Interfacial Energy and Adhesion between Acrylic Pressure Sensitive Adhesives and Release Coatings

The interfacial adhesive behavior between acrylic pressure sensitive adhesive-like networks (PSA-LNs) and poly(vinyl N-alkyl carbamate) release coatings was studied using a contact mechanical method and peel tests. Surface energy and interfacial energy were directly measured in JKR tests using a novel sample construction. The surface energy of the poly(vinyl N-alkyl carbamates) was found to be around 20 mJ/m². Interfacial energies between PSA-LNs and the release coatings were found to be quite high - between 7 and 24 mJ/m². Changes in adhesion dynamics were governed by acid-base interactions between the carbamate in the release coating and the acid groups in the PSA-LN. The length of the alkyl chain in the release coating moderated this effect. We also found a correlation between fundamental adhesion energy and peel strength. Examination of this phenomenon provides a basis for understanding the poor storage stability of PSA tapes made using alkyl carbamates and acid-containing PSAs.     

Evidence of Acid-Base Interfacial Adducts in Various Polymer/Metal Systems by IRAS: Improvement of Adhesion

The physical interactions of polymers with inorganic substrates are determined by two major contributions: Van der Waals forces and acid-base interactions, taken in the most general “Lewis” electron acceptor-donor sense. The present work shows that the work of adhesion can be very appreciably increased by the creation of interfacial acid-base interactions. Practically, polymers such as poly(ethylene-co-vinyl acetate) (EVA), terpene-phenol resins (TPR), and their blends, were solution cast on basic and acidic substrates. The nature of the interfacial bonds and the enthalpy of adduct formation through electron exchange are evidenced by Fourier transform infrared reflection-absorption spectroscopy (IRAS). Moreover, it is shown that, on the one hand, modification of the electron donor ability of the polymer functionalities reveals the amphoteric character of the substrate and, on the other hand, modification of the electron donor ability of the substrate changes the nature of the species involved in interfacial adduct formation. Then, practical adhesion tests were carried out in order to correlate the nature and strength of interfacial acid-base bonds with simultaneous increases in adhesive strengths. Thermodynamic considerations allowed us to propose estimated values of the acid-base work of adhesion, W^ab, and of the density of acid-base sites, n^ab.     

Interfacial Energy and Adhesion between Acrylic Pressure Sensitive Adhesives and Release Coatings

The interfacial adhesive behavior between acrylic pressure sensitive adhesive-like networks (PSA-LNs) and poly(vinyl N-alkyl carbamate) release coatings was studied using a contact mechanical method and peel tests. Surface energy and interfacial energy were directly measured in JKR tests using a novel sample construction. The surface energy of the poly(vinyl N-alkyl carbamates) was found to be around 20 mJ/m². Interfacial energies between PSA-LNs and the release coatings were found to be quite high – between 7 and 24 mJ/m². Changes in adhesion dynamics were governed by acid-base interactions between the carbamate in the release coating and the acid groups in the PSA-LN. The length of the alkyl chain in the release coating moderated this effect. We also found a correlation between fundamental adhesion energy and peel strength. Examination of this phenomenon provides a basis for understanding the poor storage stability of PSA tapes made using alkyl carbamates and acid-containing PSAs.     

Evidence of Acid-Base Interfacial Adducts in Various Polymer/Metal Systems by IRAS: Improvement of Adhesion

The physical interactions of polymers with inorganic substrates are determined by two major contributions: Van der Waals forces and acid-base interactions, taken in the most general “Lewis” electron acceptor-donor sense. The present work shows that the work of adhesion can be very appreciably increased by the creation of interfacial acid-base interactions. Practically, polymers such as poly(ethylene-co-vinyl acetate) (EVA), terpene-phenol resins (TPR), and their blends, were solution cast on basic and acidic substrates. The nature of the interfacial bonds and the enthalpy of adduct formation through electron exchange are evidenced by Fourier transform infrared reflection-absorption spectroscopy (IRAS). Moreover, it is shown that, on the one hand, modification of the electron donor ability of the polymer functionalities reveals the amphoteric character of the substrate and, on the other hand, modification of the electron donor ability of the substrate changes the nature of the species involved in interfacial adduct formation. Then, practical adhesion tests were carried out in order to correlate the nature and strength of interfacial acid-base bonds with simultaneous increases in adhesive strengths. Thermodynamic considerations allowed us to propose estimated values of the acid-base work of adhesion, W^ab , and of the density of acid-base sites, n^ab .     

