Dielectric barrier discharge plasma induced surface modification of polyester/cotton blended fabrics to impart water repellency using HMDSO

Continuous treatment of polyester/cotton blended fabric samples was carried with hexamethyldisiloxane (HMDSO) plasma on the pilot scale atmospheric pressure plasma reactor. The mixture of helium and argon was used as carrier gas for generating dielectric barrier discharge plasma. The effect of discharge power and treatment time on the water repellent properties of samples were evaluated with contact angle (CA) and spray test measurements. Spray test and CA results showed improved resistance to wetting with water. The effect of discharge conditions on the surface morphology and surface chemistry of plasma treated samples were investigated by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopic analysis, respectively. The presence of Si‐O‐Si and Si‐CH₃ groups in the structure of plasma polymer deposited at the surface of P/C samples was revealed by FTIR spectroscopy. Further, structural differences in HMDSO plasma polymer deposited under different discharge conditions were reported with reference to organic/inorganic nature of plasma polymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Optimization of amphiphobic structural surface thickness in relation to its functionality on stainless steel plates

Fluorine‐based amphiphobic coatings have been widely used in commercial textiles to provide water‐ and oil‐repelling abilities. However, few reports from the literature survey have discussed the surface structural effects of the coated substrate on amphiphobicity. In this research, various thickness amphiphobic coatings based on mixed epoxy, tetraethylorthosilicate, and a particular alkoxysilane with fluorinated side chains (F‐silane) were deposited on Grade 420 stainless steel plates. Film amphiphobicity is characterized by measuring the water and oil contact angles of the coating. Film morphology is examined using atomic force microscopy. The deposited films free of F‐silane are thinner than 150 nm. The films become thick at high F‐silane volume percentage with the surface cavities, ridges, and granules being masked out. On the addition of F‐silane, the water contact angle of the deposited films increases up to 105° and then reaches a plateau of ～ 107° with increasing F‐silane. In contrast, the oil contact angle increases up to 60° at first and then slowly declines with the F‐silane concentration. The total drop of oil contact angle by ～ 20° was attributed to the masking out of surface features on film thickening. This indicates that the surface oleophobicity depends on surface structures. Therefore, improving surface amphiphobicity correlates with creating more refined multiscale surface structures during the industrial manufacturing process of steel plate, prior to surface modification by F‐silane. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41003.     

Thermal,optical, and electrical characterization of thin film coated RTV 655 bilayer system

Adhesion of thin films to hydrophobic elastomeric substrates is of particular interest in the area of flexible electronics and nano‐sensor technology. Here, nanometer‐thick Au films were deposited directly onto hydrophobic RTV 655 substrates by means of sputtering, thermal evaporation, and electroless techniques without an adhesion‐promoting layer. The bilayer system was exposed to repeat thermal cycling and changes to the surface morphology of the thin film were monitored electrically and optically. Buckle formation in the as‐deposited film was attributed to stress in the film and substrate stiffness rather than thermal coefficient mismatch between films. The Au‐RTV 655 interface was water tight and maintained a strong adhesion despite repeated thermal cycles. Sputtered and thermally evaporated carbon‐coated RTV 655 substrates were also studied in parallel for comparison. Periodic arrays of buckles formed in pre‐strained RTV 655 samples showed reproducibility in their optical properties demonstrating good adhesion between the two layers without an interfacial layer. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41396.     

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.     

Surface modification of aramid fibers via ammonia‐plasma treatment

In this article, aramid fibers III were surface modified using an ammonia‐plasma treatment to improve the adhesive performance and surface wettability. The surface properties of fibers before and after plasma treatment were investigated by X‐ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy, and water contact angle measurements. The interfacial shear strength of each aramid fibers III‐reinforced epoxy composites was studied by micro‐debonding test. The ammonia‐plasma treatment caused the significant chemical changes of aramid fibers III, introducing nitrogen‐containing polar functional groups, such as ? C? N? and ? CONH? , and improving their surface roughness, which contributed to the improvement of adhesive performance and surface wettability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40250.     

