 °C (12 h). This temperature is ∼350 °C lower than the temperature at which the material is prepared conventionally using the ceramic method. The evolution of different structural phases during the reaction process is discussed. Rietveld refinement of the X-ray diffraction data shows a value of 0.60 for the oxygen deficiency δ, in consistency with the Fe{sup 3+}/Fe{sup 4+} ratio derived from the {sup 57}Fe Mössbauer data recorded at both 300 K and 78 K. The Mössbauer data suggests that the Sr{sub 3}Fe{sub 2}O{sub 6.4} nanoparticles are superparamagnetic with blocking temperatures below 78 K. The surfaces of the Sr{sub 3}Fe{sub 2}O{sub 6.4} nanoparticles were shown to have a complex structure and composition relative to those of their cores with traces of SrCO{sub 3}, SrO and SrFeO{sub 3−δ} being detected.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Sr{sub 1.98}Eu{sub 0.02}SiO{sub 4} luminescence whisker based on vapor-phase deposition: Facile synthesis, uniform morphology and enhanced luminescence properties

Highlights: • For the first time, it is possible to obtain Sr{sub 1.98}Eu{sub 0.02}SiO{sub 4} whisker. • The whiskers are smooth and uniform with L/D ratio over 50. • Durability and thermal stability of the whisker are enhanced. - Abstract: A high performance strontium silicate phosphor has been successfully synthesized though a facile vapor-phase deposition method. The product consists of single crystal whiskers which are smooth and uniform, and with a sectional equivalent diameter of around 5 μm; the aspect ratio is over 50 and no agglomeration can be observed. X-ray diffraction result confirmed that the crystal structure of the whisker was α’-Sr{sub 2}SiO{sub 4}. The exact chemical composition was Sr{sub 1.98}Eu{sub 0.02}SiO{sub 4} which was analyzed by energy dispersive spectrometer and inductively coupled plasma-mass spectrometer. The whisker shows broad green emission with peak at 523 nm ranging from 470 to 600 nm (excited at 370 nm). Compared with traditional Sr{sub 2}SiO{sub 4}:Eu phosphor, durability (at 85% humidity and 85 °C) and thermal stability of the whisker are obviously improved. Moreover, growth mechanism of the Sr{sub 1.98}Eu{sub 0.02}SiO{sub 4} whiskers is Vapor–Liquid–Solid. On a macro-scale, the product is still powder which makes it suitable for the current packaging process of WLEDs.

36 MATERIALS SCIENCE↗

Layer-by-layer shuttered molecular-beam epitaxial growth of superconducting Sr{sub 1-x}La{sub x}CuO{sub 2} thin films

Superconducting Sr{sub 1-x}La{sub x}CuO{sub 2} thin films have been grown on GdScO{sub 3} substrates by reflection high-energy electron diffraction calibrated layer-by-layer molecular-beam epitaxy. X-ray diffraction analysis has confirmed the infinite layer structure after an in situ vacuum annealing step. In situ photoemission spectroscopy indicates that the vacuum annealing step employed immediately after film growth to achieve superconducting films results in oxygen loss from the films. The superconducting critical temperature depends on the La content x, with the highest value obtained for x{approx}0.10. Resistivity as a function of temperature {rho}(T) curves of optimally doped samples show a T{sup 2} temperature dependence characteristic of a scattering process where electron-electron interactions dominate.

36 MATERIALS SCIENCE↗

An investigation of low temperature electronic phase arrest in Sm{sub 0.55}Sr{sub 0.45}MnO{sub 3} phase separated manganite

The temperature dependence of electronic-transport and magneto-transport of polycrystalline Sm{sub 0.55}Sr{sub 0.45}MnO{sub 3} manganite at low temperatures has been investigated in detail. The low temperature resistivity data show a distinct minimum in the resistivity versus temperature plots for all fields. The low temperature resistivity upturn below this minimum has been fitted to an expression, which includes three terms, namely, residual resistivity, inelastic scattering, and electron-electron (e-e) interaction or Kondo effects. It has been found that the dominating mechanism is e-e interaction. The resistivity of the sample shows strong dependence on the magnetic field–temperature history. The electronic-transport property clearly confirms that the electronic phase of the sample gets arrested to a low resistive state during field cooling and cannot return to its original state even after the magnetic field is removed. The magnetoresistance of the sample also shows a strong irreversibility with respect to the sweeping of the magnetic field between its highest positive and negative values. Moreover, the resistivity of the sample is found to be time dependent. All the observed phenomena have been explained through the phase separation scenario and kinetic arrest of electronic phase.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Alkali-metal/alkaline-earth-metal fluorine beryllium borate NaSr{sub 3}Be{sub 3}B{sub 3}O{sub 9}F{sub 4} with large nonlinear optical properties in the deep-ultraviolet region

