Open Access
Martensitic transformation controlled by electromagnetic field: from experimental evidence to wireless actuator applications
(Elsevier, 2022) Garayo Urabayen, Eneko; La Roca, Paulo Matías; Gómez Polo, Cristina; Sánchez-Alarcos Gómez, Vicente; Recarte Callado, Vicente; Pérez de Landazábal Berganzo, José Ignacio; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Gobierno de Navarra / Nafarroako Gobernua
Mechanical actuators based on shape memory alloys (SMA) are becoming a key component in the development of novel soft robotic applications and surgically implantable devices. Their working principle relies in the temperature induced martensitic transformation (MT), which is responsible of the actuation mechanism. In this work, we found experimental evidence to show that the martensitic transformation can be controlled by electromagnetic field (EF) by a wireless process in ferromagnetic shape memory alloys. It is shown that the martensitic transformation can be driven by an external EF (frequency 45 kHz) while the specific absorption rate (SAR), which was determined through real-time dynamic magnetization measurements, allows the instantaneous monitoring of the transformation evolution. On the basis of the obtained results, we propose a strategy to achieve a battery-free wireless SMA actuator that can be remotely controlled. This concept can be applicable to other SMA material that exhibit a similar magneto-structural phase transition
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
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
Modulating photocatalytic activity of nitrogen doped TiO2 nanoparticles via magnetic field
(Elsevier, 2024-07-30) Gómez Polo, Cristina; Cervera Gabalda, Laura María; Garayo Urabayen, Eneko; Beato López, Juan Jesús; Pérez de Landazábal Berganzo, José Ignacio; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
The effect of the magnetic field on the photocatalytic activity of TiO2-based nanoparticles is analyzed using a magnetically-assisted photoreactor with permanent magnets to generate a controlled uniform magnetic field, B (¿82 mT). Nitrogen doped TiO2 nanoparticles (sizes around 10 nm) were synthesized through a solvothermal method employing Ti(IV) butoxide and HNO3 (x = 0, 0.5, 1, 1.5 and 2 mL) as precursors and their structural, optical and magnetic properties were analyzed. Specifically, nitrogen doping is confirmed through Hard X-ray Photoelectron Spectroscopy (HAXPES) in those samples synthesized with low HNO3 concentrations (x = 0.5, 1). The correlation between spin polarization (magnetic susceptibility) and visible photocatalytic activity (methyl orange as a model organic pollutant) is particularly analyzed. Surprisingly, opposite effects of the magnetic field on the photocatalytic performance are found in the visible range (above 400 nm) or under UV-Vis irradiation (decrease and increase in the photocatalytic activity, respectively, under magnetic field). The Langmuir-Hinshelwood model allows us to conclude that the strong decrease in adsorption under the magnetic field (around 42 % for x = 0.5) masks the increase in the kinetic constant (close to 58 % for x = 0.5) related mainly to the effect of Lorentz forces on the reduction of the electron-hole recombination.
Open Access
Magnetic-field-assisted photocatalysis of N-TiO2 nanoparticles
(IEEE, 2023-09-04) Cervera Gabalda, Laura María; Garayo Urabayen, Eneko; Beato López, Juan Jesús; Pérez de Landazábal Berganzo, José Ignacio; Gómez Polo, Cristina; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
Nitrogen doped TiO2 nanoparticles were synthesized through solvothermal method employing Ti (IV) butoxide and HNO3 as precursors. Structural and optical characterizations confirm their nanometer nature (sizes around 10 nm) and the band-gap energy values in the UV range (3.2 eV). Nitrogen doping enhances the occurrence of optical Urbach tails extending towards the visible region. Visible photocatalytic performance (degradation of methyl orange) is correlated with maximum values in the magnetic susceptibility linked to a magnetic polarization of the anatase structure via defects (oxygen vacancies). The application of magnetic field provides a positive effect (acceleration in reaction kinetics) within the UV-Vis range.
