Assessment of bismuth oxide-based electrolytes for composite gas separation membranes

Oxide + salt composites can be used in CO2 and NOx separation membranes, where high oxide-ion conductivity is crucial to improve performance. Pursuing this goal, the stability of three different bismuth oxide-based electrolytes (Cu + V, Y and Yb-doped) against molten alkali carbonates (Li, Na, K) or nitrates (Na, K) was tested firing them in the 450–550 °C temperature range, and with endurance tests up to 100 h. A well-known ceria-based composite was used as reference (CGO - Ce0.9Gd0.1O1.95). Oxides and composites were studied by X-ray diffraction, scanning electron microscopy and impedance spectroscopy (in air, 140–650 °C temperature range). Bi2Cu0.10V0.90O5.35 easily reacts with molten salts. Bi0.75Y0.25O1.5 and Bi0.75Yb0.25O1.5 have higher stability against molten carbonates and complete stability against molten nitrates. The Y-doped oxide stability against the molten carbonates was enhanced changing the molten salt composition (Y2O3 additions) and using lower firing temperatures. Above all, composites based on Y or Yb-doped Bi2O3 with molten alkali nitrates showed impressive 6× or 3× higher electrical conductivity at 290 °C, in air (4.88 × 10−2 and 2.41 × 10−2 S cm−1, respectively) than CGO-based composites (7.72 × 10−3 S cm−1), qualifying as promising materials for NOx separation membranes.publishe

A critical look at interpretation of electrochemical impedance spectra of sol-gel coated aluminium

A proper assignment of time constants is important for the correct interpretation of the electrochemical impedance spectra of coated substrates. In this work, several model aluminium samples with different anodic oxide thicknesses were prepared and characterised. The aluminium samples were coated by a hybrid sol-gel formulation and studied by electrochemical impedance spectroscopy (EIS) during immersion in NaCl solution. A hierarchical model containing three R-C elements adequately described the impedance spectra of the coated samples. The R-C elements described the properties of sol-gel coatings, aluminium oxide layers and corrosion process. The contribution of the aluminium oxide layer to impedance was unambiguously proven to be at middle frequencies on the spectra. Furthermore, the “real” capacitances of oxide layers were obtained from two capacitance–CPE equations and their applicability was scrutinized. The obtained results presented an opportunity to determine the adhesion behaviour of the sol-gel coatings to the oxide layers, which was studied by analysing the ratio of the oxide layer capacitance of the sol-gel coated samples to the capacitance of the uncoated ones. It was demonstrated that the exposed surface area of the oxide to the electrolyte was about 60–68% and was not changing during immersion. Based on these findings, a degradation model of the sol-gel coating on anodised aluminium was proposed.publishe

Layered double hydroxide based active corrosion protective sealing of plasma electrolytic oxidation/sol-gel composite coating on AA2024

This work reports a novel approach for growing layered double hydroxide (LDH) films on any plasma electrolytic oxidation (PEO) coated AA2024 independently of the nature of the PEO coating. The specific PEO coating chosen to carry out this work is considered to be not suitable for direct LDH growth because of phase composition and morphological features. In this paper, we describe a new methodology that consists of covering the PEO coating with a thin layer of aluminum oxide based xerogel as the source of aluminate ions for subsequent in-situ LDH growth. X-ray diffraction (XRD) and scanning electron microscope (SEM) images showed a successful formation of LDHs on the surface. An improvement in terms of active corrosion protection was also demonstrated by electrochemical impedance spectroscopy (EIS) and scanning vibrating electrode technique (SVET).publishe

PEO Coatings with Active Protection Based on In-Situ Formed LDH-Nanocontainers

In the present work, for the first time Zn-Al layered double hydroxide (LDH) nanocontainers were grown in-situ on the surface and in the pores of plasma electrolytic oxidation (PEO) layer and then loaded with a corrosion inhibitor to provide an active protection. The developed LDH-based conversion process ensures partial sealing of the pores and provides an effective corrosion inhibition on demand leading to increased fault-tolerance and self-healing properties. The structure, morphology and composition of the LDH-sealed PEO coatings on 2024 aluminum alloy were investigated using SEM, TEM/FIB, XRD and GDOES. Electrochemical impedance spectroscopy and scanning vibrating electrode techniques show a remarkable increase in the corrosion resistance and fault tolerance when PEO coating is sealed with a LDH-inhibitor treatment

Gold nanorods induce early embryonic developmental delay and lethality in zebrafish (Danio rerio)

