X-ray study of structural phase transitions in nanocrystalline LaMnO3+δ perovskite

The nanocrystalline LaMnO_3+δ perovskite was synthesized by the microwave-assisted glycothermal method and calcined at several temperatures up to 1500°C. The prepared samples were examined by the X-ray powder diffraction with the aim to show that LaMnO_3+δ exhibits the size-induced structural phase transitions. The as-received nanocrystals of LaMnO_3+δ are of tetragonal, pseudo-cubic symmetry not known for bulk material. The samples calcined at temperatures 750–1100°C have trigonal symmetry known from the high-temperature phase of LaMnO₃ single crystal. The samples calcined from 1200°C to 1500°C have two phases: trigonal and orthorhombic. Thus, the observed phase sequence is inverted with respect to that of the bulk material, which is the characteristic of the size-induced mechanism of phase transitions in the nanocrystals. The critical crystallite sizes for both structural transitions were evaluated as 20 and 100?nm.     

Structural and magnetic characterisation of the perovskite oxides La0.7Ca0.3−x Na x MnO3

X-ray powder diffraction (XRD) and magnetic measurements were performed in order to investigate the effect of Na⁺ ion substitution for Ca²⁺ ions on the crystallographic structure, the character of magnetic ordering, and the effect of transition temperature in La_0.7Ca_0.3−x Na _x MnO₃ manganites series (0 ⩽ × ⩽ 0.2). All samples crystallise in an orthorhombic structure with the Pnma space group. We have found a strong dependence of structural and magnetic properties on the cation-size disorder parameter σ ². The temperature dependence of magnetization of all samples obeys the Bloch T ^3/2 law. The values of the spin wave constant at low temperature B increase with the increase of x and the Curie temperature decreases. It is concluded that the substitution of Ca by Na⁺ ions causes a decrease in total exchange integral Aof the samples.      

Phase transitions in La0.5Sr0.5FeO3−δ investigated by mechanical spectrum

The mechanical spectrum measurement was performed in ceramic La_0.5Sr_0.5FeO_3?δ from liquid nitrogen temperature to room temperature at kilohertz frequencies. From temperature dependent reduced modulus, a kink (corresponding temperature labeled as T_M) was observed which evidenced a phase transition by the mechanical spectrum at two flexural resonance frequencies. This elastic manifested phase transition is a charge disproportionation transition. Around 170 K, an internal friction peak (labeled as P1) was observed accompanied with a large modulus hardening with the decrease in temperature. Two mechanisms are proposed for P1 peak, one is elastic manifestation of magnetic freezing, and the other is the ordering or freezing of oxygen vacancies.     

La0.25Ca0.75MnO3的晶体结构研究

用X射线衍射仪测量了La0．25Ca0．75MnO3多晶粉末在300K和70K时的晶体结构衍射谱,并用Rietveld全谱拟合法对这些数据进行了拟合．结果表明,在室温时,La0．25Ca0．75MnO3由于MnO6八面体的Jahn-Teller晶格畸变,其晶体结构已发生了扭曲,晶格常数分别为a=0．53559nm,b=0．75537nm,c=0．53587nm．温度降至70K时,X射线衍射谱上出现了比室温更多的衍射峰,有些峰发生了“双峰”劈裂,但仍然具有与室温相同的晶体对称性(空间群为Prima)．70K时的晶格常数分别为a=0．53673nm,b=O．74785nm,c=O．53718nm,与300K时的晶格常数比较,a和c分别增大了O．21％和O．24％,而b减小了1．O％,这一晶体结构的巨大变化源于在电荷有序态下形成了静态的合作Jahn-Teller效应．     

