Person: López Ortega, Alberto
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López Ortega
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Alberto
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Ciencias
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InaMat2. Instituto de Investigación en Materiales Avanzados y Matemáticas
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0000-0003-3440-4444
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812023
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Publication Open Access Core-shell magnetic nanoparticles(MDPI, 2023) López Ortega, Alberto; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2This Special Issue offers readers a compilation of cutting-edge research regarding the synthesis, development, and characterization of core-shell magnetic architectures, covering a wide spectrum of nanomaterials and serving as a guide for new students of the field as well as established researchers.Publication Open Access Crossover from individual to collective magnetism in dense nanoparticle systems: local anisotropy versus dipolar interactions(Nano-Micro, 2022) Sánchez, Elena H.; Vasilakaki, Marianna; Lee, Su Seong; Normile, Peter S.; Andersson, Mikael S.; Mathieu, Roland; López Ortega, Alberto; Pichon, Benoit P.; Peddis, Davide; Binns, Chris; Nordblad, Per; Trohidou, Kalliopi; Nogués, Josep; Toro, José A. de; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Universidad Pública de Navarra / Nafarroako Unibertsitate PublikoaDense systems of magnetic nanoparticles may exhibit dipolar collective behavior. However, two fundamental questions remain unsolved: i) whether the transition temperature may be affected by the particle anisotropy or it is essentially determined by the intensity of the interparticle dipolar interactions, and ii) what is the minimum ratio of dipole–dipole interaction (Edd) to nanoparticle anisotropy (KefV, anisotropy⋅volume) energies necessary to crossover from individual to collective behavior. A series of particle assemblies with similarly intense dipolar interactions but widely varying anisotropy is studied. The Kef is tuned through different degrees of cobalt-doping in maghemite nanoparticles, resulting in a variation of nearly an order of magnitude. All the bare particle compacts display collective behavior, except the one made with the highest anisotropy particles, which presents “marginal” features. Thus, a threshold of KefV/Edd ≈ 130 to suppress collective behavior is derived, in good agreement with Monte Carlo simulations. This translates into a crossover value of ≈1.7 for the easily accessible parameter TMAX(interacting)/TMAX(non-interacting) (ratio of the peak temperatures of the zero-field-cooled magnetization curves of interacting and dilute particle systems), which is successfully tested against the literature to predict the individual-like/collective behavior of any given interacting particle assembly comprising relatively uniform particles.Publication Open Access From field-induced to zero-field SMMs associated with open/closed structures of bis(ZnDy) tetranuclear complexes: a combined magnetic, theoretical and optical study(Royal Society of Chemistry, 2024) Zabala-Lekuona, Andoni; López de Pariza, Xabier; Díaz-Ortega, Ismael F.; Cepeda, Javier; Nojiri, Hiroyuki; Gritsan, Nina P.; Dmitriev, Alexey A.; López Ortega, Alberto; Rodríguez-Diéguez, Antonio; Seco, José M.; Colacio, Enrique; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa, PJUPNA2020We have prepared a bis(compartmental) Mannich base ligand H4L (1,4,8,11-tetraaza-1,4,8,11-tetrakis(2-hydroxy-3-methoxy-5-methylbenzyl)cyclotetradecane) specifically designed to obtain bis(TMIILnIII) tetranuclear complexes (TM = transition metal). In this regard, we have succeeded in obtaining three new complexes of the formula [Zn2(μ-L)(μ-OAc)Dy2(NO3)2]·[Zn2(μ-L)(μ-OAc)Dy2(NO3)(OAc)]·4CHCl3·2MeOH (1) and [TM2(μ-H2L)2(μ-succinate)Ln2(NO3)2] (NO3)2·2H2O·6MeOH (TMII = Zn, LnIII = Dy (2); TMII = Co, LnIII = Dy (3)). Compound 1 contains two different bis(ZnDy) tetranuclear molecules that cocrystallize in the structure, in which acetato bridging ligands connect the ZnII and DyIII ions within each ZnDy subunit. This compound does not exhibit slow magnetic relaxation at