Open Access
An alternative methodology for the evaluation of photocatalytic activity of polymeric coatings by monitoring dye degradation
(MDPI, 2022) Sandúa Fernández, Xabier; Rivero Fuente, Pedro J.; Esparza Gorráiz, Joseba; Rodríguez Trías, Rafael; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2
This work provides an alternative method for evaluating the photodegradation behaviour of different types of dyes such as Methylene Blue, Rhodamine B, Congo Red, Metanil Yellow, and Malachite Green. In this methodology, the coating is dyed with the chosen colorant and two beams of light are combined and channelled to a spot on the dyed coating through an optical fibre, the first one from an ultraviolet (UV) source (which is the responsible of activating photocatalysis) and the second one from a Visible light source, which is employed to monitor changes in colour along the time. The photocatalytic coating selected for testing this methodology consists of a mat of electrospun poly (acrylic acid) (PAA) fibres that acts as base film, furtherly coated by using layer-by-layer (LbL) assembly technique for the immobilization of two different photocatalytic metal oxide precursors (TiO2 and Fe2O3) nanoparticles. The morphological characterization of the samples has been implemented by means of scanning electron microscopy (SEM), confocal microscopy, and water contact angle measurements in order to analyse the resultant thickness, roughness, electrospun fibre diameter, and wettability. The experimental results clearly demonstrate the validity of the methodology to measure the photocatalytic activity in all dyed coatings, although significant differences have been observed depending on the selected dye.
Open Access
Self-referenced optical fiber sensor based on LSPR generated by gold and silver nanoparticles embedded in layer-by-layer nanostructured coatings
(MDPI, 2022) Martínez Hernández, María Elena; Goicoechea Fernández, Javier; Rivero Fuente, Pedro J.; Sandúa Fernández, Xabier; Arregui San Martín, Francisco Javier; Ingeniaritza; Ingeniaritza Elektrikoa, Elektronikoaren eta Telekomunikazio Ingeniaritzaren; Institute of Smart Cities - ISC; Institute for Advanced Materials and Mathematics - INAMAT2; Ingeniería; Ingeniería Eléctrica, Electrónica y de Comunicación
In this work, an optical fiber sensor based on the localized surface plasmon resonance (LSPR) phenomenon has been designed for the detection of two different chemical species (mercury and hydrogen peroxide) by using Layer-by-Layer Embedding (LbL-E) as a nanofabrication technique. In the first step, silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs) have been synthesized by using a chemical protocol as a function of the strict control of three main parameters, which were polyelectrolyte concentration, a loading agent, and a reducing agent. In the second step, their incorporation into nanometric thin films have been demonstrated as a function of the number of bilayers, which shows two well-located absorption peaks associated to their LSPR in the visible region at 420 nm (AgNPs) and 530 nm (AuNPs). Finally, both plasmonic peaks provide a stable real-time reference measurement, which can be extracted from the spectral response of the optical fiber sensor, which shows a specific sensing mechanism as a function of the analyte of study.
Open Access
Visible light activation of gold nanoparticles embedded into titanium dioxide surface in electrospun polymeric coatings
(MDPI, 2024) Sandúa Fernández, Xabier; Rivero Fuente, Pedro J.; Calvopiña, Jonathan; Rodríguez Trías, Rafael; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2
This work reports the development of a functional photocatalytic coating based on a combination of polymeric electrospun fibres and nanoparticles that is intended to be activated in the visible light range. In this sense, the resulting fibres can act as an effective matrix for the incorporation of titanium dioxide (TiO2) particles, which are covered by gold nanoparticles (AuNPs), in the outer surface of the metal oxide precursor. In the first step of the process, the optical properties of the nanoparticles were determined by UV-Vis spectroscopy. The extension of the visible absorption can be associated to the localized surface plasmon resonance (LSPR) of the metallic AuNPs. In addition, the resultant particle size distribution and average particle diameter was evaluated by dynamic light scattering (DLS) measurements. Furthermore, the phase composition and porosity of the functional particle powder were analysed by an XRD and N2 adsorption test. In the second step, these synthesized particles have been successfully immobilized into a PAA + β-CD electrospun fibre matrix by using the two different deposition methods of dip-coating and solution-casting, respectively. The morphological characterization of the samples was implemented by means of scanning electron microscopy (SEM), showing uniform and homogeneous, free-beaded fibres with a random distribution of the synthesized particles deposited onto the electrospun fibres. Then, the functional coatings were removed from the substrate, and a thermogravimetric (TGA) analysis was carried out for each sample in order to obtain the precursor mass immobilized in the coating. Once the overall mass of precursor was obtained, the percentage of TiO2 particles and AuNPs in the precursor was calculated by using inductively coupled plasma atomic emission spectrometry (ICP-AES). Finally, the photocatalytic activity of both functional solution and electrospun coatings were evaluated in terms of a gradual degradation of rhodamine B (RhB) dye after continuous exposition to a visible-light lamp.
