Surface treatment of polymers. II. Effectiveness of fluorination as a surface treatment for polyethylene

An effective surface treatment for adhesive bonding of polyethylene has been developed. It involves exposing the polymer to an environment of elemental fluorine or fluorine diluted in argon. By this treatment, extensive fluorination of the surface region is effected. The fluorinated surface permits formation of strong adhesive joints by conventional adhesive bonding techniques even though the wettability of the new surface is similar to polytetrafluoroethylene. We believe that treatment of the polymer with elemental fluorine effectively eliminates the weak boundary layer associated with polyethylene by either crosslinking or by increasing the molecular weight in the surface region.     

Adhesive bonding of polyvinylidene fluoride: Effect of curing agent in PVF2 surface modification

—We have shown that certain amine and amide curing agents for epoxy resins modify the surface properties of the fluoropolymer polyvinylidene fluoride (PVF₂), thereby permitting the formation of strong adhesive joints. When PVF₂ is exposed to these curing agents at the temperatures used in preparing adhesive joints (~70°C), discoloration (darkening) occurs with concomitant gelation. This suggests that there is dehydrofluorination followed by crosslinking. Infrared spectroscopy has been used to follow the course of these reactions. In effect, the curing agent serves a dual function. It reacts with the fluoropolymer both to modify the surface region and to crosslink the epoxy resin.     

Interphase Composition in Aluminum/Epoxy Adhesive Joints

Model epoxy/aluminum adhesive joints were constructed with a geometry that allowed cracks to be propagated extremely close to the adhesive/adherend interface. The joints were fractured in air and the fracture surfaces analyzed using angle resolved X-ray photoelectron spectroscopy. Fracture occurred in a manner that left a significant amount of aluminum oxide on the epoxy side of the fracture surface and very little epoxy on the aluminum side. Aliphatic amine curing agent found associated with the aluminum oxide on both the adhesive and the adherend sides of the fracture surface was protonated by the acidic hydroxyls present in the aluminum hydroxide. Moreover, catalysis of the curing reaction by these hydroxyls resulted in an increased degree of crosslinking in the regions of the adhesive very close to the oxide surface. Thus, the aluminum oxide surface modified the structure of the adhesive in the near surface regions and resulted in the formation of a distinct interphase region with a composition different from that of the bulk adhesive.     

Interphase Composition in Aluminum/Epoxy Adhesive Joints

Model epoxy/aluminum adhesive joints were constructed with a geometry that allowed cracks to be propagated extremely close to the adhesive/adherend interface. The joints were fractured in air and the fracture surfaces analyzed using angle resolved X-ray photoelectron spectroscopy. Fracture occurred in a manner that left a significant amount of aluminum oxide on the epoxy side of the fracture surface and very little epoxy on the aluminum side. Aliphatic amine curing agent found associated with the aluminum oxide on both the adhesive and the adherend sides of the fracture surface was protonated by the acidic hydroxyls present in the aluminum hydroxide. Moreover, catalysis of the curing reaction by these hydroxyls resulted in an increased degree of crosslinking in the regions of the adhesive very close to the oxide surface. Thus, the aluminum oxide surface modified the structure of the adhesive in the near surface regions and resulted in the formation of a distinct interphase region with a composition different from that of the bulk adhesive.     

Surface modification of polyethylene by radiation-induced grafting for adhesive bonding. I. Relationship between adhesive bond strength and surface composition

A number of vinyl monomers have been surface grafted onto a polyethylene sheet by the mutual irradiation in monomer vapor and by a trapped-radical technique. The surface composition of the grafted sheets has been determined by means of ATR infrared spectrophotometry and compared with the peel strength of the joints bonded with conventional structural adhesives. In the methyl acrylate grafts followed by a saponification treatment, only the surfaces having graft compositions of more than 80 mole-% methyl acrylate give a high peel strength. A similar relationship between peel strength and surface composition is found in the surface grafts of vinyl acetate, acrylic acid, acrylamide, and methylolacrylamide. It is concluded that the formation of a surface with such a high monomer content is a necessary condition for the strong adhesive bonding of grafted polyethylenes at bonding temperatures below the softening point. Moreover, the adhesive bondability of the highly modified surfaces with epoxy adhesives is significantly enhanced by the introduction of carboxy and carbamyl radicals.     

