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1160. Han, J.H., Y. Zhang, and R. Buffo, “Surface chemistry of food, packaging and biopolymer materials,” in Innovations in Food Packaging, Han, J.H., ed., 45-60, Elsevier, Nov 2005.

This chapter discusses the physicochemical principles of surface phenomena, and provides an overview of the research regarding surface properties of biopolymers used for the manufacturing of biodegradable films. Surface properties of food packaging polymers, such as wettability, scalability, printability, dye uptake, resistance to glazing, and adhesion to food surfaces or other polymers are of central importance to food packaging designers and engineers with respect to product shelf-life, appearance, and quality control. The most commonly used food packaging polymers are low-density polyethylene, high-density polyethylene, polypropylene, polytetrafluoroethylene, and nylon. In recent years, environmental concerns have increased the interest in preparing biodegradable packaging materials. Proteins and polysaccharides are the biopolymers of prime interest, since they can be used effectively to make edible and biodegradable films to replace short shelf-life plastics. Surface properties of biopolymers provide a supplementary understanding of film behavior, leading to an enhanced design of packaging materials for specific applications.

2069. Han, S., W.-K. Choi, K.H. Yoon, S.-K. Koh, “Surface reaction on polyvinylidenefluoride (PVDF) irradiated by low energy ion beam in reactive gas environment,” J. Applied Polymer Science, 72, 41-47, (1999).

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;2-J

470. Hansen, C.M., “The three dimensional solubility parameter - key to paint component affinities, I. Solvents, plasticizers, polymers, and resins,” J. Paint Technology, 39, 104+, (1967).

The concept that the solubility parameter is a vector composed of hydrogen bonding, polar, and dispersion components is proposed and applied with success to prediction of the solubility of 33 polymers and resins in 90 solvents and 10 plasticizers. Solvents and plasticizers can be located as points in a three dimensional system, and regions of solubility are found for polymers and resins when solubility data are plotted. Non-interacting solvents which in a mixture become interacting have been found with better than 95% accuracy in over 400 cases.

471. Hansen, C.M., “The three dimensional solubility parameter - key to paint component affinities, II. Dyes, emulsifiers, mutual solubility and compatability, and pigments,” J. Paint Technololgy, 39, 505-510, (1967).

The concept that the solubility parameter is a vector composed of hydrogen bonding, polar, and dispersion components is proposed and applied with success to prediction of the solubility of 33 poylmers and resins in 90 solvents and 10 plasticizers. The application of the solubility parameter concept is described. The three dimensional solubility parameter system based on the homomorph concept has been developed on the basis of polymer solubility. The same system has been applied to the characterization of dyes, nonionic emulsifiers, and pigments. The system is also useful for selecting solvents when protective coatings are formulated with more than one polymeric solute.

472. Hansen, C.M., “The three dimensional solubility parameter - key to paint component affinities, III. Independent calculation of the parameter components,” J. Paint Technology, 39, 511+, (1967).

473. Hansen, C.M., “Characterization of surfaces by spreading liquids,” J. Paint Technology, 42, 660+, (1970).

474. Hansen, C.M., “Surface dewetting and coatings performance,” J. Paint Technology, 44, 57+, (1972).

746. Hansen, C.M., “Cohesion energy parameters applied to surface phenomena,” in Handbook of Surface and Colloid Chemistry, 2nd Ed., K.S. Birdi, ed., 539-554, CRC Press, Sep 2002.

822. Hansen, C.M., Hansen Solubility Parameters: A User's Handbook, CRC Press, Sep 1999.

872. Hansen, C.M., “Solubility Parameters,” in Paint and Coating Testing Manual, 14th Ed. of the Gardner-Sward Handbook, Koleske, J.V., ed., 383-406, ASTM, 1995.

1568. Hansen, C.M., Hansen Solubility Parameters: A User's Handbook, 2nd Ed., CRC Press, Jul 2007.

2048. Hansen, C.M., “New simple method to measure polymer surface tension,” Pigment & Resin Technology, 27, 374-378, (1998).

Surface tensions of polymers can be accurately determined by observing whether droplets of liquids spontaneously spread or not. The polymer surface tension will be higher than the surface tension of a liquid which spreads, and lower than that of a liquid which remains as a droplet.

475. Hansen, C.M., and E. Wallstrom, “On the use of cohesion parameters to characterise surfaces,” J. Adhesion, 15, 275-286, (1983).