The linear optical response and second harmonic generation (SHG) in alkali-metal/alkaline-earth-metal fluorine beryllium borate NaSr{sub 3}Be{sub 3}B{sub 3}O{sub 9}F{sub 4} are investigated by means of density functional theory. Calculations are performed using four types of exchange correlations: Ceperley-Alder local density approximation, Perdew Burke and Ernzerhof general gradient approximation, Engel-Vosko generalized gradient approximation, and the recently modified Becke-Johnson potential (mBJ). The mBJ approach brings the calculated band gap (7.20 eV) in excellent agreement with the experimental one (7.28 eV). The calculated values of the uniaxial anisotropy δε=−0.076 and the birefringence Δn(0)=0.052 indicate considerable anisotropy in the linear optical properties, which makes it favorable for the second harmonic generation. The dominant component of the second harmonic generation is χ{sub 111}{sup (2)}(ω). The value of |χ{sub 111}{sup (2)}(ω)| is about 1.2 pm/V at λ = 1064 nm in agreement with previous calculations. To analyze the origin of the high SHG of NaSr{sub 3}Be{sub 3}B{sub 3}O{sub 9}F{sub 4} single crystals, we have correlated the features of |χ{sub 111}{sup (2)}(ω)| spectra with the features of ε{sub 2}(ω) spectra as a function of ω/2 and ω. From the calculated dominant component |χ{sub 111}{sup (2)}(ω)|, we find that the microscopic first hyperpolarizability, β{sub 111}, the vector components along the dipole moment direction is 0.5 × 10{sup −30} esu at static limit and 0.6 × 10{sup −30} esu at λ = 1064 nm.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Synthesis, characterization and photo luminescence studies of uranyl doped SrBPO{sub 5}

SrBPO{sub 5}: UO{sub 2}{sup 2+} was synthesized using solid state reaction method and characterized using powder X-ray diffraction. PXRD data showed the formation of single phase confirming successful doping of UO{sub 2}{sup 2+}. Photo luminescence investigation informed stabilization of Uranium as Uranyl (UO{sub 2}{sup 2+}) in SrBPO{sub 5} matrix. Luminescence decay time data suggested two possible environments for UO{sub 2}{sup 2+} with two different life time values.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

First principle study of band structure of SrMO{sub 3} perovskites

First principle study of band structure calculations in the local density approximations (LDA) as well as in the generalized gradient approximations (GGA) have been used to determine the electronic structure of SrMO{sub 3} where M stands for Ti, Zr and Mo. Occurrence of band gap proves SrTiO{sub 3} and SrZrO{sub 3} to be insulating. A small band gap is observed in SrMoO{sub 3} perovskite signifies it to be metallic. Band structures are found to compare well with the available data in the literature showing the relevance of this approach. ABINIT computer code has been used to carry out all the calculations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Electronic and magnetic properties in Sr{sub 1-x}La{sub x}RuO{sub 3}

Here we report the structural, magnetic and transport properties in La doped SrRuO{sub 3}. The doping of La{sup 3+} modifies the ionic state of Ru by converting Ru{sup 4+} to Ru{sup +3}. However, there is modification in lattice parameters as La{sup 3+} has smaller ionic radii than that of Sr{sup 2+}. We find La doping weakens the ferromagnetic state in SrRuO{sub 3} in terms of lowering T{sub c} and decreasing the magnetic moment. The electrical resistivity shows metallic behavior in whole temperature range, however, resistivity increases with doping of La.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Magnetocaloric effect in manganites

The magnetocaloric effect (MCE) in La{sub 1-x}Sr{sub x}MnO{sub 3}, Sm{sub 0.55}Sr{sub 0.45}MnO{sub 3}, and PrBaMn{sub 2}O{sub 6} compounds is studied. The maximum values of MCE ({Delta}T{sub max}) determined by a direct method in the second and third compositions and in La{sub 0.9}Sr{sub 0.1}MnO{sub 3} are found to be much lower than those calculated from the change of the magnetic part of entropy in the Curie temperature (T{sub C}) and the Neel temperature (T{sub N}) range. The negative contribution of the antiferromagnetic (AFM) part of a sample in the La{sub 1-x}Sr{sub x}MnO{sub 3} system at 0.1 {<=} x {<=} 0.3 decreases {Delta}T{sub max} and changes the {Delta}T(T) curve shape, shifting its maximum 20-40 K above T{sub C}. Lower values of {Delta}T{sub max} are detected in the range T{sub C} = 130-142 K in polycrystalline and single-crystal Sm{sub 0.55}Sr{sub 0.45}MnO{sub 3} samples cooled in air. If such samples were cooled in an oxygen atmosphere (which restores broken Mn-O-Mn bonds and, thus, increases the volume of CE-type AFM clusters), the maximum in the temperature dependence of MCE is located at T{sub N} (243 K) for CE-type AFM clusters. A magnetic field applied to a sample during the MCE measurements transforms these clusters into a ferromagnetic (FM) state, and both types of clusters decompose at T = T{sub N}. The PrBaMn{sub 2}O{sub 6} composition undergoes an AFM-FM transition at 231 K, and the temperature dependence of its MCE has a sharp minimum at T = 234 K, where MCE is negative, and a broad maximum covering T{sub C}. The absolute values of MCE at both extrema are several times lower than those calculated from the change in the magnetic entropy. These phenomena are explained by the presence of a magnetically heterogeneous FM-AFM state in these manganites.

36 MATERIALS SCIENCE↗