The effects of corona-discharge treatment (CDT) of commercial polyethylene (PE) Linear low-density PE (LLDPE) were studied with special emphasis on the heat-seal behavior of treated films. A range of treat levels, representative of those used in industry, was obtained by varying the applied power to a commercial, on-line treater. Film surfaces were characterized by XPS and wetting-tension measurements. The primary effect of CDT on the heat-sealing behavior of LLDPE films is a transition in the failure mode of heat seals from a normal tearing or inseparable bond to a peelable seal. In addition, CDT increases the seal initiation temperature 5–17°C and decreases the plateau seal strength 5–20% as the treat level, or wetting tension, increases from 31 to 56 dynes/cm. These effects are attributed to cross-linking during corona treatment, which restricts polymer mobility near the surface and limits the extent of interdiffusion and entaglements across the seal interface. Results of heat-sealing studies with electron-beam-irradiated PE, chemically oxidized PE, and CDT polypropylene (PP) provide indirect evidence for the proposed surface cross-linking mechanism. The effect of commercial levels of slip additives on the heat-seal behavior was also investigated. copy; 1994 John Wiley & Sons, Inc.
https://onlinelibrary.wiley.com/doi/abs/10.1002/app.1994.070510113

The corona discharge technique was explored as a means of forming chemically active sites on a low-density polyethylene (LDPE) film surface. The active species thus prepared at atmospheric pressure in air was exploited to subsequently induce copolymerization of 2-hydroxyethyl methacrylate (HEMA) onto LDPE film in aqueous solution. The results showed that with the corona discharge voltage, reaction temperature, and inhibitor concentration in the reaction solution the grafting degree increased to a maximum and then decreased. As the corona discharge time, reaction time, and HEMA concentration in the reaction solution increased, the grafting degree increased. With reaction conditions of a 5 vol % HEMA concentration, 50°C copolymerization temperature, and a 2.0-h reaction time, the degree of grafting of the LDPE film reached a high value of 158.0 μg/cm² after treatment for 72 s with a 15-kV voltage at 50 Hz. Some characteristic peaks of the grafted LDPE came into view at 1719 cm⁻¹ on attenuated total reflectance IR spectra (CO in ester groups) and at 531 eV on electron spectroscopy for chemical analysis (ESCA) spectra (O_1s). The C_1s core level ESCA spectrum of HEMA-grafted LDPE showed two strong peaks at ∼286.6 eV (CO from hydroxyl groups and ester groups) and ∼289.1 eV (OCO from ester groups), and the C atom ratio in the CO groups and OCO groups was 2:1. The hydrophilicity of the grafted LDPE film was remarkably improved compared to that of the ungrafted LDPE film. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2881–2887, 2001
https://onlinelibrary.wiley.com/doi/abs/10.1002/app.1738

A starch-based biodegradable (BD) low density polyethylene (LDPE) film can be directly printable without any corona treatment, unlike virgin LDPE film. Such a film shows poor adhesion and nail scratch resistance of the ink on the printed area of the film. In order to increase the adhesion and nail scratch resistance of the ink on the printed BD film, grafting of acrylonitrile onto the BD film is carried out. The polyacrylonitrile grafted BD film shows better adhesion, nail scratch resistance, and printability. The printability of the polyacrylonitrile grafted BD film is comparable to the conventional corona treated LDPE film. The extent of printability is a function of the surface smoothness, as well as the optimum percentage of grafting on the biodegradable film. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1273–1277, 2001
https://onlinelibrary.wiley.com/doi/abs/10.1002/1097-4628(20010214)79:7%3C1273::AID-APP150%3E3.0.CO;2-L

The interfacial shear strength of an ultrahigh molecular weight (UHMW) polyethylene (PE) fiber/epoxy-resin system was greatly improved by the corona-discharge treatment of the fiber. The UHMW PE-fiber/epoxy-resin composite was prepared with corona-discharge-treated UHMW PE fiber. The mechanical properties of the composite sheet were determined by tensile testing. The tensile strength of the composite was also very much improved. However, the tensile strength of the composite was about one-half of the theoretical strength. This result was due to the molecular degradation of the PE-fiber surface caused by surface modification. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1162–1168, 2001
https://onlinelibrary.wiley.com/doi/abs/10.1002/1097-4628%2820010214%2979%3A7%3C1162%3A%3AAID-APP20%3E3.0.CO%3B2-Y

