A method and device of treating an irregularly shaped article to prepare the article for painting is provided. The device includes a burner which can produce an adjustable flame tongue which can fit into crevices, openings and other irregular topographical features of an item to be painted or otherwise coated. The burner device further provides means to apply a grafting chemical on a freshly oxidized surface. Further, the invention provides means to colorize treated objects so that they may be recognized as having been treated. In another embodiment, the grafting chemicals may be enhanced with electrolytic solutions such that electrostatic methods of painting may be subsequently employed on the item. In an alternate embodiment, the burner is adapted to spray a powder inside of a generally enclosed flame, and is used in conjunction with chop guns to manufacture glass or carbon fiber preforms.

A method and apparatus for producing a polyethylene coated paperboard material with a mirror-pocket finish and a predetermined Dyne level is disclosed herein. The apparatus and method utilizes a double corona treatment on a single polyethylene surface to create the material with the predetermined Dyne level. Such paperboard material is often used for fabrication of cups, and the like. The predetermined Dyne level is required for printing requirements. The method and apparatus allow for the production of the predetermined Dyne level material at standard laminator operating speeds.

The interfacial shear strength of an ultrahigh molecular weight (UHMW) polyethylene (PE) fiber/epoxy-resin system was greatly improved by the corona-discharge treatment of the fiber. The UHMW PE-fiber/epoxy-resin composite was prepared with corona-discharge-treated UHMW PE fiber. The mechanical properties of the composite sheet were determined by tensile testing. The tensile strength of the composite was also very much improved. However, the tensile strength of the composite was about one-half of the theoretical strength. This result was due to the molecular degradation of the PE-fiber surface caused by surface modification. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1162–1168, 2001
https://onlinelibrary.wiley.com/doi/abs/10.1002/1097-4628%2820010214%2979%3A7%3C1162%3A%3AAID-APP20%3E3.0.CO%3B2-Y

A starch-based biodegradable (BD) low density polyethylene (LDPE) film can be directly printable without any corona treatment, unlike virgin LDPE film. Such a film shows poor adhesion and nail scratch resistance of the ink on the printed area of the film. In order to increase the adhesion and nail scratch resistance of the ink on the printed BD film, grafting of acrylonitrile onto the BD film is carried out. The polyacrylonitrile grafted BD film shows better adhesion, nail scratch resistance, and printability. The printability of the polyacrylonitrile grafted BD film is comparable to the conventional corona treated LDPE film. The extent of printability is a function of the surface smoothness, as well as the optimum percentage of grafting on the biodegradable film. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1273–1277, 2001
https://onlinelibrary.wiley.com/doi/abs/10.1002/1097-4628(20010214)79:7%3C1273::AID-APP150%3E3.0.CO;2-L

The Young's equation is the well-known relationship used to describe a sessile drop at equilibrium on top of a solid surface. This relationship has been discussed thermodynamically and microscopically for purely flat surfaces in the literature. To characterize the non-flatness of a surface, one may introduce the Wenzel's roughness r defined as the area of the wall surface devided by the area of its projection onto the horizontal plane. Obviously, r is equal to 1 once the surface is flat. For r>1, it is known that Young's equation has to be modified to take into account the increase of surface. The generalization of Young's relation is the so-called Wenzel's law. In this presentation, we will study this relation within microscopic models. We will in particular show that the roughness may enhance the wetting of the substrate even at the microscopic scale.