Examples of surface characterization using cohesive energy parameters and surface energy parameters are given. In general the two approaches yield essentially equivalent results. The predictive ability of the cohesive energy approach suggests its use where directed modification of surface properties is desired.

1725. Hansen, F.K., “The measurement of surface energy of polymer by means of contact angles of liquids on solid surfaces: A short overview of frequently used methods,”, 0.

1452. Hansen, G.P., R.A. Rushing, R.W. Warren, S.L. Kaplan, and O.S. Kolluri, “Plasma treatment of polytetrafluoroethylene-ethylene copolymers for adhesive bonding,” Intl. J. Adhesion and Adhesives, 11, 247-254, (Oct 1991).

The aim of this work was to improve adhesion to tefzel using plasma surface treatment. The plasmas used were O2, and NH3. Joints ,ade from the adherends using several commercially available epoxy adhesives were tested using a double lap shear configuration. Measured bond strenghts for the treated adherends were as much as 30 times greater than those for the untreated materials. Examination of the O2 plasma-treated Tefzel by electron spectroscopy for chemical analysis indicated a surface oxidation increase of about 7–8% over the untreated material, with the oxide being primarily in the form of an ester.

1457. Hansen, G.P., R.A. Rushing, R.W. Warrent, S.L. Kaplan, and O.S. Kolluri, “Achieving optimum bond strength with plasma treatment,” in Adhesives '89, Sep 1989.

152. Hansen, M.H., M.F. Finlayson, M.J. Castille, and J.D. Goins, “The role of corona discharge treatment in improving polyethylene-aluminum adhesion: an acid-base perspective,” TAPPI J., 76, 171-177, (Feb 1993).

153. Hansen, M.H., M.F. Finlayson, and M.H. Vaughn, “Characterizing aluminum adhesion for low density polyethylene,” in 1991 Polymers, Laminations and Coatings Conference Proceedings, 349-352, TAPPI Press, Aug 1991.

476. Hansen, R.H., “Interface conversion of polymers by excited gases,” in Symposium on Interface Conversion for Polymer Coatings, Elsevier, 1968.

154. Hansen, R.H., J.V. Pascale, T. DeBenedictis, and P.M. Rentzepis, “Effect of atomic oxygen on polymers,” J. Polymer Science, 3, Part A, 2205-2214, (1965).

155. Hansen, R.H., and H. Schonhorn, “A new technique for preparing low surface energy polymers for adhesive bonding,” J. Polymer Science, Polymer Letters Edition, 4, 203-209, (1966).

Contact time of activated gas with polymer film of as little as 1 sec. under these relatively mild conditions resulted in greatly improved adhesive joint strength for polyethylene. Longer contact times were required for polymers such as polytetrafluoroethylene. Helium, argon, krypton, neon, and xenon, and even hydrogen and nitrogen were all effective crosslinking agents although the latter also changed wettability of the surface. Adhesive joints were prepared by sandwiching 1041 films of polyethylene (Marlex 5003, Phillips Petroleum Co., Bartlesville, Oklahoma) and polytetrafluoroethylene (G-80, Allied Chemical Co., Morristown, New Jersey), before and after CASING, between epoxy-coated aluminum strips (3). The values obtained for tensile shear strengths of these joints are shown in Figure 1. In these instances, the polyethylene film was treated for 10 sec. and the polytetrafluoroethylene film was treated for 10 min.

1599. Harkins, W.D., The Physical Chemistry of Surface Films, Reinhold, 1952.

156. Harkins, W.D., and H.F. Jordan, “A method for the determination of surface and interfacial tension from the maximum pull on a ring,” J. American Chemical Society, 52, 1751-1772, (1930).

157. Harrington, W., “Corona treating aids bonding,” Adhesives Age, 40, 52, (Jun 1997).

1153. Harrington, W.F. Jr., “Surface treatment of plastics,” in Coatings Technology Handbook, D. Satas, ed., Marcel Dekker, 1991 (also in Coatings Technology Handbook, 2nd Ed., D. Satas and A.A. Tracton, eds., p. 335-342, Marcel Dekker, Jan 2001, and Coatings Technology: Fundamentals, Testing, and Processing Techniques, A.A. Tracton, ed., p. 38/1-38/7, CRC Press, Oct 2006).

