Aluminum anodization in deionized water as electrolyte

Thin oxide films were prepared electrochemically on the aluminum surface using the high-voltage discharge and potentiostatic methods in deionized water as an electrolyte. The growth of continuous films occurred only at potentials lower than the breakdown potential. The films obtained by the discharge method are more uniform and can grow to a higher thickness in comparison to those formed by the potentiostatic mode, as demonstrated by electrochemical impedance spectroscopy (EIS), transmission electron microscopy (TEM), and scanning Kelvin probe force microscopy (SKPFM). The data herein obtained can be used as a reference to understand better the properties of the films produced in conventional electrolytes where apart from water other species are present

Hydrophobic DES Based on Menthol and Natural Organic Acids for Use in Antifouling Marine Coatings

Publisher Copyright: © 2023 The Authors. Published by American Chemical Society.Marine biofouling negatively impacts industries with off-shore infrastructures, such as naval, oil, and aquaculture. To date, there are no ideal sustainable, economic, and environmentally benign solutions to deal with this phenomenon. The advances achieved in green solvents, as well as its application in different industries, such as pharmaceutical and biotechnology, have promoted the emergence of deep eutectic systems (DES). These eutectic systems have applications in various fields and can be revolutionary in the marine-based industrial sector. In this study, the main objective was to investigate the potential use of hydrophobic DES (HDES) based on menthol and natural organic acids for their use as marine antifouling coatings. Our strategy encompassed the physicochemical characterization of different formulations, which allowed us to identify the most appropriate molar ratio and intermolecular interactions for HDES formations. The miscibility of the resulting HDES with the marine coating has been evaluated and proven to be successful. The Men/OL (1:1) system proved to be the most promising in terms of cost-production and thus was the one used in subsequent antifouling tests. The cytotoxicity of this HDES was evaluated using an in vitro cell model (HaCat cells) showing no significant toxicity. Furthermore, the application of this system incorporated into coatings that are used in marine structures was also studied using marine species (Mytilus edulis mussels and Patella vulgata limpets) to evaluate both their antifouling and ecotoxicity effects. HDES Men/OL (1:1) incorporated in marine coatings was promising in reducing marine macrofouling and also proved to be effective at the level of microfouling without viability impairment of the tested marine species. It was revealed to be more efficient than using copper oxide, metallic copper, or ivermectin as antifouling agents. Biochemical assays performed on marine species showed that this HDES does not induce oxidative stress in the tested species. These results are a strong indication of the potential of this HDES to be sustainable and efficiently used in marine fouling control technologies.publishersversionpublishe

Preface

This volume is a collection of original articles resulting from the contributions presented at the international conference

Sensing polymer inhomogeneity in coated metals during the early stages of coating degradation

Negative-feedback scanning electrochemical microscopy (SECM) is successfully applied to visualize spatially-resolved differences in the topography of coated metal samples upon exposure to aqueous electrolyte solutions of different composition. This method allows the investigation of the uptake of reactants from the electrolyte phase through the polymeric matrix to the metal/polymer interface to be performed even at early exposures. Yet, the method must be carefully checked to discard transport processes from the organic matrix into the solution phase, such as those related to lixiviation. In this later case, the topography of the polymer layer may evolve with time accordingly, not longer exclusively responding to the uptake by the polymer matrix of components from the electrolyte phase. Furthermore, lixiviated species may also react with the SECM tip, eventually leading to the continuous modification of the active surface area of the electrode during the measurements. In this work, the effect of lixiviation from a nickel foil coated with plasticized PVC (PVC Plastisol) on its topographic characterization by SECM was investigate

Mechanical behaviour analysis of polyester polymer mortars modified with recycled GFRP waste materials

In this study the effect of incorporation of recycled glass-fibre reinforced polymer (GFRP) waste materials, obtained by means of milling processes, on mechanical behaviour of polyester polymer mortars was assessed. For this purpose, different contents of recycled GFRP waste powder and fibres, with distinct size gradings, were incorporated into polyester based mortars as sand aggregates and filler replacements. Flexural and compressive loading capacities were evaluated and found better than unmodified polymer mortars. GFRP modified polyester based mortars also show a less brittle behaviour, with retention of some loading capacity after peak load. Obtained results highlight the high potential of recycled GFRP waste materials as efficient and sustainable reinforcement and admixture for polymer concrete and mortars composites, constituting an emergent waste management solution

How density functional theory surface energies may explain the morphology of particles, nanosheets, and conversion films based on layered double hydroxides