Characteristics of magnetic order in perovskite manganites La1−x CaxMnO3

Solid solutions of the system La_1−x Ca_xMnO₃ are synthesized, and their magnetic and electrical properties are investigated. As x is increased, the crystal lattice changes symmetrically from an orthorhombic (x=0 and x=0.8) to a cubic structure (0<x⩽0.6 and x=1). Nonstoichiometric LaMnO₃ and compositions with a low Ca content (0<x<0.4) are collinear ferromagnets. A metal-insulator transition is observed in them near the Curie temperature. Compositions with 0.6⩽x⩽0.9 exhibit a semiconductor-type conductivity and an unusual temperature behavior of the magnetization and the susceptibility with very distinct Curie and Néel temperatures. The magnetic properties of the solid solutions are explained on the basis of the model of ferro-antiferromagnetic phase separation. Zh. éksp. Teor. Fiz. 116, 1664–1675 (November 1999)     

Thermal-expansion and magnetostriction anomalies in phase transitions in La1−x SrxMnO3

A study is reported on phase transitions in the La_1?x Sr_xMnO₃ system, both spontaneous and induced by a pulsed magnetic field of up to 250 kOe, accompanied by anomalies in magnetoelastic properties. The temperatures of the polaron (charge) and magnetic ordering, as well as those of structural transitions, are observed to be in good agreement with the results obtained by other methods. Jumps in the field dependence of longitudinal and transverse magnetostriction associated with field-induced orbital ordering have been found. A strong temperature dependence of the corresponding threshold fields is observed.     

Features of high-frequency ultrasound propagation in the temperature range of structural and magnetic phase transitions in La1−x SrxMnO3 (x=0.175) manganite

The propagation of ultrasonic waves at a frequency of 770 MHz in a La_0.825Sr_0.175MnO₃ single crystal is investigated in the temperature range 350–150 K. It is found that the velocity, attenuation, and mode composition of ultrasonic waves change at temperatures of 315–280 and 220 K. These changes correlate with the structural and magnetic phase transitions and can be explained in terms of the Jahn-Teller distortions of the crystal lattice.     

Jahn-Teller Distortions Cooperating with Magnetic Interaction in the Raman Spectra of La0.75Ca0.25MnO3 Thin Film

Remarkable changes (additional peaks, frequency shift, and peak width) of Raman spectra ofa La0.75 Ca0.25MnO3 thin film have been observed during the paramagnetic insulator-ferromagnetic metal transition. The vl band (230cm^-1) hardens by lattice contraction as a result of the rearrangement of Mn06 octahedra. The Jahn-Teller distortions seem to be responsible for the broadening of v2 band (485 cm^-1) above the magnetic transition temperature Tc. It is proposed that the 438cm-1 vibration mode activated in the magnetic ordering state is associated with the rearrangement of MnO6 octahedra. The softening of v3 band (610cm^-1) below TC can be ascribed to the magnetic interaction that brings into spin-phonon coupling terms.     

Impedance behavior of excess CaO type non-stoichiometric Ca1−xZrO3−δ perovskite ceramic

Excess CaO type non-stoichiometric Ca_1?xZrO_3?δ (x = ?0.2, ?0.23) was prepared to investigate their impedance behavior in 500 °C–1100 °C temperature range. It was confirmed that grain plays predominantly role in total resistance and relaxation process. The grain boundary resistance decreases more rapidly than that of grain with the rising of temperature. The relaxation time was found reduces with temperature increases. The activation energies are calculated to be 1.19 eV of C1.2Z and 1.53 eV of C1.23Z. The excess CaO is suggested can enhance the resistance and relaxation process of grain boundary and gives rise to a higher activation energy of C1.23Z. By analyzing dielectric permittivity, polarization effect was verified works more seriously at higher temperatures especially in C1.2Z. The excess CaO was proved can relieve the polarization effect in C1.23Z.     

On the theory of magnetic phase transitions. II: “Quasi phase transitions” the magnetic structure of vivianite

The problem of appearance of peaks in the temperature dependence of the specific heat is examined on the basis of Landau's theory of second-order phase transitions. It is pointed out that not only real phase transitions but also called- “quasi phase transitions” cause peaks in the specific heat. The magnetic structure of vivianite is investigated, because it is possible that vivianite undergoes a “quasi phase transition”.     

