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The neutron powder diffraction technique has been used for structural studies of Rb2UBr6 solid electrolyte as a function of temperature. The low-, room-, and high-temperature structures have been determined. At the temperature range of 4.2-80 K, the compound crystallizes in a monoclinic unit cell in the P21/c space group. At 80 K and 853 K, the compound crystallizes in a tetragonal unit cell in the P4/mnc space group. At 300 K, the lattice constants are a = b = 7.745(1) and c = 11.064(1) (a) over bar. At the temperature range of 853-960 K, a trigonal phase is observed in the P (3) over bar ml space group.

Ceramic samples of the multiferroic perovskite Pb(Fe1-xScx)(2/3)W1/3O3 with 0 <= x <= 0.4 have been synthesized using a conventional solid-state reaction method, and investigated experimentally and theoretically using first-principle calculations. Rietveld analyses of joint synchrotron X-ray and neutron diffraction patterns show the formation of a pure crystalline phase with cubic (Fm3(_)m) structure with partial ordering in the B-sites. The replacement of Fe by Sc leads to the increase of the cation order between the B and B '' sites. As the non-magnetic Sc3+ ions replace the magnetic Fe3+ cations, the antiferromagnetic state of PbFe2/3W1/3O3 is turned into a ferrimagnetic state reflecting the different magnitude of the magnetic moments on the B ' and B '' sites. The materials remain ferroelectric relaxors with increasing Sc content. Results from experiments on annealed and quenched samples show that the cooling rate after high temperature annealing controls the degree of cationic order in Pb(Fe1-xScx)(2/3)W1/3O3 and possibly also in the undoped PbFe2/3W1/3O3.

Mn3TeO6 has a trigonal corundum related structure (space group R (3) over bar), and orders in an incommensurate antiferromagnetic (AFM) structure at T-N approximate to 24 K. A weak ferroelectric order below T* similar to 21 K has recently been reported. In order to investigate possible structural changes below T-N leading to the observed dipole order, we have performed a detailed study of the crystal and magnetic structures of Mn3TeO6 using neutron powder diffraction (NPD) in the temperature range of 5-40 K. Complementary low-temperature second harmonic generation (SHG) measurements were performed in order to confirm the reported dipole order at T*. No change in the rhombohedral symmetry associated with a possible displacive phase transition at T* was observed in the long-range structural correlations, and it appears that Mn3TeO6 keeps the same incommensurately modulated magnetic spin structure with the propagation vector k = (0; 0; 0.43) in the whole temperature range from 5 to 24 K.

Plate-like stoichiometric crystals of Ag-doped LiCu2O2 have been grown by slowly cooling Li2CO3 center dot 4(1 - x)CuO center dot 4xAgNO(3) (0 <= x <= 0.5) melts. X-ray single crystal diffraction has shown that the crystals are isostructural with LiCu2O2 and contain around 5 at % Ag (relative to the Cu atoms). The addition of silver to lithium cuprate crystals significantly increases their electrical conductivity but has little effect on the temperature behavior of their magnetic moment. The possible substitution mechanism is determined which supports Ag+ <-> Cu+, rather than Ag+ <-> Li+ in the Ag-doped LiCu2O2 crystals.

The structural, magnetic, and dielectric properties of Pb3Mn7O15 have been investigated using high-quality single crystals. Pb3Mn7O15 adopts a pseudo-hexagonal orthorhombic structure, with partially filled Kagom, layers connected by ribbons of edge-sharing MnO6 octahedra and intercalated Pb cations. There are 9 inequivalent sites in the structure for the Mn ions, which exist both as Mn3+ and Mn4+. Pb3Mn7O15 undergoes an antiferromagnetic transition below T-N similar to 67 K, with significant geometric frustration. Neutron powder diffraction on crushed single crystals allowed us to determine the low-temperature antiferromagnetic magnetic structure. We discuss the magnetic interaction pathways in the structure and possible interplay between the structural distortions imprinted by the lone-electron pair of Pb2+ cations and Mn3+/Mn4+ charge ordering.

