In this work, a new finite element modelling (FEM) approach is followed to model spatiotemporally resolved water uptake in organic coatings. To this aim, we start from a physical model, where not only Fickian diffusion of water is taken into account but also the adsorption/desorption reaction of water on the polymer matrix. Starting from a number of important coating properties and crucial model parameters, derived from gravimetric and Fourier transform infrared (FTIR) measurements as the model input, the local water concentration over the coating thickness as a function of time is modelled for a polyethylene glycol diacrylate (PEGDA) coating. The modelled water concentration is then used to calculate virtual capacitance values which are evaluated against experimental capacitance values extracted from impedance measurements. The constraints of the FEM model and ORP-EIS experiments and the discrepancies between them are critically discussed in order to carry out a meaningful model validation, eventually leading to model improvements.@en

The sol–gel process is a chemical surface preparation method based on hydrolysis and polycondensation reactions for enhanced adhesion for metallic substrates in adhesive bonding and coating applications. This paper describes an investigation into the effect of the microstructural complexity of two commonly used aerospace aluminium alloys (AAs) 2024-T3 and 7075-T6, on the response to different surface pre-treatments before deposition of the sol-gel coating and subsequent adhesive bonding. Different surface pre-treatments, including two abrasive treatments and three chemical surface pre-treatments were used, and their effect on surface chemistry, wettability and roughness was assessed. Surfaces were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, profilometry and static contact angles. A hybrid silane sol-gel film was deposited on the differently pre-treated aluminium alloys, an epoxy adhesive was applied and the adhesion properties were evaluated using pull-off testing. The role of the altered physicochemical properties of the pre-treated surfaces was related to the adhesion strength of the sol–gel reinforced epoxy/aluminium interfaces. The microstructural complexity of the aerospace alloys caused non-uniform responses to the pre-treatments, proving the importance of compatibility between material and treatment conditions. Statistical analysis revealed that, despite that overall higher adhesion values were obtained on rougher surfaces, only a strong correlation exists between the surface hydroxyl fraction and adhesion strength. The relation of roughness and water contact angle to interfacial adhesion was found to be non-significant. The findings of this study underscore the critical role of surface pre-treatments and their impact on adhesion strength in aerospace aluminium alloys, providing valuable insights for the effective utilization of sol-gel coatings in adhesive bonding and coating processes.@en

The sol-gel synthesis process is a versatile method used to produce a wide diversity of materials and is being increasingly used as a surface modification method to alter porosity, wettability, catalytic activity, biocompatibility and corrosion performance of underlying substrates. Silane sol–gel films deposited on aluminium and aluminium alloys have been widely studied as chemical conversion coatings and as coupling agent between the substrate and organic layers. This study set out to investigate the effect of the surface chemical treatment prior to sol-gel application on the interfacial adhesion properties of a hybrid sol-gel film. Different surface pre-treatments, including two abrasive treatments and three chemical surface pre-treatments were used and their effect on surface chemistry and surface roughness was assessed. Surfaces were characterized by scanning electron microscopy, x-ray photoelectron spectroscopy, roughness measurements and static contact angles. Cerium nitrate loaded hybrid sol-gel films were deposited and adhesion on commercially pure aluminium was evaluated using pull-off testing. Statistical analysis revealed that, although highest adhesion values were obtained on rougher surfaces, the strongest correlation exists between the surface hydroxyl fraction and adhesion strength.@en

