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.     

Amination of Poly(ethylene-terephthalate) polymer surface for biochemical applications

Amine functionalization of Poly(ethylene-terephthalate) (PET) films for covalent binding of peptides is described. Ammonia plasma treatments have been used to graft nitrogen-containing functional groups onto the PET surface. The samples were then analyzed by X-ray photoelectron spectroscopy (XPS) and a parametric study was performed to define the best plasma grafting conditions. For biological tests, samples were sterilized by steam autoclaving: this induces a four to fivefold loss of the nitrogen functional groups on the polymer surface. XPS does not differentiate easily between the various nitrogen groups present on the surface so it is difficult to estimate the amount of surface amine groups available for direct coupling of bioactive molecules (proteins, peptides, nucleic acids, ...). To obtain a direct measurement of the amines present, we assayed for cysteine fixation through its carboxylic group by detection of the thiolaminoacid by XPS. We obtained cysteine fixation, showing the presence of grafted primary amine functions on PET surface after ammonia plasma treatment. Radiochemical assays were also made to quantify the amount of amine groups on plasma treated PET. XPS, cysteine fixation and radiochemical assays all show the presence of amine functions on ammonia plasma treated PET.     

SURFACE REARRANGEMENTS OF OXYGEN PLASMA TREATED POLYSTYRENE： SURFACE DYNAMICS AND HUMIDITY EFFECT

The time evolution of oxygen plasma treated polystyrene(PS)surfaces was investigated upon storing them in theair under controlled humidity conditions.The methods of water contact angle,X-ray photoelectron spectroscopy(XPS),sumfrequency generation(SFG)vibrational spectroscopy,and atomic force microscopy(AFM)were used to infer the surfaceproperties and structure.Chemical groups containing oxygen were formed on the PS surface with the plasma treatment,demonstrated by water contact angle and XPS.The surface polarity decayed markedly on time,as assessed by steady increasein the water contact angle as a function of storage time,from zero to around 60°.The observed decay is interpreted as arisingfrom surface rearrangement processes to burying polar groups away from the uppermost layer of the surfaces,which is incontact with air.On the other hand,XPS results show that the chemical composition in the first 3 nm surface layer isunaffected by the surface aging,and the depth profile of oxygen is essentially the same with time.A possible change of PSsurface roughness was examined by AFM,and it showed that the increase of water contact angle during surface aging couldnot be attributed to surface roughness.Thus,it is concluded that surface aging is attributable to surface reorganization andthe motion of oxygen containing groups is confined within the XPS probing depth.SFG spectroscopy,which is intrinsicallyinterface-specific,was used to detect the chemical structure of PS surface at the molecular level after various aging times.The results are interpreted as follows.During the aging of the plasma treated PS surfaces,the oxygen containing groupsundergo reorientation processes toward the polymer bulk and/or parallel to the surface,while the CH_2 moiety stands up onthe PS surface.Our results indicate that the surface configuration changes do not require large length scale segmentalmotions or migration of macromolecules.Motions that are responsible for surface configuration changes could be relativelysmall rotational motions.The aging behaviors under different relative humidity conditions were shown to be similar from18% to 91%,whereas the kinetics of surface polarity decays were faster in higher relative humidity.Here,the surfacerearrangement of polystyrene films that were previously treated by oxygen plasma and aged,and was investigated in terms ofcontact angle after the water immersion.The contact angles of the water-immersed samples were found to change andapproach the initial values before the immersion asymptotically.     

Catalytic effect of iron wires on the syntheses of ammonia and hydrazine in a radio-frequency discharge

The catalytic effect of iron wires on plasma syntheses of ammonia and hydrazine has been studied in the nitrogen-hydrogen plasma prepared using rf discharge at a pressure of 650 Pa (5 Torr). The product was mainly ammonia including a small amount of hydrazine. When iron wires were placed in the plasma downstream of the gas flow, the yields of both products increased, about two times in ammonia and two orders of magnitude in hydrazine. The yields increased with increasing number of wires (the surface area of the catalyst). The dissociative adsorption of nitrogen molecules and/or molecular ions on the iron surface and the formation of NH_x by the reaction with hydrogen in the plasma followed by the formation of NH₃ or N₂H₄ are considered as a reaction scheme. This is supported by the identification of NH₃ with XPS of the surface of iron wires.Partly presented at the 10th International Symposium on Plasma Chemistry, August 4–9, 1991, Bochum, Germany.     

