The effect of nonpolymer-forming plasma (e.g., plasma of hydrogen, helium, argon, nitrogen) can be viewed as the following two reactions: 1) reaction of active species with polymer, and 2) formation of free radicals in polymer which is mainly due to the UV emitted by the plasma. The incorporation of nitrogen into the polymer surface by N₂ plasma and the surface oxidation by O₂ plasma are typical examples of the first effect. The latter effect generally leads to incorporation of oxygen in the form of carbonyl and hydroxyl and to some degree of cross-linking depending on the type of substrate; however, the degradation of polymer at the surface manifested by weight loss occurs in nearly all cases when polymers are exposed to plasma for a prolonged period of time. The effects of polymer-forming plasma is predominated by the deposition of polymer (plasma polymer); however, with some plasma-susceptible polymer substrates the effect of UV emission from polymer-forming plasma cannot be neglected. The mechanism of polymer formation can be explained by the stepwise reaction of active species and/or of an active specie with a molecule, and the chain addition polymerization of some organic compounds (e.g., vinyl monomers) is not the main route of polymer formation.

Plasma polymers contain appreciable amount of trapped free radicals; however, the concentration is highly dependent on the chemical structure of the monomer. In plasma polymerization, 1) triple bond and/or aromatic structure, 2) double bond and/or cyclic structure, and 3) saturated structure are three major functions which determine the rate of polymer formation and the properties of plasma polymers. The changes of some properties of plasma polymers with time are directly related to the concentration of trapped free radicals in plasma polymers. The amount of trapped free radicals in a plasma polymer is also influenced by the conditions of discharge; however, the UV irradiation from the polymer-forming plasma is not the main cause of these free radicals. Excess amount of free radicals are trapped during the process of polymer formation (rather than forming free radicals in the deposited polymer by UV irradiation). The properties of a plasma polymer is generally different from what one might expect from the chemical structure of the monomer, due to the fragmentation of atoms and/or functions during the polymerization process. This is another important factor to be considered for the modification of polymer surfaces by plasma polymerization.

The chemical species created in a low-pressure electrical discharge in oxygen attack the polymer at the surface, converting it to gaseous products. This process is interesting because: 1) the chemical changes on the resulting surface facilitate the formation of strong adhesive bonds and provide sites for the chemical attachment of other molecules, 2) significant morphological features lying below the surface may be revealed, 3) polymer can be cleanly removed from surfaces which are resistant to oxidation, and 4) dielectric breakdown frequently is preceded by the attack on the polymer of chemical species created in a corona discharge. Atomic oxygen is an important chemical species created in such a discharge. It reacts with organic substances rapidly at room temperature, but lives long enough in the low-pressure gas that it can be separated from many other reactive species created in the discharge. “Titration” with NO₂ provides a straightforward chemiluminescent means for determining the concentration of atomic oxygen to which the sample is exposed. This paper characterizes the attack of atomic oxygen, perhaps in the presence of long lived but less reactive species such as excited O₂molecules, on polymer surfaces, using electron microscopic observations of known morphological features of polyethylene to observe the changes produced by atomic oxygen. Lamellar polyethylene crystals were attacked both at the edges and the fold surfaces. Layers many microns thick were removed from spherulitic samples and replicas obtained from the surfaces thus exposed. Thick samples were thinned to the point at which they were transparent to an electron beam and interior morphological features were directly observed.

The present invention relates to a method and apparatus for the production of plastic materials having improved surface bonding properties for bonding other materials to the plastic materials. The new method comprises passing the plastic material through an electrically charged flame. The apparatus used to perform the method may have several embodiments which include an electrical power supply circuit, a discharge electrode, a burner, and a chill-roller for supporting the plastic material.

