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.     

Hydrophobic polymer films plasma-polymerized from CF4/hydrocarbon and hexafluroacetone/hydrocarbon mixtures

Polymer films were deposited from the plasma polymerization of the mixtures of hydrocarbons, ethane, ethylene, and acetylene, and tetrafluoromethane (CF₄) or hexafluoroacetone (HFA). The surface properties, the advancing contact angle of water, and surface energy of the films deposited and the chemical composition at the outermost layer of the films are discussed from the data of the angular XPS measurements. The plasma polymers deposited from the CF₄/hydrocarbon and HFA/hydrocarbon mixtures contained fluorine atoms whose content depended on the CF₄ or HFA concentration of the mixtures. The hydrophobicity of the films deposited could not be determined by the fluorine content of the films but by the chemical composition of the fluorine moieties at the outermost layer of the films. The CF₃ moieties rather than the CF₂ and CF moieties contribute largely to the hydrophobicity of the films. The plasma polymer films deposited from the HFA/acetylene (87.5 mol % HFA) showed higher hydrophobicity (the surface energy is 9.7 mJ/m²) than those from the CF₄/acetylene mixture (87.5 mol % CF₄) (the surface energy is 13 mJ/m²).     

Synthesis and characteristics of NH<Subscript>2</Subscript>-functionalized polymer films to align and immobilize DNA molecules

We developed a method to use NH₂-functionalized polymer films to align and immobilize DNA molecules on a Si substrate. The plasma-polymerized cyclohexane film was deposited on the Si substrate according to the radio frequency plasma-enhanced chemical vapor deposition method using a single molecular precursor, and it was then treated by the dielectric barrier discharge method in a nitrogen environment under atmospheric pressure. Changes in the chemistry of the surface functional groups were studied using X-ray photoelectron spectroscopy and Fourier transformed infrared spectroscopy. The wettability of the surfaces was examined using dynamic contact angle measurements, and the surface morphology was evaluated using atomic force microscopy.     

Effect of oxygen plasma treatment on non-thrombogenicity of diamond-like carbon films

The non-thrombogenicity of oxygen-plasma-treated DLC films was investigated as surface coatings for medical devices. DLC films were deposited on polycarbonate substrates by a radio frequency plasma enhanced chemical vapor deposition method using acetylene gas. The deposited DLC films were then treated with plasma of oxygen gas at powers of 15 W, 50 W, and 200 W. Wettability was evaluated by water contact angle measurements and the changes in surface chemistry and roughness were examined by X-ray photoelectron spectroscopy and atomic force microscope analysis, respectively. Each oxygen-plasma-treated DLC film exhibited a hydrophilic nature with water contact angles of 11.1°, 17.7° and 36.8°. The non-thrombogenicity of the samples was evaluated through the incubation with platelet-rich plasma isolated from human whole blood. Non-thrombogenic properties dramatically improved for both 15 W- and 50 W-oxygen-plasma-treated DLC films. These results demonstrate that the oxygen plasma treatment at lower powers promotes the non-thrombogenicity of DLC films with highly hydrophilic surfaces.     

Plasma-polymerized coatings of trimethylsilane deposited on cold-rolled steel substrates Part 2. Effect of deposition conditions on corrosion performance

Trimethyl silane (TMS) plasma-polymerized films were deposited on cold-rolled steel (CRS) under different conditions. The films were characterized by angular-dependent X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and time-of flight secondary ion mass spectrometry (TOFSIMS). The complementary information generated by these surface techniques gave detailed information on the film composition. The corrosion performance of the plasma films was estimated by electrochemical impedance spectroscopy (EIS) and by exposure in a humidity test. All films were Si-based and their composition was a function of the deposition conditions and the plasma cleaning of substrate prior to deposition. A reducing plasma for metal surface treatment resulted in a film with the highest impedance. The plasma film surfaces were highly oxidized. The contact angle was the lowest for plasma films deposited from a mixture of TMS and oxygen and their corrosion performance was the poorest.     

