J. A. Rodríguez-Velamazán

Effect of atomic order on the martensitic and magnetic transformations in Ni-Mn-Ga ferromagnetic shape memory alloys

The influence of long-range L2(1) atomic order on the martensitic and magnetic transformations of Ni-Mn-Ga shape memory alloys has been investigated. In order to correlate the structural and magnetic transformation temperatures with the atomic order, calorimetric, magnetic and neutron diffraction measurements have been performed on polycrystalline and single-crystalline alloys subjected to different thermal treatments. It is found that both transformation temperatures increase with increasing atomic order, showing exactly the same linear dependence on the degree of L2(1) atomic order. A quantitative correlation between atomic order and transformation temperatures has been established, from which the effect of atomic order on the relative stability between the structural phases has been quantified. On the other hand, the kinetics of the post-quench ordering process taking place in these alloys has been studied. It is shown that the activation energy of the ordering process agrees quite well with the activation energy of the Mn self-diffusion process.

Enhancement of ferromagnetic correlations on multiferroic TbMnO3 by replacing Mn with Co

The structural, electronic and magnetic properties of TbMn(1-x)Co(x)O(3) (0.1 ≤ x ≤ 0.9) compounds are reported. The samples are isostructural to TbMnO(3) adopting the orthorhombic distorted perovskite structure (Pbnm), except for x = 0.4, 0.5 and 0.6, where an ordered double perovskite structure (P2(1)/n) is found. X-ray absorption spectra at the Mn and Co K edges show an incomplete charge transfer between Mn and Co atoms yielding a mixed valence state Mn(3+)/Mn(4+) and Co(3+)/Co(2+) for the whole series. Neutron powder diffraction measurements show the development of a ferromagnetic ground state for the intermediate compositions (0.3 ≤ x ≤ 0.6) indicating that the ferromagnetic superexchange Mn(4+)-O-Co(2+) interaction is the strongest among a wide set of competitive interactions. The ferromagnetic ordering is, however, not fully achieved and coexists with glassy magnetic properties. With increasing concentration of Co (x ≥ 0.7) the long range ordering vanishes and only a glassy magnetic behavior with slow dynamics is found. These properties could be related to the existence of magnetically inhomogeneous small clusters arising from competitive magnetic interactions.

Neutron diffraction study of the BiFeO3 spin cycloid at low temperature

The reported observation of two anomalies in the intensity of the magnon Raman peaks of BiFeO₃ at 140 and 200 K (Singh et al 2008 J. Phys.: Condens. Mater 20 252203; Cazayous et al 2008 Phys. Rev. Lett. 101 037601) led to the hypothesis that such anomalies might originate from a spin reorientation transition. In order to test this hypothesis, we have used temperature-dependent neutron diffraction to track the evolution of the magnetic configuration in single crystals of BiFeO₃. Our results indicate that there is no average reorientation of the spins. This suggests that the magnon anomalies may instead be related to the freezing of modes that do not alter the average projection of the spins over the plane of the cycloid, as also reported for multiferroic TbMnO₃ (Senff et al 2006 J. Phys.: Condens. Mater 18 2069).

Structural and magnetic properties of Cr-doped Ni?Mn?In metamagnetic shape memory alloys

The effect of the partial substitution of Mn by Cr on the structural and magnetic properties of Ni–Mn–In metamagnetic shape memory alloys is investigated. It is found that a Cr-rich second phase appears for quite low Cr concentrations, pointing out a very low solubility of Cr in Ni–Mn–In. Nevertheless, the martensitic transformation (MT) temperature of the doped alloys can be related to the variation in the electron concentration in the matrix phase, just as it occurs in the ternary Ni–Mn–In system. The effect of magnetic field on the structural transformation has been evaluated on both a ternary and a quaternary alloy. It is shown that the presence of the second phase reduces the magnetically induced shift of the MT and the associated magnetocaloric effect, thus limiting the potential applicability of Ni–Mn–In alloys. The obtained results prevent the addition of high amounts of Cr to Ni–Mn–In.

Influence of Li+ and H+ Distribution on the Crystal Structure of Li7–xHxLa3Zr2O12 (0 ≤ x ≤ 5) Garnets

With appropriate doping or processing, Li7La3Zr2O12 (LLZO) is an excellent candidate to be used in Li batteries either as a solid electrolyte or as a separator between the Li anode and a liquid electrolyte. For both uses, the reactivity with water either from the air or in aqueous media is a matter of interest. We address here the structural changes undergone by LLZO as a result of H(+)/Li(+) exchange and relate them with the amount of H content and atomic distribution. Neutron diffraction is performed to elucidate Li and H location. Two different cubic phases derive from LLZO through H(+)/Li(+) exchange: Deep hydration up to 150 °C yields a noncentrosymmetric I4̅3d phase in which octahedral Li ions are exchanged by H ions, tetrahedral Li ions split into two sites with very different occupancies, and H ions form O4H4 entities around the less occupied tetrahedral site. Annealing above 300 °C results in a centrosymmetric Ia3̅d phase with lower H content in which Li ions occupy the usual sites of the cubic garnets and H ions occupy a split pseudooctahedral site. The centrosymmetric or noncentrosymmetric character is determined by the temperature at which exchange is performed and the H content. Both factors are not independent: at low temperature, the high H content favors H ordering around the vacant tetrahedra, while low H content and higher mobility at 350 °C lead to a disordered configuration of Li and H ions. The deeply hydrated garnets are stable up to at least 300 °C and also upon aging at room temperature.

