Icephobic Coating Based on Novel SLIPS Made of Infused PTFE Fibers for Aerospace Application.

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.

Antifungal Activity of Chitosan/Poly(Ethylene Oxide) Blend Electrospun Polymeric Fiber Mat Doped with Metallic Silver Nanoparticles.

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.

A Comparative Study in the Design of TiO2 Assisted Photocatalytic Coatings Monitored by Controlling Hydrophilic Behavior and Rhodamine B Degradation.

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 (ß-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.

Novel Design of Superhydrophobic and Anticorrosive PTFE and PAA + ß - CD Composite Coating Deposited by Electrospinning, Spin Coating and Electrospraying Techniques.

A superhydrophobic composite coating consisting of polytetrafluoroethylene (PTFE) and poly(acrylic acid)+ ß-cyclodextrin (PAA + ß-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 + ß-CD. The superhydrophilic characteristic of the electrospun PAA + ß-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 + ß-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.

In Situ Synthesis of Gold Nanoparticles in Layer-by-Layer Polymeric Coatings for the Fabrication of Optical Fiber Sensors.

A new method is proposed to tune the interferometric response of wavelength-based optical fiber sensors. Using the nanoparticle in situ synthesis (ISS) technique, it is possible to synthesize gold nanoparticles (AuNPs) within a pre-existing polymeric thin film deposited at the end-face of an optical fiber. This post-process technique allows us to adjust the optical response of the device. The effect of the progressive synthesis of AuNPs upon polymeric film contributed to a remarkable optical contrast enhancement and a very high tuning capability of the reflection spectra in the visible and near-infrared region. The spectral response of the sensor to relative humidity (RH) variations was studied as a proof of concept. These results suggest that the ISS technique can be a useful tool for fiber optic sensor manufacturing.

Icephobic and Anticorrosion Coatings Deposited by Electrospinning on Aluminum Alloys for Aerospace Applications.

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 superhydrophobic and anticorrosive behavior due to the air trapped inside the nanotextured surface. In addition, 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).

Modeling Experimental Parameters for the Fabrication of Multifunctional Surfaces Composed of Electrospun PCL/ZnO-NPs Nanofibers.

In this work, a one-step electrospinning technique has been implemented for the design and development of functional surfaces with a desired morphology in terms of wettability and corrosion resistance by using polycaprolactone (PCL) and zinc oxide nanoparticles (ZnO NPs). The surface morphology has been characterized by confocal microscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM) and water contact angle (WCA), whereas the corrosion resistance has been evaluated by Tafel polarization curves. Strict control over the input operational parameters (applied voltage, feeding rate, distance tip to collector), PCL solution concentration and amount of ZnO NPs have been analyzed in depth by showing their key role in the final surface properties. With this goal in mind, a design of experiment (DoE) has been performed in order to evaluate the optimal coating morphology in terms of fiber diameter, surface roughness (Ra), water contact angle (WCA) and corrosion rate. It has been demonstrated that the solution concentration has a significant effect on the resultant electrospun structure obtained on the collector with the formation of beaded fibers with a higher WCA value in comparison with uniform bead-free fibers (dry polymer deposition or fiber-merging aspect). In addition, the presence of ZnO NPs distributed within the electrospun fibers also plays a key role in corrosion resistance, although it also leads to a decrease in the WCA. Finally, this is the first time that an exhaustive analysis by using DoE has been evaluated for PCL/ZnO electrospun fibers with the aim to optimize the surface morphology with the better performance in terms of corrosion resistance and wettability.

Evaluation of the Photocatalytic Activity and Anticorrosion Performance of Electrospun Fibers Doped with Metallic Oxides.