持久疏水涂层织物的制备及其油水分离性能研究

以甲基三乙氧基硅烷（ MTES）为原料,采用溶胶 -凝胶法,在 MTES溶胶中引入端羟基聚二甲基硅氧烷（ PDMS-OH）柔性疏水链段,制得聚硅氧烷凝胶,研究了柔性疏水链段对聚硅氧烷凝胶的柔韧性及疏水性的影响;采用浸渍涂覆的方法,在聚酯织物表面负载聚硅氧烷凝胶,固化后制备得到涂层织物。采用红外光谱（ FT-IR）、抗弯模量和水接触角,对聚硅氧烷凝胶及织物涂层的结构、柔韧性、疏水稳定性及其耐久性进行表征。结果表明： PDMS-OH能够大幅提高涂层织物的柔韧性和疏水性,在聚硅氧烷溶胶中,加入 0. 10 mol端羟基含量为 8. 5%的 PDMS-OH时,涂层织物的静态水接触角可达到（ 138±2）°,且具有持久的稳定性;同时,油水分离实验结果表明,制备的涂层织物可以实现以正己烷、苯和苯胺为代表的烷烃、芳香烃类等油水混合物的有效分离。     

Surface energy of the plasma treated Si incorporated diamond-like carbon films

Surface energy and surface chemical bonds of the plasma treated Si incorporated diamond-like carbon films (Si-DLC) were investigated. The Si-DLC films were prepared by r.f. plasma assisted chemical vapor deposition using benzene and diluted silane (SiH₄/H₂ = 10:90) as the precursor gases. The Si-DLC films were subjected to plasma treatment using various gases like N₂, O₂, H₂ and CF₄. The plasma treated Si-DLC films showed a wide range of water contact angles from 13.4° to 92.1°. The surface energies of the plasma treated Si-DLC films revealed a high polar component for O₂ plasma treated Si-DLC films and a low polar component for CF₄ plasma treated Si-DLC films. The CF₄ plasma treated Si-DLC films indicated the minimum surface energy. X-ray photoelectron spectroscopy (XPS) revealed that the polarizability of the bonds present on the surface explains the hydrophilicity and hydrophobicity of the plasma treated Si-DLC films. We also suggest that the O₂ plasma treated surface can provide an excellent hemocompatible surface from the estimated interfacial energy between the plasma treated Si-DLC surface and human blood.     

Stresses in diamond-like carbon films

Internal stresses have been measured in diamond-like carbon (DLC) films deposited by d.c. plasma assisted chemical vapor deposition from methane, acetylene, or cyclohexane, and in nitrogen containing DLC films deposited from acetylene, or cyclohexane and nitrogen. The total hydrogen content in the films and the fraction of bound hydrogen have been analyzed by forward recoil elastic scattering and Fourier transform infrared spectroscopy respectively. It was found that in pure DLC films the stresses increase with increasing fraction of unbound hydrogen. The highest compressive stresses were obtained in the films deposited from methane and the lowest stresses in films deposited from cyclohexane. In the nitrogen containing DLC films the stresses decrease with increasing nitrogen content in the films. Stresses as low as 0.22 GPa were obtained in the films deposited from cyclohexane and nitrogen at a ratio of 1/15 in the plasma.     

Electrophoretic deposition of surface-modified titanate nanosheets via layer-by-layer assembly and deposited film properties

The surface of H₂Ti₄O₉·xH₂O titanate nanosheets was modified using the sulfonated tetrafluoroethylene-based polymer Nafion^®, via layer-by-layer assembly. The surface modification allowed the titanate nanosheets to be highly dispersed in hydrophobic organic solvents. Thick films of surface-modified nanosheets were prepared on indium tin oxide (ITO)-coated glass substrates as a negative electrode by electrophoretic deposition. The thickness of the films increased with increasing deposition time and grew to more than 8 μm in 600 s under potentiostatic conditions at 7.5 V. The electrophoretically deposited thick films showed significant hydrophobicity with contact angle for water 95°, and enhanced adsorption and higher photocatalytic activity for hydrophobic dyes such as thionine than those of thick films prepared from unmodified titanate nanosheets.     

Surface hydrophobization of CNF films by roll-to-roll HMDSO plasma deposition

Cellulosic films are typically sensitive towards moisture which limits their industrial applicability. In this study the films made from cellulose nanofibrils (CNF) were surface silylated with hexamethyldisiloxane (HMDSO) by roll-to-roll plasma deposition. The effects on surface hydrophobicity were clear and indisputable. Water contact angles of non-modified and plasma-deposited CNF films were 23° and 103°, respectively. As a result of surface silylation the relative polarity decreased from 46.8% to 0.6%. Surface hydrophobicity correlated well with the plasma deposition line speeds (0.5, 5, and 10 m/min) and the water vapor barrier properties. Silylation also decreased the oxygen transmission rates both at 50% and 80% relative humidity as compared to non-modified CNF films. All films were completely impermeable to olive oil and intact in contact with castor oil, toluene, and n-heptane or mixtures of them. The developed surface hydrophobization method can be exploited in strengthening the position of cellulosic films in high performance film applications.     

