A hyphenated optical-electrochemical set-up was used to investigate the early-stage dissolution mechanism of NdFeB permanent magnets immersed in acetic, citric, and formic acids at concentrations of 0.01 and 0.1 M. This approach enabled a direct correlation between quantifiable surface changes and dissolution behaviour under open-circuit potential (OCP) conditions. Despite minimal OCP variation (180 mV) across all conditions and rapid stabilisation within approximately 300 s, significant optically-detectable surface changes continued throughout the measurement period (1 h). This emphasises that surface dissolution kinetics, rather than thermodynamics, predominantly control the early-stage dissolution of NdFeB. Kinetic parameters obtained by fitting mean activity-level curves with a sigmoidal model revealed that higher acid concentrations result in shorter induction periods and faster surface activation. In-situ optical analysis indicated a consistent dissolution mechanism characterised initially by localised activation, followed by the progressive expansion of active sites across the surface. Post-immersion analysis confirmed preferential dissolution of rare-earth-rich phases at grain boundaries and triple points, alongside intragranular dissolution observed in 0.01 M citric acid. Among the tested conditions, dilute citric acid (0.01 M) emerges as particularly suitable medium for practical control, as its relatively long induction period (∼1378 s) allows monitoring and controlling local dissolution before rapid surface activation begins. The combined optical-electrochemical approach also revealed that, while rare-earth-rich sites are preferentially activated, early signs of matrix activation are detectable, underscoring the value of in-situ optical analysis for advancing process control in NdFeB recycling.

The growing demand for lithium-ion batteries (LiBs) for energy storage has intensified the need for the critical raw materials (CRMs) they contain, including Li, Co, Ni, and Mn. Consequently, the incentive to recycle LIBs is increasing. However, the commonly used hydrometallurgical processes often have a significant environmental footprint. Moreover, the relatively low value of certain battery materials (e.g., LiFePO₄, LFP) results in a limited incentive for their recycling. This study explores the simultaneous recycling of LFP with various types of LiNi_xMn_yCo_zO₂-containing Black Mass (BM). Leaching studies over time were conducted using stepwise additions of LFP and H₂O₂ solution (1 vol%) to a mild lixiviant of 0.63 mol/L H₂SO₄ at 50°C_. For pristine NMC 532, ± 95% leaching of Li, Ni, Co, and Mn was achieved. The Fe(II) present in LFP, as well as H₂O₂, acts as a reductant for the dissolution of Ni, Co, and Mn, later precipitating as FePO₄ to the leaching residue. The Al and Cu present in industrially treated BM further enhanced the dissolution of the transition metals via a catalyzed reaction with the iron from LFP. This resulted in complete leaching of Li, Ni, Co, and Mn for mechanically pre-treated industrial black mass samples. However, the leaching residues acquired from these samples were highly contaminated with graphite. Also, while pyrolysis of the black mass benefits the leaching of Co and Mn, it results in difficulties in subsequent removal of Fe from the pregnant leach solution. The chemical processes and their performance are described in this work.

In this work, the correlation between electrolyte transport properties and the variation of pigment volume concentration (PVC) in a series of organic coatings is explored. Using an odd random phase electrochemical impedance spectroscopy (ORP-EIS) approach, the diffusion of ions independent from water take-up is analysed. A higher PVC resulted in a more homogeneous coating morphology, which could be associated with a faster diffusion of ions following a Fickian regime and enhanced water uptake. In the case of lower pigment loading, the obtained heterogenous morphology of the coating introduced new challenges to the physical interpretation of the proposed electrochemical equivalent circuit.

An evaluation of neodymium‑iron‑boron permanent magnets (NdFeB PMs) from different end-of-life products, as a secondary resource of rare-earth elements (REEs), is presented. De-coating of PM was investigate as pre-treatment to facilitate efficient direct magnet recycling. Thus, critical aspects from disassembling to the de-coating of the magnets were addressed. A challenge for the de-coating process is that the magnets have different sizes, weights, and their coating compositions are not known beforehand. It was shown that ammonia-based solutions was thermodynamically suitable to dissolve nickel and zinc coatings selectively, while keeping the bulk magnet stable. Nevertheless, the dissolution of Zn was much faster than the Ni one, and more efficient.

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.

The anodising process parameters (voltage, temperature, and electrolyte) control the morphology and the chemical composition of the resulting anodic oxide film by altering the balance between oxide growth and oxide dissolution reactions. The porosity of the oxide film is reduced by the addition of tartaric acid to a sulfuric acid electrolyte, while anodising at elevated temperatures enhances oxide dissolution, leading to wider pores and rougher surfaces. No significant changes in the oxide chemical composition as a function of anodising parameters was found; in particular, no tartrate incorporation took place. The resistance of uncoated anodic oxide films against aggressive media and galvanic stress as a function of anodising parameters has been studied by electrochemical methods. Anodising in a mixed tartaric and sulfuric acid electrolyte improves the resistance of the anodic oxide against galvanic stress and aggressive media in comparison to sulfuric acid ano-dising processes. However, the corrosion protection performance of the anodic oxide films in com-bination with a corrosion-inhibitor loaded organic coating is not governed by the blank oxide properties but by the adhesion-enhancing morphological features formed during anodising at elevated temperatures at the oxide/coating interface.

