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Fluorosilicone rubber, essential in automotive and aerospace owing to its excellent chemical resistance, plays a pivotal role in sealing technology, addressing the industry's evolving demands. This study explores the preparation and properties of fibrillated cellulose-reinforced fluorosilicone rubber composites to enhance their stiffness and oil resistance. Fibrillated cellulose sourced as a wet cake and subjected to processing and modification is incorporated into a fluorosilicone rubber matrix. The resulting composites are analysed by tensile and compression tests, along with compressive stress-relaxation testing in air and in an oil-immersed environment. The findings demonstrate significant improvements in the mechanical properties, including an increased Young's modulus and elongation at break, whereas the tensile strength remained uncompromised throughout the testing procedures. Morphological analysis of the fracture surfaces revealed a remarkable interfacial affinity between the fibrillated cellulose and rubber matrix, which was attributed in part to the modified fatty acids and inorganic nanoparticles. The presence of fibrillated cellulose enhanced the stress-relaxation characteristics under oil-immersion conditions. These results contribute to the domain of advanced elastomer materials, with potential for applications requiring enhanced mechanical properties and superior oil resistance. [ABSTRACT FROM AUTHOR]

This study reports on the synthesis and characterization of novel perfluorinated organic polymers with azo- and azomethine-based linkers using nucleophilic aromatic substitution. The polymers were synthesized via the incorporation of decafluorobiphenyl and hexafluorobenzene linkers with diphenols in the basic medium. The variation in the linkers allowed the synthesis of polymers with different fluorine and nitrogen contents. The rich fluorine polymers were slightly soluble in THF and have shown molecular weights ranging from 4886 to 11,948 g/mol. All polymers exhibit thermal stability in the range of 350–500 °C, which can be attributed to their structural geometry, elemental contents, branching, and cross-linking. For instance, the cross-linked polymers with high nitrogen content, DAB-Z-1h and DAB-Z-1O, are more stable than azomethine-based polymers. The cross-linking was characterized by porosity measurements. The azo-based polymer exhibited the highest surface area of 770 m2/g with a pore volume of 0.35 cm3/g, while the open-chain azomethine-based polymer revealed the lowest surface area of 285 m2/g with a pore volume of 0.0872 cm3/g. Porous structures with varied hydrophobicities were investigated as adsorbents for separating water-benzene and water-phenol mixtures and selectively binding methane/carbon dioxide gases from the air. The most hydrophobic polymers containing the decafluorbiphenyl linker were suitable for benzene separation, while the best methane uptake values were 6.14 and 3.46 mg/g for DAB-Z-1O and DAB-A-1O, respectively. On the other hand, DAB-Z-1h, with the highest surface area and being rich in nitrogen sites, has recorded the highest CO2 uptake at 298 K (17.25 mg/g). [ABSTRACT FROM AUTHOR]

To select the appropriate polymer thin films for liquid oxygen composite hoses, the liquid oxygen compatibility and the cryogenic mechanical properties of four fluoropolymer films (PCTFE, ETFE, FEP and PFA) and two non-fluoropolymer films (PET and PI) before and after immersion in liquid oxygen for an extended time were investigated. The results indicated that the four fluoropolymers were compatible with liquid oxygen before and after immersion for 60 days, and the two non-fluoropolymers were not compatible with liquid oxygen. In addition, the cryogenic mechanical properties of these polymer films underwent changes with the immersion time, and the changes in the non-fluoropolymer films were more pronounced. The cryogenic mechanical properties of the two non-fluoropolymer films were always superior to those of the four fluoropolymer films during the immersion. Further analysis indicated that the fundamental reason for these changes in the cryogenic mechanical properties was the variation in the crystalline phase structure caused by the ultra-low temperature, which was not related to the strong oxidizing properties of the liquid oxygen. Analytical results can provide useful guidance on how to select the appropriate material combination to obtain a reasonable liquid oxygen composite hose structure. [ABSTRACT FROM AUTHOR]

Core–double-shell-structured nanocomposite films consisting of polyvinylidene fluoride-grafted-barium titanate (PVDF-g-BT) incorporated into a P(VDF-co-hexafluoropropylene (HFP)) copolymer matrix were produced via a solution mixing method for energy storage applications. The resulting films were thoroughly investigated via spectroscopic, thermal, and morphological analyses. Thermogravimetric data provided an enhancement of the thermal stability, while differential scanning calorimetry indicated an increase in the crystallinity of the films after the addition of PVDF-g-BT. Moreover, broadband dielectric spectroscopy revealed three dielectric processes, namely, glass–rubber relaxation (αa), relaxation associated with the polymer crystalline phase (αc), and slower relaxation in the nanocomposites resulting from the accumulation of charge on the interface between the PVDF-g-BT filler and the P(VDF-co-HFP) matrix. The dependence of the dielectric constant from the composition was analyzed, and we found that the highest permittivity enhancement was obtained by the highest concentration filler added to the largest concentration of P(VDF-co-HFP). Mechanical analysis revealed an improvement in Young's modulus for all nanocomposites versus pristine P(VDF-co-HFP), confirming the uniformity of the distribution of the PVDF-g-BT nanocomposite with a strong interaction with the copolymer matrix, as also evidenced via scanning electron microscopy. The suggested system is promising for use in high-energy-density storage devices as supercapacitors. [ABSTRACT FROM AUTHOR]

Light-colored and transparent polyimide (PI) films with good high-temperature dimensional stability are highly desired for advanced optoelectronic applications. However, in practice, the simultaneous achievement of good optical and thermal properties in one PI film is usually difficult due to the inter-conflicting molecular design of the polymers. In the present work, a series of PI-SiO2 nanocomposite films (ABTFCPI) were developed based on the PI matrix derived from hydrogenated pyromellitic anhydride (HPMDA) and an aromatic diamine containing benzanilide and trifluoromethyl substituents in the structure, 2,2′-bis(trifluoromethyl)-4,4′-bis [4-(4-aminobenzamide)]biphenyl (ABTFMB). The inorganic SiO2 fillers were incorporated into the nanocomposite films in the form of colloidal nanoparticles dispersed in the good solvent of N,N-dimethylacetamide (DMAc) for the PI matrix. The derived ABTFCPI nanocomposite films showed good film-forming ability, flexible and tough nature, good optical transparency, and good thermal properties with loading amounts of SiO2 up to 30 wt% in the system. The ABTFCPI-30 film with a SiO2 content of 30 wt% in the film showed an optical transmittance of 79.6% at the wavelength of 400 nm (T400) with a thickness of 25 μm, yellow index (b*) of 2.15, and 5% weight loss temperatures (T5%) of 491 °C, which are all comparable to those the pristine ABTFCPI-0 matrix without filler (T400 = 81.8%; b* = 1.77; T5% = 492 °C). Meanwhile, the ABTFCPI-30 film exhibited obviously enhanced high-temperature dimensional stability with linear coefficients of thermal expansion (CTE) of 25.4 × 10−6/K in the temperature range of 50 to 250 °C, which is much lower than that of the AMTFCPI-0 film (CTE = 32.7 × 10−6/K). [ABSTRACT FROM AUTHOR]

