Person: Rodríguez Trías, Rafael
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Rodríguez Trías
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Rafael
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Ingeniería
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InaMat2. Instituto de Investigación en Materiales Avanzados y Matemáticas
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0000-0003-0086-7547
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491
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Publication 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 - INAMAT2This 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.Publication Open Access Icephobic coating based on novel SLIPS made of infused PTFE fibers for aerospace application(MDPI, 2024) Vicente Gómara, Adrián; Rivero Fuente, Pedro J.; Rehfeld, Nadine; Stake, Andreas; García, Paloma; Carreño, Francisco; Mora, Julio; Rodríguez Trías, Rafael; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa, PJUPNA1929The development of slippery surfaces has been widely investigated due to their excellent icephobic properties. A distinct kind of an ice-repellent structure known as a slippery liquid-infused porous surface (SLIPS) has recently drawn attention due to its simplicity and efficacy as a passive ice-protection method. These surfaces are well known for exhibiting very low ice adhesion values (τice < 20 kPa). In this study, pure Polytetrafluoroethylene (PTFE) fibers were fabricated using the electrospinning process to produce superhydrophobic (SHS) porous coatings on samples of the aeronautical alloy AA6061-T6. Due to the high fluorine–carbon bond strength, PTFE shows high resistance and chemical inertness to almost all corrosive reagents as well as extreme hydrophobicity and high thermal stability. However, these unique properties make PTFE difficult to process. For this reason, to develop PTFE fibers, the electrospinning technique has been used by an PTFE nanoparticles (nP PTFE) dispersion with addition of a very small amount of polyethylene oxide (PEO) followed with a sintering process (380 °C for 10 min) to melt the nP PTFE together and form uniform fibers. Once the porous matrix of PTFE fibers is attached, lubricating oil is added into the micro/nanoscale structure in the SHS in place of air to create a SLIPS. The experimental results show a high-water contact angle (WCA) ≈ 150° and low roll-off angle (αroll-off) ≈ 22° for SHS porous coating and a decrease in the WCA ≈ 100° and a very low αroll-off ≈ 15° for SLIPS coating. On one hand, ice adhesion centrifuge tests were conducted for two types of icing conditions (glaze and rime) accreted in an ice wind tunnel (IWT), as well as static ice at different ice adhesion centrifuge test facilities in order to compare the results for SHS, SLIPs and reference materials. This is considered a preliminary step in standardization efforts where similar performance are obtained. On the other hand, the ice adhesion results show 65 kPa in the case of SHS and 4.2 kPa of SLIPS for static ice and <10 kPa for rime and glace ice. These results imply a significant improvement in this type of coatings due to the combined effect of fibers PTFE and silicon oil lubricant.Publication Open Access Multifunctional protective PVC-ZnO nanocomposite coatings deposited on aluminum alloys by electrospinning(MDPI, 2019) Iribarren Zabalegui, Álvaro; Rivero Fuente, Pedro J.; Berlanga Labari, Carlos; Larumbe Abuin, Silvia; Miguel, Adrián; Rodríguez Trías, Rafael; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; Ingeniería; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa, PRO-UPNA 18 (6107)This paper reports the use of the electrospinning technique for the synthesis of nanocomposite micro/nanofibers by combining a polymeric precursor with hydrophobic behavior like polyvinyl chloride (PVC) with nanoparticles of a corrosion inhibitor like ZnO. These electrospun fibers were deposited on substrates of the aluminum alloy 6061T6 until forming a coating around 100 m. The effect of varying the different electrospinning deposition parameters (mostly applied voltage and flow-rate) was exhaustively analyzed in order to optimize the coating properties. Several microscopy and analysis techniques have been employed, including optical microscopy (OM), field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Water contact angle (WCA) measurements have been carried out in order to corroborate the coating hydrophobicity. Finally, their corrosion behavior has been evaluated by electrochemical tests (Tafel curves and pitting potential measurements), showing a relevant improvement in the