zero field, but it is activated in the presence of an applied dc magnetic field and/or by Dy/Y magnetic dilution, showing two relaxation processes corresponding to each of the two different bis(ZnDy) units found in the structure. As revealed by the theoretical calculations, magnetic relaxation in 1 is single-ion in origin and takes place through the first excited state of each DyIII ion. When using the succinato dicarboxylate bridging ligand instead of acetate, compounds 2 and 3 were serendipitously formed, which have a closed structure with the succinate anion bridging two ZnDy subunits belonging to two different ligands. It should be noted that only compound 2 exhibits slow relaxation of magnetization in the absence of an external magnetic field. According to experimental and theoretical data, 2 relaxes through the second excited Kramers doublet (Ueff = 342 K). In contrast, 3 displays field-induced SMM behaviour (Ueff = 203 K). However, the Co/Zn diluted version of this compound 3Zn shows slow relaxation at zero field (Ueff = 347 K). Ab initio theoretical calculations clearly show that the weak ferromagnetic coupling between CoII and DyIII ions is at the origin of the lack of slow relaxation of this compound at zero field. Compound 2 and its diluted analogues 2Y and 3Zn show hysteresis loops at very low temperature, thus confirming their SMM behaviour. Finally, compounds 1 and 2 show DyIII based emission even at room temperature that, in the case of 2, allows us to extract the splitting of the ground 6H15/2 term, which matches reasonably well with theoretical calculations.Publication Open Access Non-linear GMI decoding in 3D printed magnetic encoded systems(Elsevier, 2023) Beato López, Juan Jesús; Algueta-Miguel, Jose M.; Galarreta Rodríguez, Itziar; Garayo Urabayen, Eneko; López Ortega, Alberto; 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; Universidad Pública de Navarra / Nafarroako Unibertsitate PublikoaThe nonlinear giant magnetoimpedance (GMI) effect was explored as a highly sensitive sensing technology in 3D-printed magnetic encoded systems. Magnetic nanoparticles with low (magnetite, Fe3O4) and high (Co ferrite, Co0.7Fe2.3O4) magnetic remanence were embedded (10 wt%) in a polymeric matrix of Polylactic Acid (PLA) and Poly-ε-caprolactone (PCL) and extruded in magnetic filaments to be 3D printed by the Fused Deposition Modelling technique (FDM). Two different geometries were constructed namely, individual magnetic strips and fixed barcoded pieces. The stray magnetic fields generated by the magnetic nanoparticles were detected through the non-linear (second harmonic) GMI voltage using a soft magnetic CoFeSiB wire as the nucleus sensor. The decoding response was analyzed as a function of the magnetization remanence of the nanoparticles, the distance between the individual magnetic strips, and the position (height) of the GMI decoding sensor. It has been shown that modification of the net magnetization direction of each individual fixed strip within the barcode geometry is possible through the application of local external magnetic fields. This possibility improves the versatility of the 3D binary encoding system by adding an additional state (0 without nanoparticles, 1 or −1 depending on the relative orientation of the net magnetization along the strips) during the codifying procedure.Publication Open Access Hardening of cobalt ferrite nanoparticles by local crystal strain release: implications for rare earth free magnets(American Chemical Society, 2022) Muzzi, Beatrice; Lottini, Elisabetta; Yaacoub, Nader; Peddis, Davide; Bertoni, Giovanni; Julián Fernández, César de; Sangregorio, Claudio; López Ortega, Alberto; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate PublikoaIn this work, we demonstrate that the reduction of the local internal stress by a low-temperature solvent-mediated thermal treatment is an effective post-treatment tool for magnetic hardening of chemically synthesized nanoparticles. As a case study, we used nonstoichiometric cobalt ferrite particles of an average size of 32(8) nm synthesized by thermal decomposition, which were further subjected to solvent-mediated annealing at variable temperatures between 150 and 320 °C in an inert atmosphere. The postsynthesis treatment