Fluorine-Free Extinguishing of a Hydrocarbon Pool Fire with a Suspension of Glass Bubbles Grafted with Nanoscale Polymer Layers.

The current most efficient solution to extinguish liquid hydrocarbon (class B) pool fires involves fire-fighting foams containing fluorinated surfactants. However, fluorocarbon surfactants are unsafe due to their environmental persistence and negative toxicological/bioaccumulative impact. To this end, we show that fluorine-free aqueous suspensions of Glass Bubbles (GB) modified with hydrophilic polymer grafted layers can efficiently extinguish hydrocarbon pool fires. Namely, GB grafted with poly(oligo (ethylene glycol) methyl ether methacrylate) (POEGMA), GB-G was fabricated employing "grafting-through" and "grafting-from" methods and used to obtain the suspensions. It was found that the GB suspension, with a grafted layer of higher molecular weight and lower grafting density (GB-GL), proved superior to the more densely grafted GB-GH and nongrafted GB-0 system. The GB-GL suspensions displayed less negative spreading coefficients and viscosities lower than those of GB-GH/GB-0 compositions. When siloxane-polyoxyethylene surfactant was added to all GB suspensions, the interfacial properties were dominated by the surfactant, with all suspensions having the same positive spreading coefficient. However, the GB-GL-surfactant composition had the lowest viscosity among the suspensions studied in this work. Specifically, the viscosity of GB-GH and GB-0 suspensions at a shear rate of 77 s-1 was ∼110% and 70% higher than that of GB-GL. Due to the lower viscosity, the GB-GL suspension demonstrated the most efficient spreading over model hydrocarbon solid (polyethylene) and liquid (hexadecane) surfaces when the surfactant was added. The suspension also showed the best performance in the retardation of hexane evaporation when placed over the heated hexane pool. After 50 min, the amount of hexane that evaporated through GB-GH and GB-0 suspensions was ∼8 and 11 times higher, respectively, compared to the GB-GL suspension. We found that the GB-GL-surfactant system was the most efficient GB suspension in extinguishing the fire due to its superior spreading and sealing ability. It was within 10% of fluorine-containing foam's fire extinguishment performance. The GB suspensions are much safer in terms of burnback resistance as a torch applied directly to the suspension after extinguishment could not reignite the fire. The GB material is recyclable, since it can be collected and reused after application to a fire.

Enhancement of Polypropylene 3D-Printed Structures via the Addition of SiC Whiskers and Microwave Irradiation.

We report on enhancing the mechanical and structural characteristics of polypropylene (PP) three-dimensional (3D)-printed structures fabricated via fused filament fabrication (FFF) by employing composite PP-based filament with subsequent microwave (MWV) treatment. The composite filament contained a minute (0.9 vol %) fraction of silicon carbide whiskers (SiCWs) and was prepared via melt blending of PP pellets with SiCW using an extruder. The surface of the whiskers was modified with trimethoxy(octadecyl) silane to improve compatibility between the polar SiCW and nonpolar PP matrix. We employed SiCWs in composite filament because of the whiskers' high thermal conductivity and ability to generate heat locally under MWV irradiation. Indeed, we were able to conduct the heating of printed parts by MWV without sacrificing the structural integrity and improving the overall adhesion between the 3D-printed polymer layers. Our modeling captures an extent of heating upon MWV irradiation observed in our experiments. In general, utilization of the composite PP/SiCW filament significantly improved the printed parts' mechanical characteristics and sintering level compared to those made from pure PP filament. Specifically, after the MWV treatment, the adjusted (for density) storage modulus of the PP/SiCW material was just ∼20% lower than that for the PP sample obtained by conventional compression molding. After the MWV irradiation, Young's modulus, yield stress, and toughness of the printed structures were increased by ∼65, 53, and 55%, respectively. We attribute the improvement of mechanical properties via MWV treatment to enhancing the entanglement level at the weld.

Highly Adhesive Antimicrobial Coatings for External Fixation Devices.

