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139. Good, R.J., and L.A. Girifalco, “A theory for the estimation of surface and interfacial energies, III. Estimation of surface energies of solids from contact angle data,” J. Physical Chemistry, 64, 561-565, (1960).

142. Good, R.J., and M.K. Chaudhury, “Theory of adhesive forces across interfaces, I. The Lifshitz-van der Waals component of interaction in adhesion,” in Fundamentals of Adhesion, Lee, L.-H., ed., 137-151, Plenum Press, Feb 1991.

The theory of the apolar components of interfacial forces was examined in the previous chapter of this volume.(1) It has been possible to develop that theory of apolar components at this time owing to the existence of quantitative, mathematically formulated theories of forces between molecules (e.g., the London theory) together with the Lifshitz electromagnetic theory of the interaction of macroscopic bodies. (See the previous chapter for references.)

1657. Good, R.J., and M.N. Koo, “The effect of drop size on contact angle,” J. Colloid and Interface Science, 71, 283, (1979).

2006. Good, W.R., “A comparison of contact angle interpretations,” J. Colloid and Interface Science, 44, 63-71, (Jul 1973).

1066. Goodwin, A., “Atmospheric pressure plasma technologies for surface modification of polymers,” in AIMCAL 2003 Fall Technical Conference, AIMCAL, Oct 2003.

145. Gorzynski, M.R., “Goniometer provides accurate measurement of bottle coatings,” Packaging Technology & Engineering, 5, 48-51, (Apr 1996).

1091. Gotoh, K., “Wettability and surface free energies of polymeric materials exposed to excimer ultraviolet light and particle deposition onto their surfaces in water,” in Polymer Surface Modification: Relevance to Adhesion, Vol. 3, K.L. Mittal, ed., 125-138, VSP, Sep 2004.

The effects of exposure to [72 nm ultraviolet (UV) excimer light in ambient air on the wettability and surface free energy of polymer films were investigated from contact angle measurements. The polymer films used were polyethylene (PE), polypropylene (PP), poly (ethylene terephthalate)(PET), nylon 6 (Ny6) and polyimide (Pl). As a measure of the wettability, the water contact angle was determined by the sessile drop and the Wilhelmy methods. For all films, considerable increase in wettability was accomplished by UV exposure within a few tens of seconds. After the UV exposure, a decrease in the wettability, the hydrophobic recovery, was observed over a time period of several days. Even after the recovery, the wettability was sufficiently higher compared to that before the UV exposure. The Lifshitz-van der Waals component and Lewis acid-base parame-ters of the surface free energy of the films were determined by contact angle measurements using certain probe liquids. The base parameter was found to increase considerably by the UV exposure. XPS analysis and AFM observation of the film surfaces showed that such increases in the wettability and the surface free energy were due to the increased atomic oxygen concentration at the film surfaces. The effect of the UV exposure on particle deposition onto PP and PET in water was also examined using spherical polyethylene and nylon 12 particles. The apparent equilibrium number of particles deposited on the polymer substrate decreased drastically after UV exposure. The particle deposition behavior was explained well in terms of the free energy change due to deposition, which was calculated from various surface free energies.

2254. Gotoh, K., A. Yasukawa, and K. Taniguchi, “Water contact angles on poly(ethylene terephthalate) film exposed to atmospheric pressure plasma,” J. Adhesion Science and Technology, 25, 307-322, (2011).

The poly(ethylene terephthalate), PET, film was exposed to atmospheric pressure plasma under various plasma processing parameters. The wettability of the PET film immediately after the exposure and after storage in air, which was determined by the sessile drop method, was strongly dependent on the plasma processing parameters. The contact angle hysteresis on the plasma-exposed PET film was examined by the Wilhelmy method. It was found that the hydrophobic recovery of the PET surface on storage after the plasma exposure was observed only for the advancing contact angle and that the receding angle remained almost the same. These experimental findings were explained on the basis of the calculation by Johnson and Dettre for the advancing and receding contact angles on model heterogeneous surfaces.

802. Gotoh, K., M. Tagawa, N. Ohmae, and M. Tagawa, “Wettability of polyimide films modified by exposure to atomic oxygen,” in Polymer Surface Modification: Relevance to Adhesion, Vol. 2, K.L. Mittal, ed., 445-460, VSP, Dec 2000.