produces a 50% increase of the coercive field, without affecting neither the remanence ratio nor the spontaneous magnetization. As a consequence, the energy product and the magnetic energy storage capability, key features for applications as permanent magnets and magnetic hyperthermia, can be increased by ca. 70%. A deep structural, morphological, chemical, and magnetic characterization reveals that the mechanism governing the coercive field improvement is the reduction of the concomitant internal stresses induced by the low-temperature annealing postsynthesis treatment. Furthermore, we show that the medium where the mild annealing process occurs is essential to control the final properties of the nanoparticles because the classical annealing procedure (T > 350 °C) performed on a dried powder does not allow the release of the lattice stress, leading to the reduction of the initial coercive field. The strategy here proposed, therefore, constitutes a method to improve the magnetic properties of nanoparticles, which can be particularly appealing for those materials, as is the case of cobalt ferrite, currently investigated as building blocks for the development of rare-earth free permanent magnets.Publication Open Access Elucidating individual magnetic contributions in bi-magnetic Fe3O4/Mn3O4 Core/Shell nanoparticles by polarized powder neutron diffraction(Wiley, 2023) Golosovsky, Igor V.; Kibalin, Iurii A.; Gukasov, Arsen; Gómez Roca, Alejando; López Ortega, Alberto; Estrader, Marta; Vasilakaki, Marianna; Trohidou, Kalliopi; Hansen, T. C.; Puente-Orench, I.; Lelièvre-Berna, E.; Nogués, Josep; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa, PJUPNA 2020Heterogeneous bi-magnetic nanostructured systems have had a sustained interest during the last decades owing to their unique magnetic properties and the wide range of derived potential applications. However, elucidating the details of their magnetic properties can be rather complex. Here, a comprehensive study of Fe3O4/Mn3O4 core/shell nanoparticles using polarized neutron powder diffraction, which allows disentangling the magnetic contributions of each of the components, is presented. The results show that while at low fields the Fe3O4 and Mn3O4 magnetic moments averaged over the unit cell are antiferromagnetically coupled, at high fields, they orient parallel to each other. This magnetic reorientation of the Mn3O4 shell moments is associated with a gradual evolution with the applied field of the local magnetic susceptibility from anisotropic to isotropic. Additionally, the magnetic coherence length of the Fe3O4 cores shows some unusual field dependence due to the competition between the antiferromagnetic interface interaction and the Zeeman energies. The results demonstrate the great potential of the quantitative analysis of polarized neutron powder diffraction for the study of complex multiphase magnetic materials.Publication 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 PublikoaAdditive 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).Publication Open Access Magnetic binary encoding system based on 3D printing and GMI detection prototype(Elsevier, 2022) Beato López, Juan Jesús; Algueta-Miguel, Jose M.; Galarreta Rodríguez, Itziar; López Ortega, Alberto; Garayo Urabayen, Eneko; Gómez Polo, Cristina; Aresti Bartolomé, Maite; Soria Picón, Eneko; Pérez de Landazábal Berganzo, José Ignacio; Ciencias; Zientziak; Ingeniería Eléctrica, Electrónica y de Comunicación; Ingeniaritza Elektrikoa, Elektronikoa eta Telekomunikazio Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; Institute of Smart Cities - ISC; Gobierno de Navarra / Nafarroako Gobernua; Universidad Pública de Navarra / Nafarroako Unibertsitate PublikoaIn this work, the feasibility of a magnetic binary encoding system using 3D printing technology is analyzed. The study has a double interest, that is, the possibility of printing a 3D piece that contains the codified information and the development of a system for its decoding. For this purpose, magnetic nanoparticles (magnetite Fe3O4) were embedded in a polymeric matrix of Polylactic Acid (PLA) and Poly-ε-caprolactone (PCL). Similar to a conventional barcode, a rectangular piece with an alternating pattern of strips with absence (only