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2549. Lopez-Santos, C., F. Yubero, J. Cotrino, and A.R. Gonzalez-Elipe, “Surface functionalization, oxygen depth profiles, and wetting behavior of PET treated with different nitrogen plasmas,” Applied Material Interfaces, 2, 980-990, (2010).

Polyethylene terephthalate (PET) plates have been exposed to different nitrogen containing plasmas with the purpose of incorporating nitrogen functional groups on its surface. Results with a dielectric barrier discharge (DBD) at atmospheric pressure and a microwave discharge (MW) at reduced pressure and those using an atom source working under ultrahigh vacuum conditions have been compared for N2 and mixtures Ar + NH3 as plasma gases. The functional groups have been monitored by X-ray Photoemission Spectroscopy (XPS). Nondestructive oxygen and carbon depth profiles for the plasma treated and one month aged samples have been determined by means of the nondestructive Tougaard’s method of XPS background analysis. The surface topography of the treated samples has been examined by Atomic Force Microscopy (AFM), while the surface tension has been determined by measuring the static contact angles of water and iodomethane. It has been found that the DBD with a mixture of Ar+NH3 is the most efficient treatment for nitrogen and amine group functionalization as determined by derivatization by reaction with chlorobenzaldehyde. It is also realized that the nitrogen functional groups do not contribute significantly to the observed increase in surface tension of plasma treated PET.

1888. Praschak, D., T. Bahners, and E. Schollmeyer, “PET surface modifications by treatment with monochromatic excimer UV lamps,” Applied Physics A: Materials Science & Processing, 66, 69-75, (Jan 1998).

2505. Borcia, C., G. Borcia, and N. Dumitrascu, “Relating surface modification to polymer characteristics,” Applied Physics A: Materials Science & Processing, 90, 507-515, (2008).

This paper aims to provide an analysis of the correlation between various plasma effects on polymers exposed to atmospheric pressure plasma. The relationship linking the surface polarity, the chemical structure and composition and the crystalline/amorphous phase contribution in the surface modification mechanisms of plasma-exposed polymers is explored. Different polymers were chosen comprising of various structures, functionality, degree of oxidation, crystallinity, and were treated under a particular experimental configuration, and dielectric barrier discharge-type. The plasma parameters and the treatment settings are observed, in relation to relevant surface properties, as surface energy components, surface topography, structural changes and chemical composition, under conditions where the gaseous environment chosen, He-N2, allows complex surface modification, by combined functionalisation and crosslinking.

434. Chang, C.-A., “Enhanced Cu-teflon adhesion by presputtering treatment: effect of surfcae morphology changes,” Applied Physics Letters, 51, 1236-1238, (1987).

1345. Briggs, D., “Surface treatments for polyolefins,” in Surface Analysis and Pretreatment of Plastics and Metals, Brewis, D.M., ed., 199-226, Applied Science, 1982.

1476. Brewis, D.M., ed., Surface Analysis and Pretreatment of Plastics and Metals, Applied Science, Feb 1982.

1509. Briggs, D., “Chemical analysis of polymer surfaces,” in Surface Analysis and Pretreatment of Plastics and Metals, Brewis, D.M., ed., 73-94, Applied Science, Feb 1982.

1510. Rance, D.G., “Thermodynamics of wetting: From its molecular basis to technological application,” in Surface Analysis and Pretreatment of Plastics and Metals, Brewis, D.M., ed., 121-152, Applied Science, Feb 1982.

1511. Dahm, R.H., “Surface treatments for polytetrafluoroethylene,” in Surface Analysis and Pretreatment of Plastics and Metals, Brewis, D.M., ed., 227-254, Applied Science, Feb 1982.

1349. Dukes, W.A., and A.J. Kinloch, “Preparing low-energy surfaces for bonding,” in Developments in Adhesives, Vol. 1, Wake, W.C., ed., Applied Science Publishers, 1977.

