Hydrogen Bonding and the Interfacial Component of Adhesion: Acid/Base Interactions of Corona-Treated Polypropylene

The effect of activation of the surface of polypropylene sheet, by a corona discharge, upon the contact angles of liquids and on the surface free energy parameters γ^LW, γ^⊕ and γ^⊖, was determined. Both advancing and retreating contact angles were measured. The “acid/base” theory of the components of surface free energy was employed.

The contact angles of water and glycerol were initially lower by as much as 30°, after treatment, and that of diiodomethane was lower by about 5°. With time, the advancing angles rose, and the γ^⊕ and γ^⊖ parameters fell, towards the values on the untreated solids, and attained more or less steady values after 5 to 10 days. The basic component, γ^⊖, was the most strongly affected by the corona treatment; it rose, typically, from 2.2 to as high as 25 mJ/m². The acidic component, γ^⊕, rose from zero to as high as 1.9 mJ/m². Its decay with time was only qualitatively the same as that of γ^⊖. The retreating angles, and the corresponding energy components, were changed in the same direction, and somewhat more strongly, than were the “advancing” data.

The well-known improvement in the property of forming strong joints or adherent coatings, after corona treatment, is no doubt due to the formation of sites or areas on the polymers where hydrogen bonds can be formed. The decay of the strength of adhesion with time is, no doubt, due to the decay of these sites or areas.     

XPS Studies of Polymer Surface Modifications and Adhesion Mechanisms

XPS has been used to elucidate the mechanisms of surface modification of low density polyethylene by electrical (“corona”) discharge treatment and by chromic acid treatment. The use of derivatisation techniques for improving the precision of functional group analysis is described. These techniques also allow the role of specific interactions in adhesion to discharge treated surfaces to be investigated. The role of residual Cr on the adhesion of deposited metal to polymer surfaces is discussed.     

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.     

Stress Transfer in Single Fiber/ Resin Tensile Tests

Microscale (25 mm gauge length) “dogbone” resin specimens with single carbon fibers embedded through the length of the specimen have been studied as a method for determining the fiber-resin interphase strength. The specimens are pulled in tension until the fiber fragments to a critical length, l_c. Evidence is presented here, based primarily on the relaxation of stress birefringence around the fiber fragment, that this test may not be an unambiguous measure of fiber-resin adhesion. Data obtained for various production lots of AS-4, AS-6, and IM-6 fibers indicate an increase in l_cd with laminate tensile strength. Although there is theoretical justification for this correlation, it requires that the interphase shear strength is relatively constant.

In those instances where interfacial adhesion was expected to be low, i.e., surface contamination or unsurface treated fiber, there was a significant increase in l_c/d and usually a distinct difference in stress birefringence compared to “good” adhesion. However, the distinction in stress birefringence was not always clear cut.     

Adhesion Studies of Fluoropolymers

A comparative study of the treatment of polytetrafluoroethylene (PTFE) and poly(vinyl fluoride) (PVF) with “Tetra-Etch” has been carried out. The treatment of PTFE resulted in extensive changes in surface chemistry and topography, whereas with PVF there was no significant change in topography and the chemical changes were much less marked. However, treatment of both polymers resulted in large increases in bond strength.

Multiple bonding experiments in which samples are repeatedly fractured and re-bonded were carried out with untreated PTFE and PVF. These resulted in moderate increases in bond strength with PTFE and large increases with PVF. The results indicate that weak boundary layer (WBL) removal is a key element in adhesion improvement by “Tetra-Etch” on PVF. With PTFE, WBL removal also improves adhesion, but the chemical and/or topographical changes introduced by the “Tetra-Etch” are required for optimum performance.     

Chemical composition and bond structure of aerosol particles of amorphous hydrogenated silicon forming from thermal decomposition of silane

Aerosol particles of amorphous hydrogenated silicon resulting from thermal decomposition of silane were investigated by hydrogen evolution, IR-, EPR-, NMR spectroscopy, and transmission electron microscopy.

The experimental data show that aerosol particles contain to a various extent {SiH₂}_n polymer structures and two types of monohydride groups SiH- “clustered” and “dilute” monohydride groups. The hydrogen atoms of the “clustered” monohydride groups are located close to each other. The “clustered” monohydride groups are inaccessible to the ambient because they are embedded in the amorphous network. The “dilute” monohydride groups are relatively isolated from each other. The majority of “dilute” monohydride groups are open to the ambient. They are located on the surface of preferentially interconnected microchannels and microvoids.