Low‐Temperature Deposition of Hexagonal Boron Nitride via Sequential Injection of Triethylboron and N2/H2 Plasma

Hexagonal boron nitride (hBN) thin films were deposited on silicon and quartz substrates using sequential exposures of triethylboron and N₂/H₂ plasma in a hollow‐cathode plasma‐assisted atomic layer deposition reactor at low temperatures (≤450°C). A non‐saturating film deposition rate was observed for substrate temperatures above 250°C. BN films were characterized for their chemical composition, crystallinity, surface morphology, and optical properties. X‐ray photoelectron spectroscopy (XPS) depicted the peaks of boron, nitrogen, carbon, and oxygen at the film surface. B 1s and N 1s high‐resolution XPS spectra confirmed the presence of BN with peaks located at 190.8 and 398.3 eV, respectively. As deposited films were polycrystalline, single‐phase hBN irrespective of the deposition temperature. Absorption spectra exhibited an optical band edge at ~5.25 eV and an optical transmittance greater than 90% in the visible region of the spectrum. Refractive index of the hBN film deposited at 450°C was 1.60 at 550 nm, which increased to 1.64 after postdeposition annealing at 800°C for 30 min. These results represent the first demonstration of hBN deposition using low‐temperature hollow‐cathode plasma‐assisted sequential deposition technique.     

High refractive index thermally stable phenoxyphenyl and phenylthiophenyl silicones for light‐emitting diode applications

Creating high refractive index (RI) thermally stable polymers for encapsulating high‐brightness light‐emitting diodes (LEDs) remains a challenge and is an opportunity for improving LED efficiencies. The best previously reported RI for a 200°C heat stable encapsulant for LEDs is 1.56. Here, we report the use of novel phenoxyphenyl and phenylthiophenyl silicone monomers to give fully formulated encapsulants with RIs above 1.60. These liquid dispensed encapsulants are highly heat stable, showing little change in optical properties after heat aging at 200°C in air for seven weeks, and were also little changed after cycling between ?10°C to 85°C over 6 months. Phenoxyphenyl(phenyl) dimethoxysilane and phenylthiophenyl(phenyl) dimethoxysilane monomers were prepared via Grignard reactions. The resulting monomers were copolymerized with commercial silicone monomers and incorporated into hydrosilation‐based thermosets designed for use as LED encapsulants. RIs for the cured polymers were 1.60 at 633 nm (1.62 at 450 nm) for the phenoxyphenyl ether system and 1.62 at 633 nm (1.65 at 450 nm) for the phenylthiophenyl ether system. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39824.     

Oxygen and water vapor gas barrier poly(ethylene naphthalate) films by deposition of SiOx plasma polymers from mixture of tetramethoxysilane and oxygen

SiO_x films were deposited from a mixture of tetramethoxysilane (TMOS) and oxygen on poly(ethylene 2,6‐naphthalate) film using ion‐assisted plasma polymerization technique (Method II) and conventional plasma polymerization technique (Method I), and were compared in chemical composition and gas barrier properties. Methods I and II were different in electrical circuit between electrodes (anode and cathode) and electric power supply. In Method I, the anode electrode was grounded, and the cathode electrode was coupled to the discharge power supply. In Method II, the anode electrode was connected with the discharge power supply, and the cathode electrode was grounded. There was not large difference in SiO_x deposition rate between the plasma polymerizations by Methods I and II. Plasma polymers deposited from TMOS/O₂ mixtures by Method II possessed smaller C/Si and O/Si atomic ratios than those deposited by Method I and showed advantage in gas barrier properties. The oxygen and water vapor permeation rates were 0.08–0.13 cm³ m^?2 day^?1 atm^?1 at 30°C at 90% RH and 0.244–0.276 g m^?2 day^?1 at 40°C at 90% RH, respectively. From these results, it can be concluded that the ion‐assisted plasma polymerization is a useful technique for deposition of gas barrier SiO_x thin films. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 915–925, 2007     

Synthesis and thermal stability properties of boron‐doped silicone resin

In this article, a novel boron‐doped silicone resin (BSR) was synthesized by hydrolysis‐polycondensation method, with propyl‐triethoxysilane (PTES), dimethyl‐diethoxysilane (DMDES), and boric acid (BA) as starting materials, using absolute ethyl alcohol as solvent and hydrochloric acid as catalyst. The structures of the BSR were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), X‐ray photoelectron spectroscopy (XPS), and gel permeation chromatography (GPC). FTIR spectra showed characteristic B? O? Si and Si? O? Si stretching modes. XPS and NMR results confirmed further that boron element was doped successfully into the main chains of the silicone resin as Si? O? B bond motifs, and hydroxyl groups from BA were condensed properly with Si? OH or Si? OR to form cross‐linked structure of BSR with narrowed molecular weight distributions in optimum experimental condition. The thermal stability of the BSR was studied by thermogravimetry analysis and derivative thermogravimetry. The thermal degradation temperature of the silicone resin improved greatly after doping element boron into the main chain, and the thermal stability of the BSR was influenced by the content of boron. The thermal degradation mechanism of this BSR was also discussed. The degradation process can be divided into two stages, the weight loss in the first stages may be corresponding to the loss of the small groups and weaker bonds in the chains, such as ? CH₃, and ? C₃H₇, the weight loss in the second stage may be corresponding to the loss of the group as ? OC₂H₅. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40934.     

