Scale-Up of Magnetocaloric NiCoMnIn Heuslers by Powder Metallurgy for Room Temperature Magnetic Refrigeration

We present a new approach for a large-scale production of the rare-earth free NiCoMnIn Heusler alloy for room temperature magnetic refrigeration applications. This class of compounds has recently attracted attention, thanks to the large reversible isothermal entropy change (ΔSiso) and adiabatic temperature change (ΔTad) associated to a first-order magnetostructural phase transition. A large-scale production method, however, has not yet been proposed. For giant magnetocaloric materials and especially for Heusler compounds, the synthesis has a predominant role in tailoring the physical–chemical properties, due to the high sensitivity of the first-order transition characteristics on chemical composition and microstructure. Up to 250 g of the nominal composition Ni45.7Co4.2Mn36.6In13.3 alloy was prepared in a unique sample starting from industrial-grade powdered elements. The phase transition temperatures and magnetocaloric properties were investigated by magnetic and direct adiabatic temperature measurements and were found to be homogeneous in the whole sample. The mechanical stability of the produced alloy and its workability were investigated. A low-temperature thermal treatment was identified and showed promising results by reducing hysteresis and transition width

Magneto-optical circular dichroism properties of fept layers with perpendicular anisotropy

Magneto-optical techniques allow the investigation of the reversal process in magnetic surfaces and granular systems and of their electronic structure. In the case of magnetic metals and their surfaces the use of VIS or nIR lights allow to explore the interband and intrabands transitions that involves the 3d band. Due to the magneto-optical effect is related with the spin-orbit coupling, this technique is quite sensible to structural and chemical orders which determine also the magnetic anisotropy [1]. In this work we investigate the magneto-optical properties at different wavelengths of nanometric films based in epitaxial FePt and Fe-FePt bilayer that exhibit perpendicular anisotropy. Magnetic circular dichroism technique (MCD) is used because it allows to investigate the magneto-optical properties and the reversal process of the entire layers. FePt films of 10 nm were deposited by RF sputtering directly on a MgO (100) single-crystal in order to obtain the epitaxial growth. The growth was performed at substrate temperatures in the range 415?C and 430 ?C. The films were obtained by alternating the deposition of very thin Fe and Pt layers with nominal thickness of about 0.2 nm. The chosen ratio between the individual thickness corresponds to a nominal atomic composition of Fe53Pt47. The ordered L10 phase growths epitaxially [2] with the c-axis perpendicular to the substrate. Lower chemical order was observed in the film annealed at 430?C. On this film a second layer of 5 nm of Fe was deposited which constitutes the bilayer Fe-FePt. The MCD hysteresis loops at 1.7 K were recorded using different continuous lasers covering the VIS-nIR spectrum range (476 nm - 904 nm). Details of the experimental set-up are described in [3]. The MCD hysteresis loop of the FePt film annealed at 415?C and measured with a wavelength 476.5 nm is represented in the figure 1. A square hysteresis loop is observed with a negative saturation MCD (-5.3 mrad) for positive magnetic fields. The large squareness ratio, near 1, and the large coercive field of 2.9 T confirm the high quality of the ordered c-axis epitaxial film and the orientation of the easy axis in this direction. The shape of MCD hysteresis loop measured using 632.8 nm is very similar to the measured with 476.5 nm, but the saturation MCD is positive and approximately 5 times smaller (+1.18 mrad). In the figure 2 the MCD hysteresis of the Fe-FePt film measured with 514.5 nm, 632.8 nm and 904.0 nm are represented. The hysteresis loop measured with the blue beam exhibits positive MCD in the saturation while with the red and n-IR beams that values are negative. Moreover the absolute saturation MCD increases with the increase of the wavelength being 13.9 mrad, -20,6 mrad and -23,4 mrad for the beams with wavelength 514.5 nm, 632.8 nm and 904.0 nm, respectively. The obtained hysteresis indicate the presence of two critical field, HC1 ≈1.3 T and HC2 ≈0.64 T being the coercive field 0.13 T. The reversal process does not indicate a full exchange coupling between the hard and soft layers. In fact micromagnetic calculations [4] indicate that 5 nm Fe layer is a thick- ness for which decoupling could be possible. Finally the shape of the hysteresis loop measured with 514,5 nm is slightly different of the loops measured with largest wavelengths, which are equal. The MCD values measured with 514,5 nm in the magnetic field range between HC1 and HC2 are small- er than the measured with larger wavelength. This suggests that modification of the MO signal due to the change of the wavelength is not similar in the Fe and FePt layers. Comparing the results, quantitatively the Fe-FePt film shows largest MCD signal than the FePt film. This difference can be due to larger Fe contain but it is not enough for explain the differences. Moreover in the Fe-FePt film the MCD changes from positive to negative values for largest wavelengths and the absolute MCD increases. The opposite behaviours are observed in the FePt film. Spectroscopic measurements are in progress to clarify these results. [1] A. Cebollada et al. Phys. Rev. B 50 (1994) 3419; H. Ebert,G.Y. Guo, G. Sch?tz IEEE Trans. Magn. 31 (1995) 3301. [2] F. Casoli, et al. IEEE Trans. Magn. 41 (2005) 3223. [3] L. Cavigli et al. J. Magn. Magn. Mater. 316 (2007) 798. [4] G. Asti et al. Phys. Rev. B 73 (2006) 09440