Spinel-type compounds of Fe-Ni-Sb-O system were synthesized as polycrystalline powders. The crystal and magnetic properties were investigated using X-ray and neutron powder diffraction, Mossbauer and X-ray absorption spectroscopy and magnetization measurements. The samples crystallize in the cubic system, space group Fd - 3 m. The distribution of cations between octahedral and tetrahedral sites was refined from the diffraction data sets using constraints imposed by the magnetic, Mossbauer and EDS results and the ionic radii. The cation distribution and the temperature dependence of the lattice parameter (a) and the oxygen positional parameter (u) were obtained. A chemical formula close to Fe0.8Ni1.8Sb0.4O4 was determined, with Sb5+ cations occupying octahedral sites, and Fe3+ and Ni2+ occupying both tetrahedral and octahedral sites. Fe3+ mainly (85/15 ratio) occupy tetrahedral sites, and conversely Ni2+ mainly reside on octahedral ones. The magnetic unit cell is the same as the crystallographic one, having identical symmetry relations. The results indicate that the compounds have a collinear ferrimagnetic structure with antiferromagnetic coupling between the tetrahedral (A) and octahedral (B) sites. Uniquely, the temperature dependence of the net magnetization of this rare earth free ferrimagnet exhibits a compensation point.

Stoichiometric polycrystalline samples of LnFe(2/3)Mo(1/3)O(3) (Ln = Nd, Pr, Ce, La) have been prepared by solid-state reaction and studied by means of x-ray and neutron powder diffraction as well as Mossbauer spectroscopy and magnetic measurements. All samples were found to be of single phase and to have Pnma symmetry with valence state +3 of Fe and Mo. It is demonstrated that the B-site cations of LnFe(2/3)Mo(1/3)O(3) in accord with LnFeO(3) order in a G-type antiferromagnetic structure with the magnetic moments aligned along the b axis. However, with significantly lower Neel temperatures than their LnFeO(3) parent compounds. The Fe-O-Fe bond lengths and bond angles and thus themagnitude of the antiferromagnetic superexchange interaction are found to systematically change with the ionic radius of Ln such that T-N increases with increasing radius. Only the CeFe2/3Mo1/3O3 compound experiences a low temperature spin reorientation from alignment along the b axis to the a axis.

The effects of Co2+ doping on the structural, magnetic and dielectric properties of the multiferroic frustrated antiferromagnet Mn3TeO6 have been investigated. Ceramic samples of the solid solution series Mn3-xCoxTeO6 were prepared by a solid-state reaction route. X-ray and neutron powder diffraction and electron microscopy techniques were combined with calorimetric, dielectric and magnetic measurements to investigate the dependence of the crystal structure and physical properties on temperature and composition. It is shown that the compounds with x <= 2.4 adopt the trigonal corundum-related structure of pure Mn3TeO6 (space group 18) in the temperature range 5-295 K and that the lattice parameters a and c and the unit-cell volume V decrease linearly with increasing Co2+ concentration. The low-temperature magnetic susceptibility and heat capacity data evidence the antiferromagnetic ordering of all samples. The Neel temperature linearly increases with Co2+ concentration x. Curie-Weiss fits of the high temperature susceptibility indicate that the magnetic frustration decreases with x. The derived magnetic structure of Mn3TeO6 can be described as an incommensurately modulated magnetic spin state with k = [0, 0, k(z)] and an elliptical spin-spiral order of spins within the chains of MnO6 octahedra. With increasing Co2+ concentration the propagation vector kz changes from 0.453 (x = 0) to 0.516 (x = 2.4). The magnetic anisotropy changes as well, leading to a reorientation of the spiral-basal plane. A possible coexistence of long-range order of electrical dipoles and magnetic moments in Mn3-xCoxTeO6 is discussed.

The complex metal oxides Ni2InSbO6 (NISO) and Ni2ScSbO6 (NSSO) have been prepared in the form of polycrystalline powders by a solid state reaction route. The crystal structure and magnetic properties of the compounds were investigated using a combination of X-ray and neutron powder diffraction, electron microscopy, calorimetric, and magnetic measurements. The compounds adopt a trigonal structure, space group R3, of the corundum related Ni3TeO6 (NTO) type. Only one of the octahedral Ni positions (Ni(2)) of the NTO structure was found to be occupied by In (Sc). NTO has noncentrosymmetric structure and is ferroelectric below 1000 K; dielectric and second harmonic measurements suggest that also NISO and NSSO are correspondingly ferroelectric. Magnetization measurements signified antiferromagnetic ordering below T-N = 60 K (NSSO) and 76 K (NISO). The magnetic structure is formed by two antiferromagnetically coupled incommensurate helices with the spiral axis along the b-axis and propagation vector k = [0, k(y),0] with k(y) = 0.036(1) (NSSO) and k(y) = 0.029(1) (NISO). The observed structural and magnetic properties of NISO and NSSO are discussed and compared with those of NTO.