Polyethylene, polypropylene, poly(vinyl fluoride) (Tedlar), polystyrene, nylon 6, poly(ethylene terephthalate) (Mylar), polycarbonate, cellulose acetate butyrate, and a poly(oxymethylene) copolymer were treated with activated helium and with activated oxygen. Mechanical strengths of adhesive-bonded specimens prepared from treated and from untreated coupons were compared. Polyethylene (PE) and polypropylene (PP) showed the greatest increases in bond strength. Oxygen and helium were both effective with polyethylene, but polypropylene showed no improvement when treated with activated helium. The results with excited helium parallel the effects of ionizing radiation on these two polymers, as does the appearance of unsaturation bands in the infrared (965 cm⁻¹ in PE, and 887 and 910 cm⁻¹ in PP). Active nitrogen produced excellent bond strength with polyethylene but not with polypropylene. Of the remaining polymers examined, Tedlar, polystyrene, and nylon 6 showed the greatest improvement in bondability after treatment, and Mylar showed moderate improvement. Polycarbonate, cellulose acetate butyrate, and the poly(oxymethylene) copolymer gave approximately two-fold increases in lap-shear bond strength. In several cases, significant differences in response to time of treatment and type of excited gas were found.

Contact angle measurements with three different liquids were performed on: (i) butyl rubber PB 101-3 (Polysar Ltd.) and (ii) Dow Corning 236 dispersion. Contact angles were measured at different temperatures within the range from 23°C (room temperature) to 120°C. The surface tensions, γsv, of the polymeric coatings at each temperature were calculated from the contact angles. The temperature coefficients of the surface tensions, d_γsv/dT, i.e., the surface entropies, were established for the temperature range covered.

Low-rate dynamic contact angles on poly(t-butyl methacrylate) (PtBMA) were measured by an automated axisymmetric drop shape analysis profile (ADSA-P). The solid surface tension of PtBMA is calculated to be 18.1 mJ/m², with a 95% confidence limit of ±0.6 mJ/m². This value was compared to previous results with different homopolymeric polymethacrylates [poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), and poly(n-butyl methacrylate) (PnBMA)] and with copolymeric polymethacrylates {poly(methyl methacrylate/ethyl methacrylate, 30/70) [P(MMA/EMA, 30/70)] and poly(methyl methacrylate/n-butyl methacrylate) [P(MMA/nBMA)]}. It was found that increasing length and size of the alkyl side chain decrease the solid surface tension, as expected. Comparison with pure alkyl surfaces suggests that the surface tension of PtBMA is dominated by the very hydrophobic t-butyl group. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2493–2504, 2000
https://onlinelibrary.wiley.com/doi/abs/10.1002/1097-4628%2820000912%2977%3A11%3C2493%3A%3AAID-APP19%3E3.0.CO%3B2-H

Poly(tetrafluoroethylene) and a fluoroethylene copolymer were surface treated with a 2.45-GHz microwave plasma to enhance their adhesion to a vinylester thermoset. The plasmas were generated with an inert gas (Ar) and with reactive gases (H₂, O₂, and N₂). The lap-joint shear stress was measured on fluoropolymer samples glued with the vinylester. In general, the stress at failure increased with increasing plasma-energy dose. The H₂ plasma yielded the best adhesion, and X-ray photoelectron spectroscopy revealed that it yielded the highest degree of defluorination of the fluoropolymer surface. The defluorination efficiency declined in the order H₂, Ar, O₂, and N₂. Contact angle measurements and scanning electron microscopy revealed that the surface roughness of the fluoropolymer depended on the rate of achieving the target energy dose. High power led to a smoother surface, probably because of a greater increase in temperature and partial melting. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 838–842, 2005
https://onlinelibrary.wiley.com/doi/abs/10.1002/app.22174

Tetrafluoroethylene–hexafluoropropylene (FEP) copolymer sheets were modified by remote H₂, N₂, O₂, and Ar plasmas, and the effects of the modification on adhesion between FEP sheets and copper metal were investigated. The four plasmas were able to modify the FEP surfaces' hydrophilicity. Defluorination and oxidation reactions on the FEP surfaces occurred with exposure to the plasma. The hydrophilic modification by H₂ plasma was best, followed by modification by O₂, Ar, and N₂ plasmas. The surface modification of FEP by all four remote plasmas was effective in improving adhesion with copper metal. The peel strength order of the FEP/Cu adhesive joints was H₂ plasma > Ar plasma > N₂ plasma > O₂ plasma. Mild surface modification is important for the adhesion improvement of FEP with Cu metal. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1258–1267, 2002
https://onlinelibrary.wiley.com/doi/10.1002/app.2293