Wettability of polyimide (PI) films modified by atomic oxygen (AO) was investigated by contact angle measurements. The PI films with/without being covered by a metal mesh were exposed to the AO beam with fluences from 1.4x 1016 to 9x 1018 atoms/cm2. The atomic force microscopy (AFM) and the X-ray photoelectron spectroscopy (XPS) were used to characterize the PI film surfaces. Both the roughness and the oxygen concentration at the PI surface increased by the AO exposure. The advancing and the receding contact angles of water on the PI films were measured both by the sessile drop method and by the Wilhelmy method. The contact angles measured by these two methods were identical for the PI samples both with/without AO exposures. In the case of the AO-exposed PI films being covered by the metal mesh, the contact angles were evaluated by the Wilhelmy method. A difference in contact angles on the exposed and the covered areas was clearly observed. It was also found that the wettability of the AO-exposed PI films was related to the amount of oxygen detected by the XPS.

2723. Gotoh, K., Y. Nagai, Y. Yonehara, and Y. Kobayashi, “Surface hydrophilization of two polyester films by atmospheric-pressure plasma and ultraviolet excimer light exposures,” J. Adhesion Science and Technology, 29, 473-486, (2015).

Polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) films were treated with an atmospheric-pressure plasma (APP) jet and a 172-nm ultraviolet (UV) excimer light in air. The advancing and receding water contact angles on both films decreased after the treatments, especially after APP treatment. After the treatments, the hydrophobic recovery was observed and almost diminished within a week. The dispersive component of the surface free energy of the two polyester films did not change due to the APP and UV exposure, whereas the acid–base component drastically increased after the treatments. The X-ray photoelectron spectroscopy results showed that the polyester film surfaces were oxidized by the treatments. From the AFM images, the topographical change on the film surfaces due to the treatments was clearly observed. It was found that the APP treatment of the PET film prevented the deposition of particulate soils in air due to the decrease in the contact area between the film and the soil particle. Furthermore, the soil release in the aqueous solutions was promoted as a result of the hydrophilization of the polyester films due to the APP treatment.

2291. Gotoh, K., Y. Nakata, M. Tagawa, and M. Tagawa, “Wettability of ultraviolet excimer-exposed PE, PI, and PTFE films determined by the contact angle measurements,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, 224, 165-173, (Aug 2003).

Effects of the exposure of ultraviolet (UV) excimer light on the physicochemical surface properties of polymer films were investigated by contact angle measurements and X-ray photoelectron spectroscopy (XPS). The UV light at wavelength of 172 nm was exposed to polyethylene (PE), polyimide (PI), and polytetrafluoroethylene (PTFE) films in ambient air. The advancing and receding contact angles of water on the unexposed and UV-exposed films were determined by the sessile drop and the Wilhelmy methods as a measure of the wettability. For the PE and PI films, remarkable decrease in the water contact angle was accomplished by the UV exposure of several or several 10 s. The XPS data showed that such increase in the wettability was attributed to the increased atomic oxygen concentration at the film surfaces. The wettability of the PTFE film did not change due to the UV exposure. When the UV-exposed PE and PI films were stored in ambient air, the increase in the water contact angle, i.e. the hydrophobic recovery, was observed over a time scale of several days. It was suggested that the gasification of the low-molecular weight oxidized materials as well as the reorientation and the migration of polymer chains in the oxidized surface layer was responsible for the hydrophobic recovery in air. The UV exposure was also attempted to the PI film being covered with a metal mesh to prepare the film having both non-exposed and UV-exposed surface regions. The differences in the advancing and receding contact angles between the both regions were observed on the continuous weight recording at constant interfacial moving velocity by the Wilhelmy method. The Wilhelmy method in combination with the UV lithography technique enabled the simultaneous evaluation of the wettabilities of the treated and untreated surfaces.

2352. Gould, D.E., and L.A. Preli Jr., “Treating of plastic coated foils,” U.S. Patent 3257303, Jun 1966.

1559. Grace, J., H.K. Zhuang, and L. Gerenser, “Importance of process conditions in polymer surface modification: a critical assessment,” in Polymer Surface Modification: Relevance to Adhesion, Vol. 4, K.L. Mittal, ed., 3-24, VSP, May 2007.