Pin site infections arise from the use of percutaneous pinning techniques (as seen in skeletal traction, percutaneous fracture pinning, and external fixation for fracture stabilization or complex deformity reconstruction). These sites are niduses for infection because the skin barrier is disrupted, allowing for bacteria to enter a previously privileged area. After external fixation, the rate of pin site infections can reach up to 100%. Following pin site infection, the pin may loosen, causing increased pain (increasing narcotic usage) and decreasing the fixation of the fracture or deformity correction construct. More serious complications include osteomyelitis and deep tissue infections. Due to the morbidity and costs associated with its sequelae, strategies to reduce pin site infections are vital. Current strategies for preventing implant-associated infections include coatings with antibiotics, antimicrobial polymers and peptides, silver, and other antiseptics like chlorhexidine and silver-sulfadiazine. Problems facing the development of antimicrobial coatings on orthopedic implants and, specifically, on pins known as Kirschner wires (or K-wires) include poor adhesion of the drug-eluting layer, which is easily removed by shear forces during the implantation. Development of highly adhesive drug-eluting coatings could therefore lead to improved antimicrobial efficacy of these devices and ultimately reduce the burden of pin site infections. In response to this need, we developed two types of gel coatings: synthetic poly-glycidyl methacrylate-based and natural-chitosan-based. Upon drying, these gel coatings showed strong adhesion to pins and remained undamaged after the application of strong shear forces. We also demonstrated that antibiotics can be incorporated into these gels, and a K-wire with such a coating retained antimicrobial efficacy after drilling into and removal from a bone. Such a coating could be invaluable for K-wires and other orthopedic implants that experience strong shear forces during their implantation.

A Novel Bio-Adhesive Mesh System for Medical Implant Applications: In Vivo Assessment in a Rabbit Model.

Injectable surgical sealants and adhesives, such as biologically derived fibrin gels and synthetic hydrogels, are widely used in medical products. While such products adequately adhere to blood proteins and tissue amines, they have poor adhesion with polymer biomaterials used in medical implants. To address these shortcomings, we developed a novel bio-adhesive mesh system utilizing the combined application of two patented technologies: a bifunctional poloxamine hydrogel adhesive and a surface modification technique that provides a poly-glycidyl methacrylate (PGMA) layer grafted with human serum albumin (HSA) to form a highly adhesive protein surface on polymer biomaterials. Our initial in vitro tests confirmed significantly improved adhesive strength for PGMA/HSA grafted polypropylene mesh fixed with the hydrogel adhesive compared to unmodified mesh. Toward the development of our bio-adhesive mesh system for abdominal hernia repair, we evaluated its surgical utility and in vivo performance in a rabbit model with retromuscular repair mimicking the totally extra-peritoneal surgical technique used in humans. We assessed mesh slippage/contraction using gross assessment and imaging, mesh fixation using tensile mechanical testing, and biocompatibility using histology. Compared to polypropylene mesh fixed with fibrin sealant, our bio-adhesive mesh system exhibited superior fixation without the gross bunching or distortion that was observed in the majority (80%) of the fibrin-fixed polypropylene mesh. This was evidenced by tissue integration within the bio-adhesive mesh pores after 42 days of implantation and adhesive strength sufficient to withstand the physiological forces expected in hernia repair applications. These results support the combined use of PGMA/HSA grafted polypropylene and bifunctional poloxamine hydrogel adhesive for medical implant applications.

Tough Bioplastics from Babassu Oil-Based Acrylic Monomer, Hemicellulose Xylan, and Carnauba Wax.