polymer) and a 5 wt% of embedded magnetic nanoparticles was 3D printed employing the Fused Deposition Modelling tech- nique (FDM). The information was decoded by means of a Giant Magnetoimpedance (GMI) sensor-based pro- totype, by scanning the surface of the piece and measuring the changes in the magnetic field. As sensor nucleus, an amorphous soft magnetic wire of nominal composition (Co0.94 Fe0.06)72.5 Si12.5 B15 was employed. The decoding prototype incorporates a homemade electronic sensor interface that permits, at the time, the GMI sensor excitation and the subsequent signal conditioning to optimize its response. The output signal enables the detection of the magnetite nanoparticles and the magnetic decoding of the encoded information (“1” and “0”, presence or absence of the magnetic nanoparticles, respectively).Publication Open Access Direct evidence of a graded magnetic interface in bimagnetic core/shell nanoparticles using electron magnetic circular dichroism (EMCD)(American Chemical Society, 2021) Pozo Bueno, Daniel del; Varela, María; Estrader, Marta; López Ortega, Alberto; Gómez Roca, Alejando; Nogués, Josep; Peiró, Francesca; Estradé, Sònia; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Universidad Pública de Navarra / Nafarroako Unibertsitate PublikoaInterfaces play a crucial role in composite magnetic materials and particularly in bimagnetic core/shell nanoparticles. However, resolving the microscopic magnetic structure of these nanoparticles is rather complex. Here, we investigate the local magnetization of antiferromagnetic/ferrimagnetic FeO/Fe3O4 core/shell nanocubes by electron magnetic circular dichroism (EMCD). The electron energy-loss spectroscopy (EELS) compositional analysis of the samples shows the presence of an oxidation gradient at the interface between the FeO core and the Fe3O4 shell. The EMCD measurements show that the nanoparticles are composed of four different zones with distinct magnetic moment in a concentric, onion-type, structure. These magnetic areas correlate spatially with the oxidation and composition gradient with the magnetic moment being largest at the surface and decreasing toward the core. The results show that the combination of EELS compositional mapping and EMCD can provide very valuable information on the inner magnetic structure and its correlation to the microstructure of magnetic nanoparticles.Publication Open Access Nanoparticle size distribution and surface effects on the thermal dependence of magnetic anisotropy(ACS Publications, 2022) Gomide, Guilherme; Cabreira Gomes, Rafael; Gomes Viana, Márcio; Cortez Campos, Álex Fabiano; Aquino, Renata; López Ortega, Alberto; Perzynski, Régine; Depeyrot, Jérõm; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Universidad Pública de Navarra / Nafarroako Unibertsitate PublikoaStandard approaches to investigate the anisotropy of nanoparticle assemblies are either by means of zero-field-cooled-field-cooled DC magnetization curves or by analyzing the coercivity at low temperatures. However, these methodologies are restricted to average values of an anisotropy constant, without probing its temperature dependence or symmetry. In this context, analyzing the thermal dependence of coercivity arises as a more comprehensive approach to assess anisotropic properties. Here, we investigate experimentally the thermal dependence of coercivity for cobalt ferrite nanoparticle samples synthesized by different methods, in a large range of nanoparticle diameters, resulting in samples with different internal structure, surface roughness, and size distribution. Our analysis consists of accounting for the size distribution and thermal dependence of the relevant variables, allowing us to access the anisotropy constant as a function of temperature. The results indicate that the surface plays an important role in the low-field determined anisotropy constants, with the thermal dependence pointing to a combination of types/sources of anisotropy affecting the coercivity. While the cubic magnetocrystalline anisotropy dominates for nanoparticles with higher diameter, the influence of surface contribution increases substantially for smaller sizes. The state of the surface is shown to be key for determining the main source of anisotropy.