Herein, we report a feasible method for forming barrel-like hybrid Cu(OH)₂-ZnO structures on α-brass substrate via low-potential electro-oxidation in 1 M NaOH solution. The presented study was conducted to investigate the electrochemical behavior of CuZn in a passive range (−0.2 V–0.5 V) and its morphological changes that occur under these conditions. As found, morphology and phase composition of the grown layer strongly depend on the applied potential, and those material characteristics can be tuned by varying the operating conditions. To the best of our knowledge, the yielded morphology of barrel-like structure has not been previously observed for brass anodizing. Additionally, photoactivity under both UV and daylight irradiation-induced degradation of organic dye (methyl orange) using Cu(OH)₂-ZnO composite was explored. Obtained results proved photocatalytic activity of the material that led to degradation of 43% and 36% of the compound in UV and visible light, respectively. The role of Cu(OH)₂ in improving ZnO photoactivity was recognized and discussed. As implied by both the undertaken research and the literature on the subject, cupric hydroxide can act as a trap for photoexcited electrons, and thus contributes to stabilizing electron-hole recombination. This resulted in improved light-absorbing properties of the photoactive component, ZnO.

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Our work provides a thorough characterization of different biochars produced by a novel 50 kW_th Indirectly Heated Bubbling Fluidized Bed Steam Reformer. This study investigates the effect of temperature and gasification agent on the physico-chemical properties of biochars. We combined macro, micro and nano characterization techniques to provide a clear picture of the biochar characteristics, surface functionality and its “inert” nature toward potential applications. Our results demonstrate that indirect gasification is capable of producing carbon-rich biochars (> 92%) with increased porosity (89–198 cm³.g⁻¹), high heating value (28–31 MJ.kg⁻¹ a.r.) and aromaticity compared to the parent biomass. All biochars have lower O/C (0.02–0.04) and H/C atomic ratios (0.09–0.19), similar to anthracite. For the range of tested gasification conditions, air/steam gasification at an equivalence ratio of 0.20 and steam-to-biomass ratio of 1.2 provides the highest biochar yield (7.3%), while maintaining syngas composition optimal. On the other hand, air gasification produces biochars with relatively high content of inorganic elements. Indirectly heated biochars are compliant with the European Biochar Certificate regarding the carbon content, O/C ratio, H/C ratio. Our biochars may provide an improvement in agricultural yield and CO₂ adsorption, especially those produced under air/steam gasification conditions. Our novel indirect design not only constitutes a promising development in the field of biomass allothermal gasification but also can help improving gasification circularity through the production of high quality biochar.

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For structural assessment and optimal design of thick-section high-strength steels in applications under harsh service conditions, it is essential to understand the cleavage fracture micromechanisms. In this study, we assess the effects of through-thickness microstructure of an 80-mm-thick quenched and tempered S690 high-strength steel, notch orientation, and crack tip constraint in cleavage nucleation and propagation via sub-sized crack tip opening displacement (CTOD) testing at −100 °C. The notch was placed parallel and perpendicular to the rolling direction, and the crack tip constraint was analysed by varying the a/W ratio: 0.5, 0.25, and 0.1. The notch orientation does not play a role, and the material is considered isotropic in-plane. Nb-rich inclusions were observed to act as the weak microstructural link in the steel, triggering fracture in specimens with the lowest CTOD values. While shallow-cracked specimens from the top section present larger critical CTOD values than deep-cracked ones due to stress relief ahead of the crack tip, the constraint does not have a significant influence in the middle due to the very detrimental microstructure in the presence of Nb-rich inclusions. Some specimens show areas of intergranular fracture due to the combined effect of C, Cr, Mn, Ni, and P segregation along with precipitation of Nb-rich inclusions clusters on the grain boundaries. Several crack deflections at high-angle grain boundaries were observed where the neighbouring sub-structure has different Bain axes.

