Structural transformations in La1 − x Ba x Mn0.98 57Fe0.02O3 + δ (x = 0.05−0.20)

Physics of the Solid State - A systematic investigation of the structural transformations in La1 ? x Ba x Mn0.98 57Fe0.02O3 + δ (x = 0.05?0.20) at different Ba concentrations and...     

Mössbauer Study of La1−x Ca x Mn1−y 57Fe y O3 with x=0,0.25; y=0.01

Temperature dependent Mössbauer measurements are done on the samples of La_1–x Ca _x Mn_1–y ⁵⁷Fe _y O₃ with x=0 and 0.25, and y=0.01. With decreasing temperature, the specimen with x=0.25 shows a paramagnetic to ferromagnetic transition around 175 K. In the specimen x=0.0, the temperature dependence of both the center shift () and the recoilless fraction (f) can be fitted very well with the Debye theory with a _D=320±50 K. But for the specimens with x=0.25, f and show distinct deviations from the Debye behavior in the temperature range in which the resistivity shows a sharp decrease. Dips observed in both the f and around the transition temperature suggest that the Jahn–Teller distortion observed in these systems is dynamic in nature.     

57Fe Mössbauer study of La0.67Ca0.33Mn1 − x Fe x O3 CMR system

The structural changes of near-equiatomic α-FeCr alloys, ground in a vibratory mill in vacuum and in argon, were followed as a function of milling time. An amorphous phase forms in both cases but at a much faster rate when milling in argon than when milling in vacuum. Amorphisation by ball-milling of α-FeCr alloys is deduced to be an intrinsic phenomenon which is however speeded-up by oxygen. The amorphous phase crystallizes into a bcc Cr-rich phase and a bcc Fe-rich phase when annealed for short times.     

Mössbauer and X-Ray studies of the dynamics of phase transformations and suppression of polymorphism in the LaMn1 − x Fe x O3 + δ compound (x = 0.015–0.500)

Physics of the Solid State - The effect of iron impurity on the structural transformations and the suppression of polymorphism of the LaMn1 ? x Fe x O3 + δ compound (x =...     

Mössbauer and Magnetic Studies of Doped Lanthanum Manganite La1 – xCaxMn0.98Fe0.02O3 + δ (x = 0.05, 0.10, 0.20): I. Nonstoichiometric Composition

Journal of Surface Investigation: X-ray, Synchrotron and Neutron Techniques - Mössbauer and magnetic studies of Ca-doped lanthanum manganites...     

Effect of doping with iron on the charge ordering in La0.33Ca0.67Mn1−y Fe y O3 (y = 0, 0.05) manganites

The formation and specific features of the superstructure in La_0.33Ca_0.67Mn_1?y Fe _y O₃ (y = 0, 0.05) manganites doped with iron are investigated using transmission electron microscopy. The electron diffraction patterns of the manganites are studied in the temperature range 90–300 K, and the high-resolution electron microscope images recorded at temperatures of 91–92 K are analyzed. In both manganites, the structural transition that is accompanied by the formation of the superstructure and which is directly observed from the appearance of additional peaks in the electron diffraction patterns occurs at a temperature that is in close agreement with the charge ordering temperature T _CO determined from the temperature dependences of the magnetization M(T). In the temperature range 90 < T < 200 K, the undoped compound has a commensurate superstructure characterized by the vector q = 1/3a* and triple the unit cell «3a × b × c» (where a ≈ b ≈ √2a _c , c ≈ 2a _c , and a _c ～ 3.9 Å is the lattice parameter of a simple perovskite). The doping with iron (5 at. %) brings about a decrease in the charge ordering temperature T _CO by 50 K and the formation of an incommensurate structure for which the magnitude of the vector q is smaller by approximately 15%. The unit cell of the superstructure in the iron-doped compound is not triple the unit cell but involves defects of ordering, such as quadrupling of the unit cell, numerous translations by a _c √2 along the a direction, and dislocation-type defects in the stripe structure of the charge ordering. These pseudoperiodic defects lead to a decrease in the magnitude of the vector q and are responsible for the incommensurability of the structure. A decrease in the charge ordering temperature T _CO due to the doping with iron and the incommensurability of the superstructure correlate with the change in the concentration of Mn³⁺ Jahn-Teller ions as a result of their replacement by Fe³⁺ non-Jahn-Teller ions.     