Direct and indirect measurement of magnetocaloric effect in NiCoMnGa alloys

The Co-substitution for Ni in the Mn-rich NiMnGa Heusler alloys changes substantially their structural and magnetic ordering. The results will be discussed within the basic thermodynamic relations

Co and In Doped Ni-Mn-Ga Magnetic Shape Memory Alloys: A Thorough Structural, Magnetic and Magnetocaloric Study

In Ni-Mn-Ga ferromagnetic shape memory alloys, Co-doping plays a major role in determining a peculiar phase diagram where, besides a change in the critical temperatures, a change of number, order and nature of phase transitions (e.g., from ferromagnetic to paramagnetic or from paramagnetic to ferromagnetic, on heating) can be obtained, together with a change in the giant magnetocaloric effect from direct to inverse. Here we present a thorough study of the intrinsic magnetic and structural properties, including their dependence on hydrostatic pressure, that are at the basis of the multifunctional behavior of Co and In-doped alloys. We study in depth their magnetocaloric properties, taking advantage of complementary calorimetric and magnetic techniques, and show that if a proper measurement protocol is adopted they all merge to the same values, even in case of first order transitions. A simplified model for the estimation of the adiabatic temperature change that relies only on indirect measurements is proposed, allowing for the quick and reliable evaluation of the magnetocaloric potentiality of new materials starting from readily available magnetic measurements

Pressure dependence of magnetism and martensitic properties in Co-doped NiMnGa alloys

NiMnGa alloys display several "giant" effects due to the interplay between magnetic and structural degrees of freedom. A large magnetization difference, between martensitic phases and austenitic phases iso f great importance to obtain higher performances due to the improbe possibilit? of driving structural trasformations by magnetic fields. A deltaM enhancement was recently achieved by adding Co to Mn-rich NiMnGa alloy

Effect of Ag content on magnetic properties of (FePt)-Ag sputtered thin films

Ordered FePt thin films deserved particular attention owing to their very large magnetocrystalline anisotropy making them attractive in high-density magnetic recording. The addiction o fan immiscibile elements such Ag promotes the formation of a granular FePt phase displaying a significant magnetoresistence effect (MR). The effect of Ag addiction on the morphological and magnetic properties of the starting Fe33Pt47 system will be clarified

Role of interface and morphology in the magnetic behaviour of perpendicular thin films based on L10 FePt

FePt L10 ordered alloy is a promising material for high-density magnetic recording, since it allows the ferromagnetic stability in particles of few nanometers. Here we present our recent studies on the correlation between magnetic and morphological/interfacial properties of FePt -based thin films, nanostructures, and nano-composite bilayers. L10 FePt (001) epitaxial thin films with high structural quality were grown on (100) MgO by sputtering r.f., using the alternate-layer deposition method. By playing with growth temperature on the one hand and post-annealing temperature and time on the other, we have been able to finely control epitaxy, structural order, and morphology from 3D laterally confined structures to continuous film, with desired grain size. In particular we have been able to decrease grain size and to optimise magnetic properties (increase of anisotropy/coercivity ratio) at the same time, by post-annealing in situ [1]. Laterally confined magnetic structures were also obtained by focused ion beam (FIB). We have shown that for suitable Ga+ doses (1?1014 ion/cm2), it is possible to transform the L10 ordered phase to the A1 disordered one, without affecting morphology, giving rise to substantial modifications of magnetic properties from hard to soft. Perpendicular 2D magnetic patterns (dots, stripes) in a soft easy-plane matrix were realized in films of continuous morphology [2]. FePt L10 has also been exploited as the hard layer of nanostructured hard-soft nanocomposite bilayers. The exploitation of the exchange-coupling between hard and soft layers in exchange-coupled media represents a possible approach to overcome the so-called "recording trilemma" [3]. The samples were prepared by growing a magnetically soft Fe layer (2 and 3.5 nm) over a hard FePt(001) layer (10 nm). Three bilayers series have been grown based on FePt epitaxial layers with high degree of chemical order (S≥0.76) and different morphologies, corresponding to different interface characteristics. The resulting hard layer anisotropy is high (K>1?107 erg/cm3), and the coercivity is increased by the grains separation (from 1.7 to 3 T). In the Fe/FePt bilayers the coercivity HC is strongly reduced compared to the hard layer value (HC/HChard down to 0.37), indicating that high anisotropy perpendicular systems with moderate coercivity can be obtained [4]. Moreover, the control of the interface morphology allows to modify the magnetic regime at fixed Fe thickness (Rigid Magnet to Exchange-Spring), due to the nanoscale structure effect on the hard/soft coupling, and to tailor the hysteresis loop characteristics

