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 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.     

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.     

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).     

Pretreatments of Hydrocarbon and Fluorocarbon Polymers

Pretreatments of polyolefins and fluoropolymers are usually necessary to achieve satisfactory adhesion for bonding and related technologies. In this paper results for various pretreatments of these polymers are presented. These are the treatment of polyolefins with aqueous reagents, dilute fluorine and a natural gas flame, the treatment of PTFE with sodium naphthalenide and the treatment of ECTFE with sodium naphthalenide and a flame. X-ray photoelectron spectroscopy was used to investigate the chemical changes caused by the treatment and the adhesion levels were discussed in relation to wetting, interactions across interfaces and weak boundary layers.     

Interphases in the Adhesive Bonding of Fluoropolymers

Strong and durable adhesive bonds may be made between polytetrafluoroethylene (PTFE) and either cyanoacrylate (CA) or epoxy adhesives, if the PTFE surface is modified by the use of a “primer” such as triphenylphosphine (TPP) or diaminodiphenylmethane (DDM). The primer mixes with the PTFE surface, and the modified surface is then capable of forming an interphase, tens to hundreds of nanometers thick, where interpenetration of the adhesive and adherend occurs. Using CA adhesives, PTFE/CA/PTFE block compression shear bond strength (ASTM D4501-85) of over 10 MPa can be achieved, with failure occurring cohesively. Initial work with epoxy adhesives indicates that the use of DDM primer gives adhesive bonds comparable in strength with those produced by modification of the fluoropolymer surface by sodium naphthalenide.     

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.     

Adhesion on Carbon-Fibre-Reinforced Plastics

The adhesion on CRFP-laminates is technically often used but the microscopic mechanisms are not yet completely understood. Besides the task to characterize the surfaces closely enough, the principal problem to predict the mechanical, physical and chemical properties of the boundary zone remains unsolved. More of less only the “try and error” method leads to the development of adhesive bonding processes, which satisfy the demands of aircraft structures concerning quality, reproducibility and durability. Experiments with varying substrates, surface pretreatments and adhesives show that all these parameters have a distinct influence on the mechanical performance of the bonds.     

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.     

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.     

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”.     

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.     

Comment on “Sodium Hydroxide Anodization of Ti-6AI-4V Adherends”, J. Adhesion 20,283 (1987)

The recent article “Sodium Hydroxide Anodization of Ti-6A1-4V Adherends” by Filbey, Wightman and Progar' is commendable in that a wide variety of analytical techniques has been used to study the surface preparation first reported by Kennedy, Kohler and Poole. We too have conducted in-depth studies of surface preparations for Ti-6A1-4V adherends with recent emphasis on chromic acid and sodium hydroxide anodization (CAA and SHA, respectively). Our initial results were in agreement with those presented by Filbey et al. (hereafter “the authors”) regarding surface composition and oxide sputter-etching efficiency. However, the results of more detailed work have shown that these observations (and the subsequent conclusions) may be influenced by instrumentation effects. We wish to highlight these briefly.     

Tissue-on-Tissue Testing of Dry Eye Formulations for Reduction of Bioadhesion

Glutaraldehyde-preserved, human umbilical cord vein graft (UCVG) was selected as a stable surrogate tissue source for testing of bioadhesion-reducing lubricants. Bioadhesion, as manifested in tissue-on-tissue friction coefficients of 0.2-0.4 for saline-lubricated UCVG, was quantitatively and persistently reduced after the instillation of a single aliquot of an ophthalmic “artificial tears” formulation containing active demulcents polyethylene glycol (PEG400) and propylene glycol (PG), as well as a gellable hydroxypropyl guar (HP Guar) in a borate-buffered solution between the “blinking” tissues. Reduced adhesion was maintained (was “substantive”), even after rinsing excess lubricant from the surfaces. Comparative tests with tissue-on-solid, and solid-on-solid, similarly lubricated couples point to a potentially unique mechanism that involves macromolecules modifying the tissue phases to provide rinse-resistant lubricity and surface protection in articulated tissue-to-tissue interfaces. Results for tissue-on-tissue couples were obtained in laboratory trials utilizing a reciprocating pin-on-disc type friction/wear test device articulating preserved human umbilical cord vein segments under increasing loads, and again after saline rinsing to determine persistence of the friction-reducing effects. A single confirmatory test using donated human cornea against vein graft tissue showed the lowest coefficient of friction, below 0.05, for the “artificial tears” formulation. Mechanistic studies employing the same test device and protocol for metal oxide (germanium)-on-metal oxide couples, as well as for metal oxide-on-tissue couples, indicated that simple increases in viscosity were not the likely sources of friction reduction, and revealed frictional values higher than measured for the similarly lubricated tissue-on-tissue couples. Thus, formulation development to minimize bioadhesion requires that appropriate simulations be used to obtain clinically predictive data for circumstances of liquid uptake into the tissues, resultant tissue swelling, and binding to impermeable adjacent materials.     

The Mechanical Behaviour of Polyimide/Copper Laminates Part 2: Peel Energy Measurements

The mechanical peel behaviour of laminates consisting of polyimide films adhered to copper foil using a modified acrylic adhesive has been studied over a wide range of test rates and temperatures. The laminates were prepared from polyimide films which had been subjected to either a “high-thermal history” or a “low-thermal history” treatment during the production of the film. The measured peel energies of the laminates could be superimposed to give a master curve of peel energy versus the reduced rate of peel test, Ra_T, where R is the rate of peel test and a_T is the time-temperature shift factor. The appropriate shift factors were a function of the test temperature and were mainly deduced from tensile tests conducted on the bulk adhesive. The “high-thermal history” laminates gave higher peel energies and the locus of failure of the laminates was mainly by cohesive fracture through the adhesive layer. At low values of log₁₀ Ra_T, i.e. Low rates of peel and high test temperatures, the “low-thermal history” laminates also failed in the adhesive layer and possessed similar peel energies to those measured for the “high-thermal history” laminates. However, at high log₁₀ Ra_T values, the peel energies measured for the “low-thermal history” laminates were lower and showed a wider scatter. These arose from a different locus of failure occurring in these “low-thermal history” laminates when tested under these conditions. Namely, it was found that most of these laminates failed in a weak boundary layer in the outer regions of the “low-thermal history” polyimide film.     

