Ferromagnetic insulating and reentrant spin glass behavior in Mg doped La0.75Sr0.25MnO3 manganites

In this study, the effect of Mg substitution on structural, magnetic and electrical properties of La_0.75Sr_0.25Mn_1?xMg_xO₃ and La_0.75Sr_0.25?xMg_xMnO₃ (nominal compositions) samples are investigated by XRD, Ac susceptibility and electrical resistivity measurements. It is found that Mg does not replace La in the perovskite lattice. Also the results show that by increasing Mg doping levels, the paramagnetic–ferromagnetic and metal–insulator transition temperatures decrease. The reason for decreasing transition temperatures with increasing Mg concentration is, that the long-range FM order has been destroyed by the Mg, which is randomly occupying Mn site. This leads to the suppression of double-exchange interaction in the Mn³⁺–O–Mn⁴⁺ networks. Also the reentrant spin glass (RSG) state accompanied by FM transition, exists in high doped samples. The RSG state could be understood on the basis of double exchange ferromagnetic interaction in Mn³⁺–O–Mn⁴⁺ and super-exchange antiferromagnetic interaction in the Mn⁴⁺–O–Mn⁴⁺ networks.     

Studies of local fields in the Pr1−xCaxMnO3 system using perturbed angular correlation spectroscopy

In this work a local probe study using perturbed angular correlation spectroscopy in Pr_1?xCa_xMnO₃ small bandwidth manganites is presented. The magnetic hyperfine field study across the Pr_1?xCa_xMnO₃ phase diagram is provided and the results are discussed in terms of mixed-phase ferromagnetic/antiferromagnetic states versus canted antiferromagnetism.     

Na(H<Subscript>2</Subscript>O)[Mn(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>(BP<Subscript>2</Subscript>O<Subscript>8</Subscript>)]: Crystal structure refinement

The crystal structure of synthetic manganese sodium borophosphate hydrate Na(H₂O)[Mn(H₂O)₂(BP₂O₈)] was refined based on X-ray diffraction data. The compound was prepared by soft hydrothermal synthesis in the MnCl₂-Na₃PO₄-B₂O₃-H₂O system. The unit-cell parameters are a= 9.602(1) Å, c= 16.037(3) Å, sp. gr. P6₅22, Z= 6, D _x = 2.57 g/cm³. The water molecules were found to be statistically distributed in the channels of the mixed anionic paraframework consisting of (BO₄) and (PO₄) tetrahedra and [MnO₄(H₂O)₂] octahedra. The hydrogen atoms of the water molecules coordinated to the Mn²⁺ cations were located and their positional and thermal parameters were refined. The crystal-chemical features of borophosphates of the general formula A _x M(H₂O)₂(BP₂O₈)(H₂O) are considered.     

Crystal and magnetic structure of the Sm<Subscript>0.45</Subscript>Sr<Subscript>0.55</Subscript>MnO<Subscript>3</Subscript> manganite studied by neutron powder diffraction

Neutron diffraction investigation of the ¹⁵²Sm_0.45Sr_0.55MnO₃ manganite is performed. The diffraction data are compared with the magnetic and transport properties of this compound. The parameters of the crystal and magnetic structures are determined. Manganite belongs to the orthorhombic system (sp. gr. Pnma) and has a perovskite-like structure in the entire temperature range under study (1.5–260 K). The ground state of the ¹⁵²Sm_0.45Sr_0.55MnO₃ manganite at low temperatures is a single-phase A-type antiferromagnetic insulator with T _N ～ 180 K.     