Mn(3)TeO(6) exhibits a corundum-related A(3)TeO(6) structure and a complex magnetic structure involving two magnetic orbits for the Mn atoms [Ivanov et al., 2011 [3]]. Mn(3-x)Cd(x)TeO(6) (x = 0, 1, 1.5, and 2) ceramics were synthesized by solid state reaction and investigated using X-ray powder diffraction, electron microscopy, and calorimetric and magnetic measurements. Cd(2+) replaces Mn(2+) cations without greatly affecting the structure of the compound. The Mn and Cd cations were found to be randomly distributed over the A-site. Magnetization measurements indicated that the samples order antiferromagnetically at low temperature with a transition temperature that decreases with increasing Cd doping. The nuclear and magnetic structure of one specially prepared (114)Cd containing sample: Mn(1.5) (114)Cd(1.5)TeO(6), was studied using neutron powder diffraction over the temperature range 2-295 K. Mn(1.5) (114)Cd(1.5)TeO(6) was found to order in an incommensurate helical magnetic structure, very similar to that of Mn(3)TeO(6) [Ivanov et al., 2011 [3]]. However, with a lower transition temperature and the extension of the ordered structure confined to order 240(10) angstrom.

A complex magnetic order of the multiferroic compound Co(3)TeO(6) has been revealed by neutron powder diffraction studies on ceramics and crushed single crystals. The compound adopts a monoclinic structure (s.g. C2/c) in the studied temperature range 2-300 K but exhibits successive antiferromagnetic transitions at low temperature. Incommensurate antiferromagnetic order with the propagation vector k(1) = (0, 0.485, 0.055) sets in at 26 K. A transition to a second antiferromagnetic structure with k(2) = (0, 0, 0) takes place at 21.1 K. Moreover, a transition to a commensurate antiferromagnetic structure with k(3) = (0, 0.5, 0.25) occurs at 17.4 K. The magnetic structures have been determined by neutron powder diffraction using group theory analysis as a preliminary tool. Different coordinations of the Co(2+) ions involved in the low-symmetry C2/c structure of Co(3)TeO(6) render the exchange-interaction network very complex by itself. The observed magnetic phase transformations are interpreted as an evidence of competing magnetic interactions. The temperature dependent changes in the magnetic structure, derived from refinements of high-resolution neutron data, are discussed and possible mechanisms connected with the spin reorientations are described.

Solid solutions of (1−x)LaFeO3–(x)PbTiO3 (0 < x < 1) have been prepared by conventional solid-state reaction. These complex perovskites have been studied by means of X-ray (XRPD) and neutron powder (NPD) diffraction, complemented with dielectric, magnetic, heat capacity and Mössbauer measurements. Complete solubility in the perovskite series was demonstrated. The NPD and XRPD patterns were successfully refined as orthorhombic (x ≤ 0.7) and tetragonal (x ≥ 0.8). A composition-driven phase transformation occurs within the interval 0.7 < x < 0.8. The samples with x < 0.5 showed evidence of long-range magnetic ordering with an G-type antiferromagnetic arrangement of the magnetic moments of the Fe3+ cations in the B-site with propagation vector k = (0,0,0). Based on the obtained experimental data, a combined structural and magnetic phase diagram has been constructed. The factors governing the structural, dielectric and magnetic properties of (1−x)LaFeO3–(x)PbTiO3 solid solutions are discussed, as well as their possible multiferroicity.

We have investigated the structural and magnetic properties of antiferroelectric A(2)CoTeO(6) perovskites with A = Cd, Ca, Sr, Pb, and Ba. All compounds are antiferromagnetic at low temperatures, with the antiferromagnetic transition temperature slightly decreasing with decreasing ionic size of the A cation. Such a decrease in antiferromagnetic interaction is not observed in A(2)(2+)CoM(6+)O(6) materials with other M6+ cations of similar ionic sizes, suggesting that Te6+ cations affect the electronic and in turn the magnetic structure of the system.

The complex metal oxide Mn(3)TeO(6) exhibits a corundum related structure and has been prepared both in forms of single crystals by chemical transport reactions and of polycrystalline powders by a solid state reaction route. The crystal structure and magnetic properties have been investigated using a combination of X-ray and neutron powder diffraction, electron microscopy, calorimetric and magnetic measurements. At room temperature this compound adopts a trigonal structure, space group R (3) over bar with a = 8.8679(1) angstrom. c = 10.6727(2) angstrom. A long-range magnetically ordered state is identified below 23 K. An unexpected feature of this magnetic structure is several types of Mn-chains. Under the action of the incommensurate magnetic propagation vector k = [0, 0, 0.4302(1)] the unique Mn site is split into two magnetically different orbits. One orbit forms a perfect helix with the spiral axis along the c-axis while the other orbit has a sine wave character along the c-axis.