Surface modification of plasma‐pretreated expanded poly (tetrafluroethylene) films by graft copolymerization

A two‐step process based on a low‐pressure helium plasma treatment followed by acrylic acid‐grafting copolymerization was used for the surface modification of expanded polytetrafluoroethylene (ePTFE) films. The effects of plasma treatment power and treatment time on the hydrophilicity of the film surface were investigated. The wettability of the ePTFE film surface was characterized by water contact angle, and the surface compositions of the untreated and treated ePTFE samples were evaluated by atomic force microscopy and XPS. Contact angle measurements revealed that the hydrophilicity of the ePTFE film surface was greatly enhanced by the combined actions of the plasma treatment and acrylic acid grafting, and the contact angle decreased from 145° to 66°. Atomic force microscopy analyses showed that the surface roughness increased after the plasma treatment. XPS analyses showed substantial increase in the concentration of carbon and oxygen atoms and a decrease in the concentration of fluorine atoms at the film surface. T‐peel strength showed an improved bonding strength between the film and an adhesive tape after the treatment. Copyright © 2012 John Wiley & Sons, Ltd.     

Plasma Catalytic Synthesis of Ammonia Using Functionalized-Carbon Coatings in an Atmospheric-Pressure Non-equilibrium Discharge

We investigate the synthesis of ammonia in a non-equilibrium atmospheric-pressure plasma using functionalized-nanodiamond and diamond-like-carbon coatings on α-Al₂O₃ spheres as catalysts. Oxygenated nanodiamonds were found to increase the production yield of ammonia, while hydrogenated nanodiamonds decreased the yield. Neither type of nanodiamond affected the plasma properties significantly. Using diffuse-reflectance FT-IR and XPS, the role of different functional groups on the catalyst surface was investigated. Evidence is presented that the carbonyl group is associated with an efficient surface adsorption and desorption of hydrogen in ammonia synthesis on the surface of the nanodiamonds, and an increased production of ammonia. Conformal diamond-like-carbon coatings, deposited by plasma-enhanced chemical vapour deposition, led to a plasma with a higher electron density, and increased the production of ammonia.     

Surface modification of polyester by oxygen‐ and nitrogen‐plasma treatment

In this paper, we present a study on the surface modification of polyethyleneterephthalate (PET) polymer by plasma treatment. The samples were treated by nitrogen and oxygen plasma for different time periods between 3 and 90 s. The plasma was created by a radio frequency (RF) generator. The gas pressure was fixed at 75 Pa and the discharge power was set to 200 W. The samples were treated in the glow region, where the electrons temperature was about 4 eV, the positive ions density was about 2 × 10¹⁵ m^?3, and the neutral atom density was about 4 × 10²¹ m^?3 for oxygen and 1 × 10²¹ m^?3 for nitrogen. The changes in surface morphology were observed by using atomic force microscopy (AFM). Surface wettability was determined by water contact angle measurements while the chemical composition of the surface was analyzed using XPS. The stability of functional groups on the polymer surface treated with plasma was monitored by XPS and wettability measurements in different time intervals. The oxygen‐plasma‐treated samples showed much more pronounced changes in the surface topography compared to those treated by nitrogen plasma. The contact angle of a water drop decreased from 75° for the untreated sample to 20° for oxygen and 25° for nitrogen‐plasma‐treated samples for 3 s. It kept decreasing with treatment time for both plasmas and reached about 10° for nitrogen plasma after 1 min of plasma treatment. For oxygen plasma, however, the contact angle kept decreasing even after a minute of plasma treatment and eventually fell below a few degrees. We found that the water contact angle increased linearly with the O/C ratio or N/C ratio in the case of oxygen or nitrogen plasma, respectively. Ageing effects of the plasma‐treated surface were more pronounced in the first 3 days; however, the surface hydrophilicity was rather stable later. Copyright © 2008 John Wiley & Sons, Ltd.     