Electrical characterization is based on a display of voltage and charge which appears as a simple parallelogram. The area is a measure of energy input per cycle and is independent of voltage waveform but very dependent on the maximum voltage. A useful model for such corona discharges employs a Zener diode to simulate the corona drop. The buffer dielectric plays a major roll in controlling the corona power, and the air gap importance depends on the electrode system employed. Proper interpretation of the voltage-charge traces provides insight as to the corona performance and serves as a diagnostic procedure for obtaining optimum performance.

An electrode and method for electrostatically treating the surface of a substrate of continuous sheet metal material, wherein the electrode comprises a rotatable, electrically conductive cylindrical member onto and off of a segmental portion of the peripheral surface of which the substrate is continuously wrapped. The cylindrical member has its peripheral surface encompassed by a non-conductive material for engaging the substrate as it passes around the cylindrical member. The non-conductive material includes an insulating barrier for insulating the substrate from the cylindrical member, and outwardly opening cavities to provide an air space between the substrate and the cylindrical member, in the area of the substrate wrapped on the cylindrical member, to enable ionization of the air in such air space for treating the substrate surface wrapped on the cylindrical member upon application of a potential difference between the cylindrical member and the substrate.

The autohesion of polyethylene sheets was markedly improved by corona discharge treatments in oxygen, nitrogen, argon and helium. Equal bond strength was produced by an equal number of discharge cycles regardless of the time or frequency of application. At a given operating voltage the power consumed in a discharge rather than the chemical nature of a gas proved to be a factor controlling the enhancement of autohesion. The detrimental effect of the oxidation upon autohesion was noted after a prolonged treatment in an oxygen corona.

The ability of corona treatment to render polyethylene film self-adherent has been previously reported and the mechanism explained. A similar effect has now been found with corona-treated poly(ethylene terephthalate) film which adheres strongly to itself when joined under conditions of heat and pressure that give no adhesion with untreated film. Poly(ethylene terephthalate) films irradiated with short-wave UV light also become self-adherent. The behavior of the adhesive joints in both cases is the same as that reported for corona-treated polythylene film in that the joint strength is zero in the presence of hydrogen-bonding liquids, but recovers completely if the joint is allowed to dry undisturbed. Chemical and physical tests have shown that the adhesive bond is a hydrogen bond between the hydrogens of phenol groups created by corona or UV irradiation in one surface with carboxyl carbonyl groups in the other surface. Thin-layer chromatography of surface extracts from corona- and UV-treated films has shown the products of treatment to be practically identical for both types of treatment, supporting the conclusion that the mechanism of corona treatment resembles that of greatly accelerated photo-oxidation.

Corona-treated polyethylene films have been reported to exhibit strong self-adhesion when joined together under conditions of heat and pressure that give no adhesion with untreated films. The present study of this effect has shown that the adhesion is completely destroyed by the application of any hydrogen-bonding liquid to the adhesive joint and that the effects of liquids is completely reversible. Joints allowed to dry recover full strength. These facts together with the results of chemical reactions conducted on the treated film surface have established that the adhesive bond is a hydrogen bond. Corona treatment forms keto groups on the polyethylene chain; these groups enolize and the enolic hydrogens bond with carbonyl groups in the adjacent sheet of film when two sheets are heated together under pressure.

Polypropylene films were treated with chromic acid mixture. The change in the treated films was investigated by comparing change in amount of 2,4-dinitrophenylhydrazones formed in the treated films with their change in wettability with water. Oxidation of the film surface zone, partial breakdown of polymer in the film surface zone, and oxidation of surface zone bared from the film inner zone seemed to occur with increase in treatment time or with increase in treatment temperature.

The thermodynamics of an idealized rough surface is treated, using the geometry of a vertical plate partially immersed in a liquid. Gravity is included explicitly in the theory. The results of this treatment are more general than those of previous studies and are more easily extended to other surface topographies. Some novel results are found, such as a delineation of the conditions under which a macroscopic contact angle of 180° will result from geometric properties of the solid surface. On rough surfaces consisting of material for which, if smooth, the equilibrium contact angle would be different from 90°, the slopes of the asperities will be a very important factor in determining the effective equilibrium contact angles.

