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.

PEO coatings design for Mg-Ca alloy for cardiovascular stent and bone regeneration applications.

Four bioactive PEO (plasma electrolytic oxidation) coatings were generated on Mg0.8Ca alloy using a Ca/P-based electrolyte and adding Si or Fas necessary. Surface characteristics, chemical composition and ion liberation of the coatings were characterized using SEM/EDS (Scanning Electron Microscopy/Energy Dispersive X-ray spectroscopy), X-ray diffraction, optical profilometry and ICP-OES (inductively coupled plasma optical emission spectrometry). Direct biocompatibility studies were performed by seeding premyoblastic, endothelial and preosteoblastic cell lines over the coatings. Biocompatibility of the coatings was also evaluated with respect to murine endothelial, preosteoblastic, preosteoclastic and premyoblastic cell cultures using extracts obtained by the immersion degradation of the PEO-coated specimens. The coatings reduced the degradation of magnesium alloy and released Mg Ca, P, Si and F. Of all the studied compositions, the Si-containing PEO coating exhibited the optimal characteristics for use in all potential applications, including bone regeneration and cardiovascular applications. Coatings with high F content negatively influenced the endothelial cells. RAW 264.7, MC3T3 and co-culture differentiation studies using extracts of PEO coated Mg0.8Ca demonstrated improved osteoclastogenesis and osteoblastogenesis processes compared to bare alloy.

Chelating agent-assisted in situ LDH growth on the surface of magnesium alloy.

In situ formation of layered double hydroxides (LDH) on metallic surfaces has recently been considered a promising approach for protective conversion surface treatments for Al and Mg alloys. In the case of Mg-based substrates, the formation of LDH on the metal surface is normally performed in autoclave at high temperature (between 130 and 170 °C) and elevated pressure conditions. This hampers the industrial application of MgAl LDH to magnesium substrates. In this paper, the growth of MgAl LDH conversion coating directly on magnesium alloy AZ91 at ambient conditions (25 °C) or elevated temperatures is reported in carbonate free electrolyte for the first time. The direct LDH synthesis on Mg alloys is enabled by the presence of organic chelating agents (NTA and EDTA), which control the amount of free and/or hydroxyl bound Mg2+ and Al3+ in the solution. The application of the chelating agents help overcoming the typical technological limitations of direct LDH synthesis on Mg alloys. The selection of chelators and the optimization of the LDH treatment process are supported by the analysis of the thermodynamic chemical equilibria.

Antimicrobial activity of 2-mercaptobenzothiazole released from environmentally friendly nanostructured layered double hydroxides.

AIMS: The objective of this work was to assess the antibacterial effect of 2-mercaptobenzothiazole (MBT), used as model-biocide, immobilized in a layered double hydroxide (LDH) structure, under different conditions of pH and salinity, envisaging possible applications of the system in active antifouling and anticorrosion coatings. METHODS AND RESULTS: Biological effects of MBT immobilized in LDH were assessed by monitoring bacterial bioluminescence of cell suspensions of either Allivibrio fischeri or a recombinant strain of Escherichia coli, as a proxy for bacterial activity. Salinity (1, 2 and 3% NaCl) and pH (4, 5, 6 and 7) of the suspension media were experimentally manipulated and biocide release tests were performed in parallel. The release profiles obtained by UV-visible spectrophotometry indicated a fast release of biocide from MBT@LDH, slightly enhanced in 3% NaCl and under alkaline conditions. However, biological effects were more pronounced at 1% NaCl and at neutral pH. CONCLUSIONS: The release and toxic effect of MBT immobilized in LDH is dependent on the concentration of solutes in the suspension medium. SIGNIFICANCE AND IMPACT OF THE STUDY: The results confirm LDH as a biologically compatible material with potential to be used for biocide delivery.

Corrosion inhibition of copper in aqueous chloride solution by 1H-1,2,3-triazole and 1,2,4-triazole and their combinations: electrochemical, Raman and theoretical studies.

Triazoles are well-known organic corrosion inhibitors of copper. 1H-1,2,3-Triazole and 1,2,4-triazole, two very simple molecules with the only difference being the positions of the nitrogen atoms in the triazole ring, were studied in this work as corrosion inhibitors of copper in 50 mM NaCl solution using a set of electrochemical and analytical techniques. The results of electrochemical tests indicate that 1H-1,2,3-triazole exhibited superior inhibitor properties but could not suppress anodic copper dissolution at moderate anodic potentials (>+300 mV SCE), while 1,2,4-triazole, although it exhibited higher anodic currents, suppressed anodic copper dissolution at very anodic potentials. Density functional theory calculations were also performed to interpret the measured data and trends observed in the electrochemical studies. The computational studies considered either the inhibitors isolated in the gaseous phase or adsorbed onto Cu(111) surface models. From the calculations, the mechanisms of the inhibitive effects of both triazoles were established and plausible mechanisms of formation of the protective films on the Cu surface were proposed. The results of this study hold positive implications for research in the areas of catalysis, and copper content control in water purification systems.

