Crystal structure and magnetic properties of Ba-ordered manganites Ln0.70Ba0.30MnO3−δ (Ln = Pr, Nd)

The structure and magnetic properties of the Ba-ordered state in solid solutions of manganites Ln_0.70Ba_0.30MnO_3?δ (Ln = Pr, Nd) with a cation ratio Ln³⁺/Ba²⁺ ? 1 are studied experimentally. The samples are obtained by two-stage synthesis. The initial stoichiometric Ba-disordered solid solutions Ln_0.70Ba_0.30MnO₃ synthesized in air according to traditional ceramic technology are characterized by the orthorhombic (Imma, Z = 4) perovskite-like unit cell and are ferromagnets with Curie temperatures T _C ≈ 173 and ≈ 143 K for Pr and Nd, respectively. The average size <D> of a crystalline in the initial samples is 5 μm. It is found that annealing of the initial samples in a vacuum of P[O₂] = 10^?4 Pa leads to their separation into three phases: (1) the anion-deficient ordered LnBaMn₂O₅ phase described by a tetragonal (P4/mmm, Z = 2) perovskite-like unit cell, as well as the phases (2) Ln₂O₃ (P $\bar 3$ m1, Z = 1) and (3) MnO (Fm $\bar 3$ m, Z = 2). Reduction leads to the formation of a nanocomposite with an average crystallite size <D> = 100 nm. Anion-deficient Ba-ordered phases of LnBaMn₂O₅ exhibit ferrimagnetic properties with Néel temperatures T _N ≈ 113 and ≈123 K for Pr and Nd, respectively. Annealing of anion-deficient samples in air at a moderate temperature of T = 800°C does not change the average size of the nanocrystallite, but noticeably alters their phase composition. Stoichiometric nanocomposites consist of two perovskite-like phases: (1) the Ba-deficient ordered stoichiometric phase LnBaMn₂O₆, which is described by a tetragonal (P4/mmm, Z = 2) unit cell and has the Curie temperatures T _C ≈ 313 (Pr) and ≈303 K (Nd), and (2) the Ba-disordered superstoichiometric phase Ln_0.90Ba_0.10MnO_3+δ, which is described by an orthorhombic (Imma, Z = 4) unit cell and has Curie temperatures T _C ≈ 138 (Pr) and ≈123 K (Nd). The two magnetic phases of the Ba-ordered nanocomposite are exchange-coupled. For the low-temperature magnetic phase, a temperature hysteresis is observed at ΔT ≈ 22 K in a field of 10 Oe and at ΔT ≈ 5 K in a field of 1 kOe. It is shown that states with different degrees of ordering of cations in the A sublattice can be obtained employing different technological conditions of treatment. The significant changes in the magnetic properties of Ba-ordered nanocomposites are explained on the basis of chemical phase separation taking into account the effect of compression, which is a consequence of the action of chemical (cation ordering) and external (surface tension) pressures.     

Phase separation in oxygen-doped cuprates

Experimental investigations of phase separation in high-T_c cuprates are reviewed with special emphasis on recent results obtained on doped La₂CuO_4+x single crystals. Particular attention is paid to the magnetic properties. The experiments give very strong evidence that magnetic polarons are responsible for macroscopic phase separation observed in La₂CuO_4+x for x>0.     

Isotopenhydrogeologische Untersuchungen Im Bacho-Delta (Vietnam)

Abstract

Abecarnil is a β-carboline with high affinity to benzodiazepine receptors. Synthesis and spectral data of the title compound are presented. [¹³C₃]. Abecarnil was synthesized in a five step synthesis. [¹³C₂]Glycine-isopropylester-hydrochloride was condensed with p-methoxy-benzaldehyde to give N-(p-methoxy-benzyliden)-[¹³C₂]glycine-isopropyl-ester. Further reaction with 5-benzyloxy-pseudogramine and the introduction of [¹³C]formaldehyde in a Pictet-Spengler reaction yielded the intermediate 1,2,3,4-tetrahydro-β-carboline derivative. The following dehydration led to [¹³C₃]Abecarnil in an overall yield of 23%     

Combined Optical/MCD/ODMR investigations of photochromism in doubly-doped Bi 12 GeO 20

Electron paramagnetic resonance is detected optically via the change of magnetic circular dichroism under microwaves at 35 v GHz. The technique is applied to Bi 12 GeO 20 samples co-doped with vanadium and a second transition metal (Cr, Mn, Co, Cu). The optical and magnetic properties of several paramagnetic defects (V Ge 4+ and Cr Ge 4+ ) are directly correlated. The basic photochromic processes occuring in samples doped with V, Mn, and Mn+V are explained. The V Ge 4+/5+ level is positioned roughly 2.2 v eV above the valence band.     

Phase transitions in La1−x CaxMnO3−x/2 manganites

The crystal structure parameters and magnetic and electrical properties of La_1?x Ca_xMnO_3?x/2 reduced manganites with 0≤x≤0.5 are established. These investigations contribute to the understanding of magnetic interactions in manganites without Mn⁴⁺ ions. It is found that these manganites show a long-range antiferromagnetic order up to x=0.09 and transform into spin glasses at 0.09<x≤0.35. The compositions in the range 0.35<x≤0.5 show a strong increase in the spontaneous magnetization and critical point associated with the appearance of spontaneous magnetization and can therefore be viewed as inhomogenious ferromagnets. The magnetic and crystal structure peculiarities of La_0.5Ca_0.5MnO_2.75 are established by the neutron diffraction method. The strongly reduced samples show a large magnetoresistance below the point where the spontaneous magnetization develops. The magnetic phase diagram of La_1?x Ca_xMnO_3?x/2 is established by magnetization measurements. The magnetic behavior is interpreted assuming that the Mn³⁺-O-Mn³⁺ magnetic interaction is anisotropic (positive-negative) in the orbitally ordered phase and isotropic (positive) in the orbitally disordered phase. Introduction of the oxygen vacancies changes the magnetic interaction sign from positive to negative, thereby leading to a spin glass state in strongly reduced compounds. The results obtained reveal unusual features of strongly reduced manganites such as a large ferromagnetic component, a high magnetic ordering temperature, and a large magnetoresistance despite the absence of Mn³⁺-Mn⁴⁺ pairs. In order to explain these results, the oxygen vacancies are supposed to be ordered.     

Anomalous acoustoelectric effect in La0.67Ca0.33MnO3 films

We have studied the acoustoelectric (AE) effect produced by surface acoustic waves (SAW) in a monolithic layered structure, composed of a piezodielectric LiNbO3 substrate and a La0.67Ca0.33MnO3 film. The experiments unexpectedly revealed in the longitudinal AE effect an anomalous contribution, invariant upon reversal of SAW propagation, which coexists with the ordinary (odd in wave vector) effect. The anomalous effect dominates near the metal-insulator transition, while the ordinary effect prevails at high and low temperatures. We show that the anomalous effect is caused by strong modulation of the film conductivity produced by the SAW elastic deformations.     

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.