We describe here the fabrication, characterization, and properties of tough bioplastics made of a babassu oil-based acrylic polymer (PBBM), hemicellulose xylan grafted with PBBM chains, and carnauba wax (CW). The plastic was primarily designed to obtain bioderived materials that can replace low-density polyethylene (LDPE) in certain food packaging applications. To obtain plastic, the radical polymerization of an original babassu oil-based acrylic monomer (BBM) in the presence of xylan macromolecules modified with maleic anhydride (X-MA) was conducted. The polymerization resulted in a material (PBBM-X) mostly consisting of highly branched PBBM/X-MA macromolecules. PBBM-X has a glass transition of 42 °C, a storage modulus of 130 MPa (at 25 °C, RT), and a Young's modulus of 30 MPa at RT. To increase the moduli, we blended PBBM-X with carnauba wax, a natural material with a high modulus and a melting temperature of ~80 °C. It was found that PBBM-X is compatible with the wax, as evidenced by the alternation of the material's thermal transitions and the co-crystallization of BBM side alkyl fragments with CW. As a result, the PBBM-X/CW blend containing 40% of the wax had a storage modulus of 475 MPa (RT) and a Young's modulus of 248 MPa (RT), which is close to that of LDPE. As polyethylene, the PBBM-X and PBBM-X/CW bioplastics have the typical stress-strain behavior demonstrated by ductile (tough) plastics. However, the bioplastic's yield strength and elongation-at-yield are considerably lower than those of LDPE. We evaluated the moisture barrier properties of the PBBM-X/(40%)CW material and found that the bioplastic's water vapor permeability (WVP) is quite close to that of LDPE. Our bioderived material demonstrates a WVP that is comparable to polyethylene terephthalate and lower than the WVP of nylon and polystyrene. Taking into account the obtained results, the fabricated materials can be considered as polyethylene alternatives to provide sustainability in plastics production in the packaging areas where LDPE currently dominates.

Poly(3-hexylthiophene)-Based Organic Thin-Film Transistors with Virgin Graphene Oxide as an Interfacial Layer.

We fabricated and characterized poly(3-hexylthiophene-2, 5-diyl) (P3HT)-based Organic thin-film transistors (OTFTs) containing an interfacial layer made from virgin Graphene Oxide (GO). Previously chemically modified GO and reduced GO (RGO) were used to modify OTFT interfaces. However, to our knowledge, there are no published reports where virgin GO was employed for this purpose. For the sake of comparison, OTFTs without modification were also manufactured. The structure of the devices was based on the Bottom Gate Bottom Contact (BGBC) OTFT. We show that the presence of the GO monolayer on the surface of the OTFT's SiO2 dielectric and Au electrode surface noticeably improves their performance. Namely, the drain current and the field-effect mobility of OTFTs are considerably increased by modifying the interfaces with the virgin GO deposition. It is suggested that the observed enhancement is connected to a decrease in the contact resistance of GO-covered Au electrodes and the particular structure of the P3HT layer on the dielectric surface. Namely, we found a specific morphology of the organic semiconductor P3HT layer, where larger interconnecting polymer grains are formed on the surface of the GO-modified SiO2. It is proposed that this specific morphology is formed due to the increased mobility of the P3HT segments near the solid boundary, which was confirmed via Differential Scanning Calorimetry measurements.

Toward Mechanical Recycling of Polystyrene/Polypropylene Blends with Bottlebrush-Modified Graphene Oxide as a Compatibilizer.

The compatibilization of immiscible polystyrene/polypropylene (PS/PP) blends with virgin graphene oxide (GO-V) and GO modified with a bottlebrush reactive copolymer layer (GO-P) is reported. This practically important blend was chosen since, currently, PS and PP are recycled to a very low degree. The amphiphilic bottlebrush copolymer synthesized by us contained hydrophobic and hydrophilic side chains and was attached to the GO nanosheets via epoxy functionality. The GO modification and the introduction of GO into the blend were conducted from water. Thus, the introduction of the compatibilizing nanomaterial can be conducted during the mechanical recycling washing stage in a real-world situation. The final blend was prepared via melt mixing using an extruder. We examined the influence of GO modification and the mixing order on the blends' morphology, rheology, and mechanical properties. Thermodynamic calculations predicted a higher interfacial activity of GO nanosheets in PS/PP/GO-P blends than that in PS/PP/GO-V blends. The morphological and rheological study assessed this prediction. It was demonstrated that the bottlebrush-modified GO-P sheets were readily driven to the PS/PP interphase. The mechanical measurements showed enhanced mechanical properties for PS/PP/GO-P blends, especially for those in which GO was first premixed with PS.

Mesoscale Modeling of Agglomeration of Molecular Bottlebrushes: Focus on Conformations and Clustering Criteria.