Polymeric films are exposed to a low energy electron beam in order to alter the permeability characteristics of the polymeric films for gases. The so treated polymeric films have enhanced utility for separating gases such as hydrogen and helium from mixtures containing same.

Ellipsometrically determined adsorption isotherms are reported for water on two types of pyrolytic carbon, on polyethylene, and on stearic acid-coated copper, for relative pressures up to close to the saturation pressure, P⁰, and for various temperatures. Contact angle data for bulk water on the same solids are included; advancing angles of 60°–90° were found. The adsorbed film thickness reaches 40–80 Å in the first two systems, but only a few angstroms in the second two; correspondingly, the surface pressures of P⁰, π⁰, are large in the first two cases and small in the second two. Large contact angle thus does not necessarily imply low π⁰. The data are fitted to a previously published potential-distortion model, which allows adsorption and contact angle behavior to be related.

The wettability of stereospecific poly(methacrylates) was studied. In the wettability of poly(methacrylates) having bulky substituents such as phenyl and chloroethyl groups, it was found that the critical surface tensions for isotactic polymers were low compared to those for attactic polymers. The steric effect of the bulky substituent on wetting was also discussed.

The wettability of a number of low energy solid surfaces, including hoof keratin and human skin, has been examined using two liquids, water and methylene iodide, and employing Wu's empirical approach to obtain γ_s^d and γ_s^P, the dispersion and polar components of the solid “surface tension.” The sum of these parameters, (γ_s^d + γ_s^p) was found to be in good agreement with reported values of γ_c, the critical surface tension, based on Zisman plots. Using the latter method, γ_c values of solids selected from the above group were determined using aqueous ethanol solutions. The values were lower than those obtained using nonpolar liquids, thus confirming earlier findings. A compilation of our own data and data from the literature reveals that the derived values of γ_c show little or no dependence on the type of solid surface, the type of alcohol or its chain length. The results can be explained in terms of adsorption of alcohol at the surface of the solid.

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.

Amorphous and graphitic carbon fibers and film surfaces are characterized by wettability measurements and surface energy analysis which isolate the (London-d) dispersion γ^d _svand (Keesom-p) polar γ^p _sv contribution to solid-vapor surface tension γ_sv =γ^d _sv + γ^p _sv Graphitized carbon fibers which are surface treated to provide strong bonding to polar matrix resins show consistent strong polar contributions to total surface tension with γ^d _sv|γ_sv ≃ γ^p _sv|γ_sv ≃ 0.50. Amorphous carbon films prepared for biological implant applications display dominant dispersion character in surface energy with γ^d _sv|γ_sv ≃ 0-74 to 0.95 and γ^p _sv|γ_sv ≃ 0.05 to 0.24.

It is shown that the best fit of experimental data to the correlation equation as used by Fowkes¹ cannot be considered as a criterion of correctness with which the mathematical formula expresses the way of polar interaction at interfaces. Examples of other evidence are given that the polar part of work of adhesion may be well represented by the geometrical mean of polar components of surface energies.

Wettability measurements and surface energy analysis are applied to isolate the (London-d) and (Keesom-p) polar contributions to solid-vapor surface tension γ_sv=γ^d _sv + γ^p _sv of surface treated graphite fibers. Surface treatments include metal coatings with Al, Cu, and Ni, chemically reducing heat treatments in H₂ and vacuum, and films of highly chlorinated polymers such as polyhexachlorobutadiene and polychloral. This study shows that the highly polar surface properties γ^p _sv|γ_sv ≃ γ^d _sv|γ_sv ≃ 0.50 of commercial graphite fibers can be modified by surface treatment to display dominant dispersion character with γ^d _sv|γ_sv ≃ 0.79 to 0.92 without substantial reduction in total surface energy γ_sv. For adsorption bonded fiber/matrix interfaces a new method of mapping the surface energy effects of an immersion phase upon the Griffith fracture energy γ_G is applied to define criteria for strong interfacial bonding under both air and water immersion.