Paramagnetic behavior of Zn1−xMnxO at room temperature

Mn‐doped ZnO were synthesized by solid state reaction and sol‐gel method respectively. It was found that samples synthesized by solid state reaction containing Mn₂O₃ and MnO₂ are a mixture of ferromagnetic and paramagnetic phases. Contrary, samples without second phases were found to be paramagnetic at room temperature. According to previous report, interface effects between Zn‐rich Mn₂O₃ and MnO₂ interfaces may be the origin of the ferromagnetic behavior observed in our samples prepared by solid reaction, so the alloy of Zn_1−xMn_xO may be paramagnetic at room temperature. Prepared by sol‐gel technique, the samples without second phases in the XRD patterns are also room‐temperature paramagnetic. Therefore we believe that the magnetism of Zn_1−xMn_xO is paramagnetic at room temperature. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Concentration Magnetic Phase Transitions in the (La1−xCaxMnO3 System

Comprehensive investigations into crystal structures, electrical and magnetic properties of the (La_1−xCa_x)MnO₃ (x = 0 ÷ 0.6) solid solutions are performed. Two concentration magnetic phase transitions are found: antiferromagnetic-ferromagnetic with x = 0.14 and ferromagnetic (T_c = 150 K) - ferromagnetic (T_c = 260 K) at f = 0.2. It is shown that the first of them is due to the crystal structure O′ O orthorhombic transition, the second - to the increase of ferromagnetic interaction at the expense of additional interaction through conduction electrons. A diagram of the magnetic states for (La_1−xCa_x)MnO₃ at x = 0 / 0.6 is given.     

Disorder in LixFePO4: From glasses to nanocrystallites

Li_xFePO₄ glasses have been prepared by fast-quenching method in the whole range of composition 0 ? x ? 1. The amorphous state of glassy materials is confirmed by X-ray diffraction. Information concerning the local environment of Li and Fe cations and the configuration of (PO₄)³⁻ oxo-anions is obtained by Fourier transform infrared (FTIR) spectroscopy. While the LiFePO₄ crystalline materials undergo a transition from the paramagnetic to the antiferromagnetic ordering at 52 K, no magnetic ordering is observed in the vitreous samples that realize random field systems, so that a spin glass-like freezing is observed at low temperature. The paramagnetic Curie temperature of Li_xFePO₄ is independent of x and shifted to θ = −60 K in the glassy state, due to a significant distortion of the FeO₆ octahedra that alters the superexchange path inside the atomic FeO₄ layers of the crystallized structure. On another hand, the PO₄ tetrahedra are not significantly distorted in the glassy phase. The results are compared with highly disordered, but nanocrystallized LiFePO₄ recently obtained at the early stage of synthesis by solid state reaction at 300 °C. In this latter case, the lack of long-range antiferromagnetic ordering is due to substitutional disorder among the cationic sublattice.     

Crystal structure of [Rb0.24(H2O)0.76]VO(H2O)(PO4), a new monoclinic variety in the series of layered vanadyl phosphates

The crystal structure of a new monoclinic variety of hydrous rubidium vanadyl phosphate [Rb_0.24(H₂O)_0.76]VO(H₂O)(PO₄) doped with Al³⁺ ions is studied by X-ray (R = 0.054) diffraction: a = 6.2655(4) Å, b = 6.2712(3) Å, c = 6.8569(5) Å, β = 107.805(7)°, space group P2₁/m, Z = 2, and D _x = 2.792 g/cm³. The new phase obtained by the hydrothermal synthesis in the V₂O₅-Rb₂CO₃-AlPO₄-H₂O system has a layer-type structure in which Rb atoms and water molecules are located between layers of vertexsharing [VO₅(H₂O)] octahedra and [PO₄] tetrahedra. Rb intercalates based on VOPO₄ · 2H₂O are described by general formula [Rb _x (H₂O)_{1 ? x} ]V _1?x ^V V _x ^IV O(H₂O)(PO₄), where x ≤ 0.5, and the amount of reduced vanadium and interlayer water molecules is determined by the amount of introduced rubidium atoms.     

Evidence of hopping of charge carriers in the clustered state of manganites

The electrical resistivity and magnetization measurements as a function of both temperature and magnetic field provide clear evidence for three temperature intervals in which the magnetic and transport properties are altered in the La_0.55Y_0.15Ca_0.3MnO₃ compound. The intermediated-T regime, called clustered state, involves the presence of both ferromagnetic and paramagnetic phases and is shown to be closely related to the colossal magnetoresistivity effect. An extra hopping conducting process is proposed to exist in this clustered state. We use both the Abeles’ model and microstructural parameters to estimate the hopping activation energy between ferromagnetic clusters. The size (density) temperature dependence and the shape of the ferromagnetic metallic clusters are revealed to play a major role in the clustered state of this manganite.     