In general, packaging materials which encapsulate light emitting diodes (LEDs) and microelectronic devices offer barrier protection against several environmental hazards such as water and ionic contaminants. However, these encapsulants may provide pathways for water and ionic contaminants to reach the metal/polymer interfaces and provoke local corrosion of electronics, which is a major reliability concern for polymer encapsulated LEDs and microelectronics. As the water and corrosive constituents play a crucial role in their reliability, water uptake kinetics, interfacial ion transport and delamination behaviour of silicone coated copper model system, mimicking a typical microelectronics packaging system, is explored in the present work. Electrochemical impedance spectroscopy (EIS) integrated with attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy studies revealed that water diffusion inside the silicone network is Fickian in nature and the evolution of the observed time constants are related to the diffusion and interfacial reactions. A decrease of impedance magnitude with time was observed in EIS measurements concurrently with water absorption bands shifting towards lower wavenumber in ATR-FTIR measurements, implying the growth of strong hydrogen bonding between water molecules and the silicone network. The estimated diffusion constant of water using the capacitance method was in the order of 7 × 10-12 m2 s−1 and the water absorption volume fraction was in the range of 0% to 0.30%. Scanning Kelvin probe studies elucidated the ion transport process occurring at the silicone/copper interface in a humid atmosphere. The interfacial ion transport process is controlled by the interfacial electrochemical reactions at the cathodic delamination front and the estimated average delamination rate is 0.43 mm h-1/2. This work demonstrates that exploring ion and water transport in the silicone coating and along the silicone/copper interface is of pivotal importance as part of a detailed reliability assessment of the polymer encapsulated LEDs and microelectronics.@en

The bonding properties of zirconium- and titanium-based conversion coatings were evaluated using model conversion solutions of H2ZrF6 and H2TiF6 with addition of various organic additives (PAA, PVA, PVP). Macroscopic testing techniques such as contact angle and pull-off adhesion measurements were performed on galvanized steel sheets. Complementary to this, molecular studies were performed on model zinc substrates using ATR-FTIR in the Kretschmann configuration. The macroscopic and molecular approaches showed a good correlation demonstrating ATR-FTIR in the Kretschmann configuration to be a valuable tool to gain fundamental insights in metal oxide-polymer interfacial phenomena. Zirconium-treated galvanized steel substrates were shown to have a higher bonding affinity for the polyester coil coat primer than titanium-treated galvanized steel substrates. The presence of organic additives did not further improve the bonding properties. Yet, organic additives initially improved the interfacial stability of titanium-treated substrates. However, on the long term, organic additives are shown to be detrimental for polyester coil coat adhesion. This adverse effect of organic additives on the long term was assigned to its selective dissolution during immersion and was most pronounced for titanium-treatments. The limited effect of organic additives in case of zirconium-treatments was attributed to the higher portion of chemical interfacial bonds, as well as its tendency for crosslinking reactions causing entanglement of polymeric compounds in the zirconium oxide structure.@en

This work focuses on the effect of surface roughness and surface chemistry on the initial adhesion strength and corrosive de-adhesion properties of adhesive bonds. The adherend used in this study is a S690 low-alloy steel whereas the adhesive is a 2-component epoxy-amine adhesive (Araldite 2015). The steel surface is subjected to different surface pre-treatment methods such as mechanical abrasion, grit blasting, zirconium conversion treatment and silane treatment. The effect of these different pre-treatments on the surface morphology, roughness and chemistry is addressed. Single-lap joint tests were performed at ambient conditions to assess the initial bond strength of the joint. Static wedge tests were performed in saltwater immersions to study the environmental ageing of the adhesive joints. Unloaded delamination of adhesive films from the steel surface was studied by means of scanning Kelvin probe (SKP) at high relative humidity. This unique combination of different techniques allows thorough evaluations of the bond performance under different environmental and loading conditions. Experimental results indicate that surface roughening plays an important role in the initial adhesion in the single-lap joint test but a minor role in the durability of the bonded steel surfaces. The improved initial adhesion is mainly attributed to the increased interfacial bond area at higher surface roughness. The presence of complex texture or morphology shows a more profound effect than the average roughness on both the initial adhesion and the durability of the interfacial adhesion. The results from the static wedge test show the large contribution of mechanical interlocking, caused by texturing of the surface, on the durability of the interfacial adhesion. In the absence of complex texture, surfaces with altered chemistry by zirconium- or silane treatment exhibit a significant increase of the initial bonding strength due to enhanced physicochemical interactions across the interface. Assessment of the interfacial delamination kinetics by SKP show that despite the absence of any surface topography, chemically altered surfaces prove to have higher resistance to delamination.@en