The surfaces of polyester (PET) fabrics and foils were modified by low-pressure RF plasmas with air, CO₂, water vapor as well as Ar/O₂ and He/O₂ mixtures. To increase the wettability of the fabrics, the plasma processing parameters were optimized by means of a suction test with water. It was found that low pressure (10–16 Pa) and medium power (10–16 W) yielded a good penetration of plasma species in the textile structure for all oxygen-containing gases and gaseous mixtures used. While the wettability of the PET fabric was increased in all cases, the Ar/O₂ plasma revealed the best hydrophilization effect with respect to water suction and aging. The hydrophilization of PET fabrics was closely related to the surface oxidation and was characterized by XPS analysis. Static and advancing contact angles were determined from the capillary rise with water. Both wetting and aging demonstrated a good comparability between plasma-treated PET fabrics and foils, thus indicating a uniform treatment. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1452–1458, 2006
https://onlinelibrary.wiley.com/doi/abs/10.1002/app.24308

The effects of argon glow discharge and selected organic solvents on the surface wettability of poly(ethylene terephthalate) (PET) and on the wettability decay of glow discharged PET films were studied. Glow discharge in argon (30 W/1 min) drastically reduced the initial water contact angle (CA) measurement of PET from 67.0 to 26.2°. The glow-discharge-induced wetting, however, decayed during the first 7 days and stabilized at 33.1°. Treatments in dimethyl sulfoxide, dimethyl formamide, pyrdine, and water at 80°C caused some improvement in surface wettability as shown by decreases of water CAs in the range of 53–56°. When the solvent and glow discharge treatments were applied consecutively on PET, additive effects on improving surface wettability were observed. The stabilized water CAs of the solvent-and-glow-discharged films ranged from 25.0 to 32.1° depending upon the solvent type. The solvent treatments prior to glow discharge either reduced the extent of CA decay or the time taken to reach stabilization on PET films. Scanning electron microscopic evaluation showed no difference between the solventtreated and the untreated PET surfaces, but a finely etched surface was observed on the glow discharged PET at a 40,000 magnification and above. The distinctly different surface of the DMSO-and-glow-discharged PET indicated that morphological changes on PET surface were induced by the solvent.

Gas plasma treatment of poly(ethylene terephthalate) nonwoven (NW–PET) was used to increase the hydrophilicity of single- and multilayer NW–PET. NW–PET was treated with a pulsatile CO₂ or with a pulsatile H₂O glow discharge. X-ray photoelectron spectroscopy (XPS) showed significantly more oxygen with CO₂ glow-discharge-treated NW–PET than with H₂O glow-discharge-treated-NW–PET surfaces. Moreover, the introduction rate of oxygen at a single layer of NW–PET was higher for a CO₂ than for a H₂O glow-discharge treatment. Titration data revealed significantly higher surface concentrations of carboxylic groups for CO₂ glow-discharge NW–PET than for H₂O glow-discharge-treated NW–PET. Mass spectrometry analysis revealed that the entire internal surface of a single layer of NW–PET was modified. XPS and contact measurements confirmed the modification of the internal surface of multilayers of NW–PET. H₂O and CO₂ glow-discharge-treated substrates consisting of six layers of NW–PET had a nonuniform surface concentration of carboxylic acid groups as determined with titration experiments. The outside layers of the substrate contained a higher surface concentration of carboxylic acid groups than did the inside layers. XPS analysis and titration data showed that the rinsing of H₂O and CO₂ glow-discharge-treated NW–PET with water changed the surface composition considerably. Part of the carboxylic acid group-containing species were washed off. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 480–494, 2000
https://onlinelibrary.wiley.com/doi/abs/10.1002/(SICI)1097-4628(20000124)75:4%3C480::AID-APP3%3E3.0.CO;2-9

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.

Plasma-treated poly-p-xylylene films have been characterized by neutron activation oxygen analysis, internal reflection (IRS) and transmission infrared spectroscopy, transmission electron microscopy (TEM), and surface contact angle measurements. The results indicate that an oxygen plasma roughens the surface and that oxygen is incorporated into the surface. Oxygen is not detected in the bulk of the sample. The infrared transmission spectra exhibited no carbonyl band, but the relative band intensities changed, indicating a change in ring substitution by a loss of chlorine in the chlorinated poly-p-xylylenes. The IRS spectra of the surface of films treated with oxygen plasma did contain carbonyl bands at 1730 and 1640 cm⁻¹. Argon and helium plasmas generally decreased the water contact angle measured on plasma-treated poly-p-xylylene surfaces more than oxygen or nitrogen plasma treatments. Regardless of the plasma utilized, the water contact angles increased with time after the treatment but did not recover to the original level. IRS spectra of the surface of films treated with argon plasma contained carbonyl bands at 1730 and 1695 cm⁻¹. The adhesion of a polyurethane thermosetting material to a poly-p-xylylene surface is greatly improved if a plasma treatment is used prior to the application of the polyurethane. The degree of improvement in adhesion was dependent on the type of plasma and the treatment time.