No single step in the coating process has more impact on film adhesion than surface preparation. Film adhesion to a plastic is primarily a surface phenomenon and requires intimate contact between the substrate surface and the coating. However, intimate contact of that plastic surface is not possible without appropriate conditioning and cleansing. Plastic surfaces present a number of unique problems for the coater. Many plastics, such as polyethylene or the fluorinated polymers, have a low surface energy. Low surface energy often means that few materials will readily adhere to the surface. Plastic materials often are blends of one or more polymer types or have various quantities of inorganic fillers added to achieve specific properties. The coefficient of thermal expansion is usually quite high for plastic compounds, but it can vary widely depending on polymer blend, filler content, and filler type. Finally, the flexibility of plastic materials puts more stress on the coating, and significant problems can develop if film adhesion is low due to poor surface preparation.

690. Hart, C.P., “Metallized films having an inherent copolyester coating,” U.S. Patent 4971863, Nov 1990.

1060. Hartland, S., ed., Surface and Interfacial Tension: Measurement, Theory, and Applications, Marcel Dekker, 2004.

1822. Hasselbacher, N., “Prestige treatment,” Converting, 27, 36-39, (Feb 2009).

1962. Hata, T., Y. Kitazaki, and T. Saito, “Estimation of the surface energy of polymer solids,” J. Adhesion, 21, 177-194, (Apr 1987).

The methods to estimate the surface tension of polymer solids using contact angles have been reviewed in the first part. They are classified into the following three groups depending on the theories or the equations applied: (1) the methods using the Young's equation alone, (2) the methods using the combined equation of Young and Good-Girifalco, and (3) the methods using the equations of work of adhesion. Some notes and comments are given for each method and results are compared with each other. The two-liquids method for rather high energy surface is also introduced.

Next, some new possibilities to evaluate the surface tension of polymer solids are presented by our new contact angle theory in consideration of the friction between a liquid drop and a solid surface. The advancing and receding angles of contact (θa and θr) are explained by the frictional tension γF and accordingly two kinds of the critical surface tension γC(γCa and γCr) are given.

This work has shown that one of the recommendable ways to evaluate γS is either the maximum γLV cos θa or the maximum γC using the advancing contact angle θa alone, and another way is the arithmetic or the harmonic mean of the γCa and γCr. A depiction to determine the γC such as ln(1 + cos θ0) vs. γLV with cos θ0 = (cos θ0 + cos θr)/2 has also been proposed.

2299. Hata. T., and T. Kasemura, “Surface and interfacial tensions of polymer melts and solutions,” in Adhesion and Adsorption of Polymers, Part A, L.-H. Lee, ed., 15-42, Plenum Press, 1980.

2364. Hatada, K., and Y. Yamaguchi, “Method for surface treatment of plastics,” U.S. Patent 3900538, Aug 1975.

2028. Hautojarvi, J., and S. Laaksonen, “On-line surface modification of polypropylene fibers by corona treatment during melt-spinning,” Textile Research J., 70, 391-396, (2000).

On-line corona treatment of polypropylene (PP) fibers during melt-spinning is studied. After extrusion of pp filaments, collected fiber tow is subjected to corona treatment prior to drawing, crimping, and cutting into staple fibers, and wettability, antistatic, and friction properties of treated fibers are characterized. Corona treatment results in an average decrease of 5-10° in the advancing contact angle and of 10-25° in the receding contact angle for water on fibers. With amounts of spin finish lower than 0.2% by weight of fiber, treated fibers have considerably better antistatic properties than untreated fibers. Treated fibers have an order of magnitude lower electrical resistance and about 50% less static charge build-up during carding than untreated fibers. In addition, there is a sharp change in wetting and friction properties of fibers with corona treatment when the amount of spin finish is between 0.12 and 0.13 wt %. These effects are attributed to improved wetting of the treated fibers by spin finishes, leading to a more uniform spreading of finish agents on the fiber surface.

3036. Hayashida, H., F. Ishibashi, H. Takahata, T. Nishin, Y. Gotoh, and Y. Sato, “New process for producing an extrusion laminated film without any chemical primer - non anchor coating extrusion laminating process,” Polymer Engineering & Science, 2018, (Apr 2004).

478. Hayes, L.J., “Surface energy of fluorinated surfaces,” J. Fluorinated Chemistry, 8, 69+, (1976).

By fluorinating the surface of a polymer, the hydrogen bonding energy of a polar surface has been defined. The contact angles for three solvent classes; nonpolar, polar and hydrogen bonding, on a polar surface results in the separation of dispersion, polar, and hydrogen bonding energies. Both critical surface tension plots and theoretical calculations were used to define the surface energy for fluorinated polyethylene.

