Oxygen plasma removal of thin polymer films

Relative rates of polymer removal in an oxygen plasma have been measured for 40 polymer samples. The rates of removal are correlated, with structural factors which enhance or retard removal. Strong backbone bonds, aromatic and polar functional groups, and metallic atoms decrease the removal rates. Weak bonds not attached to the- polymer backbone have little affect while weak bonds attached directly to the chain or in the chain greatly accelerate removal. Chlorine present in the polymer catalyzes removal. This can be mimicked by mixtures of CF₄, and O₂ for which much enhanced removal rates are observed.     

Formation of supermolecular structure in thin polymer films

The morphological structure of thin glow discharge films of thickness 100Å-6μm was investigated. The layers have well developed nodular surface structure and spherulitic structures in bulk. The size of the structure elements increases with the increase of support temperature and decreases with the increase of discharge current density and frequency. Investigations of spatial arrangement of spherulites show that spherulites exist only in the vicinity of the gold layer used as support while the upper layer is shown to be amorphous. The spherulites are built of radially arranged fibrils of about 5000Å in diameter. It is shown that crystallization of spherulites takes place during the polymerization process.     

Surface modification of polyester films by RF plasma

Plasma treatment of PET films was carried out under argon, followed by exposure to an oxygen atmosphere. The films underwent considerable changes in surface composition and morphology, as demonstrated by contact angle measurements, FTIR‐ATR, AFM, and XPS. It was found that the surface acquired oxygen containing polar functional groups such as —C=O, —OH, and —OOH, which increased in number as the plasma treatment time increased. During storage, the treated films underwent significant surface reorganization, and both the time and temperature contributed to the increase in the contact angle. As revealed by AFM measurements, these changes were accompanied by an increase in roughness in the form of ridges. The ridges were observed to grow in height with increasing treatment time, although their spacing showed little evolution. A correlation among the observations obtained from various techniques was established, giving a comprehensive picture of the structure and dynamics of plasma‐treated PET surfaces. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1083–1091, 2000     

钛酸钾晶须的表面改性及其在隔热卷材涂料中的应用

利用硅烷偶联剂KH-570对表面无机包覆SiO2前、后的六钛酸钾晶须(PTW)进行有机表面改性,比较了硅烷偶联剂改性无机包覆SiO2处理前、后的PTW对卷材涂料隔热性能的影响.采用红外光谱(IR)、热重分析(TG)方法对改性前后的PTW进行了表征.结果表明,SiO2以化学键键合在PTW表面,KH-570在PTW表面形成了有机包覆层.涂膜隔热性能测试结果表明,以9%SiO2包覆处理后再用偶联剂KH-570改性的PTW能明显改善隔热卷材涂料的隔热性能,其热反射率达到75.4%,比不含PTW的漆膜提高了34.4个百分点,比含直接用偶联剂KH-570改性的PTW的漆膜提高了12.8个百分点.     

Surface modification of Ti64-Alloy with silver silicon nitride thin films

Ti6Al4V (Ti64) alloys is an alpha-beta titanium alloy with good corrosion resistance, high strength-to-weight ratio, excellent physiochemical stability and good biocompatibility. However, Ti64 alloy loses its biocompatibility when it is introduced into human tissues due to possible toxic of Vanadium (V) and Aluminum (Al) ion release. Thus, modification using silver silicon nitride films onto Ti64 via magnetron sputtering technique was proposed. In this study, a set of experimental depositing AgSiN films on Ti64 alloys using different bias voltage (0, ?75, ?150 and ?200?V) were fabricated. The surface characterization and mechanical performance of the thin films with respect to bias voltage were studied using scanning electron microscope (SEM), atomic force microscope (AFM), X-ray diffraction (XRD), nanoindentation and scratch test. Meanwhile, the biological function of the films was tested through wettability and antibacterial tests. According to the results, all thin films showed similar morphology with the highest adhesion strength (596?mN) was obtained for AgSiN thin film deposited at ?75?V. The hardness (5.5?GPa) and elastic modulus (211.0?GPa) of sample deposited at ?150?V showed an improvement for about 50% compared to the Ti64 substrate (H?=?2.75, E?=?113.8). The lowest compressive residual stress 0.06?GPa was noted for samples that have highest adhesion strength and highest thickness. In terms of biological functionality, all films showed hydrophilic property with wetting angle observed were below 90°. An inhibition zone area that observed on Bulkholderia pseudomallei (B.Psudomallei) and Escherichia coli (E.coli) were 7 and 10?mm respectively, which proved the AgSiN films as a promising candidate to be used in antibacterial applications.     