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The initiation of corrosion can be triggered by defects in the adsorbed layer of organic inhibitors. A detailed knowledge of the intermolecular forces between the inhibitor molecules and the interfacial bonding will be decisive to unravel the mechanisms driving the corrosion initiation. In this work, adsorbed organic layers of 2-mercapto-5-methoxybenzimidazole (SH-BimH-5OMe) and 5-amino-2-mercaptobenzimidazole (SH-BimH-5NH2) were compared regarding their performance mitigating copper corrosion. Atomic force microscopy was used to address the stability and intermolecular forces of the self-assembled monolayers, using imaging and force measurement modes. For a film formed by amino-derivative molecules, a gold-coated tip frequently picked up individual molecules (molecular fishing) in force-distance measurements. For layers of the methoxy-derivative, no fishing events were observed, pointing to a constant functional layer. X-ray photoelectron spectroscopy revealed that SH-BimH-5OMe molecules form a stronger bond with the surface and more stable SAM layers on Cu surfaces as compared to SH-BimH-5NH2 molecules. Results of computational density functional theory modeling and electrochemical corrosion tests are in line with the microscopy and spectroscopy results. In particular, with aid of computational modeling the less ordered structure of the SH-BimH-5NH2 monolayer is attributed to dual bonding ability of SH-BimH-5NH2 that can adsorb with either S or NH2 groups.

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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.

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The effect of the presence of an anodic film and hybrid sol-gel coating loaded with corrosion inhibitors was evaluated as a strategy for enhanced barrier and active corrosion protection of aluminium alloy 2024-T3. In this study, AA2024-T3 specimens were anodized in a modified sulphuric-citric acid bath (SCA) as the first layer of a corrosion protective multilayer system and subsequently protected by the application of silica-based hybrid sol-gel coatings. These coatings were doped with LiNO₃ and Ce(NO₃)₃ as corrosion inhibitors and studied in comparison with the inhibitor-free sol-gel coating in terms of morphology, composition and corrosion protection of intact and scribed specimens. The anodized AA2024-T3 with an overlaying inhibitor-free sol-gel coating showed the highest impedance modulus during long-term immersion in 0.1 mol·L⁻¹ NaCl aqueous solution. Active corrosion protection of scribed coated specimens was studied by exposure to a 0.5 mol·L⁻¹ NaCl solution and evaluated by surface analytical techniques. The addition of Li- and Ce-based salts into the hybrid sol-gel formulation showed active corrosion protection compared to the inhibitor-free scribed hybrid sol-gel coating. The Ce-doped sol-gel coating showed less visual corrosion and higher active corrosion protection than the Li-containing one during the long-term immersion test in 0.5 mol·L⁻¹ NaCl. Present findings reveal that the combination of the anodic/hybrid sol-gel layers on AA2024-T3 enhances the corrosion protective properties barrier properties of both stand-alone systems and the incorporation of Li- and Ce-based inhibitors provide active corrosion.

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In this paper, we investigate the long-term adhesion strength and barrier property of our recently proposed encapsulation stack that includes PDMS-Parylene C and PECVD interlayers (SiO2 and SiC) for adhesion improvement. To evaluate the adhesion strength of our proposed stack, the sample preparation consisted in depositing approximately 25 nm of SiC and 25 nm of SiO2 on half wafers, previously coated with Parylene C. Next, $50 \mu \mathrm{m}$ PDMS was spin-coated on top. Finally, the samples were detached from the Si wafer and soaked in a PBS solution at 67°C to accelerate the aging process. Two samples were also implanted, subcutaneously, on the left and right subscapular regions of a rat. The optical inspection and peel tests performed after two months confirmed our preliminary findings and showed a significant improvement of the adhesion in our proposed encapsulation stack compared to the case of PDMS on Parylene C alone. In addition, the X-ray photoelectron spectroscopy(XPS) analysis at the interface between SiC and Parylene C showed different peaks for the interface compared to the reference spectra, which could be an indication of a chemical bond. Finally, water vapor transmission rate (WVTR) tests were performed to investigate the barrier property of our proposed encapsulation stack against water vapor transmission. The results demonstrated that the proposed stack acts as a significantly (two orders of magnitude) higher barrier against moisture compared to only Parylene C and PDMS encapsulation layers. The proposed method yields a fully transparent encapsulation stack over a broad wavelength spectrum that can be used for the conformal encapsulation of flexible devices and thus, making them compatible with techniques such as optical imaging and optogenetics.@en

