Luminescence and photo-oxidation of commercial poly(4-methylpent-1-ene)

The fluorescence and phosphorescence excitation and emission spectra of commercial poly(4-methylpent-1-ene) are examined using a fully compensated spectrofluorometer. The excitation spectra of the polymer are compared with the absorption spectra of model chromophores of those believed to be present in the polymer. The fluorescence emission is primarily associated with the presence of enone and the phosphorescence with dienone impurity chromophoric units. Bromination of cold hexane extracts of the polymer significantly reduces the intensity of the fluorescence, confirming the presence of ethylenic unsaturation. The behavior of the luminescent enone and dienone groups during irradiation under sunlight-simulated conditions is also examined. Possible mechanisms for the participation of these chromophoric units in the photo-oxidation of poly(4-methylpent-1-ene) are discussed.     

Modification of Si(100) surface by plasma-enhanced graft polymerization of allylpentafluorobenzene

Abstract - Hydrophobic fluoropolymer thin films were deposited on Si(100) substrates by plasma polymerization of allylpentafluorobenzene (APFB) under different glow discharge conditions, and in the presence and absence of Ar plasma pre-activation of the substrate surfaces. The FTIR and X-ray photoelectron spectroscopy (XPS) results suggested that the plasma polymerization proceeded mainly through the C=C bond of APFB, and the fluorinated aromatic structure in the deposited polymer films was preserved to different extents, depending on the radio-frequency (RF) power used for plasma polymerization. The use of a low RF power (~5 W) readily resulted in the deposition of thin films having nearly the same fluorinated aromatic structure as that of the APFB homopolymer. For the plasma-polymerized APFB (pp-APFB) films deposited on the Ar plasma-preactivated Si(100) surfaces, solvent extraction results suggested that the pp-APFB films became covalently tethered onto the silicon substrate surfaces. Thermogravimetric (TG) analysis results indicated that the thermal stability of the pp-APFB films had been enhanced substantially after annealing at 270°C in a vacuum oven.     

Hydrophobic properties of poly(arylene ether)s derived from linear polydimethysiloxanes and decafluorobiphenyl

A series of novel poly(arylene ether)s were synthesized with diphenol liner polydimethysiloxanes with different silicon numbers (2OH‐PDMS‐P; P = 2, 6, 10, 12, 16) and decafluorobiphenyl via a two‐step nucleophilic substitution polymerization. The chemical structures of the polymers were confirmed by Fourier transform infrared spectrometer, ¹⁹F‐NMR and ¹H‐NMR spectra. All the polymers provided outstanding hydrophobic properties, high thermal stability and good solubility. The water contact angle (WCA) first increased and then suddenly decreased with the increasing of silicon numbers in PDMS. The highest WCA about 112° was obtained when silicon numbers was ten. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46187.     

Grafting of Epoxy Resin on Surface-modified Poly(tetrafluoroethylene) Films

An epoxy/PTFE composite was prepared by curing the epoxy resin on the surface-modified PTFE film. Surface modification of PTFE films was carried out via argon plasma pretreatment, followed by UV-induced graft copolymerization with glycidyl methacrylate (GMA). The film composite achieved a 90°-peel adhesion strength above 15 N/cm. The strong adhesion of the epoxy resin to PTFE arose from the fact that the epoxide groups of the grafted GMA chains were cured into the epoxy resin matrix to give rise to a highly crosslinked interphase, as well as the fact that the GMA chains were covalently tethered on the PTFE film surface. Delamination of the composite resulted in cohesive failure inside the PTFE film and gave rise to an epoxy resin surface with a covalently-adhered fluoropolymer layer. The surface composition and microstructures of the GMA graft-copolymerized PTFE (GMA-g-PTFE) films and those of the delaminated epoxy resin and PTFE film surfaces were characterized by X-ray photoelectron spectroscopy (XPS), water contact angle and scanning electron microscope (SEM) measurements. The delaminated epoxy resin surfaces were highly hydrophobic, having water contact angles of about 140°C. The value is higher than that of the pristine PTFE film surface of about 110°. The epoxy resin samples obtained from delamination of the epoxy/GMA-g-PTFE composites showed a lower rate of moisture sorption. All the fluorinated epoxy resin surfaces exhibited rather good stability when subjected to the Level 1 hydrothermal reliability tests.     

