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.

A simple apparatus and technique are described for measuring contact angles of liquids on small-denier fibers. This technique is based on the level-surface method and can be used to obtain either advancing or receding contact angles. Contact angles determined by this method are accurate and precise and the apparatus is inexpensive, rugged, easy to operate, and suitable for routine work.

There is currently an interest in techniques to control surface and interfacial properties of polymeric materials, such as wettability, adhesion, biocompatibility, friction, and wear, for different applications and technologies and for the design of novel materials. The desired surface properties range from complete release toward all contacting gaseous, liquid or solid substances to irreversible covalent bonding to other substrates of interest. The macroscopic interfacial phenomena describing these properties are wetting, adhesion, and adsorption. They all share a common basis; they are dependent upon the intermolecular and surface forces and, on the molecular level, upon the chemical and physical details of the molecular structure of the surfaces, especially upon the availability of particular functional groups at the surface. This chapter focuses on the strategies to estimate the surface energetic from wetting and surface tension measurements. The fact that the surface chemistry of polymers might differ substantially from the average bulk chemistry is also caused by the structural features of macromolecules. Therefore, it has become a powerful tool to control the surface energetic of polymers by their chemical bulk structures.

Contact angle, electrokinetic, and X-ray photoelectron spectroscopic (XPS) measurements have been used to study the surface properties of flame- and oxygen plasma-pretreated polypropylene/ ethylenepropylene-diene monomer rubber (PP-EPDM) blends and of ethylene vinyl acetate (EVA) copolymers grafted with carboxyl group-containing monomers. The contact angles of pure test liquids (water, methylene iodide, and ethylene glycol) were used to calculate the dispersive and polar components of the surface free energy according to Owens and Wendt, and the acid-base parameters according to Van Oss and co-workers. In addition, the acid-base properties of the differently pretreated polymers could be evaluated quantitatively by measuring the zeta potential vs. the pH in a 10^-3 mol/l KCI solution. The zeta potential measurements show that oxygen plasma-treated PP-EPDM and grafted EVA indicate an acidic surface character, whereas the flame-treated PP-EPDM blends possess both acidic and basic surface groups. The basic surface character of flame-treated PP-EPDM injection-moulded sheets could be enhanced by the presence of sterically hindered amine light stabilizers in the blend. This increase in the basic surface character was not only proved by zeta potential measurements, but also by the contact angle method according to Van Oss and co-workers. These results correlate with an increase of the oxygen content in the surface region and the occurrence of nitrogen-containing functional groups detected by XPS. The plasma-treated surface region of PP-EPDM blends contained an increased amount of carboxyl group-containing species (O=C-O). Flame-treated surfaces with additional light stabilizers in the blend indicated an increased concentration C-OH groups together with protonated nitrogen in the surface region. It was found that the adhesion strength of water-based primers was higher at these surfaces. A general interrelation between the acidic and basic parameters determined by zeta potential measurements, on the one hand, and the acidic and basic parameters determined by contact angle measurements, on the other hand, could not be found. A direct correlation was found between the increasing acidic character of EVA grafted with different amounts of carboxyl group-containing monomers and the decrease in the receding contact angle.

The solid-vapour surface tension has been determined by contact angle measurements with polar and non-polar liquids on flat solid surfaces using Axisymmetric Drop Shape Analysis (ADSA) and by capillary penetration experiments on rough and porous solids. For smooth and inert, well prepared solid surfaces (PTFE, FC 721 on mica, FEP, PET) the plot of γ_lvcosΘ versus γ_lv yields smooth curves which are consistent with the equation of state approach to calculate solid-vapour and solid-liquid interfacial tensions. Other experimental patterns of contact angle data are caused by surface roughness and non-inert solids which may result in contact angles incompatible to Young’s equation. An alternative way to obtain the solidvapour surface tension of rough and porous solids are capillary penetration experiments. The determination of the penetration velocity of liquids into rough and porous solids yields Kγ_lv coΘ versus γ_lv plots, which provide γ_sv values for these systems; K is an unknown parameter of the constant geometry of the porous solid. The application of this concept was demonstrated for a hydrophobic PTFE powder and for hydrophilic Cellulose membranes.

The solid surface tension γsv of hydrophobic polymer powders has been determined using the capillary penetration technique. By plotting Kγlv cos ζ, where K is a geometric factor, versus the liquid surface tension γlv, the following values of γsv were directly derived from the curves: poly(tetrafluoroethylene) γsv = 20.4 mJ/m², polypropylene γsv = 30.2 mJ/m², polyethylene γsv = 34.4 mJ/m², and polystyrene γsv = 27.5 mJ/m². These values are in good agreement with the γsv values obtained from contact angle measurements on flat and smooth solid surfaces of the same materials. If the contact angles were first calculated from the capillary penetration experiments, which is the usual procedure applied in the literature, distinctly higher contact angles were obtained. Obviously these angles are affected by the powder morphology and are therefore meaningless contact angles in terms of a surface energetic interpretation.