Dielectric studies of phase transitions in the ferroelectric CdTiO3 and the Sr1−x CdxTiO3 solid solution

Temperature dependences of the permittivity and of the dielectric hysteresis loops in ceramic samples of nominally pure CdTiO₃ and a Sr_1?x Cd_xTiO₃ solid solution were studied. At 76.5±0.5 K, CdTiO₃ was established to undergo a ferroelectric phase transition close to the tricritical point. The temperature dependence of spontaneous polarization of CdTiO₃ is described within the Landau theory of phase transitions with the critical order parameter exponent ≈0.25. The phase diagram of the Sr_1?x Cd_xTiO₃ solid solution was drawn in (T, x) coordinates, and the critical concentration x _c =0.002, above which an induced polar state sets in the solid solution, was determined.     

Structural and magnetic inhomogeneities,phase transitions, 55Mn nuclear magnetic resonance,and magnetoresistive properties of La0.6 − x Nd x Sr0.3Mn1.1O3-δ ceramics

The structure, lattice imperfection, and properties of ceramic samples La_{0.6 ? x} Nd _x Sr_0.3Mn_1.1O_3-δ (x = 0–0.4) have been investigated using the X-ray diffraction, resistive, magnetic (χ_ac, ⁵⁵Mn NMR), magnetoresistive and microscopic methods. It has been shown that there is a satisfactory agreement between the concentration decrease in the lattice parameters a of the rhombohedral (x = 0, 0.1, 0.2) and cubic (x = 0.3, 0.4) perovskite structures and the average ionic radii $\bar R$ for the lattice containing anion vacancies, cation vacancies, and nanostructured clusters with Mn²⁺ ions in A-positions. With an increase in the neodymium concentration x, the vacancy-type imperfection increases, the cluster-type imperfection decreases, the temperatures of metal-semiconductor phase transition T _ms and ferromagnetic-paramagnetic phase transition T _C decrease, and the content of the ferromagnetic phase decreases. The anomalous hysteresis is associated with the appearance of unidirectional exchange anisotropy induced in a clustered perovskite structure consisting of a ferromagnetic matrix and a planar antiferromagnetic cluster coherently coupled with it. An analysis of the asymmetrically broadened ⁵⁵Mn NMR spectra has revealed a high-frequency electronic double exchange (Mn³⁺-O^2?-Mn⁴⁺) ? (Mn⁴⁺-O^2?-Mn³⁺) and an inhomogeneity of the magnetic and charge states of manganese due to the heterogeneous environment of the manganese ions by other ions and defects. The observed changes in the resonant frequency and width of the resonance curve are caused by changes in the ratio Mn³⁺/Mn⁴⁺ and magnetic inhomogeneity. An increase in the neodymium concentration x leads to a decrease in the ferromagnetic phase content determined from the dependences 4πNχ_ac(T) and the ⁵⁵Mn NMR curves. The phase diagram characterizes an interrelation between the composition, the imperfection of the structure, and the transport, magnetic, and magnetoresistive properties of lanthanum neodymium manganite perovskites. It has been found that there is a correlation between the imperfection, magnetic inhomogeneity, coercive force, and magnetoresistance effect exhibited by the perovskite structure.     