Open Access
Antifungal activity of chitosan/poly (ethylene oxide) blend electrospun polymeric fiber mat doped with metallic silver nanoparticles
(MDPI, 2023) Murillo Larrey, Leire; Rivero Fuente, Pedro J.; Sandúa Fernández, Xabier; Rodríguez Trías, Rafael; Pérez Garrido, María Gumersinda; Ingeniería; Ingeniaritza; Institute for Multidisciplinary Research in Applied Biology - IMAB; Institute for Advanced Materials and Mathematics - INAMAT2
In this work, the implementation of advanced functional coatings based on the combination of two compatible nanofabrication techniques such as electrospinning and dip-coating technology have been successfully obtained for the design of antifungal surfaces. In a first step, uniform and beadless electrospun nanofibers of both polyethylene oxide (PEO) and polyethylene (PEO)/chitosan (CS) blend samples have been obtained. In a second step, the dip-coating process has been gradually performed in order to ensure an adequate distribution of silver nanoparticles (AgNPs) within the electrospun polymeric matrix (PEO/CS/AgNPs) by using a chemical reduction synthetic process, denoted as in situ synthesis (ISS). Scanning electron microscopy (SEM) has been used to evaluate the surface morphology of the samples, showing an evolution in average fiber diameter from 157 ± 43 nm (PEO), 124 ± 36 nm (PEO/CS) and 330 ± 106 nm (PEO/CS/AgNPs). Atomic force microscopy (AFM) has been used to evaluate the roughness profile of the samples, indicating that the ISS process induced a smooth roughness surface because a change in the average roughness Ra from 84.5 nm (PEO/CS) up to 38.9 nm (PEO/CS/AgNPs) was observed. The presence of AgNPs within the electrospun fiber mat has been corroborated by UV-Vis spectroscopy thanks to their characteristic optical properties (orange film coloration) associated to the Localized Surface Plasmon Resonance (LSPR) phenomenon by showing an intense absorption band in the visible region at 436 nm. Energy dispersive X-ray (EDX) profile also indicates the existence of a peak located at 3 keV associated to silver. In addition, after doping the electrospun nanofibers with AgNPs, an important change in the wettability with an intrinsic hydrophobic behavior was observed by showing an evolution in the water contact angle value from 23.4° ± 1.3 (PEO/CS) up to 97.7° ± 5.3 (PEO/CS/AgNPs). The evaluation of the antifungal activity of the nanofibrous mats against Pleurotus ostreatus clearly indicates that the presence of AgNPs in the outer surface of the nanofibers produced an important enhancement in the inhibition zone during mycelium growth as well as a better antifungal efficacy after a longer exposure time. Finally, these fabricated electrospun nanofibrous membranes can offer a wide range of potential uses in fields as diverse as biomedicine (antimicrobial against human or plant pathogen fungi) or even in the design of innovative packaging materials for food preservation.