The ability of polypropylene (PP) to adhere to mild steel depends to a large extent on the surface characteristics of both PP and steel. The adhesion of PP was improved by treatment in a cold plasma from oxidizing gases (O₂, H₂O, etc.). This surface functionalization was followed ex situ by means of contact angle measurements and XPS (X-ray photelectron spectroscopy) analysis. The polymer/steel assembly was fabricated by hot-pressing in vacuum, or after exposure to ambient air. Adhesion to steel, as determined by the lap-shear test, increased when the PP was treated with Ar-containing plasma gas and joined to steel after exposure to room atmosphere. Correlations between the polarity, the atomic (O/C, N/C) ratio, the dispersive component of the surface energy, and the degree of PP/steel adhesion are discussed.

The effect of forced air-plasma pre-treatment, Lectro-treat (TM), on polypropylene has been investigated using X-ray photoelectron spectroscopy (XPS), angle-resolved XPS (AR-XPS), and atomic force microscopy (AFM). The pre-treatment process is found to induce both surface chemistry changes and topographical changes. The parameters of the pre-treatment process can be optimised from these observations. The Lectro-treat pre-treatment process has been used for adhesive bonding of a demonstrator component: a bumper assembly. The adhesively bonded bumpers performed successfully in standard automotive tests.

We compare two surface treatments of biaxially-oriented polypropylene (BOPP), which are carried out in the same dielectric barrier discharge (DBD) apparatus, namely air corona, and N₂ atmospheric pressure glow discharge (APGD). Changes in the surface energy and chemistry are investigated by contact angle measurements, by X-ray photoelectron spectroscopy (XPS) and by attenuated total reflectance infrared spectroscopy (ATR-FTIR). It is shown that N₂ APGD treatment leads to a higher surface energy than air corona treatment, and to the formation of mostly amine, amide, and hydroxyl functional groups at the polypropylene surface. Finally, hydrophobic recovery of the treated film is studied; for both treatment types, the increased surface energy is found to decay in a similar manner with increasing storage time after treatment.

X-ray photoelectron spectroscopy (XPS) and contact angle measurements were used to characterize the surface modification and possible production of low molecular weight reaction products on biaxially oriented polypropylene (BOPP) and on low density polyethylene (LDPE) films treated by atmospheric pressure glow discharge (APGD) in pure nitrogen and by air corona. We have observed that surface degradation is more pronounced for air corona treatments in the case of both polymers.

The surface degradation and production of low molecular weight oxidized materials (LMWOM) on biaxially oriented polypropylene (BOPP) and low-density polyethylene (LDPE) films was investigated and compared for two different dielectric barrier discharge (DBD) treatment types, namely air corona and nitrogen atmospheric pressure glow discharge (N₂ APGD). Contact angle measurements, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) analyses were performed in conjunction with rinsing the treated films in water. It is shown that N₂ APGD treatments of both polyolefins result in much less surface degradation, therefore, allowing for a significantly higher degree of functionalization and better wettability. Hydrophobic recovery of the treated films has also been studied by monitoring their surface energy (γ_s) over a period of time extending up to several months after treatment. Following both surface modification techniques, the treated polyolefin films were both found to undergo hydrophobic recovery; however, for N₂ APGD modified surfaces, γ_s ceases to decrease after a few days and attains a higher stable value than in the case of air corona treated films. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1291–1303, 2004
https://onlinelibrary.wiley.com/doi/abs/10.1002/app.21134

The low temperature plasma produced by a surface barrier discharge generated in nitrogen at atmospheric pressure has been used for the treatment of polyester nonwoven (PET NW) fabrics. Surface modifications of three types of PET NW with different square weights (25, 50 and 80 g/m(2)) have been investigated. To determine the treated PET NW hydrophilicity, the strike-through time was measured. The optimum treatment time acceptable for technological applications was looked out with respect to the ageing phenomena. The obtained results show significant improvement in the wettability of PET NW. The effect of increasing wettability is considerably reduced with the increase of material square weight. The method has the potential to be suitable for industrial technologies, especially for thin materials.

In this paper, we present a simple, yet novel, method, utilizing scraping to obtain continuous rough microstructures over large areas, leading to a tunable wettability conversion from hydrophilicity to superhydrophobicity on polymer surfaces. A series of polymers ranging from hydrophobic to hydrophilic were used, and we found that the wettability of these polymer surfaces could be modified by the scraping process, irrespective of their hydrophobicity or hydrophilicity. More importantly, those polymers with contact angle ranging from 65° to 90° on their smooth surfaces also exhibit enhanced hydrophobicity after scraping. Our results indicate that 65° is the critical value which is more suitable to define hydrophobicity and hydrophilicity for polymer materials.