Embargo
Boosting Li-S batteries through the synergistic effect of recycled ferrites and external magnetic induction
(Elsevier, 2024-11-20) Bonilla, Álvaro; Jiménez Blasco, Uxua; Gómez-Cámer, Juan Luis; Garayo Urabayen, Eneko; Pérez de Landazábal Berganzo, José Ignacio; Caballero, Álvaro; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Gobierno de Navarra / Nafarroako Gobernua, PC003-04 3D-MAGNET
Despite being considered one of the most promising energy storage technologies, lithium-sulfur batteries (LSBs) are limited in terms of commercialization by the shuttle effect and slow reaction kinetics. In this work, we demonstrate for the first time that the use of recycled ferrite in conjunction with an external magnetic field generated by a permanent magnet can enhance the reaction kinetics and the adsorption of polysulfides (LiPSs), and hence the electrochemical stability. An in-depth kinetic study shows that under the effect of an external magnetic field, the electrode has lower polarization, a higher Li+ diffusion coefficient and a lower activation energy between electrochemical stages. The electrode also has a capacity retention up to 40 % higher and half the capacity loss per cycle at a high rate of 1C. At an ultra-high rate of 10C, the electrode has a capacity of 507 mAh g−1 after 150 cycles and an areal capacity of up to 3 mAh cm−2 at an ultra-high loading of 13 mg cm−2. In addition to the promising results observed in electrochemical terms, our approach is also more sustainable due to the use of a recycled electronic material obtained via dry milling, thereby avoiding the use of fossil carbons.
Open Access
Steering the synthesis of Fe3O4 nanoparticles under sonication by using a fractional factorial design
(Elsevier, 2021) Echeverría Morrás, Jesús; Moriones Jiménez, Paula; Garrido Segovia, Julián José; Ugarte Martínez, María Dolores; Cervera Gabalda, Laura María; Garayo Urabayen, Eneko; Gómez Polo, Cristina; Pérez de Landazábal Berganzo, José Ignacio; Ciencias; Zientziak; Estadística, Informática y Matemáticas; Estatistika, Informatika eta Matematika; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa; Gobierno de Navarra / Nafarroako Gobernua
Superparamagnetic iron oxide nanoparticles (MNPs) have the potential to act as heat sources in magnetic hyperthermia. The key parameter for this application is the specific absorption rate (SAR), which must be as large as possible in order to optimize the hyperthermia treatment. We applied a Plackett-Burman fractional factorial design to investigate the effect of total iron concentration, ammonia concentration, reaction temperature, sonication time and percentage of ethanol in the aqueous media on the properties of iron oxide MNPs. Characterization techniques included total iron content, Fourier Transform Infrared Spectroscopy, X-Ray Diffraction, High Resolution Transmission Electron Microscopy, and Dynamic Magnetization. The reaction pathway in the coprecipitation reaction depended on the initial Fe concentration. Samples synthesized from 0.220 mol L−1 Fe yielded magnetite and metastable precipitates of iron oxyhydroxides. An initial solution made up of 0.110 mol L−1 total Fe and either 0.90 or 1.20 mol L−1 NH3(aq) led to the formation of magnetite nanoparticles. Sonication of the reaction media promoted a phase transformation of metastable oxyhydroxides to crystalline magnetite, the development of crystallinity, and the increase of specific absorption rate under dynamic magnetization.
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
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
Fe-C nanoparticles obtained from thermal decomposition employing sugars as reducing agents
(Elsevier, 2020) Cervera Gabalda, Laura María; Pérez de Landazábal Berganzo, José Ignacio; Garayo Urabayen, Eneko; Monteserín, María; Larumbe Abuin, Silvia; Martín, F.; Gómez Polo, Cristina; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Gobierno de Navarra / Nafarroako Gobernua; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
The aim of the work is to present a comparative analysis (structural and magnetic) of Fe-C nanocomposites obtained by the thermal decomposition of sugars (fructose, glucose and sucrose) employing FeCl3 as Fe3+ precursor. The thermal decomposition was followed through Thermogravimetry (TGA) and Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction, High Resolution Transmission Electron Microscopy (HRTEM) and Raman spectroscopy. The results indicate the reduction of Fe3+ under the performed thermal treatments and the achievement at high annealing temperatures of Fe-C nanostructures (coexistence of α-Fe and Fe3C nanoparticles surrounded by a carbon matrix). The magnetic characterization performed by dc SQUID magnetometry, shows an antiferromagnetic response in the initial stages of the decomposition process, and a ferromagnetic behavior linked to the Fe-based nanoparticles. The magnetic induction heating was analyzed through the ac hysteresis loops. Moderate Specific Absorption Rate (SAR) is obtained in Fe-C nanoparticles (~ 70 W/gFe), ascribed to the large nanoparticle size. The combination of porous carbon structure and ferromagnetic response of the Fe-C nanoparticles (i.e. local temperature increase under ac magnetic field) enlarge the emerging applications of these carbonaceous nanocomposites.