Functional liquid fluoroelastomers are in high demand in new energy fields. And these materials have potential applications in high-performance sealing materials and as electrode materials. In this study, a novel high-performance hydroxyl-terminated liquid fluoroelastomer (t-HTLF) with a high fluorine content, temperature resistance, and curing efficiency was synthesised from a terpolymer of vinylidene fluoride (VDF), tetrafluoroethylene (TFE), and hexafluoropylene (HFP). A carboxyl-terminated liquid fluoroelastomer (t-CTLF) with controllable molar mass and end-group content was first prepared from a poly(VDF-ter-TFE-ter-HFP) terpolymer using a unique oxidative degradation method. Subsequently, an efficient "one-step" reduction of the carboxyl groups (COOH) in t-CTLF into hydroxyl groups (OH) was achieved via the functional-group conversion method using lithium aluminium hydride (LiAlH4) as the reductant. Thus, t-HTLF with a controllable molar mass and end-group content and highly active end groups was synthesised. Owing to the efficient curing reaction between OH and isocyanate groups (NCO), the cured t-HTLF exhibits good surface properties, thermal properties, and chemical stability. The thermal decomposition temperature (Td) of the cured t-HTLF reaches 334 °C, and it exhibits hydrophobicity. The oxidative degradation, reduction, and curing reaction mechanisms were also determined. The effects of solvent dosage, reaction temperature, reaction time, and ratio of the reductant to the COOH content on the carboxyl conversion were also systematically investigated. An efficient reduction system comprising LiAlH4 can not only achieve an efficient conversion of the COOH groups in t-CTLF to OH groups but also the in situ hydrogenation and addition reactions of residual double bonds (C=C) groups in the chain, such that the thermal stability and terminal activity of the product are improved while maintaining a high fluorine content. [ABSTRACT FROM AUTHOR]

Fluorinated polymers are attractive due to their special thermal, surface, gas separation, and other properties. In this study, new diblock, multiblock, and random copolymers of cyclooctene with two fluorinated norbornenes, 5-perfluorobutyl-2-norbornene and N-pentafluorophenyl-exo-endo-norbornene-5,6-dicarboximide, are synthesized by ring-opening metathesis copolymerization and macromolecular cross-metathesis in the presence of the first- to third-generation Grubbs' Ru-catalysts. Their thermal, surface, bulk, and solution characteristics are investigated and compared using differential scanning calorimetry, water contact angle measurements, gas permeation, and light scattering, respectively. It is demonstrated that they are correlated with the chain structure of the copolymers. The properties of multiblock copolymers are generally closer to those of diblock copolymers than of random ones, which can be explained by the presence of long blocks capable of self-organization. In particular, diblock and multiblock fluorine-imide-containing copolymers show a tendency to form micelles in chloroform solutions well below the overlap concentration. The results obtained may be of interest to a wide range of researchers involved in the design of functional copolymers. [ABSTRACT FROM AUTHOR]

This study concerns the one-step radiografting of flax fabrics with phosphonated and fluorinated polymer chains using (meth)acrylic monomers: dimethyl(methacryloxy)methyl phosphonate (MAPC1), 2-(perfluorobutyl)ethyl methacrylate (M4), 1H,1H,2H,2H-perfluorooctyl acrylate (AC6) and 1H,1H,2H,2H-perfluorodecyl methacrylate (M8). The multifunctionalization of flax fabrics using a pre-irradiation procedure at 20 and 100 kGy allows simultaneously providing them with flame retardancy and hydro- and oleophobicity properties. The successful grafting of flax fibers is first confirmed by FTIR spectroscopy. The morphology of the treated fabrics, the regioselectivity of grafting and the distribution of the fluorine and phosphorus elements are assessed by scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (SEM-EDX). The flame retardancy is evaluated using pyrolysis combustion flow calorimetry (PCFC) and cone calorimetry. The hydro- and oleophobicity and water repellency of the treated fabrics is established by contact angle and sliding angle measurements, respectively. The grafting treatment of flax irradiated at 100 KGy, using M8 and MAPC1 monomers (50:50) for 24 h, allows achieving fluorine and phosphorus contents of 8.04 wt% and 0.77 wt%, respectively. The modified fabrics display excellent hydro-oleophobic and flame-retardant properties with water and diiodomethane contact angles of 151° and 131°, respectively, and a large decrease in peak of heat release rate (pHRR) compared to pristine flax (from 230 W/g to 53 W/g). Relevant results are also obtained for M4 and AC6 monomers in combination with MAPC1. For the flame retardancy feature, the presence of fluorinated groups does not disturb the effect of phosphorus. [ABSTRACT FROM AUTHOR]

Light guiding is used to direct light from an emitting source to a different location. It is frequently realized through a clad–core structure with a difference in the refractive index of the materials. This paper explores the possibility of combining a fluoropolymer (THV) film of low refractive index, serving as a cladding layer, with a polycarbonate (PC) core, via injection molding. Pristine THV lacks adherence to the PC. However, when treated with O 2 plasma prior to overmolding, bonding can be established that was quantified in peel tests. The effect of this surface treatment was further investigated by adjusting the plasma treatment duration and time to overmolding. Furthermore, parameter studies comprising the four molding parameters, namely packing pressure, injection speed, melt temperature, and mold temperature, were performed. Numerical injection molding simulations assessed the prevailing temperatures at the PC–THV boundary. Consequently, the temperature–time integral could be calculated and linked with the measured peel strengths by fitting a proportionality constant. While the plasma treatment duration showed minor influence, the activation diminished with time, halving the measured peel loads within 24 h. The adhesion was experimentally found to increase with a lower packing pressure, faster injection speed, and higher melt and mold temperature. Those same molding relations influencing the peel loads were also found with the temperature–time integral when scaled by the proportionality constant in the simulations ( R 2 = 85 % ). Apparently, adhesion is added by molding settings which promote higher interface temperatures that prevail for longer. Hereby, the faster injection speed increases the melt temperature through shear heating. A higher packing pressure, in contrast, presumably increases the heat transfer at the PC–THV interface, accelerating the cooling. The measured peel loads were 0.3–1.6 N/mm for plasma-treated samples and nearly zero for pristine THV. [ABSTRACT FROM AUTHOR]

Corrosion of structural parts not only reduces the service life of the equipment but also causes safety accidents, so building a long-lasting anti-corrosion coating on its surface is the key to solving this problem. Under the action of alkali catalysis, n-octyltriethoxysilane (OTES), dimethyldimethoxysilane (DMDMS), and perfluorodecyltrimethoxysilane (FTMS) hydrolyzed and polycondensed co-modified graphene oxide (GO), modified to synthesize a self-cleaning superhydrophobic material fluorosilane-modified graphene oxide (FGO). The structure, film morphology, and properties of FGO were systematically characterized. The results showed that the newly synthesized FGO was successfully modified by long-chain fluorocarbon groups and silanes. FGO presented an uneven and rough morphology on the substrate surface, the water contact angle was 151.3°, and the rolling angle was 3.9°, which caused the coating to exhibit excellent self-cleaning function. Meanwhile, the epoxy polymer/fluorosilane-modified graphene oxide (E-FGO) composite coating adhered to the carbon structural steel's surface, and its corrosion resistance was detected by the Tafel curve and EIS impedance. It was found that the current density of the 10 wt% E-FGO coating (Icorr) was the lowest (1.087 × 10−10 A/cm2), which was approximately 3 orders of magnitude lower than that of the unmodified epoxy coating. This was primarily due to the introduction of FGO, which formed a continuous physical barrier in the composite coating and gave the composite coating excellent hydrophobicity. This method might provide new ideas for advances in steel corrosion resistance in the marine sector. [ABSTRACT FROM AUTHOR]

