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The thermodynamic and kinetic simulations based on the re-assessment of the thermodynamic and kinetic database of the Ni-Ti-Cu system were employed to predict the phenomena of mechanical alloying, spark plasma sintering and thermal properties of the intriguing Ni-Ti-Cu system. Thermodynamic calculations are presented for the stable and unstable phases of NiTiCu materials and support a correlation with the evolving microstructure during the technological process. Also, the thermal conductivity, the thermal diffusivity and the specific heat of spark plasma sintered and aged Cu-alloyed NiTi-based shape memory alloys (NiTiCu) with two compositions, Ni45Ti50Cu5 and Ni40Ti50Cu10, are evaluated and the influence of mechanical alloying and precipitates on thermal properties is discussed. Measurements of these thermal properties were carried out from 25 °C up to 175 °C using the laser flash method, as well as differential scanning calorimetry. The thermal hysteresis of the 20 mm diameter samples was between 8.8 and 24.5 °C. The observed T0 temperatures from DSC experimental transformation features are in reasonable accordance with the thermodynamic predictions. The determined k values are between 20.04 and 26.87 W/m K and in agreement with the literature results. Moreover, this paper can provide some suggestions for the preparation of NiTiCu shape memory alloys and their applications.

When a severe plastic deformation (SPD) process is performed at high temperatures, it becomes more versatile. Designed originally for the bulk nanoconstruction of hard-to-deform alloys, high-speed high-pressure torsion (HSHPT) is an SPD method used in this research for assembling multiple layers of shape memory nanocomposites. Three hard-to-deform magnetic alloys in the cast state were used. Soft magnetic shape memory alloys, NiFeGa and FePdMn, and a potentially hard magnetic alloy, CoZr, were assembled in various composites. Both grain refinement and strong layer bonding were achieved in ZrCo/FePdMn and ZrCo/NiFeGa composites in seconds. The very short SPD time is specific to HSHPT because of the intense friction that occurs under high pressures, which generates huge amounts of heat. After SPD, the temperature rises in bulk material like a pulse, being dissipated mostly through heat conduction. The SPD parameters were carefully controlled with an advanced automation system using a programmable logic controller. Nevertheless, the major drawbacks of high-pressure torsion were overcome, and large SPD discs were obtained. Various investigation techniques (optical microscopy, scanning electron microscopy, energy dispersive spectroscopy and atomic force microscopy) show well-defined interfaces as well as a fine and ultrafine structure.

In our work, the kinetics of martensitic transformations and the influence of thermal treatments on martensitic transformations, as well as the related magnetic properties of the Ni49Mn32Ga19 ferromagnetic shape memory melt-spun ribbons, have been investigated. Thermal treatments at 673 K for 1, 4 and 8 h can be considered an instrument for fine-tuning the performance parameters of alloys. One-hour thermal treatments promote an improvement in the crystallinity of these otherwise highly textured ribbons, reducing internal defects and stress induced by the melt-spinning technique. Longer thermal treatments induce an important magnetization rise concomitantly with a slight and continuous increase in martensitic temperatures and transformation enthalpy. The activation energy, evaluated from differential scanning calorimeter experimental data with a Friedman model, significantly increases after thermal treatments as a result of the multi-phase coexistence and stabilization of the non-modulated martensitic phase, which increases the reverse martensitic transformation hindrance.

The influence of processing on the martensitic transformation and related magnetic properties of the Ni55Fe18Nd2Ga25 ferromagnetic shape memory alloy, as bulk and ribbons prepared by the melt spinning method and subjected to different thermal treatments, is investigated. Structural, calorimetric, and magnetic characterizations are performed. Thermal treatment at 1173 K induces a decrease in both the Curie and the martensitic transformation temperatures, while a treatment at 673 K produces the structural ordering of the ribbons, hence an increase in TC. A maximum value of the magnetic entropy variation of −5.41 J/kgK was recorded at 310 K for the as quenched ribbons. The evaluation of the magnetoresistive effect shows a remarkable value of −13.5% at 275 K on the bulk sample, which is much higher than in the ribbons.

MoO2-Fe2O3 nanoparticle systems were successfully synthesized by mechanochemical activation of MoO2 and α-Fe2O3 equimolar mixtures throughout 0–12 h of ball-milling. The role of the long-range ferromagnetism of MoO2 on a fraction of more defect hematite nanoparticles supporting a defect antiferromagnetic phase down to the lowest temperatures was investigated in this work. The structure and the size evolution of the nanoparticles were investigated by X-ray diffraction, whereas the magnetic properties were investigated by SQUID magnetometry. The local electronic structure and the specific phase evolution in the analyzed system versus the milling time were investigated by temperature-dependent Mössbauer spectroscopy. The substantially shifted magnetic hysteresis loops were interpreted in terms of the unidirectional anisotropy induced by pinning the long-range ferromagnetic order of the local net magnetic moments in the defect antiferromagnetic phase, as mediated by the diluted magnetic oxide phase of MoO2, to those less defect hematite nanoparticles supporting Morin transition. The specific evolutions of the exchange bias and of the coercive field versus temperature in the samples were interpreted in the frame of the specific phase evolution pointed out by Mössbauer spectroscopy. Depending on the milling time, a different fraction of defect hematite nanoparticles is formed. Less nanoparticles supporting the Morin transition are formed for samples exposed to a longer milling time, with a direct influence on the induced unidirectional anisotropy and related effects.