Adhesion of flame-treated polyolefins to styrene butadiene rubber

Samples of polyethylene and polypropylene have been submitted to repeated short duration (75 ms) flame treatments, at optimum flaming conditions. Surface energies of untreated and flamed specimens were determined by liquid contact angle measurements. It appears that the surface energy of polyethylene increases much more than that of polypropylene after flame treatment. The flamed polymer surfaces were further examined by electron spectroscopy, Fourier Transform IR spectroscopy and secondary ions mass spectrometry. The adhesion properties of modified polymer surfaces were studied by testing in peel the bonded Styrene Butadiene Rubber/polyolefins assemblies. Scanning electron microscopy (SEM) and water contact angle measurements have been used to observe the locus of failure. Good correlations were obtained between surface energy and adhesion strength, the increase in adhesion strength being particularly important for flamed PE/SBR assemblies. In addition, the peeling in a liquid medium allowed the determination of the respective contribution to adhesion of chemical and physical interactions. It is shown that a major part of the adhesion strength increase is of chemical origin, particularly for the bonded flamed PE/SBR assemblies.     

The effect of surface energetics and molecular interdiffusion on adhesion in multicomponent polymer systems

The interfacial region of coated plastics is an example of a multicomponent polymer system. Practical adhesion, as determined by the peel test, has been found to be strongly dependent on the composition of the system and the degree of interaction between its components. Several interactions are possible during the coating process of polypropylene (PP)/ethylenepropylene-diene-monomer (EPDM) blends with chlorinated polyolefin (primer) and polyurethane (PUR) paint. Wettability, a necessary but not sufficient condition alone for molecular interdiffusion, was found to be good in all cases. The lack of interfacial adhesion between PP and PUR and between EPDM and PUR was explained by high interfacial tensions calculated from surface energetics, which, in turn, were determined by contact angle and inverse gas chromatography (IGC) measurements. The improvement of interfacial adhesion between PUR and PP by chlorinated polyolefin was explained by acid-base interactions detected by IGC. The creation of surface topography by extraction of low molecular weight fractions during the coating process does not influence the adhesion. Molecular interdiffusion was shown to be facilitated by solvents.     

An FT-IR Study on Interfacial Interactions in Ethylene Copolymers/Aluminium Laminates in Relation to Adhesion Properties

The effect of three different functional groups in ethylene copolymers on the adhesion with aluminium was studied. The interface in polymer/metal laminates was analyzed by FT-IR, and the adhesion mechanism for each functional group was evaluated. Laminate samples were prepared by solution casting or by hotpressing polymeric film onto the aluminium substrate. In the latter case, the interface was exposed by solvent extraction. The interfacial structures developed by the different copolymers were correlated to the mechanical strength of hotpressed laminates, which was measured by a peel test. The polymer surfaces were further characterized by contact angle measurements.

Polar functional groups, carboxylic acid and butyl ester in hotpressed laminates were found to form Lewis acid/base interactions with the aluminium oxide. The strength of the interfacial interactions was correlated to the concentration and acidity/basicity of the group, the acid group being the most efficient. A silane functional group provided strong adhesion to the laminates at a much lower concentration than the polar groups. Silanols as well as Al-O-Si linkages were detected at the polymer/aluminium interface.     

Role of acid-base interfacial bonding in adhesion

The strength of macroscopic adhesive bonds of polymers is known to be directly proportional to the microscopic exothermic interfacial energy changes of bond formation, as measured by Dupre's 'work of adhesion'. Since the work of adhesion can be very appreciably increased by interfacial acid-base bonding with concomitant increases in adhesive bond strength, it is important to understand the acid-base character of polymers and of the surface sites of substrates or of the reinforcing fillers of polymer composites. The best known acid-base bonds are the hydrogen bonds; these are typical of acid-base bonds, with interaction energies dependent on the acidity of the hydrogen donor and on the basicity of the hydrogen acceptor. The strengths of the acidic or basic sites of polymers and of inorganic substrates can be easily determined by spectroscopic or calorimetric methods, and from this information one can start to predict the strengths of adhesive bonds. An important application of the new knowledge of interfacial acid-base bonding is the predictable enhancement of interfacial bonding accomplished by surface modification of inorganic surfaces to enhance the interfacial acid-base interactions.     