The complex metal oxides Mn(2)ASbO(6) (A = In, Sc) with a corundum-related structure A(3)BO(6) were prepared as polycrystalline powders by a solid-state reaction route. Their crystal structure and magnetic properties were investigated by using a combination of X-ray and neutron powder diffraction, electron microscopy, calorimetric, and magnetic measurements. At room temperature, these compounds adopt a trigonal structure, space group R (3) over bar, with a = 8.9313(1) angstrom, c = 10.7071(2) angstrom (for In) and a = 8.8836(1) angstrom, c = 10.6168(2) angstrom (for Sc), which persists down to 1.6 K. The Mn and A cations were found to be randomly distributed over the A sites. The overall behavior of the magnetization of Mn(2)InSbO(6) and that of Mn(2)ScSbO(6) are quite similar. In spite of the relatively large amount of Mn ions on the A site, only short-range magnetism is observed. Neutron diffraction patterns of Mn(2)InSbO(6) showed no evidence of a long-range magnetic ordering at 1.6 K, instead only a weak diffuse magnetic peak was observed at low temperatures. The factors governing the observed structural and magnetic properties of Mn(2)ASbO(6) are discussed and compared with those of other Mn-containing complex metal oxides with a corundum-related structure. The influence of the A cation sublattice on the magnetic properties is also considered.

The perovskite (Bi0.5Pb0.5)(Fe0.5Zr0.5)O3 was synthesized by solid-state reaction in an attempt to find magnetoelectric materials, in which ferroelectricity and ferromagnetism coexist. This complex perovskite has been studied by X-ray and neutron powder diffraction in combination with magnetic measurements. The compound crystallizes in the orthorhombic space group Pbam with a √2ap, b 2√2ap and c 2ap (with ap 4.057 Å). The field and temperature dependence of the magnetization combined with neutron diffraction data showed antiferromagnetic behavior with the Neel temperature, TN 450 K. Rietveld refinements of neutron powder diffraction data collected at different temperatures, between 10 and 700 K, have been carried out in order to extract information about the thermal evolution of the nuclear and magnetic structures. A distorted orthorhombic perovskite structure was found within the whole temperature interval. The Bi/Pb and Fe/Zr ions were found to be partially ordered over the perovskite A-site and disordered over the B-site. The neutron diffraction patterns of the (Bi0.5Pb0.5)(Fe0.5Zr0.5)O3 sample showed evidence of a long-range magnetic ordering below TN with a propagation vector k = (0,0,0) and an antiferromagnetic arrangement of the magnetic moments of the Fe3+ cations in the B-site. This is consistent with an Ay-type magnetic structure. The factors governing the structural and magnetic properties of (1 − x)BiFeO3–xPbZrO3 solid solutions are discussed and compared with those of pure BiFeO3 and PbZrO3. A solid solution strategy for developing magnetoelectric properties in BiFeO3-based compounds is described, with th

The complex perovskite Ba2CoTeO6 (BCTO) has been synthesised, and the crystal structure and magnetic properties have been investigated using a combination of X-ray and neutron powder diffraction, electron microscopy and dielectric, calorimetric and magnetic measurements. It is shown that at room temperature this compound adopts the 6L-trigonal perovskite structure, space group P (3) over barm (s.g. 164) (a = 5.7996(1) angstrom, c = 14.2658(3) angstrom). The structure comprises dimers of face-sharing octahedra as well as octahedra which share only vertices with their neighbours. Dielectric measurements indicate a diffuse transition of antiferroelectric nature near 280 K. A long-range antiferromagnetically ordered state has been identified from neutron diffraction and magnetic studies. The magnetic diffraction peaks were registered below the magnetic transition at about 15 K and a possible model for the magnetic structure is proposed. The structural and magnetic features of this compound are discussed and compared with those of other Co-based quaternary oxides adopting the perovskite structure.