2916. Siedelmann, L.J.W., J.W. Bradley, M. Ratova, J. Hewitt, J. Moffat, and B. Kelly, “Reel-to-reel atmospheric pressure dielectric barrier discharge (DBD) plasma treatment of polypropylene films,” Applied Sciences, 7, 337+, (Mar 2017).

Atmospheric pressure plasma treatment of the surface of a polypropylene film can significantly increase its surface energy and, thereby improve the printability of the film. A laboratory-scale dielectric barrier discharge (DBD) system has therefore been developed, which simulates the electrode configuration and reel-to-reel web transport mechanism used in a typical industrial-scale system. By treating the polypropylene in a nitrogen discharge, we have shown that the water contact angle could be reduced by as much as 40° compared to the untreated film, corresponding to an increase in surface energy of 14 mNm−1. Ink pull-off tests showed that the DBD plasma treatment resulted in excellent adhesion of solvent-based inks to the polypropylene film.

1364. Chang, K., and R.K. Force, “Time-resolved pyrene fluorescence for determination of polymer surface polarity: correlations with surface tension,” Applied Spectroscopy, 49, 211-215, (Feb 1995).

2088. Onyiriuka, E.C., L.S. Hersh, and W. Hertl, “Surface modification of polystyrene by gamma-radiation,” Applied Spectroscopy, 44, 808-811, (1990).

38. Breuer, J., S. Metev, G. Sepold, et al, “Laser-induced photochemical adherence enhancement,” Applied Surface Science, 46, 336-341, (1990).

45. Burrell, M.C., and J.J. Chera, “Surface analysis of BPA-polycarbonate/poly(butylene terephthalate) blends by x-ray photoelectron spectroscopy,” Applied Surface Science, 35, 110-120, (1988).

262. Occhiello, E., M. Morra, F. Garbassi, and J. Bargon, “On the application of XPS, SSIMS, and QCM to study the surface of a CF4/O2 plasma treated polycarbonate,” Applied Surface Science, 36, 285-295, (1989).

265. Occhiello, E., M. Morra, F. Garbassi, D. Johnson, and P. Humphrey, “SSIMS studies of hydrophobic recovery: oxygen plasma treated PS,” Applied Surface Science, 47, 235-242, (1991).

813. Borcia, G., C.A. Anderson, and N.M.D. Brown, “The surface oxidation of selected polymers using an atmospheric pressure air dielectric barrier discharge: Part II,” Applied Surface Science, 225, 186-197, (Mar 2004).

In this paper, we report and discuss the results of the surface treatment, using an atmospheric pressure dielectric barrier discharge (DBD), of selected polymer films which have no bonded oxygen in their intrinsic structures. Contact angle, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) data are presented with respect to post-treatment characterisation and the dependence of these outcomes on the salient processing variables: energy dissipated, exposure duration and inter-electrode gap. Under the treatment conditions used, remarkably uniform treatment and markedly stable modified surface properties result from the test surfaces exposed to the discharge, even at transit speeds simulating those associated with continuous on-line processing. The DBD system thus described, provides chemically mild and mechanically non-destructive means of altering surface properties, targeting improved surface characteristics and potentially better application performance.

1293. Neagu, E, and R. Neagu, “Polymer surface treatment for improvement of metal-polymer adhesion,” Applied Surface Science, 72, 231-234, (Nov 1993).

1295. Laurens, P., M. Ould Bouali, F. Meducin, and B. Sadras, “Characterization of modifications of polymer surfaces after excimer laser treatments below the ablation threshold,” Applied Surface Science, 154-155, 211-216, (2000).

1363. Borcia, G., C.A. Anderson, and N.M.D. Brown, “The surface oxidation of selected polymers using an atmospheric pressure air dielectric barrier discharge. Part I,” Applied Surface Science, 221, 203-214, (Jan 2004).