Plasma web treatment is a common practice for promoting adhesion, wettability and other surface or interfacial properties in the conversion industry. While the objective of creating new surface functional groups is conceptually simple, it can be difficult to choose the most appropriate kind and configuration of plasma source, the most appropriate feed gas composition and the most appropriate operating pressure for a given application. Such difficulties arise from the variety of species that can be formed in the plasma and the variety of possible plasma-surface interactions that can occur. A brief review of the importance of various plasma parameters (eg, specific energy, species concentrations, and energy distributions) and an example relating nitrogen uptake in poly (ethylene-2, 6-naphthalate) to plasma diagnostic data in a low-radiofrequency capacitivelycoupled nitrogen plasma are presented. The importance of driving frequency and treatment configuration is discussed in detail. Uptake kinetics for samples treated at floating potential at low radiofrequency is compared with that for samples treated in the cathode sheath. Analysis of the treatment kinetics is based on a simple model of surface saturation. This approach can be used not only to compare practical treatment results as a function of process conditions, but also to compare different treatment techniques in a practical manner.

1115. Grace, J.M., Plasma Web Treatment, Society of Vacuum Coaters, Mar 2005.

2396. Grace, J.M., J. Chen, L.J. Gerenser, and D.A. Glocker, “Use of glow discharge treatment to promote adhesion of aqueous coatings to substrate,” U.S. Patent 5538841, Jul 1996.

2397. Grace, J.M., J. Chen, L.J. Gerenser, and D.A. Glocker, “Use of glow discharge treatment to promote adhesion of aqueous coatings to substrate,” U.S. Patent 5582921, Dec 1996.

2413. Grace, J.M., L.J. Gerenser, C.J. Landry-Coltrain, K.D. Sieber, et al, “High-efficiency plasma treatment of paper,” U.S. Patent 6565930, May 2003.

1745. Grace, J.M., L.J. Gerenser, K.D. Sieber, et al, “High-efficiency plasma treatment of polyolefins,” U.S. Patent 6399159, 2002.

1746. Grace, J.M., and L.J. Gerenser, “Plasma treatment of polymers,” J. Dispersion Science and Technology, 24, 305-341, (2003).

Plasma treatment of polymers encompasses a variety of plasma technologies and polymeric materials for a wide range of applications and dates back to at least the 1960s. In this article we provide a brief review of the United States patent literature on plasma surface modification technologies and a brief review of the scientific literature on investigations of the effects of plasma treatment, the nature of the plasma environment, and the mechanisms that drive the plasma–surface interaction. We then discuss low‐radio‐frequency capacitively coupled nitrogen plasmas and their characteristics, suggesting that they provide significant plasma densities and populations of reactive species for effective plasma treatments on a variety of materials, particularly when placing the sample surface in the cathode sheath region. We further discuss surface chemical characterization of treated polymers, including some results on polyesters treated in capacitively coupled nitrogen plasmas driven at 40 kHz. Finally, we connect plasma characterization with surface chemical analysis by applying a surface sites model to nitrogen uptake of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) treated in a 40 kHz nitrogen plasma. This example serves to suggest an interesting practical approach to comparisons of plasma treatments. In addition, it suggests an approach to defining the investigations required to conclusively identify the underlying treatment mechanisms.

1569. Graham, W.G., “Plasma science and technology,” in Plasma Technologies for Textiles, Shishoo, R., ed., 1-24, Woodhead Publishing, Mar 2007.

1502. Grande, J.A., “Now plasma-treat the resin, not the molded part,” Plastics Technology, 52, 32-33, (Dec 2006).

1672. Granqvist, B., J. Jarnstrom, C.M. Tag, M. Jarn, and J.B. Rosenholm, “Acid-base properties of polymer-coated paper,” J. Adhesion Science and Technology, 21, 465-485, (2007).

The wetting behavior of a series of polymer-coated papers has been studied. Different ways of determining the acid–base properties of the polymers are presented. The well-known van Oss–Chaudhury–Good (vOCG) bi–bi polar model is compared with more simplified mono–bi polar and mono–mono polar models. The effect of surface roughness on the wetting was also studied with atomic force microscopy. The overall wetting of each probe liquid was evaluated by calculating the work of adhesion to the polymer surfaces. It is shown that ethylene glycol and water may be considered as mono polar liquids, which simplifies the original vOCG-model. It is also shown that in most cases the surface energy values are in the same range when using both the complex bi–bi polar approach and the simpler mono–mono polar approach. The different polymers used are found to be of a predominating basic character.

