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We observe nonequilibrium dynamical magnetic behavior in the magnetically ordered phase of a Tsai-type Tb-Au-Si quasicrystal approximant system. The magnetic texture in the ordered phase is found to exhibit scalar spin chirality (SSC) order, inferring that SSC is the order parameter of the present magnetic system. We further find that the introduction of “pseudo-Tsai” clusters, associated with additional Tb atoms in the structure, induces spin-glass dynamics. We discuss the observed dynamical magnetic behavior in the Tb-Au-Si systems, considering the effect of the pseudo-Tsai clusters on the magnetic configuration and local spin chirality.

Dense systems of magnetic nanoparticles may exhibit dipolar collective behavior. However, two fundamental questions remain unsolved: i) whether the transition temperature may be affected by the particle anisotropy or it is essentially determined by the intensity of the interparticle dipolar interactions, and ii) what is the minimum ratio of dipole-dipole interaction (E-dd) to nanoparticle anisotropy (KefV, anisotropy.volume) energies necessary to crossover from individual to collective behavior. A series of particle assemblies with similarly intense dipolar interactions but widely varying anisotropy is studied. The K-ef is tuned through different degrees of cobalt-doping in maghemite nanoparticles, resulting in a variation of nearly an order of magnitude. All the bare particle compacts display collective behavior, except the one made with the highest anisotropy particles, which presents "marginal" features. Thus, a threshold of KefV/E-dd approximate to 130 to suppress collective behavior is derived, in good agreement with Monte Carlo simulations. This translates into a crossover value of approximate to 1.7 for the easily accessible parameter T-MAX(interacting)/T-MAX(non-interacting) (ratio of the peak temperatures of the zero-field-cooled magnetization curves of interacting and dilute particle systems), which is successfully tested against the literature to predict the individual-like/collective behavior of any given interacting particle assembly comprising relatively uniform particles.

In cluster-based quasicrystals, tetrahedra located in conventional Tsai clusters may be replaced by single rare-earth (R) ions at the cluster centers (pseudo-Tsai clusters). In this study, we investigate the effect of the pseudo-Tsai cluster incorporation on the magnetic structures of two approximants, the Tsai-type Tb-Au-Si [denoted TAS(0)] and Ho-Au-Si [denoted HAS(52)] with partial replacement of conventional Tsai clusters by pseudo-Tsai clusters, up to 52%. The mixture of Tsai and pseudo-Tsai clusters can be considered a different source of randomness/disorder other than the conventional chemical mix sites (Au/Si). The effect of the latter has been previously discussed regarding the origin/cause of spin-glass-like ordering and Anderson localization of electronic states in quasicrystals and approximant crystals. Single crystal neutron diffraction experiments at 2 K were performed and bulk physical properties (magnetization and specific heat) were investigated. In addition, earlier collected powder neutron diffraction data of TAS(14) with 14% replacement was reanalyzed in light of the results on TAS(0) and HAS(52). We find that the arrangement of ordered magnetic spins in the icosahedral shells of these phases is similar, while the cluster-center R magnetic states are different. In the case of TAS(14), the cluster-center Tb magnetic moments seem to affect the arrangement of surrounding icosahedral magnetic moments, and the magnetic structure of the icosahedral shell deviates from that of TAS(0). In the case of HAS(52), however, the icosahedral R magnetic moments are less affected by the cluster-center R, while the averaged cluster-center R magnetic moments are significantly diminished. We discuss these results considering the magnetic ordering effect on the bulk physical properties.

We investigate the critical behavior and magnetocaloric effects of the Gd-Au-Si (GAS) ferromagnetic quasicrystal approximants, Gd13.7Au72.7Si13.6 [referred to as GAS(0)] and Gd15.4Au68.6Si16.0 [GAS(100)]. The former is a conventional Tsai-type 1/1 approximant crystal, while the latter has a slightly different atomic decoration from the Tsai type (thus referred to as “pseudo-Tsai” type). Their critical exponents at the ferromagnetic transitions are close to those of the mean-field theory. Both GAS systems exhibit an interesting magnetic-field dependence of the specific heat, which is reflected in the behavior of their magnetocaloric effect (MCE). The MCE is characterized by an adiabatic cooling (heating) effect over a relatively broad temperature range below ∼30 K, which stems from a broad feature in the specific heat.

