Effect of Surface Energetics of Substrates on Adhesion Characteristics of Poly (p-xylylenes)

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.     

Adhesion of glow discharge polymers to metals and polymers

Adhesion of glow discharge polymers to metals and polymers in an adhesive joint was measured by lap-shear test and immersion in hot water of 70°C °C for an extended time. A glow discharge polymer was deposited onto polymers [polyethylene and poly(tetrafluoroethylene)] and metals (aluminum and stainless steel) prior to when the polymer and metal were joined. It is found that the lap-shear strength is enhanced by coating the surfaces of these substrates with plasma film produced from methane, ethylene, and acetylene, and that deterioration of the adhesive bonding part, when immersed in hot water of 70°C, is strongly dependent on the gas used as well as operational conditions where a polymer film is formed. The adhesion of a polymer produced from methane on the polymer and metal is strong enough to apply for durable, adhesive joints.     

Adhesion between polymer substrates and plasma films from tetramethylsilane and tetramethyltin by glow discharge polymerization

Adhesion between various polymer substrates and plasma films, which had been prepared from either tetramethylsilane or tetramethyltin by glow discharge polymerization and deposited on the surface of the polymer, was evaluated by the Scotch tape test and by lap-shear strength. It was found that the plasma films exhibited fairly good adhesion to the polymer substrates (with the exception of polypropylene). The position where failure occurred was determined by X-ray fluorescence analysis, scanning electron microscopy and energy diffractive X-ray analysis. This position was at an inner layer of the plasma film (cohesive failure of plasma film), within the polymer substrate (material failure of polymer) or at the interface between polymer substrate and plasma film (adhesive failure) depending upon the polymer substrate. These results indicate an important aspect of durability of surface modification by glow discharge polymerization.     

Effect of plasma polymer deposition methods on copper corrosion protection

The behavior of plasma polymer coating for Cu corrosion protection was investigated in dc cathodic polymerization, with and without anode magnetron enhancement, af magnetron glow discharge polymerization, and rf glow discharge polymerization. The combination of visual and scanning electron microscopy observations established general trends in an accelerated wet/dry cycle corrosion testing environment containing 0.1N chloride ions. Dc anodic magnetron cathodic polymerization of TMS offered the best Cu corrosion protection due to an enhanced deposition uniformity and adhesion of the deposited plasma polymer to the Cu substrate. No corrosion was observed after 25 wet/dry cycle accelerated corrosion tests when uncoated Cu suffered a severely generalized attack in one cycle. Superior corrosion protection was also performed by an af plasma polymerized coating of C₄F₁₀ + H₂ (1 : 1) at a low-energy input density and of methane at high-energy input and high deposition thickness carried out in the range of this study. The application of plasma polymers which showed high water vapor permeation resistance and surface dynamic stability ǵreatly reduced the pitting densities. © 1996 John Wiley & Sons, Inc.     

A glow discharge treatment to immobilize poly(ethylene oxide)/poly(propylene oxide) surfactants for wettable and non-fouling biomaterials

A non-fouling (protein resistant) polymer surface was achieved using an argon glow discharge treatment of a polyethylene surface which had been precoated with various poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) (PEO-PPO-PEO) tri-block copolymer surfactants. The surfactant is first deposited on the polymer surface via a solvent swelling and evaporation method. Then the coated surfactant is immobilized on the substrate surface by an inert gas discharge treatment. ESCA and water contact angle () measurements on treated and solvent washed surfaces show significant increases in both surface O/C ratios and surface water wettability (0 < 30°) compared to LDPE control surfaces, revealing the presence of PEO on the treated surfaces. A great reduction of fibrinogen adsorption on the modified surfaces is also observed for the highest PEO content surfactants. This simple surface modification process may have wide applicability to obtain wettable polymer surfaces in general, and non-fouling biomaterial surfaces in specific.     