The complex perovskite Pb2CoTeO6 (PCTO) has been prepared as polycrystalline powders by a solid state reaction route, and the crystal structure and magnetic properties have been investigated using a combination of X-ray and neutron powder diffraction, electron microscopy, dielectric, calorimetric and magnetic measurements. It was shown that at room temperature this compound adopts a trigonal perovskite structure, space group R (3) over bar (a = 5.6782(1) angstrom, c = 13.8552(3) angstrom). The compound undergoes a number of temperature-induced phase transitions and adopts four different structures in the temperature range 5 500 K: monoclinic in P2(1)/n (5 < T < 125 K, tilt system (a(+)b(-)b(-))), monoclinic in I2/m (125 < T < 210 K, tilt system (a(0)b(-)b(-))), rhombohedral in R (3) over bar (210 < T < 370 K, tilt system (a(-)a(-)a(-))), and finally cubic in Fm (3) over barm (above 370 K without any tilting). These structural phase transitions are coupled to changes in the dielectric constant and the heat capacity around 210 and 370 K. A long-range antiferromagnetically ordered state has been identified from neutron powder diffraction and magnetic studies at different temperatures. Magnetic diffraction peaks were registered below the transition at about 16 K and a possible model for the magnetic structure is proposed. Possible coexistence of long-range ordering of the electrical dipoles and the magnetic moments at low temperatures making PCTO a potential multiferroic candidate is discussed.

The structural and magnetic properties of the perovskite Sr2MnSbO6 have been studied. Combining neutron and X-ray powder diffraction data, the temperature evolution of the structural parameters was investigated with the Rietveld method between 2 and 1000 K. The crystal structure is tetragonal (space group I4/m) within the temperature interval of 2–750 K and cubic (space group Fm-3m) above 750 K. Both octahedral B-site positions were found to be partially occupied by Mn and Sb, but with different Mn/Sb ratios. The magnetic susceptibilities showed irreversibility between field cooled and zero-field cooled (ZFC) conditions and spin glass like magnetic dynamics including aging and memory phenomena at temperatures below 30 K; all appearing well above a broad maximum at 13 K in the ZFC susceptibility curves. This suggests that the material reaches an unconventional spin-glass state at low temperatures, possibly arising from a competitive situation between the double exchange (ferromagnetism) and the super-exchange (antiferromagnetism). Neutron diffraction patterns showed no evidence of a long-range magnetic ordering at 2 K which is consistent with spin glass behavior. The factors governing the observed structural and magnetic properties of Sr2MnSbO6 are discussed and compared with those of other quaternary Mn- and Sb-containing perovskites. Graphs of the temperature of magnetic phase transitions as functions of the cation size were constructed and are discussed for the AB3+1/2B5+1/2O3 series with isomorphous substitution of B3+ and B5+ cations. Possible influence of the A-cation sublattice on magnetic properties is also shortly considered.

The structural and magnetic properties of the complex metal oxides Pb(Mn1/2Nb1/2)O3 (PMNO) and Pb(Mn1/4Fe1/4Nb1/2)O3 (PMFNO), which belong to a class of disordered perovskites have been studied. The magnetic susceptibilities of PMNO showed hysteresis between field cooled and zero-field cooled conditions below the transition of 15 K, suggesting that the material has a spin-glass feature. Neutron diffraction patterns of PMNO showed no evidence of a long-range magnetic ordering at 1.5 K, which is consistent with spin-glass behavior. Rietveld refinements of neutron powder diffraction data collected at different temperatures between 1.5 and 700 K have been carried out in order to extract structural information. The crystal structure of this compound is cubic (space group Pmm) within the whole temperature interval. The Mn and Nb ions were found to be disordered over the perovskite B-sites. The main feature of this structure is the positional disorder at the Pb site, the importance of which in connection with the ferroic transitions is briefly discussed. The Pb cations show a positional disorder shifting from their high-symmetry positions along the [1 1 1] direction. The effect of Fe-doping on PMNO has been studied. The substitution of Fe at the Mn site in PMFNO results in a small changes of the magnetic properties without significant differences in the crystal structures. The factors governing the observed structural and magnetic properties of PMNO and PMFNO are discussed and compared with those of other quaternary Mn-containing perovskites. For the PbB3+1/2Nb1/2O3 series with the isomorphous substitution B3+, graphs of average lattice parameters of the perovskite phase and the temperatures of ferroelectric and magnetic phase transitions as functions of the B3+ cation radius were constructed and are discussed. Influence of A-cation sublattice on magnetic properties is als