Characterization of superhydrophobic a-C:F thin film deposited on porous silicon via laser ablation of a PTFE target

Fluorinated amorphous carbon (a-C:F) thin films are deposited on both flat silicon and porous silicon (PS) surfaces via laser ablation of a polished polytetrafluoroethylene (PTFE). Porous silicon (PS) is prepared by anodic etching of p-type silicon wafers in HF based solution. The film deposited on the flat silicon surface exhibits a highly hydrophobic state with water contact angle (WCA) of ~ 146°. In comparison, the surface of film deposited on PS layer shows a roll-off superhydrophobic state, where the water droplet is seen to roll off without wetting its surface with contact angle hysteresis of ~ 4.5°. Micro-Raman results show that the graphite domain of the film deposited on PS has higher disorder level and lower average gain size. The effect of substrate porosity on chemical composition of deposited films has been investigated by using both Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). It is found that the porous substrate improves the incorporation of the fluorine into the film. Atomic force microscopy (AFM) results revealed that the film deposited on PS has higher surface roughness and lower grain size as compared to the film deposited on flat silicon surface.     

Superhydrophobic and oleophilic micro‐nano hierarchical Pd‐decorated SiO2 layers

This paper reports a novel fluorinated micro‐nano hierarchical Pd‐decorated SiO₂ structure (hereafter called Pd/SiO₂), which was formed by the deposition of Pd nanoparticles (NPs) on SiO₂ microspheres. The SiO₂ layers with microscale roughness were fabricated by electrospraying a solution prepared using the sol‐gel process. Subsequently, the Pd NPs were deposited using an ultraviolet reduction process. The resulting surfaces exhibited a micro‐nano hierarchical morphology. After fluorination, the micro‐nano hierarchical surface exhibited outstanding water repellency with a water contact angle (WCA) of 170° and a sliding angle <5°, indicating excellent superhydrophobic properties. The layers exhibited good long‐term durability and excellent ultraviolet resistance. Interestingly, the surface was oleophilic (CA of oil ~10°). These results show the potential of employing superhydrophobic fluorinated Pd/SiO₂ layers in smart devices, such as self‐cleanable surfaces and intelligent water/oil separation systems.     

Clickable poly(ionic liquid)s for modification of glass and silicon surfaces

Covalent attachment of poly(ionic liquid)s (PILs) by click chemistry on glass or silicon (Si) surfaces was performed. Poly[1-(4-vinylbenzyl)-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] (polyVBBI⁺Tf₂N⁻), and copolymers of polyVBBI⁺Tf₂N⁻ with fluorescein O-methacrylate were synthesized by conducting an atom transfer radical polymerization (ATRP) from initiators containing azide or thioacetate groups. The azide- and thiol-terminated PILs were then successfully grafted onto alkyne and alkene modified glass/Si wafers by thermal azide–alkyne cycloaddition and photoinitiated thiol-ene click reactions, respectively. The modified surfaces were characterized by contact angle measurements and ellipsometry. The fluorescent PIL functionalized surfaces showed strong fluorescence under UV irradiation. This procedure of tethering PILs to substrates also provides an easy way to change the surface hydrophilicity by replacing the anions in the grafted PILs. The present approach could be readily applied for surface modifications with other types of PILs or their copolymers to achieve different functionalities on various surfaces.     