resultant corrosion resistance of the coated aluminum alloys.Publication Open Access Icephobic and anticorrosion coatings deposited by electrospinning on aluminum alloys for aerospace applications(MDPI, 2021) Vicente Gómara, Adrián; Rivero Fuente, Pedro J.; García, Paloma; Mora, Julio; Carreño, Francisco; Rodríguez Trías, Rafael; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; IngenieríaAnti-icing or passive strategies have undergone a remarkable growth in importance as a complement for the de-icing approaches or active methods. As a result, many efforts for developing icephobic surfaces have been mostly dedicated to apply superhydrophobic coatings. Recently, a different type of ice-repellent structure based on slippery liquid-infused porous surfaces (SLIPS) has attracted increasing attention for being a simple and effective passive ice protection in a wide range of application areas, especially for the prevention of ice formation on aircrafts. In this work, the electrospinning technique has been used for the deposition of PVDF-HFP coatings on samples of the aeronautical alloy AA7075 by using a thickness control system based on the identification of the proper combination of process parameters such as the flow rate and applied voltage. In addition, the influence of the experimental conditions on the nanofiber properties is evaluated in terms of surface morphology, wettability, corrosion resistance, and optical transmittance. The experimental results showed an improvement in the micro/nanoscale structure, which optimizes the superhydro-phobic and anticorrosive behavior due to the air trapped inside the nanotextured surface. In addi-tion, once the best coating was selected, centrifugal ice adhesion tests (CAT) were carried out for two types of icing conditions (glaze and rime) simulated in an ice wind tunnel (IWT) on both as-deposited and liquid-infused coatings (SLIPs). The liquid-infused coatings showed a low water adhesion (low contact angle hysteresis) and low ice adhesion strength, reducing the ice adhesion four times with respect to PTFE (a well-known low-ice-adhesion material used as a reference).Publication Open Access The role of the fiber/bead hierarchical microstructure on the properties of pvdf coatings deposited by electrospinning(MDPI, 2021) Vicente Gómara, Adrián; Rivero Fuente, Pedro J.; Rodríguez Trías, Rafael; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa, PJUPNA1929Among the various polymeric options employed for the deposition of electrospun coat-ings, poly(vinylidene fluoride) (PVDF) has been widely investigated thanks to its excellent mechanical properties, high chemical resistance, and good thermal stability. In this work, the electrospin-ning technique is used for the fabrication of functional PVDF fibers in order to identify and evaluate the influence of the experimental conditions on the nanofiber properties in terms of optical trans-mittance, wettability, corrosion resistance, and surface morphology. Some of these properties can play a relevant role in the prevention of ice formation in aircrafts. According to this, a matrix of 4 × 4 samples of aluminum alloy AA 6061T6 was successfully coated by controlling two operational input parameters such as the resultant applied voltage (from 10 up to 17.5 KV) and the flow rate (from 800 up to 1400 µL/h) for a fixed polymeric precursor concentration (15 wt.%). The experimental results have shown a multilevel fiber-bead structure where the formation of a fiber mesh directly depends on the selected operational parameters. Several microscopy and surface analysis techniques such as confocal microscopy (CM), field emission scanning electron microscopy (FE-SEM), UV/vis spectroscopy, and water contact angle (WCA) were carried out in order to corroborate the morphology, transmittance, and hydrophobicity of the electrospun fiber composite. Finally, the corrosion behavior was also evaluated by electrochemical tests (Tafel curves measurement), show-ing that the presence of electrospun PVDF fibers produces a relevant improvement in the resultant corrosion resistance of the coated aluminum alloys. