Experimental Observation of Vacancy-assisted Martensitic Transformation Shift in Ni-Fe-Ga Alloys.

Positron annihilation lifetime spectroscopy is used to experimentally demonstrate the direct relationship between vacancies and the shift of the martensitic transformation temperature in a Ni_{55}Fe_{17}Ga_{28} alloy. The evolution of vacancies assisting the ordering enables shifts of the martensitic transformation up to 50 K. Our results confirm the role that both vacancy concentration and different vacancy dynamics play in samples quenched from the L2_{1} and B2 phases, which dictate the martensitic transformation temperature and its subsequent evolution. Finally, by electron-positron density functional calculations V_{Ni} is identified as the most probable vacancy present in Ni_{55}Fe_{17}Ga_{28}. This work evidences the capability of vacancies for the fine-tuning of the martensitic transformation temperature, paving the way for defect engineering of multifunctional properties.

Ni doped Fe3O4 magnetic nanoparticles.

In this work, the effect of nickel doping on the structural and magnetic properties of Fe3O4 nanoparticles is analysed. Ni(x)Fe(3-x)O4 nanoparticles (x = 0, 0.04, 0.06 and 0.11) were obtained by chemical co-precipitation method, starting from a mixture of FeCl2 x 4H2O and Ni(AcO)2 x 4H2O salts. The analysis of the structure and composition of the synthesized nanoparticles confirms their nanometer size (main sizes around 10 nm) and the inclusion of the Ni atoms in the characteristic spinel structure of the magnetite Fe3O4 phase. In order to characterize in detail the structure of the samples, X-ray absorption (XANES) measurements were performed on the Ni and Fe K-edges. The results indicate the oxidation of the Ni atoms to the 2+ state and the location of the Ni2+ cations in the Fe2+ octahedral sites. With respect to the magnetic properties, the samples display the characteristic superparamagnetic behaviour, with anhysteretic magnetic response at room temperature. The estimated magnetic moment confirms the partial substitution of the Fe2+ cations by Ni2+ atoms in the octahedral sites of the spinel structure.

Temperature and time dependent magnetic phenomena in a nearly stoichiometric Ni(2)MnGa alloy.

In this work, the temperature and time dependence of the magnetic properties of a polycrystalline Ni(49.7)Mn(24.1)Ga(26.2) alloy is analysed. The law of approach to magnetic saturation has been employed to estimate the magnetic anisotropy in the three structural phases of the alloy (martensitic, pre-martensitic and austenitic). The temperature dependences of magnetic parameters, such as the magnetic susceptibility and coercive field, are interpreted in terms of the changes in the magnetic anisotropy taking place with the structural transformations. The strong magnetocrystalline anisotropy is confirmed to mainly control the magnetic response of the low temperature martensitic phase. Furthermore, magnetic relaxation studies (magnetic after-effect) have been employed to analyse the main differences between the magnetization processes in the three characteristic structural phases. The time decay of the magnetization displays a distinctive response in the pre-martensitic state. The results (logarithmic time decay of the remanent magnetization and field dependence of the magnetic viscosity) indicate the thermally activated nature of the relaxation process.

Magnetic properties of nickel and cobalt catalysts supported on nanoporous oxides.

The aim of this work is to use magnetic measurements as a research tool in the study of possible metal-support interactions in nickel and cobalt nanoporous catalysts. Several physicochemical techniques, namely nitrogen adsorption, X-ray diffraction, temperature-programmed reduction and chemical analysis, were used to analyze the role of the preparation method and the nature of the support on the existence of such metal-support interactions and to relate them with the magnetic response of these nanoporous systems. The catalysts were prepared by incipient wetness impregnation and precipitation-deposition with two commercial oxides, gamma-Al2O3 and SiO2, as supports. The magnetic behavior of the catalysts is drastically affected by the existence of interactions between the metal and the support during the preparation procedure. The samples with weak metal-support interactions have characteristic magnetic behavior of antiferromagnetic metal oxide nanoparticles, while the ones having strong interactions display spin-glass like behavior.

Giant direct and inverse magnetocaloric effect linked to the same forward martensitic transformation.

Metamagnetic shape memory alloys have aroused considerable attraction as potential magnetic refrigerants due to the large inverse magnetocaloric effect associated to the magnetic-field-induction of a reverse martensitic transformation (martensite to austenite). In some of these alloys, the austenite phase can be retained on cooling under high magnetic fields, being the retained phase metastable after field removing. Here, we report a giant direct magnetocaloric effect linked to the anomalous forward martensitic transformation (austenite to martensite) that the retained austenite undergoes on heating. Under moderate fields of 10 kOe, an estimated adiabatic temperature change of 9 K has been obtained, which is (in absolute value) almost twice that obtained in the conventional transformation under higher applied fields. The observation of a different sign on the temperature change associated to the same austenite to martensite transformation depending on whether it occurs on heating (retained) or on cooling is attributed to the predominance of the magnetic or the vibrational entropy terms, respectively.

Determination of the vibrational contribution to the entropy change at the martensitic transformation in Ni-Mn-Sn metamagnetic shape memory alloys: a combined approach of time-of-flight neutron spectroscopy and ab initio calculations.

