Structure-Property Relationships for Fluorinated and Fluorine-Free Superhydrophobic Crack-Free Coatings.

In this study, particle loading, polyfluorinated alkyl silanes (PFAS or FAS) content, superhydrophobicity, and crack formation for nanocomposite coatings created by the spray coating process were investigated. The formulations comprised hydrophobic silica, epoxy resin, and fluorine-free or FAS constituents. The effect of FAS content and FAS-free compositions on the silica and epoxy coatings' chemistry, topography, and wetting properties was also studied. All higher particle loadings (~30 wt.%) showed superhydrophobicity, while lower particle loading formulations did not show superhydrophobic behavior until 13% wt. FAS content. The improved water repellency of coatings with increased FAS (low particle loadings) was attributed to a combination of chemistry and topography as described by the Cassie state. X-ray photoelectron spectroscopy (XPS) spectra showed fluorine enrichment on the coating surface, which increases the intrinsic contact angle. However, increasing the wt.% of FAS in the final coating resulted in severe crack formation for higher particle loadings (~30 wt.%). The results show that fluorine-free and crack-free coatings exhibiting superhydrophobicity can be created.

Fully Recyclable Cured Polymers for Sustainable 3D Printing.

The most prevalent materials used in the Additive Manufacturing era are polymers and plastics. Unfortunately, these materials are recognized for their negative environmental impact as they are primarily nonrecyclable, resulting in environmental pollution. In recent years, a new sustainable alternative to these materials has been emerging: Reversible Covalent Bond-Containing Polymers (RCBPs). These materials can be recycled, reprocessed, and reused multiple times without losing their properties. Nonetheless, they have two significant drawbacks when used in 3D printing. First, some require adding new materials every reprinting cycle, and second, others require high temperatures for (re)printing, limiting recyclability, and increasing energy consumption. This study, thus, introduces fully recyclable RCBPs as a sustainable approach for radiation-based printing technologies. This approach enables multiple (re)printing cycles at low temperatures (50 °C lower than the lowest reported) without adding new materials. It involves purposefully synthesized polymers that undergo reversible photopolymerization, composed of a tin-based catalyst. An everyday microwave oven quickly depolymerized these polymers, obtaining complete reversibility.

The Mechanical Properties Relationship of Radiation-Cured Nanocomposites Based on Acrylates and Cationic Polymerized Epoxies and the Composition of Silane-Modified Tungsten Disulfide Nanoparticles.

The effect of semiconducting tungsten disulfide (WS2) nanoparticles (NPs), functionalized by either methacryloxy, glycidyl, vinyl, or amino silanes, has been studied in photocuring of acrylate and epoxy resins (the latter photocured according to a cationic mechanism). The curing time, degree of curing (DC), thermal effects, and mechanical properties of the radiation-cured resins were investigated. X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) analyses confirmed that a silane coating was formed (1-4 nm) on the NPs' surface having a thickness of 1-4 nm. Fourier transition infrared (FTIR) was used to determine the DC of the nanocomposite resin. The curing time of the epoxy resin, at 345-385 nm wavelength, was 10 to 20 s, while for acrylate, the curing time was 7.5 min, reaching 92% DC in epoxy and 84% in acrylate. The glass transition temperature (Tg) of the photocured acrylates in the presence of WS2 NPs increased. In contrast to the acrylate, the epoxy displayed no significant variations of the Tg. It was found that the silane surface treatments enhanced the DC. Significant increases in impact resistance and enhancement in shear adhesion strength were observed when the NPs were treated with vinyl silane. A previous study has shown that the addition of WS2 NPs at a concentration of 0.5 wt.% is the optimal loading for improving the resin's mechanical properties. This study supports these earlier findings not only for the unmodified NPs but also for those functionalized with silane moieties. This study opens new vistas for the photocuring of resins and polymers in general when incorporating WS2 NPs.

Tetra-Dentate Cycloaddition Catalysts for Rapid Photopolymerization Reactions.

[4 + 4] and [2 + 2] cycloadditions are unique reactions since they form and deform cycloadducts under irradiation due to their inherent reversible nature. Whereas promising for the field of recycling, these reactions usually suffer from two major shortcomings: long reaction durations (hours) and the requirement of high-intensity light (∼100 W/cm2), typically at a short wavelength (<330 nm). We demonstrate several tetra-dentate catalysts that can overcome these fundamental limitations. Among them is a tin complex that enables 76% conversion within only 2 min of irradiation at 395 nm, much faster than the known ruthenium-based catalyst, under irradiation with light intensity two orders of magnitude lower than that reported in the literature. Due to the short photopolymerization time, low intensity (27 mW/cm2), and long UV light (395 nm), this unique complex opens new avenues for recycling three-dimensional printing products based on photopolymerization of cycloaddition reactions.