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.

Solid solutions of La0.75Bi0.25Fe1−xCrxO3 (x = 0.1, 0.25, 0.5, and 0.75) prepared by conventional solid state reaction have been studied by means of X-ray powder diffraction (XRPD), neutron powder diffraction (NPD) and magnetic measurements. The NPD and XRPD patterns indicate orthorhombic structure (space group Pnma) for all compositions in the whole temperature range investigated (4–900 K). The lattice parameters of La0.75Bi0.25Fe1−xCrxO3 were found to decrease with the Cr content. It was established that the Fe3+ and Cr3+ cations are randomly positioned at the B-site of the perovskite structure. All samples order antiferromagnetically below transition temperatures that decrease with increasing Cr content, from around 700 K for x = 0.1 to about 300 K for x = 0.75. The antiferromagnetic arrangement of the Fe3+/Cr3+ magnetic moments in the B-site is of G-type along the x-axis (Gx mode) with propagation vector k = (0,0,0) for all concentrations of Cr. Effects of the composition on several structural distortion parameters were investigated and an anomalous variation of the octahedral deformation with Cr content was found. Whilst the overall octahedral deformation varies irregularly with increasing Cr content, the octahedral tilting was found to decrease monotoneously.

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.

A novel synthesis method, "arc-melting-self-flux", has been developed and a series of five Tsai-type 1/1 approximant crystals in the Tb-Au-Si system have been synthesized. The synthesis method, by employing a temperature program which oscillates near the melting and nucleation points of the approximants, has provided high-quality and large single crystals in comparison to those obtained from the standard arc-melting-annealing and self-flux methods. The atomic structures of the approximants have been determined from single-crystal X-ray diffraction data and described using concentric atomic clusters with icosahedral symmetry. The compounds are nearly isostructural with subtle variations; two types of atomic clusters which mainly vary at their cluster centers are observed. One type contains a Tb site at the center, and the other contains a disordered tetrahedron decorated with Au/Si mixed sites. Both cluster types can be found coexisting in the approximants. The compounds have different average weighted ratios of central Tb to disordered tetrahedron in the bulk material. Furthermore, a strategy for chemically tuning magnetic behavior is presented. Magnetic property measurements on the approximants revealed that the magnetic transition temperature (T-c) decreases as the occupancy of the central Tb site increases. T-c decreased from 11.5 K for 0% occupancy of the central Tb to 8 K for 100% occupancy. Enhanced magneto crystalline anisotropy is observed for the approximants with higher central Tb occupancy in comparison to their low central Tb occupancy counterparts. Hence, the previously reported "ferrimagnetic-like" magnetic structure model remains valid.

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 atomic and magnetic structure of the 1/1 Tb(14)Au(70)Si(16) quasicrystal approximant has been solved by combining x-ray and neutron diffraction data. The atomic structure is classified as a Tsai-type 1/1 approximant with certain structural deviations from the prototype structures; there are additional atomic positions in the so-called cubic interstices as well as in the cluster centers. The magnetic property and neutron diffraction measurements indicate the magnetic structure to be ferrimagnetic-like below 9Â K in contrast to the related Gd(14)Au(70)Si(16) structure that is reported to be purely ferromagnetic.

Magnetic and magnetocaloric properties of high-purity, giant magnetocaloric polycrystalline and single-crystalline Fe2P are investigated. Fe2P displays a moderate magnetic entropy change, which spans over 70 K and the presence of strong magnetization anisotropy proves this system is not fully itinerant but displays a mix of itinerant and localized magnetism. The properties of pure Fe2P are compared to those of giant magnetocaloric (Fe,Mn)2(P,A) (where A = As, Ge, Si) compounds helping understand the exceptional characteristics shown by the latter, which are so promising for heat pump and energy conversion applications.

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 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 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.

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.