Open Access
Influence of structural defects on the properties of metamagnetic shape memory alloys
(MDPI, 2020) Pérez de Landazábal Berganzo, José Ignacio; Sánchez-Alarcos Gómez, Vicente; Recarte Callado, Vicente; Lambri, Osvaldo Agustín; López García, Javier; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias
The production of µ-particles of Metamagnetic Shape Memory Alloys by crushing and subsequent ball milling process has been analyzed. The high energy involved in the milling process induces large internal stresses and high density of defects with a strong influence on the martensitic transformation; the interphase creation and its movement during the martensitic transformation produces frictional contributions to the entropy change (exothermic process) both during forward and reverse transformation. The frictional contribution increases with the milling time as a consequence of the interaction between defects and interphases. The influence of the frictional terms on the magnetocaloric effect has been evidenced. Besides, the presence of antiphase boundaries linked to superdislocations helps to understand the spin-glass behavior at low temperatures in martensite. Finally, the particles in the deformed state were introduced in a photosensitive polymer. The mechanical damping associated to the Martensitic Transformation (MT) of the particles is clearly distinguished in the produced composite, which could be interesting for the development of magnetically-tunable mechanical dampers.
Open Access
Giant direct and inverse magnetocaloric effect linked to the same forward martensitic transformation
(Springer Nature, 2017) Pérez de Landazábal Berganzo, José Ignacio; Recarte Callado, Vicente; Sánchez-Alarcos Gómez, Vicente; Beato López, Juan Jesús; Rodríguez Velamazán, José Alberto; Sánchez Marcos, J.; Gómez Polo, Cristina; Cesari, Eduard; Fisika; Institute for Advanced Materials and Mathematics - INAMAT2; Física
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.
Open Access
Monitoring structural transformations in metamagnetic shape memory alloys by non-contact GMI technology
(IOP Publishing, 2023) Beato López, Juan Jesús; La Roca, Paulo Matías; Algueta-Miguel, Jose M.; Garayo Urabayen, Eneko; Sánchez-Alarcos Gómez, Vicente; Recarte Callado, Vicente; Gómez Polo, Cristina; Pérez de Landazábal Berganzo, José Ignacio; Ciencias; Ingeniería Eléctrica, Electrónica y de Comunicación; Institute for Advanced Materials and Mathematics - INAMAT2; Institute of Smart Cities - ISC; Zientziak; Ingeniaritza Elektrikoa, Elektronikoaren eta Telekomunikazio Ingeniaritzaren
Different applications based on metamagnetic shape memory alloy (MSMA) require monitoring the evolution of the martensitic transformation (MT) to optimize the actuation mechanism. To avoid interaction with the active material, a non-contact technique would be ideal. Nevertheless, non-contact detection involves complex methods like diffraction, optical analysis, or electromagnetic technology. The present work demonstrates that the MT can be monitored without interaction with the active material using a low-cost technology based on the Giant Magnetoimpedance (GMI) effect. The GMI sensor is based on a (CoFe)SiB soft magnetic wire submitted to an alternating current and whose second harmonic voltage variation allows to detect changes in the strength of the stray magnetic fields linked to the metamagnetic phase transition. The sensor has been tested using the MT of a NiMnInCo MSMA. A specific application for environmental temperature control using the non-contact GMI sensor is proposed.
Open Access
Effect of high-energy ball-milling on the magnetostructural properties of a Ni45Co5Mn35Sn15 alloy
(Elsevier, 2021) López García, José Luis; Sánchez-Alarcos Gómez, Vicente; Recarte Callado, Vicente; Rodríguez Velamazán, José Alberto; Unzueta, Iraultza; García, José Ángel; Plazaola, Fernando; La Roca, Paulo Matías; Pérez de Landazábal Berganzo, José Ignacio; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Gobierno de Navarra / Nafarroako Gobernua, PC017-018 AMELEC
The effect of high-energy ball-milling on the magnetostructural properties of a Ni45Co5Mn35Sn15 alloy in austenitic phase at room temperature has been analyzed by neutron and high-resolution X-ray diffraction. The ball milling promotes a mechanically-induced martensitic transformation as well as the appearance of amorphous-like non-transforming regions, following a double stage; for short milling times (below 30 min), a strong size reduction and martensite induction occur. On the opposite, for longer times, the increase of strains predominates and consequently a larger amount of non-transforming regions appears. The effect of the microstructural defects brought by milling (as dislocations) on both the enthalpy change at the martensitic transformation and the high field magnetization of the austenite has been quantitatively estimated and correlated to the internal strains. Contrary to what occurs in ternary Ni-Mn-Sn alloys, the mechanically-induced defects do not change the ferromagnetic coupling between Mn atoms, but just cause a net reduction on the magnetic moments.