The different contributions to the entropy change linked to the austenite-martensitic transition in a Ni-Mn-Sn metamagnetic shape memory alloy have been determined by combining different experimental techniques. The vibrational contribution has been inferred from the vibrational density of states of both the martensitic and austenite phases. This has been accomplished by combining time-of-flight neutron scattering measurements and ab initio calculations. Further, the electronic part of the entropy change has also been calculated. Since the martensitic transformation takes place between two paramagnetic phases, the magnetic contribution can be neglected and the entropy change can be reduced to the sum of two terms: vibrational and electronic. The obtained value of the vibrational contribution ([Formula: see text]) nearly provides the total entropy change measured by calorimetry ([Formula: see text]), the difference being the electronic contribution within the experimental error.

Effect of a SiO2 coating on the magnetic properties of Fe3O4 nanoparticles.

In this work the effect of a SiO2 coating on the magnetic properties of Fe3O4 nanoparticles obtained by the sol-gel method is analyzed. Two sets of samples were prepared: Fe3O4 nanoparticles and Fe3O4@SiO2 core-shell composites. The samples display the characteristic spinel structure associated with the magnetite Fe3O4 phase, with the majority of grain sizes around 5-10 nm. At room temperature the nanoparticles show the characteristic superparamagnetic behavior with mean blocking temperatures around 160 and 120 K for Fe3O4 and Fe3O4@SiO2, respectively. The main effect of the SiO2 coating is reflected in the temperature dependence of the high field magnetization (µ(0)H = 6 T), i.e. deviations from the Bloch law at low temperatures (T < 20 K). Such deviations, enhanced by the introduction of the SiO2 coating, are associated with the occurrence of surface spin disordered effects. The induction heating effects (magnetic hyperthermia) are analyzed under the application of an AC magnetic field. Maximum specific absorption rate (SAR) values around 1.5 W g(-1) were achieved for the Fe3O4 nanoparticles. A significant decrease (around 26%) is found in the SAR values of the SiO2 coated nanocomposite. The different heating response is analyzed in terms of the decrease of the effective nanoparticle magnetization in the Fe3O4@SiO2 core-shell composites at room temperature.

Transformation behavior of Ni-Mn-Ga in the low-temperature limit.

The magnetic, magnetocaloric and thermal characteristics have been studied in a Ni(50.3)Mn(20.8)Ga(27.6)V(1.3) ferromagnetic shape memory alloy (FSMA) transforming martensitically at around 40 K. The alloy shows first a transformation from austenite to an intermediate phase and then a partial transformation to an orthorhombic martensite, all the phases being ferromagnetically ordered. The thermomagnetization dependences enabled observation of the magnetocaloric effect in the vicinity of the martensitic transformation (MT). The Debye temperature and the density of states at the Fermi level are equal to θ(D) = (276 ± 4) K and 1.3 states/atom eV , respectively, and scarcely dependent on the magnetic field. The MT exhibited by Ni-Mn-Ga FSMAs at very low temperatures is distinctive in the sense that it is accompanied by a hardly detectable entropy change as a sign of a small driving force. The enhanced stability of the cubic phase and the low driving force of the MT stem from the reduced density of states near the Fermi level.

Temperature dependence of magnetic susceptibility in the vicinity of martensitic transformation in ferromagnetic shape memory alloys.

Temperature dependences of low-field quasistatic magnetic susceptibility in the vicinity of martensitic transitions in an NiFeGa alloy are studied both by experiment and analytically. Pronounced reversible jumps of the magnetic susceptibility were observed near the martensitic transition temperature. A general description of the temperature dependences of the susceptibility in ferromagnetic austenite and martensite phases and the susceptibility jump at the transition is suggested. As a result, the main factors governing the temperature dependences of the magnetic susceptibility in the magnetic shape memory alloys are revealed. The magnetic susceptibility jump value is found to be related to changes of: (i) magnetic anisotropy; (ii) magnetic domain wall geometrical constraints (those determined by the alignment and size of twin variants) and (iii) mean magnetic domain spacing.

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.

Vibrational and magnetic contributions to the entropy change associated with the martensitic transformation of Ni-Fe-Ga ferromagnetic shape memory alloys.

Ferromagnetic shape memory alloys undergo a martensitic transformation accompanied by a change in the magnetic and vibrational properties. However, these property changes are not independent. In this paper, the interplay between magnetic and vibrational properties in the martensitic transformation entropy change has been analyzed for Ni-Fe-Ga ferromagnetic shape memory alloys. The martensitic transformation entropy change has a magnetic and a vibrational contribution, ΔS(p−>m)=ΔS(vib)(p−>m) + ΔS(mag)(p−>m). Using a mean field approximation for the magnetic entropy, the full entropy ΔS(p−>m) has been decomposed and the magnetic contribution ΔS(mag)(p−>m) calculated. Upon removing the magnetic term, the vibrational entropy ΔS(vib)(p−>m) does not change substantially in the composition range where T(M) is below T(C). This latter contribution to the martensitic transformation entropy change has been analyzed using a Debye distribution for the density of states and a proportion of Einstein modes that account for the anomalous phonon mode of the austenite.