Layered double hydroxides for corrosion-related applications: main developments from 20 years of research at CICECO

This work describes the main advances carried out in the field of corrosion protection using layered double hydroxides (LDH), both as additive/pigmentbased systems in organic coatings and as conversion films/pre-treatments. In the context of the research topic “Celebrating 20 years of CICECO”, the main works reported herein are based on SECOP’s group (CICECO) main advances over the years. More specifically, this review describes structure and properties of LDH, delving into the corrosion field with description of pioneering works, use of LDH as additives to organic coatings, conversion layers, application in reinforced concrete and corrosion detection, and environmental impact of these materials. Moreover, the use of computational tools for the design of LDH materials and understanding of ion-exchange reactions is also presented. The review ends with a critical analysis of the field and future perspectives on the use of LDH for corrosion protection. From the work carried out LDH seem very tenable, versatile, and advantageous for corrosion protection applications, although several obstacles will have to be overcome before their use become commonplace.publishe

Localized holes and delocalized electrons in photoexcited inorganic perovskites: Watching each atomic actor by picosecond X-ray absorption spectroscopy

We report on an element-selective study of the fate of charge carriers in photoexcited inorganic CsPbBr3 and CsPb(ClBr)3 perovskite nanocrystals (NCs) in toluene solutions using time-resolved X-ray absorption spectroscopy with 80 ps time resolution. Probing the Br K-edge, the Pb L3-edge and the Cs L2-edge, we find that holes in the valence band are localized at Br atoms, forming small polarons, while electrons appear as delocalized in the conduction band. No signature of either electronic or structural changes are observed at the Cs L2-edge. The results at the Br and Pb edges suggest the existence of a weakly localized exciton, while the absence of signatures at the Cs edge indicates that the Cs+ cation plays no role in the charge transport, at least beyond 80 ps. These results can explain the rather modest charge carrier mobilities in these materials.Comment: 19 pages, 3 figure

The Influence of PSA Pre-Anodization of AA2024 on PEO Coating Formation: Composition, Microstructure, Corrosion, and Wear Behaviors

In the frame of the current work, it was shown that plasma electrolytic oxidation (PEO) treatment can be applied on top of phosphoric sulfuric acid (PSA) anodized aluminum alloy AA2024. Being hard and well-adherent to the substrate, PEO layers improve both corrosion and wear resistance of the material. To facilitate PEO formation and achieve a dense layer, the systematic analysis of PEO layer formation on the preliminary PSA anodized layer was performed in this work. The microstructure, morphology, and composition of formed PEO coatings were investigated using scanning electron microscopy (SEM), x-ray diffraction (XRD), and glow-discharge optical emission spectroscopy (GDOES). It was shown that under constant current treatment conditions, the PSA layer survived under the applied voltage of 350 V, whilst 400 V was an intermediate stage; and under 450 V, the PSA layer was fully converted after 5 min of the treatment. The comparison test with PEO formation on the bare material was performed. It was confirmed that during the "sparking" mode (400 V) of PEO formation, the PEO coatings, formed on PSA treated AA2024, were more wear resistant than the same PEO coatings on bare AA2024

The Stability and Chloride Entrapping Capacity of ZnAl-NO2 LDH in High-Alkaline/Cementitious Environment

In this work, the ZnAl-NO2 LDH (layered double hydroxide) is investigated as a possible additive for mitigating the chloride-induced corrosion of steel in reinforced concrete. The investigation focused on the stability and chloride binding capacity of this LDH in the pH range typical of cementitious materials. Until pH = 12.5 the material was stable and effective in capturing chloride ions from the surrounding aqueous environment. For higher pH, precisely that of hydrated cement, the LDH was partially dissolved and OH− preferentially entrapped instead of Cl−. These results suggested that ZnAl-NO2 has excellent chloride entrapping capability at neutral pH, but this is reduced with increasing pH. However, when the LDH was incorporated into mortars, the chloride ingress was delayed, signifying that the dissolution of LDH leads to a secondary mechanism responsible for chloride capture

Conduction electron spin resonance in AlB2

ABSTRACT: This work reports on electron spin resonance experiments in oriented single crystals of the hexagonal AlB2 diboride compound (P6/mmm, D16h structure) which display conduction electron spin resonance. The X-band electron spin resonance spectra showed a metallic Dysonian resonance with g-value and intensity independent of temperature. The thermal broadening of the anisotropic electron spin resonance linewidth 1H tracks the T-dependence of the electrical resistivity below T ' 100 K. These results confirm the observation of a conduction electron spin resonance in AlB2 and are discussed in comparison with other boride compounds. Based on our main findings for AlB2 and the calculated electronic structure of similar layered honeycomb-like structures, we conclude that any array of covalent B–B layers potentially results in a conduction electron spin resonance signal. This observation may shed new light on the nature of the non-trivial conduction electron spin resonance-like signals of complex f-electron systems such as β-YbAlB4. Keywords: AlB2, Conduction electron, Dysonian resonance, Spin resonance