The adhesion capabilities of sulfuric acid and tartaric-sulfuric-acid anodic oxide films on cladded AA2024-T3 aluminium substrates have been investigated in a quantitative manner. A relatively simple, versatile and industrially applicable test methodology based on DIN EN ISO 29862 has been used. In addition, the effect of anodising process parameters on the oxide film morphology has been studied and correlated with the adhesion results. The process parameters considered are the chemistry of the acidic pickling pre-treatment step, the addition of tartaric acid to the sulfuric acid electrolyte, the formation voltage, and the electrolyte temperature. The suggested tape peel adhesion test is able to differentiate among pre-treatments and anodising conditions showing a good correlation with the morphological features at the ultimate surface. High peel adhesion strengths are measured when topographies such as pore mouth widening and dissolution-driven roughness take place. These morphologies are typically found in anodic layers formed at elevated electrolyte temperatures. The proposed method can be beneficial for a fast assessment of anodising parameters for good adhesion, which is of special interest for the industrial optimisation of anodising processes.

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.

Diamond is known as a promising electrode material in the fields of cell stimulation, energy storage (e.g., supercapacitors), (bio)sensing, catalysis, etc. However, engineering its surface and electrochemical properties often requires costly and complex procedures with addition of foreign material (e.g., carbon nanotube or polymer) scaffolds or cleanroom processing. In this work, we demonstrate a novel approach using laser-induced periodic surface structuring (LIPSS) as a scalable, versatile, and cost-effective technique to nanostructure the surface and tune the electrochemical properties of boron-doped diamond (BDD). We study the effect of LIPSS on heavily doped BDD and investigate its application as electrodes for cell stimulation and energy storage. We show that quasi-periodic ripple structures formed on diamond electrodes laser-textured with a laser accumulated fluence of 0.325 kJ/cm² (800 nm wavelength) displayed a much higher double-layer capacitance of 660 μF/cm² than the as-grown BDD (20 μF/cm²) and that an increased charge-storage capacity of 1.6 mC/cm² (>6-fold increase after laser texturing) and a low impedance of 2.74 ω cm² turn out to be appreciable properties for cell stimulation. Additional morphological and structural characterization revealed that ripple formation on heavily boron-doped diamond (2.8 atom % [B]) occurs at much lower accumulated fluences than the 2 kJ/cm² typically reported for lower doping levels and that the process involves stronger graphitization of the BDD surface. Finally, we show that the exposed interface between sp² and sp³ carbon layers (i.e. the laser-ablated diamond surface) revealed faster kinetics than the untreated BDD in both ferrocyanide and RuHex mediators, which can be used for electrochemical (bio)sensing. Overall, our work demonstrates that LIPSS is a powerful single-step tool for the fabrication of surface-engineered diamond electrodes with tunable material, electrochemical, and charge-storage properties.

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.]

Copper foil was anodized in 1 M KOH at potentials ranging from −400 to −100 mV vs. Ag|AgCl electrode. Cyclic voltammetry showed a distinct peak with a maximum at around −150 mV. For anodizing at −100 and −200 mV, nanowires with diameters of ca. 19 and 24 nm respectively were found to be grown. Moreover, photoluminescence and X-ray diffraction show that the dominant phase is the CuO phase. At lower potentials, cuboidal micron sized crystals were formed and Cu₂O was found to be the major phase.

Zirconium-based conversion treatment of zinc, aluminium and magnesium oxides have been studied in-situ using ATR-FTIR in a Kretschmann geometry. This set-up was coupled to an electrochemical cell, which allowed to obtain chemical and electrochemical information simultaneously as a function of conversion time. This elucidated the strong relation between physico-chemical surface properties and zirconium-based conversion kinetics. Whereas the surface hydroxyl density of zinc and aluminium increased during conversion, magnesium (hydr)oxide was shown to dissolve in the acid solution. Due to this dissolution, strong surface alkalization can be expected, explaining the rapid conversion kinetics. AES depth profiling was used to determine the final oxide thickness and elemental composition. This confirmed that magnesium is most active and forms a zirconium oxide layer approximately 10 times thicker than zinc. On the other hand, the presence of zirconium oxide on aluminium is very low and can be considered as not fully covering the metal oxide. Additionally, the converted oxide chemistry was related to the bonding mechanisms of amide functionalized molecules using ATR-FTIR and XPS. It was shown that inclusion of zirconium altered the acid-base properties, increasing the substrate proton donating capabilities in case of magnesium oxide and increasing hydrogen bonding and Bronsted interactions due to increased surface hydroxide fractions on zinc and aluminium substrates.