Magnetic and electrical properties of weakly doped manganese-deficient La1 − x Ca x Mn1 − z O3 manganites

Samples of La_{1 ? x} Ca _x Mn_{1 ? z} O_{3 + δ} (x = 0.05?0.15) with deficient manganese and excess oxygen δ do not pass into a metallic state and have low spin ordering temperatures T _C at acceptor Mn⁴⁺ concentrations near the percolation threshold. These results are explained by carrier localization in clusters near cation vacancies. A break in the carrier transport chain Mn-O-Mn in the form of absent manganese favors cluster formation and decreases the double exchange energy and T _C of the samples. Closeness to the percolation threshold results in strong (more than four orders of magnitude) changes in the electrical resistivity in a magnetic field. The changes in the cluster sizes with the temperature and the magnetic field that are determined from the magnetotransport properties are satisfactorily described in the model of phase separation into small-radius metallic droplets in a dielectric paramagnetic and an antiferromagnetic matrices.     

Dynamical transport behavior in electron-doped manganites La0.4Ca0.6(Mn1−x Ru x )O3

Measurements of the dynamical electrical transport behavior are performed on electron-doped manganites La_0.4Ca_0.6(Mn_1−x Ru _x )O₃ (x=0 and 0.02). An undoped sample possesses a robust charge-ordered antiferromagnetic ground state, and only a positive resistivity relaxation can be observed. However, a low-temperature negative relaxation behavior arises after inducing a few ferromagnetic orders to the charge-ordered matrix by tiny Ru doping. We assigned this difference to the dynamical competition between ferromagnetic metallic and charge-ordered insulating phases. Consistently, for a doped sample, the crossover from positive to negative resistivity relaxation behavior ensues around T=115 K, which is just below the ferromagnetic Curie temperature.     

Mössbauer characterization of Nd0.7Sr0.3(Mn1−x57Fex)O3 (x=0.02–0.15)

The magnetic structure of colossal magneto-resistive Nd_0.7Sr_0.3(Mn_1−x⁵⁷Fe_x)O₃ (x=0.02, 0.05, 0.10, and 0.15) has been studied by Mössbauer spectroscopy in magnetic fields up to 60 kG. ⁵⁷Fe ions appear to spread over two different magnetic phases. One of them remains ferromagnetic for all values of x, but the other one changes from canted to anti-ferromagnetic with increasing x. For x=0.02 and 0.05, the latter magnetic phase is comprised of small clusters, which are very sensitive temperature and strongly influenced by the applied fields.     

EPR study on the La2/3Ca1/3Mn1−x Cu x O y system

The interaction between Mn and Cu ions is studied by measuring the resistance and electron paramagnetic resonance (EPR) at different temperatures of the Cu-doped compound La_2/3Ca_1/3Mn_1−xCu_xO_y. A new transition inR-T curve and substantial enhancement in magnetoresistance are induced by the substitution of Mn ions by Cu ions. The EPR measurement shows that two resonance signals appear at temperature lower than the spin-ordering temperature of Mn ions. A tentative interpretation for the observed phenomena is proposed by considering the interaction between the Cu/Mn ions besides the Mn³⁺/Mn⁴⁺ ions.     

Magnetic order in Sr x Ca1−x Cu0.99 57Fe0.01O2

Sr _x Ca_1–x Cu_0.99 ⁵⁷Fe_0.01O₂ was studied forx=0.13, 0.15, and 0.17. Mössbauer spectroscopy and magnetization measurements indicate magnetic ordering characteristic of spin glass systems withT _f70K forx=0.15 and 0.13.     

Magnetic relaxation spectrum of ferrites Mn x Fe3−x O4+γ

The initial permeability disaccommodation in ferritesMn _x Fe₃–xO₄₊ , 0·5x1, was studied in a temperature range around –200°C to +180°C. Four separate bands were found in the relaxation spectrum of these ferrites.

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Mn _x Fe_3–x O₄₊

Mn _x Fe_3–x O₄₊ , 0,5x1, –200°C +180°C. .