466. Grant, J.L., D.S. Dunn, and D.J. McClure, “Argon and oxygen sputter etching of polystyrene, polypropylene, and poly(ethylene terephthalate) thin films,” J. Vacuum Science and Technology, A6, 2213-2220, (1988).

Surface chemical modification of polymer thin films induced by sputter etching was studied by x‐ray photoelectron spectroscopy (XPS) and infrared reflection–absorption spectroscopy (IRRAS). The polymers studied were polystyrene, polypropylene, and poly(ethylene terephthalate) (PET). Oxygen and argon sputter etching of these polymers causes surface oxidation and possibly crosslinking; trends in polymer oxidation can be correlated with the etchant gas, etch power, and initial material properties. For polystyrene and polypropylene, the predominant new functionalities formed are CDouble BondO and CSingle BondO groups; the breadth of the infrared absorption bands suggests that many different types of these groups exist. For PET, the predominant damage mechanism is crosslinking, with only a slight degree of oxidation resulting from oxygen sputter etching. This work suggests that the information provided by XPS and IRRAS is highly complimentary and will be useful in future studies of polymer functionalization and derivatization.

945. Gray, V.R., “Contact angles, their significance and measurement,” in S.C.I. Monograph #25 : Wetting, 99-119, S.C.I., 1966.

1213. Green, M.D., F.J. Guild, and R.D. Adams, “Characterisation and comparison of industrially pre-treated homopolymer polypropylene, HF135M,” Intl. J. Adhesion and Adhesives, 22, 81-90, (2002).

The effects of 13 pre-treatments were examined to determine their effect on the surface region of homopolymer polypropylene. Five of the pre-treatments were examined in detail due to excellent joint strengths. They were: corona discharge, flame, fluorination, low-pressure vacuum plasma and atmospheric plasma. The pre-treatments were examined using X-ray photoelectron spectroscopy (XPS), angle resolved XPS (AR-XPS) and atomic force microscopy (AFM), to determine surface chemistry and topography. Of the 13 pre-treatments examined, it was found that the first five all showed the highest surface chemical modification of the pre-treatments studied. It was identified that the surface chemistry, concentration depth and topography varied widely across the five pre-treatments. However, all have been shown to have similar bond strengths with polyurethane adhesives, indicating that a number of significant factors were responsible for bond strength. It is surmised that the depth of the functional group concentration is the determinant joint strength parameter and not the O : C ratio or surface roughness.

146. Greene, R., “High energy system prepares molded parts,” Modern Plastics, 68, 30-31, (Aug 1991).

1899. Greenwood, O.D., R.D. Boyd, J. Hopkins, and J.P.S. Badyal, “Atmospheric silent discharge versus low-pressure plasma treatment of polyethylene, polypropylene, polyisobutylene, and polystyrene,” J. Adhesion Science and Technology, 9, 311-326, (1995) (also in Polymer Surface Modification: Relevance to Adhesion, K.L. Mittal, ed., p. 17-32, VSP, May 1996).

Polyethylene, polypropylene, polyisobutylene, and polystyrene films have been exposed to high- and low-pressure non-equilibrium electrical air discharges. The modified surfaces have been characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Atmospheric silent discharge treatment causes a greater level of topographical disruption, whereas surface oxygenation is dependent on the chemical nature of the polymer substrate and its reactivity towards the electrical discharge medium. Oxygen incorporation occurs much more readily for the unsaturated polystyrene surface than for the saturated polyethylene, polypropylene, and polyisobutylene substrates.

1576. Greger, R., “Pre-treatment of plastics with low-pressure plasma prior to flocking,” Flock, 7, 107, (2002).

1174. Gregory, B.H., Extrusion Coating: A Process Manual, Trafford Publishing, May 2005.

467. Gregory, B.H., D. Michiels, and W.D. McIntyre, “Adhesion improvement by ozone treatment,” in 1982 Paper Synthetics Conference Proceedings, 167-172, TAPPI Press, 1982.

