Effect of the Molecular Length of n-Alkylsilanes on the Adhesion at a Rubber/Glass Interface

The effect on the peeling energy, G, of glass/styrene-butadiene rubber (SBR) assemblies of the length, N, of the alkyl chain, ranging from 4 to 30 carbon atoms, of silane coupling agents is determined. Experimentally, it is shown that G strongly increases with N. Therefore, considering that the rheological model of adhesion (or model of multiplying factors) is valid, G is assumed equal to the product of three terms: the reversible adhesion energy, W. at the interface, the viscoelastic dissipation factor, φ, of SBR and a “molecular factor” to be determined. Finally, it appears that this latter factor depends linearly on N. Such a result should be consistent with an extraction (“suction”) process of the silane alkyl links from bulk SBR during peeling experiments.     

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.     

Improvement of the Durability of Zinc-Coated Steel/Epoxy Bonded Joints

The durability properties of bonded lap shear joints made from an epoxy/dicyandiamide adhesive and hot-dipped galvanized (G2F) or electroplated-phosphated (EZ2) steel have been investigated. The degradation mechanisms have been studied after three accelerated ageing tests: the “cataplasme humide” (“C.H.T.”), immersion (“I.T.”), and salt spray (“S.S.T.”) tests. X-ray photoelectron spectroscopy (XPS) analysis of fracture surfaces after ageing have shown that anodic dissolution of the zinc-coating is responsible for debonding in all cases and that intergranular corrosion phenomena account for poorer performances of the hot-dipped galvanized substrate during “C.H.T.” and “I.T.” Silane coupling agents were successfully used as primers on both substrates to increase the hydrolytic stability of the metal/adhesive interface. XPS results indicate that both the interfacial dissolution of the phosphate coating of EZ2 and intergranular corrosion of G2F are delayed for silane-primed specimens. The observed improvements do not appear to depend on the nature of the silane coupling agents. Alkylsilanes have been found to perform as well as silanes having a group capable of reacting with the epoxy/dicyandiamide system.

Additional tests were carried out in view of the possible application of organosilane reagents as additives in corrosion-protective oils. Good durability properties have been obtained by priming the metal coupons with a standard oil/silane mixture prior to bonding.

When corrosion was the controlling degradation mechanism as is the case during the salt spray test, silane treated specimens did not generally perform better than control specimens.     

The effect of flexible substrates on pressure-sensitive adhesive performance

The adhesive fracture energy (fracture toughness) of tapes during globally elastic unpeeling is often calculated from the relation “G=P/b(1−cos θ)”. We show that while this expression is correct for elastic peeling from rigid substrates, it gives misleading results when peeling from reversible flexible substrates. A two-dimensional analysis is presented for peeling from non-linear elastic substrates that give consistent fracture energies from experimental data.     

Application of the Island Blister Test for Thin Film Adhesion Measurement

The island blister test has recently been proposed as an adhesion test which allows the peel of thin, well-adhered films without exceeding the tensile strength of the film. The island blister test site is a modification of the standard blister test site, consisting of a suspended membrane of film with an “island” of substrate at the film center. The membrane support and island are secured to a rigid plate and the film is pressurized, peeling the film inward off the island. A model for this inward or “annular” peel indicates that even for systems of good adhesion, peel can be initiated at low enough pressures to prevent film failure by making the center island sufficiently small relative to the size of the film.

We have fabricated island blister test sites using micromachining techniques and have used them to measure the debond energy of polymer films on various substrates. The peel data obtained from these island sites match well to the behavior predicted by a simple fracture mechanics analysis. This paper reports the fabrication of the island test sites, the experimental verification of the test, and the results of application of the test to polyimide films on metallic and polymeric substrates.     

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).     

Fracture Toughness of a Silane Coupled Polymer-Metal Interface: Silane Concentration Effects

Fracture toughness of joints made from a glassy, 343,000 molecular weight polystyrene block bonded to chromic-sulfuric acid etched or phosphoric acid anodized aluminum are investigated. The fracture tests are performed with a 90-degree peel apparatus under “dry” laboratory conditions and “wet” conditions created by submerging the apparatus in a temperature controlled water bath. The bond strengths are controlled using various concentrations of styrl silane coupling agent added directly into the styrene monomer solution that polymerizes against the aluminum. Ellipsometric measurements on smooth silicon surfaces verify that the thickness of bound polymer is controlled by the silane to polystyrene mole ratio. X-ray photoelectron spectroscopy (XPS) analysis of fractured surfaces indicates that the fracture is near the aluminum surface. Both the wet and dry fracture energy as a function of bound polymer thickness on acid etched aluminum joints resemble quite closely the adhesion literature results obtained by fracturing pairs of fused, immiscible glassy polymers. Reasons for this similarity are discussed.     