Co and In Doped Ni-Mn-Ga Magnetic Shape Memory Alloys: A Thorough Structural, Magnetic and Magnetocaloric Study

In Ni-Mn-Ga ferromagnetic shape memory alloys, Co-doping plays a major role in determining a peculiar phase diagram where, besides a change in the critical temperatures, a change of number, order and nature of phase transitions (e.g., from ferromagnetic to paramagnetic or from paramagnetic to ferromagnetic, on heating) can be obtained, together with a change in the giant magnetocaloric effect from direct to inverse. Here we present a thorough study of the intrinsic magnetic and structural properties, including their dependence on hydrostatic pressure, that are at the basis of the multifunctional behavior of Co and In-doped alloys. We study in depth their magnetocaloric properties, taking advantage of complementary calorimetric and magnetic techniques, and show that if a proper measurement protocol is adopted they all merge to the same values, even in case of first order transitions. A simplified model for the estimation of the adiabatic temperature change that relies only on indirect measurements is proposed, allowing for the quick and reliable evaluation of the magnetocaloric potentiality of new materials starting from readily available magnetic measurements

Studio delle proprietà meccaniche e smorzanti dei compositi in fibra di carbonio nano-rinforzati.

Nella tesi in esame ci si pone come obiettivo principale quello di indagare il comportamento meccanico e dinamico di un materiale composito nano-rinforzato. Il composito posto in esame risulta essere un materiale innovativo in quanto unisce un prepreg in fibra di carbonio con fibre unidirezionali e membrane di nano-fibre in gomma. Negli ultimi anni si è notata una crescente esigenza nel settore industriale volta a diminuire le vibrazione in sistemi meccanici sottoposti a sollecitazioni periodiche, come ad esempio, mandrini per macchine automatiche o rulli per il settore tissue o covering, tutto questo giustifica la ricerca portata avanti in questa tesi che consiste nello sviluppare un materiale composito innovativo in grado di attenuare le vibrazioni senza d’altra parte aumentarne il peso. Sono da tempo riconosciute le alte capacita smorzanti della gomma, ma spesso l’integrazione nei materiali compositi avviene attraverso l’inserimento di una strato spesso di gomma tra due layer rigidi (struttura a sandwich), questo porta ad un aumento considerevole del peso e dello spessore, caratteristiche che possono rendere un materiale composito meno attraente in alcuni campi di applicazione. Lo smorzamento o damping risulta essere un fenomeno impegnativo da studiare nei materiali metallici perché esso è influenzato da innumerevoli fattori. Per quanto riguarda i materiali compositi la sfida diventa ancora più impegnativa data la loro natura intrinsecamente eterogenea. Concludendo, dalle prove sperimentali, è emerso un incremento notevole delle prestazioni smorzanti dei provini nano-modificati, lasciando inalterate le prestazioni meccaniche

Crystal Structures of Modulated Martensitic Phases of FSM Heusler Alloys

Multifunctional ferromagnetic shape memory Heusler alloys are frequently characterized by structural modulation in martensitic phases. In particular, modulated martensitic phases, showing the higher magnetic field induced strain (MFIS) performance, are the most promising candidates for technological applications. Depending on the composition, as well as pressure and temperature conditions, this periodic structural distortion, consisting of shuffling of atomic layers along defined crystallographic directions, accompanies the martensitic transformation. Over the years, different Ni-Mn-Ga modulated martensitic structures have been observed and classified depending upon the periodicity of corresponding ideal nM superstructure (where n indicates the number of basic unit cells constituting the superlattices). On the other hand, it has been demonstrated that in most cases such structural modulation is incommensurate and the crystal structure has been fully determined by applying superspace formalism. The results, obtained by structure refinements on powder diffraction data, suggest a unified crystallographic description of the modulated martensitic structures, here presented, where every different “nM” periodicity can be straightforwardly represented