Fluorinated polymers have unique wettability and protein adsorption properties. The site-specific alteration of these properties could expand their application to different research areas. In this work, a fluorinated homopolymer and two of its copolymers with 4-vinylbenzyl glycidyl ether (VBGE) are synthesized by free radical polymerization. The produced polymers are then used to develop resist formulations by the addition of a photoacid generator. Films of these formulations are exposed to ultraviolet radiation through a binary mask and heated to create the pattern. It is found that the water contact angle values of the exposed films areas are reduced compared to those of the unexposed ones, with the exception of pentafluorophenyl methacrylate (PFMA) homopolymer film. This is attributed to the reaction of the epoxy groups creating x-links and producing hydroxyl groups and the cleavage of the pentafluorophenyl group from the ester group leading to carboxylic acid groups. Both modifications on the exposed areas are verified by FTIR spectroscopy and ToF-SIMS analysis. In addition, the biomolecules adsorption ability of the exposed area is increasing 10–15 times compared to the unexposed one for the PFMA homopolymer and the PFMA/VBGE 1:1 copolymer. Thus, the proposed polymers and patterning procedure could find application to spatially directed immobilization of biomolecules and/or cells onto a surface for both biosensing and tissue engineering purposes. [ABSTRACT FROM AUTHOR]

Due to the growing demand for versatile hybrid materials that can withstand harsh conditions (below −40 °C), fluorosilicone copolymers are becoming promising materials that can overcome the limited operating temperature of conventional rubber. In order to synthesize a fluorosilicone copolymer, a potent initiator capable of simultaneously initiating various siloxane monomers in anionic ring-opening polymerization (AROP) is required. In this study, tetramethyl ammonium silanolate (TMAS), a quaternary ammonium (QA) anion, was employed as an initiator for AROP, thereby fluoro-methyl-vinyl-silicone (FVMQ) and fluoro-hydrido-methyl-silicone (FHMQ) were successfully synthesized under optimized conditions. FT-IR, NMR, and GPC analyses confirmed that the chain length and functional group content of FVMQ and FHMQ are controlled by changing the ratio of the components. Moreover, fluorine-involved liquid silicone rubber (F-LSR) was prepared with FVMQ as the main chain and FHMQ as a crosslinker. The tensile strength, elongation, and hardness of each F-LSR sample were measured. Finally, it was confirmed through TGA, DSC, TR-test, and embrittlement testing that elastic retention at low temperatures improved even though the heat resistance slightly decreased as the trifluoropropyl group increased in F-LSR. We anticipate that the optimization of fluorosilicone synthesis initiated by QA and the comprehensive characterization of F-LSRs with different fluorine content and chain lengths will be pivotal to academia and industry. [ABSTRACT FROM AUTHOR]

To date, PTFE, PFA, and FEP-based fluoropolymer coatings have proven unbeatable in many services due to their excellent chemical inertness, very low wettability, thermal resistance, high non-stick properties, and good applicability. In use, these coatings usually suffer service cycles with consequent deterioration, and it is of great interest to determine the intensity and type of wear caused in addition to the deterioration that occurs in their properties. In this work, the response of three polymeric coatings of interest applied to aluminum substrates, after being subjected to the action of abrasive particles of aluminum corundum, glass, and plastic projected under pressure, has been studied. During the application of a given wear cycle, the hardness, surface roughness, surface texture, and thickness of the coating have been measured, in addition to the slip angle and surface transmittance to analyze the evolution of each type of coating. The results allowed a concise evaluation of the performance of three fluoropolymeric coatings of great interest, differentiating the induced erosive wear phenomena and contributing complete information to facilitate the correct selection for users with practical application purposes and as a basis for future research work focused on advancements in this field. [ABSTRACT FROM AUTHOR]

Polymer electrolytes (PEs) based on poly(ethylene oxide) (PEO) have gained increasing interest in lithium-ion batteries (LIBs) and are expected to solve the safety issue of commercial liquid electrolytes due to their excellent thermal and mechanical stability, suppression of lithium dendrites and shortened battery assembly process. However, challenges, such as high interfacial resistance between electrolyte and electrodes and poor ionic conductivity (σ) at room temperature (RT), still limit the use of PEO-based PEs. In this work, an in situ PEO-based polymer electrolyte consisting of polyethylene glycol dimethacrylate (PEGDMA) 1000, lithium bis(fluorosulfonyl)imide (LiFSI) and DMF is cured on a LiFePO4 (LFP) cathode to address the above-mentioned issues. As a result, optimized PE shows a promising σ and lithium-ion transference number (tLi+) of 6.13 × 10−4 S cm−1 and 0.63 at RT and excellent thermal stability up to 136 °C. Moreover, the LiFePO4//Li cell assembled by in situ PE exhibits superior discharge capacity (141 mAh g−1) at 0.1 C, favorable Coulombic efficiency (97.6%) after 100 cycles and promising rate performance. This work contributes to modifying PEO-based PE to force the interfacial contact between the electrolyte and the electrode and to improve LIBs' performance. [ABSTRACT FROM AUTHOR]

Bicomponent photoluminescent polymer optical fibers (PL-POFs) have been melt-spun and in-situ drawn to different extents. The results suggest that scattering in the sheath can effectively increase the photoluminescent dye excitation probability in the fiber core. The core/sheath PL-POFs are made of a semi-crystalline fluoropolymer sheath of low refractive index (RI) and an amorphous cycloolefin polymeric core of high RI, which is doped with a luminescent dye. The axial light emission, as well as the guiding attenuation coefficients of the core/sheath PL-POFs, have been measured using a side-illumination set-up. The incident blue laser is down-converted to red light, which is re-emitted and partially guided by the core. The axial light emission is measured at the fiber tip as a function of the distance from the illumination position to the integrating sphere. It is demonstrated that the presence of a semi-crystalline sheath significantly enhances the axial light emission and that it also lowers the attenuation coefficient, compared to the emission and guiding properties of PL core-only fibers. Additionally, the attenuation coefficient has been found to be lower in more strongly drawn PL-POFs. Wide-angle X-ray diffraction and small-angle X-ray scattering experiments reveal structural differences in differently drawn PL-POFs that can be linked to the observed differences in the optical properties. [ABSTRACT FROM AUTHOR]

Composite materials are the most variative type of materials employed in almost every task imaginable. In the present study, a synthesis of a novel perfluoroalkyltriethoxysilane is reported to be used in creating composites with polyhexafluoropropylene—one of the most indifferent and adhesion-lacking polymers existing. The mechanism of adhesion of hexafluoropropylene is proved to be due to chemical structural coherence of perfluoroalkyltriethoxysilane to a link of polyhexafluoropropylene chain. The ability of perfluoroalkyltriethoxysilane to attach to surfaces was studied by FT-IR spectroscopy of modified glass microspheres. Although the perfluoroalkyltriethoxysilane surface modifier allowed partial adhesion of polyhexafluoropropylene, some detachment took place; therefore, the surface nanostructuring was used to increase its specific area by aluminum foil anodizing. An anodized aluminum surface was studied by scanning electron microscopy. The resulting composite consisting of anodized aluminum, perfluoroalkyl surface modifier, and polyhexafluoropropylene layer was proved to be stable, showed no signs of detachment, and is a promising material for usage in harsh environments. [ABSTRACT FROM AUTHOR]