Surface modification of poly(ethylene terephthalate) (PET) film by an argon (Ar) plasma was investigated as a function of the distance from the Ar plasma zone. Changes in distance between the PET film and the Ar plasma zone had a strong influence on the surface modification of the film. The direct Ar plasma treatment (distance between the PET film and Ar plasma zone = 0 cm) was effective in hydrophilic surface modification, but heavy etching reactions occurred during the modification. On the other hand, the remote Ar plasma treatment (distance between the PET film and Ar plasma zone = 80 cm) modified the PET film surfaces to be hydrophilic without heavy etching reactions, although the hydrophilicity of the PET was lower than that by the direct Ar plasma. The remote Ar plasma treatment was distinguished from the direct Ar plasma treatment from the viewpoint of degradation reactions. The remote Ar plasma treatment rather than the direct Ar plasma treatment was an adequate procedure for surface modification and caused less polymer degradation on the film surface. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 808–815, 2001
https://onlinelibrary.wiley.com/doi/10.1002/1097-4628(20010131)79:5%3C808::AID-APP50%3E3.0.CO;2-B

Polyolefin plastomer films formulated with slip and antiblock were blown on a wide die gap with and without two Dynamar^™ polymer processing additives (PPAs). A wide die gap was used so that melt fracture-free film could be obtained with no PPA present for comparison purposes. The films were analyzed for the following properties: surface tension (on treated films), gloss, haze, clarity, transmittance, hot tack, heat seal, COF and block. In addition, the surface of films was examined using ESCA (Electron Spectroscopy for Chemical Analysis) and SSIMS (Static Secondary Ion Mass Spectrometry) to determine the surface chemical composition. PPAs when used at typical dose levels were shown to have essentially no effect on the surface and optical properties of plastomer films.

The adhesive properties of isotactic polypropylene with different degrees of crystallinity, surface-modified by corona discharge plasma have been studied, during the process of ageing. Considerable decrease in the surface free energy and its polar component was observed. A significant correlation was found between the mechanical work of adhesion to polyvinyl acetate and the polar fraction during ageing. The influence of the crystallinity of the polymer on the resulting adhesion parameters of aged polypropylene foil was confirmed. © 2001 Society of Chemical Industry

A technique for generating active species with the One Atmosphere Uniform Glow Discharge Plasma (OAUGDP) has been developed and used to sterilize and increase the surface energy, wettability and wickability of nonwoven fabrics. The OAUGDP is a non-thermal, fourth-state-of-matter plasma with the classical characteristics of a low pressure DC normal glow discharge that operates in air (and other gases) at atmospheric pressure. No vacuum system or batch processing is necessary, and a wide range of applications to fabrics and polymeric webs can be accommodated in a parallel plate plasma reactor. In addition to directly exposing webs and workpieces to active species for surface energy increase in a parallel-plate reactor, we have shown that active species capable of sterilization can be convected at near room temperature to a remote exposure chamber. This technology is simple, produces many effects that can be obtained in no other way, generates minimal pollutants or unwanted byproducts, and is suitable for online treatment of webs, films, and fabrics.

Early exposures of nonwoven fabrics to the OAUGDP required minutes to produce relatively small increases of surface energy. These durations appeared too long for commercial application to fast-moving webs. Recent improvements in OAUGDP power density, plasma quality and impedance matching of the power supply to the parallel plate plasma reactor have made it possible to raise the surface energy of a variety of polymeric webs (PP, PET, PE, etc.) to levels in the range of 60 to 70 dynes/cm with one second of exposure. In most cases these high surface energies were not durable, and fell off to 50 dynes/cm after periods of weeks to months. Here, we report the exposure of nonwoven fabrics made of PP and PET at the UTK Textiles and Nonwovens Development Center (TANDEC) to an impedance matched parallel plate OAUGDP for durations ranging from one second to several tens of seconds. Data will be reported on the surface energy, wettability and wickability as functions of time of exposure, and of the aging effect after exposure. We will report the use of a OAUGDP with air as the working gas to sterilize a broad range of microorganisms on a variety of surfaces, and in several distinct applications. These include a Remote Exposure Reactor to sterilize large workpieces 20 centimeters or more from the plasma-generating region, and a sterilizable air filter.