Cathodic disbondment resistance with reactive ethylene terpolymer blends

Adhesion to metallic substrates can be improved through the addition of polar functional groups, which bond with surface groups on the metal substrate. Additionally, polar interactions have been shown to increase adhesive strength even in wet environments (such as in the case for cathodic protection). A polymer blend is proposed as a coating material to provide adequate protection against the diffusion of moisture and air to the metallic surface along with superior adhesion even in the presence of wet and corrosive environments to resist cathodic disbondment. A reactive ethylene terpolymer (RET) of ethylene/n-butyl acrylate/glycidyl methacrylate (E/nBA/GMA) was compounded with HDPE to develop a potential coating material. The HDPE component offers high chemical and moisture resistance to permeation, while the RET component provides the material with high polarity and reactivity, which enhances adhesion to the substrates to be coated. The introduction of the reactive ethylene terpolymer decreases the magnitude of cathodic disbondment area of polyethylene coatings. After applying a cathodic potential to the coating substrate, the adhesive strength was observed to remain the same for silane-pretreated steel dollies. Without silane pretreatment, post-CD adhesive loss resembles that of the open circuit “wet” condition. EDAX data in conjunction with oxygen and water vapor transmission rates suggest an initial stage of disbondment where interfacial oxide is dissolved resulting in the delamination of coating around the initial defect. This initial disbondment zone acts like a moving crack tip creating larger areas of disbondment where interfacial bonds are degraded by the ingress of moisture and ions along the interface.     

Preliminary experiment of surface hardening of polymers by glow discharge polymerization

Polymers including polyethylene, polycarbonate, and polytetrafluoroethylene were modified by glow discharge polymerization to enhance surface hardness. The surface hardness of the polymer substrates could be improved by glow discharge polymerizations of silicon-containing compounds. The mixture of tetramethylsilane (TMS) and oxygen was more effective than tetramethoxysilane to improve the surface hardness. The surface hardness improved by the glow discharge polymerization strongly depended on the nature of the polymer substrates to be modified. The adhesion between polymer films prepared from the TMS/O₂ mixture by glow discharge polymerization and the polymer substrates was good.     

Surface Silanization of Polyethylene for Enhanced Adhesion

Low density polyethylene has been treated using a novel surface treatment process “SICOR” (“SIIane-on-CORona” treated polymer) in order to enhance adhesion with a range of adhesives including polyure-thane, methacrylate and cyanoacrylate. The process comprises two steps, i.e corona discharge followed by application of an organo-functional silane. The incorporation of surface hydroxyl groups onto the polymer surface enables organo-silane to create the hydrogen or covalent bonds with the oxidized polymer surface. The possibility of the creation of these bonds has been investigated using FTIR, XPS and wettability studies. The adhesion enhancement due to the new process is significant. Frequently, the strength increase exceeds 200% compared with the corona discharge treatment and more than 300% compared with LDPE priming using the “Loctite 770” polyolefin primer. The process is shown to be as good as, or better than, plasma treatment in terms of the strength increase following substrate treatment prior to adhesive bonding.     

Atmospheric Pressure Plasma Polymerised Primer to Promote Adhesion of Silicones

By combining a liquid primer and a plasma jet system, a new route to improved adhesion on various substrates has been developed. The liquid primer is introduced as an aerosol into a plasma jet and the resultant active species are deposited as a polymer coating on adjacent surfaces. Careful control of the plasma parameters produced a dry polymerised coating with functional chemistry designed to enhance the adhesion of silicone sealants to two substrates. This paper describes the surface chemistry and adhesion properties of various coatings on both a plastic and a metal substrate. Selected surface analysis techniques were coupled to both wet and dry adhesion testing to characterise the factors that control adhesion within the system. Mechanical testing indicates that adhesion was improved by several orders of magnitude.     