The synthesis and characterization of a platform of novel functional fluorinated gradient copolymers soluble in liquid and supercritical CO2 is reported. These functional copolymers are bearing different types of complexing units (pyridine, triphenylphosphine, acetylacetate, thioacetate, and thiol) which are well-known ligands for various metals. They have been prepared by reversible addition–fragmentation chain-transfer (RAFT) polymerization in order to obtain well-defined gradient copolymers. The copolymers have been characterized by proton nuclear magnetic resonance (1H-NMR) spectroscopy, matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry, thermal gravimetric analysis (TGA), dynamical scanning calorimetry (DSC) and cloud point measurements in dense CO2. All the investigated metal-complexing copolymers are soluble in dense CO2 under mild conditions (pressure lower than 30 MPa up to 65 °C), confirming their potential applications in processes such as metal-catalyzed reactions in dense CO2, metal impregnation, (e.g., preparation of supported catalysts) or metal extraction from various substrates (solid or liquid effluents). Particularly, it opens the door to greener and less energy-demanding processes for the recovery of metals from spent catalysts compared to more conventional pyro- and hydro-metallurgical methods. [ABSTRACT FROM AUTHOR]

To increase the human lifespan, healthcare monitoring devices that diagnose diseases and check body conditions have attracted considerable interest. Commercial AgCl-based wet electrodes with the advantages of high conductivity and strong adaptability to human skin are considered the most frequently used electrode material for healthcare monitoring. However, commercial AgCl-based wet electrodes, when exposed for a long period, cause an evaporation of organic solvents, which could reduce the signal-to-noise ratio of biosignals and stimulate human skin. In this context, we demonstrate a dry electrode for a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)-based blended polymer electrode using a combination of PEDOT:PSS, waterborne polyurethane (WPU) and ethylene glycol (EG) that could be reused for a long period of time to detect electrocardiography (ECG) and electromyography (EMG). Both ECG and EMG are reliably detected by the wireless real-time monitoring system. In particular, the proposed dry electrode detects biosignals without deterioration for over 2 weeks. Additionally, a double layer of a polyimide (PI) substrate and fluorinated polymer CYTOP induces the strong waterproof characteristics of external liquids for the proposed dry electrodes, having a low surface energy of 14.49 mN/m. In addition, the proposed electrode has excellent degradability in water; it dissolves in hot water at 60 °C. [ABSTRACT FROM AUTHOR]

Polymer waveguide phase modulators exhibit stable low-power phase modulation owing to their exceptional thermal confinement and high thermo-optic effect, and thus, have the merit of thermal isolation between channels, which is crucial for an optical phased array (OPA) beam scanner device. In this work, a waveguide phase modulator was designed and fabricated based on a high-refractive-index fluorinated polyimide. The propagation loss of the polyimide waveguide and the temporal response of the phase modulator were characterized. Moreover, the transfer function of the phase modulator including multiple poles and zeros was obtained from the measured frequency response. The polyimide waveguide modulator device demonstrated a fast response time of 117 μs for 1 kHz input signal, however, for 1 mHz step-function input, it exhibited an additional 5% phase change in 5 s. [ABSTRACT FROM AUTHOR]

This study proposes to use reactive copolymers based on glycidyl methacrylate and fluoroalkyl methacrylates with a low fluorine content in the monomer unit as agents to reduce the surface free energy (SFE). This work reveals the effect of the structure and composition of copolymers on the SFE and water-repellent properties of these coatings. On a smooth surface, coatings based on copolymers of glycidyl methacrylate and fluoroalkyl methacrylates with fluorine atoms in the monomer unit ranging from three to seven are characterized by SFE values in the range from 25 to 13 mN/m, which is comparable to the values for polyhedral oligomeric silsesquioxanes and perfluoroalkyl acrylates. On textured aluminum surfaces, the obtained coatings provide time-stable superhydrophobic properties with contact angles up to 170° and sliding angles up to 2°. The possibility of using copolymers based on glycidyl methacrylate and fluoroalkyl methacrylates for the creation of self-cleaning polymer coatings is shown. [ABSTRACT FROM AUTHOR]

A review of the available standard codes to perform accelerated aging tests on polymers was presented by the authors, evidencing a general lack of indications on how to correlate the results of the accelerated aging tests for each different class of polymers with those obtained on naturally exposed materials. 35267735 10 Frigione M., Rodríguez-Prieto A. Can Accelerated Aging Procedures Predict the Long Term Behavior of Polymers Exposed to Different Environments? As any other natural or industrial material, polymers can experience some kind of degradation during their service life, resulting in minor to severe changes in their properties. The degradation of the polypropylenes under investigation was manifested in a shift of the melting point of the polymers to higher temperatures, with an increase in the degree of crystallization, both phenomena probably due to a degradation of the amorphous fraction of the polymer. [Extracted from the article]

We developed a method for characterizing permeation parameters in hydrogen sorption and desorption processes in polymers using the volumetric measurement technique. The technique was utilized for three polymers: nitrile butadiene rubber (NBR), ethylene propylene diene monomer (EPDM), and fluoroelastomer (FKM). The total uptake ( C ∞ ), total desorbed content ( C 0) , diffusivity in sorption (Ds), and diffusivity in desorption (Dd) of hydrogen in the polymers were determined versus the sample diameter used in both processes. For all the polymers, the diameter dependence was not detected for C ∞ and C 0 . The average C ∞ and C 0 at 5.75 MPa were 316 wt∙ppm and 291 wt∙ppm for NBR, 270 wt∙ppm and 279 wt∙ppm for EPDM, and 102 wt∙ppm and 93 wt∙ppm for FKM. The coincidence of C ∞ and C 0 in the sorption and desorption process indicated physisorption upon introducing hydrogen molecules into the polymers. The larger Dd in the desorption process than Ds could be attributed to an increased amorphous phase and volume swelling after decompression. The equilibrium time to reach the saturation of the hydrogen content in both processes was experimentally confirmed as proportional to the squared radius and consistent with the COMSOL simulation. This method could be used to predict the equilibrium time of the sorption time, depending on the radius of the polymers without any measurement. [ABSTRACT FROM AUTHOR]

Fluorinated polymers constitute a unique class of materials that exhibit a combination of suitable properties for a wide range of applications, which mainly arise from their outstanding chemical resistance, thermal stability, low friction coefficients and electrical properties. Furthermore, those presenting stimuli-responsive properties have found widespread industrial and commercial applications, based on their ability to change in a controlled fashion one or more of their physicochemical properties, in response to single or multiple external stimuli such as light, temperature, electrical and magnetic fields, pH and/or biological signals. In particular, some fluorinated polymers have been intensively investigated and applied due to their piezoelectric, pyroelectric and ferroelectric properties in biomedical applications including controlled drug delivery systems, tissue engineering, microfluidic and artificial muscle actuators, among others. This review summarizes the main characteristics, microstructures and biomedical applications of electroactive fluorinated polymers. [ABSTRACT FROM AUTHOR]

Ablend of Polyvinylidene Fluoride (PVDF) and SiO2 microspheres inN,N-Dimethylformamide (DMF) underwent phase inversion to form a PVDF/SiO2 membrane with SiO2 microspheres in the membrane's pores. Subsequently, the SiO2 microspheres have been used as platforms for in site Ag nanoparticles (NPs) synthesis, forming a composite membrane. Benefitting from the full exposure of Ag NPs to the reactants, the composite membrane shows high catalytic reactivity when catalyzing the reduction of p-nitrophenol under a cross-flow. The catalytic reaction follows the first-order kinetics, and the reaction rate increases with an increase in the amount of Ag NPs in the membrane, the reaction temperature, and the operating pressure. What is more, highly purified products can be produced and separated from the reactants in a timely manner by using the composite membrane. [ABSTRACT FROM AUTHOR]

