Surface modification of ethylene‐co‐tetrafluoroethylene films by remote plasmas

The surface modifications of ethylene‐co‐tetrafluoroethylene (ETFE) surfaces by six plasmas (direct H₂, Ar, and O₂ plasmas and remote H₂, Ar, and O₂ plasmas) were investigated with two questions in mind: (1) what plasma could effectively modify ETFE surfaces and (2) which of the CF₂? CF₂ and CH₂? CH₂ components in ETFE was selectively modified? The plasma exposure led to a weight loss from the ETFE surfaces and changes in the chemical composition on ETFE surfaces. The weight‐loss rate showed a strong dependence on what plasma was used for the modification. The remote H₂ plasma led to the lowest rate of weight loss in the six plasma exposures, and the direct O₂ plasma led to the highest rate of weight loss. During exposure to the plasmas, defluorination occurred, and two new C_1s components [? CH₂? CHF? CH₂? and ? CH₂? CH(O? R)? CF_x? , and ? CH₂? CHF? CF₂? , ? CH₂? C(O)? CF_x? , and ? CF_x? C(O)? O? ] were formed on the modified ETFE surfaces. Defluorination was strongly influenced by what plasma was used for the modification. The remote H₂ and Ar plasmas showed high defluorinations of 55 and 51%, respectively. The remote O₂ plasma showed a low defluorination of only 25%. Conclusively, the remote H₂ and Ar plasma exposure effectively modified ETFE surfaces. With the exposure of these surfaces to the remote H₂ plasma, the CF₂? CF₂ component was predominantly modified, rather than the CH₂? CH₂ component. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2871–2882, 2002     

Isoelectric points of plasma‐modified and aged silicon oxynitride surfaces measured using contact angle titrations

Acid‐base properties of metal oxides and polymers can control adhesion properties between materials, electrical properties, the physical structure of the material and gas adsorption behavior. To determine the relationships between surface isoelectric point, chemical composition and aging effects, plasma‐surface treatment of amorphous silicon oxynitride (SiO_xN_y) substrates was explored using Ar, H₂O vapor, and NH₃ inductively coupled rf plasmas. Overall, the Ar plasma treatment resulted in nonpermanent changes to the surface properties, whereas the H₂O and NH₃ plasmas introduced permanent chemical changes to the SiO_xN_y surfaces. In particular, the H₂O plasma treatments resulted in formation of a more ordered SiO₂ surface, whereas the NH₃ plasma created a nitrogen‐rich surface. The trends in isoelectric point and chemical changes upon aging for one month suggest that contact angle and composition are closely related, whereas the relationship between IEP and composition is not as directly correlated. Copyright © 2010 John Wiley & Sons, Ltd.     

Introduction of Primary Amino Groups on Poly(ethylene terephthalate) Surfaces by Ammonia and a Mix of Nitrogen and Hydrogen Plasma

With the aim of introducing primary amino groups on the surface of poly(ethylene terephthalate) (PET), two methods were compared—the use of ammonia or a combination of nitrogen and hydrogen low-pressure microwave plasma. Several plasma parameters were optimized on the reactor to increase the –NH₂ surface density, which was estimated by colorimetric titration and X-ray photoelectron spectroscopy (XPS). These techniques show that whatever the plasma treatment, almost 2 –NH₂/nm2 are incorporated on PET films. Emission spectroscopy highlighted a correlation between the density of primary amino groups and the ratio between an NH peak intensity and an Ar peak intensity (I_NH/I_Ar). Variation in surface hydrophilicity with aging in air after plasma treatment was monitored with contact angle measurements and showed a hydrophobic recovery. This was confirmed by XPS, which suggests also that surfaces treated by NH₃ plasma are more stable than surfaces treated by N₂/H₂.     

Plasma reactions of self-assembled monolayers to model oxygen atom effects on polymers

The plasma treatment of self-assembled monolayers of octadecyl mercaptan on gold substrates has been investigated as a model for oxygen atom effects on polymers. Both O₂ and H₂O low pressure gas plasmas have been used. X-ray photoelectron spectroscopy has revealed that the two plasma treatments differ from each other in the extent of oxidation and etch rate with O₂ being the more aggressive plasma. The results have confirmed that the plasma modification of organic surfaces involves a balance between surface oxidation and surface etching. The well-defined structure of the monolayer enables quantitation of these atom-substrate reactions. © 1998 John Wiley & Sons, Ltd.     