This paper reports the development and characterization of a multifunctional coating that combines anticorrosion and photocatalytic properties, deposited by means of the electrospinning technique. In the first step, a functional electrospun fiber mat composed of poly(acrylic acid) (PAA) and ß-cyclodextrin (ß-CD) was obtained, showing high water insolubility and great adhesion increased by means of a thermal crosslinking process (denoted as PAA + ß-CD). In the second step, the fibers were doped with particles of titanium dioxide (denoted as PAA + ß-CD/TiO2) and titanium dioxide plus iron oxide (denoted as PAA + ß-CD/TiO2/Fe2O3). The morphology and fiber diameter of the electrospun mats were evaluated by using confocal microscopy, whereas the presence of the metal oxides in the electrospun fibers was corroborated by scanning electron microscopy (SEM) and X-ray fluorescence (XRF), respectively. In addition, electrochemical tests in saline solution revealed that the sample composed of PAA + ß-CD/TiO2/Fe2O3 showed the highest corrosion protection efficiency of all the samples, which was directly associated to lower corrosion current density and higher corrosion potential. Furthermore, the paper reports a novel approach to in situ determination of methylene blue (MB) degradation onto the coating. The results revealed complete degradation of MB, which is perfectly appreciated by total discoloration of the film in the irradiated zone (from bluish to a white spot). The main conclusions of this research are the efficiency of the electrospun system PAA + ß-CD/TiO2/Fe2O3 for developing photocatalytic activity and corrosion protection and the utility of the dry MB discoloration tests to evaluate photocatalytic activity.

Antibacterial Activity of Photocatalytic Metal Oxide Thin Films Deposited by Layer-by-Layer Self-Assembly.

This paper reports the use of the Layer-by-Layer self-assembly (LbL) as an efficient technique for the fabrication of thin-films with antibacterial activity. The LbL coatings are composed of a positive polyelectrolyte such as Poly(allylamine hydrochloride) (PAH) and an anionic polyelectrolyte such as Poly(sodium 4-styrene sulfonate) solution (PSS). In addition, these polyelectrolytes can be also used as an adequate encapsulating agent of specific metal oxide precursors such as titanium dioxide (TiO2) and iron oxide (Fe2O3) nanoparticles, making possible the fabrication of hybrid thin films composed of organic polymeric chains related to the polyelectrolytes and inorganic structure associated to the metal oxide nanoparticles. Four different LbL coatings have been fabricated and a comparative study about the resultant topographical, optical and wettability properties is presented by using light interferometry, atomic force microscopy (AFM), UV-Vis spectroscopy and water contact angle (WCA) measurements. In addition, X-ray fluorescence (XRF) has been also employed in order to corroborate the presence of metal oxide precursors inside the polymeric chains of the polyelectrolytes. Finally, the antibacterial tests have demonstrated that LbL coatings composed of metal oxide nanoparticles produce an enhancement in the efficacy and antibacterial activity.

The Role of the Fiber/Bead Hierarchical Microstructure on the Properties of PVDF Coatings Deposited by Electrospinning.

Among the various polymeric options employed for the deposition of electrospun coatings, 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 electrospinning 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 transmittance, 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), showing that the presence of electrospun PVDF fibers produces a relevant improvement in the resultant corrosion resistance of the coated aluminum alloys.

Designing Multifunctional Protective PVC Electrospun Fibers with Tunable Properties.

In 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.

Self-Referenced Optical Fiber Sensor for Hydrogen Peroxide Detection based on LSPR of Metallic Nanoparticles in Layer-by-Layer Films.

Intensity-based optical fiber sensors are one of the most studied sensor approaches thanks to their simplicity and low cost. Nevertheless, their main issue is their lack of robustness since any light source fluctuation, or unexpected optical setup variation is directly transferred to the output signal, which, significantly reduces their reliability. In this work, a simple and robust hydrogen peroxide (H2O2) optical fiber sensor is proposed based on the Localized Surface Plasmon Resonance (LSPR) sensitivity of silver and gold metallic nanoparticles. The precise and robust detection of H2O2 concentrations in the ppm range is very interesting for the scientific community, as it is a pathological precursor in a wide variety of damage mechanisms where its presence can be used to diagnose important diseases such as Parkinson's disease, diabetes, asthma, or even Alzheimer's disease). In this work, the sensing principle is based the oxidation of the silver nanoparticles due the action of the hydrogen peroxide, and consequently the reduction of the efficiency of the plasmonic coupling. At the same time, gold nanoparticles show a high chemical stability, and therefore provide a stable LSPR absorption band. This provides a stable real-time reference that can be extracted from the spectral response of the optical fiber sensor, giving a reliable reading of the hydrogen peroxide concentration.

Layer-by-Layer Nano-assembly: A Powerful Tool for Optical Fiber Sensing Applications.

