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.
Open Access
Nanoscale engineering of cobalt-gallium co-doped ferrites: a strategy to enhance high-frequency theranostic magnetic materials
(American Chemical Society, 2025-07-01) Galarreta Rodríguez, Itziar; Liguori, Deborah; Garayo Urabayen, Eneko; Muzzi, Beatrice; Cervera Gabalda, Laura María; Rubio Zuazo, Juan; Gomide, Guilherme; Depeyrot, Jérõm; López Ortega, Alberto; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Publica de Navarra / Nafarroako Unibertsitate Publikoa
The nanoscale engineering of doped iron oxide magnetic nanoparticles has attracted significant interest in recent years for high-frequency theragnostic applications, where simultaneous diagnosis and therapy are required. In particular, their ability to generate localized heating under alternating magnetic fields makes them ideal candidates for magnetic hyperthermia, a noninvasive cancer treatment technique. However, understanding the complex interplay between multiple dopant cations and their impact on dynamic magnetic behavior remains a significant challenge. In this work, we present a comprehensive study on how two differently marked cations (Co2+ and Ga3+) can modify both the magnetic properties of these nanoparticles and their efficiency in heat generation under alternating magnetic fields. To this end, a series of nanoparticles with the formula CoxGa0.15Fe2.85-xO4 (0 < x < 0.3) was prepared via thermal decomposition, enabling the production of monodisperse nanocrystals with high crystallinity and precise stoichiometric control. Their exhaustive structural and magnetic characterization confirmed site-selective incorporation of Ga3+ into tetrahedral sites and Co2+ into octahedral sites. Increasing the cobalt content within the gallium-doped framework leads to enhanced magnetocrystalline anisotropy and higher saturation magnetization, both crucial parameters for efficient heat dissipation in magnetic hyperthermia. The study further demonstrates that the dynamic magnetic response of these nanostructures is strongly influenced by the interplay between doping composition, anisotropy, and the amplitude of the applied magnetic field. These findings highlight the effectiveness of nanoscale codoping strategies in fine-tuning magnetic behavior and optimizing the performance of spinel ferrite nanoparticles for advanced biomedical and technological applications, particularly high-frequency magnetic hyperthermia.
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.
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
Nanoparticle size distribution and surface effects on the thermal dependence of magnetic anisotropy
(American Chemical Society, 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 Publikoa
Standard 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.