Surface Properties of Low Density Polyethylene upon Low-Temperature Plasma Treatment with Various Gases

The surface of a LDPE was modified by Ar, O₂, N₂, CO₂ gaseous plasma. The changes in surface morphology and surface wettability were investigated using AFM and SEM. The surface chemical changes of LDPE were also characterized by FTIR-ATR. The SEM and AFM results demonstrated variable changes in surface roughness for different types of plasma gas used, the changes being more for the Ar and N₂ plasma treatments. Considering the nature of the LDPE film, XRD studies were carried out to determine changes in the percentage crystalinity. The results showed that all low pressure O₂, Ar, N₂, CO₂ gas plasmas improved the wettability of LDPE films. Contact angles decreased significantly depending on the discharge powers and exposure times. Surface morphology was also found to vary with plasma discharge powers, exposure times, and the type of gas being used. Ar and N₂ gas plasmas in general produced more superior results.     

Modification of polysulfone membranes 4. Ammonia plasma treatment

The effect of NH₃ and NH₃/Ar plasma on ultrafiltration polysulfone membranes have been studied. Results of contact angle, FTIR-ATR and X-ray photoelectron spectroscopy experiments clearly showed that both plasmas introduced hydrophilic, nitrogen- and oxygen-containing moieties on the polymer surface and that NH₃/Ar plasma was more efficient. That plasma was also more aggressive--signs of strong etching could be seen on the SEM pictures. Redeposition of etched material seemed to take place inside the pores. On the contrary, ammonia plasma was soft and caused cleaning the surface and pores enlargement. Performance of ammonia plasma modified membranes was greatly improved and independent on solution pH. The last observation proved amphoteric character of the surface. NH₃/Ar plasma treatment gave membranes of acidic surface and filtration indices not so good as for ammonia plasma.     

Modification,degradation, and stability of polymeric surfaces treated with reactive plasmas

The degradation, modification, and stability of polymeric surfaces exposed to chemically reactive O₂ and H₂O‐vapor plasmas were investigated. Specifically, the effects of these plasmas on etching rate, surface morphology, wetting instability, and fluid‐holding capability were studied. Wetting instability is reflected by hydrophobic recovery and can be examined by the Wilhelmy balance method. Although hydrophobic recovery is usually attributed to surface configuration change, there are actually two types: reversible and permanent. Reversible hydrophobic recovery is caused by surface configuration change, whereas permanent hydrophobic recovery is caused by the creation of oxidized surface oligomers. This study distinguishes the two by identifying differences in the shapes of the corresponding Wilhelmy force loops and in the fluid‐holding parameter. The presence of surface oligomers was most detrimental to wetting stability and fluid‐holding capability but could be controlled via the type of reactive gas, the discharge conditions, and the polymer substrate. In general, polymers most susceptible to O₂‐plasma etching had the least surface oligomers and vice versa, whereas H₂O‐vapor plasma suppressed surface oligomers on polymers less susceptible to etching. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3028–3042, 2000     

PMMA Surface Functionalization Using Atmospheric Pressure Plasma for Development of Plasmonically Active Polymer Optical Fiber Probes

In this paper, we demonstrate the development of plasmonically active PMMA optical fiber probes by the attachment of gold nanoparticles to the probe surface functionalized by means of flowing post-discharges from dielectric barrier discharge (DBD) plasmas for the first time. Polymer optical fiber (POF) probes (U shape to improve absorbance sensitivity) were subjected to reactive gas atmospheres in the post-discharge region of a coaxial DBD plasma reactor run at atmospheric pressure in different gases (Ar, Ar + 10 % O₂, O₂, N₂, N₂ + 0.5 % H₂). Plasma treatments in Ar or N₂ gave rise to water-stable electrophilic functional groups on PMMA surface, whereas the amine groups generated by N₂-containing plasmas were not stable. Subsequently, PMMA surfaces were treated with hexamethylene diamine (HMDA) to obtain stable amine groups through the reaction of electrophilic groups. Gold nanoflowers (AuNF, 37 nm, peak 570 nm) binding to the amine functionalized fiber probes was monitored in real-time by recording the optical absorbance changes at 570 nm with the help of a UV–vis spectrometer. Absorbance response from Ar or N₂ plasma treated probes are 100 and 60 times, respectively, that of untreated control probes. A 25 fold improvement in absorbance response was obtained for Ar plasma treated POF in comparison with only HMDA treated POF. The shelf life of the hence fabricated plasmonically active probes was found to be at least 3 months. In addition, plasmonic activity of U-bent fiber probes treated in Ar plasma is better than the conventional wet-chemical activation by environmentally hazardous acid pre-treatment approaches.     

