Producció, caracterització i estudi magnètic d’aliatges heusler ni-mn-sn-x amb memòria de forma

Zusammenfassung

Shape memory alloys witch exhibit magnetically induced phase transformations at room temperatures are the most interesting for magnetic cooling applications. Heusler type alloys (both stoichiometric and non-stoichiometric) are among the most studied systems, as they permit the change of the transition temperatures due to compositional variations. The first Heusler alloys that have been studied in depth are Ni- Mn-Ga alloys. However, to overcome the high cost of Gallium and low martensitic transformation temperature, the search for Ga-free alloys has been recently endeavoured, principally, by introducing In, Sn or Sb. The purpose of this work is the production and characterization of non-stoichiometric Heusler alloys based on a Ni-Mn-Sn composition, with copper or Palladium doping. The effect of doping element will be determined, on the crystalline structure, the phase transition temperatures, the thermodynamic and magnetocaloric parameters. On the other hand, a heat treatment will be exerted on Ni-Mn-Sn-Cu alloys then characterize them in the same way. Shape memory alloys will be produced in the first step, by arc melting technique, to produce the bulk and then by melt spinning, to obtain shape memory ribbons. Produced samples are characterized by scanning electron microscopy (SEM) technique, to check the morphological structure of the alloys, microanalysis technique (EDX) to have the final composition experimentally, X-ray diffraction technique (XRD) to extract information from the crystal structure, differential scanning calorimetry (DSC) to study the thermal and thermodynamic variations induced by structural phase transformations and finally magnetometry techniques (Physical property measurement system, PPMS: VSM, resistivity, hysteresis cycles) to characterize the phase transformations behaviour and magnetocaloric effect under applied external magnetic fields. Among the results obtained in the present work it can be concluded that both Cu-doped and Pd-doped alloys have similar morphology. The reversible austenite-martensite transformation was detected in all ribbons. Cu or Pd doping tends to increase the structural transition temperatures. These changes in the magnetic and martensitic transformation temperatures are confirmed report directly to the ratio (e/a) of the alloy. Moreover, it’s emphasized the fact that Pd doped alloys show a good magnetocaloric effect (the maximum variation of ΔS is approximately 4.5 J / (Kg.K) for an applied magnetic field of 50 kOe and the refrigeration capacity is 28 J / kg). This dependence must allow the selection of the appropriate composition for the production of alloys with transformation into a desired temperature range. On the other hand, measurements of DRX, DSC and magnometry carried out on Ni-Mn-Sn-Cu alloys after application of thermal cycles of heating-cooling of 100 times, allowed us to certify the great stability of the alloys and the shape memory effect (minor change in phase transformation temperatures and curie temperatures)