Corona discharge treatment of isotactic polypropylene surfaces in N₂ and CO₂ was investigated by contact angle measurements and ESCA. The electrical characteristics of the discharges as well as the influence of indirect parameters (moment of air contact and ageing time) and direct parameters (applied charge, electrical field strength and film temperature) on the surface modification were determined. These investigations showed that electrons, emitted by photo effect are the dominant charge carriers and the main cause of surface activation. The active species in the surfaces (presumably radicals) can either perform crosslinking and H-abstraction or react with the discharge gas. In the N₂-discharge the polymer radicals can only react with atomic or excited nitrogen whereas in CO₂ they also react with ground state molecules. If the samples are brought into air contact after discharge leftover radicals are oxidized by atmospheric oxygen. In addition a UV-radiation causing activation in a surface layer was found. The bulk of the polymer is not influenced by corona discharge.

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

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

We discuss the behavior of a liquid partially wetting a solid surface, when the contact angle at equilibrium θ₀ is small, but finite. The solid is assumed to be either flat, but chemically heterogeneous (this in turn modulating the interfacial tensions), or rough. For weak heterogeneities, we expect no hysteresis, but the contact line becomes wiggly. For stronger heterogeneities, we first discuss the behavior of the contact line in the presence of a single, localized defect, and show that there may exist two stable positions for the line, obtained by a simple graphic construction. Hysteresis shows up when the strength of the defect is above a certain threshold. Extending this to a dilute system of defects, we obtain formulas for the “advancing” and “receding” contact angles θ_a, θ_r, in terms of the distribution of defect strength and defect sharpness. These formulas might be tested by controlled contamination of a solid surface.

Three nonpolar organic polymers containing small amounts of polar functionality were studied with regard to their surface characteristics. Two of the materials, potassium chlorate/sulfuric acid-oxidized polyethylene and poly(ethylene-co-acrylic acid) display variable surface polarities which can be reversibly accessed by heating films of the polymers in air or aqueous sodium hydroxide. Sodium-reduced Teflon–FEP did not exhibit this characteristic. A combination of contact angle, ESCA, and ATR IR data are used to display that the surface changes are caused by migration of functional groups within the outer few tens of angstroms of the surface.

Molecular dynamics simulations have been carried out for liquid water between flat hydrophobic surfaces. The surfaces produce density oscillations that extend at least 10 Å into the liquid, and significant molecular orientational preferences that extend at least 7 Å into the liquid. The liquid structure nearest the surface is characterized by “dangling” hydrogen bonds; i.e., a typical water molecule at the surface has one potentially hydrogen‐bonding group oriented toward the hydrophobic surface. This surface arrangement represents a balance between the tendencies of the liquid to maximize the number of hydrogen bonds on the one hand, and to maximize the packing density of the molecules on the other. A detailed analysis shows that the structural properties of the liquid farther from the surface can be understood as effects imposed by this surface structure. These results show that the hydration structure of large hydrophobic surfaces can be very different from that of small hydrophobic molecules.

A thermodynamic model is used to predict the adsorption of nonionic surfactants on latexes with different polarity. The model, which is based upon the Flory-Huggins theory of polymer solutions, predicts that the adsorption decreases as the polarity of the latex increases. It is predicted that adsorption should occur even when it is unfavorable to replace a surface-water contact with a surfacesurfactant contact. This is due to a lower number of unfavorable hydrocarbon-water contacts when the surfactant is adsorbed, compared to when it is free in solution. It is also predicted that it is in principle possible to determine the latex polarity or solubility parameter, from adsorption measurements, provided that a similar experiment is carried out on a latex with known polarity, or solubility parameter.

Surface and interface characterization of polymeric materials has not enjoyed the multi-technique approach which typifies other types of materials. X-ray photoelectron spectroscopy (XPS) has dominated, despite several major disadvantages. New approaches are discussed which either improve XPS (particularly derivatization techniques) or utilize ‘static’ secondary ion mass spectrometry (SIMS) to overcome these limitations, with examples of their application in materials problem solving.

Titanium films, 1 μm thick were electron‐beam evaporated onto polyethylene (PE) that had been pretreated in situ by 2 keV Ar⁺ bombardment. A measure of the film adhesion was obtained by measuring the pull strength required to remove the Ti films. A strong dependence of the adhesion on the ion dose was found. The pull strength had a maximum of approximately 20 MPa after a dose of 6×10¹⁴ ions/cm² but decreased for higher ion doses. Without any ion bombardment prior to deposition, the adhesion was very poor with a pull strength of approximately 2 MPa. XPS analysis was used to examine the effect of the ion bombardment on the chemistry of the PE substrate and the Ti/PE interface. Untreated PE samples were contaminated with surface impurities and probably also with low molecular weight hydrocarbons. As the adhesion is maximized, most of the impurities are removed by the ion bombardment. The strong adhesion is suggested to be due to formation of a carbidelike Ti–C interfacial layer, detected by XPS.

Aluminium and titanium surfaces have been treated by corona discharge in air and gave bonds of strength similar to those obtained by conventional chemical treatment.

The present invention relates to improvements in treatment rolls for the corona discharge treatment of polymeric films whereby the same are rendered receptive to printing inks and the like. More particularly, the invention is directed to a treatment roll and method for use as an electrode in a corona discharge device, the roll being comprised of a metal substrate having a porous ceramic coating, the interstices in said coating being filled with silicone polymer, the roll evincing a high resistance to wear and electrical breakdown, whereby higher volumes of material may be processed.