Adhesion of evaporated metallic films onto polyethylene and poly(tetrafluoroethylene): Importance of surface crosslinking

Ni, Fe, Ti, Al, Au, and Cu were each evaporated and deposited onto both sides of polyethylene and poly(tetrafluoroethylene) (PTFE) films. Adhesive joint strengths of the different metal–polymer–metal composites were compared and subsequent surface modifications due to metalization were investigated. Studies show no change in wettability of polyethylene or PTFE after a metal layer was deposited onto their surfaces and subsequently removed. There was also no evidence of oxidation or unsaturation of the surface. Gel fractions of polyethylene show a definite correlation between joint strength and crosslink at the surfaces of the different metal–polymer composites. Metals forming the strongest joints with polyethylene yield the greatest amount of crosslinking. Conversely, metals forming the weakest joints result in the least amount of crosslinking.     

Adhesive bonding of polyethylene

The treatment of polyethylene film with aqueous ammonium peroxydisulfate solutions prior to adhesive bonding to aluminum has been studied. Such pretreatments resulted in the formation of adhesive joints of high strengths when bonded with a conventional epoxy adhesive. The effect on the tensile shear strength of adhesive joints of variations in the treatment time and temperature and the peroxydisulfate concentration has been examined. The use of certain catalysts for the reaction has also been studied. Tensile shear strengths at least as high as with other pretreatment methods have been obtained.     

Study of the effect of a shock-wave treatment on adhesive interactions in polymer-metal joints

The complex effect of shock-wave and thermal treatments on the adhesion of thermoplastic polymer coatings to aluminum and its alloys is studied. Being subjected to explosive loading, polymers are activated via the rupture of chemical bonds and the formation of free radicals and new functional groups. Subsequent thermal treatment leads to the activation of oxygen, resulting in the formation of chemical bonds between a polymer and a metal surface. The mechanism of thermal oxidation is considered. The optimum temperature-time regimes of the shock-wave treatment are determined, which permits obtaining polymer coatings on aluminum alloys in joints whose strength is 2–3 times higher than for joints obtained with unmodified materials. Powdered fluoroplastic and ultrahigh-molecular-mass polyethylene are used as adhesive materials.     

A reactive acrylic adhesive for bonding polyolefins

An acrylic adhesive was developed for forming strong, water resistant structural joints with polyolefins. This two-component, lightly crosslinked, methyl methacrylate (MMA) based adhesive consisted of an anaerobic curing system in one part with a copper (II) salt catalyst in the other. Bonds formed with low density polyethylene (LDPE) resulted in substrate failure upon block shear testing throughout the open time of the adhesive (45 min). The interdiffusion of the monomers into the substrates, and their subsequent polymerization was followed using several infrared spectroscopy (IR) techniques. The interphase of mixed LDPE and adhesive was determined to be as thick as 1.7 mm using IR microscopy. It was concluded that the strong adhesion in the aforementioned joints was the result of the interpenetration of the adhesive into the substrates.     

Molecular Structure of Polymer/Metal Interphases

The molecular structure of interphases in aluminum/epoxy and steel/epoxy adhesive joints was characterized using infrared spectroscopy. In one series of experiments, adhesive joints were prepared by curing beams of epoxy against aluminum or steel substrates. When the joints were cooled to room temperature, the residual stresses were sufficient for crack propagation along the interface. The adhesive and substrate failure surfaces were then analyzed with reflection-absorption infrared spectroscopy (RAIR), attenuated total reflection infrared spectroscopy (ATR) and X-ray photo-electron spectroscopy (XPS). When an epoxy/anhydride adhesive was cured against aluminum substrates primed with an aminosilane coupling agent, amide and imide groups were formed in the interphase. Chemical reaction between the primary amine of the primer and the anhydride of the curing agent precluded chemical bridge formation between the primer and adhesive. Metal cations from the 2024 aluminum substrate reacted with the anhydride to form carboxylate salts on the surface. When an epoxy/tertiary amine adhesive was cured against steel substrates, evidence of oxidation of the primary amine to imine was observed in the interphase.     

Molecular Structure of Polymer/Metal Interphases

The molecular structure of interphases in aluminum/epoxy and steel/epoxy adhesive joints was characterized using infrared spectroscopy. In one series of experiments, adhesive joints were prepared by curing beams of epoxy against aluminum or steel substrates. When the joints were cooled to room temperature, the residual stresses were sufficient for crack propagation along the interface. The adhesive and substrate failure surfaces were then analyzed with reflection-absorption infrared spectroscopy (RAIR), attenuated total reflection infrared spectroscopy (ATR) and X-ray photo-electron spectroscopy (XPS). When an epoxy/anhydride adhesive was cured against aluminum substrates primed with an aminosilane coupling agent, amide and imide groups were formed in the interphase. Chemical reaction between the primary amine of the primer and the anhydride of the curing agent precluded chemical bridge formation between the primer and adhesive. Metal cations from the 2024 aluminum substrate reacted with the anhydride to form carboxylate salts on the surface. When an epoxy/tertiary amine adhesive was cured against steel substrates, evidence of oxidation of the primary amine to imine was observed in the interphase.     