Plasma Polymerization Modified Polyvinylidene Fluoride (PVDF) Membrane Development and Characterization for Degumming of Soybean Oil

Unmodified and surface‐modified polyvinylidene fluoride (PVDF) membranes were tested for their ability to degum soybean crude oil and crude oil miscellas. The membrane was modified with 1,1,1,3,3,3‐hexafluoro‐2‐propanol or hexamethyldisiloxane (HMDSO) by radio‐frequency plasma polymerization at 10–100 W glow discharge power and 1–30 min contact time. The membranes were characterized by contact angle measurements, attenuated total reflectance Fourier transform infrared spectroscopy, atomic force microscopy, and scanning electron microscopy. Modification of the PVDF membrane with HMDSO at 60 W power for 5 min increased the interfacial free energy between water and solid surface from 30 ± 2 to 64 ± 2 mJ/m². This membrane was tested for permeate flux and phospholipid rejection with crude oil and different concentrations of miscella. Although formation of the polymer film on the membrane tended to decrease membrane pore size, the modified membrane had an oil flux as good as the unmodified membrane did. In addition, the modified‐membrane improved the phospholipid rejection and removed 76 % of the phospholipids from the crude oil and 81–90 % of the phospholipids from crude oil miscellas.     

Effect of Boron Nitride (BN) on Luminescent Properties of Y3Al5O12:Ce Phosphors and their White Light‐Emitting Diode Characteristics

This article reports a low‐cost yellow‐emitting Y₃Al_5‐xB_xO_12‐xN_x:Ce³⁺ phosphor with an enhanced luminescent intensity and excellent thermal stability for white light‐emitting diodes (LEDs). It was synthesized by a simple gas‐pressure sintering (GPS) process. The effect of B³⁺–N^3? incorporation on the optical properties of Y₃Al₅O₁₂:Ce³⁺ phosphor was investigated. The addition of appropriate amounts of boron nitride (BN) leads to a marked increase in photoluminescent intensity and a slight shift of its emission spectra toward the blue region, which is assigned to the improved crystallinity and increased particle size. Especially, the prepared oxynitride phosphor does not exhibit any thermal quenching under high temperature, and the emission intensity at 250°C even increases up to 175% of that measured at 20°C. Finally, the white LED flat lamp with luminous efficiency as high as 101 lm/W, color rendering index of 72, and correlated color temperature of about 6600 K is successfully realized by using YAG:Ce³⁺ phosphor doped with 0.5 molar ratio BN, which is acceptable and promising for general indoor illuminations to replace fluorescent or incandescent lamps.     

Thermodynamic Stability of Low‐k Amorphous SiOCH Dielectric Films

Si–O–C‐based amorphous or nanostructured materials are now relatively common and of interest for numerous electronic, optical, thermal, mechanical, nuclear, and biomedical applications. Using plasma‐enhanced chemical vapor deposition (PECVD), hydrogen atoms are incorporated into the system to form SiOCH dielectric films with very low dielectric constants (k). While these low‐k dielectrics exhibit chemical stability as deposited, they tend to lose hydrogen and carbon (as labile organic groups) and convert to SiO₂ during thermal annealing and other fabrication processes. Therefore, knowledge of their thermodynamic properties is essential for understanding the conditions under which they can be stable. High‐temperature oxidative drop solution calorimetry measurement in molten sodium molybdate solvent at 800°C showed that these materials possess negative formation enthalpies from their crystalline constituents (SiC, SiO₂, C, Si) and H₂. The formation enthalpies at room temperature become less exothermic with increasing carbon content and more exothermic with increasing hydrogen content. Fourier transform infrared spectroscopy (FTIR) spectroscopy examined the structure from a microscopic perspective. Different from polymer‐derived ceramics with similar composition, these low‐k dielectrics are mainly comprised of Si–O(C)–Si networks, and the primary configuration of carbon is methyl groups. The thermodynamic data, together with the structural analysis suggest that the conversion of sp² carbon in the matrix to surface organic functional groups by incorporating hydrogen increases thermodynamic stability. However, the energetic stabilization by hydrogen incorporation is not enough to offset the large entropy gain upon hydrogen release, so hydrogen loss during processing at higher temperatures must be managed by kinetic rather than thermodynamic strategies.     