Use of the Blister Test to Study the Adhesion of Brittle Materials. Part II. Application

Using a modified form of the blister test, where the adhesive layer was between the substrate and a massive base, instead of as a continuous sheet on top of the substrate, we determined the interfacial fracture energy F for a series of interfaces where a brittle material (ice) was adhering to various substrates. Fracture energies obtained were compared with work of adhesion values measured for water on the same substrates. Fracture energy, which contains within it both a reversible contribution due to intermolecular interactions across the interface (work of adhesion) and an irreversible contribution due to collective dissipative processes, was found to rise rapidly with modest increases in work of adhesion. The observed relation suggests that the irreversible contribution to fracture energy is influenced strongly by the intermolecular interactions at the interface.     

Evaluation of compatibility in SAN/EPDM blends by determination of the adhesion parameters

A series of various types (different structures) of ethylene-polypropylene-diene-graft-polystyrene (EPDM-g-PS) copolymers were synthesized and their surface property variations were studied using surface analysis techniques such as surface contact angle measurement. Pre-synthesized graft copolymers were added (5 phr) in styrene-acrylonitrile (SAN)/ethylene-propylene-diene (EPDM) blends composition of 95/5 and 90/10. The adhesion parameters at the interface, that is work of adhesion, the interfacial energy and the coefficient of wetting were calculated and correlated to the differential scanning measurements measurements and SEM micrographs in order to study the effect of graft copolymers on compatibility of SAN/EPDM blends. It is obvious that depending of the graft copolymer’s structure, various interactions between the components in the blend will be established, resulting in better adhesion which implicates improvement of compatibility in blends. Also, from the results, it can be seen that differences in structures of the added compatibilizer are clearly reflected in the adhesion parameters results, making this an acceptable method to determine whether two polymers are compatible. Morphology of the blends with the graft copolymers is significantly finer and the dispersed size is more uniformly distributed in comparison to the neat SAN/EPDM blend. The conditions of the optimal adhesion parameters with compatibilizer location at the interface, predicting by the thermodynamical models, correlated well with the improvement of the morphology and thermal measurements.     

Use of the Blister Test to Study the Adhesion of Brittle Materials. Part II. Application

Using a modified form of the blister test, where the adhesive layer was between the substrate and a massive base, instead of as a continuous sheet on top of the substrate, we determined the interfacial fracture energy F for a series of interfaces where a brittle material (ice) was adhering to various substrates. Fracture energies obtained were compared with work of adhesion values measured for water on the same substrates. Fracture energy, which contains within it both a reversible contribution due to intermolecular interactions across the interface (work of adhesion) and an irreversible contribution due to collective dissipative processes, was found to rise rapidly with modest increases in work of adhesion. The observed relation suggests that the irreversible contribution to fracture energy is influenced strongly by the intermolecular interactions at the interface.     

An FT-IR Study on Interfacial Interactions in Ethylene Copolymers/Aluminium Laminates in Relation to Adhesion Properties

The effect of three different functional groups in ethylene copolymers on the adhesion with aluminium was studied. The interface in polymer/metal laminates was analyzed by FT-IR, and the adhesion mechanism for each functional group was evaluated. Laminate samples were prepared by solution casting or by hotpressing polymeric film onto the aluminium substrate. In the latter case, the interface was exposed by solvent extraction. The interfacial structures developed by the different copolymers were correlated to the mechanical strength of hotpressed laminates, which was measured by a peel test. The polymer surfaces were further characterized by contact angle measurements.

Polar functional groups, carboxylic acid and butyl ester in hotpressed laminates were found to form Lewis acid/base interactions with the aluminium oxide. The strength of the interfacial interactions was correlated to the concentration and acidity/basicity of the group, the acid group being the most efficient. A silane functional group provided strong adhesion to the laminates at a much lower concentration than the polar groups. Silanols as well as Al-O-Si linkages were detected at the polymer/aluminium interface.     