Shear strength of adhesively bonded polyolefins with minimal surface preparation

Interest in polyethylene and polypropylene bonding has increased in the last years. However, adhesive joints with adherends which are of low surface energy and which are chemically inert present several difficulties. Generally, their high degree of chemical resistance to solvents and dissimilar solubility parameters limit the usefulness of solvent bonding as a viable assembly technique. One successful approach to adhesive bonding of these materials involves proper selection of surface pre-treatment prior to bonding. With the correct pre-treatment it is possible to glue these materials with one or more of several adhesives required by the applications involved. A second approach is the use of adhesives without surface pre-treatment, such as hot melts, high tack pressure-sensitive adhesives, solvent-based specialty adhesives and, more recently, structural acrylic adhesives as such 3M DP-8005^® and Loctite 3030^®.In this paper, the shear strengths of two acrylic adhesives were evaluated using the lap shear test method ASTM D3163 and the block shear test method ASTM D4501. Two different industrial polyolefins (polyethylene and polypropylene) were used for adherends. However, the focus of this study was to measure the shear strength of polyethylene joints with acrylic adhesives. The effect of abrasion was also studied. Some test specimens were manually abraded using 180 and 320 grade abrasive paper. An additional goal of this work was to examine the effect of temperature and moisture on mechanical strength of adhesive joints.     

Optimization of adhesive joints of low density polyethylene (LDPE) composite laminates with polyolefin foam using corona discharge plasma

In this work, surface modification of low density polyethylene (LDPE) film has been carried out to optimize adhesive joints with polyolefin foam for uses in technological applications. LDPE films were modified in a continuous way using corona discharge plasma with different powers, ranging from 200 to 600 W and several film advance rates in the 5–20 m min^?1 range. Changes in surface wettability have been studied with contact angle measurements and subsequent solid surface energy calculation. A polyurethane adhesive was used to join the LDPE film to a polyethylene foam. Mechanical performance of the adhesive joints has been determined by T‐peel tests and also the aging effects of several hydrothermal conditions have been studied to evaluate the usefulness of these laminate composites in technological applications. Results show that corona discharge powers between 400 and 600 W are suitable in terms of wettability improvement; on other hand, a slight decrease in surface wettability as the film advance rate increases is detected but the overall changes as a consequence of the film advance rate in the 5–20 m min^?1 range are small if compared to changes derived from working powers in the 200–600 W range. Adhesive joints offer excellent mechanical performance and good durability in hydrothermal conditions thus being appropriate for technical applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Enhancement of adhesive joint strength by surface texturing

Proper substrate preparation is an indispensible step for achieving strong adhesive joints. One consequence of such surface treatment is the enhancement of degree of mechanical interlocking between polymers and substrates, which, according to the literature, seems to increase the strength of the joint. A novel method based on photolithography is developed to texture aluminum oxide surface by controlling the pit size and its spatial distribution. Surface profile, surface physical chemical properties of this sample, and the lap shear strength of epoxy adhesive joints are compared with those of the phosphoric acid anodized (PAA) sample. It is shown that the lap shear strength of the textured sample is superior to that of the PAA sample. Surface profile data and mathematical analysis suggest that the inferiority of the PAA sample is probably due to the trapped air in the large pit in the surface resisting the penetration of adhesives. It also concludes that the high surface area provided by the multitude small pits in PAA sample is far from being fully utilized. This study opens up a new avenue to rationally improve the strength of adhesive joint by controlling the surface profile, the surface chemical properties, and the pressure during bond formation.     

Improved adhesion of LDPE films to polyolefin foams for automotive industry using low-pressure plasma

The use of polymer films for technical applications has increased considerably in the last years, since they offer good balanced properties. Polymer films find many applications as individual materials or as laminates with other films, foams, membranes, etc. In these cases it is necessary to improve the low intrinsic surface energy of polymer films to ensure their optimum mechanical performance. In this work, low-pressure glow discharge plasma with different gases is used to improve the adhesive properties of a low-density polyethylene (LDPE) film, to obtain the optimum mechanical response of laminates with polyolefin foam for automotive applications (steering wheels). The results show a remarkable increase in T-peel strength of the adhesive joints. Furthermore, since automotive industry is characterized by high technical requirements, the evaluation of the durability of the adhesive joints (in terms of storage conditions: temperature and relative humidity) shows that the T-peel strength of adhesive joints is subjected to an aging process that slightly decreases their mechanical performance, but does not restrict the use of these laminates in automotive uses.     