The transition from ferromagnet to cluster-glass in La1−xTbxMn1/2Sc1/2O3

We report the structural and magnetic properties of the La(1-x)Tb(x)Mn(1/2)Sc(1/2)O(3) series. LaMn(1/2)Sc(1/2)O(3) shows a long range ferromagnetic ordering in agreement with a fully polarized Mn-sublattice. The substitution of La with Tb produces structural changes which affect the magnetic properties. This substitution leads to a contraction in the unit cell volume that mainly reduces the M-O-M bond angle (M = Mn, Sc). The bending of this angle decreases the Mn-O-Mn superexchange interaction and enhances the competition between nearest-neighbour and next-nearest-neighbour interactions. Accordingly, the magnetic ground state changes from ferromagnetic to a glassy magnetic state. Large thermal irreversibility between zero-field-cooled and field-cooled conditions is observed for all samples. The study of the dynamic magnetic properties has been performed using the frequency dependent real part of the ac magnetic susceptibility. The use of both the Vogel-Fulcher law and the conventional critical slowing down law yields similarly good accuracies in the fits. The relaxation times obtained from both laws concur with the existence of a cluster-glass for x ≥ 0.5 samples.

Influence of Magnetic Field on Magnetostructural Transition in Ni46.4Mn32.8Sn20.8 Heusler Alloy

A Mn-enriched Ni46.4Mn32.8Sn20.8 Heusler alloy has been prepared by the induction melting and casting method. The samples used were annealed at 900°C during 72 h with a subsequent water quench. The magnetostructural transformation (MST) in the vicinity of Tm=230K and Ta=250K has been found, and characterized by DSC, magnetization and resistivity measurements. Changes in the crystal structure due to the MST were observed using neutron diffraction at different temperatures. The crystal structure of martensitic phase shows a good fits to the 4-layered orthorhombic martensite with a Pmma space group. The linear shift of transformation temperatures was found in the entire high magnetic field range up 14T to be dTm/dB0 = -1.50 K/T and dTa/dB0 = -1.26 K/T, whereas in the low field range we found an increase of both characteristic temperatures. The entropy changes at the MST were evaluated using the Clausius-Clapeyron relationship. The transformation-induced magnetoresistance has been measured.

Low temperature neutron diffraction studies in [Mn3(suc)2(ina)2]n: an homometallic molecular 3D ferrimagnet.

Neutron diffraction techniques have been used to determine the low temperature crystal structure and to shed light on the magnetic behavior of the [Mn(3)(suc)(2)(ina)(2)](n) (suc = succinate and ina = isonicotinate) complex. The ferromagnetic signal observed below T(c) ≈ 5 K in this compound is due to a noncompensation of homometallic spins in the 3D framework. The Mn(II) magnetic moments obtained from neutron diffraction refinements are slightly lower than those observed for isolated Mn(II) ions; this can be due to covalent spin delocalization or geometrical magnetic fluctuations. A small discrepancy between the value of the magnetic moments of each Mn(II) site is also observed [Mn(1) 4.1(2) μ(B) and the Mn(2) 3.9(1) μ(B)]. These differences between the theoretical and observed manganese magnetic moments are not unexpected in this large spin metal complex, and qualitatively reasonable given the synergistic interaction between the metal ions through oxo-bridge. The competition among different interactions, principally those covalent through organic ligands and dipolar interaction, drive to a final 3D ferrimagnetic order.

Evolution of magnetoelectric properties of Sc-diluted TbMnO3

The magnetoelectric properties of the TbMn(1-x)Sc(x)O3 series have been studied at low temperatures by means of heat capacity, magnetic measurements and impedance spectroscopy. TbMnO3 exhibits as expected three transitions upon lowering the temperature corresponding to the magnetic ordering of the two sublattices (Mn and Tb) and the ferroelectric transition. Ferroelectricity disappears with Sc dilution for x > 0.1 because the non-collinear magnetic arrangement is destroyed. The dilution of Mn with a non-magnetic ion is also detrimental to the magnetic ordering of both Mn and Tb sublattices. The system evolves to a magnetic glassy state for the intermediate compositions. Formal TbScO3 shows Sc-deficiency and long range magnetic ordering of Tb(3+) moments in the ab-plane brought by the direct interaction between Tb(3+) ions. This ordering is different from the one found in TbMnO3 due to the lack of magnetic coupling between Tb- and Mn-sublattices. A small substitution of Sc by Mn in TbScO3 destroys the Tb ordering giving rise to a magnetic glass behaviour. This effect is ascribed to the partial polarization of Tb sublattice by the paramagnetic Mn which competes with the direct Tb-Tb exchange.

Evidence of large magneto-dielectric effect coupled to a metamagnetic transition in Yb2CoMnO6

The double perovskite Yb2CoMnO6 has been synthesized with an almost perfect checkerboard arrangement of Co2+ and Mn4+ cations in the B-sublattice of the perovskite cell. It presents an anomaly in the electric capacitance and a strong magneto-dielectric effect at about 40 K whose interplay with the microscopic magnetic behavior has been investigated by means of neutron diffraction, magnetization, pyroelectric, and relative dielectric permittivity measurements. We show that the onset of an E-type antiferromagnetic ordering of Co2+ and Mn4+ moments monitored by neutron diffraction provokes the noticeable jump of the relative dielectric permittivity (∼9%) at about 40 K. It is also shown that this jump can be totally suppressed by application of a magnetic field of μ0H = 5 T. Neutron experiments and magnetic measurements confirm that such a suppression leading to a significant magneto-dielectric effect is driven by a metamagnetic phase transition from the peculiar E-type ordering of 3d moments into a collinear...