The dispersion force component of surface free energy, γ, and the nondispersive interaction free energy between solid and water, I, were determined by the two-liquid contact-angle method, i.e., by the measurement of contact angles of water drops on plain solids in hydrocarbon, for commercialy available organic polymers such as nylons, halogenated vinyl polymers, polyesters, etc. A method to estimate the I values from the knowledge of the polymer composition is also proposed, on the basis of the assumption of the spherical monomer unit and the sum of interactions between functional groups and water molecules at the surface.

The fiber/epoxy resin adhesion increases after plasma treatment on ultrahigh molecular weight polyethylene (UHMW-PE) fibers. The surface modification of UHMW-PE monofilaments was studied using a combination of techniques: contact-angle measurements, SEM, and pullout tests. The results may be summarized as follows: Infiuenced by different plasma parameters and draw ratios of the monofilaments, the adhesion increases by at least four times by plasma treatment. Failure in the pullout tests involve rupture within a treated monofilament and the skin of it was peeled off; the degree of peeling-off is affected by different plasma treatment conditions and draw ratios of the monofilaments. There is only a slight decrease in the surface energy of the treated monofilaments with aging time. Ways of combining plasma etching with other chemical treatments to further improve the fiber/resin adhesion have also been studied. © 1993 John Wiley & Sons, Inc.
https://onlinelibrary.wiley.com/doi/abs/10.1002/app.1993.070471116

Low pressure oxygen plasma has been used to improve the surface wettability of a polyurethane film. The modifications induced by the plasma treatment in the material were analyzed using contact angle measurements. X-ray photoelectron spectroscopy technique was used for surface characterization of the plasma-treated films. Atomic force microscopy and scanning electron microscopy were used to analyze topography changes due to the plasma-etching mechanism. The results show a much better surface wettability of the film even for short exposure times, with a considerable increase in the surface energy values. As expected, functionalization with oxygen plasma is mainly because of surface oxidation with species like (CO, CO, OH, etc). An aging process with regard to polar groups rearrangement has been observed, thus promoting a partial hydrophobic recovery. Besides functionalization, the surface wettability of the material improves as a consequence of a slight increase in surface roughness because of the etching effect of oxygen plasma.

Polymer films of poly(ethylene terephthalate), polypropylene, and cellophane were surface treated with tetrafluoromethane plasma under different time, power, and pressure conditions. Contact angles for water and methylene iodide and surface energy were analyzed with a dynamic contact angle analyzer. The stability of the treated surfaces was investigated by washing them with water or acetone, followed by contact angle measurements. The plasma treatments decreased the surface energies to 2–20 mJ/m² and consequently enhanced the hydrophobicity and oleophobicity of the materials. The treated surfaces were only moderately affected after washing with water and acetone, indicating stable surface treatments. The chemical composition of the material surfaces was analyzed with X-ray photoelectron spectroscopy (XPS) and revealed the incorporation of about 35–60 atomic % fluorine atoms in the surfaces after the treatments. The relative chemical composition of the C ls spectra's showed the incorporation of —CHF— groups and highly nonpolar —CF₂— and —CF₃ groups in the surfaces and also —CH₂—CF₂— groups in the surface of polypropylene. The hydrophobicity and oleophobicity improved with increased content of nonpolar —CF₂—, —CF₃, and —CH₂—CF₂— groups in the surfaces. For polyester and polypropylene, all major changes in chemical composition, advancing contact angle, and surface energy are attained after plasma treatment for one minute, while longer treatment time is required for cellophane. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1591–1601, 1997
https://onlinelibrary.wiley.com/doi/abs/10.1002/(SICI)1097-4628(19971121)66:8%3C1591::AID-APP21%3E3.0.CO;2-5