In this paper, we report and discuss the results of the surface treatment, using an atmospheric pressure dielectric barrier discharge (DBD), of selected polymer films which have no bonded oxygen in their intrinsic structures. Contact angle, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) data are presented with respect to post-treatment characterisation and the dependence of these outcomes on the salient processing variables: energy dissipated, exposure duration and inter-electrode gap. Under the treatment conditions used, remarkably uniform treatment and markedly stable modified surface properties result from the test surfaces exposed to the discharge, even at transit speeds simulating those associated with continuous on-line processing. The DBD system thus described, provides chemically mild and mechanically non-destructive means of altering surface properties, targeting improved surface characteristics and potentially better application performance.

1367. Cui, N.Y., and N.M.D. Brown, “Modification of the surface properties of a polypropylene (PP) film using an air dielectric barrier discharge plasma,” Applied Surface Science, 189, 31-38, (Apr 2002).

1373. Hochart, F., J. Levalois-Mitjaville, R. De Jaeger, L. Gengembre, J. Grimblot, “Plasma surface treatment of poly (acrylonitrile) films by fluorocarbon compounds,” Applied Surface Science, 142, 574-578, (Apr 1999).

1640. Cui, N.-Y., C.A. Anderson, B.J. Meenan, and N.M.D. Brown, “Surface oxidation of a Melinex 800 PET polymer material modified by an atmospheric dielectric barrier discharge studied using X-ray photoelectron spectroscopy and contact angle measurement,” Applied Surface Science, 253, 3865-3871, (Feb 2007).

Surface properties of a Melinex 800 PET polymer material modified by an atmospheric-pressure air dielectric barrier discharge (DBD) have been studied using X-ray photoelectron microscopy (XPS) and contact angle measurement. The results show that the material surface treated by the DBD was modified significantly in chemical composition, with the highly oxidised carbon species increasing as the surface processing proceeds. The surface hydrophilicity was dramatically improved after the treatment, with the surface contact angle reduced from 81.8° for the as-supplied sample to lower than 50° after treatment. Post-treatment recovery effect is found after the treated samples were stored in air for a long period of time, with the ultimate contact angles, as measured, being stabilised in the range 58–69° after the storage, varying with the DBD-treatment power density. A great amount of the C–O type bonding formed during the DBD treatment was found to be converted into the CDouble BondO type during post-treatment storage. A possible mechanism for this bond conversion has been suggested.

1645. Wang, K., W. Wang, D. Yang, Y. Huo, and D. Wang, “Surface modification of polypropylene non-woven fabric using atmospheric nitrogen dielectric barrier discharge plasma,” Applied Surface Science, 256, 6859-6864, (Sep 2010).

In this paper, a dielectric barrier discharge operating in nitrogen at atmospheric pressure has been used to improve the surface hydrophilic property of polypropylene (PP) non-woven fabric. The changes in the hydrophilic property of the modified PP samples are investigated by the contact angle measurements and the variation of water contact angle is obtained as a function of the energy density; micrographs of the PP before and after plasma treatment are observed by scanning electron microscopy (SEM) and the chemical composition of the PP surface before and after plasma treatment is also analyzed by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The results show that the surface hydrophilic property of the PP samples is greatly improved with plasma treatment for a few seconds, as evidenced by the fact that the contact angle of the treated PP samples significantly decreases after plasma treatment. The analysis of SEM shows that the surface roughness of the treated PP samples increases due to bonding and etching in plasma processing. The analyses of FTIR and the C1s peak in the high-resolution XPS indicate that oxygen-containing and nitrogen-containing polar functional groups are introduced into PP surface in plasma processing. It can be concluded that the surface hydrophilic property of the modified PP samples has been obviously improved due to the introduction of oxygen-containing and nitrogen-containing polar groups and the increase of the surface roughness on the PP surface.

1734. Seidel, C., H. Kopf, B. Gotsmann, T. Vieth, H. Fuchs, and K. Reihs, “Ar plasma treated and Al metallised polycarbonate: an XPS, mass spectroscopy and SFM study,” Applied Surface Science, 150, 19-33, (1999).