远程等离子体处理对聚四氟乙烯表面的功能化改性

采用远程氩等离子体对聚四氟乙烯(PTFE)膜进行了表面改性研究,通过接触角测定仪、扫描电子显微镜(SEM)和X射线光电子能谱仪(XPS)等手段,分析研究了改性后材料表面结构、性能的变化。结果表明:PTFE表面经远程氩等离子体处理后,表面微观形态和表面化学成分均发生了变化,且处理效果优于常规氩等离子体。远程氩等离子体可以在一定程度上抑制电子、离子的刻蚀作用,强化自由基反应,使材料表面获得更好的改性效果。经远程氩等离子体短时间(100s)处理后,PTFE表面的F/C比例从1.97降至1.44,O/C比例从0.015增至0.086;表面的水接触角从108°减小到53°;表面自由能从22.4×10-5N·cm-1增加至52.3×10-5N·cm-1。     

Surface modification of PET films by pulsed argon plasma

The rf power was modulated (discharge on‐time of 10 μs and discharge off‐time of 50–500 μs), for pulsed argon (Ar) and oxygen (O₂) plasmas used to irradiate PET film surfaces to modify the film surfaces. From data regarding the contact angle for the modified PET film surfaces and chemical analyses with XPS, effects of the rf power modulation on the surface modification are discussed. The pulsed Ar and O₂ plasmas are effective in modification of the PET film surface. There is no difference in the contact angle between the pulsed plasma and the continuous plasma. Furthermore, the pulsed Ar plasma is advantageous in formation of hydroxyl groups on the PET film surfaces. The rf power modulation has a possibility to modify into peculiar surfaces. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2845–2852, 2002     

Surface modification of amorphous carbon thin films by 1,3-dipolar cycloaddition

Amorphous carbon thin film surfaces were successfully modified by 1,3-dipolar cycloaddition of nitrones, generated by the condensation of 4-(trifluoromethyl)benzaldehyde and N-methylhydroxylamine. Amorphous carbon thin films were deposited by electron cyclotron resonance sputtering and consisted of mainly sp²-hybridized carbon. The modification of amorphous carbon thin film surfaces with organic molecules was confirmed by X-ray photoelectron spectroscopy (XPS), Raman, and atomic force microscopy (AFM). F 1s, N 1s, and C 1s electron spectra revealed the existence of organic molecules on the surface of modified amorphous carbon thin films. The surface coverage increased with reaction temperature, reactant concentration, and reaction time.     

Surface modification of polymeric nanocomposite thin films using supercritical carbon dioxide

We report on an efficient and environmentally friendly means to modify surface properties of polymer films supported for nanoparticles. Ultrathin polystyrene (PS) films (<300 Å), in which inorganic nanoparticles were embedded, were exposed to supercritical carbon dioxide (scCO₂). The swollen structure was then preserved by quickly evaporating CO₂. X-ray reflectivity (XR) results showed that this procedure produced polymeric nanocomposite films with a low-density region of about 150Å at the polymer/air interface. The formation of the low-density layer was independent of the nature of the particles, indicating that the surface modification through exposure to scCO₂ may be a universal phenomenon regardless of a choice of nanoparticles.     

Surface modification of polyimide films via plasma polymerization and deposition of allylpentafluorobenzene

Plasma polymerization of allylpentafluorobenzene (APFB) on the plasma-pretreated polyimide (PI) films was carried out. The fluorinated aromatic groups of the plasma-polymerized APFB (pp-APFB) could be preserved, to a large extent, by controlling the glow discharge parameters. The effect of the glow discharge parameters, including the type of the carrier gas and the input RF power, on the surface composition and chemical structure of the pp-APFB films were studied by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and time-of-flight secondary ion mass spectrometry. The surface topography of the APFB plasma-polymerized PI (pp-APFB-PI) films was studied by atomic force microscopy. For plasma polymerization carried out at a high RF power and using argon as the carrier gas, an ultra-hydrophobic pp-APFB-PI surface was also obtained. The ultra-hydrophobic surface exhibited advancing/receding water contact angles (θ_A/θ_R) of 174°/135°. The effectiveness of the carrier gas in defluorinating the pp-APFB films followed the order of O₂>N₂>H₂>Ar. Thus, the role of the carrier gas in improving the surface hydrophobicity of the resulting pp-APFB-PI films followed the order of O₂22® tape adhesion test.     