Specific effects of nanometer scale size on magnetic ordering in La1−xCaxMnO3 (x = 0.1, 0.3 and 0.6) manganites

To check the impact of nano-size originated effects on the magnetic ordering in doped manganites, X-band electron magnetic resonance measurements were performed on nanometer sized and bulk samples of La_1?xCa_xMnO₃ (x = 0.1, 0.3 and 0.6). The model fittings of EPR signal parameters and complementary magnetic measurements indicate that bulk La_0.9Ca_0.1MnO₃ shows inhomogeneous confinement of charge carriers, leading to its mixed magnetic ordering. The carriers mobility within impurity-like band and ferromagnetic (FM)-like ground state are observed on nanocrystals of the same composition. The bulk La_0.7Ca_0.3MnO₃ demonstrates homogeneous FM order and band-like carrier mobility. The surface magnetic disorder in its nano-counterpart leads to appearance of two magnetic phases – a core phase (bulk-like in properties) and a surface phase with notably reduced temperature of magnetic ordering; neither double-exchange interaction nor carriers mobility exist between these phases. The size reduction induced effects in La_0.4Ca_0.6MnO₃ are: an increase of surface FM-like component and a decrease of the charge-ordering temperature. These findings allow us to conclude that the nano-scale effect on magnetic ordering in La_1?xCa_xMnO₃ system weakens progressively upon stabilization of the low temperature magnetic ground state with Ca-doping.     

Hexagonal frustrated RMnO3 manganites (R = Y, Lu) under high pressure

The crystalline and magnetic structures of YMnO₃ and LuMnO₃ hexagonal manganites under pressures of 0–6 GPa and in the temperature range 10–295 K have been investigated by neutron diffraction. Application of pressure leads to a significant decrease in the ordered magnetic moment of Mn ions (at T = 10 K) from 3.27 (0 GPa) to 1.52 μ_B (5 GPa) for YMnO₃ and from 2.48 (0 GPa) to 1.98 μ_B (6 GPa) for LuMnO₃. Under high pressures, spin reorientation of Mn magnetic moments and a change in the symmetry of the antiferromagnetic structure are observed in YMnO₃. The relationship between the triangular lattice distortion parameter and the symmetry of the triangular antiferromagnetic state of RMnO₃ hexagonal manganites is discussed.     

Study of the effects of isotopic substitution 16O → 18O in Sm1 ? xSrxMnO3-type (x = 0.45 and 0.50) manganites by powder neutron diffraction

The results of neutron diffraction studies of the effect of the isotopic substitution ¹⁶O → ¹⁸O in Sm_{1 − x} Sr_xMnO₃-type (x = 0.45 and 0.50) manganites are considered. The parameters of the crystal and magnetic structures of the samples are determined in the temperature range 1.4–300.0 K. It is shown that the isotopic substitution considerably changes the phase diagram of manganites. The results of the earlier macroscopic studies of the same samples are confirmed. __________ Translated from Kristallografiya, Vol. 49, No. 6, 2004, pp. 995–1002. Original Russian Text Copyright ? 2004 by Kurbakov, Trunov, André.     