Plasma-chemical modification is frequently used to improve the adaption of polymer surfaces to biological environments. In this regard amino functional groups play a key role. They provide an excellent basis for subsequent modifications with specific biomolecules. It would be of great value to get an amino functionalization independent of the specific material in use. The paper reports on an investigation concerning the feasibility of such an universal plasma functionalization procedure. Two different downstream microwave plasma sources were taken to apply a procedure, which was developed for high-grade modification of polystyrene (PS), to a number of other polymers including polyetheretherketone (PEEK), polyethyleneterephthalate (PET), polyethylenenaphthalate (PEN), polycarbonate (PC), polyethylene (PE), polymethylmethacrylate (PMMA) and fluorinated polymers. In many cases, very similar results were obtained. At maximum 5% of the surface were covered by nitrogen functional groups. In some cases, about 50% of total nitrogen functional groups were amino groups. The results suggest that a downstream ammonia plasma treatment indeed is a fairly universal method for high performance amino functionalization of polymeric biomaterials.

The adhesion of polypropylene and printing with various dyestuffs represents a serious problem which cannot be solved in satisfactory manner without modification. Because of practical usability, simple manipulation, suitability to continuous modification processes and efficiency the modification by plasma produced by electric discharge at atmospheric pressure in the medium of air oxygen was used. The free surface energy value of discharge-plasma pretreated biaxially oriented polypropylene in the course of short-time aging was determined. The free surface energy of modified polypropylene two weeks after modification exceeds the empirically established value 38 mJ.m^-2, that is regarded as a condition of acceptable surface modification of discharge plasma modified polypropylene foils.

Surface modification of iPP in vapors of phosphoryl chloride under UV irradiation is an effective method for the increase of adhesive properties. Phosphoryl chloride acts as an sensitizer that decomposes under the effect of UV irradiation.

Contact angle data for sets of probe liquids allow the determination of components of solid surface energies which in turn can be used to calculate the work of adhesion of other materials to the solid surface. There is much debate currently about the correct choice of the acid–base components for the probe liquids. For many systems, the strength of adhesion measured independently correlates well with the calculated work of adhesion. Recent trends in this area include adhesion under water and the adhesion of bacterial and other cells to immersed solids.

Dielectric barrier discharge (DBD) is the discharge involved in corona treatment, widely used in industry to increase the wettability or the adhesion of polymer films or fibers. Usually DBD's are filamentary discharges but recently a homogeneous glow DBD has been obtained. The aim of this paper is to compare polypropylene surface transformations realized with filamentary and glow DBD in different atmospheres (He, N₂, N₂ + O₂ mixtures) and to determine the relative influence of both the discharge regime and the gas nature, on the polypropylene surface transformations. From wettability and XPS results it is shown that the discharge regime can have a significant effect on the surface transformations, because it changes both the ratio of electrons to gas metastables, and the space distribution of the plasma active species. This last parameter is important at atmospheric pressure because the mean free paths are short (∼μm). These two points explain why in He, polypropylene wettability increase is greater by a glow DBD than by a filamentary DBD. In N₂, no significant effect of the discharge regime is observed because electrons and metastables lead to the same active species throughout the gas bulk. The specificity of a DBD in N₂ atmosphere compared to an atmosphere containing oxygen is that it allows very extensive surface transformations and a greater increase of the polypropylene surface wettability. Indeed, even in low concentration and independently of the discharge regime, when O₂ is present in the plasma gas, it controls the surface chemistry and degradation occurs.

A summary is given of different elementary processes influencing the thermal balance and energetic conditions of substrate surfaces during plasma processing. The discussed mechanisms include heat radiation, kinetic and potential energy of charged particles and neutrals as well as enthalpy of involved chemical surface reactions. The energy and momentum of particles originating from the plasma or electrodes, respectively, influence via energy flux density (energetic aspect) and substrate temperature (thermal aspect) the surface properties of the treated substrates. The various contributions to the energy balance are given in a modular mathematical framework form and examples for an estimation of heat fluxes and numerical values of relevant coefficients for energy transfer, etc. are given. For a few examples as titanium film deposition by hollow cathode arc evaporation, silicon etching in CF4 glow discharge, plasma cleaning of contaminated metal surfaces, and magnetron sputtering of aluminum the energetic balance of substrates during plasma processing will be presented. Furthermore, the influence of the resulting substrate temperature on characteristic quantities as etching or deposition rates, layer density, microstructure, etc. will be illustrated for some examples, too.