Block copolymers of poly(vinylidene fluoride) (PVDF) with either styrene or methyl methacrylate (MMA) were synthesized and analyzed with respect to the type of the crystalline phase occurring. PVDF with iodine end groups (PVDF-I) was prepared by iodine transfer polymerization either in solution with supercritical CO2 or in emulsion. To activate all iodine end groups Mn2(CO)10 is employed. Upon UV irradiation Mn(CO)5 radicals are obtained, which abstract iodine from PVDF-I generating PVDF radicals. Subsequent polymerization with styrene or methyl methacrylate (MMA) yields block copolymers. Size exclusion chromatography and NMR results prove that the entire PVDF-I is converted. XRD, FT-IR, and differential scanning calorimetry (DSC) analyses allow for the identification of crystal phase transformation. It is clearly shown that the original β crystalline phase of PVDF-I is changed to the β crystalline phase in case of the block copolymers. For ratios of the VDF block length to the MMA block length ranging from 1.4 to 5 only β phase material was detected. [ABSTRACT FROM AUTHOR]

Solution-processed bulk heterojunction solar cells have experienced a remarkable acceleration in performances in the last two decades, reaching power conversion efficiencies above 10%. This impressive progress is the outcome of a simultaneous development of more advanced device architectures and of optimized semiconducting polymers. Several chemical approaches have been developed to fine-tune the optoelectronics and structural polymer parameters required to reach high efficiencies. Fluorination of the conjugated polymer backbone has appeared recently to be an especially promising approach for the development of efficient semiconducting polymers. As a matter of fact, most currently best-performing semiconducting polymers are using fluorine atoms in their conjugated backbone. In this review, we attempt to give an up-to-date overview of the latest results achieved on fluorinated polymers for solar cells and to highlight general polymer properties' evolution trends related to the fluorination of their conjugated backbone. [ABSTRACT FROM AUTHOR]

Proton exchange membranes (PEMs) are a key component of a proton exchange membrane fuel cell. Sulfonated polyimides (SPIs) were doped by protic ionic liquid (PIL) to prepare composite PEMs with substantially improved conductivity. SPIs were synthesized from diamine, 2,2-bis[4-(4-amino-phenoxy)phenyl]propane (BAPP), sulfonated diamine, 4,4'-diamino diphenyl ether-2,2'-disulfonic acid (ODADS) and aromatic anhydride. BAPP improved the mechanical and thermal properties of SPIs, while ODADS enhanced conductivity. A PIL, 1-vinylimidazolium trifluoromethane-sulfonate ([VIm][OTf]), was utilized. [VIm][OTf] offered better conductivity, which can be attributed to its vinyl chemical structure attached to an imidazolium ring that contributed to ionomer-PIL interactions. We prepared sulfonated polyimide/ionic liquid (SPI/IL) composite PEMs using 50 wt% [VIm][OTf] with a conductivity of 7.17 mS/cm at 100 °C, and in an anhydrous condition, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride (DSDA) was used in the synthesis of SPIs, leading to several hundred-times improvement in conductivity compared to pristine SPIs. [ABSTRACT FROM AUTHOR]

A series of fluorinated sulfonated poly (ether amide)s (SPAs) were synthesized for proton exchange membrane fuel cell applications. A polycondensation reaction of 4,4'-oxydianiline, 2-sulfoterephthalic acid monosodium salt, and tetrafluorophenylene dicarboxylic acids (terephthalic and isophthalic) or fluoroaliphatic dicarboxylic acids produced SPAs with sulfonation degrees of 80-90%. Controlling the feed ratio of the sulfonated and unsulfonated dicarboxylic acid monomers afforded random SPAs with ion exchange capacities between 1.7 and 2.2 meq/g and good solubility in polar aprotic solvents. Their structures were characterized using NMR and FT IR spectroscopies. Tough, flexible, and transparent films were obtained with dimethylsulfoxide using a solution casting method. Most SPA membranes with 90% sulfonation degree showed high proton conductivity (>100 mS/cm) at 80°C and 100% relative humidity. Among them, two outstanding ionomers (ODA-STA-TPA-90 and ODA-STA-IPA-90) showed proton conductivity comparable to that of Nafion 117 between 40 and 80 °C. The influence of chemical structure on the membrane properties was systematically investigated by comparing the fluorinated polymers to their hydrogenated counterparts. The results suggest that the incorporation of fluorinated moieties in the polymer backbone of the membrane reduces water absorption. High molecular weight and the resulting physical entanglement of the polymers chains played a more important role in improving stability in water, however. [ABSTRACT FROM AUTHOR]

In this study, the effect of plasma treatment on glass-cloth-containing polytetrafluoroethylene (GC–PTFE) was investigated. Previous plasma studies investigated pure PTFE (which does not contain glass cloth) but not GC–PTFE. The effect of Ar + H2O plasma treatment on GC–PTFE was investigated. The Ar + H2O plasma-treated GC–PTFE sheets were thermally compressed to stainless steel (SUS304) foils without using adhesive, and the GC–PTFE/SUS304 adhesion strengths were measured using a 90° peel test. The adhesion strength increased with the increase in the plasma treatment time (0.8 and 1.0 N/mm at 20 s and 300 s, respectively). Thus, strong adhesion between GC–PTFE/SUS304 was achieved without adhesive. This improvement in the adhesion properties of GC–PTFE can be attributed to the generation of oxygen-containing functional groups and the decrease in the surface roughness of the samples. Thereafter, the adhesion properties of GC–PTFE and pure PTFE were compared. Because, unlike pure PTFE, GC–PTFE has no weak boundary layer, GC–PTFE exhibited better adhesion properties than pure PTFE under short plasma treatment times. [ABSTRACT FROM AUTHOR]

The ecofriendly poly(vinyl alcohol) (PVA) used to modify the catalyst layer, or the use of novel ionic liquid-incorporated Zn-ion conducting polymer electrolyte membranes, or solid polymer blend electrolytes (SPBEs) based on natural chitosan (CS) and methylcellulose (MC) are proposed. A comparison between commercial membranes such as Nafion 117 and Nafion 212 and Nafion membranes prepared by three different procedures, Nafion-recast, Nafion uncrystallized, and Nafion 117-oriented, was conducted. Kim et al. [[8]] synthesized a thermally crosslinked sulfonated polyphenylsulfone (CSPPSU) polymer and different wt% of PVA (5, 10, and 20); then, a CSPPSU-vinylon membrane was synthesized using a formalization reaction. [Extracted from the article]