Facile preparation of bimodal polyethylene with tunable molecular weight distribution from ethylene polymerization catalyzed by binary catalytic system in the presence of diethyl zinc

A series of novel honeycomb films of tri- and octa-arm polystyrene-b-poly(tert-butyl acrylate) star polymers prepared by atom transfer radical polymerization and nitroxide mediated radical polymerization, respectively, have been fabricated. The type of solvents, specifically their miscibility in water is one of essential parameters to construct ordered pore structures. The tri- and octa-arm star polymers yield well-ordered microporous film specifically in 10 to 30 g/L CHCl₃ solution. The contact angle of glass slide substrate (54.57°) is adjusted to 41.06° by plasma treatment and to 12.21° by coating the glass slide with highly hydrophilic hyperbranched polyglycidol. The ordered honeycomb films are created on the hydrophobic substrates, but the ordered films are not formed on the hydrophilic substrates. Microspheres with the diameters ranging from hundreds of nanometers to several micrometers are also obtained by a slight modification of breath figure method.     

Preparation and enhanced mechanical properties of hydroxyapatite hybrid hydrogels via novel photocatalytic polymerization

Hydroxyapatite (HA) hybridized poly(N-isopropylacrylamide)-co-acrylic acid (PNIPAM-co-AAc) hydrogel on thermoplastic polyurethane (TPU) were successfully prepared via photocatalytic polymerization technique. Low temperature plasma processing of HMDSZ and O₂ plasma were deposition on substrate. The HA/hydrogel were stabilized by HA of which the wettability was modified by calcium nitrate and ammonium phosphate dibasic. The HA gradually increases with the increase of time cycles. The deposition of organic silicone group by the HMDSZ on the TPU substrate is hydrophobic surface. When deposition of O₂, the water contact angles (WCA) was changed to <10° and surface hydrophilicity. The materials were characterized by OM, SEM, FT-IR, XPS and XRD. The results showed that the NIPAM: AAc (1:1 mol) polymers possess macropores ranging from 2 to 20 μm, and their large numbers of carboxyl groups and hydroxyl groups result in a favorable adsorption capacity for HA. Swelling studies indicated that NIPAM: AAc (1:1 mol) was 446 ± 0.3%. This work provided a promising alternative method for the fabrication of polymer materials with tunable and interconnected pores structures for the HA.     

Fast photo-switched wettability and color of surfaces coated with polymer brushes containing spiropyran

An intelligent photo-responsive spiropyran (SP)-contained surface that combines reversible wettability conversion with photochromic behavior was prepared on etched silicon substrates by atom transfer radical polymerization. The heterocyclic ring cleavage of SP moieties under UV irradiation leads to the change of the surface wettability and color. Water contact angle (CA) of the prepared surfaces change from 138.8° ± 1.3° to 42.7° ± 1.7° after 5 min under 365 nm UV irradiation and recover to its original state after 20 min of visible light irradiation, accompanied by the color change between yellowish and purple. To our knowledge, this result is the highest and fastest CA variation reported for surfaces containing SPs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Improvement of Interfacial Adhesion of Glass Fiber/Epoxy Composite by Using Plasma Polymerized Glass Fibers

This study intends to produce plasma polymer thin films of γ-glycidoxypropyltrimethoxysilane (γ-GPS) on glass fibers in order to improve interfacial adhesion of glass fiber-reinforced epoxy composites. A low frequency (LF) plasma generator was used for the plasma polymerization of γ-GPS on the surface of glass fibers at different plasma powers and exposure times. X-ray photoelectron spectroscopy (XPS) and SEM analyses of plasma polymerized glass fibers were conducted to obtain some information about surface properties of glass fibers. Interlaminar shear strength (ILSS) values and interfacial shear strength (IFSS) of composites reinforced with plasma polymerized glass fiber were evaluated. The ILSS and IFSS values of non-plasma polymerized glass fiber-reinforced epoxy composite were increased 110 and 53%, respectively, after plasma polymerization of γ-GPS at a plasma power of 60 W for 30 min. The improvement of interfacial adhesion was also confirmed by SEM observations of fractured surface of the composites.     