Dynamic Wetting Properties of Silica-Poly (Acrylic Acid) Superhydrophilic Coatings.

Superhydrophilic coatings based on a hydrophilic silica nanoparticle suspension and Poly (acrylic acid) (PAA) were prepared by dip coating. Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) were used to examine the morphology of the coating. The effect of surface morphology on the dynamic wetting behavior of the superhydrophilic coatings was studied by changing the silica suspension concentration from 0.5% wt. to 3.2% wt. while keeping the silica concentration in the dry coating constant. The droplet base diameter and dynamic contact angle with respect to time were measured using a high-speed camera. A power law was found to describe the relationship between the droplet diameter and time. A significantly low experimental power law index was obtained for all the coatings. Both roughness and volume loss during spreading were suggested to be responsible for the low index values. The water adsorption of the coatings was found to be the reason for the volume loss during spreading. The coatings exhibited good adherence to the substrates and retention of hydrophilic properties under mild abrasion.

Stretchable Conductive Tubular Composites Based on Braided Carbon Nanotube Yarns with an Elastomer Matrix.

We report an innovative approach to creating stretchable conductive materials composed of a tubular shell made from braided carbon nanotube yarns (CNTYs) embedded in an elastomeric matrix. For stretchable electronics, both mechanical properties and electrical conductivities are of interest. Consequently, both the mechanical behavior and electrical conductivities under large deformations were investigated. A new hyperelastic composite model was developed to predict the large deformation response to applied stress for a braid in a tubular elastomer composite. The composite demonstrated a hyperelastic response due to the architecture of the braid, and the behavior was affected by the braiding angle, braid modulus, and volume fraction of fibers. The elastomer matrix was considered a neo-Hookean material and represented by the Yeoh model. An interaction parameter was proposed to account for the effect of the elastomer/braid cooperative restriction as observed in experimental and calculated results. This novel approach enabled the determination of the constitutive behavior of the composite in large deformations (>150%), taking into account the elastomer and yarn properties and braid configurations. The model exhibited good agreement with the experimental results. As the CNTYs are conductive, a stretchable conductive composite was obtained having a resistivity of 5.01 × 10-4 and 5.67 × 10-5 Ω·cm for the 1-ply and 4-ply composites, respectively. The resistivity remained constant through cyclic loading under large deformations in tension until mechanical failure. The material has potential for use in stretchable electronics applications.

Wetting Characteristics of Nanosilica-Poly (acrylic acid) Transparent Anti-Fog Coatings.

The effect of particle loading on the wetting properties of coatings was investigated by modifying a coating formulation based on hydrophilic silica nanoparticles and poly (acrylic acid) (PAA). Water contact angle (WCA) measurements were conducted for all coatings to characterize the surface wetting properties. Wettability was improved with an increase in particle loading. The resulting coatings showed superhydrophilic (SH) behavior when the particle loading was above 53 vol. %. No new peaks were detected by attenuated total reflection (ATR-FTIR). The surface topography of the coatings was studied by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The presence of hydrophilic functional groups and nano-scale roughness were found to be responsible for superhydrophilic behavior. The surface chemistry was found to be a primary factor determining the wetting properties of the coatings. Adhesion of the coatings to the substrate was tested by tape test and found to be durable. The antifogging properties of the coatings were evaluated by exposing the films under different environmental conditions. The SH coatings showed anti-fogging behavior. The transparency of the coatings was significantly improved with the increase in particle loading. The coatings showed good transparency (>85% transmission) when the particle loading was above 84 vol. %.

Effect of Protein Adsorption on Air Plastron Behavior of a Superhydrophobic Surface.