The surface of poly(ethylene terephthalate) (PET) film was modified by low-temperature plasma with O₂, N₂, He, Ar, H₂, and CH₄ gases, respectively. After being treated by low-temperature plasma, their surface wettability and chemical composition were investigated by means of electron spectroscopy for chemical analysis (ESCA) and contact angle measurement. The result shows that the surface wettability of PET can be improved by low-temperature plasma, and the effect of the modification is due mainly to the kind of the gases. Mainly because of the contribution of hydrogen bonding force γ[STACK]^c_S[ENDSTACK], the surface wettability of PET treated with O₂, N₂, He, and Ar plasma for a short time (3 min) increase sharply, and the surface wettability is also improved by H₂ plasma treatment; but the CH₄ plasma treatment does not improve the wettability of PET. ESCA shows that the effect of wettability of PET is tightly related to the presence of polar functional groups that reside in the outermost surface layer of PET. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1327–1333, 1999
https://onlinelibrary.wiley.com/doi/abs/10.1002/%28SICI%291097-4628%2819990606%2972%3A10%3C1327%3A%3AAID-APP13%3E3.0.CO%3B2-0

The surface free energy and surface structure of poly(tetrafluoroethylene) (PTFE) film treated with low temperature plasma in O₂, Ar, He, H₂, NH₃, and CH₄ gases are studied. The contact angles of the samples were measured, and the critical surface tension γ_c (Zisman) and γ_c (max) were determined on the basis of the Zisman's plots. Furthermore, the values of nonpolar dispersion force γ^a_s, dipole force γ^b_s, and hydrogen bonding force γ^c_s to the surface tensions for the plasma-treated samples were evaluated by the extended Fowkes equation. Mainly because of the contribution of polar force, the surface free energy and surface wettability of PTFE film which was treated with H₂, He, NH₃, Ar, and CH₄ for a short time increased greatly. Electron spectroscopy for chemical analysis (ESCA) shows that the reason was the decrease of fluorine and the increase of oxygen or nitrogen polar functional group on the surface of PTFE. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1733–1739, 1997
https://onlinelibrary.wiley.com/doi/abs/10.1002/(SICI)1097-4628(19970328)63:13%3C1733::AID-APP4%3E3.0.CO;2-H

Films of poly(methyl methacrylate) (PMMA), polystyrene, and a styrene/acrylic terpolymer have been cast from solutions of varying thermodynamic quality and the film properties studied by inverse gas chromatography and by critical surface tension measurements. Surface properties of the non-polar polystyrene were independent of solvent medium, but significant variations in these properties were observed in the case of PMMA and the terpolymer. Solvent balance also appeared to affect the bulk properties of the latter films, as judged by the penetration rates of interacting liquids. The observations indicate the feasibility of controlling film properties of the solid by the appropriate selection of solution media; a time-dependent variation in solid properties is to be expected, however, as the film structure attains an equilibrium state.

The molecular parameters of poly(vinyl alcohol) have enormous effects on its physical and chemical properties. Therefore, the surface characteristics of poly(vinyl alcohol) films are also determined by the molecular parameters. In this study, the dependence of the surface free energy on the molecular weight, degree of saponification, and stereoregularity of poly(vinyl alcohol) films has been evaluated with contact-angle measurements. The surface free energy of poly(vinyl alcohol) films increases with decreases in the syndiotactic dyad content, molecular weight, and degree of saponification. The polar component of the surface energy is not affected by the deviation of the molecular weight and degree of saponification very much. However, it decreases with increases in the syndiotactic dyad content and ranges from 11.64 to 4.35 dyn/cm.
© 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007 https://onlinelibrary.wiley.com/doi/abs/10.1002/app.26010

To enhance polyimide-to-polyimide adhesion, we have investigated the effect of surface modification in water vapor plasma. The use of a water vapor plasma to treat a fully cured polyimide (PMDA–ODA) surface before subsequent layers of polyimide are applied results in dramatically enhanced interfacial adhesion. The polyimide-to-polyimide interfacial adhesion strength attained following water vapor plasma treatment exceeds the cohesive strength of the applied polyimide layer. The effect of surface modification in water vapor plasma on metal-to-polyimide adhesion has also been investigated. The use of a water vapor plasma to treat a fully cured polyimide (PMDA–ODA) surface prior to metallization results in increased metal-to-polymer interfacial adhesion. A study of both electroless and vacuum-deposited metal was conducted. The use of contact-angle measurements, peel tests, Fourier transform infrared spectroscopy, optical emission spectroscopy, nuclear forward scattering, and X-ray photoelectron spectroscopy has led us to a preliminary understanding of the resulting surface modification and the subsequent effect of adhesion promotion. © 1992 John Wiley & Sons, Inc.
https://onlinelibrary.wiley.com/doi/abs/10.1002/app.1992.070461216