Adhesion of the plasma polymer of trimethylsilane to aluminum alloys

The adhesion of a plasma polymer and the corrosion protection offered to aluminum alloy substrates depends on the cleanliness of the substrate surface and the state of oxides on the aluminum alloy surface. Both factors are dependent on what type of alloy is used, and consequently, the best preparation of the substrate surface differs on the type of aluminum alloy. Oxygen plasma treatment is effective for the elimination of organic surface contamination, but plasma treatment, such as that of mixed argon and hydrogen, cannot be used to modify the surface state of oxides on these alloys. This is because oxides of aluminum are stable and thus resist plasma modification, and prolonged plasma treatment has been observed to change concentrations of alloy components at the surface due to the heating of the alloy. Chemical cleaning of the surface is necessary before the application of the plasma polymer used for corrosion protection enhancement. Once the surface was properly prepared, a plasma polymer of trimethylsilane (TMS), prepared by cathodic polymerization, adhered well to aluminum alloys investigated in this study. Major adhesive failure, however, occurred as a consequence of reactor contamination when hexafluoroethane (HFE) plasma treatment of initially formed TMS plasma polymers was employed. Plasma pretreatment of the substrate with O₂ or postplasma treatment of the plasma polymer of TMS with Ar (instead of HFE) was effective in eliminating the surface‐contamination effect on the adhesion. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1387–1398, 2002     

Direct current cathodic glow discharge polymerization of methane and butane

The deposition of a polymeric material on the surface of the cathode of a direct current (dc) glow discharge was investigated for methane and butane. The cathode region of a dc glow discharge is not a plasma in a strict sense. Consequently, the deposition of a polymeric material to the cathode surface differs significantly from so-called plasma polymerization of the same monomer (starting gas or vapor) that deposits on a substrate placed in a glow discharge plasma. Using methane and n-butane, the influence of the molecular weight of the monomer (M), volume flow rate, and discharge power on the deposition rate in a dc glow discharge were investigated and compared with those in an audio frequency and a radio frequency glow discharge. It was found that the deposition rate expressed in (thickness growth rate)/(M) is linearly proportional to the current density, which implies that cathodic polymerization is controlled by the cathode region parameter (not plasma parameters). The refractive indices (632.8 nm) for the cathodic polymers are in the range of 2.2–2.4 while those for plasma polymers are in the range of 1.5–1.7. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 237–245, 1998     

Über den Einfluß der Grenzflächenspannung auf die Haftfestigkeit

The values of adhesion between four diffrent adhesive,and (i) steel substrates whose surface energy had been altered by adsorption, and (ii) several polymer having different surface energies, had been measured. The results show that the adhesion has a maximum value when the surface energy of the hardened adhesive is equals to that of the substrate, i.e. when the interfacial energy adhesive/substrate is a minimum. The adhesion of the adhesives to the polymer was much smaller than to the steel sprcimens and the dependence of the adhesion onm the interfacial energy was sharper in the case of the polymers. The decrease of the adhesion with increasing interfacial energy was fiund to be greater if the liquid adhesive wets the substrate badly than the steel speciman.     

Wettability enhancement of polystyrene with electron cyclotron resonance plasma with argon

Polystyrene cell‐culture substrates were treated with argon glow discharge to make their surfaces hydrophilic. The process was novel in that it used a microwave electron cyclotron resonance (ECR) source for polymer surface modification. The substrates were processed at different microwave powers and time periods, and the surface modification was assessed with by measurement of the water contact angle. A decrease in contact angle was observed with increasing microwave power and processing time. Beyond a certain limit of power and duration of exposure, however, surface deterioration occurred. The optimum conditions for making the surfaces hydrophilic without deterioration of the samples were identified. The plasma parameters were assessed by Langmuir probe measurement. Fourier transform infrared spectroscopy with attenuated total reflectance showed evidence for the induction of hydrophilicity on the surface. The surface micromorphology was examined with scanning electron microscopy. The results prove that the ECR glow discharge was an efficient method for enhancing the wettability of the polymer surfaces. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1618–1623, 2003     