Non-fluorinated,room temperature curable hydrophobic coatings by sol–gel process

Non-fluorinated hydrophobic silica surfaces were generated on soda lime glass (SLG) substrates using hexamethyldisilazane (HMDS) as a surface modifying agent. Silica coatings were fabricated by dip coating of a sol derived from base catalyzed hydrolysis and condensation of tetraethoxysilane (TEOS). Two methodologies were adopted to generate the hydrophobic surface; one where the hydrophilic silica coated surface was treated by immersion into different concentrations of alcoholic solutions of HMDS varying from 2.5 wt% to 15 wt%. In the other method, HMDS was directly added to a mixture of TEOS, water, ethanol, and ammonium hydroxide and coatings were deposited using this sol by dip coating and spray coating. Water contact angles (WCA) were measured to study the effect of HMDS treatment times and concentrations on hydrophobicity in the first case, and in the second case, WCA were measured for dip and spray coated samples. UV–visible transmission, scratch resistance, and thermal stability of the coatings were determined. The WCA increased from 66 ± 2° to 125 ± 4° after the treatment of the silica coatings with HMDS. In case of coatings generated from direct addition of HMDS to silica sol, WCA varied from 145 ± 2° to 166 ± 4° for dip and spray coated surfaces respectively. Surface morphology was studied to explain the difference in hydrophobicity of coatings generated using the two methods.     

Statically non-wetting electrospun perfluorocyclobutyl (PFCB) aryl ether polymer doped with room temperature ionic liquid (RTIL)

A statically non-wetting, electrospun surface of non volatile room temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium hexafluorophosphate, (BMIM-PF₆), hosted in a solution-processable, semi-fluorinated perfluorocyclobutyl (BP-PFCB) aryl ether polymer was successfully prepared by electrospinning and compared with a surface prepared by spin casting. The surface properties of undoped and BMIM-PF₆ doped systems were analyzed by water contact angle (WCA) and atomic force microscopy (AFM). BMIM-PF₆ doped BP-PFCB surfaces prepared by spin casting showed a WCA of 90° while non-woven electrospun surfaces with the same BMIM-PF₆ concentration showed high degree of hydrophobicity with a WCA greater than 150°. Morphologies of the electrospun surfaces were characterized by scanning electron microscopy (SEM). The surface composition was analyzed by energy-dispersive X-ray spectroscopy (EDXS) and attenuated total reflectance infrared spectroscopy (ATR-IR). Thermal analysis of the electrospun, non-woven surfaces of the doped and the undoped system of BP-PFCB were done by TGA.     

The Effect of Fluoropolymer on Wettability Alteration of Sandstone at Elevated Temperatures

Gas condensate reservoirs are generally recovered using a pressure depletion drive. Gas can condensate into the liquid phase near the wellbore region when the reservoir pressure falls below the dew point pressure, which can kill gas deliverability. Wettability alteration is an effective means of overcoming this problem; core wettability can be altered from liquid-wet to gas-wet to alleviate the effect of condensate accumulation near the wellbore region. To establish the effect of fluoropolymer on wettability alteration in a gas-condensate reservoir, a gas-wetting alteration agent was synthesized by emulsion polymerization using different molar ratios of fluorine-containing monomers and acrylic monomers. FTIR and SEM were performed to analyze the structure of the gas-wetting agent. Contact angle measurements were used to assess surface alteration by the Owens two-liquid method. The effects of alteration agent concentration, salt concentration, pH and temperature on gas-wetting alteration were also evaluated. Results showed that the best molar ratio of fluoropolymer monomer to acrylic monomers was 1:2. The egg-like structure of the fluoropolymer latex on the core surface mainly contributes to gas-wetting alteration. The contact angles of brine and oil can be altered from 23° and 0° to 137° and 67° by 1 wt% FP-2 treatment, respectively. The surface free energy of the core was reduced from 67.52 to 1.66 mN/m. Moreover, the treated cores remain gas-wetting up to 100 g L^?1 of salt solution, 120 °C and within the pH range of 5–7. This novel gas-wetting alteration agent can be used to solve the problem of liquid blocking effects in gas condensate reservoirs and improve gas recovery significantly.     