Launching of jets and the vertical structure of accretion disks

The launching of magnetohydrodynamic outflows from accretion disks is considered. We formulate a model for the local vertical structure of a thin disk threaded by a poloidal magnetic field of dipolar symmetry. The model consists of an optically thick disk matched to an isothermal atmosphere. The disk is supposed to be turbulent and possesses an effective viscosity and an effective magnetic diffusivity. In the atmosphere, if the magnetic field lines are inclined sufficiently to the vertical, a magnetocentrifugal outflow is driven and passes through a slow magnetosonic point close to the surface. We determine how the rate of mass loss varies with the strength and inclination of the magnetic field. In particular, we find that for disks in which the mean poloidal field is sufficiently strong to stabilize the disk against the magnetorotational instability, the mass loss rate decreases extremely rapidly with increasing field strength, and is maximal at an inclination angle of 40-50 degrees. For turbulent disks with weaker mean fields, the mass loss rate increases monotonically with increasing strength and inclination of the field, but the solution branch terminates before achieving excessive mass loss rates. Our results suggest that efficient jet launching occurs for a limited range of field strengths, and a limited range of inclination angles in excess of 30 degrees. In addition, we determine the direction and rate of radial migration of the poloidal magnetic flux, and discuss whether configurations suitable for jet launching can be maintained against dissipation.Comment: 20 pages, 10 figures, revised version, to be published in the Astrophysical Journa

A strategy for the rapid identification of fungal metabolites and the discovery of the antiviral activity of pyrenocine a and harzianopyridon

The isolation and identification of bioactive metabolites from complex extracts obtained from microbial growth media is a time consuming, costly, and labor-intensive task. A strategy to rapidly identify secondary metabolites isolated from extracts obtained from the culture media of marine-derived and endophytic fungal strains is described. Identification was achieved by HPLC-UV-MS and 1H NMR analyses in combination with data obtained from the Dictionary of Natural Products. Among the compounds identified, (-)-naphthoquinoneimine, citreorosein, emodin, pyrenocine A and harzianopyridone displayed moderate to potent antiviral activity. (-)-Naphthoquinoneimine was isolated as the enantiomer of its previously reported dextrorotatory congener, while 6,7-dihydroxy-2,2-dimethyl-4-chromanone is herein reported for the first time as a natural product396720731CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPBEX 4498-14-32010/50190-2; 2013/50228-8; 2011/08064-2; 2008/00331-9; 2013/23153-

Interrelationship between TP53 gene deletion, protein expression and chromosome 17 aneusomy in gastric adenocarcinoma

Background: This study evaluates the existence of numerical alterations of chromosome 17 and TP53 gene deletion in gastric adenocarcinoma. the p53 protein expression was also evaluated, as well as, possible associations with clinicopathological characteristics.Methods: Dual-color fluorescence in situ hybridization and immunostaining were performed in twenty gastric cancer samples of individuals from Northern Brazil.Results: Deletion of TP53 was found in all samples. TP53 was inactivated mainly by single allelic deletion, varying to 7-39% of cells/case. Aneusomy of chromosome 17 was observed in 85% of cases. Chromosome 17 monosomy and gain were both observed in about half of cases. Cells with gain of chromosome 17 frequently presented TP53 deletion. the frequency of cells with two chr17 and one TP53 signals observed was higher in diffuse than in intestinal-type GC. Immunoreactivity of p53 was found only in intestinal-type samples. the frequency of cells with two chr17 and two TP53 signals found was higher in samples with positive p53 expression than in negative cases in intestinal-type GC.Conclusion: We suggest that TP53 deletion and chromosome 17 aneusomy is a common event in GC and other TP53 alterations, as mutation, may be implicated in the distinct carcinogenesis process of diffuse and intestinal types.Financiadora de Estudos e Projetos (FINEP CT-INFRA/FADESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fed Univ Para, Inst Biol Sci, Humans Cytogenet Lab, BR-66075900 Belem, Para, BrazilUniv Fed Piaui, Dept Biol, Campus Minist Reis Velloso Parnaiba, Teresina, PI, BrazilUniversidade Federal de São Paulo, Dept Morphol, Div Genet, São Paulo, BrazilUniv Fed Ceara, Sch Med, Dept Pathol, Mol Genet Lab, Fortaleza, Ceara, BrazilFed Univ Para, Joao de Barros Barreto Univ Hosp, BR-66075900 Belem, Para, BrazilUniversidade Federal de São Paulo, Dept Morphol, Div Genet, São Paulo, BrazilFinanciadora de Estudos e Projetos (FINEP CT-INFRA/FADESP): 0927-03. RRBWeb of Scienc