Cathodic disbondment resistance with reactive ethylene terpolymer blends

Adhesion to metallic substrates can be improved through the addition of polar functional groups, which bond with surface groups on the metal substrate. Additionally, polar interactions have been shown to increase adhesive strength even in wet environments (such as in the case for cathodic protection). A polymer blend is proposed as a coating material to provide adequate protection against the diffusion of moisture and air to the metallic surface along with superior adhesion even in the presence of wet and corrosive environments to resist cathodic disbondment. A reactive ethylene terpolymer (RET) of ethylene/n-butyl acrylate/glycidyl methacrylate (E/nBA/GMA) was compounded with HDPE to develop a potential coating material. The HDPE component offers high chemical and moisture resistance to permeation, while the RET component provides the material with high polarity and reactivity, which enhances adhesion to the substrates to be coated. The introduction of the reactive ethylene terpolymer decreases the magnitude of cathodic disbondment area of polyethylene coatings. After applying a cathodic potential to the coating substrate, the adhesive strength was observed to remain the same for silane-pretreated steel dollies. Without silane pretreatment, post-CD adhesive loss resembles that of the open circuit “wet” condition. EDAX data in conjunction with oxygen and water vapor transmission rates suggest an initial stage of disbondment where interfacial oxide is dissolved resulting in the delamination of coating around the initial defect. This initial disbondment zone acts like a moving crack tip creating larger areas of disbondment where interfacial bonds are degraded by the ingress of moisture and ions along the interface.     

Adhesion of glow discharge polymers

Various reaction parameters in a propylene glow discharge polymerization were investigated with the objective of synthesizing films having good adhesion to metal and glass substrate. Monomer flow rate (at a constant pumping efficiency) was found to exert a significant effect on the quality of polymer adhesion to substrates. Good adhering polymeric films were obtained only at high flow rates where the deposition rate decreases with an increase in monomer flow rate. This observation applied also to ethylene, propane, allyl bromide, and ?-caprolactam. Transmission electron microscopy of the freshly deposited polymer films indicated a defect-free structure of the polymer surface obtained at high flow rates. The polymer surface obtained at low flow rates had a bead structure superimposed by uniformly placed circular defects.     

Development of improved polypropylene adhesive bonding by abrasion and atmospheric plasma surface modifications

The present work deals with the problematic adhesive bonding of substrates with low surface energy. Different approaches have been explored with the aim of creating adequate adhesive joints based on polyolefinic substrate and polyurethane adhesive. The selected material under study was polypropylene (PP) as adherend, and a commercial Sikaflex^®-252 polyurethane one component based structural adhesive (PU) as joint fluid. Among the diverse pre-treatments typically used to prepare surfaces prior to bonding, mechanical abrasion with emery paper of 80 grain size, the use of a chemical primer and atmospheric pressure air plasma torch (APPT) were the selected methods to facilitate the application of the PU by means of surface energy enhancement as well as to create a correct mechanical interlocking of the adherent–adhesive interface. Changes in the wettability of the polymer were evaluated by contact angle measurements following the UNE EN 828:2010. Surface energy was calculated both in terms of Owens approximation and acid–base considerations, leading to the possibility of determining a relationship between changes in surface energy and adhesion. Changes in the chemical composition of the surface were studied by X-ray photoelectron spectroscopy (XPS), electron diffraction X-Ray (EDX) probe and attenuated total multiple reflection mode infrared spectroscopy (ATR-FTIR). Morphological modifications were investigated with scanning electron microscopy (SEM). Variations in the strength of single-lap PP–PP joints with the treatments were evaluated by lap shear tests following the UNE-EN 1465:2008 standard. Experimental evidence supports the superiority of the APPT treatment to increase wettability and adhesion of polyolefinic surfaces, especially when combined with the use of a primer.     