Controlling the surface topology and hence the hydrophobicity of amorphous carbon thin films

Amorphous carbon films with different surface topologies were synthesized on a Si substrate by plasma enhanced chemical vapor deposition at various pressures using acetylene as a carbon precursor. The samples were characterized by scanning electron microscopy, atomic force microscopy and Fourier transformed infrared spectroscopy. The contact angles for water with the as-prepared carbon films were measured and found to vary in the range 40-145^o. The surface energies of the as-prepared carbon films have been calculated using the Owens method in the hydrophilic region for the two liquids namely water and glycerol. It was found that with the decrease of polar component of the surface energy the surface gradually became hydrophobic. The contact angle was also found to be independent of the pH of water from extremely acidic to extremely basic.     

AFM study of the vinyl triethoxysilane (A-151) film prepared by spraying deposition and dipping deposition

The vinyl triethoxysilane (A-151) film was prepared by the spraying deposition and dipping deposition technique. The surface topography and growth behavior of A-151 films was investigated by using atomic force microscopy (AFM) and static water contact angle measurements. The results indicate that the topography was strongly affected by the treatment conditions. The surface topography of silane film was changed from the islands morphology to the network morphology with the increasing temperature of SiO₂ substrate, and the larger self-polymerized silane aggregation will be formed by using the ultrasonic technology. The hydrophobicity of the SiO₂ substrate was improved after A-151 deposition.     

Adhesion aspects of poly(p-xylylene) to SiO2 surfaces using γ-methacryloxypropyltrimethoxysilane as an adhesion promoter

The use of organo-silanes as coupling agents offers the potential to create novel structures using materials that would otherwise suffer from poor adhesion. γ-methacryloxypropyltrimethoxysilane (γ-MAPTS) layers were deposited on hydroxylated SiO₂ surfaces using both vapor and solution deposition techniques. The films were characterized using variable angle spectroscopic ellipsometry, infrared spectroscopy, contact-angle measurements and X-ray photoelectron spectroscopy. Film thickness was relatively constant at ～6 Å for solution deposition times from 2 min to 2 h at 60° C. Water contact angle increased from 0° to 45° after silane deposition from solution. Room temperature vapor-deposited γ-MAPTS films showed similar thicknesses to those of solution deposited films but a markedly lower contact angle of 10°. Parylene N was chemical vapor deposited on the γ-MAPTS films and its adhesion was tested using the Scotch^® Tape test. The γ-MAPTS improved adhesion of parylene N to the hydroxylated surface, with the adhesion for the vapor deposited silane films exhibiting a temperature and time dependence.     

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     

Electro-assisted preparation of dodecyltrimethoxysilane/TiO2 composite films for corrosion protection of AA2024-T3 (aluminum alloy)

Thin films of organosilanes have been successfully used as the alternative to toxic chromate coatings for surface pretreatment of metals and alloys. To further improve their corrosion performance, in the present work nano-scaled TiO₂ particles were added to the dodecyltrimethoxysilane (DTMS) films coated onto AA2024-T3 substrates, by using either the dip-coating or the cathodically electro-assisted deposition process. The obtained composite films were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), water contact angle measurements, Fourier transform reflection-absorption IR (FTRA-IR) and electrochemical impedance spectroscopy (EIS). The results show that these two techniques (nanoparticles incorporation and the electro-assisted deposition) both facilitate the deposition process of silane films, giving thicker deposit and higher coverage surface along with higher roughness and hydrophobicity, and thereby improve their corrosion resistance. Moreover, the corrosion performance of silane films is further improved by the combined use of nanoparticles modification and electro-assisted deposition.     

Surface and Corrosion Characteristics of a-C:H/Fluorocarbon Films

Fluorocarbon films were deposited on type 301 stainless steel substrates from mixtures of hexafluoroethane (HFE) or hexafluoroacetone (HFA) and acetylene and argon in a radio-frequency (13.56 MHz) plasma discharge. A 10 nm thick polysilicon interlayer was deposited prior to fluorocarbon film deposition to obtain good adhesion. To prevent film failure. a-C:H layer was deposited on the polysilicon layer prior to fluorocarbon film deposition, resulting in a-C:H/fluorocarbon composite film structures. The influence of the feed gas composition on the properties of the layered structure was investigated. Surface energies of the films were calculated from the film contact angle values obtained with water and diiodomethane. The composition of the surface layer of these films was characterized using X-ray photoelectron spectroscopy (XPS). The resistance offered by these a-C:H/fluorocarbon film structures to anodic breakdown in an electrolyte containing 0.1 M NaCl and 0.1 M Na₂SO₄ was studied using a potentiostatic technique. The anodic current density for the coated type 301 stainless steel samples was at least 3 orders of magnitude smaller than that for the bare sample and more than an order of magnitude smaller than that observed with samples coated with only the (equally thick) a-C:H layer. The resistance offered by the layered coatings to solution penetration increased with increasing fluorine content in the films.     