Mass spectrometer-wall probe diagnostic of Ar discharges containing SF6 and/or O2: Reactive ions in etching plasmas

Positive and negative ions of Ar/SF₆ and Ar/SF₆/O₂ plasmas (etching plasmas) and of Ar/O₂ plasmas (cleaning plasmas) in Pyrex tubes have been investigated using a mass spectrometer-wall probe diagnostic technique. The measurement of negative ions proved to be a very sensitive method for the detection of wall material. In etching plasmas with small admixtures of SF₆, oxygen was found as the only representative of wall material. At larger amounts of SF₆, silicon could be detected. In cleaning plasmas with small admixtures of O₂ applied to a previously etched Pyrex surface, fluorine was found, indicating the reversal of fluoridation by oxygenation.     

NH3 Plasma Treatments of PET for Enhancing Aluminum Adhesion

A NH₃ plasma process has been studied for enhancing the adhesion of aluminum coatings on polyethyleneterephtalate (PET) films. According to our peel strength results, NH₃ plasmas increase markedly the adhesion of aluminum on PET compared to O₂ discharges, with a much shorter treatment time. A tentative model of nonhindered growth of Al-coating based on the Lewis basic character of the functionalities grafted by NH₃ plasma is proposed for Al-polymer interactions, and for explaining the various steps in the process. The effects of power input and treatment time on the polymer surface chemistry and on the metal-polymer peel strength have been evaluated. Treatment times as short as 0.1 s at 100 W proved to be the best conditions in NH₃ plasmas, for a significant increase in Al/PET adhesion, while longer treatments have a detrimental effect. This may explain why most authors have not discovered the benefits of NH₃ plasmas for improving the adhesion of metals on PET, and have preferred O₂ or air treatments. The relative basicity of PET grafted with N-containing functionalities has been measured by means of X-ray Photoelectron Spectroscopy (XPS) analysis of samples exposed to vapors of trichloromethane, a Lewis acid molecular probe. The Al/PET adhesion was evaluated by means of a 180° Peel Test.     

Surface characterization and properties of plasma‐modified cyclic olefin copolymer/layered silicate nanocomposites

In this study, cyclic olefin copolymer (COC)/layered silicate nanocomposites (CLSNs) were prepared by the intercalation of COC polymer into organically‐modified layered silicate through the solution mixing process. Both X‐ray diffraction data and transmission electron microscopy images of CLSNs indicate most of the swellable silicate layers were disorderedly intercalated into the COC matrix. The effect of layered silicate on the mechanical and barrier properties of the fabricated nanocomposites shows significant improvements in the storage modulus and water permeability when compared with that of neat COC matrix. Surfaces of COC and CLSN films were modified by a mixture of oxygen (O₂) and nitrogen (N₂) plasmas with various treated times, system pressures, and radio frequency (RF) powers. The surfaces of plasma‐modified COC and CLSN were investigated using scanning probe microscopy and contact‐angle measurements. The exposure of the COC and CLSN film to the plasmas led to the combination of etching reactions of polymer surface initiated by plasma and the following addition reactions of new functional groups onto polymer surfaces to change the topology of COC film surfaces. The surface roughness was closely related to how high and how long the RF power was input into the system. The plasmas also led to changes in the surface properties of the CLSN surfaces from hydrophobic to hydrophilic; and the contact angle of water on the surface decreases. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2745–2753, 2005     

Surface modifications of PET in argon atmospheric pressure plasma: Gas flow rate effect

The correlation between plasma optical properties and the treated polyethylene terephthalate (PET) surface characteristics have been studied at various Ar flow rate. The rotational T_rot and vibrational T_vib temperatures of APPJ were determined from SPS emission band. The pristine and plasma-treated PET surfaces were characterized by several techniques including X-ray photoelectrons spectroscopy (XPS), Raman spectroscopy, contact angle (CA), and atomic force microscope (AFM). The CA decreased rapidly in the flow rate range 1–3 L/min and weakly dependent as flow rate > 3 L/min. XPS results showed that C 1s % of plasma-treated PET surfaces decreases and has a minimum for samples treated at 3–4 L/min, while O 1s has a maximum at the same flow rate range. The carbon C 1s peak of pristine and plasma treated PET samples resolved into five subcomponents: C–C, C–O, C=O, O–C=O, and π–π bonds with variable percentage ratio accordance to the plasma gas flow rate. Raman data revealed a partial loss in the crystallinity of the treated PET samples and also confirm the incremental of C–O band at Ar flow rate of 3 L/min. AFM images showed that the surface roughness of treated PET films increases as Ar flow rate increases.     