Photocatalytic functional coatings of TiO2 thin films on polymer substrate by plasma enhanced atomic layer deposition

We prepared photocatalytic TiO₂ thin films which exhibited relatively high growth rate and low impurity on polymer substrate by plasma enhanced atomic layer deposition (PE-ALD) from Ti(NMe₂)₄ [tetrakis (dimethylamido) Ti, TDMAT] and O₂ plasma to show the self-cleaning effect. The TiO₂ thin films with anatase phase and bandgap energy about 3.3 eV were deposited at growth temperature of 250 °C and the photocatalytic effects were compared with commercial Activ glass. From contact angles measurement of water droplet and photo-induced degradation test of organic liquid, TiO₂ thin films with anatase phases showed superhydrophilic phenomena and decomposed organic liquid after UV irradiation. The anatase TiO₂ thin film on polymer substrate showed highest photocatalytic efficiency after 5 h UV irradiation. We attribute the highest photocatalytic efficiency of TiO₂ thin film with anatase structure to the formation of suitable crystalline phase and large surface area.     

Surface properties of commercial polymer films following various gas plasma treatments

Surface properties of a number of commercial thermoplastic polymer films were investigated before and after brief exposures to RF induced, low temperature gas plasmas. Water wettability and adhesion of vapor deposited aluminum to thin films (8–12 micron) of polyethylene, polypropylene, polyester, polysulfone, polycarbonate, and polyvinylidene fluoride films were studied before and after treatments with oxygen, 96% CF₄/4% O₂, and helium plasmas. Treatment with oxygen plasmas showed the greatest change in water wettability for polyvinylidene fluoride and polypropylene films, while treatment with 96% CF₄/4% O₂ showed dramatic changes in wettability of polycarbonate, polysulfone, and polystyrene. Excellent adhesion of aluminium was found for polymers that had been previously exposed to gas plasmas.     

Electrodes covered with thin,permeable polymer films

Because of the recent interest in electrodes modified with thin polymer films the question of permeability of such films to electrolytes and electroactive species is discussed. Glow-discharge polymer films prepared on platinum electrodes from 4-vinylpyridine were used as model systems. They were investigated mainly with electrochemical techniques. ln particular, the analysis of the electrode impedance over a frequency range of 10–3000 Hz gave valuable information about the structure of the metal—polymer interface in presence of the electrolyte.The films prepared on the anode of the glow discharge were found to act as semi-permeable membranes. Hydrogen could be oxidized on the platinum—polymer interface of these polymer covered electrodes at rates comparable to uncovered platinum, while the films were impermeable to iron ions. The matrix prepared on the cathode was more rigid due to cross-links, and thus less permeable.The polymer matrix was more or less electroactive itself. This was probably due to quinone-type groups formed with oxygen and water after the glow-discharge polymerization process. The oxidation and reduction of these groups gave rise to a Warburg-type contribution to the electrode impedance.     

Noble gas permeability of polymer films and coatings

Permeabilities of noble gases, particularly argon, krypton, and xenon, were measured through a number of polymer films and coatings. Extrapolation of the log of the permeation coefficient versus the square of the gas molecular diameter was used to estimate radon permeability. An equation has been developed that can predict permeability to these noble gases as a function of the base polymer structure of the coating.     