Corrosion resistance and chemical stability of super-hydrophobic film deposited on magnesium alloy AZ31 by microwave plasma-enhanced chemical vapor deposition

A super-hydrophobic film was successfully deposited on magnesium alloy AZ31 by the microwave plasma-enhanced chemical vapor deposition (MPECVD) process. The film surface showed a static water contact angle of more than 150°. The hydrophobicity and root mean square roughness of the film surface increased with an increase in deposition time. The anticorrosion resistance of the deposited film was estimated by electrochemical impedance spectroscopy (EIS) measurements. The EIS measurements and appropriate equivalent circuit models revealed that the super-hydrophobic film considerably improved the anticorrosion resistant performance of magnesium alloy AZ31. The anticorrosion mechanism of the super-hydrophobic film was also considered. Moreover, the chemical stability of the super-hydrophobic film in acidic, neutral, and alkaline aqueous solutions was investigated. The super-hydrophobic film showed high chemical stability in acidic and neutral aqueous solutions.     

Antifungal behavior of silicon-incorporated diamond-like carbon by tuning surface hydrophobicity with plasma treatment

Silicon-incorporated diamond-like carbon (Si-DLC), an amorphous material containing Si atoms with sp³- and sp²-hybridized carbon, is a promising biomaterial for versatile biomedical applications due to its excellent mechanical properties, chemical inertness, biocompatibility, and antimicrobial capability. However, the antifungal properties of plasma-treated Si-DLC have not been systematically evaluated. In this study, Si-DLC coatings were deposited by chemical vapor deposition and further treated with either oxygen or fluorine plasma to render the surface anchored with different functional groups and hydrophobicity. Surface roughness was probed with atomic force microscopy, whereas bonding character and surface composition were assessed using Raman and X-ray photoelectron spectroscopy. Wettability and surface charge were investigated via water contact angle and zeta potential measurements. Antifungal assessment was performed using a Candida albicans multi-well plate screening technique and crystal violet biomass quantification. The results demonstrate that oxygen plasma–treated Si-DLC exhibited hydrophilic properties, lower negative zeta potential, and significant antifungal behavior. This material can potentially be applied on surfaces for the prevention of reduced nosocomial infections.     

Wettability of porous two‐dimensional ZnO nanocrystal films

Large‐scale two‐dimensional ZnO nanocrystal films on aluminum substrate were fabricated by a one‐step hydrothermal method under mild conditions, where all the ZnO nanocrystals had a lamellar structure generally perpendicular to the substrates and formed network‐like porous configurations. The morphologies of the films were dependent on both the reaction temperature and concentration of zinc. The wettability of the ZnO films was assessed by measuring the water contact angle without any surface functionalisation. The porous structures of the as‐prepared films could effectively enhance its hydrophobicity and the water contact angle ranged from 40° to 135° depending on the surface morphology and the arrangement of ZnO planes, indicating a simple and promising route to make aluminum surface waterproof and even self‐cleaning. The hydrophobic ZnO surface could be switched to hydrophilic state by UV irradiation.     

Influence of argon plasma on the deposition of Al2O3 film onto the PET surfaces by atomic layer deposition

In this paper, polyethyleneterephthalate (PET) films with and without plasma pretreatment were modified by atomic layer deposition (ALD) and plasma-assisted atomic layer deposition (PA-ALD). It demonstrates that the Al₂O₃ films are successfully deposited onto the surface of PET films. The cracks formed on the deposited Al₂O₃ films in the ALD, plasma pretreated ALD, and PA-ALD were attributed to the energetic ion bombardment in plasmas. The surface wettability in terms of water contact angle shows that the deposited Al₂O₃ layer can enhance the wetting property of modified PET surface. Further characterizations of the Al₂O₃ films suggest that the elevated density of hydroxyl -OH group improve the initial growth of ALD deposition. Chemical composition of the Al₂O₃-coated PET film was characterized by X-ray photoelectron spectroscopy, which shows that the content of C 1s reduces with the growing of O 1s in the Al₂O₃-coated PET films, and the introduction of plasma in the ALD process helps the normal growth of Al₂O₃ on PET in PA-ALD.