Etching Characteristics and Mechanisms of Mo and Al2O3 Thin Films in O2/Cl2/Ar Inductively Coupled Plasmas: Effect of Gas Mixing Ratios

An investigation of etching behaviors for Mo and Al₂O₃ thin films in O₂/Cl₂/Ar inductively coupled plasmas at constant gas pressure (6 mTorr), input power (700 W) and bias power (200 W) was carried out. It was found that an increase in Ar mixing ratio for Cl₂/Ar plasma results in non-monotonic etching rates with the maximums of 160 nm/min at 60 % Ar for Mo and 27 nm/min at 20 % Ar for Al₂O₃. The addition of O₂ in the Cl₂/Ar plasma causes the non-monotonic Mo etching rate (max. 320 nm/min at 40–45 % O₂) while the Al₂O₃ etching rate decreases monotonically. The model-based analysis of etching kinetics allows one to relate the non-monotonic etching rates in Cl₂/Ar plasma to the change in the etching regime from the ion-flux-limited mode (at low Ar mixing ratios) to the neutral-flux-limited mode (for high Ar mixing ratios). In the Cl₂/O₂/Ar plasma, the non-monotonic Mo etching rate is probably due to the change in reaction probability.     

Effects of Ar‐ and Ar/O2‐plasma‐treated amorphous and crystalline polymer surfaces revealed by ToF‐SIMS and principal component analysis

The effects of argon (Ar) and a mixture of Ar and oxgyen(Ar/O₂) plasmas on amorphous and semi‐crystalline poly(bisphenol A hexane ether) thin films were investigated by time‐of‐flight secondary ion mass spectroscopy (ToF‐SIMS) and principal component analysis (PCA). PCA results of the ToF‐SIMS spectra indicate that an Ar/O₂ plasma produced less physical sputtering and had a higher chemical reactivity than did an Ar plasma, regardless of whether an amorphous or a crystalline surface was involved. However, the chemical differences between the Ar‐ and Ar/O₂‐plasma‐treated semi‐crystalline films were much smaller. The observed results can be explained by the higher resistance of the polymer crystalline regions to physical sputtering and chemical etching. Copyright © 2013 John Wiley & Sons, Ltd.     

Surface modification with nitrogen-containing plasmas to produce hydrophilic,low-fouling membranes

Nitrogen-based plasma systems such as N₂, NH₃, Ar/NH₃, and O₂/NH₃ were used to modify microporous polyethersulfone membranes. Treatments were designed to alter the surface chemistry of the membranes to create permanently hydrophilic surfaces. Contact angle measurements taken initially, as well as 1 year post-treatment confirmed that treatments using O₂/NH₃ plasmas (with a 5:3 gas flow ratio) were successful in achieving our designed goals. Analyses by FT-IR and XPS established the incorporation of NH_x and OH species in the PES membranes. Moreover, the plasma penetrates the thickness of the membrane, thereby modifying the entire membrane cross-section. Optical emission spectroscopy studies of excited state species present in the modifying gases revealed the presence of OH^*, which was not present in a 100% ammonia plasma, suggesting OH^* must play a critical role in the membrane modification process. Investigations using bubble point analysis, differential scanning calorimetry, and scanning electron microscopy demonstrate there is no damage occurring under these specific treatment conditions. The usefulness of this treatment is revealed by increased water flux, reduced protein fouling, and greater flux recovery after gentle cleaning when compared to an untreated membrane.     

Properties of low-molecular-weight polyethylene treated with gas plasma

Polyethylene films were evaporated in gas plasmas of Ar, N₂, O₂, and H₂O. The deposits were analyzed by infrared (IR) spectroscopy to determine the concentration of characteristic functional groups. The deposit prepared in Ar-atmosphere had a rather high concentration of methyl group and many double bonds were produced in the film. The deposits prepared in Ar- and N₂-plasmas produced similar spectra, which showed twice the concentration of methyl group than the deposit in Ar-atmosphere and also contained a few carbonyl and hydroxyl groups. The film treated in O₂-plasma contained the largest amount of carbonyl group and the lowest number of double bonds among the plasma-treated deposits. Dielectric loss curves against temperature for the deposits treated in these plasmas showed a broad peak near 20°C. For O₂-plasma-treated film the loss tangent curves showed a sharp maximum. The activation energy for the relaxation of Ar-, O₂-, and H₂O-plasma-treated films had the same value of 50.6 kcal/mol. The observed relaxation in the films prepared in gas plasmas was considered due to the β process and was attributed to the motion of oxidized branched polyethylene.     