Growth and characterization of fluorocarbon thin films grown from trifluoromethane (CHF3) using pulsed‐plasma enhanced CVD

Trifluoromethane (CHF₃) was used as a precursor gas in pulsed‐plasma enhanced CVD to deposit fluorocarbon films onto Si substrates. The film composition, as measured by X‐ray photoelectron spectroscopy (XPS) of the C1s peak, was observed to change as the plasma duty cycle was changed by varying the plasma off‐time; this offers a route to control the molecular architecture of deposited films. FTIR results indicate that the film is primarily composed of CF_x components, with little or no C H incorporation into the film. The rms roughness of the films is extremely low, approaching that of the Si substrate; the low growth rate and consequent high‐power input/thickness is believed to be partly responsible. CHF₃ produces films with higher % CF₂ compared to other hydrofluorocompound (HFC) monomers (CH₂F₂ and C₂H₂F₄). However, the deposition kinetics for all three HFC gases display similar trends. In particular, at a fixed on‐time of 10 ms, the deposition rate per pulse cycle reaches a maximum at an off‐time of approximately 100 ms. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 842–849, 2000     

Surface tailoring of an ethylene propylene diene elastomeric terpolymer via plasma‐polymerized coating of tetramethyldisiloxane

In the research presented here, we explore the use of a low‐energy plasma to deposit thin silicone polymer films using tetramethyldisiloxane (TMDSO) (H(CH₃)₂? Si? O? Si? (CH₃)₂H) on the surface of an ethylene propylene diene elastomeric terpolymer (EPDM) in order to enhance the surface hydrophobicity, lower the surface energy and improve the degradation/wear characteristics. The processing conditions were varied over a wide range of treatment times and discharge powers to control the physical characteristics, thickness, morphology and chemical structure of the plasma polymer films. Scanning electron microscopy (SEM) shows that pore‐free homogeneous plasma polymer thin films of granular microstructure composed of small grains are formed and that the morphology of the granular structure depends on the plasma processing conditions, such as plasma power and time of deposition. The thicknesses of the coatings were determined using SEM, which confirmed that the thicknesses of the deposited plasma‐polymer films could be precisely controlled by the plasma parameters. The kinetics of plasma‐polymer film deposition were also evaluated. Contact angle measurements of different solvent droplets on the coatings were used to calculate the surface energies of the coatings. These coatings appeared to be hydrophobic and had low surface energies. X‐ray photoelectron spectroscopy (XPS) and photoacoustic Fourier‐transform infrared (PA‐FT‐IR) spectroscopy were used to investigate the detailed chemical structures of the deposited films. The optimum plasma processing conditions to achieve the desired thin plasma polymer coatings are discussed in the light of the chemistry that takes place at the interfaces. Copyright © 2004 Society of Chemical Industry     

Porous water repellent silica coatings on glass by sol–gel method

Development of the solid surfaces with water-repellent and self-cleaning ability has attracted much research interest in recent years. In the present research work, we have prepared water repellent silica coatings on glass at room temperature (~27 °C) by sol gel process and surface silylation technique. Coating sol was prepared by keeping the molar ratio of tetramethoxysilane (TMOS), methanol (MeOH) and water (H₂O) constant at 1:12.36:4.25, respectively, with 0.01 M NH₄F. The dip coated silica films were surface silylated using two different silylating agents namely hexamethyldisiloxane (HMDSO) and hexamethyldisilazane (HMDZ). The HMDSO and HMDZ in hexane solvent were varied from 0 to 1 vol.% and silylation period was varied from 1 to 3 h. The HMDSO and HMDZ modified films showed dense and porous surface morphology, respectively. The HMDSO modified silica films showed static water contact angle of 122° whereas HMDZ modified films showed 165°. The HMDZ modified films displayed the extreme water repellency comparing with that of lotus leaves. The silica films were characterized by surface profilometer, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared microscopy, thermal and chemical aging tests, optical transmission and static water contact angle measurements.     