Reversibly light-switchable wettability between superhydrophobicity and superhydrophilicity of hybrid ZnO/bamboo surfaces via alternation of UV irradiation and dark storage

Functional bamboo surfaces with reversibly tunable wettability have become much sought after because of their usefulness in sustainable material protection strategies and industrial applications. In this paper, the hybrid ZnO/bamboo surfaces with reversibly light-switchable wettability between superhydrophobicity and superhydrophilicity were successfully prepared via a hydrothermal method at low temperature. The bamboo substrates served as adhesion, and the well-aligned ZnO nanosheet arrays (WZNA) were deposited on the bamboo surfaces after a hydrothermal process. A subsequent chemical treatment with octadecyltrichlorosilane (OTS) led to a superhydrophobic surface with a water contact angle (WCA) up to 153°. Under UV irradiation, the WCA decreased gradually, and the surface eventually became superhydrophilic because of hydroxyl absorption on the ZnO surfaces. The wetting behavior of the WZNA can be reversibly switched between superhydrophilic and superhydrophobic via alternation of UV exposure for 12 h and dark storage for 10 days.     

Plasma polymerization coating of silica fillers for Epoxy Molding Compounds (EMCs)

Silica fillers for Epoxy Molding Compounds (EMCs) were modified via plasma polymerization coating of acrylonitile, acrylic acid and dimethyl phosphite with RF plasma (13.56 MHz). The resulting samples were characterized by DSC, FT-IR and contact angle measurements. EMC samples were prepared from silica fillers, biphenyl epoxy resin, phenol novolac and triphenyl phosphine, and cured at 175°C for 4 h. Flexural strength of the EMC samples was evaluated in a 3-point bending mode with an Instron 5567 at a crosshead speed of 1 mm/min both at RT and 250°C, and failure surfaces were analyzed by SEM. Some samples were exposed to 121°C, 2 atm pressure and 100% RH for 12, 24 and 32 h, and then to 250°C for 10 min prior to testing at RT. Plasma polymer coating of silica with acrylonitrile greatly improved the flexural strength of EMC at RT as well as at 250°C, followed by acrylic acid and dimethyl phosphite. Exposing EMC samples to 121 °C, 2 atm pressure and 100% RH for 32 h decreased the flexural strength by 13% when the silica was coated with acrylonitrile plasma polymer, compared to the 21% decrease in the control sample. Plasma polymer coating of silica also increased the Tg of the EMC, and lowered water absorption and CTE in the rubbery region. Therefore, enhanced properties by plasma polymer coating of silica with acrylonitrile or acrylic acid can be attributed to nitrile or carboxylic acid groups, as confirmed by FT-IR, which can react with epoxy groups in the base resin, as evidenced by DSC analysis.     

Self-Assembled Monolayers of Vinyltriethoxysilane and Vinyltrichlorosilane Deposited on Silicon Dioxide Surfaces

Abstract

This study was aimed at deposition of self-assembled monolayers (SAMs) using vinyltriethoxysilane (VTES) and vinyltrichlorosilane (VTCS) molecules chemisorbed on silicon dioxide surfaces. The kinetics of SAM formation on planar glass substrates and silicon wafers was characterized by contact angle measurements. The surface free energy and its dispersion and polar components enabled to estimate the time of immersion required to deposit compact SAMs. Adsorption of organosilane molecules as a function of immersion time was characterized by X-ray photoelectron spectroscopy. The SAM thickness was evaluated by spectroscopic ellipsometry. Surface topography of deposited layers was investigated by atomic force microscopy (AFM). The VTCS/glass combination exhibited the fastest kinetics but the deposit was not uniform and included local agglomerates. The hydrophobic vinyl groups at deposit surface resulted in a surface free energy of 32 mJ/m².     