The ability to tune the composition of nanostructured thin films is a hot topic for the design of functional coatings with advanced properties for sensing applications. The control of the structure at the nanoscale level enables an improvement of intrinsic properties (optical, chemical or physical) in comparison with the traditional bulk materials. In this sense, among all the known nanofabrication techniques, the layer-by-layer (LbL) nano-assembly method is a flexible, easily-scalable and versatile approach which makes possible precise control of the coating thickness, composition and structure. The development of sensitive nanocoatings has shown an exceptional growth in optical fiber sensing applications due to their self-assembling ability with oppositely charged components in order to obtain a multilayer structure. This nanoassembly technique is a powerful tool for the incorporation of a wide variety of species (polyelectrolytes, metal/metal oxide nanoparticles, hybrid particles, luminescent materials, dyes or biomolecules) in the resultant multilayer structure for the design of high-performance optical fiber sensors. In this work we present a review of applications related to optical fiber sensors based on advanced LbL coatings in two related research areas of great interest for the scientific community, namely chemical sensing (pH, gases and volatile organic compounds detection) as well as biological/biochemical sensing (proteins, immunoglobulins, antibodies or DNA detection).

Optical Fiber Sensors Based on Polymeric Sensitive Coatings.

Polymer technology is one of the fastest growing fields of contemporary research due to the possibility of using a wide variety of synthetic chemical routes for obtaining a polymeric network with a well-defined structure, resulting in materials with outstanding macroscopic properties. Surface engineering techniques based on the implementation of polymeric structures can be used as an interesting tool for the design of materials with functional properties. In this sense, the use of fabrication techniques for the design of nanostructured polymeric coatings is showing an important growth due to the intrinsic advantages of controlling the structure at a nanoscale level because physical, chemical, or optical properties can be considerably improved in comparison with the bulk materials. In addition, the presence of these sensitive polymeric coatings on optical fiber is a hot topic in the scientific community for its implementation in different market niches because a wide variety of parameters can be perfectly measured with a high selectivity, sensitivity, and fast response time. In this work, the two main roles that a polymeric sensitive matrix can play on an optical fiber for sensing applications are evaluated. In a first section, the polymers are used as a solid support for the immobilization of specific sensitive element, whereas in the second section the polymeric matrix is used as the chemical transducer itself. Additionally, potential applications of the optical fiber sensors in fields as diverse as biology, chemistry, engineering, environmental, industry or medicine will be presented in concordance with these two main roles of the polymeric sensitive matrices.

Micro and Nanostructured Materials for the Development of Optical Fibre Sensors.

The measurement of chemical and biomedical parameters can take advantage of the features exclusively offered by optical fibre: passive nature, electromagnetic immunity and chemical stability are some of the most relevant ones. The small dimensions of the fibre generally require that the sensing material be loaded into a supporting matrix whose morphology is adjusted at a nanometric scale. Thanks to the advances in nanotechnology new deposition methods have been developed: they allow reagents from different chemical nature to be embedded into films with a thickness always below a few microns that also show a relevant aspect ratio to ensure a high transduction interface. This review reveals some of the main techniques that are currently been employed to develop this kind of sensors, describing in detail both the resulting supporting matrices as well as the sensing materials used. The main objective is to offer a general view of the state of the art to expose the main challenges and chances that this technology is facing currently.

Nanomaterials for Functional Textiles and Fibers.

Nanoparticles are very interesting because of their surface properties, different from bulk materials. Such properties make possible to endow ordinary products with new functionalities. Their relatively low cost with respect to other nano-additives make them a promising choice for industrial mass-production systems. Nanoparticles of different kind of materials such as silver, titania, and zinc oxide have been used in the functionalization of fibers and fabrics achieving significantly improved products with new macroscopic properties. This article reviews the most relevant approaches for incorporating such nanoparticles into synthetic fibers used traditionally in the textile industry allowing to give a solution to traditional problems for textiles such as the microorganism growth onto fibers, flammability, robustness against ultraviolet radiation, and many others. In addition, the incorporation of such nanoparticles into special ultrathin fibers is also analyzed. In this field, electrospinning is a very promising technique that allows the fabrication of ultrathin fiber mats with an extraordinary control of their structure and properties, being an ideal alternative for applications such as wound healing or even functional membranes.