Surface modification of polyimide films via plasma polymerization and deposition of allylpentafluorobenzene

Plasma polymerization of allylpentafluorobenzene (APFB) on the plasma-pretreated polyimide (PI) films was carried out. The fluorinated aromatic groups of the plasma-polymerized APFB (pp-APFB) could be preserved, to a large extent, by controlling the glow discharge parameters. The effect of the glow discharge parameters, including the type of the carrier gas and the input RF power, on the surface composition and chemical structure of the pp-APFB films were studied by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and time-of-flight secondary ion mass spectrometry. The surface topography of the APFB plasma-polymerized PI (pp-APFB-PI) films was studied by atomic force microscopy. For plasma polymerization carried out at a high RF power and using argon as the carrier gas, an ultra-hydrophobic pp-APFB-PI surface was also obtained. The ultra-hydrophobic surface exhibited advancing/receding water contact angles (θ_A/θ_R) of 174°/135°. The effectiveness of the carrier gas in defluorinating the pp-APFB films followed the order of O₂>N₂>H₂>Ar. Thus, the role of the carrier gas in improving the surface hydrophobicity of the resulting pp-APFB-PI films followed the order of O₂22® tape adhesion test.     

Effect of Plasma-Polymerized Primers on the Durability of Aluminum/Epoxy Adhesive Bonds

The durability of aluminum/epoxy adhesive joints prepared from substrates pretreated by plasma etching and then deposition of plasma-polymerized primers was determined using the wedge crack testing method. Plasma etching and polymerization were conducted using both direct current (DC) and microwave (2.45 GHz) driven plasma systems. Plasma-polymerized primers were deposited using trimethysilane (TMS) and hexa-methyldisiloxane (HMDSO) to form siloxane-like and silica-like films, respectively. Plasma etching with argon and argon/hydrogen plasmas was used as a substrate pre-treatment. In some cases etching with an oxygen plasma was used as a post-treatment to give a silica-like surface to siloxane-like films deposited from TMS. Adhesive joints were prepared using two different epoxy adhesives, Cytec FM-300 and FM-123-2. Differences in initial adhesion were observed for primer films with chemical differences. Siloxane-like primer films were not wetted by the adhesive and resulted in poor wedge test results. Silica-like primer films were not wetted by the adhesive and resulted in poor wedge test results. Silica-like primer films deposited onto aluminum substrates resulted in wedge specimens with good adhesion and durability. The initial crack was cohesive within the adhesive. However, crack growth occurred at the interface between the adhesive and silica-like primer. Durability of the wedge specimens was essentially invariant of the type of microwave plasma pretreatment for grit-blasted aluminum substrates that were coated with silica-like primers before bonding with FM-123-2.     

Thin Film Adhesion: Effect of Glow Discharge on Substrate

Glow discharge treatment of soda lime glass and silica substrates prior to depositing copper films in oil-free ultra high vacuum as well as in conventional vacuum has been found to increase film adhesion suggesting that gross contamination removal is not the only effect of importance in this method of improving film adhesion. There is evidence from Auger electron emission spectroscopy for sorption of gas from the discharge into the substrate surface layers. Desorption of gases from the substrate also appears to take place. A difference in electron emission from a variety of insulating surfaces following glow discharge was observed in a scanning electron microscope, the sign of the change depending on the nature of the discharge gas. No sputtered material from system components could be detected on the substrate and there was no detectable micro-roughening nor net surface electric charge.     

Thin Film Adhesion: Effect of Glow Discharge on Substrate

Glow discharge treatment of soda lime glass and silica substrates prior to depositing copper films in oil-free ultra high vacuum as well as in conventional vacuum has been found to increase film adhesion suggesting that gross contamination removal is not the only effect of importance in this method of improving film adhesion. There is evidence from Auger electron emission spectroscopy for sorption of gas from the discharge into the substrate surface layers. Desorption of gases from the substrate also appears to take place. A difference in electron emission from a variety of insulating surfaces following glow discharge was observed in a scanning electron microscope, the sign of the change depending on the nature of the discharge gas. No sputtered material from system components could be detected on the substrate and there was no detectable micro-roughening nor net surface electric charge.