Surface and interface morphology and structure of amorphous carbon thin and multilayer films

We review the implementation of X-ray reflection (reflectivity and scattering) techniques for the study of amorphous Carbon (a-C, a-C:H, ta-C) thin and multilayer films and in particular in the determination of the film density and surface and interface morphology, which are intrinsically significant for ultra-thin films. We present studies of various a-C and a-C:H films, which include in particular: i) the morphology of a-C/Si interface, ii) the surface morphology and density evolution during sputter growth of a-C, iii) the morphology of the sp²-rich a-C/sp³-rich a-C interfaces in multilayer a-C films, iv) the universal correlation between the film density and the refractive index of a-C and a-C:H films. We also compare and validate the experimental results with relative results from Monte-Carlo simulations within an empirical potential scheme. The computational results shed light on the atomistic mechanisms determining the structure and morphology of the a-C interfaces between individual sp²- and sp³-rich a-C layers and between a-C and Si substrates.     

Correlation of morphology and barrier properties of thin microwave plasma polymer films on metal substrate

The barrier properties of thin model organosilicon plasma polymers layers on iron are characterised by means of electrochemical impedance spectroscopy (EIS). Tailored thin plasma polymers of controlled morphology and chemical composition were deposited from a microwave discharge. By the analysis of the obtained impedance diagrams, the evolution of the water uptake ?, coating resistance and polymer capacitance with immersion time were monitored and the diffusion coefficients of the water through the films were calculated. The impedance data correlated well with the chemical structure and morphology of the plasma polymer films with a thickness of less than 100 nm. The composition of the films were determined by means of infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The morphology of the plasma polymer surface and the interface between the plasma polymer and the metal were characterised using atomic force microscopy (AFM). It could be shown that, at higher pressure, the film roughness increases which is probably due to the adsorption of plasma polymer nanoparticles formed in the plasma bulk and the faster film growth. This leads to voids with a size of a few tens of nanometers at the polymer/metal interface. The film roughness increases from the interface to the outer surface of the film. By lowering the pressure and thereby slowing the deposition rate, the plasma polymers perfectly imitate the substrate topography and lead to an excellent blocking of the metal surface. Moreover, the ratio of siloxane bonds to methyl-silyl groups increases which implies that the crosslink density is higher at lower deposition rate. The EIS data consistently showed higher coating resistance as well as lower interfacial capacitance values and a better stability over time for the film deposited at slower pressure. The diffusion coefficient of water in thin and ultra-thin plasma polymer films could be quantified for the smooth films. The measurements show that the quantitative evaluation of the electrochemical impedance data requires a detailed understanding of the film morphology and chemical composition. In addition, the measured diffusion coefficient of about 1.5×10⁻¹⁴ cm² s⁻¹ shows that plasma polymers can act as corrosion resistant barrier layers at polymer/metal interfaces.     

Spin coating of thin and ultrathin polymer films

The spin coating of thin (> 200 nm thick) and ultrathin (< 200 nm thick) polymer films is examined in several solvents of varying volatility over a broad range of polymer solution concentrations and spin speeds. Experimentally measured film thicknesses are compared with a simple model proposed by Bornside, Macosko, and Scriven, which predicts film thickness based on the initial properties of the polymer solution, solvent, and spin speed. This model is found to predict film thickness values within 10% over the entire range of conditions explored, which gave film thicknesses from 10 nm to 33 μ:m. The model underpredicts film thickness for cases in which a very volatile solvent is used or the initial concentration of polymer is high, while overpredicting film thickness for cases in which a low volatility solvent is used or the initial polymer concentration is very low. These deviations are a consequence of how the model decouples fluid flow and solvent evaporation.     

Thermal stability of the optical properties of plasma deposited diamond-like carbon thin films

In present paper we studied the optical constants of the diamond-like carbon (DLC) films and their changes with annealing. The multisample modification of combined variable angle spectroscopic ellipsometry and near normal spectroscopic reflectometry was used. The optical constants of the DLC films were simulated by our recently published six-parameter dispersion model employing a parameterization of the density of electronic states (DOS). Based on the dispersion model parameters the density of π and σ electrons were evaluated. We showed that from our model and the independently determined hydrogen atomic fraction of the films before and after annealing the ratio between momentum matrix elements of π → π* and σ → σ* transitions and the correct sp³-to-sp² carbon bonding configuration ratio can be calculated. It is worth to notice that the first quantity is usually assumed to be equal to unity but we showed that this assumption may cause a significant error in the determination of the sp³-to-sp² ratio. Therefore, our suggested method represents a novelty in this field.