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.Publication 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 GobernuaThis 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.Publication Open Access Designing multifunctional protective PVC electrospun fibers with tunable properties(MDPI, 2020) Rivero Fuente, Pedro J.; Rosagaray Burdaspar, Iker; Fuertes Bonel, Juan Pablo; Rodríguez Trías, Rafael; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; Ingeniería; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa, PJUPNA1929In this work, the electrospinning technique is used for the fabrication of electrospun functional fibers with desired properties in order to show a superhydrophobic behavior. With the aim to obtain a coating with the best properties, a design of experiments (DoE) has been performed by controlling several inputs operating parameters, such as applied voltage, flow rate, and precursor polymeric concentration. In this work, the reference substrate to be coated is the aluminum alloy (60661T6), whereas the polymeric precursor is the polyvinyl chloride (PVC) which presents an intrinsic hydrophobic nature. Finally, in order to evaluate the coating morphology for the better performance, the following parameters-such as fiber diameter, surface roughness (Ra, Rq), optical properties, corrosion behavior, and wettability-have been deeply analyzed. To sum up, this is the first time that DoE has been used for the optimization of superhydrophobic or anticorrosive surfaces by using PVC precursor for the prediction of an adequate surface morphology as a function of the input operational parameters derived from electrospinning process with the aim to validate better performance.Publication Open Access Novel design of superhydrophobic and anticorrosive PTFE and PAA + B - CD composite coating deposited by electrospinning, spin coating and electrospraying techniques(MDPI, 2022) Vicente Gómara, Adrián; Rivero Fuente, Pedro J.; Urdiroz Urricelqui, Unai; García, Paloma; Mora, Julio; Palomares, F. Javier; Rodríguez Trías, Rafael; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2A superhydrophobic composite coating consisting of polytetrafluoroethylene (PTFE) and poly(acrylic acid)+ β-cyclodextrin (PAA + β-CD) was prepared on an aluminum alloy AA 6061T6 substrate by a three-step process of electrospinnig, spin coating, and electrospraying. The electrospinning technique is used for the fabrication of a polymeric binder layer synthesized from PAA + β-CD. The superhydrophilic characteristic of the electrospun PAA + β-CD layer makes it suitable for the absorption of an aqueous suspension with PTFE particles in a spin-coating process, obtaining a hydrophobic behavior. Then, the electrospraying of a modified PTFE dispersion forms a layer of distributed PTFE particles, in which a strong bonding of the particles with each other and with the PTFE particles fixed in the PAA + β-CD fiber matrix results in a remarkable improvement of the particles adhesion to the substrate by different heat treatments. The experimental results corroborate the important role of obtaining hierarchical micro/nano multilevel structures for the optimization of superhydrophobic surfaces, leading to water contact angles above 170°, very low contact angle of hysteresis (CAH = 2°) and roll-off angle (αroll−off < 5°). In addition, a superior corrosion resistance is obtained, generating a barrier to retain the electrolyte infiltration. This study may provide useful insights for a wide range of applications.Publication Open Access Electrospinning technique as a powerful tool for the design of superhydrophobic surfaces(IntechOpen, 2020) Rivero Fuente, Pedro J.; Vicente Gómara, Adrián; Rodríguez Trías, Rafael; Ingeniería; Ingeniaritza; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa, PJUPNA1929The development of surface engineering techniques to tune-up the composition, structure, and function of materials surfaces is a permanent challenge for the scientific community. In this chapter, the electrospinning process is proposed as a versatile technique for the development of highly hydrophobic or even superhydrophobic surfaces. Electrospinning makes possible the fabrication of nanostructured ultrathin fibers, denoted as electrospun nanofibers (ENFs), from a wide range of polymeric materials that can be deposited on any type of surface with arbitrary geometry. In addition, by tuning the deposition parameters (mostly applied voltage, flow rate, and distance between collector/needle) in combination with the chemical structure of the polymeric precursor (functional groups with hydrophobic behavior) and its resultant viscosity, it is possible to obtain nanofibers with highly porous surface. As a result, functionalized surfaces with water-repellent behavior can be implemented in a wide variety of industrial applications such as in corrosion resistance, high efficient water-oil separation, surgical meshes in biomedical applications, or even in energy systems for long-term efficiency of dye-sensitized solar cells, among others.Publication 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 - INAMAT2In 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.