1643. Hazlett, R.D., “On surface roughness effects in wetting phenomena,” J. Adhesion Science and Technology, 6, 625-633, (1992) (also in Contact Angle, Wettability and Adhesion: Festschrift in Honor of Professor Robert J. Good, K.L. Mittal, ed., p. 173-181, VSP, Nov 1993).

638. Heath, R.J., “Review of the surface coating of polymeric substrates. Need to adopt surface and interfacial science priciples to improve product quality,” Progress in Rubber and Plastics Technology, 6, 369-401, (1990).

Many coatings materials are based on polymeric materials and sometimes difficulties arise when trying to marry them to polymer substrates of low surface energy and relatively inert molecular structure. Through the application of tailored coating formulation, substrate surface pretreatment and suitable coating process these problems may be eliminated to produce coated polymers with high bond strength properties.

1431. Hedenqvist, M.S., A. Merveille, K. Odelius, A.-C. Albertsson, and G. Bergman, “Adhesion of microwave-plasma-treated fluoropolymers to thermoset vinylester,” J. Applied Polymer Science, 98, 838-842, (Oct 2005).

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

2540. Hegemann, D., H. Brunner, and C. Oehr, “Plasma treatment of polymers for surface and adhesion improvement,” Nuclear Instruments and Methods in Physics Research, Section B, 208, 281-286, (Aug 2003).

Different plasma treatments in a rf discharge of Ar, He, or N2 are used to etch, cross-link, and activate polymers like PC, PP, EPDM, PE, PS, PET and PMMA. Due to the numerous ways a plasma interacts with the polymer surface, the gas type and the plasma conditions must be adjusted on the polymer type to minimize degradation and aging effects. Wetting and friction properties of polymers can be improved by a simple plasma treatment, demonstrated on PC and EPDM, respectively. However, the deposition of ultra-thin layers by plasma enables the adjustment of wetting properties, using siloxane-based or fluorocarbon films, and further reduction of the friction coefficient, applying siloxane or a-C:H coatings. Nevertheless, the adhesion of plasma-deposited coatings should be regarded, which can be enhanced by depositing a graded layer.

1215. Heitz, C., “A generalized model for partial discharge processes based on a stochastic process approach,” J. Physics D: Applied Physics, 32, 1012-1023, (1999).

A general framework for the physical description of partial discharge (PD) processes is presented that holds for different types of PD causing defects. A PD process is treated as a stochastic process consisting of short duration discharges (point-like in time) and charge carrier drift/recombination intervals between these discharges. It is determined by few basic physical parameters and, in a stochastic process framework, can be described in a closed form by a master equation. Since usually only the fast discharges can be measured as PD signals, a restricted possibility of observing a PD process results. The link between the stochastic process and observable quantities is derived.

A specific type of measurements is reported, the so-called phase-resolved partial discharge (PRPD) patterns. Here the total charge transferred during a discharge and the time or alternating current phase at which the discharge occurs are measured. Thus each discharge event is described by the two quantities, charge and phase angle. The modelling of the observation process is explicitly derived for this case. However, the used method can easily be generalized to other types of PD measurements.

The proposed approach yields new possibilities for the interpretation and analysis of PD patterns. Features of PD patterns can be derived analytically from the process parameters. Conversely, quantitative information about the discharge physics can be gained from measured patterns. Some limiting cases of model parameter values leading to typical pattern features are discussed explicitly.

Examples are presented that demonstrate the applicability of the model for three different discharge types (internal discharge in a gas-filled void, surface discharge in oil, corona in air).

2678. Hejda, F., P. Solar, and J. Kousal, “Surface free energy determination by contact angle measurements - a comparison of various approaches,” in WDS '10 Proceedings, Part III, 25-30, MATFYZ Press, 2010.

One of the parameters characterizing the surfaces of materials is the surface free energy. The most common way to determine its value is to measure the surface tension by the sessile drop method. In this case a contact angle between the surface and the edge of droplets of liquids is measured. There are various approaches to calculate the surface free energy from the contact angle measurements. We made a review and a direct comparison of the most widely used methods and testing liquids in order to re-evaluate their advantages and disadvantages. In the presented work we discuss the limits of applicability of the examined methods. We confirm that methods using a pair of liquids give results dependent on the liquids chosen. Using a pair of non-polar and polar liquid yielded most reliable results. This is even more clear when two-liquid method is transformed into a multiple-liquid method. The algorithms developed during the work will be implemented into liquid contact angle analysis software.


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