Using dissipative particle dynamics, we characterize dynamics of aggregation of molecular bottlebrushes in solvents of various qualities by tracking the number of clusters, the size of the largest cluster, and an average aggregation number. We focus on a low volume fraction of bottlebrushes in a range of solvents and probe three different cutoff criteria to identify bottlebrushes belonging to the same cluster. We demonstrate that the cutoff criteria which depend on both the coordination number and the length of the side chain allows one to correlate the agglomeration status with the structural characteristics of bottlebrushes in solvents of various qualities. We characterize conformational changes of the bottlebrush within the agglomerates with respect to those of an isolated bottlebrush in the same solvents. The characterization of bottlebrush conformations within the agglomerates is an important step in understanding the relationship between the bottlebrush architecture and material properties. An analysis of three distinct cutoff criteria to identify bottlebrushes belonging to the same cluster introduces a framework to identify both short-lived transient and long-lived agglomerates; the same approach could be further extended to characterize agglomerates of various macromolecules with complex architectures beyond the specific bottlebrush architecture considered herein.

Towards a Long-Chain Perfluoroalkyl Replacement: Water and Oil Repellent Perfluoropolyether-Based Polyurethane Oligomers.

Original perfluoropolyether (PFPE)-based oligomeric polyurethanes (FOPUs) with different macromolecular architecture were synthesized (in one step) as low-surface-energy materials. It is demonstrated that the oligomers, especially the ones terminated with CF3 moieties, can be employed as safer replacements to long-chain perfluoroalkyl substances/additives. The FOPU macromolecules, when added to an engineering thermoplastic (polyethylene terephthalate, PET) film, readily migrate to the film surface and bring significant water and oil repellency to the thermoplastic boundary. The best performing FOPU/PET films have reached the level of oil wettability and surface energy significantly lower than that of polytetrafluoroethylene, a fully perfluorinated polymer. Specifically, the highest level of the repellency is observed with an oligomeric additive, which was made using aromatic diisocyanate as a comonomer and has CF3 end-group. This semicrystalline oligomer has a glass transition temperature (Tg) well above room temperature, and we associate the superiority of the material in achieving low water and oil wettability with its ability to effectively retain CF3 and CF2 moieties in contact with the test wetting liquids.

Highly Oil-Repellent Thermoplastic Boundaries via Surface Delivery of CF3 Groups by Molecular Bottlebrush Additives.

We fabricated thermoplastic surfaces possessing extremely limited water and oil wettability without employment of long-chain perfluoroalkyl (LCPFA) substances. Namely, by taking advantage of the structure and behavior of original oleophobic perfluoropolyether (PFPE) methacrylate (PFM) molecular bottlebrush (MBB) additive we obtained polymeric surfaces with oil contact angles well above 80° and surface energy on the level of 10 mN/m. Those angles and surface energies are the highest and the lowest respective values reported to date for any bulk solid flat organic surface not containing LCPFA. We show experimentally and computationally that this remarkable oil repellency is attributed to migration of small quantities of the oleophobic MBB additives to the surface of the thermoplastics. Severe mismatch in the affinity between the densely grafted long side chains of MBB and a host matrix promotes stretching and densification of mobile side chains delivering the lowest surface energy functionalities (CF3) to the materials' boundary. Our studies demonstrate that PFM can be utilized as an effective low surface energy additive to conventional thermoplastic polymers, such as poly(methyl methacrylate) and Nylon-6. We show that films containing PFM achieve the level of oil repellency significantly higher than that of polytetrafluoroethylene (PTFE), a fully perfluorinated thermoplastic. The surface energy of the films is also significantly lower than that of PTFE, even at low concentrations of PFM additives.

Adhesion and Stability of Nanocellulose Coatings on Flat Polymer Films and Textiles.