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

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

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

Through the controlled use of selected pretreatments, significant improvements to adhesion levels can be realised. Pretreatment options include chemical activation, corona discharge treatment, plasma-induced modifications and grafting. Using such methods, adhesion levels that render substrates fit for the intended purpose can be achieved. Such improvements can be realised without compromising the inherent properties of the materials being treated. Various approaches are considered as is the nature of the adhesion process. Several reasonably recent examples of the use of surface activation are presented.

Ultra-high modulus polyethylene (UHMPE) fibres have been treated using a novel 'non-plasma' treatment allowing the incorporation of various chemical functional groups onto the polymer surface. The process comprises two steps: corona discharge treatment, followed by silanization of the polymer surface by a solution of an organo-functional silane. Corona discharge treatment incorporates oxygen-containing functionalities, e.g. reactive hydroxyl groups, onto the polymer surface. The presence of reactive -OH groups provides the possibility of covalent linkage of any organo-functional silane to the corona discharge-treated polymer in the form of a fibre, film, sheet, or powder. The effectiveness of the process was assessed by examining the interlaminar fracture energy and flexural modulus and by SEM analysis of the fracture surfaces of composites fabricated from the untreated, corona discharge-treated, ammonia plasma-treated, and the amine-grafted (using the novel process) UHMPE fabric. A significant improvement in interfacial adhesion was confirmed by increases in the interlaminar fracture energies and flexural moduli. The effectiveness of the process investigated is similar to the ammonia plasma treatment. SEM analysis of the fracture surfaces indicated a change in the fracture mode from purely adhesive for unmodified fibres, through to mixed failure mode for corona-treated material, to highly cohesive-in-fibre surface for amine-grafted UHMPE fibres. XPS analysis confirmed the incorporation of the amine groups onto the surface of polyethylene treated using the novel method.

This paper reviews the theoretical principles of macromolecular design of polymer interface/interphase systems for obtaining maximum adhesion. Subsequently, a relatively simple and industry-feasible technology for surface grafting connector molecules is discussed in detail and supported by a range of experimental examples. It is shown, in agreement with contemporary theory, that the use of chemically attached graft chemicals of controlled spatial geometry and chemical functionality enables a significant increase in the strength and fracture energy of the interphase, to the point of cohesive fracture of the substrate, or that of an adjacent medium such as adhesives, paints or elastomers. This occurs even after prolonged exposure of bonded or painted materials to adverse environments such as hot water, thermal shock, UV radiation and other hostile ambients.

Surface modifications of polyetheretherketone (PEEK) made by chemical etching or oxygen plasma treatment were examined in this study. Chemical etching caused surface topography to become irregular with higher roughness values R_a and R_q. Oxygen plasma treatment also affected surface topography, unveiling the spherulitic structure of PEEK. R_a, R_q and surface area significantly increased after plasma treatment; topographical modifications were, nonetheless, moderate. Wetting angle measurements and surface energy calculations revealed an increase of wettability and surface polarity due to both treatments. XPS measurements showed an increase of surface oxygen concentration after both treatments. An O:C ratio of 3.10 for the plasma-treated PEEK surface and 4.41 for the chemically-etched surface were determined. The results indicate that surface activation by oxygen plasma treatment for subsequent coating processes in supersaturated physiological solutions to manufacture PEEK for biomedical appiications is preferable over the chemical etching treatment.

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.

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.

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.

The finding that the dispersion force contributions to the surface free energies of octane and water are equal enabled a simple method to be developed to characterize the hydrophilic nature of solid surfaces. This technique involves measuring octane contact angles on solid surfaces under water. Nonhydrophilic solids unable to interact by polar forces exhibit a predicted 50° contact angle, whereas those able to interact by polar forces give values greater than 50°. The greater the contact angle, the stronger are the polar interactions. The deviation of the contact angle from 50° can be used to evaluate, Isw, defined as the interfacial stabilization energy from the nondispersion (polar) forces.

The dispersion force contributions to the surface free energies of octane and water are equal—21.8 dyn/cm. Octane's surface free energy has no polar component, whereas water has a polar contribution of 50.2 dyn/cm. Therefore, the increase in the contact angle of octane on various polar polymer surfaces underwater is a quantitative measure of the interfacial stabilization energy from polar forces. Octane contact angles were measured underwater on polyethylene, polytetrafluoroethylene, and polyethyleneglycolterephthalate surfaces before and after surface oxidation in a low temperature asher. The octane contact angles increased in each case as the surfaces became oxidized. When simple lap joints were prepared from these polymers and then broken in an Instron Tester, the measured breaking forces correlated well with the octane contact angles. Breaking strength increases of 1.1, 1.2, and 1.8 psi were realized with the polyethylene, polytetrafluoroethylene, and polyethyleneglycolterephthalate, respectively, when the polar forces were increased by 1 erg/cm².

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.