Polyvinylidenefluoride (PVDF) was irradiated by a keV Ar⁺ ion in O₂ environment for improving adhesion between PVDF and Pt, and reaction between PVDF and the ion beam has been investigated by X-ray photoelectron spectroscopy (XPS). The adhesion test between Pt and the modified PVDF was carried out by boiling test, in which the specimens were kept in boiling water for 4 h. Two failure modes (buckling up due to weak adhesion and crack formation due to strong adhesion) of Pt films have been observed in the system. Contact angle of PVDF was reduced to 31 from 75° by the irradiation of 1 × 10¹⁵ Ar⁺ ions/cm² with oxygen flow rate of 8 sccm. The surface of the irradiated PVDF became more rough as ion dose increased. The improved adhesion mechanism and identification of newly formed chemical species have been confirmed by Carbon 1s and Fluorine 1s X-ray photoelectron core-level spectra. The main reaction occurred at the irradiated PVDF surface is an ion-beam-induced oxidation accompanied with preferential sputtering of fluorine. Newly formed chemical species at interface are regarded as ester and carboxyl groups. Adhesion of the Pt–PVDF interface was improved by ion irradiation in O₂ environment. This improvement is originated from the presence of carbon—oxygen bonds on the irradiated PVDF surface. Comparison of failure modes on the irradiated PVDF at various conditions after the boiling test shows that adhesion of Pt film is largely affected by the product of ion-assisted reaction. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 41–47, 1999
https://onlinelibrary.wiley.com/doi/abs/10.1002/(SICI)1097-4628(19990404)72:1%3C41::AID-APP4%3E3.0.CO;2-J

Excitation with low temperature helium or helium/water plasma and subsequent exposure to air of polyacrylonitrile (PAN) ultrafiltration membranes was used to hydrophilize the surface of these materials. We analyzed the effectiveness of this approach as a function of plasma operating variables including gas phase composition, plasma power, treatment time, and system pressure. Following the changes in physical and chemical composition of the PAN surface resulting from these modifications was a major aspect of this work. Techniques such as the captive bubble contact angle method, ellipsometry, ESCA, and FTIR-ATR were all used. In addition, the formation and lifetime of peroxides during these processes were determined. At low powers (≤ 25 W) and short treatment periods (≤ 30 s), the main chemical conversion of PAN surfaces was simultaneous hydrophilization and stabilization via PAN cyclization. Relatively small water permeability changes were observed as a result of such treatment. © 1995 John Wiley & Sons, Inc.
https://onlinelibrary.wiley.com/doi/abs/10.1002/app.1995.070560304

A semicontinuous, if capacitively coupled plasma polymerization apparatus was designed and constructed to coat the internal surface of a small-diameter plastic tubing. The glow zone was restricted to a small area to obtain a uniform coating of plasma polymer over the entire length of tubing (13 m long). It was found that a uniform coating can be achieved by maintaining the glow discharge parameters and velocity of moving substrate. In such a reactor, it was found that the deposition rates obtained for plasma polymers of tetrafluoroethylene, hexafluoroethane, and hexafluoroethane/hydrogen were very high compared with those polymerized in a conventional plasma polymerization apparatus. Special attention was needed to avoid deposition of an excessively thick coating, which was found to damage the barrier characteristics of the coating

A large-volume microwave plasma (LMP) apparatus has been used to polymerize organosilicone and styrene vapors onto paper substrates. Polymerization rates were established in the active glow of the plasma and in the dark, downstream volume of the reactor. Rates decrease from about 70 Ä/s in the former to about 1 Ä/s in the latter space. Surface modifications of paper substrates were studied by measurements of contact angles, of resistivity, and of charge retention properties. Plasmapolymer layers increased water contact angles from about 45 for control paper samples to> 110 for plasma-treated specimens. Resistivity was increased by up to four orders of magnitude, and the charge retention of coated papers was increased significantly. Controlled variations of the environment into which materials were placed immediately after plasma polymerization led to changes in the property balance of paper, confirming that plasma-polymer surfaces remain in active states for some time following quenching of the plasma.