Structure of rare-earth phosphate glasses by X-ray and neutron diffraction

Previous diffraction studies of the structures of rare-earth phosphate glasses (R₂O₃)_x(P₂O₅)_1−x are extended to glasses with smaller R³⁺ ions with R = Sm, Gd, Dy, Er, Yb, Y for x = ∼0.25 and with R = Nd, Sm, Gd for x = ∼0.15. Parameters for the P–O, R–O and O–O first-neighbor peaks were obtained by Gaussian fitting. P–P and R–P distances were estimated from the positions of peak maxima. Effects of residual silica or alumina contents present as a result of glass processing were taken into account for selected samples. The P–O coordination number, N_PO, and the P–O, O–O, P–P distances are consistent with the presence of phosphate tetrahedra and are insensitive to the R species and the R₂O₃ content. Rare-earth coordination numbers, N_RO, decrease from ∼8 to ∼6.5 when x is increased from ∼0.15 to ∼0.25. N_OO and N_PP decrease with increasing R₂O₃ content indicating the network disintegration. The numbers N_RO of the metaphosphate glasses (x = ∼0.25) decreases from ∼7 to ∼6 when R is changed from La to Yb. This change is also indicated by the behavior of the R–O distances and by constant number densities of atoms. The decrease in N_RO with increasing R₂O₃ content is due to the reduction in the number of terminal O (O_T) available for coordination of the R³⁺ ions (six at metaphosphate composition). Especially for smaller R³⁺ ions sharing O_T between two R sites is not favored. The decrease by ∼0.04 nm of the prominent R–R first-neighbor distance with a change of R from La to Yb at the metaphosphate composition is indicated by a shift to higher magnitude of scattering vector of the shoulder occurring in front of the first main diffraction peak.     

Crystal structures and magnetic properties ofA 2MnCl6 salts (A = NH4 +, K+ and Rb+)

The temperature dependence of the magnetic susceptibility ofA ₂MnCl₆ salts (A = NH₄ ⁺, K⁺, Rb⁺) has been measured, and their crystal structures determined using powder X-ray diffraction methods. The structures of these simple cubic salts are governed by thex coordinate of the halide ion. The magnetic and the structural data suggest the presence of antiferromagnetic interactions between adjacent MnCl ₆ ^2– octahedra across bridges of the type as were found in related iridium salts: the susceptibility and the structural data have been used to estimate separately the values of ratios of the exchange integrals between pairs of salts; the agreement is better than 6 %.Research performed under the auspices of the U.S. Atomic Energy Commission.     

Structure of titanophosphate glasses studied by X-ray and neutron diffraction

The structure of binary (TiO₂)_x(P₂O₅)_1−x glasses with x = 0.60, 0.65 and a ternary K₂O–TiO₂–P₂O₅ (KTP) glass were studied by X-ray and neutron diffraction. The experiments were performed at the high-energy beamline BW5 of the synchrotron DORIS (Hamburg/Germany) and at the GEM instrument of the neutron source ISIS (Chilton/UK). Gaussian fitting of well-resolved first-neighbor peaks in the correlation functions of the binary glasses with TiO₂ contents of 0.65 and 0.60 result in Ti–O coordination numbers of 5.65 ± 0.2 and 5.9 ± 0.2, respectively. Distorted TiO₆ octahedra and isolated PO₄ units form the glassy networks, with a small number of lower coordinated Ti sites for the 0.65 TiO₂ glass. For comparison, only TiO₆ octahedra are found for a ternary K₂O–TiO₂–P₂O₅ glass. The Ti–O coordination numbers are compared with a structural model where all oxygen atoms occupy sites in Ti–O–Ti, Ti–O–P or P–O–P bridges. The presence of three-coordinated oxygens must be assumed for the binary glasses, whereas a structure with nearly all oxygen atoms forming network bridges exists for the ternary KTP glass.     

Magnetic properties of amorphous metals

Neutron scattering has provided unique information about the nature of magnetism in amorphous alloys. This paper reviews some of the results obtained principally on two ribbon-form metallic glass systems - (Fe_xNi_1?x)₇₅P₁₆B₅Al₃ and Fe_xB_1?x. The former exhibits three states depending on composition: pure ferromagnetism, re-entrant spin glass, and ordinary spin glass. The neutron results provide evidence for the coexistence of spin glass and ferromagnetic correlations in the intermediate regime. The alloys of Fe and B show Invar phenomena which result in anomalously small values of the effective spin-wave stiffness calculated from low-temperature magnetization and Mössbauer data. The long-wavelength spin waves as measured by the neutrons do not reflect the rapid demagnetization found in the bulk results, implying the presence of excitation processes other than long-wave-length spin waves.     