     

Properties of the ceramic manganite (La0.65Ca0.35)1 − x Mn1 + x O3 ± Δ (x = 0.2) sintered at temperatures of 1000–1450°C

It has been shown that the ceramics (La_0.65Ca_0.35)_{1 ? x} Mn_{1 + x} O_{3 ± Δ} (x = 0.2) sintered at temperatures up to 1450°C is formed as a composite material consisting of manganite and manganese oxide grains. It has been found that, at a sintering temperature of 1450°C, the manganite grain size abruptly increases, which is accompanied by the formation of a nanometer-sized layered structure. It has been revealed for the first time that the temperature dependence of the magnetoresistance of the ceramic manganite with this structure is characteristic of single crystals.     

On the microstructure of the charge density wave observed in La1− x Ca x MnO3

We have used low temperature (90?K) transmission electron microscopy to investigate the ‘charge ordering’ modulation in the mixed valent manganite, La_{1? x} Ca _x MnO₃. It has been stated that Mn³⁺ and Mn⁴⁺ ions order at low temperature to produce a structural modulation composed of supercells whose size is an integer multiple of the unmodulated unit cell. Here, we use convergent beam electron diffraction to show that the periodicity of the modulation need not be an integer multiple of the undistorted cell, even on the smallest scales. We therefore suggest that this modulation is a charge density wave with a uniform periodicity. We show that the modulation wavevector lies close to the a* axis of the crystal but need not be exactly collinear. A typical grain of size 0.5?µm in La_0.48Ca_0.52MnO₃ had a wavevector which varied on a scale of tens of nanometres with an average of ?q??=?0.450a * and a standard deviation Δq?=?0.004?a* in its magnitude and Δθ?=?0.56° in its direction at 90?K. The magnitude of the wavevector in this composition fell by 20% as the temperature was increased from 90?K to room temperature. This change occurred by nucleation and growth. Although weak, the modulation was still present at room temperature, some 30?K above the ‘charge ordering temperature’.     

Lattice distortion-induced phase transformations in La1 − y Pr y MnO3 + δ manganites

The structural and magnetic phase transformations that occur in the system of self-doped La_{1 ? y} Pr _y MnO_{3 + δ} (δ ≈ 0.1, 0 ≤ y ≤ 1) manganites in the temperature range 4.2–300 K are studied by X-ray diffraction and measuring the temperature and field dependences of dc magnetization. The low-temperature magnetic phase transformations induced by the substitution of Pr for La correlate well with the structural phase transformations at T = 300 K, which indicates a strong coupling of the electronic and magnetic subsystems of La_{1 ? y} Pr _y MnO_{3 + δ} manganites with the crystal lattice. The anomalies of the magnetic and structural properties detected in this work in the form of peaks and inflection points in the concentration dependences of the magnetization and lattice parameters of the pseudocubic phase of La_{1 ? y} Pr _y MnO_{3 + δ} (0.1 ≤ y ≤ 0.7) in the temperature range 4.2–300 K are explained in terms of the existing concepts of the effect of Fermi surface nesting on the renormalization of the density of states and the hole dispersion near E _F in the presence of a strong coupling of holes with low-frequency optical phonons, which results in their transformation into quasiparticles. The narrow peak in the magnetization curve M(y) of La_{1 ? y} Pr _y MnO_{3 + δ} that is detected near y = 0.3 at T = 4.2 K is assumed to correspond to the peak of coherence of quasiparticles with a low energy of coupling with the crystal lattice near E _F, which was found earlier in the photoelectron emission spectra of manganites. The disappearance of the narrow magnetization peak with increasing Pr concentration is explained by the transition of charge carriers from the mode of “light” holes weakly coupled to one of the soft phonons to the mode of “heavy” holes strongly coupled to several phonons. The transition between phases with strongly different effective quasiparticle masses proceeds jumpwise; that is, it has features of the metal-insulator Mott transition and is accompanied by the transition from 3D to 2D quasiparticle motion in planes ab.     