Renewable nanocellulose materials received increased attention owing to their small dimensions, high specific surface area, high mechanical characteristics, biocompatibility, and compostability. Nanocellulose coatings are among many interesting applications of these materials to functionalize different by composition and structure surfaces, including plastics, polymer coatings, and textiles with broader applications from food packaging to smart textiles. Variations in porosity and thickness of nanocellulose coatings are used to adjust a load of functional molecules and particles into the coatings, their permeability, and filtration properties. Mechanical stability of nanocellulose coatings in a wet and dry state are critical characteristics for many applications. In this work, nanofibrillated and nanocrystalline cellulose coatings deposited on the surface of polymer films and textiles made of cellulose, polyester, and nylon are studied using atomic force microscopy, ellipsometry, and T-peel adhesion tests. Methods to improve coatings' adhesion and stability using physical and chemical cross-linking with added polymers and polycarboxylic acids are analyzed in this study. The paper reports on the effect of the substrate structure and ability of nanocellulose particles to intercalate into the substrate on the coating adhesion.

Surface modification of polypropylene surgical meshes for improving adhesion with poloxamine hydrogel adhesive.

Tissue adhesive has notable clinical benefits in hernia repair fixation. A novel poloxamine tissue adhesive was previously shown to successfully bond collagen tissue with adequate adhesive strength. In application related to attachment of polypropylene (PP) mesh, the adhesive strength between the mesh and poloxamine hydrogel adhesive is limited by the hydrophobicity of PP monofilaments and lack of covalent bond formation. The purpose of this study was to compare two different surface modifications [bovine serum albumin (BSA) adsorption and poly-glycidyl methacrylate/human serum albumin (PGMA/HSA) grafting] of PP mesh for improving the adhesive strength between poloxamine hydrogel adhesive and PP mesh. The PGMA/HSA surface modification significantly improved the adhesive strength for meshes attached with poloxamine hydrogel tissue adhesive compared with unmodified meshes and meshes modified by BSA adsorption. An area of 1 cm2 adhesive provided for a maximum adhesive strength of 65-70 kPa for meshes modified by PGMA/HSA, 4-13 kPa for meshes modified by BSA, and 22-45 kPa for unmodified meshes. Optical microscopy and infrared spectroscopy (FTIR) confirmed the improved adhesive strength was achieved through mechanical interlock of the hydrogel tissue adhesive into the PP mesh pores and chemical bonding of the albumin after successful PGMA/HSA grafting onto the PP monofilaments. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 107B: 1047-1055, 2019.

Attainment of Water and Oil Repellency for Engineering Thermoplastics without Long-Chain Perfluoroalkyls: Perfluoropolyether-Based Triblock Polyester Additives.

For decades, water and oil repellency of engineering thermoplastics has been achieved with introduction of long-chain perfluoroalkyl substances and moieties (C nF2 n+1, n ≥ 7). However, their bioaccumulative and toxicological impact is now widely recognized and, consequently, the substances have been phased out of industrial production and applications. To this end, we have synthesized fluorinated oligomeric triblock polyesters (FOPBs), which do not possess the long-chain perfluoroalkyl segments and serve as effective low-surface-energy additives to engineering thermoplastics. More specifically, we obtained original perfluoropolyether (PFPE)-based triblock copolymers, in which two identical fluorinated blocks were separated by a short nonfluorinated polyester block made of poly(ethylene isophthalate) (PEI). It was found that when FOPBs were added to poly(ethylene terephthalate), nylon-6, and poly(methyl methacrylate) films they readily migrate to the film surface and in doing so imparted significant water and oil repellency to the thermoplastic boundary. The water/oil wettability of the films modified with FOPB is considerably lower than the wettability of the films modified with an analogous PFPE-based polyester, which differs from FOPB only by the absence of the short nonfluorinated PEI middle block. We associate the superiority of the triblock copolymers in terms of water and oil repellency with their ability to form brushlike structures on polymer film surfaces.

En Route to Practicality of the Polymer Grafting Technology: One-Step Interfacial Modification with Amphiphilic Molecular Brushes.