Activation of PET Using an RF Atmospheric Plasma System

The plasma treatment of polymer surfaces is routinely used to enhance surface properties prior to adhesive bonding or biomolecule interaction. This study investigates the influence of plasma treatment conditions on the surface activation of polyethylene terephthalate (PET) using the SurFx Atomflo? 400L plasma source. In this study the effect of applied plasma power, processing speed, gas composition and plasma applicator nozzle to substrate distance were examined. The level of polymer surface activation was evaluated based on changes to the water contact angle (WCA) of PET samples after plasma treatment. PET surface properties were also monitored using surface energy and X-ray photoelectron spectroscopy (XPS) analysis. The heating effect of the plasma was monitored using thermal imaging and optical emission spectroscopy (OES) techniques. OES was also used as a diagnostic tool to monitor the change in atomic and molecular species intensity with changes in experimental conditions in both time and space. XPS analysis of the PET samples treated at different plasma powers indicated that increased oxygen content on samples surfaces accounted for the decreases observed in WCAs. For the first time a direct correlation was obtained between polymer WCA changes and the OES measurement of the atomic hydrogen Balmer H_α and molecular OH line emission intensities.     

Influence of O2 Plasma on Surface Properties of PC-TiO2 Nanocomposite Film

In this work, polycarbonate-TiO₂ nanocomposite films were prepared with different percentages. The aim was to consider the effect of O₂ LF plasma (50 Hz) on the hydrophilicity, surface energy, and surface morphology of polycarbonate and polycarbonate-TiO₂ nanocomposite. Structure of samples was determined by using X-ray diffraction analysis. In comparison with the reference sample, the samples’ structure did not change after plasma treatment. Surface properties of polycarbonate and polycarbonate-TiO₂ nanocomposite films were studied by X-ray photoelectron spectroscopy (XPS), contact angle measurement, atomic force microscopy (AFM), and Vickers microhardness tester. XPS analysis showed that the surface of samples became more oxidized due to plasma treatment. The water contact angle significantly decreased from 88° to 15° after plasma treatment. It was observed that the hardness of the nanocomposite films was not modified after plasma treatment.     

Plasma chemical synthesis. II. Effect of wall surface on the synthesis of ammonia

The plasma synthesis of ammonia was stuided at pressures of 1–5 torr and flow rates of up to 200 torr cm³ min^–1 using Pyrex and silver surfaces cooled to 77 K. The N conversion to ammonia was about 13% in experiments in which the afterglow was trapped on the Pyrex surface. By quenching the plasma rather than the afterglow, the percent N conversion could be doubled using the Pyrex surface and quadrupled using the silver surface. Increasing the hydrogen pressure and/or hydrogen discharge cleaning decreased the percent N conversion; nitrogen discharge conditioning had no significant effect. With increasing nitrogen flow rate the percent N conversion decreased linearly in the quenched plasma reaction on the silver surface, suggesting nitriding and reduction by hydrogen to form ammonia. The exponential decrease of the percent N conversion in the quenched afterglow reaction on the Pyrex surface is explained by the formation and/or dissociation of adsorbed N₂ determining the ammonia yield at 77 K.     

Surface modification of expanded poly(tetrafluoroethylene) by means of microwave plasma treatment for improvement of adhesion and growth of human endothelial cells

Surface modification of expanded poly(tetrafluoroethylene) (ePTFE) vascular prostheses was carried out by means of low pressure microwave plasma treatment. Hydrogen/ water vapour mixtures (containing excess of hydrogen) were shown to be efficient with respect to functionalization of PTFE. The results of treatments in dependence on various gas pressures and treatment times were detected by physicochemical techniques (zeta potential, wetting measurements) and by surface spectroscopy (XPS, ATR-FTIR). Furthermore, adhesion and proliferation of human endothelial cells from umbilical cord (HUVEC) onto modified ePTFE were observed in vitro in culture media. The results of this biological test of plasma treated materials correlate well with physicochemical surface parameters.     