1907. Elsner, C., M. Lenk, L. Prager, and R. Mehnert, “Windowless argon excimer source for surface modification,” Applied Surface Science, 252, 3616-3624, (Mar 2006).

The article describes applications of a novel windowless argon excimer source for surface modification. Experimental results on etching of polymeric surfaces, degradation of organic surface residues, surface activation and modification of gas permeability and selectivity of polymeric membranes are presented. Moreover, radical formation from the excimer source and surface curing of liquid acrylates are examined. Typical treatment times are in the range of minutes for photolytic decomposition effects and seconds for UV curing effects. The surface modification effects induced by the argon excimer source were analysed by XPS, ESR, IR-spectroscopy, white light reflection spectroscopy, scanning electron microscopy, micro-hardness and permeation measurements.

1980. Frerichs, H., J. Stricker, D.A. Wesner, and E.W. Kreutz, “Laser-induced surface modification and metallization of polymers,” Applied Surface Science, 86, 405-410, (Feb 1995).

2068. Guruvenket, S., G. Mohan Rao, M. Komath, and A.M. Raichur, “Plasma surface modification of polystyrene and polyethylene,” Applied Surface Science, 236, 278-284, (Sep 2004).

Polystyrene (PS) and polyethylene (PE) samples were treated with argon and oxygen plasmas. Microwave electron cyclotron resonance (ECR) was used to generate the argon and oxygen plasmas and these plasmas were used to modify the surface of the polymers. The samples were processed at different microwave powers and treatment time and the surface modification of the polymer was evaluated by measuring the water contact angle of the samples before and after the modification. Decrease in the contact angle was observed with the increase in the microwave power for both polystyrene and polyethylene. Plasma parameters were assessed using Langmuir probe measurements. Fourier transform infrared spectroscopy showed the evidence for the induction of oxygen-based functional groups in both polyethylene and polystyrene when treated with the oxygen plasma. Argon treatment of the polymers showed improvement in the wettability which is attributed to the process called as CASING, on the other hand the oxygen plasma treatment of the polymers showed surface functionalization. Correlation between the plasma parameters and the surface modification of the polymer is also discussed.

2091. Sheng, E., I. Sutherland, D.M. Brewis, and R.J. Heath, “An X-ray photoelectron spectroscopy study of flame treatment of polypropylene,” Applied Surface Science, 78, 249-254, (1994).

2423. Gomathi, N., and S. Neogi, “Surface modification of polypropylene using argon plasma: Statistical optimization of the process variables,” Applied Surface Science, 255, 7590-7600, (2009).

Low pressure plasma treatment using radiofrequency (rf) discharge of argon gas was employed to improve the hydrophilicity of polypropylene. The effects of argon plasma on the wettability, surface chemistry and surface morphology of polypropylene were studied using static contact angle measurements, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Increase in surface energy of polypropylene was observed as a result of argon plasma treatment. SEM and AFM images revealed the increased surface roughness. A set of identified process variables (rf power, pressure, argon flow rate and time) were used in this study and were optimized using central composite design (CCD) of response surface methodology (RSM). A statistical model was developed to represent the surface energy in terms of the process variables mentioned above. Accuracy of the model was verified and found to be high.

2546. Kurdi, J., H. Ardelean, P. Marcus, P. Jonnard, and F. Arefi-Khonsari, “Adhesion properties of aluminum-metallized/ammonia plasma-treated polypropylene: Spectroscopic analysis (XPS, EXES) of the aluminum/polypropylene interface,” Applied Surface Science, 189, 119-128, (Apr 2002).

2555. Pykonen, M., H. Sundqvist, J. Jarnstrom, O.-V. Kaukoniemi, and M. Tuominen, “Effects of atmospheric plasma activation on surface properties of pigment-coated and surface-sized papers,” Applied Surface Science, 255, 3217-3229, (Dec 2008).

