A critical review of some fundamentals of surface chemistry revealed several areas in which current interpretations of data or interrelationships are erroneous or misleading.

Correct forms of fundamental equations interrelating surface energies, equilibrium contact angles and adhesion are given and plotted in a convenient, illuminating, dimension-less form. These curves provide a basis for comparing some recently published empirical equations with the fundamental ones showing that discrepancies result from changing values of the interaction parameter φ.

In this paper we describe the preparation and preliminary characterization of diblock copolymers with a low surface energy block. These polymers were prepared by modifying the isoprene block in styreneisoprene-based block copolymers with either short perfluoroalkyl or dimethyl siloxy ‘fingers’. Specifically, the diene block of a styrene-isoprene block copolymer containing a large proportion of pendent vinyl groups (1,2- and 3,4-isoprene) was reacted with the appropriate hydrosilane in the presence of non-acidic Pt catalyst. The degree of attachment of hydrosilane was as high as 50% of the pendent unsaturations. Pendent vinyl groups were converted more efficiently than pendent methyl vinyl groups. These block copolymers, when mixed with the styrene homopolymer, exhibited surface segregation behaviour which depended on both polymer molecular weight and processing conditions. The surface segregation properties of the resulting block copolymers were studied by a variety of techniques which include contact angle measurements, and either X-ray photoelectron spectroscopy or Rutherford backscattering spectrometry. Contact angles as high as 110° were measured for both the siloxane- and perfluoroalkane-modified materials.

The effect of plasma treatment on surface characteristics of polyethylene terephthalate films was investigated using helium and oxygenated-helium atmospheric plasmas. Sample exposure to plasma was conducted in a closed ventilation test cell inside the main plasma chamber with variable exposure times. The percent weigh loss of the samples showed an initial increase followed by decrease with extended exposure time, indicating a combined mechanism of etching and redeposition. The wettability as measured by the contact angle showed a sharp initial increase followed by a steady-state trend with increased exposure time, suggesting a change in surface functionality. Atomic force microscopy analysis revealed increase in surface roughness, as well as evidence of redeposition of etched volatiles. Functionality changes were measured using X-ray photoelectron spectroscopy and these changes were correlated to the new plasma-induced properties. © 2004 The Electrochemical Society. All rights reserved.

In order to investigate the effect of atmospheric pressure plasmas on adhesion between aramid fibers and epoxy, aramid fibers were treated with atmospheric pressure helium/air for 15, 30 and 60 s on a capacitively-coupled device at a frequency of 5.0 kHz and He outlet pressure of 3.43 kPa. SEM analysis at 10 000× magnification showed no significant surface morphological change resulted from the plasma treatments. XPS analysis showed a decrease in carbon content and an increase in oxygen content. Deconvolution analysis of C1s, N1s and O1s peaks showed an increase in surface hydroxyl groups that can interact with epoxy resin. The microbond test showed that the plasma treatment for 60 s increased interfacial shear strength by 109% over that of the control (untreated). The atmospheric pressure plasma increased single fiber tensile strength by 16-26%.

The maximum bubble pressure method for the determination of surface tension has been modified for use with thermally unstable, viscous, opaque polymers at high temperatures. A value of 35.1 dynes/cm. was obtained for nylon 66 at 285°C. The order of this value and those for other polymers has been compared with the values for simpler compounds. Further evidence for the persistence of association between polyamide molecules in the molten state is presented.

Ion bombardment of polymer surfaces is a method used in promoting metal/polymer adhesion. The adhesion of these multicomponent interfaces can be attributed to chemical bonding, physical bonding, or a combination of both. By evaluating the resistivity of thin films of Cr, TaSiz, Pd and Au deposited on polymer, the interfacial reactivity was determined, and the contribution due to chemical bonding identified. The adhesion strength of these interfaces, determined by peel strength measurements, increases with interfacial reactivity. Interfacial reactivity increases with the total energy of all the ions bombarding the polymer surface (dosage). Cr and TaSi₂ show extensive interfacial reactivity than noble Au and Pd.

A detailed X-ray photoelectron spectroscopy study of a plasma-modified polystyrene (PS) surface was carried out after N₂ plasma treatment. PS surfaces were found to be highly hydrophilic and reactive as it readily picks up oxygen giving rise to oxyfunctionalities on the surface. The plasma treatment also led to a slow chain scission with carboxyl, forming carbonate linkage.

