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 Publikoa
In 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).
Open Access
Core-shell magnetic nanoparticles
(MDPI, 2023) López Ortega, Alberto; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
This 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.
Open Access
Fe3O4-SiO2 mesoporous core/shell nanoparticles for magnetic field-induced ibuprofen-controlled release
(American Chemical Society, 2022-12-23) García Rodríguez, Lucía; Garayo Urabayen, Eneko; López Ortega, Alberto; Galarreta Rodríguez, Itziar; Cervera Gabalda, Laura María; Cruz Quesada, Guillermo; Cornejo Ibergallartu, Alfonso; Garrido Segovia, Julián José; 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, PJUPNA2020; Gobierno de Navarra / Nafarroako Gobernua
Hybrid magnetic nanoparticles made up of an iron oxide, Fe3O4, core and a mesoporous SiO2 shell with high magnetization and a large surface area were proposed as an efficient drug delivery platform. The core/shell structure was synthesized by two seed-mediated growth steps combining solvothermal and sol—gel approaches and using organic molecules as a porous scaffolding template. The system presents a mean particle diameter of 30(5) nm (9 nm magnetic core diameter and 10 nm silica shell thickness) with superparamagnetic behavior, saturation magnetization of 32 emu/g, and a significant AC magnetic-field-induced heating response (SAR = 63 W/gFe3O4, measured at an amplitude of 400 Oe and a frequency of 307 kHz). Using ibuprofen as a model drug, the specific surface area (231 m2/g) of the porous structure exhibits a high molecule loading capacity (10 wt %), and controlled drug release efficiency (67%) can be achieved using the external AC magnetic field for short time periods (5 min), showing faster and higher drug desorption compared to that of similar stimulus-responsive iron oxide-based nanocarriers. In addition, it is demonstrated that the magnetic field-induced drug release shows higher efficiency compared to that of the sustained release at fixed temperatures (47 and 53% for 37 and 42 °C, respectively), considering that the maximum temperature reached during the exposure to the magnetic field is well below (31 °C). Therefore, it can be hypothesized that short periods of exposure to the oscillating field induce much greater heating within the nanoparticles than in the external solution.
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; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa, PJUPNA2020
Dense 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.
Open Access
High-temperature superspin glass and low-temperature glassy exchange bias in passivated FeCo nanoparticles
(Elsevier, 2025-05-15) López Martín, Raúl; Lepesant, Mathieu; Lacroix, Lise-Marie; Toro, José A. de; López Ortega, Alberto; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
Conventional powders, dense systems of magnetic nanoparticles, often combine intra- and inter-particle magnetically glassy properties, which may complicate their interpretation. To shed light on this matter, we have studied 9 nm FeCo particles synthesized by thermal co-decomposition of metal amides after a passivation layer around 2 nm thick has formed in ambient conditions. The saturation magnetization, 117 emu/g, is consistent with the above metallic core/ferrite shell picture. The high magnetic moment and concentration of the particles yield, via strong interparticle interactions, a remarkable room temperature superspin glass-like phase (with freezing temperature above 350 K) for such small particles, as confirmed by the de Almeida-Thouless analysis. Additionally, we detect a spin glass-like freezing at the atomic scale (within the particles). Its corresponding feature, a small hump under small fields in the temperature dependence of the magnetization, closely agrees with the onset of the exchange bias effect (∼ 60 K) measured, unlike it is customary, with repeated field-coolings. The spin-disordered nature of the core/shell interface is further proved by a strong training effect of the exchange bias field, among others. This magnetic behavior offers an indirect proof of structural interface disorder even in fully passivated metallic particles.
Embargo
Competitive size effects in antiferromagnetic ferrimagnetic core shell nanoparticles for large exchange bias
(American Chemical Society, 2024-12-04) López Ortega, Alberto; Muzzi, Beatrice; Julián Fernández, César de; Sangregorio, Claudio; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
A family of exchange-coupled core—shell (CS) nanoparticles composed of an antiferromagnetic (AFM) core (Co0.3Fe0.7O) and a ferrimagnetic (FiM) shell (Co0.6Fe2.4O4) was investigated to unravel the role played by the dimension of the two components on the magnetic properties of the system. The series comprises three samples with different core diameters (2, 5, and 16 nm) and fixed shell thickness of ~2 nm. Although a strong core and shell magnetic coupling occurs in all the samples, the final properties of the hybrid nanosystems are greatly influenced by the size of the two counterparts. Indeed, while the larger sample can be described as a classic TC > TN exchange-bias, where TC and TN denote the ordering temperature of the FiM and AFM phases, respectively, on reducing the size, the blocking transition of the FiM shell decreases to values well below the TN of the AFM. In the first case, the FiM-AFM exchange-bias effect is determined by the magnetic ordering of the AFM core; in the other cases, it is due to the reduction of the thermal-driven magnetic fluctuations of the ordered FiM shell. On the other hand, the AFM properties of the core regions also are extremely sensitive to the particle size reduction, showing, for the smallest sample, the effect of the coupling between the two phases to appear at temperature well below TN displayed by the bulk system, indicating the potential presence of a blocking transition in the AFM core for small particles. These findings highlight the significant influence of the size of the AFM and FiM components on the hybrid system's ultimate properties. This result is potentially relevant for defining the working conditions of nanodevices exploiting exchange-bias phenomena, which have been recently proposed in the literature for application in several technological fields, ranging from rare-earth free magnets, spintronics, optoelectronics, and magnetic-refrigeration.
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).
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 Publikoa
In 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.
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 2020
Heterogeneous 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.
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, PJUPNA2020
We 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.