Atmospheric‐pressure spin plasma jets processing of polymethylmethacrylate surface using experimental design methodology

Atmospheric‐pressure spin plasma jets (APSPJs) have been developed to induce surface modifications on polymethylmethacrylate (PMMA). In this study, an experimental design methodology was used to investigate the influence of process parameters [such as radio frequency (RF) power, processing gap, and number of treatment cycles] on the characteristics of PMMA surface treated by APSPJs. It was observed from the atomic force microscope (AFM) and scanning electron microscope (SEM) results that the surface morphology of PMMA treated by direct plasma is much rougher than that treated by remote plasma. The direct plasma used in APSPJs processing created a substantial amount of nanostructure grains. Moreover, the measured XPS results showed that the O/C ratios of the PMMA surface were substantially increased and subsequently water contact angle decreased on direct plasma treatment. This decrease is due to an increase of oxygen‐containing functional groups on the PMMA surface by the APSPJs processing. From the statistical analysis, the RF power and the processing gap were found to play a major role in enhancing the hydrophilic properties of PMMA surface. In contrast, the number of treatment cycles played only a secondary role in this case. Finally, in this study the APSPJs processing was demonstrated to be an effective method for surface modification of PMMA by controlling processing parameters during the treatment process. Copyright © 2009 John Wiley & Sons, Ltd.     

Manipulating the surface properties of polyacrylamide with nitrogen plasma

Polyacrylamide (PAL) was physically adsorbed onto a hydroxylated silicon surface to form a uniform PAL film and the up-top PAL thin film was treated by nitrogen (N₂) plasma for surface modification. The atomic composition of the modified surface of the PAL film adsorbed on silicon substrate was analyzed with Fourier Transform Infrared Spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The surface energy of PAL film was calculated from the data of contact angle of three-probe liquid. The FTIR results show an increase of peak intensity at 1214 cm⁻¹ (NH₂ stretch vibration) after the nitrogen plasma treatment, which confirms that the nitrogen was grafted to the PAL surface in the process of N₂-plasma treatment. The XPS results show that the ratio of relative intensity of N1s to O1s increases with increasing the plasma treatment time, which further affirms the formation of the amine groups on the PAL surface after the nitrogen plasma treatment. The surface tension increases with increasing the plasma grafting time. However, the surface energy decreases rapidly at the early stage when stored in air and approaches to an equilibrium value. It suggests that some physically-adsorbed ions and alkyl radicals on PAL surface can rapidly lose their activities. The increase of the surface tension of the plasma treated PLA films is due to the amine groups covalently grafted to PAL surface.     

Improvement of PBO fiber surface and PBO/PPESK composite interface properties with air DBD plasma treatment

The interface of fibrous composites is a key factor to the whole properties of the composites. In this study, the effects of air dielectric barrier discharge (DBD) plasma discharge power density on surface properties of poly(p‐phenylene benzobisoxazole) (PBO) fiber and the interfacial adhesion of PBO fiber reinforced poly(phthalazinone ether sulfone ketone) (PPESK) composite were investigated by several characterization methods, including XPS, SEM, signal fiber tensile strength, interlaminar shear strength, and water absorption. After the air DBD plasma treatment at a power density of 41.4 W/cm³, XPS analysis showed that some polar functional groups were introduced on the PBO fiber surface, especially the emergence of a new oxygen‐containing group (?O–C = O group). SEM observations revealed that the air DBD plasma treatment had a great influence on surface morphologies of the PBO fiber, while the signal fiber tensile strength results showed only a small decline of 5.9% for the plasma‐treated fiber. Meanwhile, interlaminar shear strength value of PBO/PPESK composite was increased to 44.71 MPa by 34.5% and water absorption of the composite decreased from 0.46% for the untreated specimen to 0.27%. The results showed that the air DBD plasma treatment can effectively improve the properties of the PBO fiber surface and the PBO/PPESK composite interface. Results obtained from the above analyses also showed that both the fiber surface and the composite interface performance would be reduced when an undue plasma discharge power density was applied. Copyright © 2011 John Wiley & Sons, Ltd.     

Biaxially Oriented Polypropylene (BOPP) Surface Modification by Nitrogen Atmospheric Pressure Glow Discharge (APGD) and by Air Corona

We compare two surface treatments of biaxially-oriented polypropylene (BOPP), which are carried out in the same dielectric barrier discharge (DBD) apparatus, namely air corona, and N₂ atmospheric pressure glow discharge (APGD). Changes in the surface energy and chemistry are investigated by contact angle measurements, by X-ray photoelectron spectroscopy (XPS) and by attenuated total reflectance infrared spectroscopy (ATR-FTIR). It is shown that N₂ APGD treatment leads to a higher surface energy than air corona treatment, and to the formation of mostly amine, amide, and hydroxyl functional groups at the polypropylene surface. Finally, hydrophobic recovery of the treated film is studied; for both treatment types, the increased surface energy is found to decay in a similar manner with increasing storage time after treatment.     