Silver Loading on DBD Plasma-Modified Woven PET Surface for Antimicrobial Property Improvement

In this work, the hydrophilic improvement of a woven PET surface was accomplished by a plasma technique. The woven PET surface was plasma-treated by dielectric barrier discharge (DBD) under various operating conditions (electrode gap distance, plasma treatment time, input voltage, and input frequency) and various gaseous environments (air, O₂, N₂, and Ar) in order to improve its hydrophilicity. It was experimentally found that a decrease in electrode gap distance and an increase in input voltage increased the electric field strength, leading to higher hydrophilicity of the PET surface characterized by wickability and contact angle measurements. In comparisons among the studied environmental gases, air gave the highest hydrophilicity, being comparable to O₂, while Ar and N₂ gave lower hydrophilicity of the woven PET surface. The optimum conditions for a maximum hydrophilicity of the PET surface were an electrode gap distance of 4 mm, a plasma treatment time of 10 s, an output voltage of 15 kV, and a frequency of 350 Hz under air environment. After the plasma treatment under the obtained optimum conditions, the woven PET was loaded with Ag particles using a AgNO₃ aqueous solution in order to obtain the antimicrobial property. The plasma-treated woven PET loaded with Ag particles exhibited good antimicrobial activity against both E. coli (gram-negative bacteria) and S. aureus (gram-positive bacteria).     

Influence of dielectric barrier plasma treatment of ZnMgAl alloy-coated steel on the adsorption of organophosphonic acid monolayers

The adsorption of octadecyl phosphonic acid (ODPA) on oxide-covered surfaces of ZnMgAl alloy coatings is described as a function of a dielectric barrier discharge (DBD) pretreatment step. The ODPA monolayer formation enables the investigation of the influence of the DBD treatment on the resulting interfacial bond formation and surface coverage. Surface characterisation by means of surface spectroscopy (PM-IRRAS, XPS) and surface electrochemistry (cyclic voltammetry) showed that the DBD pretreatment with Ar, Ar/O₂ and Ar/H₂O gas mixtures leads to improved barrier properties of the adsorbed ODPA monolayer. Moreover, during ODPA monolayer formation from ethanolic solution, a partial etching of the surface oxide layer occurs.     

Highly Efficient Low‐Temperature Plasma‐Assisted Modification of TiO2 Nanosheets with Exposed {001} Facets for Enhanced Visible‐Light Photocatalytic Activity

Anatase TiO₂ nanosheets with exposed {001} facets have been controllably modified under non‐thermal dielectric barrier discharge (DBD) plasma with various working gas, including Ar, H₂, and NH₃. The obtained TiO₂ nanosheets possess a unique crystalline core/amorphous shell structure (TiO₂@TiO_2?x), which exhibit the improved visible and near‐infrared light absorption. The types of dopants (oxygen vacancy/surface Ti³⁺/substituted N) in oxygen‐deficient TiO₂ can be tuned by controlling the working gases during plasma discharge. Both surface Ti³⁺ and substituted N were doped into the lattice of TiO₂ through NH₃ plasma discharge, whereas the oxygen vacancy or Ti³⁺ (along with the oxygen vacancy) was obtained after Ar or H₂ plasma treatment. The TiO₂@TiO_2?x from NH₃ plasma with a green color shows the highest photocatalytic activity under visible‐light irradiation compared with the products from Ar plasma or H₂ plasma due to the synergistic effect of reduction and simultaneous nitridation in the NH₃ plasma.     

A GC-system for the analysis of residual geothermal gases

Summary The gases evolved from geothermal fields, after condensation of H₂O, CO₂, H₂S and NH₃ in caustic solution, contain He, H₂, Ar, O₂, N₂, CH₄ and higher hydrocarbons. The analysis for the major components in these residual gas mixtures can be achieved by use of two simple gas chromatographs in parallel, and using 5Å molecular sieve. The separation of He and H₂ to baseline is achieved by using low temperatures (30°C) coupled with a relatively long column; and the difficult separation of Ar and O₂ is achieved by use of a cryogenically cooled column. The use of switching valves to backflush and bypass columns ensures that a minimum time for analysis can be achieved whilst retaining baseline separations of the He/H₂ and Ar/O₂ pairs.