809. Greig, S., “Corona treatment - an update for running waterbased inks,” Flexible Packaging, 5, 36-39, (May 2003).

1346. Greig, S., “Web Treatment - Going Solventless,” Sherman Treaters Ltd., 2005.

995. Greig, S., P.B. Sherman, R. Pitman, and C. Barley, “Adhesion promoters: Corona flame and ozone - a technology update,” Presented at TAPPI Polymers, Laminations, & Coatings Conference Proceedings 2000, Aug 2000.

1114. Greig, S., and N. Jadon, “Corona, ozone and flame treaters for extrusion coating lines,” in 8th European Polymers, Films, Laminations and Extrusion Coatings Conference, TAPPI Press, May 2001.

1483. Greiveldinger, M., and M.E.R. Shanahan, “A critique of the mathematical coherence of acid-base interfacial free energy theory,” J. Colloid and Interface Science, 215, 170-178, (1999).

Acid/base theory has, over the last decade or so, been developed to describe interfacial free energies, or tensions, in wetting theory. An approach put forward by van Oss and co-workers, involving van der Waals/Lifshitz and Lewis electron acceptor/donor contributions to surface/interfacial free energies, has often been employed. The present study considers use of this theory for evaluating surface data for various polymeric surfaces employing known, characterized liquid probes for obtaining contact angle data. Results are analyzed using extended matrix analyses, originally proposed for treating the dispersive/polar interpretation of wetting results, and good agreement with literature values is obtained. By “inverting” the system, i.e., by treating the known solids as probes and rederiving surface data for liquids, inconsistencies are found to arise. Results for wetting of the same polymers and mica, using a two-liquid system (n-octane/water), are exploited to attempt to rederive the surface characteristics of water. Again, serious incoherence is manifest. Despite the conceptual interest of acid/base theory, clearly the mathematical formulation is presently inadequate. Copyright 1999 Academic Press.

2389. Gribbin, J.D., L. Bother, and P. Dinter, “Process for passing a hydrophobic substrate through a corona discharge zone and simultaneously introducing an adhesive promoting aerosol,” U.S. Patent 5271970, Dec 1993.

936. Griese, E.W. Jr., “Surface energy and surface tension,” Cork Ind., Dec 1994.

937. Griese, E.W. Jr., “Surface energy & printing success,” Cork Ind., Feb 1995.

668. Griesser, H.J., T.R. Gengenbach, L. Dai, S. Li, and R.C. Chatelier, “Plasma surface modifications for structural and biomedical adhesion applications,” in First International Congress on Adhesion Science and Technology: Festschrift in Honor of Dr. K.L. Mittal on the Occasion of his 50th Birthday, W.J. van Ooij and H.R. Anderson, Jr., eds., 307-328, VSP, 1998.

We discuss plasma surface modifications applied to perfluorinated polymers and polyolefins to achieve structural adhesive bonding or for biomedical purposes such as adhesion and proliferation of cells, and interfacial immobilization of biologically active molecules. We compare the properties of surface modifications performed in non-depositing plasma treatments with those of thin coatings produced in depositing plasma vapours (plasma polymerization), with particular emphasis on changes, on subsequent storage, to the properties and composition of the surface layers (‘ageing’). Such changes usually proceed for extended periods of time after plasma processing. Polymer surfaces treated in non-depositing plasmas generally are unstable, showing an increase in the air/water contact angles over days and weeks due to surface reorientation motions. Concurrently, the composition of the surface layers is also affected by post-plasma chemical reactions: originating from trapped radicals, oxidative chain reactions lead to the production of substantial amounts of oxygen-containing groups. These reactions also convert some of the groups originally incorporated into the surface layers by the plasma treatment; for instance, amine groups are converted to amide groups as evidenced by shifts in the XPS N 1s binding energy. Plasma polymer coatings analogously undergo oxidative compositional changes with time, and are capable of some surface reorganization. Thus, the nature and densities of the chemical groups on plasma-treated surfaces and plasma polymer coatings can change considerably with time. The relative contributions by concurrent reorientation motions and oxidative reactions to the compositional changes vary markedly between different plasma-prepared surfaces, but usually both processes contribute to the ageing of a surface. The generally long time constants of the reorientation of plasma polymer surfaces suggest that their limited, slow mobility may be neglected when interpreting interactions with adsorbing proteins.

2781. Grindstaff, T.H., “A simple apparatus and technique for contact angle measurements on small-denier single fibers,” Textile Research J., 39, 958+, (1969).

 

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