Open Access
Polycaprolactone/MSMA composites for magnetic refrigeration applications
(Wiley, 2024-09-06) Sánchez-Alarcos Gómez, Vicente; Khanna, Deepali; La Roca, Paulo Matías; Recarte Callado, Vicente; Lambri, Fernando Daniel; Bonifacich, Federico Guillermo; Lambri, Osvaldo Agustín; Royo Silvestre, Isaac; Urbina Yeregui, Antonio; Pérez de Landazábal Berganzo, José Ignacio; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
A high filling load (62% weight) printable magnetic composite has been elaborated from the dispersion of magnetocaloric Ni45Mn36.7In13.3Co5 metamagnetic shape memory alloy microparticles into a PCL polymer matrix. The composite material has been prepared by solution method, resulting in a very homogeneous particles dispersion into the matrix. The structural transitions in the polymer are not affected by the addition of the metallic microparticles, which in turn results in a significant increase of the mechanical consistency. The good ductility of the elaborated composite allows its extrusion in flexible printable filaments, from which 3D pieces with complex geometries have been grown. The heat transfer of the composite material has been assessed from finite element simulation. In spite of the achievable magnetocaloric values are moderated with respect to the bulk, numerical simulations confirm that, in terms of heat transference, a PCL/Ni-Mn-In-Co wire is more efficient than a bulk Ni-Mn-In-Co cubic piece containing the same amount of magnetic active material. The quite good magnetocaloric response of the composite and the possibility to print high surface/volume ratio geometries make this material a promising candidate for the development of heat exchangers for clean and efficient magnetic refrigeration applications.
Open Access
Room temperature huge magnetocaloric properties in low hysteresis ordered Cu-doped Ni-Mn-In-Co alloys
(Elsevier, 2022) La Roca, Paulo Matías; López García, Javier; Sánchez-Alarcos Gómez, Vicente; Recarte Callado, Vicente; Rodríguez Velamazán, José Alberto; Pérez de Landazábal Berganzo, José Ignacio; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Gobierno de Navarra / Nafarroako Gobernua, PC017–018 AMELEC
The reduction of the thermal hysteresis in first order magnetostructural transition is a determining factor to decrease energy losses and to improve the efficiency of magnetocaloric cooling based systems. In this work, a Cu doped NiMnInCo metamagnetic shape memory alloy (MMSMA) exhibiting a narrow thermal hysteresis (around 5 K) at room temperature has been designed. In this alloy, the induced L21 ordering process affects the phase stability in an unusual way compared to that observed in NiMnInCo and other NiMn based alloys. This ordering produces an increase in the Curie temperature of the austenite but hardly affects the mar tensitic transformation temperatures. As a consequence, the ordering increases the magnetization of the austenite without changing the transformation temperatures, doubles the sensitivity of the transformation to magnetic fields (the Claussius-Clapeyron slope goes from 2.1 to 3.9 K/T), improves the magnetocaloric effect, the reversibility and finally, enhances the refrigeration capacity. In addition, the magnetic hysteresis losses are among the lowest reported in the literature and the effective cooling capacity coefficient RCeff reaches 86 J/Kg for 2 T (15 % higher than those found in Ni-Mn based alloys) and 314 J/Kg for 6 T fields. Therefore, the ordered alloy possesses an excellent combination of low thermal hysteresis and high RCeff, not achieved previously in metamagnetic shape memory alloys near room temperature.
Open Access
Thermal degradation of type I collagen from bones
(Tech Science Press, 2016) Lambri, Melania Lucila; Giordano, E. D.; Bozzano, P. B.; Pérez de Landazábal Berganzo, José Ignacio; Recarte Callado, Vicente; Fisika; Institute for Advanced Materials and Mathematics - INAMAT2; Física; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
The denaturation processes of collagen in the temperature range between 450 K and 670 K are revealed through studies performed on cow rib bones by means of mechanical spectroscopy, differential scanning calorimetry, thermogravimetry, scanning electron microscopy and infrared spectroscopy. The conformational change of the collagen molecules from a triple helix structure to a random coil was found at around 510 K. It was determined that the transformation is developed through the viscous movement of fibrils with an activation energy of (127 ± 8) kJ/mol. The second stage of massive bulk deterioration of the collagen was found at around 600 K, which leads to the loss of the mechanical integrity of the bulk collagen. In addition, an easy-to-handle viscoelastic procedure for obtaining the activation energy of the denaturation process from mechanical spectroscopy studies was also shown.