Thermally stimulated currents (TSC) are studied in the temperature range between 30 and 130°C on positively corona-charged high-density polyethylene films. TSC spectra from these charged films strongly depend on the order of the processes: heat-treatment of the sample films prior to charging and vacuum deposition of metallic electrodes. They also depend on the electrode materials. Observed TSC behaviors are explained in terms of the thermal influence of the vacuum deposition of metallic electrodes. Charge stability of these charged films is also studied for samples with Al and Bi electrodes.

The invention provides a novel method for preventing bleeding of a plasticizer or other additive ingredients contained in a shaped article of a vinyl chloride-based resin composition on to the surface of the article by the treatment with low temperature plasma. Different from conventional procedures for the plasma treatment, much improved reliability and reproducibility as well as effectiveness are obtained by subjecting the article to intermittent exposure to the plasma atmosphere instead of continuous exposure. In the inventive method, the overall treatment time is an alternate sequence of exposure times, each being of the length of 0.001 second to 1000 seconds, and repose times, each being also of the length of 0.001 second to 1000 seconds. The gas for the plasma atmosphere is desirably an inorganic gas selected from the gases other than oxygenic gases, halogen containing gases and sulfur containing gases.

Ethylene-co-tetrafluoroethylene copolymer (ETFE) films were modified by four plasmas: direct and remote H2 plasmas and direct and remote O2 plasmas; and the hydrophobic recovery process of these plasma-modified surfaces was investigated using water contact angle measurements and angular XPS. The water contact angle measurements showed important aspects for the hydrophobic recovery process. (1) All plasma-modified ETFE surfaces, regardless of the kind and mode of plasmas, showed increases in the contact angle with increasing aging time. The increase continued for 5 days after finishing the plasma modification, and stopped after 5 days. (2) The plasmamodified surfaces after the aging process never reverted back to the same level of the contact angle as for the unmodified (original ETFE) surfaces. (3) The contact angle after the aging process was strongly dependent on to what plasma the ETFE surfaces were exposed in the modification. (4) The aging temperature influenced the contact angle value after the aging process. The angular XPS measurements also provided a detailed description of the chemical composition of the topmost layer. (1) The chemical composition at the topmost layer of the surfaces altered during the aging process. (2) CH₂-CH₂-CHF, and CH₂-CHF-CH₂ and CH₂-CH(OH)-CF₂ groups disappeared from the topmost layer during the aging process; and CH₂-CH₂-CH₂, and CH₂-CH₂-CF2 and CH₂-CH(OH)-CHF groups appeared at the topmost layer. (3) Such disappearance and appearance occurred on all plasma-modified surfaces regardless of the kind (H₂ or O₂ plasma) or mode (direct or remote plasma) of plasmas used for the modification. This may be due to segmental mobility of CH₂-CH₂-CH₂ sequences rather than of CF₂-CF₂-CF₂ sequences.

Poly(ethylene terephthalate) (PET) film surfaces were modified by argon (Ar), oxygen (O₂), hydrogen (H₂), nitrogen (N₂), and ammonia (NH₃) plasmas, and the plasma-modified PET surfaces were investigated with scanning probe microscopy, contact-angle measurements, and X-ray photoelectron spectroscopy to characterize the surfaces. The exposure of the PET film surfaces to the plasmas led to the etching process on the surfaces and to changes in the topography of the surfaces. The etching rate and surface roughness were closely related to what kind of plasma was used and how high the radio frequency (RF) power was that was input into the plasmas. The etching rate was in the order of O₂ plasma > H₂ plasma > N₂ plasma > Ar plasma > NH₃ plasma, and the surface roughness was in the order of NH₃ plasma > N₂ plasma > H₂ plasma > Ar plasma > O₂ plasma. Heavy etching reactions did not always lead to large increases in the surface roughness. The plasmas also led to changes in the surface properties of the PET surfaces from hydrophobic to hydrophilic; and the contact angle of water on the surfaces decreased. Modification reactions occurring on the PET surfaces depended on what plasma had been used for the modification. The O₂, Ar, H₂, and N₂ plasmas modified mainly CH₂ or phenyl rings rather than ester groups in the PET polymer chains to form CO groups. On the other hand, the NH₃ plasma modified ester groups to form CO groups. Aging effects of the plasma-modified PET film surfaces continued as long as 15 days after the modification was finished. The aging effects were related to the movement of CO groups in ester residues toward the topmost layer and to the movement of CO groups away from the topmost layer. Such movement of the CO groups could occur within at least 3 nm from the surface. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3727–3740, 2004
https://onlinelibrary.wiley.com/doi/abs/10.1002/polb.20234

Surface modification of poly(lactic acid) (PLA) film surface by Ar-plasma was investigated by contact angle measurements and XPS in order to answer the following two questions. (1) Could the Ar-plasma modify the PLA film surfaces? (2) What chemical reactions occurred on the film surfaces during the Ar-plasma treatment? The Ar-plasma treatment did not lead to hydrophilic modification of the PLA film surface, but to degradation reactions of the PLA film. Poor modification may be due to instability of the carbon radicals formed from CO bond scission in the PLA chains by the Ar-plasma.