Interaction between the “dilute” SiH groups and atmospheric oxygen results in formation of OSiH groups in which hydrogen and oxygen are bonded to a common silicon atom. Evidently, the interaction occurs throw the oxygen reaction with weak bonds associated with “dilute” monohydride groups. There is no interaction between oxygen and both “clustered” SiH groups and {SiH₂}_n chain because the former are inaccessible to atmospheric oxygen and the latter has presumably no weak bonds in the chains.     

Influence of corona treatment on adhesion and mechanical properties in metal/polymer/metal systems

The effect of corona treatment (CT) on the adhesion at the metal–polymer interface was studied. Metal/polymer/metal laminates were manufactured by the laboratory roll‐bonding process with preliminary corona surface treatment of the polymer core: a polyethylene and polypropylene sheet as well as steel sheet. It was treated with corona discharge to increase its surface energy and the adhesion to metal, an austenitic steel. The adhesion, which was measured by T‐peel and shear tests, was increased by 43% of crack peel and 22% of mean peel resistance respectively, after 120 s CT. On the basis of scanning electron spectroscopy observations, improvements in the adhesive properties were attributed to the change in the interfacial morphology. In mechanical tests, yield and tensile strengths were strongly influenced by CT, indicating that these laminates were sensitive to interfacial phenomena. However, elongation at rupture of the composites was found to be unchanged. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

The role of surface modification in digital printing on polymer‐coated packaging boards

Digital printing is increasingly being used for package printing. One of the major techniques of digital printing is dry‐toner electrophotography. This paper evaluates the printability of three different extrusion coatings used for packaging boards: low‐density polyethylene (PE‐LD), ethylene methyl acrylate (E/MA) and polyethylene terephthalate (PET). Extrusion coatings in general have an impervious, chemically inert, nonporous surface with low surface energies that cause them to be non‐receptive to bonding with toners. The most common methods used in improving the adhesion properties of polymer coatings are different surface treatments. These increase the surface energy and also provide the polar molecular groups necessary for good bonds between the toner and polymer molecules. The polymer coatings have been modified with electrical corona discharge treatment. The effects of corona on polymer surfaces and the correlation between surface modification and print quality have been evaluated. Results show that sufficiently high surface energy and surface‐charge uniformity are necessary for even print quality and toner adhesion. E/MA and PET have the required surface‐energy level without the corona treatment, but PE‐LD needs surface modification in order to succeed in the electrophotographic process. E/MA also has exceptional surface‐charge properties compared with PET and PE‐LD. Polym. Eng. Sci. 44:2052–2060, 2004. © 2004 Society of Plastics Engineers.     

Pretreatments of Fluoropolymers

In the present study the mechanisms and effectiveness of various pretreatments for fluoropolymers were studied. The pretreatments were “Tetra-Etch,” various plasmas, flame and potassium hydroxide. “Tetra-Etch” was found to be much more reactive than potassium hydroxide (KOH) towards fluoropolymers. The plasma treatment of PTFE showed that it was possible to get substantial increases in adhesion with little or no chemical change to the polymer. However, to obtain large increases in adhesion it may be necessary to modify PTFE chemically as with “Tetra-Etch.” Consideration of the bonding of these fluoropolymers shows that sharp interfaces between these substrates and adhesives do not exist.     

Adhesion Between Metals and Polymers as a Three-Dimensional System

Adhesion science in a technical sense is the study of reactions in boundary layers. From a macroscopic point of view the result is the adhesive joint strength dependent on the magnitude of the adhesion forces without hints on the nature of these forces. So the question of the nature of adhesion has at least to be answered for technical applications by using other measurement techniques. From the microscopic point of view adhesion is of interdisciplinary nature, where molecules or atoms act with each other across the interface. Mainly adhesive bonds are based on these interactions of different bodies like metals and polymers or other material discontinuities. So far we can speak about a “chemical adhesion”. But in practice there we realize a “technical adhesion” with more or less sharp discontinuities.     

