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Register a new userField-Induced Magnetization Steps in Intermetallic Compounds and Manganese Oxides: The Martensitic Scenario
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Field-induced magnetization jumps with similar characteristics are observed at low temperature for the intermetallic germanide Gd5Ge4and the mixed-valent manganite Pr0.6Ca0.4Mn0.96Ga0.04O3. We report that the field location -and even the existence- of these jumps depends critically on the magnetic field sweep rate used to record the data. It is proposed that, for both compounds, the martensitic character of their antiferromagnetic-to-ferromagnetic transitions is at the origin of the magnetization steps.
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X-ray amorphous manganese oxides were prepared by reduction of sodium permanganate by lithium iodide in aqueous medium (MnOx-I) and by decomposition of manganese carbonate at moderate temperature (MnOx-C). TEM showed that these materials are not amorphous, but nanostructured, with a prominent spinel substructure in MnOx-C. These materials intercalate lithium with capacities up to 200 mAh/g at first cycle (potential window 1.8-4.3 V) and 175 mAh/g at 100th cycle. Best performances for MnOx-C are obtained with cobalt doping. Potential electrochemical spectroscopy shows that the initial discharge induces a 2-phase transformation in MnOx-C phases, but not in MnOx-I ones. EXAFS and XANES confirm the participation of manganese in the redox process, with variations in local structure much smaller than in known long-range crystallized manganese oxides. X-ray absorption spectroscopy also shows that cobalt in MnOx-C is divalent and does not participate in the electrochemical reaction.
To obtain single crystals by solution growth, an exposed primary solidification surface in the appropriate, but often unknown, equilibrium alloy phase diagram is required. Furthermore, an appropriate crucible material is needed, necessary to hold the molten alloy during growth, without being attacked by it. Recently, we have used the comparison of realistic simulations with experimental differential thermal analysis (DTA) curves to address both these problems. We have found: 1) complex DTA curves can be interpreted to determine an appropriate heat treatment and starting composition for solution growth, without having to determine the underlying phase diagrams in detail. 2) DTA can facilitate identification of appropriate crucible materials. DTA can thus be used to make the procedure to obtain single crystals of a desired phase by solution growth more efficient. We will use some of the systems for which we have recently obtained single-crystalline samples using the combination of DTA and solution growth as examples. These systems are TbAl, Pr$_7$Ni$_2$Si$_5$, and YMn$_4$Al$_8$.
The electronic structure is found to be understandable in terms of free-atom term values and universal interorbital coupling parameters, since self-consistent tight-binding calculations indicate that Coulomb shifts of the d-state energies are small. Special-point averages over the bands are seen to be equivalent to treatment of local octahedral clusters. The cohesive energy per manganese for MnO, Mn2O3, and MnO2, in which manganese exists in valence states Mn2+, Mn3+, and Mn4+, is very nearly the same and dominated by the transfer of manganese s electrons to oxygen p states. There are small corrections, one eV per Mn in all cases, from couplings of minority-spin states. Transferring one majority-spin electron from an upper cluster state to a nonbonding oxygen state adds 1.67 eV to the cohesion for Mn2O3, and two transfers adds twice that for MnO2 . The electronic and magnetic properties are consistent with this description and appear to be understandable in terms of the same parameters.
We study the temperature dependence of strain under constant magnetic-fields in Ni-Mn based ferromagnetic Heusler alloys in the form Ni-Mn-$X$ ($X$: Ga, In, Sn, Sb) which undergo a martensitic transformation. We discuss the influence of the applied magnetic-field on the nucleation of ferromagnetic martensite and extract information on the easy-axis of magnetization in the martensitic state.
Neutron diffraction is used to probe the (H,T) phase diagram of magneto-electric (ME) LiNiPO4 for magnetic fields along the c-axis. At zero field the Ni spins order in two antiferromagnetic phases. One has commensurate (C) structures and general ordering vectors (0,0,0), the other one is incommensurate (IC) with ordering vector (0,q,0). At low temperatures the C order collapses above 12 Tesla and adopts an IC structure with modulation vector parallel to (0,q,0). We show that C order is required for the ME effect and establish how electric polarization results from a field-induced reduction of the total magneto-elastic energy.
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