Surface modification with polymer grafting is a versatile tool for tuning the surface properties of a wide variety of materials. From a practical point of view, such a process should be readily scalable and transferable between different substrates and consist of as least number of steps as possible. To this end, a cross-linkable amphiphilic copolymer system that is able to bind covalently to surfaces and form permanently attached networks via a one-step procedure is reported here. This system consists of brushlike copolymers (molecular brushes) made of glycidyl methacrylate, poly(oligo(ethylene glycol) methyl ether methacrylate), and lauryl methacrylate, which provide the final product with tunable reactivity and balance between hydrophilicity and hydrophobicity. The detailed study of the copolymer synthesis and properties has been carried out to establish the most efficient pathway to design and tailor this amphiphilic molecular brush system for specific applications. As an example of the applications, we showed the ability to control the deposition of graphene oxide (GO) sheets on both hydrophilic and hydrophobic surfaces using GO modified with the molecular brushes. Also, the capability to tune the osteoblast cell adhesion with the copolymer-based coatings was demonstrated.

Designing Highly Thermostable Lysozyme-Copolymer Conjugates: Focus on Effect of Polymer Concentration.

Designing biomaterials capable of functioning in harsh environments is vital for a range of applications. Using molecular dynamics simulations, we show that conjugating lysozymes with a copolymer [poly(GMA- stat-OEGMA)] comprising glycidyl methacrylate (GMA) and oligo(ethylene glycol) methyl ether methacrylate (OEGMA) results in a dramatic increase of stability of these enzymes at high temperatures provided that the concentration of the copolymer in the close vicinity of the enzyme exceeds a critical value. In our simulations, we use triads containing the same ratio of GMA to OEGMA units as in our recent experiments (N. S. Yadavalli et al., ACS Catalysis, 2017, 7, 8675). We focus on the dynamics of the conjugate at high temperatures and on its structural stability as a function of the copolymer/water content in the vicinity of the enzyme. We show that the dynamics of phase separation in the water-copolymer mixture surrounding the enzyme is critical for the structural stability of the enzyme. Specifically, restricting water access promotes the structural stability of the lysozyme at high temperatures. We identified critical water concentration below which we observe a robust stabilization; the phase separation is no longer observed at this low fraction of water so that the water domains promoting unfolding are no longer formed in the vicinity of the enzyme. This understanding provides a basis for future studies on designing a range of enzyme-copolymer conjugates with improved stability.

Magnetic Submicron Mullite Coatings with Oriented SiC Whiskers.

Addressing the challenge of making ceramic thin films with the in-plane-oriented nanorods, we propose to decorate the nanorods with magnetic nanoparticles and orient them using the external magnetic field. As an illustration, the mullite thin films with embedded and oriented SiC nanorods were synthesized. The SiC nanorods were decorated with the Fe3O4 nanoparticles. A two-step processing route was developed when the nanorods are first oriented in a sacrificial polymer layer. Then, the polymer film with the aligned nanorods was removed by heat-treatment. In the second step, a sol-gel/dip-coating method was applied to produce the mullite composite film. The main challenge was to guarantee that all of the nanorods that were initially randomly distributed in the polymer would have time to rotate toward the field direction before complete solidification of the sacrificial layer. Theoretical and experimental analyses of the orientational distribution of the nanorod axes were conducted to identify a relationship between the polymer viscosity and processing parameters of the system. In contrast to the ferromagnetic nanorods, the rate of rotation of paramagnetic nanorods and their time of alignment are more sensitive to the magnetic field. This methodology allows manufacturing of different ceramic films with aligned nanorods and making nonmagnetic ceramic coating magnetic.

Highly Conductive and Transparent Reduced Graphene Oxide Nanoscale Films via Thermal Conversion of Polymer-Encapsulated Graphene Oxide Sheets.

Despite noteworthy progress in the fabrication of large-area graphene sheetlike nanomaterials, the vapor-based processing still requires sophisticated equipment and a multistage handling of the material. An alternative approach to manufacturing functional graphene-based films includes the employment of graphene oxide (GO) micrometer-scale sheets as precursors. However, search for a scalable manufacturing technique for the production of high-quality GO nanoscale films with high uniformity and high electrical conductivity is still continuing. Here we show that conventional dip-coating technique can offer fabrication of high quality mono- and bilayered films made of GO sheets. The method is based on our recent discovery that encapsulating individual GO sheets in a nanometer thick molecular brush copolymer layer allows for the nearly perfect formation of the GO layers via dip coating from water. By thermal reduction the bilayers (cemented by a carbon-forming polymer linker) are converted into highly conductive and transparent reduced GO films with a high conductivity up to 104 S/cm and optical transparency on the level of 90%. The value is the highest electrical conductivity reported for thermally reduced nanoscale GO films and is close to the conductivity of indium tin oxide currently in use for transparent electronic devices, thus making these layers intriguing candidates for replacement of ITO films.