Solid solutions of the perovskites (1 - x)BiFeO3-xPbZrO3 with x ranging from 0 to 0.2 were synthesized by solid-state reaction in an attempt to find magnetoelectric materials, in which ferroelectricity and ferromagnetism coexist. These complex perovskites have been studied by X-ray and neutron powder diffractions, magnetic and Mössbauer spectroscopic measurements. All samples are single phase with rhombohedrally distorted perovskite structure. The field and temperature dependences of the magnetization of (1 - x)BiFeO3-xPbZrO3 samples showed antiferromagnetic behavior with Neel temperatures, TN = 635 K (x = 0.1) and 500 K (x = 0.2); a weak ferromagnetic moment appeared at TN in both samples reaching about 0.01 μB/Fe at low temperature for the x = 0.1 sample. Mössbauer spectra also support the existence of the magnetic order and are consistent with the presence of high-spin Fe3+ cations located in the octahedral B-site position. Rietveld refinements of neutron powder diffraction data collected at different temperatures, between 10 and 700 K, have been carried out. The structure of these compounds is a rhombohedrally distorted perovskite (space group R3c) within the whole temperature interval. The Bi/Pb and Fe/Zr ions were found to be disordered over the perovskite A- and B-sites, respectively. Neutron diffraction patterns showed evidence of a long-range magnetic ordering below TN with a G-type antiferromagnetic arrangement of the magnetic moments of Fe3+ cations in the B-site. The effect of PbZrO3 doping on BiFeO3 results in a noticeable lattice expansion and a significant decrease of TN. The factors governing the observed structural and magnetic properties of (1 - x)BiFeO3-xPbZrO3 are discussed and compared with those of pure BiFeO3.

Perovskite oxides with the composition La1−xNdxFe0.5Cr0.5O3 (x = 0.10, 0.15 and 0.20) have been studied. The samples have been prepared using the standard solid-state reaction method in air. The X-ray and neutron diffractograms indicates that the samples crystallize in the orthorhombic perovskite structure with space group Pnma (No. 62). The Nd-substitution causes minor changes in the cell parameters and bond lengths but the nuclear structure remains orthorhombic in the whole range of substitutions and in the temperature range of 10–700 K. The magnetic structure of the samples at room temperature and below is G-type antiferromagnetic with an average magnetic moment of the Fe/Cr ions of 3.29(3) μB/atom at 10 K independent of the Nd content. At room temperature the average magnetic moment of the Fe/Cr ions reduces to 1.23 μB/atom. At temperatures below 250 K a weak but increasing uncompensated spontaneous magnetic moment develops that reaches a magnitude of about 0.5 emu/g (or 0.02 μB per Fe/Cr site) at 10 K. This moment saturates rather rapidly in the magnetization versus magnetic field curve and is at higher field superposed on the response of the antiferromagnetic spin system.

A study of the crystallographic and magnetic structures of the double perovskite Sr3Fe2TeO9 has been carried out on a polycrystalline sample using neutron powder diffraction (NPD) data between 10 and 650 K. An analysis of the NPD patterns at room temperature has shown that this compound crystallises in the tetragonal space group I4/m with a = 5.5614(7) Å and c = 7.867(1) Å and has a partially ordered arrangement of Fe and Te at the B-sites. The compound undergoes an I4/m → Fm-3m improper ferroelectric phase transition near 460 K. A low-temperature ferrimagnetic ordering (below TN = 260 K) has been followed from the magnetisation measurements and sequential NPD data analysis. In good agreement with magnetic measurements the ferrimagnetic structure with very weak magnetisation is defined by the propagation vector k = (0, 0, 0). In addition to the obtained experimental results on magnetic and electric properties some aspects of magnetoelectricity in this perovskite are also discussed and compared with those of another quaternary oxide Sr3Fe2B6+O9.

The complex perovskite lead iron tungsten niobium oxide, Pb(Fe0.6W0.2Nb0.2)O3 (PFWN) which belongs to the class of disordered magnetoelectrics, has been studied by X-ray and neutron powder diffraction, magnetic and Mössbauer spectroscopic measurements. Structural, dielectric and magnetic properties of PFWN are presented and reviewed. Magnetic measurements indicate that the most important interactions are of antiferromagnetic nature yielding TN = 300 K, however, with indications of a reentrant spin glass behaviour below 20 K. The parameters of Mössbauer spectra also support the existence of the magnetic order and are consistent with the presence of high-spin Fe3+ cations located in the octahedral B-site. Rietveld refinements of diffraction data at different temperatures between 10 and 700 K have been carried out. The long-range structure of PFWN is cubic (space group Pm−3m) over the whole temperature interval. The Fe, W and Nb cations were found to be disordered over the perovskite B-sites. The Pb cations show a position disorder along the 111 direction shifting from their high-symmetry position. At the temperatures below TN, an antiferromagnetic arrangement of the magnetic moments of Fe3+ cations in the B-site is proposed in accordance with the antiferromagnetic properties of PFWN. The factors governing the observed nuclear and magnetic structures of PFWN are discussed and compared with those of pure Pb(Fe0.67W0.33)O3, Pb(Fe0.5Nb0.5)O3 and other quaternary Pb-based perovskites containing iron.