Polyolefins and fluoropolymers have a major drawback: they don't adhere to polymer surfaces properly. If these substrates do have to be coated, however, there are three different approaches to improving adhesion. One is to change the coating, another is to modify the polymer surface, and the third is to apply some kind of adhesion promoter. One successful process which could solve this problem comprises a combination of a plasma pre-treatment and an additional thin acrylated photoinitiator coating. The result is that the purely physical bond gives rise to a covalent chemical bond between the polymer surface and the coating. Further advantages offered by this process are discussed in this article.

This paper is aimed at calculating the electric field in the point-to-plane electrode system with the plate covered with a dielectric layer. With charge accumulation on the dielectric surface by corona discharge, the field in the dielectric is increased at the expense of a decrease in the gas gap. The charge accumulation on the dielectric surface proceeds to the maximum possible value when the normal component of the surface field vanishes. With the dielectric layer fully-charged, the percentage decrease of the field in the gas gap is maximum at the dielectric surface and declines along the gap axis to vanish at the point tip. The percentage decrease of the field becomes more pronounced with the increase of the diameter of the dielectric layer. The effect of inter-electrode spacing and the dielectric layer thickness on the field distribution is investigated. An accurate method of charge simulation was used for field calculation irrespective of the thickness of the dielectric layer and the gap geometry. With ion flow along the flux lines from the stressed point to the ground plane, the field enhancement factor increases and the volume charge density decreases along the flux lines. The voltages of the ion flow threshold and corona quenching are calculated and compared with previous measurements. The method of calculation is extended to calculate how high the surface potential of the charged dielectric needs to be to trigger a micro-spark in the electrostatic discharges from grounded point electrodes.

The results of an X-ray photoelectron spectroscopic investigation of the oxidation of surface layers of low-density polyethylene (LDPE) and biaxially oriented polypropylene (BOPP) films are presented. The analysis was performed using different take-off angles, namely 10°, 30°, and 90°; thus, the depths of the examined layers were 0.6, 1.9, and 3.7 nm, respectively. It was found that the course of the oxidation process in the surface layers was similar for both polymer films. However, for treatment energies lower than 5 kJ/m², the extent of the oxidation was higher for the LDPE film, whereas for energies above this value, the BOPP film was more oxidized. As detected by X-ray photoelectron spectroscopy (XPS), desorption of oxygen from the film surface occurs for both polymers during the treatment.

Several methods for the determination of both the surface free energy of polymer materials and the conditions necessary to perform contact angle measurements are discussed. The effects of the corona-treatment energy on the surface free energy and on the adhesion of acrylic adhesive were studied using a biaxially-oriented polypropylene film. The surface free energy was determined by the Owens-Wendt, and van Oss-Chaudhury-Good approaches, as well as with the wettability method, using different liquids. The presented results confirm that the surface free energy value depended on both the method used and the nature of probe liquids. Thus, it cannot be considered as a parameter characterizing unambiguously the surface layer of a corona-treated film. The values of the surface free energy for different film samples can be compared with one another only if determined using the same method and the same liquids. The variations of particular components of the surface free energy with the corona-treatment energy depend on e.g. the nature of probe liquids, which makes interpretation of the observed effects difficult.