Electrosynthesis and characterization of an electrochromic material from poly(1,6‐bis(2‐thienyl)pyrene) and its application in electrochromic device

Electrochemical polymerization of 1,6‐bis(2‐thienyl)pyrene (BTP) could be achieved in acetonitrile/dichloromethane (ACN/DCM) (1:1, by volume) solution containing sodium perchlorate (NaClO₄) as a supporting electrolyte. The resulting polymer poly(1,6‐bis(2‐thienyl)pyrene) (PBTP) were characterized by cyclic voltammetry, UV–vis spectroscopy, and scanning electron microscopy. The resulting polymeric film has distinct electrochromic properties and exhibits three different colors under various potentials. Moreover, the PBTP film showed reasonable optical contrast (DT %) at 700 nm is found to be 29% and satisfactory response time is measured as 1.3 s. An electrochromic device (ECD) based on PBTP and poly(3,4‐ethylenedioxythiophene) was also constructed and characterized. This ECD has these qualities: quick switching time, reasonable contrast, and good optical memories and redox stability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39770.     

Functionalized multi‐wall carbon nanotubes/silicone rubber composite as capacitive humidity sensor

Functionalized multi‐wall carbon nanotubes (MWCNTs) treated by mixed acids have been used to develop a capacitive humidity sensor based on MWCNTs/silicone rubber (SR) composite film. The MWCNTs/SR composites were prepared through conventional solution processed method. The micrographs of MWCNTs/SR composites were observed by transmission electron microscopy (TEM) and scanning electron microscope. The FT‐IR spectra demonstrated the successfully grafting of ? OH groups on the treated MWCNTs. The sensing properties of the composite at different relative humidity (RH) and frequency were characterized and linear sensing responses of the MWCNTs/SR composites to RH were observed. The treated MWCNTs/SR composite film (Tr‐film) had higher sensitivity than that of the untreated MWCNTs/SR composite film (Un‐film). Experimental data indicate that the Tr‐film exhibits an excellent long‐term stability, small hysteresis, and fine reproducibility. The response and recovery time of the Tr‐film were 30 and 27 s, respectively. Thereby, such Tr‐film had potential applications as humidity sensors. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40342.     

Effects of aging on radiofrequency-sputtered polyethylene film

The effects of aging on polyethylene film deposited by radiofrequency sputtering on a quartz crystal microbalance were examined by measuring its resonance frequency and conductance, and by measuring the contact angle of the film to distilled water. The film sputtering was observed using in situ optical emission spectroscopy. The fabricated film was observed using atomic force microscopy, and analyzed using Fourier transform-infrared and electron spin-resonance spectroscopies. The longer the film was exposed to air, its weight increased and the film became softer. Increase in hydrophilicity of the surface, decrease in spin concentration in the film, and enrichment of the oxygenated moieties in the film were observed. These indicate that the film structure is reconstructed by the reactions between radical sites in the film and reactive species in the air, such as oxygen and water, and by the movement of hydrophilic moieties inside the film towards the surface. When stored in vacuum, the film hardened and oxidation slowered. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1869–1877, 1999     

Zein film: Effects of dielectric barrier discharge atmospheric cold plasma

Dielectric barrier discharge atmospheric plasma is a novel nonthermal technology for the food and packaging industry. The effects of dielectric barrier discharge plasma on the surface, structural, thermal, and moisture sorption properties of edible zein films have been examined. Plasma treatment increased the surface roughness and equillibrium moisture content of the zein film in a direct relationship with the applied voltage level. No significant difference in the thermal stability of the zein film is also observed after plasma treatment. Dielectric barrier discharge plasma treatments of zein film lead to a change in the protein conformation which is confirmed by X‐ray diffraction and Fourier transform Infrared spectroscopy. The evaluation of films modifications by plasma discharge will contribute to enhance the in‐package decontamination studies of food products by plasma. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40803.     

Hybrid multilayer thin-film fabrication by atmospheric deposition process for enhancing the barrier performance

In this paper, a multilayer barrier thin film, based on polyvinylidene difluoride (PVDF)–silicon dioxide (SiO₂), has been fabricated on a PET substrate through a novel method of joint fabrication techniques. The inorganic SiO₂ thin film was deposited using a roll-to-roll atmospheric atomic layer deposition system (R2R-AALD), while the organic PVDF layer was deposited on the surface of SiO₂ through the electrohydrodynamic atomization (EHDA) technique. The multilayer barrier thin films exhibited very good surface morphology, chemical composition, and optical properties. The obtained values for arithmetic surface roughness and water contact angle of the as-developed multilayer barrier thin film were 3.88 nm and 125°, respectively. The total thickness of the multilayer barrier thin film was 520 nm with a high optical transmittance value (85–90%). The water vapor transmission rate (WVTR) of the barrier thin film was ~?0.9?×?10^?2 g m^?2 day^?1. This combination of dual fabrication techniques (R2R-AALD and EHDA) for the development of multilayer barrier thin films is promising for gas barrier applications.