A new surface modification technique for PET films is proposed. This technique, called VPI modification technique, is a combination of two processes: The first step involves the deposition of vinylphthalimide (VPI) on the PET film surfaces, followed by Ar plasma irradiation of the VPI-covered film surfaces. The VPI modification technique led to large increases in the N/C atom ratio on the PET film surfaces. On the VPI-modified PET film surface, a new N_ls peak containing two components due to amide groups as well as imide groups appeared. The C_ls signal for the VPI-modified PET film surface also showed a new component due to ketone groups. These changes indicate that VPI reacted with the PET film surfaces to form nitrogen-containing groups. VPI modification made PET film surfaces hydrophilic. The VPI-modified film surfaces showed a decrease in water contact angle from 73 degrees to 48–56 degrees.

Poly(phenylene sulfide) (PPS) films were modified by Ar, O₂, N₂ and NH₃ plasmas in order to improve their adhesion to copper metal. All four plasmas modified the PPS film surfaces, but the NH₃ plasma modification was the most effective in improving adhesion. The NH₃ plasma modification brought about large changes in the surface topography and chemical composition of the PPS film surfaces. The peel strength for the Cu/plasma-modified PPS film systems increased linearly with increasing surface roughness, R_a or R_rms, of the PPS film. The plasma modification also led to considerable changes in the chemical composition of the PPS film surfaces. A large fraction of phenylene units and a small fraction of sulfide groups in the PPS film surfaces were oxidized during the plasma modification process. Nitrogen functional groups also were formed on the PPS film surfaces. The NH₃ plasma modification formed S—H groups on the PPS film surfaces by reduction of S—C groups in the PPS film. Not only the mechanical interlocking effect but also the interaction of the S—H groups with the copper metal may contribute to the adhesion of the Cu/PPS film systems.

ETFE film surfaces were modified by CO₂, O₂ and Ar plasmas in order to form carboxylic groups on their surfaces, and the possibility that carboxylic groups could be predominantly introduced into the CH₂–CH₂ component rather than the CF₂–CF₂ component in the ETFE polymer chains was investigated from the viewpoint of chemical composition analyzed by XPS. The CO₂ plasma modification was more effective in the selectivity of the CH₂CH₂ component for the introduction of carboxylic groups, as well as in the concentration of the carboxylic groups formed on the film surfaces than O₂ plasma modification. The concentration of carboxylic groups formed on the ETFE film surfaces by the CO₂ plasma modification was 1.40–1.50 groups per 100 carbons. Topographical changes on the ETFE film surfaces by the plasma modification were also investigated by scanning probe microscopy.

The surface modification of polyethylene surfaces by NO-plasma irradiation was investigated from the point of view of the hydrophilicity and chemical composition. The hydrophilicity was evaluated from the advancing contact angle of water and the surface energy. The chemical composition of the modified surfaces was determined by diffuse reflectance Fourier transform infrared spectroscopy and XPS. NO-plasma irradiation for 5 min made the polyethylene surfaces hydrophilic. The advancing contact angle of water on the modified polyethylene surfaces reached 28 deg, and the surface energy was 57.6 mJ/m². The incorporation of oxygen and nitrogen moieties on the polyethylene surfaces occurred during the NO-plasma irradiation. The main oxygen moieties were carbonyl groups, hydroxyl groups, and ether linkages; the nitrogen moieties were amino groups. NO-plasma irradiation was more effective in improving the hydrophilicity than the O₂ plasma, N₂ plasma, or corona discharge treatment.

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
https://onlinelibrary.wiley.com/doi/abs/10.1002/app.10865

Surface modification of poly(tetrafluor oethylene) (PTFE) by NH₃-plasma treatment was investigated by means of contact angle measurement, XPS, and ATR FT/IR spectroscopy. The modified surfaces were adhesively bonded to nitril rubber. The NH₃-plasma irradiation made PTFE surfaces hydrophilic. The contact angle of water on the modified PTFE surface was 16 deg, and the surface energy was 62-63 mJ/m². The NH₃-plasma irradiation improved adhesion between PTFE and nitril rubber using a phenol-type adhesive. The peel strength of the joints reached 8.1 × 10³ N/m. Carbonyl and amido groups were created on PTFE surfaces by the NH₃-plasma irradiation. The mechanism of the improvement of adhesion by the NH₃-plasma irradiation is discussed.