This study has characterized the energetics of both the liquid state and the solid state of two commercially available epoxy resins: a DGEBA- and a TGMDA-based epoxy system. The surface properties of the liquid epoxies were evaluated by wetting measurements using a dynamic contact angle analysis (DCA). The Lifshitz-van der Waals components of the surface tension were found to be similar for both epoxy systems, while the acid-base components were found to be slightly different. Two different techniques were used to characterize the cured epoxy surface properties: wetting measurements and vapor adsorption measurements by means of inverse gas chromatography (IGC). The Lifshitz-van der Waals components of the surface energy were observed to be nearly the same for both epoxies, confirming that both resins have the same potential for non-specific interactions, in both liquid and solid states. Evaluations of the acid-base components of the work of adhesion by DCA and the Gibbs free energy change by IGC suggest that both cured epoxies show non-negligible specific interactions with both acidic and basic probes. However, computations of the accepticity and donicity parameters showed that both cured epoxies are predominantly basic, but also possess non-negligible acidity. It is likely that the presence of water on the solid surface contributes to the acidic character of the cured epoxies. The temperature dependence of the liquid surface tension for both epoxy systems was investigated. The same temperature dependence was observed: the surface tension decreased with temperature, following a linear regression. Corrections for viscous-drag effects on the liquid surface tension measurements were also made.

Chemical composition, morphology, and crystalline structure of low density polyethylene (LDPE) films surface grafted with acrylic acid (AA) using corona discharge were studied by attenuated total reflection infrared (ATR-IR), electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and wide angle X-ray diffraction (WAXD) techniques. The grafted film surface is covered with grafted chains. After grafting for 3.0 h in 20% aqueous solution of AA, the depth of the grafted layer is more than 10 nm. A grain structure was observed on the grafted surfaces which was probably caused by the isolated dispersion of active sites generated by corona discharge, and these active sites initiated the graft copolymerization. However, surfaces of grafted films were smoother than that of ungrafted ones. DSC curves of grafted films show a small peak at about 100°C due to vaporization of adsorbed water. The longer the graft copolymerization time, i.e. the higher the graft degree of AA on LDPE, the higher the amount of adsorbed water. The position of each peak in WAXD patterns, crystal axial length, crystal plane distance and crystal grain size remain almost unchanged during the graft copolymerization time of 2.0 h. However, when the graft copolymerization time reaches 3.0 h, twin peaks at about 21.4° and 22.0° are observed, indicating that a different crystal form is formed at longer copolymerization time, i.e. at a higher graft degree.

The effects of the specimen temperature of low-density polyethylene (LDPE) in O₂ plasma treatment were studied to enhance the amount of hydrophilic functional groups introduced and to reduce the aging effect. The specimen temperature was varied from 25°C to 100°C. The smallest water contact angle was obtained with the 45°C specimen and the largest amount of hydrophilic functional groups was introduced with the 100°C specimen, as determined by X-ray photoelectron spectroscopy (XPS). Therefore, a two-step plasma treatment with two different specimen temperatures, i.e. 100°C followed by 45°C, decreased the water contact angle and reduced the aging effect. It appears that the hydrophilic functional groups introduced were located at the specimen surface (about 0.5 nm) at low temperature and that the aging effect was reduced due to the hydrophilic functional groups formed inside (0.5-8 nm) at high specimen temperature. The aging rate and the diffusion coefficient were also estimated, depending on the specimen temperature, using the experimental aging data.

The electron beam-initiated surface modification of films prepared from various blends of low-density polyethylene (LDPE), ethylene vinyl acetate (EVA), and ditrimethylol propane tetraacrylate (DTMPTA) was carried out over a range of radiation doses (20-500 kGy) and concentrations of DTMPTA. The films were characterized by Fourier transform infrared-attenuated total reflectance (FT-ATR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), contact angle measurements, and peel adhesion. The printability of the films was also measured. FT-ATR and XPS revealed that the surface polarity of the films made from a 50 : 50 blend of LDPE and EVA increased up to a radiation dose of 100 kGy, compared with the unirradiated sample. The polarity decreased after 100 kGy radiation. Surface pitting and roughness were observed in the SEM photomicrographs of the same films, irradiated at higher radiation doses. Higher values of the surface energy were obtained at 100 kGy for the samples without DTMPTA and for the samples containing 3 wt% DTMPTA. Excellent printability was observed for all the films irradiated above an irradiation dose of 20 kGy. The data on the printability and peel adhesion of the irradiated films could be explained by surface energy, XPS, and SEM results.