Mesoscopic magnetic inhomogeneities in the low-temperature phase and structure of Sm1−x SrxMnO3 (x < 0.5) perovskite

Results are presented of studies of the ¹⁵⁴Sm_1?x Sr_xMnO₃ system using neutron powder diffraction and small-angle polarized neutron scattering. An analysis of the neutron diffraction spectra showed that at T < 180 K these exhibit typical Jahn-Teller distortions of the manganese-oxygen octahedrons which persist under further cooling and on transition of the sample to a metallic magnetically ordered state. The magnetic contribution to the diffraction is satisfactorily described using the (A _x (A _y )F _z ) model and is interpreted as the coexistence of ferromagnetic and antiferromagnetic phases. The exaggerated widths of the diffraction lines indicate an appreciable contribution from microdeformations evidently associated with the inhomogeneity of the system. Small-angle polarized neutron scattering showed that the Sm system for x = 0.4 and 0.25 is magnetically inhomogeneous in the low-temperature phase. Ferromagnetic correlations occur on scales of around 200 Å and having dimensions greater than 1000 Å which, combined with the temperature hysteresis of the magnetic small-angle scattering intensity observed for an x = 0.4 sample in the low-temperature phase, suggests that the transition is of a percolation nature.     

Influence of processing conditions on the crystal structure and magnetic behavior of La0.7Ca0.3MnO3±δ samples

In this work we report crystallographic structure variations and the related modifications on the magnetic behavior of La_0.7Ca_0.3MnO_3±δ introduced by heat-treatments in different synthesis atmospheric conditions. We have prepared polycrystalline ceramic samples using a modified polymeric precursors method, which produces highly homogeneous specimens.The use of argon atmosphere enlarges the crystalline c-axis as detected by Rietveld refinements. As a consequence, an improvement in the magnetic transition temperature T_C of the samples was observed.Our results also indicate that different heat-treatment conditions change the magnetic interactions between the ferromagnetic (F) and antiferromagnetic (AF) structures of these systems. Our conclusions rely on the use of AC magnetic susceptibility measurements as the experimental tool for measuring these variations.     

Magnetic and piezoelectric properties of the Bi1 − x La x FeO3 system near the transition from the polar to antipolar phase

The crystal structure, piezoelectric and magnetic properties of the Bi_{1 ? x} La _x FeO₃ solid-solution system near the structural transition between the rhombohedral and orthorhombic phases (0.15 ≤ x ≤ 0.2) have been investigated. The regions of existence of the polar rhombohedral and orthorhombic phases have been determined, and the sequence of structural transitions as a function of the lanthanum ion concentration and temperature has been studied. The maximum piezoelectric signal is found for the solid solution with the composition x = 0.16, which has a single-phase rhombohedral structure. The relation between the type of crystal structure distortions and the increase in the magnetization upon the concentration-driven structural transition from the polar to antipolar phase has been established.     

Comparative study of the magnetic and electrical properties of Pr1−xBaxMnO3−δ manganites depending on the preparation conditions

Magnetization, electrical resistivity and magnetoresistance of Pr_0.50Ba_0.50MnO_3−δ manganites with perovskite structure have been investigated as a function of preparation conditions. It was found that the as-prepared samples (prepared in air) show T_C=110 K (first order phase transition), whereas for those annealed in flowing argon the T_C value increases up to 340 K without change of cubic symmetry (second order phase transition). Ferromagnet–paramagnet transition is accompanied by both a metal–insulator transition and a magnetoresistance peak. The X-ray study has revealed that the samples annealed in argon have broad peaks apparently due to microstrains and crystal structure defects. The argon-treated samples improve the magnetization after subsequent annealing in air at T⩽1000°C. T_C of argon-treated samples is stable with respect to annealing in air up to 1300°C where it becomes again 110 K. In contrast, a treatment in vacuum destroys the ferromagnetic order. Auger-spectroscopy has not revealed any additional ions except Pr, Ba, Mn and O for all the samples. External pressure enhances the Curie point of the sample prepared in air at a rate of 43 K/GPa. We have observed that the samples Pr_1−xBa_xMnO_3−δ, x⩾0.30, exhibited the above-mentioned effect of increasing T_C after treatment in flowing argon without changes of the phase state, whereas the samples x<0.30 decomposed into different phases. The dramatic increase of T_C after argon treatment is supposed to result from microstrains and crystal structure defects in the sample.