Interfacial and surface tensions of polymers are important in the technology of plastics, coatings, textiles, films, and adhesives through their roles in the processes of wetting, adsorption, and adhesion. Because of experimental difficulty due to high viscosity, however, reliable measurements of these quantities were not reported until 1965 for surface tensions [l, 2] and 1969 for interfacial tensions [3, 4]. A body of scattered data has been accumulated in the literature. This review will evaluate, compile, and interpret these results.

Low-temperature radiofrequency excited gas plasma was applied to the surfaces of a number of polymers. Polymers that are known to crosslink as well as those that only degrade under irradiation were included in the investigation. Surface changes were studied by viscosity, gel content, and contact-angle measurements. Changes in adhesive bond strength were used as a measure of overall practical effects of plasma treatment. In each case the response of the polymer surface to an oxidizing (oxygen) and a nonoxidizing (helium) plasma environment is discussed. Further indications of the nature of the surface changes were suggested by statistical treatment of the bond-strength data.

Exposure of polyethylene film to UV radiation at wavelengths of ≤2537 Å is sufficient to induce surface crosslinking and to facilitate the formation of strong adhesive joints to these surfaces with conventional adhesives. Reduction of the vapor pressure in the reaction vessel to about 1 torr apparently maximizes the efficiency of the crosslinking process. Examination of the treated films which have been exposed for times necessary to form strong adhesive joints has revealed an absence of surface oxidation. It appears that crosslinking to improve the mechanical strength of the surface region of the polyethylene is sufficient to allow the formation of strong adhesive joints.

An equation of state is developed which allows the surface tension of a low-energy solid to be determined from a single contact angle formed by a liquid which is chemically inert with respect to the solid and whose liquid surface tension is known. The equation of state is obtained using two independent methods. In the first one, similar arguments to those in previous papers are used; however, the qualitative argument, based on the general appearance of plots, is replaced by computer curve fitting and statistical analysis. The second method, which has not been employed heretofore, treats the solid surface tension as an adjustable parameter. Molecular arguments in conjunction with the interaction parameter Φ are used to eliminate poor choices of the solid surface tension. The results are in excellent agreement with the first method.

The range of validity of the equation of state and practical points in its application are discussed.

By combining four techniques—X-ray photoelectron spectroscopy (ESCA), soft X-ray spectroscopy, contact-angle hysteresis, and electron microscopy—a powerful method to elucidate the nature of solid surfaces is created. ESCA provides semiquantitative elemental analysis of the uppermost 5–100 Å of the sample. Soft X-ray spectroscopy extends the elemental analysis to a depth of about a micron. Contact-angle measurements can be interpreted in terms of the distribution of surface energy and roughness, and a view of the microtopography is obtained with the electron microscope. This method of surface characterization has been applied to several problems in fluoropolymer surface chemistry. For example, certain sodium complex solutions are shown to react with fluoropolymer surfaces, removing most of the fluorine and leaving a sponge-like surface with characteristics of an unsaturated, oxidized hydrocarbon. Also analyzed are surface changes that occur upon exposure of these sodium-etched films to environmental conditions. In another application, films of poly(tetrafluorethylene/hexafluoropropylene) melted and recrystallized against a gold substrate were analyzed. The unusual wettability of such films has been attributed to the presence of a “transcrystalline” surface region, but our analysis indicates the presence at the surface of a very thin layer of materials with the characteristics of an oxidized hydrocarbon. The increased wettability is evidently due to the presence of this layer.

Chromic acid solutions were used to oxidatively etch linear (high density) and branched (low density) polyethylene and isotactic polypropylene. Etched surfaces were characterized by surface IR spectroscopy, wettability, electron microscopy and aqueous adhesive bonding (peel test). Polypropylene was found to etch rapidly, but showed little residual chemical or topographical change. The polyethylenes etched more slowly, especially in the case of the linear polymer, but showed large changes in surface chemistry as a result of oxidative attack. Adhesion onto polyolefin films and fabric increased very rapidly during the first few seconds of attack. This increase is interpreted in terms of wettability, topography and cohesive strength of the surface layer. The differences in etch behavior between the polyolefins is interpreted in terms of ease of oxidative attack at branch points, and surface accessibility to the acid.