The surface chemistry and surface energies of materials are important to performance of many products and processes—sometimes in as yet unrecognized ways. This article has been written for the researchers who wish to calculate solid surface energy (SE) from contact angle data. In this article, we describe various methods of calculations and their assumptions. The theoretical and experimental approaches for understanding the solid surface free energy using various methods are discussed in this article. Researchers concerned with many fields such as printing, dyeing, coating, adhesion, pharmaceuticals, composite materials, textiles, polymers, and ceramics should have interest in this topic. SE calculated by various methods for polyethylene surface treated in air plasma is discussed. Using contact angle data, the values of surface roughness using Wenzels equation, have been obtained and correlated to surface roughness calculated from AFM data.
© 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008 https://onlinelibrary.wiley.com/doi/abs/10.1002/app.27446

The bondability of the following polymers as a function of length of exposure to excited helium or oxygen was investigated: low-density polyethylene, high-density polyethylene (two types), poly(4-methyl-1-pentene), poly(vinyl fluoride), poly(vinylidene fluoride), FEP Teflon, poly(oxymethylene) copolymer, nylon 6, nylon 66, poly(ethylene terephthalate), and polystyrene. Generally, the bond strength increase rapidly initially and then remains nearly constant, perhaps decreasing in some cases at long exposure times. A method is presented for calculating bond strength-versus-exposure time curves. The calculated curves generally fit the data reasonably well. Polypropylene showed a rapid increase in bondability with exposure to excited oxygen. Helium was ineffective toward this polymer under normal conditions, but could produce good bond strength at higher temperatures.

The surface of polypropylene (PP) films was activated by RF plasma method with the use different gases: argon, air, water vapor, and acetic acid vapor. Plasma was diagnosed based on spectra emitted by gas plasma using the method of optical emission spectroscopy. The effectiveness of these processing gases during plasma treatment was analyzed. The effects of PP activation were assessed with the use of IR-ATR absorption spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, and the analysis of the surface free energy components based on liquid contact angle. The activation of PP surface by plasma treatment resulted in the increased energy of PP surface layer to the extent being dependent on the type of processing gases and in the formation of new chemical groups on it. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011. https://onlinelibrary.wiley.com/doi/abs/10.1002/app.34486

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(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

In the present work, contact angles formed by drops of diethylene glycol, ethylene glycol, formamide, diiodomethane, water, and mercury on a film of polypropylene (PP), on plates of polystyrene (PS), and on plates of a liquid crystalline polymer (LCP) were measured at 20°C. Then the surface energies of those polymers were evaluated using the following three different methods: harmonic mean equation and geometric mean equation, using the values of the different pairs of contact angles obtained here; and Neumann's equation, using the different values of contact angles obtained here. It was shown that the values of surface energy generated by these three methods depend on the choice of liquids used for contact angle measurements, except when a pair of any liquid with diiodomethane was used. Most likely, this is due to the difference of polarity between diiodomethane and the other liquids at the temperature of 20°C. The critical surface tensions of those polymers were also evaluated at room temperature according to the methods of Zisman and Saito using the values of contact angles obtained here. The values of critical surface tension for each polymer obtained according to the method of Zisman and Saito corroborated the results of surface energy found using the geometric mean and Neumann's equations. The values of surface energy of polystyrene obtained at 20°C were also used to evaluate the surface tension of the same material at higher temperatures and compared to the experimental values obtained with a pendant drop apparatus. The calculated values of surface tension corroborated the experimental ones only if the pair of liquids used to evaluate the surface energy of the polymers at room temperature contained diiodomethane. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1831–1845, 2000
https://onlinelibrary.wiley.com/doi/abs/10.1002/(SICI)1097-4628(20000620)76:12%3C1831::AID-APP14%3E3.0.CO;2-Q

A technique has been developed for estimating the hydrogen bonding and London dispersion force components of liquid surface tension and solid surface free energy levels. The technique relies on (a) measuring contact angles generated by sessile drops of liquids on solids and (b) performing calculations based on theories of thermodynamic wetting of solids by liquids. The technique is used to estimate interfacial force components of certain liquids and papers typical of those used in xerographic processing.

The aim of this study was to analyze how corona dosages above recommended levels affect film surface energy and hydrophobic recovery of such treated film surfaces as well as laminate bond strength of laminates made of these films. The adhesive for lamination was a polyurethane-adhesive with a dry film thickness of ∼5 µm. Polar and dispersive parts of the surface energy were measured frequently according to DIN 55660-2 (Owens–Wendt–Rabel-and-Kaelble method) for up to 140 days after corona treatment. The corona dosage had a value of up to 280 W min/m². Laminate bond strength was measured according to DIN 55543-5. The effect of corona treatment was highest for low-density polyethylene (PE-LD) films, mean for biaxial-oriented polypropylene (PP-BO) films, and lowest for biaxial-oriented poly(ethylene terephthalate) (PET-BO) films. With increasing storage time, surface energy decreased, as expected. The higher the effect of corona treatment, the faster the polar part of surface energy decreased. At PE-LD, laminate bond strength increased with a higher corona dosage from 0.05 to 8.87 mN/15 mm, whereas at PET-BO and PP-BO laminate bond strength was so high that samples teared before delamination during bond strength testing. By our results is shown that corona dosages above recommended levels resulted in higher laminate bond strength. Only at PP-BO a reduction of laminate bond strength due to “overtreatment” was be observed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45842. https://onlinelibrary.wiley.com/doi/abs/10.1002/app.45842