Heat-assisted plasma (HAP) treatment using He gas is known to improve the adhesive-bonding and adhesive-free adhesion properties of polytetrafluoroethylene (PTFE). In this study, we investigated the effects of He and Ar gaseous species on the HAP-treated PTFE surface. Epoxy (EP) adhesive-coated stainless steel (SUS304) and isobutylene–isoprene rubber (IIR) were used as adherents for the evaluation of the adhesive-bonding and adhesive-free adhesion properties of PTFE. In the case of adhesive bonding, the PTFE/EP-adhesive/SUS304 adhesion strength of the Ar-HAP-treated PTFE was the same as that of the He-HAP-treated PTFE. In the case of adhesive-free adhesion, the PTFE/IIR adhesion strength of the Ar-HAP-treated PTFE was seven times lower than that of the He-HAP-treated PTFE. The relation among gaseous species used in HAP treatment, adhesion properties, peroxy radical density ratio, surface chemical composition, surface modification depth, surface morphology, surface hardness, and the effect of irradiation with vacuum ultraviolet (VUV) and UV photons were investigated. The different adhesive-free adhesion properties obtained by the two treatments resulted from the changes in surface chemical composition, especially the ratios of oxygen-containing functional groups and C–C crosslinks. [ABSTRACT FROM AUTHOR]

Modification and functionalization of polymer surface properties is desired in numerous applications, and a standard technique is a treatment with non-equilibrium gaseous plasma. Fluorinated polymers exhibit specific properties and are regarded as difficult to functionalize with polar functional groups. Plasma methods for functionalization of polyvinylidene fluoride (PVDF) are reviewed and different mechanisms involved in the surface modification are presented and explained by the interaction of various reactive species and far ultraviolet radiation. Most authors used argon plasma but reported various results. The discrepancy between the reported results is explained by peculiarities of the experimental systems and illustrated by three mechanisms. More versatile reaction mechanisms were reported by authors who used oxygen plasma for surface modification of PVDF, while plasma sustained in other gases was rarely used. The results reported by various authors are analyzed, and correlations are drawn where feasible. The processing parameters reported by different authors were the gas pressure and purity, the discharge configuration and power, while the surface finish was predominantly determined by X-ray photoelectron spectroscopy (XPS) and static water contact angle (WCA). A reasonably good correlation was found between the surface wettability as probed by WCA and the oxygen concentration as probed by XPS, but there is hardly any correlation between the discharge parameters and the wettability. [ABSTRACT FROM AUTHOR]

In this research study, we developed a voltammetric electrochemical sensor probe with a copolymer Nafion (Sulfonated Tetrafluoroethylene-based Fluoro-polymer) decorated with hydrothermally prepared sandwich-type CuO/ZnO nanospikes (NSs) onto a glassy carbon electrode (GCE) for reliable thiourea (TU) detection. The detailed characterizations in terms of structural morphology, binding energy, elemental compositions, grain size and crystallinity for synthesized NSs were performed by field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) analysis, respectively. The differential pulse voltammetric (DPV) analysis for TU showed good linearity at current-versus-TU concentration on the calibration plot in the 0.15~1.20 mM range, which is defined as a dynamic detection range (LDR) of TU in a phosphate buffer solution. Considering the slope of LDR over the GCE-coated NSs surface area (0.0316 cm2), the TU sensor sensitivity (0.4122 µA µM−1 cm−2) was obtained. Besides this, the low limit (LOD) for TU detection was calculated and found to be 23.03 ± 1.15 µM. The fabricated Nafion/CuO/ZnO NSs/GCE sensor probe was created as a reliable sensor based on reproducibility, interference effect, stability and response time. Real bio-samples were investigated and the results confirm the anticipated reliability of the TU sensor probe. Thus, this is a noble way to develop enzyme-free electrochemical sensors that could be an alternative approach for the detection of chemicals in the field of enzyme-free biosensor development technology. [ABSTRACT FROM AUTHOR]

A self-assembled co-hydrogel system with sol-gel two-phase coexistence and mucoadhesive properties was developed based on the combined properties of fluoroalkyl double-ended poly(ethylene glycol) (Rf-PEG-Rf) and poly(acrylic acid) (PAA), respectively. We have synthesized an Rf-PEG-g-PAA (where g denotes grafted) copolymer and integrated it into the Rf-PEG-Rf physically cross-linked micellar network to form a co-hydrogel system. Tensile strengths between the co-hydrogel surfaces and two different sets of mucosal surfaces were acquired. One mucosal surface was made of porcine stomach mucin Type II, while the other one is a pig small intestine. The experimental results show that the largest maximum detachment stresses (MDSs) were obtained when the Rf-PEG-g-PAA's weight percent in the dehydrated polymer mixture is ~15%. Tensile experiments also found that MDSs are greater in acidic conditions (pH = 4–5) (123.3 g/cm2 for the artificial mucus, and 43.0 g/cm2 for pig small intestine) and basic conditions (pH = 10.6) (126.9 g/cm2, and 44.6 g.cm2, respectively) than in neutral pH (45.4 g/cm2, and 30.7 g.cm2, respectively). Results of the rheological analyses using shear strain amplitude sweep and frequency sweep reveal that the Rf-PEG-g-PAA was physically integrated into the Rf-PEG-Rf micellar network, and the co-hydrogels remain physically cross-linked in three-dimensional micellar networks with long-term physical dispersion stability. Therefore, the co-hydrogel system is promising for drug delivery applications on mucosal surfaces. [ABSTRACT FROM AUTHOR]

Polymer based composite coatings represent an important class of materials for various applications [[1], [3], [5], [7], [9]] due to their capabilities to couple the elastic, optical, or wettability properties of the polymers with the mechanical, physical, and chemical properties of metals, dielectrics, or ceramics. The most known feature of the plasma enhanced CVD (PECVD) technique is that the generated polymeric films are chemically stable and have strongly cross-linked structures, in comparison with the polymers produced by initiated chemical vapor deposition method (iCVD) which are linear. [Extracted from the article]

This literature review covers the solubility and processability of fluoropolymer polyvinylidine fluoride (PVDF). Fluoropolymers consist of a carbon backbone chain with multiple connected C–F bonds; they are typically nonreactive and nontoxic and have good thermal stability. Their processing, recycling and reuse are rapidly becoming more important to the circular economy as fluoropolymers find widespread application in diverse sectors including construction, automotive engineering and electronics. The partially fluorinated polymer PVDF is in strong demand in all of these areas; in addition to its desirable inertness, which is typical of most fluoropolymers, it also has a high dielectric constant and can be ferroelectric in some of its crystal phases. However, processing and reusing PVDF is a challenging task, and this is partly due to its limited solubility. This review begins with a discussion on the useful properties and applications of PVDF, followed by a discussion on the known solvents and diluents of PVDF and how it can be formed into membranes. Finally, we explore the limitations of PVDF's chemical and thermal stability, with a discussion on conditions under which it can degrade. Our aim is to provide a condensed overview that will be of use to both chemists and engineers who need to work with PVDF. [ABSTRACT FROM AUTHOR]

Functional coatings for application on surfaces are of growing interest. Especially in the textile industry, durable water and oil repellent finishes are of special demand for implementation in the outdoor sector, but also as safety-protection clothes against oil or chemicals. Such oil and chemical repellent textiles can be achieved by coating surfaces with fluoropolymers. As many concerns exist regarding (per)fluorinated polymers due to their high persistence and accumulation capacity in the environment, a durable and resistant coating is essential also during the washing processes of textiles. Within the present study, different strategies are examined for a durable resistant cross-linking of a novel fluoropolymer on the surface of fibers. The monomer 2-((1,1,2-trifluoro-2-(perfluoropropoxy)ethyl)thio)ethyl acrylate, whose fluorinated side-chain is degradable by treatment with ozone, was used for this purpose. The polymers were synthesized via free radical polymerization in emulsion, and different amounts of cross-linking reagents were copolymerized. The final polymer dispersions were applied to cellulose fibers and the cross-linking was induced thermally or by irradiation with UV-light. In order to investigate the cross-linking efficiency, tensile elongation studies were carried out. In addition, multiple washing processes of the fibers were performed and the polymer loss during washing, as well as the effects on oil and water repellency were investigated. The cross-linking strategy paves the way to a durable fluoropolymer-based functional coating and the polymers are expected to provide a promising and sustainable alternative to functional coatings. [ABSTRACT FROM AUTHOR]