Mild plasma cleaning of metal surfaces was shown to be effective in removing organic contaminants. Auger electron spectroscopy and surface wettability measurements were used to evaluate the plasma cleaning procedure and to provide a comparison with conventional solvent cleaning methods.

An improved electrode for use in apparatus for the treatment of the surface of a thin sheet of material includes an electrically conductive cylindrical core, a thin layer of dielectric material covering the cylindrical surface of the core, and an outer layer or sheath of electrically conductive material insulated from the core and completely surrounding the dielectric material. The electrode cooperates with one or more stationary electrodes in corona treatment apparatus to reduce the possibility of electrode arcing and to establish an electric field in the electrode gap with greater efficiency than the prior art.

The relationship between wetting and pressure-sensitive adhesion was studied using an adhesive composed of poly(butyl acrylate) and various adherends of different surface tension. The amount of adhesive deposit was determined quantitatively by tracer technique although the unbonding process was apparently observed as interface failure. The adhesive force and amount of deposit were both dependent on the critical surface tension of the adherends. Maximum tack value and contamination were observed with adherends whose critical surface tension was close to that but a little higher than that of the adhesive. The adhesive force obtained was lower than cohesive strength of adhesive. From this evidence, a mechanism for pressure-sensitive adhesion was discussed: the bond breaks in the addesive mass around the very minute spots where interaction is at work between adhesive and adherend. Inasmuch as the density of the minute spots per unit area depends on the surface tension, the adhesive force also depends on the surface tension.

Three methods of interpretation of contact angles in terms of surface tension of liquid and solid are correlated. It is shown that the critical surface tension for wetting γ_c is dependant in a specific way on the nature of the liquid system used regardless of the nature of the solid. Equations are derived which express the limiting values γ_c may assume for a liquid/solid system. γ_c is also correlated with the Good-Girifalco treatment of contact angles and experimentally determined values of the parameter φ are compared with theoretical calculations from molar volumes of normal alcohol-paraffin wax interfaces.

The Fowkes method of contact angle interpretation is used to derive values for the polar and dispersion force components of liquid surface tensions for three alcohol/water solution series and two organic acid/water solutions.

The wettability of oxidized polyethylene films was studied with pure liquids (water and methylene iodide) and practically nonpolar mixtures of Decalin and methylene iodide. A linear variation was found of the wettability of these films with the chemical composition of their surfaces (determined by adsorption of radioactive ⁴⁵Ca ions).

A value of γ_s^d for the polyethylene was found with the nonpolar mixtures of methylene iodide and Decalin and the values of the solid-liquid polar interactions (I_sl^P) for oxidized polyethylene were deduced.

Dipole-dipole and induced dipole-dipole interactions between the pure liquids and the oxidized and unoxidized polyethylene were calculated for two possible orientations of the hydrocarbon chains to the surface and compared with the experimental results. Generally a poor agreement was obtained, mainly due to the difficulty in estimating the correct values for the distances between molecules or groups. However, a better agreement was obtained assuming that the chains were perpendicular to the surface.

Experiment has shown that the nitrogen corona-induced autohesion of polyethylene and the nitrogen-corona induced sorption of iodine by polyethylene both follow similar mechanisms. The controlling factor is postulated to be the formation of short-lived electrets within the polymer surface.

The resultant surface activation of polymers by corona discharges has been found to be markedly influenced by the type and purity of gases used in the corona. In this work it is shown that for the nitrogen gas corona treatment (15 KV, 15 mins) of polyethylene and polypropylene, traces of oxygen, >0.5% and <0.15% respectively, are sufficient to produce chemical changes in the polymer surface.