Open Access
119Sn Mössbauer spectroscopy for assessing the local stress and defect state towards the tuning of Ni-Mn-Sn alloys
(AIP Publishing, 2017) Unzueta, Iraultza; López García, Javier; Sánchez-Alarcos Gómez, Vicente; Recarte Callado, Vicente; Pérez de Landazábal Berganzo, José Ignacio; Fisika; Institute for Advanced Materials and Mathematics - INAMAT2; Física
The influence of defects and local stresses on the magnetic properties and martensitic transformation in Ni50Mn35Sn15 is studied at macroscopic and atomic scale levels. We show that both the structural and magnetic properties of the alloy are very sensitive to slight microstructural distortions. Even though no atomic disorder is induced by milling, the antiphase boundaries linked to dislocations promote the antiferromagnetic coupling of Mn, resulting in a significant decrease in the saturation magnetization. On the other hand, the temperature range of the transformation is considerably affected by the mechanically induced local stresses, which in turn does not affect the equilibrium temperature between the austenitic and martensitic phases. Finally, we demonstrate that the recovery of the martensitic transformation is directly related to the intensity of the non-magnetic component revealed by 119Sn Mössbauer spectroscopy. This result opens the possibility of quantifying the whole contribution of defects and the local stresses on the martensitic transformation in Ni-Mn-Sn alloys.
Open Access
Changes in the crystalline degree in neutron irradiated EPDM viewed through infrared spectroscopy and inelastic neutron scattering
(Rede Latino-Americana de Materiais, 2018) Lambri, Osvaldo Agustín; Giordano, E. D.; Bonifacich, Federico Guillermo; Pérez de Landazábal Berganzo, José Ignacio; Recarte Callado, Vicente; Física; Fisika; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
The changes in the degree of crystallinity in commercial Ethylene Propylene Diene rubber-type M (EPDM) irradiated with neutrons at different doses has been studied by means of inelastic neutron scattering and infrared absorption spectroscopy experiments. EPDM samples were taken from the housing of non-ceramic electrical insulators which are used in outdoor transmission lines of 66 kV. Inelastic neutron scattering spectra were recorded at 5 K with an accessible energy-transfer range between 180 - 3500 cm-1. Infrared studies were performed at room temperature with an energy transfer between 4000 - 400 cm-1. Controlled neutron irradiation allows to obtain different volume fraction and size of crystalline zones in EPDM. The obtained results are discussed and correlated with studies of differential scanning calorimetry, dynamic mechanical analysis and positron annihilation lifetime spectroscopy from where the changes in crystallinity in EPDM were indirectly studied. Inelastic neutron scattering studies were not appropriate for determining the changes in the crystallinity degree in neutron irradiated commercial EPDM. In contrast, from infrared absorption spectroscopy the changes in crystallinity could be determined successfully.
Open Access
Magnetically activated 3D printable polylactic acid/polycaprolactone/magnetite composites for magnetic induction heating generation
(Springer, 2023) Galarreta Rodríguez, Itziar; López Ortega, Alberto; Garayo Urabayen, Eneko; Beato López, Juan Jesús; La Roca, Paulo Matías; Sánchez-Alarcos Gómez, Vicente; Recarte Callado, Vicente; Gómez Polo, Cristina; Pérez de Landazábal Berganzo, José Ignacio; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
Additive manufacturing technology has attracted the attention of industrial and technological sectors due to the versatility of the design and the easy manufacture of structural and functional elements based on composite materials. The embedding of magnetic nanoparticles in the polymeric matrix enables the development of an easy manufacturing process of low-cost magnetically active novel polymeric composites. In this work, we report a series of magnetic composites prepared by solution casting method combining 5 to 60 wt.% of 140 ± 50 nm commercial Fe3O4 nanoparticles, with a semi-crystalline, biocompatible, and biodegradable polymeric blend made of polylactic acid (PLA) and polycaprolactone (PCL). The composites were extruded, obtaining 1.5 ± 0.2 mm diameter continuous and flexible filaments for fused deposition modelling 3D printing. The chemical, magnetic, and calorimetric properties of the obtained filaments were investigated by differential scanning calorimetry, thermogravimetric analysis, magnetometry, and scanning electron microscopy. Furthermore, taking advantage of the magnetic character of the filaments, their capability to generate heat under the application of low-frequency alternating magnetic fields (magnetic induction heating) was analyzed. The obtained results expose the versatility of these easy manufacturing and low-cost filaments, where selecting a desired composition, the heating capacity can be properly adjusted for those applications where magnetic induction plays a key role (i.e., magnetic hyperthermia, drug release, heterogeneous catalysis, water electrolysis, gas capture, or materials synthesis).