Exchange interactions in hydrogen-induced amorphous YFe2

The magnetic properties of hydrogen-induced amorphous (HIA) YFe₂H_x (x = 1.8, 3.0 and 3.4) alloys have been investigated by means of ⁵⁷Fe Mössbauer spectroscopy and atomic pair distribution analysis. The exchange integral (J) estimated from the temperature dependence of the average ⁵⁷Fe hyperfine field shows a tendency to decrease with decreasing the average Fe–Fe interatomic separation. Moreover, an abrupt drop of J is evident at an average Fe–Fe interatomic separation of about 0.25 nm, which is the empirical threshold where the magnetic interaction between Fe moments changes from ferromagnetic to antiferromagnetic. The absence of a spin-glass state in HIA YFe₂(H) is well understood by the enhancement of J through the volume expansion induced by the absorption of hydrogen.     

Crystal structure of Rb<Subscript>2</Subscript>Mn<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>[P<Subscript>2</Subscript>O<Subscript>7</Subscript>]<Subscript>2</Subscript>, a new representative of the family of hydrated diphosphates

The crystal structure of Rb₂Mn₃(H₂O)₂[P₂O₇]₂, a new phase obtained in the form of single crystals under hydrothermal conditions in the MnCl₂–Rb₃PO₄–H₂O system, is determined by X-ray diffraction (Xcalibur-S-CCD diffractometer, R = 0.0270): a = 9.374(2), b = 8.367(2), c = 9.437(2) Å, ß = 99.12(2)°, space group P2₁/c, Z = 2, D_x = 3.27 g/cm³. A correlation between the unit-cell parameters and the size of cations forming the crystal structures of isostructural A₂M₃(H₂O)₂[P₂O₇]₂ diphosphates (A = K, NH₄, Rb, or Na; _M = Mn, Fe, Co, or Ni) is revealed. It is shown that, due to the topological similarity, the structures of diphosphates and orthophosphates of the farringtonite structural type can undergo mutual transformations.     

Two diastereomers of 2-[[β-(N-phenylamino)-α-methylphenethyl]-methylamino]-N,N-dimethylacetamide

The structures of two diastereomers ((1R,2R) and (1R,2S)) of the title compound have been determined. The molecular conformation of the (1R,2R) isomer is heavily influenced by strong intramolecular hydrogen bonding between the secondary and tertiary amine groups (N(1)…N(2) 2.629(8) Å; N(4)…N(5) 2.628(8) Å). In the (1R,2S) isomer no intramolecular interaction is observed, but somewhat weaker intermolecular hydrogen bonding does occur between the secondary amine and the carbonyl group of a neighboring molecule (N(1)…O(1) 2.960(6) Å) related by a 2₁ screw operation along thea-axis (x1/40). No close intermolecular contacts are observed for the (1R,2R) isomer. Crystal data for (1R,2R); monoclinic,P2₁ (No. 4),a=18.588(5),b=16.743(4),c=6.062(1) Å, β=97.26(2)^o,V=1871.5(8) A³, Z=4,D _cale=1.16 g/cm³. Crystal data for (1R,2S): orthorhombic,P2₁2₁2₁ (No. 19),a=8.008(2),b=9.985(3),c=23.458(5)Å,V=1875.8(6) ų, Z=4,D _cale=1.15 g/cm³.     

Properties and structure of cesium phosphate glasses

A series of Cs-phosphate glasses, xCs₂O(1−x)P₂O₅, where 0?x?0.60, were prepared. The glass transition temperature (T_g) decreases with the initial addition of Cs₂O to P₂O₅, from 637 K at x=0 to 472 K at x=0.16. There is little change in T_g with further additions of Cs₂O up to x=0.60. The ³¹P magic angle spinning nuclear magnetic resonance (MAS NMR) spectra show that Cs₂O additions systematically convert the cross-linked ultraphosphate network of ν-P₂O₅ to a chain-like metaphosphate structure as x approaches 0.50. The ¹³³Cs MAS NMR spectra show a 90 ppm increase in isotropic chemical shift (δ_iso) with increasing Cs₂O content, which indicates a decrease in the average electron density around the Cs⁺ ions, more covalent Cs-O bonding, and a shorter average Cs-O bond length. The physical properties and spectroscopic results are interpreted using a structural model that considers the effects of composition on the average coordination environment of Cs⁺ ions.