Enhancement of polymer film adhesion using acid-base interactions determined by contact angle measurements

Quantitative correlations among surface chemical composition, acid-base thermodynamics, adhesion strength, and locus-of-failure are demonstrated. Four types of functional Teflon surfaces were prepared: two acidic (containing hydroxyl and carboxyl groups), and two basic (containing acetyl and dinitrobenzoate groups). X-Ray photoelectron spectroscopy (XPS) and attenuated total reflection infrared (ATR-IR) spectroscopy were used to characterize the molecular structure of the surface region. Contact angle adsorption isotherms were determined using phenol as an acidic probe and tetrahydrofuran (THF) as a basic probe. The carboxylated surface had a higher molar ?H^ab with basic THF than the hydroxylated surface, and neither surface had any interaction with the acidic phenol probe. The acetylated surface behaved as a base, interacting with phenol but not with THF, while the dinitrobenzoyl surface had both acidic and basic character. Adhesion tests were carried out in the 180° peel mode using post-chlorinated poly(vinyl chloride) as a model acidic adhesive between pairs of each type of film. The two surfaces with basic character had significant peel strengths, while the two acidic surfaces had very low peel strengths. Scanning electron microscopy (SEM) of the basic failure surfaces showed significant plastic deformation of the Teflon polymer, while the acidic failure surfaces showed no deformation. XPS analysis of the failure surfaces confirmed interfacial failure for the acid-acid pairs, and bulk FEP failure for the acid-base pairs. These results demonstrate directly and quantitatively the enhancement of adhesive bond strength through acid-base interactions.     

Modification of a nitrile-phenolic bonding agent by addition of an interfacial agent: effect on the practical adhesion between nitrile rubber and metal

—The mechanism of vulcanization bonding of a nitrile rubber (NBR) elastomer to metal with a single-coat nitrile-phenolic bonding agent is discussed. A nitrile-phenolic bonding agent consisting of NBR, phenol formaldehyde (PF) resin, and vulcanizing agents was modified with an interfacial agent (p-cresol formaldehyde resin) and the effect of interfacial agent addition on the practical adhesion between metal and the NBR elastomer after vulcanization was investigated. The adhesion strength was measured in terms of the metal-to-NBR elastomer peel strength using the bonding agent. The addition of p-cresol formaldehyde (PCF) resin to the bonding agent with a proportionate reduction of PF resin initially improved the peel strength; a maximum was reached at about 20% PCF content and then decreased with a further increase in the PCF content. The improvement in peel strength produced by the addition of PCF resin is attributed to the increased chemical bonding between NBR and the phenolic resin. The drop in peel strength above 20% PCF content is explained by the increased diffusion of the bonding agent into the NBR elastomer, away from the bond line, leading to a starved glue line. The mechanism for the optimum performance at about 20% PCF resin content is believed to be due to the balance of diffusion and chemical crosslinking.     

Plasma Modifications to the Interface in Carbon Fiber Reinforced Thermoplastic Matrices

Radio frequency glow discharge oxygen plasma was used to modify the surfaces of PAN-based and mesophase pitch-based carbon fibers. Surface chemical changes to the fibers were monitored by X-ray photoelectron spectroscopy and by fiber wetting studies evaluated in terms of dispersive-polar components of surface energy and acid-base contribution to the work of adhesion. Physical changes to these fibers were monitored by scanning electron microscopy. Stress transferability of these fibers was evaluated by the embedded single fiber test in poly(methyl methacrylate), poly(ethyl methacrylate), poly(methacrylonitrile) and poly(vinyl chloride) as these matrices offered varying degrees of dispersive-polar and acid-base character. Experimentally determined critical aspect ratios were compared to the theoretical work of adhesion determined by dispersive-polar interactions and with the Lewis acid-base nature of the matrices.     

Probing adhesion spectroscopically: rheo-photoacoustic FT-IR spectroscopy and work of adhesion

Physico-chemical changes at the interface between two polymer surfaces have a significant effect on adhesion and the molecular level processes associated with it. Although rheo-photoacoustic (RPA) Fourier transform infrared (FT-IR) spectroscopy was developed to establish the origin of polymer-polymer interfacial interactions, no correlations were made between the spectroscopic data and the work of adhesion. In this study, we attempt to provide a relationship between the vibrational energy changes in the C-H stretching region in polyethylene, induced by the interfacial stresses resulting from elongations of the polyethylene-polydimethylsiloxane double-layer system, and the work of adhesion. Stresses induced in the interfacial regions allow a correlation between the film thickness and the vibrational energy changes in the symmetric C-Η bands.     