Protein fouling on critical biointerfaces causes significant public health and clinical ramifications. Multiple strategies, including superhydrophobic (SHP) surfaces and coatings, have been explored to mitigate protein adsorption on solid surfaces. SHP materials with underwater air plastron (AP) layers hold great promise by physically reducing the contact area between a substrate and protein molecules. However, sustaining AP stability or lifetime is crucial in determining the durability and long-term applications of SHP materials. This work investigated the effect of protein on the AP stability using model SHP substrates, which were prepared from a mixture of silica nanoparticles and epoxy. The AP stability was determined using a submersion test with real-time visualization. The results showed that AP stability was significantly weakened by protein solutions compared to water, which could be attributed to the surface tension of protein solutions and protein adsorption on SHP substrates. The results were further examined to reveal the correlation between protein fouling and accelerated AP dissipation on SHP materials by confocal fluorescent imaging, surface energy measurement, and surface robustness modeling of the Cassie-Baxter to Wenzel transition. The study reveals fundamental protein adsorption mechanisms on SHP materials, which could guide future SHP material design to better mitigate protein fouling on critical biointerfaces.

Hybrid Sol-Gel Superhydrophobic Coatings Based on Alkyl Silane-Modified Nanosilica.

Hybrid sol-gel superhydrophobic coatings based on alkyl silane-modified nanosilica were synthesized and studied. The hybrid coatings were synthesized using the classic Stöber process for producing hydrophilic silica nanoparticles (NPs) modified by the in-situ addition of long-chain alkyl silanes co-precursors in addition to the common tetraethyl orthosilicate (TEOS). It was demonstrated that the long-chain alkyl substituent silane induced a steric hindrance effect, slowing the alkylsilane self-condensation and allowing for the condensation of the TEOS to produce the silica NPs. Hence, following the formation of the silica NPs the alkylsilane reacted with the silica's hydroxyls to yield hybrid alkyl-modified silica NPs having superhydrophobic (SH) attributes. The resulting SH coatings were characterized by contact angle goniometry, demonstrating a more than 150° water contact angle, a water sliding angle of less than 5°, and a transmittance of more than 90%. Confocal microscopy was used to analyze the micro random surface morphology of the SH surface and to indicate the parameters related to superhydrophobicity. It was found that a SH coating could be obtained when the alkyl length exceeded ten carbons, exhibiting a raspberry-like hierarchical morphology.

Electrical Properties Enhancement of Carbon Nanotube Yarns by Cyclic Loading.

Carbon nanotube yarns (CNTYs) possess low density, high conductivity, high strength, and moderate flexibility. These intrinsic properties allow them to be a preferred choice for use as conductive elements in high-performance composites. To fully exploit their potential as conductive reinforcing elements, further improvement in their electrical conductivity is needed. This study demonstrates that tensile cyclic loading under ambient conditions improves the electrical conductivity of two types of CNTYs. The results showed that the electrical resistance of untreated CNTYs was reduced by 80% using cyclic loading, reaching the resistance value of the drawn acid-treated CNTYs. Scanning electron microscopy showed that cyclic loading caused orientation and compaction of the CNT bundles that make up the CNTYs, resulting in significantly improved electrical conductivity of the CNTYs. Furthermore, the elastic modulus was increased by 20% while preserving the tensile strength. This approach has the potential to replace the environmentally unfriendly acid treatment currently used to enhance the conductivity of CNTYs.

Poly (Dimethylsiloxane) Coating for Repellency of Polar and Non-Polar Liquids.

The wettability of poly (dimethylsiloxane) (PDMS) coating on plasma-treated glass was studied at room temperature using polar and non-polar liquids. The wettability was investigated regarding the liquids' surface tensions (STs), dielectric constants (DCs) and solubility parameters (SPs). For polar liquids, the contact angle (CA) and contact angle hysteresis (CAH) are controlled by the DCs and non-polar liquids by the liquids' STs. Solubility parameter difference between the PDMS and the liquids demonstrated that non-polar liquids possessed lower CAH. An empirical model that integrates the interfacial properties of liquid/PDMS has been composed. Accordingly, the difference between the SPs of PDMS and the liquid is the decisive factor affecting CAH, followed by the differences in DCs and STs. Moreover, the interaction between the DCs and the SPs is of importance to minimize CAH. It has been concluded that CAH, and not CA, is the decisive attribute for liquid repellency of PDMS coating.

Polymers in the Medical Antiviral Front-Line.