To improve the adhesion between poly(p-phenylene terephthalamide), PPTA, fiber and silicone rubber, the surface modification of PPTA was investigated. Combining plasma treatment and coupling agent treatment with the silicone adhesive was found to be effective in improving adhesion. The combination process made the pull-out force of the PPTA yarn/silicone rubber composite 2.5 times higher, compared with the plasma treatment or the coupling agent treatment alone. The plasma treatment led to the elimination of carbonized layer from the PPTA yarn surface and the formation of oxygen functionalities including CO and CO groups. The elimination of the carbonaceous deposits from the PPTA surface and the interaction between the silicone adhesive and the oxygen functionalities created by the plasma treatment contribute to the improvement of adhesion with silicone rubber.

Kapton films were treated with seven plasmas: Ar-, N₂-, O₂-, CO-, CO₂-, NO-, and NO₂- plasmas. Surface properties and chemical composition of the plasma-treated Kapton films were investigated from the contact angle measurement, and the IR and XPS spectra. The plasmas, especially NO- and NO₂-plasma, made the Kapton film surface hydrophilic. The XPS and IR spectra showed that the plasma led to the modification of the imide groups in the Kapton film to secondary amide and carboxylate groups.

Surface modification of poly(ethylene terephthalate) (PET) film by an argon (Ar) plasma was investigated as a function of the distance from the Ar plasma zone. Changes in distance between the PET film and the Ar plasma zone had a strong influence on the surface modification of the film. The direct Ar plasma treatment (distance between the PET film and Ar plasma zone = 0 cm) was effective in hydrophilic surface modification, but heavy etching reactions occurred during the modification. On the other hand, the remote Ar plasma treatment (distance between the PET film and Ar plasma zone = 80 cm) modified the PET film surfaces to be hydrophilic without heavy etching reactions, although the hydrophilicity of the PET was lower than that by the direct Ar plasma. The remote Ar plasma treatment was distinguished from the direct Ar plasma treatment from the viewpoint of degradation reactions. The remote Ar plasma treatment rather than the direct Ar plasma treatment was an adequate procedure for surface modification and caused less polymer degradation on the film surface. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 808–815, 2001
https://onlinelibrary.wiley.com/doi/10.1002/1097-4628(20010131)79:5%3C808::AID-APP50%3E3.0.CO;2-B

FEP sheets were modified with a remote hydrogen plasma and the effects of the modification on the adhesion between copper metal and FEP sheets were investigated. The remote hydrogen plasma treatment is able to make FEP surfaces hydrophilic. In the remote hydrogen plasma treatment process, both defluorination and oxidation occur on the FEP surface. The oxidation reactions on the FEP surface form oxygen functional groups such as CO and CO groups. Modification of the FEP surface by the remote hydrogen plasma is effective in improving the adhesion of copper metal. The peel strength of the Cu/FEP system increased form 0 to 195 mN/5 mm, and the failure mode changed from the Cu metal/FEP polymer interface to within the FEP polymer layer. Remote hydrogen plasma treatment may be a preferable pretreatment of the FEP surface for adhesion with copper metal.

To draw a relationship between surface concentration of the siloxane segment and adhesion performance, surface properties of the polydimethylsiloxane—poly(methyl methacrylate) block copolymers(PDMS-b-PMMA) prepared via poly(azo-containing siloxaneamide)s and their PMMA blends have been studied by measurements of FT-IR spectra, water contact angle, ESCA spectra and 180° peel strength toward pressure-sensitive adhesive tape. The water contact angles of the chloroform-cast blend films increased abruptly with siloxane bulk concentrations, or siloxane contents, particularly, on the air-side surfaces to reach almost 100° in low siloxane content. A marked increase of the contact angle was observed in the blends containing siloxane chain length (SCL) of longer than 2000. ESCA data evidently confirmed for these blend systems that the siloxane segments with low surface energy were accumulated or enriched mainly on the air-side surface, and that, on the other hand, polar PMMA segments with high surface energy were oriented to the glass-side surface and the inside of the films. This surface accumulation behavior of the siloxane segments reflected the 180° peel strength, as a measure of adhesion performance. The water contact angle and 180° peel strength were unequivocally correlated to the siloxane surface concentration estimated from ESCA data. Conversely, in the compression-molded blend films made by a hydraulic press between a Teflon and a stainless steel plate, the extent of surface accumulation of the PDMS segment was lower than that of the chloroform-cast films, suggesting lower degree of segment migration in hot-press films, probably due to substrate surface energy and lower relaxation in the blend melts.