Contact-angle measurements, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS or ESCA) were used to characterize flame-treated biaxially oriented polypropylene (PP) films. While the surface of PP treated in a fuel-lean flame is highly oxidized, no watersoluble low-molecular-weight oxidized material (LMWOM) is formed by the flame treatment. A new computational model, SPIN, was used to determine the chemical composition of the impinging flames used to modify the PP. The SPIN model indicates that the species primarily responsible for the surface oxidation of the PP are OH, HO₂, H₂O₂, and O₂. Because the concentration of atomic O in the flame is low, there is little scission of the PP chains and no formation of LMWOM. AFM indicates that a 'nodular' surface topography is generated during the flame oxidation of the PP. The surface topographical features generated by flame treatment are probably the result of the agglomeration of intermediate-molecular-weight materials.

Scanning electron microscope and goniometer were used to investigate morphology and wetting property of polypropylene membrane surfaces modified by plasma treatment using different reagents. Surface morphology was significantly affected by the types of reagents. X-ray photoelectron spectroscopy and attenuated total refection-Fourier transform infrared spectroscopy were used to characterize the chemical structure of polypropylene membrane surfaces modified by Freon-116 gas plasma treatment. Many fluorine atoms were observed on the polypropylene surface, and its concentration increased to saturation with increasing plasma treatment time. The wetting behavior of plasma treated polypropylene membrane was well explained in relation with morphology and chemical structure.

Improvement of the paint adhesion to a polypropylene (PP) bumper has been investigated without using a primer by treating the bumper surface with O₂, H₂O, and acetylene plasmas. All the plasma treatments resulted in an increase of the adhesion strength in dry conditions. The adhesion strength could be increased up to a value comparable to that obtained by applying a primer. The treated surfaces were quite stable for 7 days in air. After exposure to wet conditions, however, the adhesion strengths for both O₂ and H₂O plasma-treated samples decreased significantly, while the adhesion strength for the acetylene plasma-treated sample did not change much.

The hydrophobic recovery of polydimethylsiloxane elastomers was studied after exposure to partial electrical discharge. Silicone elastomers that were thoroughly extracted of free oligomeric impurities as well as those deliberately contaminated with low molecular weight (LMW) silicone fluids were used for these studies. Contact angle and X-ray photoelectron spectroscopy revealed that the recovery rates of the oxidized extracted samples are strongly influenced by the applied voltage, humidity, and aging condition. The recovery rates increase considerably as the applied voltage and the humidity during discharge increase. Remarkably, the oxidized samples stored under high vacuum (10⁻⁷ Torr) exhibit lower recovery rates than those aged in air. Free silicone fluid, when added to the elastomer, affects the recovery rate as well; however, significant recovery is seen even without any added fluid. These results imply that the LMW species that are formed in situ during electrical discharge are sufficient to cause the hydrophobic recovery of oxidized PDMS elastomers.

The use of plasma treatment for the modification of polystyrene microtiter wells has been evaluated by contact angle measurements, X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The contact angle data suggests that the effect of plasma treatment is first to clean the surface of volatile contamination, increasing the hydrophobicity, and then to introduce oxygen functionality into the surface, decreasing the hydrophobicity. The cleaning effect appears to occur in the first few seconds of treatment while the oxygenation effect increases with increased exposure to the plasma. The XPS and ToF-SIMS measurements show increasing surface oxygen concentration with plasma treatment time, with a concomitant reduction in aromaticity. Scanning tunnelling microscopy (STM) imaging reveals that plasma treatment significantly affects the adsorption of bovine serum albumin (BSA). Untreated surfaces exhibited areas where no BSA adsorption occurred. These regions ranged in size between 20 and 60 nm in diameter. Plasma treated surfaces, however, exhibited no such areas, with BSA adsorption appearing to be more uniform across the surface. The regions on the untreated surfaces where no BSA adsorption occurred are thought to be hydrocarbon (volatile) in nature possibly from the moulding process, which is removed in the first few seconds of plasma treatment.