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.
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.
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
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; Ingeniería
Anti-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).
Open Access
Effect of the temperature in the mechanical properties of austenite, ferrite and sigma phases of duplex stainless steels using hardness, microhardness and nanoindentation techniques
(MDPI, 2017) Argandoña Salinas, Gorka; Berlanga Labari, Carlos; Biezma Moraleda, María Victoria; Rivero Fuente, Pedro J.; Peña, Julio; Rodríguez Trías, Rafael; Mekanika, Energetika eta Materialen Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; Ingeniería Mecánica, Energética y de Materiales
The aim of this work is to study the hardness of the ferrite, austenite and sigma phases of a UNS S32760 superduplex stainless steel submitted to different thermal treatments, thus leading to different percentages of the mentioned phases. A comparative study has been performed in order to evaluate the resulting mechanical properties of these phases by using hardness, microhardness and nanoindentation techniques. In addition, optical microscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD) have been also used to identify their presence and distribution. Finally, the experimental results have shown that the resulting hardness values were increased as a function of a longer heat treatment duration which it is associated to the formation of a higher percentage of the sigma phase. However, nanoindentation hardness measurements of this sigma phase showed lower values than expected, being a combination of two main factors, namely the complexity of the sigma phase structure as well as the surface finish (roughness).
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
Evaluation of functionalized coatings for the prevention of ice accretion by using icing wind tunnel tests
(MDPI, 2020) Rivero Fuente, Pedro J.; Rodríguez Trías, Rafael; Larumbe Abuin, Silvia; Monteserín, María; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; Ingeniería; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa, PJUPNA1929
Ice accretion presents serious safety issues, as airplanes are exposed to supercooled water droplets both on the ground and while flying through clouds in the troposphere. Prevention of icing is a main concern for both developers and users of aircraft. The successful solution of this problem implies the combination of active and passive methods and the use of advanced sensors for early detection of icing and monitoring of ice accretion and de-icing processes. This paper focuses on the development of passive solutions. These include advanced anti-icing coatings deposited by a variety of chemical methods including sol-gel, advanced paints based on polyester combined with fluorinated derivatives and applied by electrostatic spray deposition and conventional silicone-based paints modified by adding alumina nanoparticles. Water contact angle has been measured in all cases, demonstrating the hydrophobic character of the coatings. An ice accretion test has been carried out in a laboratory scale icing wind tunnel (IWT) located in a cold climate chamber. Three different studies have been undertaken: ice accretion measurement, durability of the anti-icing behavior after several icing/de-icing cycles and ice adhesion testing by means of the double lap shear test (DLST) methodology. All the studied coatings have shown significant anti-icing behavior which has been maintained, in some cases, beyond 25 cycles. Although these results are still far from any possible application for aeronautic components, they provide interesting insights for new developments and validate the laboratory scale tests.
Open Access
Comparative study of electrospun polydimethylsiloxane fibers as a substitute for fluorine-based polymeric coatings for hydrophobic and icephobic applications
(MDPI, 2024-11-30) Vicente Gómara, Adrián; Rivero Fuente, Pedro J.; Santos, Cleis; Rehfeld, Nadine; Rodríguez Trías, Rafael; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Univertsitate Publikoa, PJUPNA1929
The development of superhydrophobic, waterproof, and breathable membranes, as well as icephobic surfaces, has attracted growing interest. Fluorinated polymers like PTFE or PVDF are highly effective, and previous research by the authors has shown that combining these polymers with electrospinning-induced roughness enhances their hydro- and ice-phobicity. The infusion of these electrospun mats with lubricant oil further improves their icephobic properties, achieving a slippery liquid-infused porous surface (SLIPS). However, their environmental impact has motivated the search for fluorine-free alternatives. This study explores polydimethylsiloxane (PDMS) as an ideal candidate because of its intrinsic properties, such as low surface energy and high flexibility, even at very low temperatures. While some published results have considered this polymer for icephobic applications, in this work, the electrospinning technique has been used for the first time for the fabrication of 95% pure PDMS fibers to obtain hydrophobic porous coatings as well as breathable and waterproof membranes. Moreover, the properties of PDMS made it difficult to process, but these limitations were overcome by adding a very small amount of polyethylene oxide (PEO) followed by a heat treatment process that provides a mat of uniform fibers. The experimental results for the PDMS porous coating confirm a hydrophobic behavior with a water contact angle (WCA) ≈ 118° and roll-off angle (αroll-off) ≈ 55°. In addition, the permeability properties of the fibrous PDMS membrane show a high transmission rate (WVD) ≈ 51.58 g∙m−2∙d−1, providing breathability and waterproofing. Finally, an ice adhesion centrifuge test showed a low ice adhesion value of 46 kPa. These results highlight the potential of PDMS for effective icephobic and waterproof applications.
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, PJUPNA1929
The 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.
Open Access
Setting a comprehensive strategy to face the runback icing phenomena
(Elsevier, 2023) Mora, Julio; García, Paloma; Carreño, Francisco; González, Miguel; Gutiérrez, Marcos; Montes, Laura; Rico, Victor J.; López-Santos, Carmen; Vicente Gómara, Adrián; Rivero Fuente, Pedro J.; Rodríguez Trías, Rafael; Larumbe Abuin, Silvia; Acosta, Carolina; Ibáñez-Ibáñez, Pablo; Corozzi, Alessandro.; Raimondo, Mariarosa; Kozera, Rafal; Przybyszewski, Bartlomiej; González-Elipe, Agustín R.; Borrás, Ana; Redondo, Francisco; Agüero, Alina; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2
The development of anti-icing robust surfaces is a hot topic nowadays and particularly crucial in the aeronautics or wind energy sectors as ice accretion can compromise safety and power generation efficiency. However, the current performance of most anti-icing strategies has been proven insufficient for such demanding applications, particularly in large unprotected zones, which located downstream from thermally protected areas, may undergo secondary icing. Herein, a new testing methodology is proposed to evaluate accretion mechanisms and secondary icing phenomena through, respectively, direct impact and running-wet processes and systematically applied to anti-icing materials including commercial solutions and the latest trends in the state-of-the-art. Five categories of materials (hard, elastomeric, polymeric matrix, SLIPS and superhydrophobic) with up to fifteen formulations have been tested. This Round-Robin approach provides a deeper understanding of anti-icing mechanisms revealing the strengths and weaknesses of each material. The conclusion is that there is no single passive solution for anti-ice protection. Thus, to effectively protect a given real component, different tailored materials fitted for each particular zone of the system are required. For this selection, shape analysis of such a component and the impact characteristics of water droplets under real conditions are needed as schematically illustrated for aeronautic turbines.