Super-hydrophilicity is a desired but rarely reported surface finish of polymer materials, so the methods for achieving such a property represent a great scientific and technological challenge. The methods reported by various authors are reviewed and discussed in this paper. The super-hydrophilic surface finish has been reported for polymers functionalized with oxygen-rich surface functional groups and of rich morphology on the sub-micrometer scale. The oxygen concentration as probed by X-ray photoelectron spectroscopy should be above 30 atomic % and the roughness as determined by atomic force microscopy over a few nm, although most authors reported the roughness was close to 100 nm. A simple one-step oxygen plasma treatment assures for super-hydrophilicity of few polymers only, but the technology enables such a surface finish of almost any fluorine-free polymer providing a capacitively coupled oxygen plasma that enables deposition of minute quantities of inorganic material is applied. More complex methods include deposition of at least one coating, followed by surface activation with oxygen plasma. Fluorinated polymers require treatment with plasma rich in hydrogen to achieve the super-hydrophilic surface finish. The stability upon aging depends largely on the technique used for super-hydrophilization. [ABSTRACT FROM AUTHOR]

Fluorinated polymers are renowned for their chemical inertness and thus poor wettability and adhesion of various coatings. Apart from chemical methods employing somewhat toxic primers, gaseous plasma treatment is a popular method for the modification of surface properties. Different authors have used different plasmas, and the resultant surface finish spans between super-hydrophobic and super-hydrophilic character. Some authors also reported the hydrophobic recovery. The review of recent papers is presented and discussed. Correlations between plasma and/or discharge parameters and the surface finish are drawn and the most important conclusions are summarized. The concentration of oxygen in the surface film as probed by X-ray photoelectron spectroscopy is inversely dependent on the concentration of oxygen in gaseous plasma. The predominant mechanism leading to hydrophilic surface finish is bond scission by deep ultraviolet radiation rather than functionalization with reactive oxygen species. [ABSTRACT FROM AUTHOR]

Mixed ionic-electronic conductors, such as poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) are postulated to be the next generation materials in energy storage and electronic devices. Although many studies have aimed to enhance the electronic conductivity and mechanical properties of these materials, there has been little focus on ionic conductivity. In this work, blends based on PEDOT stabilized by the polyelectrolyte poly(diallyldimethylammonium) (PolyDADMA X) are reported, where the X anion is either chloride (Cl), bis(fluorosulfonyl)imide (FSI), bis(trifluoromethylsulfonyl)imide (TFSI), triflate (CF3SO3) or tosylate (Tos). Electronic conductivity values of 0.6 S cm−1 were achieved in films of PEDOT:PolyDADMA FSI (without any post-treatment), with an ionic conductivity of 5 × 10−6 S cm−1 at 70 °C. Organic ionic plastic crystals (OIPCs) based on the cation N-ethyl-N-methylpyrrolidinium (C2mpyr+) with similar anions were added to synergistically enhance both electronic and ionic conductivities. PEDOT:PolyDADMA X / [C2mpyr][X] composites (80/20 wt%) resulted in higher ionic conductivity values (e.g., 2 × 10−5 S cm−1 at 70 °C for PEDOT:PolyDADMA FSI/[C2mpyr][FSI]) and improved electrochemical performance versus the neat PEDOT:PolyDADMA X with no OIPC. Herein, new materials are presented and discussed including new PEDOT:PolyDADMA and organic ionic plastic crystal blends highlighting their promising properties for energy storage applications. [ABSTRACT FROM AUTHOR]

Novel triethoxysilane and dimethyl phosphonate functional vinylidene fluoride (VDF)-containing terpolymers, for potential applications in Eu ion extraction from water, were produced by conventional radical terpolymerization of VDF with vinyltriethoxylsilane (VTEOS) and vinyldimethylphosphonate (VDMP). Although initial attempts for the copolymerization of VTEOS and VDMP failed, the successful terpolymerization was initiated by peroxide to lead to multiple poly(VDF-ter-VDMP-ter-VTEOS) terpolymers, that had different molar percentages of VDF (70–90 mol.%), VTEOS (5–20 mol.%) and VDMP (10 mol.%) in 50–80% yields. The obtained terpolymers were characterized by 1H, 19F, 29Si and 31P NMR spectroscopies. The crosslinking of such resulting poly(VDF-ter-VDMP-ter-VTEOS) terpolymers was achieved by hydrolysis and condensation (sol–gel process) of the triethoxysilane groups in acidic media, to obtain a 3D network, which was analyzed by solid state 29Si and 31P NMR spectroscopies, TGA and DSC. The thermal stability of the terpolymers was moderately high (up to 300 °C under air), whereas they display a slight increase in their crystallinity-rate from 9.7% to 12.1% after crosslinking. Finally, the dimethyl phosphonate functions were hydrolyzed into phosphonic acid successfully, and the europium ion extraction capacity of terpolymer was studied. The results demonstrated a very high removal capacity of Eu(III) ions from water, up to a total removal at low concentrations. [ABSTRACT FROM AUTHOR]

Using a lotus leaf as our model, we fabricated an extremely low surface energy micro/nanostructured coating for textiles that repel oil, water, and chemical warfare agents (CWAs) using a simple process that is suitable for large scale production. This coating, called "OmniBlock", consisted of approximately 200-nm silica nanoparticles, tetraethylorthosilicate, 3-glycidoxypropyl trimethoxysilane, and a perfluorooctanoic acid-free fluoropolymer (Fluorolink S10) that was cross-linked between Si-O-Si groups via a sol-gel process. The perfluorooctanoic acid-free fluoropolymer-coated silica nanoparticles were simply applied to the surface of a cotton fabric by a dip–dry–cure process, forming dense, continuous, and uniform layers of OmniBlock coating. OmniBlock modified the surface of the cotton fibers, creating a rough, high surface area uniform coating with many micro-crevasses. As a result, n-dodecane, water, and CWAs beaded up without wetting the surface, exhibiting large contact angles of 154° for water and 121° for n-dodecane, with a small shedding angle of 5° and contact angle hysteresis of 3.2° for water. The designed coating showed excellent liquid repellence properties against three types of CWAs: 129°, 72°, and 87° for sulfur mustard (HD), soman (GD), and VX nerve agents, respectively. Furthermore, OmniBlock coating shows good mechanical properties under tensile strength and wash tests. This remarkable ability to repel CWAs is likely to have potential military applications in personal protective equipment systems requiring self-cleaning functions. [ABSTRACT FROM AUTHOR]