Antiviral polymers are part of a major campaign led by the scientific community in recent years. Facing this most demanding of campaigns, two main approaches have been undertaken by scientists. First, the classic approach involves the development of relatively small molecules having antiviral properties to serve as drugs. The other approach involves searching for polymers with antiviral properties to be used as prescription medications or viral spread prevention measures. This second approach took two distinct directions. The first, using polymers as antiviral drug-delivery systems, taking advantage of their biodegradable properties. The second, using polymers with antiviral properties for on-contact virus elimination, which will be the focus of this review. Anti-viral polymers are obtained by either the addition of small antiviral molecules (such as metal ions) to obtain ion-containing polymers with antiviral properties or the use of polymers composed of an organic backbone and electrically charged moieties like polyanions, such as carboxylate containing polymers, or polycations such as quaternary ammonium containing polymers. Other approaches include moieties hybridized by sulphates, carboxylic acids, or amines and/or combining repeating units with a similar chemical structure to common antiviral drugs. Furthermore, elevated temperatures appear to increase the anti-viral effect of ions and other functional moieties.

Hybrid Antibacterial and Electro-conductive Coating for Textiles Based on Cationic Conjugated Polymer.

The development of efficient synthetic strategies for incorporating antibacterial coatings into textiles for pharma and medical applications is of great interest. This paper describes the preparation of functional nonwoven fabrics coated with polyaniline (PANI) via in situ polymerization of aniline in aqueous solution. The effect of three different monomer concentrations on the level of polyaniline coating on the fibers comprising the fabrics, and its electrical resistivities and antibacterial attributes, were studied. Experimental results indicated that weight gains of 0.7 and 3.0 mg/cm2 of PANI were achieved. These levels of coatings led to the reduction of both volume and surface resistivities by several orders of magnitude for PANI-coated polyester-viscose fabrics, i.e., from 108 to 105 (Ω/cm) and from 109 to 105 Ω/square, respectively. Fourier Transform Infrared (FTIR) Spectroscopy and Scanning Electron Microscopy (SEM) confirmed the incorporation of PANI coating with an average thickness of 0.4-1.5 µm, while Thermogravimetric Analysis (TGA) demonstrated the preservation of the thermal stability of the pristine fabrics. The unique molecular structure of PANI, consisting of quaternary ammonium ions under acidic conditions, yielded an antibacterial effect in the modified fabrics. The results revealed that all types of PANI-coated fabrics totally killed S. aureus bacteria, while PANI-coated viscose fabrics also demonstrated 100% elimination of S. epidermidis bacteria. In addition, PANI-coated, PET-viscose and PET fabrics showed 2.5 log and 5.5 log reductions against S. epidermidis, respectively.

The effect of composition and thermodynamics on the surface morphology of durable superhydrophobic polymer coatings.

Durable superhydrophobic coatings were synthesized using a system of silica nanoparticles (NPs) to provide nanoscale roughness, fluorosilane to give hydrophobic chemistry, and three different polymer binders: urethane acrylate, ethyl 2-cyanoacrylate, and epoxy. Coatings composed of different binders incorporating NPs in various concentrations exhibited different superhydrophobic attributes when applied on polycarbonate (PC) and glass substrates and as a function of coating composition. It was found that the substrate surface characteristics and wettability affected the superhydrophobic characteristics of the coatings. Interfacial tension and spreading coefficient parameters (thermodynamics) of the coating components were used to predict the localization of the NPs for the different binders' concentrations. The thermodynamic analysis of the NPs localization was in good agreement with the experimental observations. On the basis of the thermodynamic analysis and the experimental scanning electron microscopy, X-ray photoelectron spectroscopy, profilometry, and atomic force microscopy results, it was concluded that localization of the NPs on the surface was critical to provide the necessary roughness and resulting superhydrophobicity. The durability evaluated by tape testing of the epoxy formulations was the best on both glass and PC. Several coating compositions retained their superhydrophobicity after the tape test. In summary, it was concluded that thermodynamic analysis is a powerful tool to predict the roughness of the coating due to the location of NPs on the surface, and hence can be used in the design of superhydrophobic coatings.

Characterization of Hybrid Epoxy Nanocomposites.

This study focused on the effect of Multi Wall Carbon Nanotubes (MWCNT) content and its surface treatment on thermo-mechanical properties of epoxy nanocomposites. MWCNTs were surface treated and incorporated into two epoxy systems. MWCNT's surface treatments were based on: (a) Titania coating obtained by sol-gel process and (b) a nonionic surfactant. Thermo-mechanical properties improvement was obtained following incorporation of treated MWCNT. It was noticed that small amounts of titania coated MWCNT (0.05 wt %) led to an increase in the glass transition temperature and stiffness. The best performance was achieved adding 0.3 wt % titania coated MWCNT where an increase of 10 °C in the glass transition temperature and 30% in storage modulus were obtained.