The use of biomass pellets as a source of renewable energy has increased in recent times. However, pellet storage during transportation can compromise their properties, due to fluctuating temperature and humid environments. Here, we show that extended storage of one month at 40 °C and 85% relative humidity causes significant biomass pellet degradation. This was evidenced by higher pellet porosity, weight gain, increased inclusion body formation and creation of an internal network of cracks. We quantify the inclusion and pore growth processes at the surface and within the pellets, which has implications for subsequent thermochemical conversion. The global bioenergy transition may depend upon biomass pellets, and this study shows that storage conditions are critical in the supply chain, so to maintain their quality. Without the development of stronger policies to avoid premature degradation of biomass pellets, they may not realize their full potential as a bioenergy source.

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Formation of hemispherical pom-pom-like clusters of nanowires during potentiostatic oxidation of copper in NH₄HCO₃ is reported. High-purity copper was oxidized in a three-electrode setup at constant electrode potential ranging from 200 mV to 1000 mV vs. Ag|AgCl|sat. KCl for 14 h. The obtained clusters of nanwires were examined using FE-SEM, XRD and XPS techniques. The diameter of nanowires, composed mainly of CuO, Cu₂O, Cu(OH)₂, and Cu₄O₃, was ca. 50–70 nm. The diameter of the clusters strongly depends both on the applied potential and the time of electrooxidation, and was found to be in the range of 1–3 μm. The mechanism for the formation of such nanowires clusters is proposed.

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Biomass pellets provide a pivotal opportunity in promising energy transition scenarios as a renewable source of energy. A large share of the current utilization of pellets is facilitated by intensive global trade operations. Considering the long distance between the production site and the end-user locations, pellets may face fluctuating storage conditions, resulting in their physical and chemical degradation. We tested the effect of different storage conditions, from freezing temperatures (−19 °C) to high temperature (40 °C) and humidity conditions (85% relative humidity), on the physicochemical properties of untreated and torrefied biomass pellets. Moreover, the effect of sudden changes in the storage conditions on pellet properties was studied by moving the pellets from the freezing to the high temperature and relative humidity conditions and vice versa. The results show that, although storage at one controlled temperature and RH may degrade the pellets, a change in the temperature and relative humidity results in higher degradation in terms of higher moisture uptake and lower mechanical strength. @en

Molybdenum oxide (MoO_x) is attractive for applications as hole-selective contact in silicon heterojunction solar cells for its transparency and relatively high work function. However, the integration of MoO_x stacked on intrinsic amorphous silicon (i)a-Si:H layer usually exhibits some issues that are still not fully solved resulting in degradation of electrical properties. Here, we propose a novel approach to enhance the electrical properties of (i)a-Si:H/MoO_x contact. We manipulate the (i)a-Si:H interface via plasma treatment (PT) before MoO_x deposition minimizing the electrical degradation without harming the optical response. Furthermore, by applying the optimized PT, we can reduce the MoO_x thickness down to 3.5 nm with both open-circuit voltage and fill factor improvements. Our findings suggest that the PT mitigates the decrease of the effective work function of the MoO_x (WF_MoOx) thin layer when deposited on (i)a-Si:H. To support our hypothesis, we carry out electrical simulations inserting a dipole at the (i)a-Si:H/MoO_x interface accounting the attenuation of WF_MoOx caused by both MoO_x thickness and dipole. Our calculations confirm the experimental trends and thus provide deep insight in critical transport issues. Temperature-dependent J-V measurements demonstrate that the use of PT improves the energy alignment for an efficient hole transport.

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