The effect of corona and ozone treatment on the adhesion of ink to the surface of polyethylene

Low density polyethylene sheet was subjected to treatment by corona discharge in oxygen, nitrogen, helium and argon; in addition some sheets were treated with ozone gas. The bond strength between two similarly treated sheets was then measured using a commercial flexographic ink as an adhesive. The results showed that although surface oxidation improved both the ink adhesion and the wetting properties of polyethylene it is not a necessary prerequisite for good bonding. When the sheet was subjected to electrical discharge in nitrogen, argon or helium, considerable enhancement of ink adhesion was obtained without any detectable change in the surface chemistry of the polymer. The results indicate that ink adhesion after treatment in various gases follows closely the trends established previously in corona-induced autohesion of polyethylene. This suggests that the mechanism of bonding is similar in the two cases.     

Functionalization of Polymer Surfaces Using Excimer VUV Systems and Silent Discharges. Application to Electroless Metallization

New approaches for electroless plating of nonconductive polymers or polymer-based materials are described. In this work, polyimide substrates were surface-functionalized (i) in nitrogenated (ammonia at reduced pressure) and oxygenated (air at atmospheric pressure) atmospheres under assistance of vacuum-ultraviolet (VUV) irradiation (use of a xenon silent discharge excimer source) or (ii) directly in air at atmospheric pressure using a dielectric-barrier discharge (DBD) device. After functionalization, the substrates were “activated” by dipping in a dilute acidic PdCl₂ solution or by spin-coating of a thin metal-organic film (from a solution of palladium acetate (PdAc) in chloroform). The catalytic activity of the so-deposited palladium species toward the electroless deposition of nickel was studied before and after a VUV post-irradiation (in air at atmospheric or reduced pressure) with a view to understanding better the role of the reducer (sodium hypophosphite) within the electroless bath.

This work confirms the specific interest of grafting nitrogenated functionalities onto polymer surfaces for attaching covalently the palladium-based catalyst (in particular in the case of the PdCl₂ route), forming thus strong Pd - N - C bonds at the metal/polymer interface. This results from the strong chemical affinity of palladium toward nitrogen. On the other hand, when oxygenated functionalities are surface-grafted, the conventional two-step procedure using SnCl₂ and PdCl₂ solutions can be proposed due to the strong chemical affinity of tin toward oxygen. The Ni deposits obtained under these different conditions pass the standard Scotch^®-tape test and, therefore, exhibit a good practical adhesion. For this same purpose, it is interesting to note that the DBD treatment operating in air at atmospheric pressure causes an increase of the surface roughness and, therefore, an improvement in adhesion of metallic films when their initiation is catalyzed through the PdAc route. In addition, this work demonstrates that extensive research still has to be performed to understand and improve the Ni/polymer adhesion when the PdAc route associated with a VUV irradiation is considered.     

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.     

Changes in the Peeled Surfaces of Copper Thin Films Deposited on Polyimide Substrates After Heat Treatment

Peel strength between a copper (Cu) thin film and a polyimide (pyromellitic dianhydride-oxydianiline, or PMDA-ODA) substrate is reduced by heat treatment at 150°C in air. In this work, we investigated the peel strength, the morphology of the interface between Cu films and polyimide substrates using optical microscopy and electron microscopy, and chemical change of the interface using Auger electron spectroscopy (AES) and micro X-ray photoelectron spectroscopy (XPS). The analysis showed that CuO “lumps” were present on the peeled surface of PMDA-ODA after heat treatment at 150°C in air. The peeled surfaces of other polyimide substrates were also analyzed: biphenyl dianhydride-para phenylene diamine (BPDA-PDA) and biphenyl dianhydride-oxydianiline (BPDA-ODA). CuO lumps were present on the peeled surface of BPDA-ODA after the heat treatment, but not that of BPDA-PDA. Compared with the adhesion strength for the Cu thin film, the adhesion strength was high for the Cu/PMDA-ODA and Cu/BPDA-ODA laminates, but the adhesion strength was very low for the Cu/BPDA-PDA laminate. This low strength is the reason that CuO lumps were not detected on the peeled surface of the BPDA-PDA substrate. These CuO lumps were related to the adhesion degradation of the Cu/polyimide laminates after the heat treatment.     

Adhesion Between Rubbers and Grafted Solids

The adhesion energy, G (at low separation velocities), between a rubber and a solid surface, is expected to increase when flexible chains, chemically identical to the rubber, are attached to the surface. This can be set up with or without chemical binding of the chains to the rubber (“bound” chains or “free” chains).     

