Open Access
Tailoring the structural and magnetic properties of Co-Zn nanosized ferrites for hyperthermia applications
(Elsevier, 2018) Gómez Polo, Cristina; Recarte Callado, Vicente; Cervera Gabalda, Laura María; Beato López, Juan Jesús; López García, Javier; Rodríguez Velamazán, José Alberto; Ugarte Martínez, María Dolores; Mendonça, E. C.; Duque, J. G. S.; Zientziak; Estatistika, Informatika eta Matematika; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Estadística, Informática y Matemáticas; Gobierno de Navarra / Nafarroako Gobernua
A comparative study of the magnetic properties (magnetic moment, magnetocrystalline anisotropy) and hyperthermia response in Co-Zn spinel nanoparticles is presented. The CoxZn1-xFe2O4 nanoparticles (x = 1, 0.5, 0.4, 0.3, 0.2 and 0.1) were synthesized by co-precipitated method and the morphology and mean crystallite size (around 10 nm) of the nanoparticles were analysed by TEM Microscopy. Regarding the magnetic characterization (SQUID magnetometry), Co-Zn nanoparticles display at room temperature anhysteretic magnetization curves, characteristic of the superparamagnetic behavior. A decrease in the blocking temperature, T-B, with Zn content is experimentally detected that can be ascribed to the reduction in the mean nanoparticle size as x decreases. Furthermore, the reduction in the magnetocrystalline anisotropy with Zn inclusion is confirmed through the analysis of TB versus the mean volume of the nanoparticles and the law of approach to saturation. Maximum magnetization is achieved for x = 0.5 as a result of the cation distribution between octahedral and tetrahedral spinel sites, analysed by neutron diffraction studies. The occurrence of a canted spin arrangement (Yafet-Kittel angle) is introduced to properly fit the magnetic spinel structures. Finally, the heating capacity of these spinel ferrites is analyzed under ac magnetic field (magnetic hyperthermia). Maximum SAR (Specific Absorption Rate) values are achieved for x = 0.5 that should be correlated to the maximum magnetic moment of this composition.
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
Routes for enhanced magnetism in Ni-Mn-In metamagnetic shape memory alloys
(Elsevier, 2019) López García, Javier; Sánchez-Alarcos Gómez, Vicente; Recarte Callado, Vicente; Pérez de Landazábal Berganzo, José Ignacio; Fabelo, O.; Cesari, Eduard; Rodríguez Velamazán, José Alberto; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias
The authors provide in-depth physical insight into the enhancement of the magnetic properties of metamagnetic shape memory alloys produced by thermal treatment and cobalt doping. They use neutron scattering to study the atomic order and magnetic structures in the austenitic phases of Ni50Mn34In16 and Ni45Co5Mn37In13 alloys in two different states induced by thermal treatments. The increase of the magnetization in the austenite phase, particularly by cobalt doping, is explained by the enhanced ferromagnetic coupling between the magnetic moments located in octahedral sites. The spin density maps obtained from polarized neutron diffraction reveal the magnetic interaction pathways responsible for this coupling scheme.
Open Access
Magnetocaloric effect enhancement driven by intrinsic defects in a Ni45Co5Mn35Sn15 alloy
(Elsevier, 2019) Sánchez-Alarcos Gómez, Vicente; López García, Javier; Unzueta, Iraultza; Pérez de Landazábal Berganzo, José Ignacio; Recarte Callado, Vicente; Beato López, Juan Jesús; García, José Ángel; Plazaola, Fernando; Rodríguez Velamazán, José Alberto; Fisika; Institute for Advanced Materials and Mathematics - INAMAT2; Física
The influence of mechanically-induced defects on the magnetostructural properties is analyzed in a Ni-Co-Mn-Sn alloy subjected to soft milling and subsequent annealing treatments. It is found that, opposite to what occurs in Ni-Mn-Sn ternary alloys, the annealing treatment affects the magnetic properties in a different way in martensite and in austenite. In particular, the saturation magnetization significantly increases in martensite after annealing whereas just a very slight variation is observed in austenite. This leads to the interesting fact that the presence of microstructural defects, far for worsening, makes the magnetocaloric effect to be higher in the as-milled state than after annealing. This behavior is explained as the result of the combination of the effect of defects on the Mn-Mn distance, the effect of Co on the magnetic exchange coupling between Mn atoms, and the effect of defects on the vibrational entropy change at the martensitic transformation.
Open Access
Long-range atomic order and entropy change at the martensitic transformation in a Ni-Mn-In-Co metamagnetic shape memory alloy
(MDPI, 2014) Sánchez-Alarcos Gómez, Vicente; Recarte Callado, Vicente; Pérez de Landazábal Berganzo, José Ignacio; Cesari, Eduard; Rodríguez Velamazán, José Alberto; Física; Fisika
The influence of the atomic order on the martensitic transformation entropy change has been studied in a Ni-Mn-In-Co metamagnetic shape memory alloy through the evolution of the transformation temperatures under high-temperature quenching and post-quench annealing thermal treatments. It is confirmed that the entropy change evolves as a consequence of the variations on the degree of L21 atomic order brought by thermal treatments, though, contrary to what occurs in ternary Ni-Mn-In, post-quench aging appears to be the most effective way to modify the transformation entropy in Ni-Mn-In-Co. It is also shown that any entropy change value between around 40 and 5 J/kgK can be achieved in a controllable way for a single alloy under the appropriate aging treatment, thus bringing out the possibility of properly tune the magnetocaloric effect.
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
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.