Atmospheric Plasma Surface Activation of Poly(Ethylene Terephthalate) Film for Roll-To-Roll Application of Transparent Conductive Coating

An effective surface activation is crucial for high-speed roll-to-roll coating of functional films for printed electronics applications. In this article, we report a study of surface treatment of three types of poly(ethylene terephthalate) (PET) films by an argon/oxygen atmospheric pressure plasma and an ambient air atmospheric pressure plasma to obtain the required wettability for subsequent slot die coating of transparent conductive polymer layer using a poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) ink. Prior to plasma treatment, the PET surfaces, which differ in manufacturing process of their preparation, were characterized by X-ray photoelectron spectroscopy. The surface changes after the plasma treatments were characterized by water contact angle measurement and atomic force microscopy. We found that the water contact angles of the three types of untreated PET surfaces were 80.9°, 75.9°, and 66.3°, respectively, and the water contact angles after argon/oxygen plasma treatment at treatment speed of 1 m · min^?1 decreased to 36.2°, 31.9°, and 40.9°, respectively. These conditions were stable from 1 up to 4 days, which are longer than reported values of 15–60 min and sufficient for roll-to-roll coating processes.     

Atmospheric pressure plasma activation as a surface pre-treatment for the adhesive bonding of aluminum 2024

A low-temperature, atmospheric pressure helium and oxygen plasma has been used for the surface preparation of aluminum 2024 prior to adhesive bonding. The plasma converted the aluminum from a water contact angle (WCA) of 79° to down to 38° within 5 s of exposure, while sanding reduced the WCA to only 51°. Characterization of the aluminum surface by X-ray photoelectron spectroscopy revealed a decrease in carbon contamination from 70 to 36% and an increase in the oxygen content from 22 to 50% following plasma treatment. Similar trends were observed for sanded surfaces. Lap shear results demonstrated bond strengths of 30?±?2?MPa for the sanded aluminum vs. 33?±?1?MPa for plasma-treated aluminum, where sol–gel and primer coatings were added to the surface preparation. Following seven days of aging, wedge crack extension tests revealed cohesive failure percentages of 86, 92, and 96% for sanded, plasma-treated, and sanded/plasma-treated aluminum, respectively. These results indicate that atmospheric pressure plasmas are an attractive alternative to acid treatment or abrasion techniques for surface preparation prior to bonding.     

Improving hydrophobicity on polyurethane-based synthetic leather through plasma polymerization for easy care effect

This study reports on the deposition of a hydrophobic coating on polyurethane (PU)-based synthetic leather through a plasma polymerization method and investigates the hydrophobic behavior of the plasma-coated substrate. The silicon compound of hexamethyldisiloxane (HMDSO), inactive gas argon (Ar), and toluene were used to impart surface hydrophobicity to a PU-based substrate. Surface hydrophobicity was analyzed by water contact angle measurements. Surface hydrophobicity was increased by deposition of compositions of 100% HMDSO, 3:1 HMDSO/toluene, and 1:1 HMDSO/toluene. Optimum conditions of 40 W, 30 s plasma treatment resulted in essentially the same initial contact angle results of approximately 100° for all three treatment compositions. The initial water contact angle for untreated material was about 73°. A water droplet took 1800 s to spread out on the plasma-treated sample after it had been placed on the sample surface. An increase in plasma power also led to a decrease in contact angle, which may be attributed to oxidization of HMDSO during plasma deposition. XPS analysis showed that plasma polymerization of HMDSO/toluene compositions led to a significant increase in atomic percentage of Si compound responsible for the hydrophobic surface. The easy clean results for the treated and untreated PU-based synthetic leather samples clearly showed that the remaining stain on the plasma-polymerized sample was less than that of untreated sample. The plasma-formed coating was both hydrophobic and formed a physical barrier against water and stain.