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.     

Plasma Chemical Modification of Polycarbonate Surfaces for Electroless Plating

The preliminary steps of the “electroless” metallization of polycarbonate are investigated by XPS. They consist of the chemisorption of a catalyst (Pd) on the surface to be metallized. The corresponding surface can be activated either by chemical etching or by reactive or non-reactive gas plasma treatment. Therefore, the surface treatment of polycarbonate determines the palladium adsorption. It is shown here that a surface carrying oxygenated functions adsorbs palladium through Sn²⁺ ions which are themselves bonded to oxygen atoms. On the other hand, a surface on which nitrogenated groups have been grafted (by NH₃ or N₂ plasma treatment) chemisorbs palladium directly on these nitrogen atoms. Reaction mechanisms are proposed in both cases and a new and simplified process for making the surfaces catalytic is proposed.     

Condensation of aldehydes for environmentally friendly synthesis of 2-methyl-3-phenyl-propanal by heterogeneous catalysis

Eco-friendly synthesis in “one-pot” of 2-methyl-3-phenyl-propanal from benzaldehyde and propanal was studied using a multifunctional catalyst as an alternative to the three-step conventional process involving basic, acidic and hydrogenating catalysts. Mg(Al)O mixed oxides obtained from hydrotalcite precursor achieved the two first steps of condensation and dehydration. Addition of water to the solvent improves the activities and selectivities of Mg(Al)O, thanks to the reconstruction of the lamellar structure with OH⁻ as compensating anions, acting as Brønsted basic sites. Mg(Al)O was then used as support for a multifunctional catalyst impregnated with Pd. Pd/Mg(Al)O led to 45% dihydrocinnamaldehyde selectivity at 43% conversion in benzaldehyde in the “one-pot” process.     

THE INFLUENCE OF PROCESS PARAMETERS ON THE INTERFACIAL CHEMISTRY OF γ-GPS ON ALUMINIUM: A REVIEW

Within the “International Collaborative Programme on Organosilane Adhesion Promoters” (ICOSAP), scientists from the U.S. and Europe contributed to the understanding of an organosilane primer process, based on an aqueous solution of γ-glycidoxypropyl trimethoxysilane (γ-GPS), used currently for aerospace repair purposes. Parameters such as temperature of cure, ageing time, and concentration of the aqueous solution have been investigated, and this work reviews the effect that each variable has on the process, and the resulting integrity of the GPS/aluminium interface. The aim of the work was to provide a more environmentally friendly replacement for pretreatments containing Cr(VI) that are currently used, such as chromic acid anodising and acid etching employed for the structural adhesive bonding of aluminium.

The formation of covalent interfacial bonding is shown to be a function of the hydrolysis and condensation of the silane molecules in solution as well as the type of solvent used. The curing temperature of the aqueous film on the aluminium is also shown to have an effect on the chemistry of the resulting primer film and its efficacy as an adhesion promoter. All these parameters must be optimised to obtain durability that matches that obtained by a phosphoric acid anodising pretreatment. This work reports on the various studies performed towards this aim carried out within the remit of the ICOSAP initiative, with a particular emphasis on the interfacial chemistry between γ-GPS and the aluminium substrate, and indicates the manner in which the results point the way towards a viable, environmentally friendly pretreatment for the adhesive bonding of aluminium for aerospaceapplications.     

Water transport and condensation in fluoropolymer films

This report explores phenomena related to the undesired condensation of water in or under fluoropolymer films. Condensation of water in or under polymer films will occur when the local vapor pressure is higher than that corresponding to the local dew point vapor pressure. This can happen for any type of polymer film, including fluoropolymer films, even though solubility of water in the film may be extremely low. A “cold” substrate, for example, can readily lead to water condensation under a fluoropolymer film, and therefore to a reduction of adhesion or to complete delamination. These problems will not be so severe and may, indeed, disappear for acid-resistant fluoropolymer films exposed to hot and/or concentrated acids, such as sulfuric acid. The vapor pressure (activity) of the water in the acid is so reduced that condensation in or under the film will not occur at the usual temperatures encountered in practice.

Diffusion coefficients, permeation coefficients, and solubilities for water in selected fluoropolymers (PVDF, ETFE, ECTFE, PFA, MFA, FEP, and PTFE) have been measured at 90°C. The diffusion coefficients are greater than 3×10⁻⁷ cm²/s at this temperature. This means that a change in the environment will result in a new equilibrium condition for absorption, desorption, and/or permeation in practical fluoropolymer coatings within a maximum of a day or so for all of the materials tested. Practical free film thicknesses near 2 mm were used.

Approximate diffusion coefficients have also been measured by a new technique at 20°C for comparison. When the environment changes, a new condition for equilibrium is established at room temperature after times varying from several days to 2 months in these experiments which used the same practical film thicknesses. The technique involves following release of dissolved tritiated water (HTO) from a film while it is immersed in a scintillation liquid (gel) in a glass counting vial. The counting rate increases to an equilibrium level in proportion to the extent of diffusion of HTO out of the sample.