Plasma treatment of PET films was carried out under argon, followed by exposure to an oxygen atmosphere. The films underwent considerable changes in surface composition and morphology, as demonstrated by contact angle measurements, FTIR-ATR, AFM, and XPS. It was found that the surface acquired oxygen containing polar functional groups such as CO, OH, and OOH, which increased in number as the plasma treatment time increased. During storage, the treated films underwent significant surface reorganization, and both the time and temperature contributed to the increase in the contact angle. As revealed by AFM measurements, these changes were accompanied by an increase in roughness in the form of ridges. The ridges were observed to grow in height with increasing treatment time, although their spacing showed little evolution. A correlation among the observations obtained from various techniques was established, giving a comprehensive picture of the structure and dynamics of plasma-treated PET surfaces. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1083–1091, 2000
https://onlinelibrary.wiley.com/doi/abs/10.1002/1097-4628%2820001031%2978%3A5%3C1083%3A%3AAID-APP170%3E3.0.CO%3B2-5

The sheets prepared by the extrusion of the melt of poly(butylene succinate) were treated with inorganic gas plasmas. Bionolle, the commercially available polyester, was also used, and the treatment effects were compared. Plasma susceptibility by the continuous plasma of 13.56 MHz and by pulsed plasmas was evaluated by the weight loss rates by etching. Advancing and receding contact angles of water (θa , θr ) on the plasma-treated sheets were obtained by the Wilhelmy method. Decay of hydrophilicity was considerable in θa , but θr was less changed. The biodegradation was examined by the preliminary soil-burial tests. The polymer sheets were biologically degraded, and the characteristic morphology appeared on the surface according to the SEM observation.

High performance polymer, Polyether Ether Ketone (PEEK) (service temperature −250°C to +300°C, tensile strength: 120 MPa) is gaining significant interest in aerospace and automotive industries. In this investigation, attention is given to understand adhesion properties of PEEK, when surface of the PEEK is modified by two different plasma processes (i) atmospheric pressure plasma and (ii) low pressure plasma under DC Glow Discharge. The PEEK sheets are fabricated by ultra high temperature resistant epoxy adhesive (DURALCO 4703, service temperature −260°C to +350°C). The surface of the PEEK is modified through atmospheric pressure plasma with 30 and 60 s of exposure and low pressure plasma with 30, 60, 120, 240, and 480 s of exposure. It is observed that polar component of surface energy leading to total surface energy of the polymer increases significantly when exposed to atmospheric pressure plasma. In the case of low pressure plasma, polar component of surface energy leading to total surface energy of the polymer increases with time of exposure up to 120 s and thereafter, it deteriorates with increasing time of exposure. The fractured surface of the adhesively bonded PEEK is examined under SEM. It is observed that unmodified PEEK fails essentially from the adhesive to PEEK interface resulting in low adhesive bond strength. In the case of surface modified PEEK under atmospheric pressure plasma, the failure is entirely from the PEEK and essentially tensile failure at the end of the overlap resulting in significant increase in adhesive bond strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Effects of corona treatment and aging on commercially produced corona discharged polypropylene (PP) films were followed via surface sensitive roughness analysis by atomic force microscopy (AFM), water contact angle (WCA), and X-ray photoelectron spectroscopic (XPS) measurements. Roughness analysis by AFM gave similar results for both untreated and corona-treated samples. The measured water contact angle decreased after corona treatment but increased with aging. XPS findings revealed that corona treatment caused an increase in the O-containing species on the surface of the films, but the measured O/C atomic ratio decreased with aging. The angle dependence of the observed XPS O/C atomic ratio further revealed that surface modifications by the corona treatment were buried into the polymer away from the surface as a function of aging. This is attributed to a surface rearrangement of the macromolecules in agreement with the findings of Garbassi et al. on oxygen–plasma-treated polypropylene. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1846–1850, 1999