The Fracture Mechanics of the Pin and Collar Test for High Temperature Anaerobic Adhesives

A mechanical test method for the studies of high-temperature anaerobic adhesives has been established, based on fracture mechanics, by modifying the standard test method of collar and pin test. Linear Elastic Fracture Mechanics approach was applied to the establishment of the relationship between adhesive fracture surface energy “R”, fracture load and crack length. Hence, from the joints containing a given artificial flaw the adhesive fracture surface energy can be determined; alternatively, from the strength of the joints without artificial flaws the inherent flaw size “a_i” can be calculated to account for the decrease of joint strength.

The experimental techniques were applied to examine the mechanical behaviour of the joint system based on high temperature anaerobic adhesives. It was found that the joints cured at room-temperature had higher adhesive fracture surface energy but lower joint strength than the joints postcured at high temperatures. The “a_i” data explained this interesting phenomenon. The joints cured at room-temperature had extraordinarily large “a_i”, which was found to be formed by the uncured adhesive near the edges of the joints and the adhesive further cured in the postcure processes to reduce the “a_i”. Also, the growth of intrinsic flaw was found to be responsible for the deterioration of the joints in a short-term, high-temperature ageing process.     

Model Studies of the Effect of Surface Roughness and Mechanical Interlocking on Adhesion

The apparent strength of adhesion has been measured for a soft elastic layer adhering to model porous substrates, consisting of rigid plates containing regular arrays of cylindrical holes. Two contributions to the apparent strength have been identified and compared with the predictions of a simple theoretical treatment. The first is adhesion to the surface itself. Because “rough” surfaces have greater area for bonding, the strength of adhesion was increased by as much as twenty-fold. The second arises from the work of breaking deeply embedded or entangled strands in order to detach the overlayer. Contributions from this mechanism were as much as several hundred times the (low) intrinsic strength of adhesion. Satisfactory agreement was obtained with theory in both cases. Measurements were also made using cloth substrates, when the adhering layer penetrated the cloth completely. The work of detaching and breaking permeating strands was again much larger than the intrinsic strength of adhesion, in reasonable agreement with theoretical predictions.     

Adhesion of Patterned Reactive Interfaces

We demonstrate the role of chemical surface patterns on the adhesion of soft, elastomeric interfaces. The microscale patterns consist of periodic variation of two types of silane surface chemistries: a reactive silane that bonds covalently with the soft elastomer and a passive silane that is weakly adhered with the elastomer. Using an adhesion test based on 90° peel geometry, we demonstrate that the tuning of adhesion depends on the spatial distribution of the reactive silane groups. Given our material system and pattern symmetries, an enhancement in adhesion energy is observed in a majority of the patterns. The mechanism of enhancement is associated with the shape of the contact line. Specifically, the reactive silane interfaces play a significant role in defining the width of the contact line. In instances where enhancement is observed, the width of the contact line increases because of the “pinning” of the contact line by the reactive interfaces. These results emphasize the importance of contact line interaction with the pattern shapes and demonstrate opportunities for using well-defined two-dimensional patterns to actively tune polymer adhesion.     

Mechanism of corona treatment on polyolefin films

This paper reviews recent studies on the mechanism of corona treatment of polyolefin films, specifically the chemical and physical changes of this process and the self-adhesion mechanism. Corona discharge of polymeric films introduces polar groups into the surfaces, which increases the surface energy and, as a consequence, improves substrate wettability and adhesion. The main chemical mechanism of corona treatment is oxidation. In addition, corona treatment can crosslink surface regions and increase the film cohesive strength.     

New and Improved Tests for Adhesion

Three new methods are discussed for measuring the work G_a, required to detach unit area of an adhering material from a substrate. The first is a simple modification of the Outwater double-torsion test for long rectangular plates, bonded together. This method is suitable for evaluating aluminum-epoxy bonds, for example, or the transverse strength of fibrous composites. The second is a pull-off test for long strips adhering to a rigid surface. It seems suitable for adhesive tapes and laminates. The third is a reconsideration of the “blister” test for films and coatings, in which a circular debond at the interface is made to grow by internal pressure. The relation obtained between pull-off force F for a strip, or blow-off pressure P for a layer, takes the unusual form:

F⁴ (or P⁴) ∞ KG³_a

where K is the tensile stiffness of the detaching layer. This dependence arises from the non-linear (cubic) relation between load or pressure and deflection in these configurations. Nevertheless, the product Fθ, where θ is the angle of detachment of a strip, or Py, where y is the height of a “blister”, give direct measures of the strength of adhesion G_a, independent of the stiffness of the adhering material and of the extent of detachment.