Polymer-based nanocomposites have recently received considerable attention due to their unique properties, which makes them feasible for applications in optics, sensors, energy, life sciences, etc. The present work focuses on the synthesis of nanocomposites consisting of a polytetrafluorethylene-like matrix in which metallic nano-silver are embedded, by using multiple magnetron plasmas. By successively exposing the substrate to separate RF magnetrons using as combination of target materials polytetrafluorethylene (PTFE) and silver, individual control of each deposition process is insured, allowing obtaining of structures in which silver nanoparticles are entrapped in-between two PTFE layers with given thicknesses. The topographical and morphological characteristics investigated by means of Scanning Electron Microscopy and Atomic Force Microscopy techniques evidenced the very presence of Ag nanoparticles with typical dimension 7 nm. The chemical composition at various depositing steps was evaluated through X-ray Photoelectron Spectroscopy. We show that the presence of the top PTFE layer prevents silver oxidation, while its thickness allows the tailoring of optical properties, as evidenced by spectroellipsometry. The appearance of chemical bonds between silver atoms and PTFE atoms at interfaces is observed, pointing out that despite of pure physical deposition processes, a chemical interaction between the polymeric matrix and metal is promoted by plasma. [ABSTRACT FROM AUTHOR]

The use of [Mn(RF)(CO)5] (RF = CF3, CHF2, CH2CF3, COCF2CH3) to initiate the radical polymerization of vinylidene fluoride (F2C=CH2, VDF) and the radical alternating copolymerization of vinyl acetate (CH2=CHOOCCH3, VAc) with tert-butyl 2-(trifluoromethyl)acrylate (MAF-TBE) by generating primary RF• radicals is presented. Three different initiating methods with [Mn(CF3)(CO)5] (thermal at ca. 100 °C, visible light and UV irradiations) are described and compared. Fair (60%) to satisfactory (74%) polyvinylidene fluoride (PVDF) yields were obtained from the visible light and UV activations, respectively. Molar masses of PVDF reaching 53,000 g·mol−1 were produced from the visible light initiation after 4 h. However, the use of [Mn(CHF2)(CO)5] and [Mn(CH2CF3)(CO)5] as radical initiators produced PVDF in a very low yield (0 to 7%) by both thermal and photochemical initiations, while [Mn(COCF2CH3)(CO)5] led to the formation of PVDF in a moderate yield (7% to 23%). Nevertheless, complexes [Mn(CH2CF3)(CO)5] and [Mn(COCHF2)(CO)5] efficiently initiated the alternating VAc/MAF-TBE copolymerization. All synthesized polymers were characterized by 1H and 19F NMR spectroscopy, which proves the formation of the expected PVDF or poly(VAc-alt-MAF-TBE) and showing the chaining defects and the end-groups in the case of PVDF. The kinetics of VDF homopolymerization showed a linear ln[M]0/[M] versus time relationship, but a decrease of molar masses vs. VDF conversion was noted in all cases, which shows the absence of control. These PVDFs were rather thermally stable in air (up to 410 °C), especially for those having the highest molar masses. The melting points ranged from 164 to 175 °C while the degree of crystallinity varied from 44% to 53%. [ABSTRACT FROM AUTHOR]

Novel fluorinated polyhedral oligomeric silsesquioxane (POSS) acrylic copolymers were synthesized by the radical solution polymerization. The superhydrophobic coating was prepared using a one-step breath figure method. Chemical constitution, morphology, hydrophobicity, and anticorrosion ability of as-prepared coatings were investigated by the corresponding equipment. The addition of proper fluorinated POSS can synchronously promote the formation of the micro-nano convex structure and the enrichment of fluorinated groups on the surface. Compared to commercial acrylic coating, the fluorinated POSS coating presented enhanced anticorrosion performance. The impedance was the highest and the corrosion current density was the lowest for superhydrophobic coating with 25 wt % fluorinated POSS. [ABSTRACT FROM AUTHOR]

Polymeric dielectrics are employed extensively in the power transmission industry, thanks to their excellent properties; however, under normal operating conditions these materials tend to degrade and fail. In this study, samples of low-density polyethylene, polypropylene, polymethyl methacrylate, and polytetrafluorethylene were subjected to corona discharges under nitrogen and air atmospheres. The discharges introduced structural modifications over the polymer surface. From a chemical perspective, the alterations are analogous among the non-fluorinated polymers (i.e., polyethylene (PE), polypropylene (PP), and polymethyl methacrylate (PMMA)). A simulation of the corona discharge allowed the identification of highly reactive species in the proximity of the surface. The results are consistent with the degradation of insulating polymers in high-voltage applications due to internal partial discharges that ultimately lead to the breakdown of the material. [ABSTRACT FROM AUTHOR]

An alternating fluorinated copolymer based on chlorotrifluoroethylene (CTFE) and butyl vinyl ether (BVE) was synthesized by RAFT/MADIX living/controlled polymerization in the presence of S-benzyl O-ethyl dithiocarbonate (BEDTC). Then, using the obtained poly(CTFE-alt-BVE) as a macro chain transfer agent (macro-CTA), a block copolymer was prepared by chain extension polymerization of vinyl acetate (VAc). After a basic methanolysis process, the poly(vinyl acetate) (PVAc) block was transferred into poly(vinyl alcohol) (PVA). Finally, a novel fluorinated polyurethane with good surface properties due to the mobility of the flexible fluorinated polymer chains linked to the network was obtained via reaction of the copolymer bearing the blocks of PVA with isophorone diisocyanate (IPDI) as a cross-linking agent. [ABSTRACT FROM AUTHOR]

The mechanical properties of composites are highly dependent on the interfacial interaction. In the present work, inspired by marine mussel, the adhesion between energetic crystals of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) and polymer binders was improved. Three types of linear polymeric agents of glycidyl azide polymer (GAP), polyethylene glycol (PEG), and polytetramethylene ether glycol (PTMEG) were grafted onto TATB particles bridged through polydopamine (PDA) films. SEM images showed that 5% grafting contents could evidently form roughness shells on the surface. With a reinforcement at the interface produced by grafting shells, the mechanical properties of polymer-bonded explosives (PBXs) exhibited outstanding mechanical performance, especially for the PTMEG-grafting sample. Examined by the contact-angle test, the PTMEG-grafting sample possessed a value of polar component similar to that of fluoropolymer, leading to an excellent wettability of the two phases. Additionally, different contents of PTMEG were grafted to reveal that the mechanical properties could be improved even with content as little as 0.5 wt.% PTMEG. These results might highlight a correlation between interfacial interaction and macroscopic properties for mechanically energetic composites, while providing a versatile route of grafting on highly loaded composites. [ABSTRACT FROM AUTHOR]

The coatings with fluoropolymer resins rich in fluorinated ethylene propylene (FEP) and polytetrafluoroethylene (PTFE) are applied as anti-adherent coatings on aluminum–magnesium substrates for use in food containers. In many cases, due to wear, they must be stripped for the application of a new coating on the same substrate. There are several processes for this: blasting, plasma, pyrolysis, chemical processes, laser, high pressure water, and combinations of these. This work focuses on the characterization of the main factors that condition the FEP coating removal process by a continuous wave (CW) Nd:YAG laser, and on the determination of the efficiency of this type of technology used for this purpose. Stripping surface per unit of time and energy consumption per unit area has been determined among other efficiency indicators. Regarding the characterization of the coating object of study, its thickness, surface roughness, contact angle, microhardness and absorbance-reflectance responses have been determined, and the results have been compared with those obtained in the case of PTFE. In addition, to evaluate the mechanical damage caused in the substrate after coating removal by (CW) Nd:YAG laser, the tensile strength, Vickers hardness, Ra and Rz roughness, and the substrate thickness have been measured and analyzed. [ABSTRACT FROM AUTHOR]