Pigment-coated, surface-sized, and surface-sized copy papers were treated with conventional corona, experimental pilot-scale plasma and laboratory-scale plasma. All the treatments increased the surface energy and oxidized the surface. The changes in the surface chemistry depended on treatment time and composition of the substrate surface. It seems that plasma especially oxidizes the long polymer chains, such as surfactants and other paper chemicals, on the surface of the paper. The ToF-SIMS distribution maps indicated that the pilot-scale treatment led to an uneven CO+ group distribution, whereas laboratory scale treatment gave a more even distribution of CO+ groups. In addition to chemical changes, topographical changes due to plasma treatment were detected. The RMS roughness increased for pigment-coated paper, whereas plasma treatment induced small nodules between the paper pigment particles with pigmented and surface-sized paper. The increase in roughness was also found to increase the wettability. This serves as a demonstration of roughness-induced increase of surface energy of the samples.

2563. Wang, C., J.-R. Chen, and R. Li, “Studies on surface modification of poly(tetrafluoroethylene) film by remote and direct Ar plasma,” Applied Surface Science, 254, 2882-2888, (Feb 2008).

Poly(tetrafluoroethylene) (PTFE) surfaces are modified with remote and direct Ar plasma, and the effects of the modification on the hydrophilicity of PTFE are investigated. The surface microstructures and compositions of the PTFE film were characterized with the goniometer, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Results show that the remote and direct plasma treatments modify the PTFE surface in morphology and composition, and both modifications cause surface oxidation of PTFE films, in the forming of some polar functional groups enhancing polymer wettability. When the remote and direct Ar plasma treats PTFE film, the contact angles decrease from the untreated 108–58° and 65.2°, respectively. The effect of the remote Ar plasma is more noticeable. The role of all kinds of active species, e.g. electrons, ions and free radicals involved in plasma surface modification is further evaluated. This shows that remote Ar plasma can restrain the ion and electron etching reaction and enhance radical reaction.

2615. Gururaj, T., R. Subasri, K.R.C. Soma Raju, and G. Padmanabham, “Effect of plasma pretreatment on adhesion and mechanical properties of UV-curable coatings on plastics,” Applied Surface Science, 257, 4360-4364, (Feb 2011).

An attempt was made to study the effect of plasma surface activation on the adhesion of UV-curable sol-gel coatings on polycarbonate (PC) and polymethylmethacrylate (PMMA) substrates. The sol was synthesized by the hydrolysis and condensation of a UV-curable silane in combination with Zr-n-propoxide. Coatings deposited by dip coating were cured using UV-radiation followed by thermal curing between 80 °C and 130 °C. The effect of plasma surface treatment on the wettability of the polymer surface prior to coating deposition was followed up by measuring the water contact angle. The water contact angle on the surface of as-cleaned substrates was 80° ± 2° and that after plasma treatment was 43° ± 1° and 50° ± 2° for PC and PMMA respectively. Adhesion as well as mechanical properties like scratch resistance and taber abrasion resistance were evaluated for coatings deposited over plasma treated and untreated surfaces.

2858. Zdziennicka, A., K. Szymczyk, J. Krawczyk, and B. Janczuk, “Some remarks on the solid surface tension determination from contact angle measurements,” Applied Surface Science, 405, 88-101, (May 2017).

2970. Lai, J., B. Sunderland, J. Xue, et al, “Study on hydrophilicity of polymer surfaces improved by plasma treatment,” Applied Surface Science, 252, 3375-3379, (Mar 2006).

