For more than six decades, chromic acid anodizing (CAA) has been the central process in the surface pre-treatment of aluminum for adhesively bonded aircraft structures. Unfortunately, this electrolyte contains hexavalent chromium (Cr(VI)), a compound known for its toxicity and carcinogenic properties. To comply with the new strict international regulations, the Cr(VI)-era will soon have to come to an end. Anodizing aluminum in acid electrolytes produces a self-ordered porous oxide layer. Although different acids can be used to create this type of structure, the excellent adhesion and corrosion resistance that is currently achieved by the complete Cr(VI)-based process is not easily matched. This paper provides a critical overview and appraisal of proposed alternatives to CAA, including combinations of multiple anodizing steps, pre- and post anodizing treatments. The work is presented in terms of the modifications to the oxide properties, such as morphological features (e.g., pore size, barrier layer thickness) and surface chemistry, in order to evaluate the link between fundamental principles of adhesion and bond performance.[Figure not available: see fulltext.]@en

Using adhesives for connection technology has many benefits. It is cost-efficient, fast, and allows homogeneous stress distribution between the bonded surfaces. This paper gives an overview on the current state of knowledge regarding the technologically important area of adhesive materials, as well as on emergent related technologies. It is expected to fill some of the technological gaps between the existing literature and industrial reality, by focusing at opportunities and challenges in the adhesives sector, on sustainable and eco-friendly chemistries that enable bio-derived adhesives, recycling and debonding, as well as giving a brief overview on the surface treatment approaches involved in the adhesive application process, with major focus on metal and polymer matrix composites. Finally, some thoughts on the connection between research and development (R&D) efforts, industry standards and regulatory aspects are given. It contributes to bridge the gap between industry and research institutes/academy. Examples from the aeronautics industry are often used since many technological advances in this industry are innovation precursors for other industries. This paper is mainly addressed to chemists, materials scientists, materials engineers, and decision-makers.@en

The long-term strength and durability of an adhesive bond is dependent on the stability of the oxide-adhesive interface. As such, changes in the chemistry of the oxide and/or the adhesive are expected to modify the interfacial properties and affect the joint performance in practice. The upcoming transition to Cr(VI)-free surface pretreatments makes it crucial to evaluate how the incorporation of electrolyte-derived sulfate and phosphate anions from, respectively, phosphoric acid anodizing and sulfuric acid anodizing affect the interfacial chemical properties. Hence, different types of featureless aluminum oxides with well-defined surface chemistries were prepared in this study. The relative amounts of O2−, OH−, , and surface species were quantified using x-ray photoelectron spectroscopy. Next, bonding with two types of commercial aerospace adhesive films was assessed by peel and bondline corrosion tests. The presented results indicate that the durability of the oxide-adhesive interface depends on the interplay between oxide and adhesive chemistries. Epoxy adhesion is highly affected by changes in the oxide surface chemistry, especially the amount of surface hydroxyls. However, the performance of anodic oxides with a lower hydroxyl fraction can be significantly enhanced by the presence of covalent bonds using a silane coupling agent, γ-amino propyl triethoxy. On the contrary, results with Redux 775 adhesive exhibit very low sensitivity to variations in the surface chemistry. Bondline corrosion resistance of the joints is mainly determined by the nature of the adhesive, independent of the varying oxide chemistries.@en

For more than six decades, chromic acid anodizing has been the main step in the surface treatment of aluminum for adhesively bonded aircraft structures. Soon this process, known for producing a readily adherent oxide with an excellent corrosion resistance, will be banned by strict international environmental and health regulations. Replacing this traditional process in a high-demanding and high-risk industry such as aircraft construction requires an in-depth understanding of the underlying adhesion and degradation mechanisms at the oxide/resin interface resulting from alternative processes. The relationship between the anodizing conditions in sulfuric and mixtures of sulfuric and phosphoric acid electrolytes and the formation and durability of bonding under various environmental conditions was investigated. Scanning electron microscopy was used to characterize the oxide features. Selected specimens were studied with transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy to measure resin concentration within structurally different porous anodic oxide layers as a function of depth. Results show that there are two critical morphological aspects for strong and durable bonding. First, a minimum pore size is pivotal for the formation of a stable interface, as reflected by the initial peel strengths. Second, the increased surface roughness of the oxide/resin interface caused by extended chemical dissolution at higher temperature and higher phosphoric acid concentration is crucial to assure bond durability under water ingress. There is, however, an upper limit to the beneficial amount of anodic dissolution above which bonds are prone for corrosive degradation. Morphology is, however, not the only prerequisite for good bonding and bond performance also depends on the oxides’ chemical composition.@en