Calcium doping effects in57Fe : La2−x Ca x CuO4−y oxides

La_2–x Ca _x Cu_0.99Fe_0.01O_4–y samples with 0.00 x 0.30 were studied by X-ray diffraction and Mössbauer spectroscopy after heat treatment under different atmospheres (air, oxygen and helium). The variation of the relative population and the hyperfine interactions of the sites as well as the change in the lattice parameters were obtained.On leave from National Center for Scientific Research, PO Box 6990, Havana, Cuba.     

Evolution of structural,magnetic and magnetocaloric properties in Sn-doped manganites La0.57Nd0.1Sr0.33Mn1−x Sn x O3 (x = 0.05–0.3)

Structural and magnetic properties of manganites series La_0.57Nd_0.1Sr_0.33Mn_1?x Sn _x O₃ with (0.05 ≤ x ≤ 0.30) have been investigated, and the critical exponents and magnetocaloric effect are studied around the room temperature, to shed light on Sn substitution influence. A solid-state reaction method was used in the preparation. A structural study using Rietveld refinement of XRD patterns indicates rhombohedral structure with R \( \overline{3} \) c space group for (0.05 ≤ x ≤ 0.20) and shows the existence of a secondary phase attributed to the neodymium tin oxide (Nd₂Sn₂O₇) pyrochlore for x = 0.3. The variation of the magnetization (M) vs. temperature (T), under an applied magnetic field of 0.05 T, reveals a ferromagnetic–paramagnetic transition at the Curie temperature T _C. In addition, it was discovered that increasing the tin content leads to a reduction in magnetization and a lowering of T _C from 282 K (x = 0.05) to 158 K (x = 0.20) with increasing Sn substitution. The samples exhibit the characteristics of spin/cluster-glass state which is evident from (zero-field-cooled and field-cooled) magnetization vs. temperature curves. Indeed, the thermal evolution of magnetization in the ferromagnetic phase at low temperature varies as T ^3/2, in accordance with Bloch’s law. The spin-stiffness constant D obtained from the Bloch constant was determined. A large magnetocaloric effect has been observed in both samples (x = 0.05 and x = 0.10): the maximum entropy change, \( \left| {\varDelta S_{\text{M} }^{\text{peak}} } \right| \) , reaches the highest value of 3.22 J/kg K under a magnetic field change of 5 T with a RCP value of 56 J/kg for x = 0.10 composition. This opens an interesting opportunity to this compound to compete with materials which work as magnetic refrigerants near room temperature. Besides, we show that the samples follow the conventional behavior of a second-order ferromagnetic transition. This was possible by investigating the critical behavior at the transition region by adopting the modified Arrott plot method. The values of the critical exponents (β, γ, δ and n) are determined and they are between those predicted by the three-dimensional Heisenberg model.     

Spin states of cobalt and the thermodynamics of Sm1 − x Ca x CoO3 − δ solid solutions

In the rare-earth SmCoO₃ perovskite, Co³⁺ ions at low temperatures appear to be in the low-spin state with S = 0, t _2g ² e _g ⁰ . If Ca²⁺ ions partially substitute Sm³⁺ ions, oxygen deficient Sm_{1 ? x} Ca _x CoO_{3 ? δ} solid solutions with δ = x/2 appear. The oxygen deficiency leads to the formation of pyramidally coordinated cobalt ions Co _pyr ³⁺ in addition to the existing cobalt ions Co _oct ³⁺ within the oxygen octahedra. Even at low temperatures, these ions have a magnetic state, either S = 1, t _2g ⁵ e _g ¹ or S = 2, t _2g ⁴ e _g ² . At low temperatures, the magnetization of Sm_{1 ? x} Ca _x CoO_{3 ? δ} is mainly determined by the response of Co _pyr ³⁺ ions. Owing to the characteristic features of the crystal structure of the oxygen deficient perovskite, these ions form a set of nearly isolated dimers. At high temperatures, the magnetization of Sm_{1 ? x} Ca _x CoO_{3 ? δ} is mainly determined by the response of Co _oct ³⁺ ions, which exhibit a tendency to undergo the transition from the S = 0, t _2g ⁶ e _g ⁰ state to the S = 1, t _2g ⁵ e _g ¹ or S = 2, tt _2g ⁴ e _g ² state. In addition, the magnetization and specific heat of the solid solutions under study include the contribution from the rare-earth subsystem, which undergoes a magnetic ordering at low temperatures.