Due to their unique electronic and optical features, gold nanoparticles (AuNP) have received a great deal of attention for application in different fields such as catalysis, electronics, and biomedicine. The large-volume manufacturing predicted for future decades and the inevitable release of these substances into the environment necessitated an assessment of potential adverse human and ecological risks due to exposure to AuNP. Accordingly, this study aimed to examine the acute and developmental toxicity attributed to a commercial suspension of Au nanorods stabilized with cetyltrimethylammonium bromide (CTAB-AuNR) using early embryonic stages of zebrafish (Danio rerio), a well-established model in ecotoxicology. Zebrafish embryos were exposed to CTAB-AuNR (0–150 µg/L) to determine for developmental assessment until 96 hr post fertilization (hpf) and lethality. Uptake of CTAB-AuNR by embryos and nanoparticles potential to induce DNA damage was also measured at 48 and 96 hpf. Analysis of the concentration-response curves with cumulative mortality at 96 hpf revealed a median lethal concentration (LC50,96h) of 110.2 μg/L. At sublethal concentrations, CTAB-AuNR suspensions were found to produce developmental abnormalities such as tail deformities, pericardial edema, decreased body length, and delayed eye, head, and tail elongation development. Further, less than 1% of the initial concentration of CTAB-AuNR present in the exposure media was internalized by zebrafish embryos prior to (48 hpf) and after hatching (96 hpf). In addition, no marked DNA damage was detected in embryos after exposure to CTAB-AuNR. Overall, CTAB-AuNR suspensions produced lethal and sublethal effects on zebrafish embryos with possible repercussions in fitness of adult stages. However, these results foresee a low risk for fish since the observed effects occurred at concentrations above the levels expected to find in the aquatic environment.This work was supported by FEDER funds through the program COMPETE—Programa Operacional Factores de Competitividade,” and by the Portuguese Foundation for Science and Technology (FCT), within the CESAM’s strategic program (UID/AMB/50017/2013), the research project Synchrony (PTDC/AAG-MAA/2140/2012). This research was also partially supported by FCT and the European Regional Development Fund (ERDF), in the framework of the program PT2020 and of ERA-NET SIINN through project NanoToxClass (ERA-SIINN/0001/2013). The materials characterization performed was also 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, and also the project MAGICOAT (PTDC/CTM-BIO/2170/2014). JT thanks FCT for the research grant IF/00347/2013

Metastable perovskite Bi1-xLaxFe0.5Sc0.5O3 phases in the range of the compositional crossover

Perovskite ceramics of the Bi1- xLaxFe0.5Sc0.5O3 composition (0.30 ≤ x ≤ 0.35) that cannot be sintered in bulk form as a single phase using the conventional ceramic route were successfully prepared using the high-pressure/high-temperature technique. It has been shown that the room-temperature compositional crossover from the antipolar phase whose incommensurate modulation of displacements of Bi/La and oxygen is described by the Imma(00γ)s00 superspace group to the non-polar Pnma phase occurs in the narrow range between x = 0.33 and x = 0.34 with no phase coexistence. The features of this compositional crossover are discussed in comparison with that observed in the Bi1- xLaxFeO3 system.publishe

Photocatalytic deposition of hydroxyapatite onto titanium dioxide nanotubular layer with fine tuning of layer nanoarchitecture

A new effective method of photocatalytic deposition of hydroxyapatite (HA) onto semiconductor substrates is proposed. Highly ordered nanotubular TiO2 (TNT) layer formed on titanium via its anodization is chosen as the photoactive substrate. The method is based on photodecomposition of phosphate anion precursor, triethyl phosphate (TEP), on the semiconductor surface with following reaction of formed phosphate anions with calcium cations presented in the solution. HA can be deposited only on irradiated areas, providing the possibility of photoresist free HA patterning. It is shown that HA deposition can be controlled via pH, light intensity and duration of the process. Energy-dispersive X-ray spectroscope profile analysis and glow discharge optical emission spectroscopy of HA modified TNT proves that HA deposits over the entire TNT depth. High biocompatibility of the surfaces is proven by protein adsorption and pre-osteoblast cell growth

Use of synergistic mixture of chelating agents for in situ LDH growth on the surface of PEO-treated AZ91

The principal possibility to grow layered double hydroxide (LDH) at ambient pressure on plasma electrolytic oxidation (PEO) treated magnesium alloy AZ91 in the presence of chelating agents is demonstrated for the first time. It avoids hydrothermal autoclave conditions, which strongly limit wide industrial application of such coating systems, and the presence of carbonate ions in the electrolyte, which lead to the formation of “passive” non-functionalizable LDH. A combination of chelating agents (sodium diethylenetriamine-pentaacetate (DTPA) and salicylate) were introduced to the treatment solution. The role of each additive and the influence of treatment bath composition on the LDH formation processes are discussed. A synergistic effect of DTPA and salicylate during LDH formation is discovered and its possible explanation is proposed

Plasma electrolytic oxidation of PSA pre-anodized AA2024 alloy

Метод плазменного электролитического окисления (ПЭО) позволяет формировать износостойкие и коррозионно-стойкие покрытия с хорошей адгезией к поверхности сплава. Однако существует необходимость в обработке ПЭО не только на поверхности чистого сплава, но и с предварительно нанесенными анодными слоями. Это исследование объединяет различные условия ПЭО-обработки алюминиевого сплава АА2024 с предварительно сформированным анодированным слоем фосфорно-серной кислоты (ПСА)

Electrochemical deposition of zinc from deep eutectic solvent on barrier alumina layers

The direct use of high-ordered porous templates of anodic aluminium oxide for formation of nanostructures via electrochemical deposition is difficult because the presence of the of barrier alumina layer in the bottom of pores. In this paper, zinc electrodeposition from a solution of ZnCl2 in a choline chloride/ethylene glycol eutectic mixture on dense alumina layers of different thicknesses was studied. In a potentiostatic regime, the deposition on a barrier layer was found to be hardly possible even when the layer is a native alumina film (about 2 nm thick). Choline and ethylene glycol form an adsorbed stable layer at the alumina/electrolyte interface and thereby block the access of zinc chloride anions to the electrode. It has been shown that zinc can be directly deposited on a barrier layer by means of application of a combined potential mode in which an AC component of 50 mV superimposed on the DC potential of -1.6 V. Increasing the temperature of the eutectic solution allows zinc electrodeposition in a potentiostatic regime already at 50 degrees C. By application of any of these conditions, zinc can be deposited on a barrier alumina layer up to about 60 nm thick. The range of frequencies of the AC component and the temperature range where the deposition is optimal were considered. The mechanism of unblocking of the electrode by the alternating potential and by the temperature rise has been suggested. (C) 2015 Elsevier Ltd. All rights reserved