Peel Adhesion: Rate Dependence of Micro Fracture Processes

The micro-fracture mechanism of peeling is studied by means of a “bond stress analyses” which permits direct measurement of the distribution of normal or “cleavage” type stresses localized at the propagating boundary of failure. Improved instrumentation now permits direct stress analysis over nearly three decades of peeling rate. Experimental stress distributions are presented for an acrylic adhesive peeled from stainless steel. This study covers the transition region from elastomeric to flow state response where the viscoelastic transition from apparent interfacial to cohesive failure is observed for this acrylic copolymer. The major features of the cleavage stress distribution are qualitatively interpreted in terms of a cavitation-filamentation model which describes entanglement slippage as the dominant rate factor for cleavage response.     

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.     

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.     

Electrodeposition of silane films on aluminum alloys for corrosion protection

In this paper, three types of protective silane films, methyltrimethoxysilane (MTMS), vinyltrimethoxysilane (VTMS) and dodecyltrimethoxysilane (DTMS) were prepared on aluminum alloys AA 2024-T3 by electrodeposition technique. The Reflection-Absorption Fourier Transform IR (FTRA-IR) measurements showed that, the silane films were successfully deposited through chemical bonding between silane agents and Al alloys. Electrochemical impedance spectroscopy (EIS) tests indicated that in comparison with those by conventional “dip-coating” method, silane films electrochemically prepared at cathodic potentials exhibited obviously higher corrosion resistances. “Critical potential” was all observed for each silane system. Silane films prepared at this potential performed the highest corrosion resistance. The scanning electron microscopy (SEM) images indicated a potential dependence of surface morphology of silane films. The highest compactness was obtained at the “critical potential”. Due to the presence of long hydrophobic dodecyl chain in bone structure, DTMS films displayed the highest barrier properties.     

Stress Distribution during Peeling of Adhesive Tapes

The pattern of stress distribution observed during the peeling of pressure sensitive tapes is not adequately described by existing theoretical analyses of peel, which make over-simplifying assumptions. In particular, the consequence of filamentation or “legging” in the peeling zone is neglected by the theories. In the present work an attempt is made to assess the effect of filamentation by analysis of the peeling profile obtained by photography. The deflection of the backing film from its unrestricted “bent beam” configuration is interpreted in terms of a “filamentation force”. The stress distributions obtained show that filamentation makes an important contribution to the peel force and show good correlation with the results obtained from related systems by a different experimental method.     

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.     

Measurement of the Surface Free Energy of Amorphous Cellulose by Alkane Adsorption: A Critical Evaluation of Inverse Gas Chromatography (IGC)

Surface energies of amorphous cellulose “beads” were measured by IGC at different temperatures (50 to 100°C) using n-alkane probes (pentane to undecane). The equation of Schultz and Lavielle was applied which relates the specific retention volume of the gas probe to the dispersive component of the surface energy of the solid and liquid, γ^d_s and γ^d_l, respectively, and a parameter (“a”) which represents the surface area of the gas probe in contact with the solids. At 50°C, γ^d_s was determined to be 71.5 mJ/m², and its temperature dependence was 0.36 mJ m^-2 K^-1. Compared with measurements obtained by contact angle, IGC results were found to yield higher values, and especially a higher temperature dependence, d(γ^d_s)/dT. Various potential explanations for these elevated values were examined. The surface energy, as determined by the Schultz and Lavielle equation, was found to depend mostly on the parameter “a”. Two experimental conditions are known to affect the values of “a”: the solid surface and the temperature. While the surface effect of the parameter “a” was ignored in this study, the dependence of the surface energy upon temperature and probe phase was demonstrated to be significant. Several optional treatments of the parameter “a” were modeled. It was observed that both experimental imprecision, but mostly the fundamental difference between the liquid-solid vs the gas-solid system (and the associated theoretical weakness of the model used), could explain the differences between γ^d_s and d(γ^d_s)/dT measured by contact angle and IGC. It was concluded that the exaggerated temperature dependence of the IGC results is a consequence of limitations inherent in the definition of parameter “a”.     