Open Access
Desarrollo de recubrimientos funcionales nanoestructurados basados en la incorporación de óxidos metálicos fotocatalíticos
(2024) Sandúa Fernández, Xabier; Rivero Fuente, Pedro J.; Rodríguez Trías, Rafael; Ingeniería; Ingeniaritza; Gobierno de Navarra / Nafarroako Gobernua
Este trabajo se centra en el desarrollo de recubrimientos fotocatalíticos funcionales mediante la incorporación de óxidos metálicos. Inicialmente se realiza la funcionalización y optimización de un recubrimiento fotocatalítico, con el TiO2 como precursor principal. Para ello, se elabora un estudio comparativo con diversas técnicas de deposición, capaces de inmovilizar el precursor TiO2 en una matriz de fibras poliméricas obtenidas por la técnica de electrospinning, empleando para ello el polímero PAA. Una vez identificadas las dos técnicas de inmovilización que mejores resultados presentan, se elabora un nuevo estudio comparativo en donde se introducen diferentes óxidos metálicos (WO3, Fe2O3, SrTiO3) como elementos coadyuvantes del TiO2. De este estudio se obtiene la combinación de compuestos activos y la técnica de inmovilización más funcional. Una vez obtenido el recubrimiento fotocatalítico óptimo, se realiza con éste un estudio de degradación de diferentes tintes orgánicos, para así estudiar la tendencia de degradación que presentan estos tintes depositados en un mismo tipo de recubrimiento fotocatalítico. Por último, con el fin de obtener un recubrimiento que también pueda ser activado en el rango visible de la luz, se sintetizan nanopartículas de oro en la superficie de las partículas de TiO2, para activar el efecto de resonancia localizada de plasmones superficiales (LSPR). De esta manera, la fotocatálisis puede ser activada con una fuente que emite dentro del espectro visible.
Open Access
Complex selective manipulations of thermomagnetic programmable matter
(Springer Nature, 2022) Irisarri Erviti, Josu; Ezcurdia Aguirre, Íñigo Fermín; Sandúa Fernández, Xabier; Galarreta Rodríguez, Itziar; Pérez de Landazábal Berganzo, José Ignacio; Marzo Pérez, Asier; Ciencias; Zientziak; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; Institute of Smart Cities - ISC
Programmable matter can change its shape, stiffness or other physical properties upon command. Previous work has shown contactless optically controlled matter or magnetic actuation, but the former is limited in strength and the latter in spatial resolution. Here, we show an unprecedented level of control combining light patterns and magnetic fields. A mixture of thermoplastic and ferromagnetic powder is heated up at specific locations that become malleable and are attracted by magnetic fields. These heated areas solidify on cool down, and the process can be repeated. We show complex control of 3D slabs, 2D sheets, and 1D filaments with applications in tactile displays and object manipulation. Due to the low transition temperature and the possibility of using microwave heating, the compound can be manipulated in air, water, or inside biological tissue having the potential to revolutionize biomedical devices, robotics or display technologies.
Open Access
Design of photocatalytic functional coatings based on the immobilization of metal oxide particles by the combination of electrospinning and layer-by-layer deposition techniques
(MDPI, 2022) Sandúa Fernández, Xabier; Rivero Fuente, Pedro J.; Esparza Gorráiz, Joseba; Conde, Ana; Rodríguez Trías, Rafael; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; Gobierno de Navarra / Nafarroako Gobernua
This work reports the design and characterization of functional photocatalytic coatings based on the combination of two different deposition techniques. In a first step, a poly(acrylic acid) + β-Cyclodextrin (denoted as PAA+ β-CD) electrospun fiber mat was deposited by using the electrospinning technique followed by a thermal treatment in order to provide an enhancement in the resultant adhesion and mechanical resistance. In a second step, a layer-by-layer (LbL) assembly process was performed in order to immobilize the metal oxide particles onto the previously electrospun fiber mat. In this context, titanium dioxide (TiO2 ) was used as the main photocatalytic element, acting as the cationic element in the multilayer LbL structure. In addition, two different metal oxides, such as tungsten oxide (WO3 ) and iron oxide (Fe2O3 ), were added into PAA anionic polyelectrolyte solution with the objective of optimizing the photocatalytic efficiency of the coating. All of the coatings were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM) images, showing an increase in the original fiber diameter and a decrease in roughness of the mats because of the LbL second step. The variation in the wettability properties from a superhydrophilic surface to a less wettable surface as a function of the incorporation of the metal oxides was also observed by means of water contact angle (WCA) measurements. With the aim of analyzing the photocatalytic efficiency of the samples, degradation of methyl blue (MB) azo-dye was studied, showing an almost complete discoloration of the dye in the irradiated area. This study reports a novel combination method of two deposition techniques in order to obtain a functional, homogeneous and efficient photocatalytic coating.