The magnetic and structural properties of oxygen-deficient perovskites with composition Ba3Fe2WO9-6 (BFWO) have been systematically studied for two different oxygen contents corresponding to delta = 0.00 and 0.55 in the chemical formula in order, to determine and correlate their chemical composition, structural and magnetic properties. The evolution of nuclear and magnetic structures with temperature has been investigated by neutron powder diffraction. It was shown that at room temperature the stoichiometric compound (delta = 0.00) adopts a hexagonal 6H-perovskite structure (space group P6(3)/mmc). This phase, when heated at high temperature under a stream of Ar gas, transforms to an oxygen-deficient phase delta = 0.55), which is an ordered cubic perovskite structure (space group Fm-3m). The crystallographic and magnetic properties of the obtained phases are compared, and it is clear that the magnetic properties are significantly affected by oxygen non-stoichiometry. These changes of magnetic properties for such a slight decrease in oxygen content are interpreted as a result of structural transformations. Together with the experimental results based on neutron powder diffraction data a discussion of some aspects of the structural transformation (P6(3)/mmc -> Fm-3m) is presented.

A new compound, IrMnSi, has been synthesized, and its crystal structure and magnetic properties have been investigated by means of neutron powder diffraction, magnetization measurements, and first-principles theory. The crystal structure is found to be of the TiNiSi type (ordered Co2P, space group Pnma). The Mn-projected electronic states are situated at the Fermi level, giving rise to metallic binding, whereas a certain degree of covalent character is observed for the chemical bond between the Ir and Si atoms. A cycloidal, i.e., noncollinear, magnetic structure was observed below 460 K, with the propagation vector q=[0,0,0.4530(5)] at 10 K. The magnetism is dominated by large moments on the Mn sites, 3.8μB∕atom from neutron diffraction. First-principles theory reproduces the propagation vector of the experimental magnetic structure as well as the angles between the Mn moments. The calculations further result in a magnetic moment of 3.2μB for the Mn atoms, whereas the Ir and Si moments are negligible, in agreement with observations. A calculation that more directly incorporates electron-electron interactions improves the agreement between the theoretical and experimental magnetic moments. A band mechanism is suggested to explain the observed magnetic order.

Effects of magnesium substitution on the magnetic properties of Nd0.7Sr0.3MnO3 have been investigated by neutron powder diffraction and magnetization measurements on polycrystalline samples of composition Nd0.7Sr0.3MnO3, Nd0.6Mg0.1Sr0.3MnO3, Nd0.6Mg0.1Sr0.3Mn0.9Mg0.1O3, and Nd0.6Mg0.1Sr0.3Mn0.8Mg0.2O3. The pristine compound Nd0.7Sr0.3MnO3 is ferromagnetic with a transition temperature occurring at about 210 K. Increasing the Mg-substitution causes weakened ferromagnetic interaction and a great reduction in the magnetic moment of Mn. The Rietveld analyses of the neutron powder diffraction (NPD) data at 1.5 K for the samples with Mg concentration, y=0.0 and 0.1, show ferromagnetic Mn moments of 3.44(4) and 3.14(4) μB, respectively, which order along the [001] direction. Below 20 K the Mn moments of these samples become canted giving an antiferromagnetic component along the [010] direction of about 0.4 μB at 1.5 K. The analyses also show ferromagnetic polarization along [001] of the Nd moments below 50 K, with a magnitude of almost 1 μB at 1.5 K for both samples. In the samples with Mg substitution of 0.2 and 0.3 only short range magnetic order occurs and the magnitude of the ferromagnetic Mn moments is about 1.6 μB at 1.5 K for both samples. Furthermore, the low-temperature NPD patterns show an additional very broad and diffuse feature resulting from short range antiferromagnetic ordering of the Nd moments.

A detailed neutron powder diffraction and calorimetric study was conducted to determine the influence of increasing Mn-substitution on the crystal and the magnetic structures of hematite, α-Fe2O3. The study was initiated to determine, if Mn substitution may be responsible for unusual ferromagnetic properties of natural hematite samples from the Kalahari Mn field, South Africa. Natural as well as synthetic Mn-bearing hematite samples with the compositional range Fe2−xMnxO3 (x=0 to 0.176) were examined. Calorimetric measurements were performed to determine the Néel TN and the Morin TM temperature transitions. All studied hematite samples, irrespective of chemical composition, display weak ferromagnetism at 295 K and coexistence of weak ferromagnetic and antiferromagnetic phases at 10 K. A slight decrease of the total magnetic moment and TM but a drastic decrease of TN can be attributed to increasing Mn-substitution. The results illustrate that Mn substitution may contribute but cannot be the sole reason for the unusual magnetic properties of natural hematite samples.