Contact angle measurements have been carried out on various solid substrates using water-propanol mixtures and α-bromonaphthalene as wetting liquids. These substrates were: polytetrafluorethylene, Parafilm, polyethylene, polyurethane, polystyrene, polymethylmethacrylate, fluorapatite, and hydroxyapatite. The dispersion and the polar components of the surface free energy, γ_s^d and γ_s^p have been calculated from the geometric mean equation. Two approaches have been considered: (1) neglecting the spreading pressure π_e and (2) taking π_e into account (Dann's method). The results show that both approaches actually yield the same results for the surface free energy, γ_s, if a proper interpretation of the approaches is considered. All data indicate, that approach (1) gives γ_s values determined on the adsorbed liquid layer, whereas in approach (2) the free energies of the bare solid surfaces are found.

The surface tension and the dispersion and polar components of the surface tension for solids and liquids were estimated by contact angle measurement in order to apply these concepts to a detergency study. Two approximation methods, the extended Fowkes' equation and Wu's equation, were adopted for the calculations. Among the twelve experimental liquid pairs, methylene iodide/water and tricresyl phosphate/water gave values for paraffin, polyethylene, and polystyrene close to the average for the twelve pairs. Values for cellulost acetate and cellophane were there fore obtained using these two pairs. The results showed that the dispersion force component becomes larger with increasing degree of acetylation, while the polar force component becomes smaller.

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.

The surface contact angle of glycerol and of water on polystyrene (PS) films has been found to depend on the extent of uniaxial draw for atactic PS. The contact angle depends on direction for the smooth films of PS drawn by solid state coextrusion. Results as a function of draw ratio to values over 4 on these noncrystalline PS samples, M_w = 6 × 10⁵, have also been interrelated with other measures of orientation such as the anisotropy of surface and bulk properties measured, respectively, by dichroic reflectance infrared spectroscopy and by birefringence.

The effects of the modification of polystyrene (PS), polyethylene (PE), poly(vinyl chloride) (PVC), silicone rubber (SR), and fluorinated ethylene propylene (FEP) copolymer by radio frequency glow discharge in a helium environment were presented in part I. The hydrated polymer surfaces were characterized by XPS, SEM, visual microscopy, and by contact angle measurements. In general, exposure of the polymers to RFGD produced an oxidized hydrophilic surface, yet the roughness of the surface was unaltered by the relatively mild plasma conditions used. In this article, the frictional behavior of oxidized and unoxidized SR, PE, and FEP in distilled water, isotonic saline, and blood plasma environments is examined experimentally. The results are discussed in relation to the properties generally believed to affect frictional phenomena and to the surface properties as determined in part I. Results indicate that RFGD-treated SR generates less friction than untreated SR when dragged across all untreated and treated polymer surfaces, whether the medium is distilled water or an isotonic saline solution. Friction is consistently lower in a blood plasma medium between all surfaces investigated, most probably because of the presence of adsorbed proteins at the polymer interfaces.

The previously observed, but unexplained, deleterious effect of high relative humidity on the efficiency of electrical (‘corona’) discharge treatment for rendering polypropylene film printable has been re-examined. The effect of film temperature during treatment has also been studied. A consistent explanation of both effects based on the degree of surface coverage by physically adsorbed water is put forward, supported by X-ray photoelectron spectroscopy analysis of treated film surfaces.

An apparatus for corona effect surface treatment of sheet materials, comprising a metal electrode and an insulating material coated electrode, between which the materials to be treated are inserted, wherein in the inside of said coated electrode a cooling fluid is caused to flow.

In investigating the effect of the surface energetics of substrate materials on the adhesion characteristics of poly(p-xylylene) and poly(chloro-p-xylylene) by the “Scotch Tape” method, it was found that if the substrates had not been preconditioned (treated with argon or a methane plasma), the adhesion was poor. The characteristics of water resistant adhesion that were observed when coated substrates were boiled in 0.9% sodium chloride solution were found to vary from excellent (when the polymer did not peel from the substrate after three cycles of 8 hours of boiling and 16 hours at room temperature) to poor (when the polymer peeled off almost immediately). It was noticed that water resistant adhesion depends on the hydrophobicity of the substrate material (the greater the hydrophobicity, the greater the adhesion) and is not related to the dry adhesive strength of poly(p-xylylene). The oxygen glow discharge treatment of the substrates decreased both the dry and wet adhesive strength of the polymer. The effect of the argon glow discharge treatment depended on the surface energetics of the substrate, and the methane glow discharge treatment increased both the dry and wet adhesive strength of the polymer. These preconditioning processes are discussed in terms of the sputtering of the material from the wall of the reactor in contact with the plasma and the deposition of the plasma polymer of the sputtered material on the substrate surface.

The invention provides a novel method for preventing bleeding of a plasticizer or other additive ingredients contained in a shaped article of a vinyl chloride-based resin composition on to the surface of the article by the treatment with low temperature plasma. Different from conventional procedures for the plasma treatment, much improved reliability and reproducibility as well as effectiveness are obtained by subjecting the article to intermittent exposure to the plasma atmosphere instead of continuous exposure. In the inventive method, the overall treatment time is an alternate sequence of exposure times, each being of the length of 0.001 second to 1000 seconds, and repose times, each being also of the length of 0.001 second to 1000 seconds. The gas for the plasma atmosphere is desirably an inorganic gas selected from the gases other than oxygenic gases, halogen containing gases and sulfur containing gases.

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

Specific reactions for the derivatization of oxygen-containing functional groups in polymer surfaces have been developed in order to improve the precision of analysis by X-ray photoelectron spectroscopy (xps). These have been used to probe the chemical composition of low density polyethylene (ldpe) surface-modified by electrical discharge treatment. Simultaneously the effect of derivatizing particular groups on the auto-adhesive behaviour of these surfaces has been examined. Two independent specific interaction mechanisms have been identified.