Toward a Long-Chain Perfluoroalkyl Replacement: Water and Oil Repellency of Polyethylene Terephthalate (PET) Films Modified with Perfluoropolyether-Based Polyesters.

Original perfluoropolyethers (PFPE)-based oligomeric polyesters (FOPs) of different macromolecular architecture were synthesized via polycondensation as low surface energy additives to engineering thermoplastics. The oligomers do not contain long-chain perfluoroalkyl segments, which are known to yield environmentally unsafe perfluoroalkyl carboxylic acids. To improve the compatibility of the materials with polyethylene terephthalate (PET) we introduced isophthalate segments into the polyesters and targeted the synthesis of lower molecular weight oligomeric macromolecules. The surface properties such as morphology, composition, and wettability of PET/FOP films fabricated from solution were investigated using atomic force microscopy, X-ray photoelectron spectroscopy, and contact angle measurements. It was demonstrated that FOPs, when added to PET film, readily migrate to the film surface and bring significant water and oil repellency to the thermoplastic boundary. We have established that the wettability of PET/FOP films depends on three main parameters: (i) end-groups of fluorinated polyesters, (ii) the concentration of fluorinated polyesters in the films, and (iii) equilibration via annealing. The most effective water/oil repellency FOP has two C4F9-PFPE-tails. The addition of this oligomeric polyester to PET allows (even at relatively low concentrations) reaching a level of oil repellency and surface energy comparable to that of polytetrafluorethylene (PTFE/Teflon). Therefore, the materials can be considered suitable replacements for additives containing long-chain perfluoroalkyl substances.

Enhancing Mechanical and Thermal Properties of Epoxy Nanocomposites via Alignment of Magnetized SiC Whiskers.

This research is focused on the fabrication and properties of epoxy nanocomposites containing magnetized SiC whiskers (MSiCWs). To this end, we report an original strategy for fabrication of magnetically active SiCWs by decorating the whiskers with magnetic (iron oxide) nanoparticles via polymer-polymer (poly(acrylic acid)/poly(2-vinyl pyridine)) complexation. The obtained whiskers demonstrated a substantial magnetic response in the polymerizing epoxy resin, with application of only a 20 mT (200 G) magnetic field. We also found that the whiskers chemically reacted with the epoxy resin, causing formation of an extended interphase near the boundary of the whiskers. The SiC whiskers oriented with the magnetic field demonstrated positive effects on the behavior of epoxy-based nanocomposites. Namely, the aligned MSiCWs enhanced the thermomechanical properties of the materials significantly above that of the neat epoxy and epoxy nanocomposite, with randomly oriented whiskers.

Multi-Frequency Measurement of Volatile Organic Compounds With a Radio-Frequency Interferometer.

We present a radio-frequency (RF) sensor and its measurement results of three volatile organic compounds (VOCs) at multiple frequency points from ∼ 2 to ∼ 11 GHz, which is a convenient range in our examination. The sensor is based on a simple RF interferometer and uses two coplanar waveguides (CPWs), A and B of 5 and 25 mm length, respectively, as VOC sensing electrodes. Approximately 70-nm-thick poly copolymer films are coated on CPW surfaces for VOC adsorption and concentration. It is shown that ethanol, acetone, and isopropyl (IPA) induce frequency-dependent RF responses, which are also VOC-dependent. Thus, the frequency-dependent properties provide a possible new approach for better VOC sensing selectivity. With CPW A, the limit-of-detections (LODs) are ∼ 600 ppm for ethanol, ∼ 270 ppm for acetone, and ∼ 330 ppm for IPA at 9.29 GHz. With CPW B, the LODs are roughly four times better. These LODs are also better than most of other RF VOC sensor results. In the future work, it is promising to further improve RF sensitivity and selectivity significantly.