Conversion films based on layered double hydroxides constitute an important and environmentally friendly technology for the corrosion protection of aeronautical structures. Unfortunately, the morphology of layered double hydroxide (LDH) conversion films is still not well understood. In the present work, the structure and driving forces behind the morphology of zinc−aluminum LDH conversion films on aluminum alloy 2024 (AA2024) are explained from the perspective of molecular modeling. Since LDH particles are the core structures of LDH conversion films, the first step in this work was to understand the relation between structure and morphology of the particles themselves and the single-layer nanosheets that constitute them. Results regarding LDH’s crystallites, particles, and conversion films obtained using X-ray diffraction (XRD), dynamic light scattering (DLS), scanning electron microscopy (SEM), and atomic force microscopy (AFM) are interpreted using periodic model density functional theory (DFT) calculations. On the basis of the understanding of the formation of LDH particles and their exfoliation to obtain single-layer nanosheets, for the first time, LDH conversion films have been modeled using periodic model DFT. The results point to a preferential orientation of the cationic layers perpendicular to the surface, thus explaining the film morphology (SEM and AFM) and providing a rational for their crystallization process.publishe

Sonication accelerated formation of Mg-Al-phosphate layered double hydroxide via sol-gel prepared mixed metal oxides

Single-phase magnesium-aluminium layered double hydroxide (LDH) intercalated with dihydrogen phosphate was successfully produced by hydration of nanopowder of the respective mixed metal oxide (MMO) obtained using sol-gel based method followed by a two-step anion exchange hydroxide-to-chloride and chloride-to-phosphate. The MMO with the metal cation ratio of Mg/Al = 2:1 was prepared using the aqueous sol-gel method. Processes of the parent Mg2Al-OH LDH formation and the successive anion-exchanges, ОН- → Cl- and Cl- → H2PO4-, were considerably accelerated via the application of high-power (1.5 kW) ultrasound. The crystalline phases formed at all stages of the Mg2Al-H2PO4 LDH production were characterized using X-ray diffraction, scanning electron microscopy, scanning transmission electron microscopy, inductive coupled plasma optical emission spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Based on the data of chemical analysis and the XRD data, the type of the intercalated phosphate anion was determined and the arrangement of this anion in the interlayer was modelled.publishe

Improving the functionality and performance of AA2024 corrosion sensing coatings with nanocontainers

The compatibility between nanocontainers and coating formulations is perhaps the last frontier in the quest for functional coatings. Sensing coatings for early metallic corrosion detection is an urgently needed technology by aeronautical companies to mitigate the costs of corrosion through continuous monitoring. In this work, we revisit phenolphthalein encapsulated silica nanocapsules, which were incorporated into a water-based lacquer, resulting in a novel corrosion sensing coating for aluminum alloy 2024 with improved functionality and standard performance. The ability of the coatings to detect corrosion by color change was investigated by immersion and salt-spray tests. During these tests, it was clearly demonstrated that encapsulation of the active compound is essential to obtain a functional coating, since the shell of the silica nanocapsules minimizes the detrimental interaction of the active compound with the coating formulation. The compatibility between nanostructured additives and coatings is almost never taken into consideration in the literature. Herein this aspect evidences the positive effects of active agent encapsulation, which is explored in terms of reactivity, viscoelastic properties, curing, thermal stability, release and leaching studies, hardness, mechanical properties and corrosion resistance. Computer simulations based on the density functional theory and periodic structural models were performed to unveil the interaction mode of phenolphthalein with the metallic surface.This work was developed in the scope of the project CICECO – Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (Ref. FCT UID/CTM/50011/2013), financed by national funds through the FCT/ MEC and when applicable co-financed by FEDER under the PT2020 Partnership Agreement. This work has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreements No 645662. It was also financed in the framework of the project reference PTDC/QEQQFI/ 4719/2014, Project 3599 – Promover a Produção Científica e Desenvolvimento Tecnológico e a Constituição de Redes Temáticas (3599-PPCDT) and FEDER funds through COMPETE 2020, Programa Operacional Competitividade e Internacionalização (POCI). The authors also thank financial support from FCT and COMPETE (Programa Investigador FCT). JT thanks FCT for the research grant IF/00347/ 2013.publishe

Magnetic phenomena in co-containing layered double hydroxides

Magnetic behavior of CoII(n)AlIII layered double hydroxides (LDHs) (n=Co/Al=2 and 3) intercalated with nitrate was studied as a function of temperature. Both LDH compounds are paramagnetic above about 8K. A rapid increase of their magnetic moments occurs below this temperature until the moments reach the maximum values at Tmax of 4.0K and 3.2K for Co(2)Al-NO3 and Co(3)Al-NO3, respectively. Below Tmax, the zero-field-cooled and the field-cooled static magnetization curves are strongly different. Along with this low-temperature phenomena, Co(2)Al-NO3 and Co(3)Al-NO3 demonstrate anomalous behavior of their temperature dependence magnetic susceptibility in a highertemperature range: between 75 and 175K, both the paramagnetic Curie temperature and the effective magnetic moment change in a non-monotonous way. Possible structural reasons of the observed magnetic behavior of the CoII(n)AlIII LDHs are discussed.publishe