Open Access
An optical fiber sensor for Hg2+ detection based on the LSPR of silver and gold nanoparticles embedded in a polymeric matrix as an effective sensing material
(MDPI, 2021-07-07) Martínez Hernández, María Elena; Sandúa Fernández, Xabier; Rivero Fuente, Pedro J.; Goicoechea Fernández, Javier; Arregui San Martín, Francisco Javier; Ingeniería Eléctrica, Electrónica y de Comunicación; Ingeniaritza Elektrikoa, Elektronikoa eta Telekomunikazio Ingeniaritza; Institute of Smart Cities - ISC; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
In this work, an optical fiber sensor based on the localized surface plasmon resonance (LSPR) phenomenon is presented as a powerful tool for the detection of heavy metals (Hg2+). The resultant sensing film was fabricated using a nanofabrication process, known as layer-by-layer embedding (LbL-E) deposition technique. In this sense, both silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs) were synthesized using a synthetic chemical protocol as a function of a strict control of three main parameters: polyelectrolyte concentration, loading agent, and reducing agent. The use of metallic nanostructures as sensing materials is of great interest because well-located absorption peaks associated with their LSPR are obtained at 420 nm (AgNPs) and 530 nm (AuNPs). Both plasmonic peaks provide a stable real-time reference that can be extracted from the spectral response of the optical fiber sensor, giving a reliable monitoring of the Hg2+ concentration.
Open Access
Application of symmetric neural networks for bead geometry determination in wire and arc additive manufacturing (WAAM)
(MDPI, 2025-02-21) Fernández Zabalza, Aitor; Veiga Suárez, Fernando; Suárez, Alfredo; Uralde Jiménez, Virginia; Sandúa Fernández, Xabier; Alfaro López, José Ramón; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2
The accurate prediction of weld bead geometry is crucial for ensuring the quality and consistency of wire and arc additive manufacturing (WAAM), a specific form of directed energy deposition (DED) that utilizes arc welding. Despite advancements in process control, predicting the shape and dimensions of weld beads remains challenging due to the complex interactions between process parameters and material behavior. This paper addresses this challenge by exploring the application of symmetrical neural networks to enhance the accuracy and reliability of geometric predictions in WAAM. By leveraging advanced machine learning techniques and incorporating the inherent symmetry of the welding process, the proposed models aim to precisely forecast weld bead geometry. The use of neuronal networks and experimental validation demonstrate the potential of symmetrical neural networks to improve prediction precision, contributing to more consistent and optimized WAAM outcomes.
Open Access
A comparative study in the design of TIO2 assisted photocatalytic coatings monitored by controlling hydrophilic behavior and rhodamine b degradation
(MDPI, 2023) Sandúa Fernández, Xabier; Rivero Fuente, Pedro J.; Conde, Ana; Esparza Gorráiz, Joseba; Rodríguez Trías, Rafael; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2
This work presents a comparative study related to the photocatalytic efficiency associated with wettability measurements and organic dye degradation, as well as other relevant properties (i.e., corrosion resistance, roughness, wettability, and adhesion to a substrate). The photocatalytic precursors are titanium dioxide nanoparticles (TiO2 NPs) which are dispersed onto a polymeric electrospun fiber matrix by using three different deposition techniques such as electrospraying, spraying, and dip-coating, respectively. In this work, the host electrospun matrix is composed of poly(acrylic acid) fibers crosslinked with cyclodextrin (β-CD), which shows a good chemical affinity and stability with the other deposition techniques which are responsible for incorporating the TiO2 NPs. In order to evaluate the efficacy of each coating, the resultant photocatalytic activity has been monitored by two different tests. Firstly, the reduction in the water contact angle is appreciated, and secondly, the degradation of an organic dye (Rhodamine B) is observed under UV irradiation. In addition, the final roughness, adherence, and pitting corrosion potential have also been controlled in order to determine which solution provides the best combination of properties. Finally, the experimental results clearly indicate that the presence of TiO2 NPs deposited by the three techniques is enough to induce a super hydrophilic behavior after UV irradiation. However, there are notable differences in photocatalytic efficiency on the Rhodamine B as a function of the selected deposition technique.