Plasma Modifications to the Interface in Carbon Fiber Reinforced Thermoplastic Matrices

Radio frequency glow discharge oxygen plasma was used to modify the surfaces of PAN-based and mesophase pitch-based carbon fibers. Surface chemical changes to the fibers were monitored by X-ray photoelectron spectroscopy and by fiber wetting studies evaluated in terms of dispersive-polar components of surface energy and acid-base contribution to the work of adhesion. Physical changes to these fibers were monitored by scanning electron microscopy. Stress transferability of these fibers was evaluated by the embedded single fiber test in poly(methyl methacrylate), poly(ethyl methacrylate), poly(methacrylonitrile) and poly(vinyl chloride) as these matrices offered varying degrees of dispersive-polar and acid-base character. Experimentally determined critical aspect ratios were compared to the theoretical work of adhesion determined by dispersive-polar interactions and with the Lewis acid-base nature of the matrices.     

Wet adhesion of low-VOC coatings on wood: A quantitative analysis

Adhesion of coatings on wood is most critical under wet conditions. However, the mechanisms controlling the adhesion are not well understood. Therefore, a quantitative analysis of coating adhesion on wood is needed. A new technique is presented to measure the wet adhesion quantitatively based on measuring the forces needed to peel the coating from the wood with a tape. Differences in peel forces corresponded to areas in the wood with a lower or a higher degree of coating penetration. Coatings with better penetration and substrate wetting showed an improved adhesion and the better adhering coatings had an increased level of cohesive failure in the coating. Chemical analysis of the air-faced and wood-faced side of the coatings showed differences in chemical composition. The stored strain energy due to hygroscopic stress could reduce the actual level of adhesion significantly. Surface energy effects did not contribute to reduced adhesion after exposure to water. The interfacial work of adhesion between coating and wood was very much lower than the measured force and lacked correlation with measured differences in adhesion. Therefore, it can be concluded that mechanical anchoring plays a dominant role in obtaining good adhesion of a coating on wood.     

Adhesion of Polypropylene Fiber to Cement Matrix

Abstract

In this research, the adhesion of polypropylene (PP) fibers to cementitious matrix has been investigated and the chemical bonding and mechanical interlocking between PP fiber and hardened cement paste has been studied. Furthermore, thermodynamic work of adhesion and loss-function (dissipation energy) has been calculated in the PP-cement matrix model system. To investigate the work of adhesion, the pull-out test has been used. Also, the surface free energy and contact angle of the PP monofilaments and cement matrix have been measured using a tensiometer and the fiber–cement interfacial interactions and thermodynamic work of adhesion and loss-function were calculated. Scanning electron microscopy (SEM) analysis was used to study the fiber–cement matrix interfacial transition zone (ITZ). The results showed that the application of theories of polymer–polymer adhesion in fiber–cement matrix systems was feasible. To verify the accuracy of the method, the adhesion of two other fibers (nylon 6,6 and acrylic polymer) was studied.     

Interfacial and Bulk Contributions to Peeling Energy

Thin polyurethane films, having low adhesion to dried protein, were developed as candidate materials for non-adhesive surgical dressings. In order to model wound-adhesion, gelatine was cast from solution on to the film and allowed to dry. The film was peeled from the gelatine at 180° peel angle, and the peel force measured as a function of the temperature of test. The dynamic mechanical properties of the films were measured over the range -90°C to 110°C and values of tan δ were determined at the temperatures employed for peeling. Thus, a correlation was obtained between peeling energy and tan δ for each of eight films.

The generalised theory of fracture mechanics states that the adhesive failure energy is given by the product of an interfacial energy term and a “loss function” involving the hysteresis ratio of the material. If the strains are small the hysteresis ratio is proportional to tan δ. The experimental results show excellent agreement with the theory, but the interfacial term turns out to be much greater than the true interfacial energy (or thermo-dynamic work of adhesion). The reason for this result is discussed.