The influence of the rapid solidification technique and heat treatment on the martensitic transformation, magnetic properties, thermo- and magnetic induced strain and electrical resistivity is investigated for the Cu doped NiMnGa Heusler-based ferromagnetic shape memory ribbons. The martensitic transformation temperatures are unexpectedly low (below 90 K—which can be attributed to the disordered texture as well as to the uncertainty in the elements substituted by the Cu), preceded by a premartensitic transformation (starting at around 190 K). A thermal treatment slightly increases the transformation as well as the Curie temperatures. Additionally, the thermal treatment promotes a higher magnetization value of the austenite phase and a lower one in the martensite. The shift of the martensitic transformation temperatures induced by the applied magnetic field, quantified from thermo-magnetic and thermo-magnetic induced strain measurements, is measured to have a positive value of about 1 K/T, and is then used to calculate the transformation entropy of the ribbons. The magnetostriction measurements suggest a rotational mechanism in low fields for the thermal treated samples and a saturation tendency at higher magnetic fields, except for the temperatures close to the phase transition temperatures (saturation is not reached at 5 T), where a linear volume magnetostriction cannot be ruled out. Resistivity and magnetoresistance properties have also been measured for all the samples.

This work focuses on the temperature evolution of the martensitic phase ε (hexagonal close packed) induced by the severe plastic deformation via High Speed High Pressure Torsion method in Fe57Mn27Si11Cr5 (at %) alloy. The iron rich alloy crystalline structure, magnetic and transport properties were investigated on samples subjected to room temperature High Speed High Pressure Torsion incorporating 1.86 degree of deformation and also hot-compression. Thermo-resistivity as well as thermomagnetic measurements indicate an antiferromagnetic behavior with the Néel temperature (TN) around 244 K, directly related to the austenitic γ-phase. The sudden increase of the resistivity on cooling below the Néel temperature can be explained by an increased phonon-electron interaction. In-situ magnetic and electric transport measurements up to 900 K are equivalent to thermal treatments and lead to the appearance of the bcc-ferrite-like type phase, to the detriment of the ε(hcp) martensite and the γ (fcc) austenite phases.

The equimolar oxide mixture β-Ga2O3—α-Fe2O3 was subjected to high-energy ball milling (HEBM) with the aim to obtain the nanoscaled GaFeO3 ortho-ferrite. X-ray diffraction, 57Fe Mössbauer spectroscopy, and transmission electron microscopy were used to evidence the phase structure and evolution of the equimolar nano-system β-Ga2O3—α-Fe2O3 under mechanochemical activation, either as-prepared or followed by subsequent calcination. The mechanical activation was performed for 2 h to 12 h in normal atmosphere. After 12 h of HEBM, only nanoscaled (~20 nm) gallium-doped α-Fe2O3 was obtained. The GaFeO3 structure was obtained as single phase, merely after calcination at 950 °C for a couple of hours, of the sample being subjected to HEBM for 12 h. This temperature is 450 °C lower than used in the conventional solid phase reaction to obtain gallium orthoferrite. The optical and magnetic properties of representative nanoscaled samples, revealing their multifunctional character, were presented.

Severe plastic deformation (SPD) is widely considered to be the most efficient process in obtaining ultrafine-grained bulk materials. The aim of this study is to examine the effects of the SPD process on Ni-Fe-Ga ferromagnetic shape memory alloys (FSMA). High-speed high-pressure torsion (HSHPT) was applied in the as-cast state. The exerted key parameters of deformation are described. Microstructural changes, including morphology that were the result of processing, were investigated by optical and scanning electron microscopy. Energy-dispersive X-ray spectroscopy was used to study the two-phase microstructure of the alloys. The influence of deformation on microstructural features, such as martensitic plates, intragranular γ phase precipitates, and grain boundaries’ dependence of the extent of deformation is disclosed by transmission electron microscopy. Moreover, the work brings to light the influence of deformation on the characteristics of martensitic transformation (MT). Vickers hardness measurements were carried out on disks obtained by SPD so as to correlate the hardness with the microstructure. The method represents a feasible alternative to obtain ultrafine-grained bulk Ni-Fe-Ga alloys.