不同聚乙烯辐致凝胶效应的比较研究

研究比较了不同聚乙烯的辐致凝胶效应。实验表明，聚乙烯的辐致凝胶效应与其分子的线性程度和结晶度有关。分子的线性程度越高，则辐射过程中产生的自由基在相互耦合形成交联时所遇到的空间阻力将愈小。同时，线性程度的增加，将使聚乙烯的结晶度提高，被束缚在晶区边界处的相互靠近的链段也就愈多。晶区自由基存在向边界迁移的趋势，这就使该区域的自由基浓度增加，所以就越容易形成交联。但是，结晶度越高，聚合物中的缺陷就越多，在空气氛中辐射时就越容易发生氧化。更高的剂量率可以抑制空气氛辐射时伴随的氧化反应，在辐射的后期作用尤为明显。     

Improving the adhesion of polyethylene surfaces using Side-Chain crystalline block copolymer

While polyethylene is widely used in consumer products, its use in other applications is limited because of low adhesive properties. In this study, the adhesive properties of high-density polyethylene were improved by a facile chemical treatment which was no require the special equipment or reagents. This simple treatment enabled the homogeneous modification of a polyethylene surface by dipping in a dilute solution containing a side-chain crystalline block copolymer (SCCBC) for a short time. SCCBC comprises of a block copolymer with one monomer containing long alkane side chains that form the side-chain crystalline units and the other that contains functional monomers. The adhesive strength of the high-density polyethylene film modified by SCCBC, as determined using a T-peel test and tensile shear test, was stronger than the non-modified high-density polyethylene substrate. Furthermore, this facile method imparted these strong adhesive properties to high-density polyethylene over a wide variety of treatment conditions such as temperature of SCCBC solution, concentration, dipping time and types of solvent.     

Synthesis and properties of allyloxyethyl 2-cyanoacrylate adhesive

Allyloxyethyl 2-cyanoacrylate monomer was synthesized and characterized for the first time. It was found that this monomer retains the typical properties of cyanoacrylate adhesives such as fast setting time at room temperature, adhesion to most materials, and high strength of bonded joints. Because of its long ester group and the reactive allyl group, this cyanoacrylate monomer produces adhesive bonds which have improved elasticity and heat resistance. IR and DSC studies showed crosslinking of the adhesive layer when subjected to elevated temperature, which explains the increased tensile shear strength of steel bonded joints. It was found that allyloxyethyl 2-cyanoacrylate can also be used as a crosslinking component for cyanoacrylate adhesives, based on ethyl 2-cyanoacrylate. Less than 10% of allyloxyethyl 2-cyanoacrylate in the mixture is needed for increasing, over three times, the tensile shear strength of the adhesive joint after ageing at 100°C.     

Influence de l'epaisseur de l'adhésif et du vieillissement sur les propriétés mécaniques dynamiques d'un assemblage: Adhésif structural/acier inoxydable

Dynamic mechanical properties of bounded joints—stainless steel/epoxy adhesive—are investigated as a function of the thickness of the adhesive and aging conditions. The viscoelastic properties of the bounded joints have been investigated by Dynamic Thermo Mechanical Analysis (DTMA). The glass transition temperature (T_g) showed a dependence on both the chemical/electrochemical pretreatments of the substrate and the thickness of the adhesive in the bounded joint. The crosslinking density in the adhesive thus seemed more important in the interfacial region than in adhesion bulk. The water uptake induces a plasticization of the adhesive and a decrease in T_g. The most stable bounded joints were obtained by carrying out sulfochromic acid anodization as a pretreatment step. The most important stability of the bounded joints was obtained with the sulfochromic anodization of the substrate.     

Characterization of polyurethane adhesives containing nanosilicas of different particle size

Three nanosilicas with different particle sizes were added to a polyurethane adhesive (PU). The filled adhesives were characterized by thermal gravimetric analysis (TGA), dynamic mechanical analysis (DMA), transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and contact angle measurements. Adhesive strength was evaluated from single lap shear test of solvent wiped stainless steel/polyurethane adhesive joints.Addition of nanosilica filler altered the degree of phase separation between the hard and soft segments in the polyurethane, in different extent depending on the nanosilica particle size. Furthermore, upon curing higher degree of crosslinking was obtained in the nanosilica filled polyurethane. The nanosilicas agglomerated into the polyurethane matrix. On the other hand, the addition of nanosilica increased the surface energy of the polyurethane to a greater extent by increasing the nanosilica particle size and moderate increase in the single lap shear strength of stainless steel/polyurethane adhesive joints was obtained.