Surface properties of polycarbonate (PC), polypropylene (PP), polyethylene terephthalate (PET) samples treated by microwave-induced argon plasma have been studied with contact angle measurement, X-ray photoelectron spectroscopy (XPS) and scanned electron microscopy (SEM). It is found that plasma treatment modified the surfaces both in composition and roughness. Modification of composition makes polymer surfaces tend to be highly hydrophilic, which mainly depended on the increase of ratio of oxygen-containing group as same as other papers reported. And this experiment further revealed that CDouble BondO bond is the key factor to the improvement of the hydrophilicity of polymer surfaces. Our SEM observation on PET shown that the roughness of the surface has also been improved in micron scale and it has influence on the surface hydrophilicity.

2978. Pandiyaraj, K.N., V. Selvarajan, R.R. Deshmukh, and C. Gao, “Modification of surface properties of polypropylene (PP) film using DC glow discharge air plasma,” Applied Surface Science, 255, 3965-3971, (Jan 2009).

The industrial use of polypropylene (PP) films is limited because of undesirable properties such as poor adhesion and printability. In the present study, a DC glow discharge plasma has been used to improve the surface properties of PP films and make it useful for technical applications. The change in hydrophilicity of modified PP film surface was investigated by contact angle (CA) and surface energy measurements as a function of exposure time. In addition, plasma-treated PP films have been subjected to an ageing process to determine the durability of the plasma treatment. Changes in morphological and chemical composition of PP films were analyzed by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The improvement in adhesion was studied by measuring T-peel and lap shear strength. The results show that the surface hydrophilicity has been improved due to the increase in the roughness and the introduction of oxygen-containing polar groups. The AFM observation on PP film shows that the roughness of the surface increased due to plasma treatment. Analysis of chemical binding states and surface chemical composition by XPS showed an increase in the formation of polar functional groups and the concentration of oxygen content on the plasma-processed PP film surfaces. T-peel and lap shear test for adhesion strength measurement showed that the adhesion strength of the plasma-modified PP films increased compared with untreated films surface.

2998. Trantidou, T., T. Prodromakis, and C. Toumazou, “Oxygen plasma induced hydrophilicity of parylene-C thin films,” Applied Surface Science, 261, 43-51, (Nov 2012).

This paper investigates the surface modification of Parylene-C thin films under various oxygen plasma treatment conditions, such as power intensity (50:400 W) and exposure time (1:20 min). The extent of hydrophilicity was investigated through contact angle measurements, and correlations between treatment parameters, film thickness, restoration of hydrophobicity and etching rates were experimentally established. We also demonstrate the selective modification of Parylene-C films, facilitating distinct hydrophilic and hydrophobic areas with μm-resolution that can be exploited in self-alignment applications.

3000. Thompson, R., D. Austin, C. Wang, A. Neville, and L. Lin, “Low-frequency plasma activation of nylon 6,” Applied Surface Science, 544, (Apr 2021).

In the study reported in this paper, a series of reproducible conditions were employed to uniformly functionalize nylon 6 surfaces using a commercially available, low-frequency (40 kHz), low-pressure plasma system, utilizing oxygen plasma as a reactive gas. Initially, the plasma-treated samples were investigated using static contact angle measurements, showing a progressive increase in wettability with increasing plasma activation time between 10 and 40 s. Such an increase in wettability (and therefore increase in adhesive capabilities of the surfaces) was attributed to the creation of surface C-OH, C=O, and COOH groups. These surface-chemical modifications were characterized using x-ray photoelectron spectroscopy (XPS) and static secondary ion mass spectrometry (SSIMS). Surface radical densities were also shown to increase following plasma activation, having been quantified using a radical scavenging method based on the molecule 2,2-diphenyl-1-picrylhydrazyl (DPPH). The samples were imaged and analyzed using scanning electron microscopy (SEM) and atomic force microscopy (AFM), to confirm that there had been no detectable alteration to the surface roughness or morphology. Additionally, the “hydrophobic recovery” or “ageing” of the activated polymer samples, post-plasma treatment, was also investigated in terms of wettability and surface-chemistry, with the wettability of the sample surfaces decreasing over time due to a reduction in surface-oxygen concentration.

 

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