Modification of active carbon and zeolite as ammonia separation materials for a new de-NO<Subscript>x</Subscript> process with ammonia on-site synthesis

Ammonia adsorption and desorption behavior of surface treated active carbon (AC) and ion-exchanged Y zeolite, as ammonia separation and storage materials for a new de-NO_x process with ammonia on-site synthesis, were studied. Surface oxidized AC adsorbed more ammonia than non-treated AC due to ammonium ion formation. These materials were found to increase weak adsorption of ammonia and to be useful for pressure swing adsorption. Transition metal ion exchanged Y-zeolite adsorbed more ammonia (both weak and strong form) than Na Y-zeolite due to ammine complex formation. These materials adsorb and desorb more ammonia than treated AC when used for temperature swing adsorption.     

Plasma treatments of PET meshes for fuel-water separation applications

Sulphur hexafluoride (SF(6)) plasma treatments and hexamethyl disiloxane (HMDSO) plasma polymerisation were performed on poly(ethylene terephthalate) (PET) meshes and the resulting wettability against liquids having very different surface tensions were investigated at the light of a possible use of the materials in the fuel/water separation technology. Surface modification of the meshes owing to HMDSO plasma polymerisation followed by SF(6) plasma treatment was also investigated. Hydrophobic performances were characterised refining the conventional Wilhelmy dynamic contact angle (DCA) technique, using several reference solutions having the surface tension values between 20-72 mN/m. Measurements of the water intrusion pressure (WIP) of the treated samples were also performed. Surface modifications on the plasma treated meshes were investigated by means of Fourier-transform infrared absorption spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) analysis. SF(6) and HMDSO plasma treatments decrease the surface energy of the PET meshes, lowering the liquid surface tension at which the wettable/unwettable transition occurs and increasing the WIP. Moreover, an increase in hydrophobic performances was achieved with HMDSO plasma polymerisation followed by SF(6) plasma treatment.     

Plasma modified polymers as a support for enzyme immobilization II. Amines plasma

Polysulfone films were modified by ammonia, n-butylamine and allylamine remote plasma using various sample-to-plasma distances. Contact angle measurements, FTIR-ATR and XPS spectroscopy proved the presence of polar, including amine, groups on the modified surface. Presence of argon in the plasma environment made the plasma more stable and in most cases left the surface more hydrophilic but with a lower amount of nitrogen moieties on it. Glucose isomerase was successfully immobilized on the plasma-treated samples. Its activity correlates well with the concentration of C-N bonds on the surface. The highest enzyme activity was achieved for samples treated with allylamine/Ar plasma close to the plasma edge.     

A quantitative model for the surface restructuring of repeatedly plasma treated silicone rubber

Surface restructuring in ambient air of medical grade silicone rubber surfaces modified by repeated RF plasma treatments using various discharge gases including oxygen, argon, carbon dioxide and ammonia, was studied quantitatively. From advancing and receding water contact angle data, the fraction of the surface covered by mobile and immobile polar groups, and a characteristic time constant of the restructuring process were calculated. For argon plasma treated surfaces, the fraction of immobile polar groups increased with repeated plasma treatments, but remained relatively constant for samples repeatedly treated by an ammonia plasma. The use of an oxygen plasma only yielded incorporation of mobile polar groups but not of immobile polar groups. The increase in the restructuring time constants of argon and ammonia plasma treated silicone rubber with the number of plasma treatments suggested enhanced crosslinking of the silicone rubber by these plasmas. In contrast, when an oxygen plasma was repeatedly used, the restructuring time constant decreased suggesting chain cleavage by an oxygen plasma. Tentatively, the carbon dioxide plasma treatment of silicone rubber may initially (up to 3–4 repeated treatments) yield chain cleavage, while the occurrence of crosslinking is indicated after more repetitions.     

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.