Adhesion Mechanisms at Amine-Cured Epoxy/Aluminium Interfaces

Because the structure and the chemical composition of the interface can have a large effect on the adhesion properties of polymeric materials to metallic surfaces, many investigations have concentrated on the study of the interphase region. However, the complexity of the materials often leads to the use of model compounds to mimic the interfacial reaction. We have presented a critical discussion of three different approaches which have been used to understand the adhesion mechanism at amine-cured epoxy/aluminium interfaces: i) fracture of “real world” joints; ii) deposition of model (amino-alcohol) molecules on “real world” substrates; i) deposition of model (amino-alcohol) molecules on clean, oxidised and hydroxylated Al (100) surfaces. We have shown that model compounds can adequately duplicate the interface chemistry observed in “real world” joints. However, a detailed understanding of the exact nature of the interactions and of the role of the different reactive sites can only be achieved through studies performed on a model surface under controlled ultrahigh vacuum conditions.     

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.     

The Effect of Water on Matrix/Filler Adhesion in a Polyurethane Elastomer

The static “moduli”, failure stresses and dynamic moduli of both filled and unfilled polyurethanes were measured over a range of equilibrium water contents and these results are compared with those obtained from dry controls. Where barium sulphate was employed as the major filler component, it is shown that the presence of as little as ∼0.7% water results in a profound degradation of mechanical properties with the loss of most of the contribution attributable to the presence of fillers as a result of hydrolytic disruption of filler/matrix adhesion. A quantitative relationship between water content and mechanical properties is established and the mechanics of the water/polymer/filler interaction are considered. Less dramatic effects were observed when barium sulphate was replaced by iron oxide and these were apparently further reduced by the use of a silane coupling agent.     

Surface Mechanical Properties of the Spore Adhesive of the Green Alga Ulva

The mechanical properties of the adhesive produced by spores of the green, marine, fouling alga Ulva linza are reported. Atomic force microscopy studies were performed and nanoindentation data were analyzed using a model for an asymmetric indenter. Freshly secreted adhesive is characterized by multiple layers. We found that the modulus of the outer ∼600-nm thick layer was about 0.2 ± 0.1 MPa, whereas the modulus of the inner layer was about 3 ± 1 MPa. Older adhesive showed the formation of a “crust” of harder material with a yield strength of ∼20 MPa at a loading rate of 2.5 × 10^-6 N · s^-1. Mechanical properties under tension are also described, and extension profiles that showed either constant or nonlinear force changes with tip-sample separation were observed. Models for both kinds of behavior are described. The work of adhesion between poly-dimethylsiloxane (PDMS)-coated AFM tips and the adhesive was determined to be less than 1.5 mJ · m^-2.     

Properties of the Photon Emission Accompanying the Peeling of a Pressure-Sensitive Adhesive

During the peeling of pressure-sensitive adhesives, it is well known that visible light is emitted from the region near the detachment zone. This photon emission due to adhesive failure is a unique form of triboluminescence. In this paper, we further investigate the properties of this light from the peeling of a filament tape with a natural rubber-resin adhesive from its backing at various peel speeds. We show conclusively that small electrostatic discharges are the major source of this radiation. Total intensity vs time measurements show that the light consists of very intense bursts with typical duration of 50 ns which frequently induce additional discharges for times as long as 50—100μs. Time resolved spectra of these emissions show them to be dominated by the line spectrum of molecular nitrogen for both the initial burst and those that follow in the next 0.1—100μs. Thus, the “after-emission” is not due to phosphorescence of the polymer(s), but due to these additional electrostatic discharges.     

Recent Aspects of Glass Fiber-Resin Interfaces

The recent developments in Auger spectroscopy have been used to define the composition of two glass fiber surfaces. The effect of fiber surface area on the interlaminar shear strength was also investigated. The chemistry of several silane “coupling agents” has been studied from the standpoint of its chemical form when it is applied to the glass fibers, and has in part been determined using a gas chromatographic technique. The relative thermal stability of some silanes in high temperature resin matrices was determined. A comparison of a treatment of glass fibers with aqueous and non-aqueous systems is made.