A study of the crystallographic and magnetic structure of the double perovskite Sr2CoMoO6 (SCMO) has been carried out on a polycrystalline sample using neutron powder diffraction (NPD) data between 10 and 700 K. An analysis of the NPD patterns at room temperature has shown that this compound crystallises in the tetragonal space group I4/m with a = 5.5616(1) Å and c = 7.9470(2) Å and has a 1:1 ordered arrangement of Co and Mo at the B-sites. This compound undergoes a I4/m → Fm3m improper ferroelectric phase transition near 560 K. A low-temperature antiferromagnetic ordering (below TN = 36 K) has been followed from sequential NPD data analysis. The antiferromagnetic structure is defined by the propagation vector k = (1/2, 0, 1/2). In addition to the obtained experimental results on magnetic and electric properties some aspects of magnetoelectricity in this perovskite are also discussed.

A complex perovskite with composition Ca3Fe2WO9 has been synthesised, and the temperature evolution of nuclear and magnetic structures investigated by neutron powder diffraction. It was shown that at room temperature this compound adopts a monoclinic perovskite structure belonging to space group P121/n1 (, , ), β=90.04(2)°). The partial B-site ordering, of the Fe+3 and W+6 cations, at (2c) and (2d) sites was determined. At low temperatures the magnetic diffraction peaks were registered and a possible model for the magnetic structure was proposed in accordance with the ferrimagnetic properties of the title compound. The magnetic structure is defined by a propagation vector k=(1/2,1/2,0) and can be described as an array of ferromagnetic (20−1) layers, which couple antiferromagnetically to each other. All the Fe moments within a layer are aligned parallel (or anti-parallel) to the c-axis. The structural and magnetic features of this compound are discussed and compared with those of some other quaternary oxides A3Fe2WO9 (A=Ba, Sr, Pb).

Magnesium substitution in Nd0.7Sr0.3MnO3 has been studied by neutron powder diffraction. Polycrystalline samples of nominal compositions Nd0.7Sr0.3Mn1−yMgyO3 with y=0.0, 0.1, 0.2 and 0.3 were synthesized by the standard solid-state reaction method. Rietveld refinements of the neutron powder diffraction data showed that all samples had distorted perovskite structure of orthorhombic symmetry. Mg initially preferred to substitute for Nd and only at Mg concentration greater than 0.1, a substantial substitution for Mn occurred. Our study also showed that Mg-substitution did not change the crystal structure of Nd0.7Sr0.3MnO3.

The complex perovskite with composition Ba3Fe2WO9 (BFWO) has been synthesised, and the evolution of nuclear and magnetic structures with temperature has been investigated by neutron powder diffraction. It was shown that at room temperature this compound adopts the 6H-perovskite structure, space group P63/mmc (a=5.7584(2) Å, c=14.1019(9) Å), in which the cation sites within the face-sharing octahedra are occupied by Fe and W cations and those within the corner-sharing octahedra are occupied by Fe exclusively. The magnetic diffraction peaks were registered at low temperatures and a possible model for the magnetic structure was proposed in accordance with the ferrimagnetic properties of BFWO. The magnetic structure can be described as an array of ferromagnetic layers of Fe moments along the c-axis, and adjacent layers coupled antiferromagnetically. Structural and magnetic features of this compound are discussed and compared with those of other quaternary oxides adopting the 6H-perovskite structure.

The structural properties of complex perovskite lead iron tungstate, Pb(Fe2/3W1/3)O3 (PFW) which belongs to a class off disordered magnetoelectrics has been studied by neutron powder diffraction. Rietveld refinement of neutron powder diffraction data collected at different temperatures, between 10 and 700 K, have been carried out in order to extract structural information. The long-range structure of PFW is a cubic one (space group Pmm) within the whole temperature interval. The PFW sample demonstrated very low thermal expansion at lower temperatures. The iron and tungsten ions were found to be disordered over the perovskite B-sites. Pb cations show a position disorder shifting from their high-symmetry positions along the [1 1 1] direction. Furthermore, in order to obtain a good agreement with experiment at low temperatures, below TN, it was necessary to assign non-zero magnetic moments to the iron ions, these being in a co-linear antiferromagnetic arrangement in accordance with the antiferroelectric properties of PFW. The magnetic structure can be described with a doubling of the unit cell axes. The factors governing the observed nuclear and magnetic structures of PFW are discussed and compared with those of other quaternary iron-containing perovskites.