Novel electrochemical method of fast and reproducible fabrication of metallic nanoelectrodes.

A novel electrochemical wire etching method of fabrication of ultrasharp nanoelectrodes is reported. Tungsten wires can be sharpened to less than 10 nm tip radius in a reproducible manner in less than 1 min by using controllable hydrodynamic electrolyte flow combined with optimized electrochemical etching parameters. The method relies on the variations of the electric field at the surface of a metal wire, while the electrolyte solution is in motion, rather than on the ionic gradient generated in a static solution.

Melting temperature of metal polycrystalline nanowires electrochemically deposited into the pores of anodic aluminum oxide.

The arrays of metallic nanowires are considered as promising precursors for 1D semiconductor nanostructures after appropriate treatment at temperatures close to the melting point. Therefore the melting behaviour of the metallic structures in oxide templates is a key parameter for the subsequent conversion process. The present paper focuses on understanding of the effect of mechanical stress generated during heating on the melting point of the metal nanowires deposited into the pores of anodic alumina. Extremely high local compressive stress appears due to the difference in the thermal coefficients of the oxide template and nanowires inside the pores. The effect of the composite structural parameter that may be related to the concentration of nanowires on the melting temperature has been investigated. A numerical model predicting the melting point has been developed for composites with indium, tin, and zinc nanowires. The simulation results obtained using the suggested model were compared with the experimental data.

Nanocontainer-based corrosion sensing coating.

The present paper reports on the development of new sensing active coating on the basis of nanocontainers containing pH-indicating agent. The coating is able to detect active corrosion processes on different metallic substrates. The corrosion detection functionality based on the local colour change in active cathodic zones results from the interaction of hydroxide ions with phenolphthalein encapsulated in mesoporous nanocontainers which function as sensing nanoreactors. The mesoporous silica nanocontainers are synthesized and loaded with pH indicator phenolphthalein in a one-stage process. The resulting system is mesoporous, which together with bulkiness of the indicator molecules limits their leaching. At the same time, penetration of water molecules and ions inside the container is still possible, allowing encapsulated phenolphthalein to be sensitive to the pH in the surrounding environment and outperforming systems when an indicator is directly dispersed in the coating layer.The performed tests demonstrate the pH sensitivity of the developed nanocontainers being dispersed in aqueous solutions. The corrosion sensing functionality of the protective coatings with nanocontainers are proven for aluminium- and magnesium-based metallic substrates. As a result, the developed nanocontainers show high potential to be used in a new generation of active protective coatings with corrosion-sensing coatings.

A copper-deficient tetragonal phase derived from chalcopyrite CuGaS2.

Direct synthesis of CuGaS(2) from elemental ingredients in a two-zone furnace resulted in a macroseparation of Cu-rich and Ga-rich regions over the crystallization volume. In the Cu-rich parts of the ingot, a near-stoichiometric CuGaS(2) chalcopyrite phase (I42d) and copper sulfides were found. In the Ga-rich part, along with a chalcopyrite phase with some Cu deficiency, a new tetragonal phase I4m2 with composition close to Cu(5)Ga(9)S(16) and the crystal lattice parameters a = 3.7777(2) Å, c = 5.2483(4) Å was revealed. It was concluded that this Cu-deficient chalcopyrite-like phase is not an ordered defect compound (ODC). As opposed to the systems Cu-Ga-Se and Cu-Ga-Te, in a system based on sulfur, the ODC phenomenon is unlikely to occur.

Hydroxyapatite microparticles as feedback-active reservoirs of corrosion inhibitors.

This work contributes to the development of new feedback-active anticorrosion systems. Inhibitor-doped hydroxyapatite microparticles (HAP) are used as reservoirs, storing corrosion inhibitor to be released on demand. Release of the entrapped inhibitor is triggered by redox reactions associated with the corrosion process. HAP were used as reservoirs for several inhibiting species: cerium(III), lanthanum(III), salicylaldoxime, and 8-hydroxyquinoline. These species are effective corrosion inhibitors for a 2024 aluminum alloy (AA2024), used here as a model metallic substrate. Dissolution of the microparticles and release of the inhibitor are triggered by local acidification resulting from the anodic half-reaction during corrosion of AA2024. Calculated values and experimentally measured local acidification over the aluminum anode (down to pH = 3.65) are presented. The anticorrosion properties of inhibitor-doped HAP were assessed using electrochemical impedance spectroscopy. The microparticles impregnated with the corrosion inhibitors were introduced into a hybrid silica-zirconia sol-gel film, acting as a thin protective coating for AA2024, an alloy used for aeronautical applications. The protective properties of the sol-gel films were improved by the addition of HAP, proving their applicability as submicrometer-sized reservoirs of corrosion inhibitors for active anticorrosion coatings.

Enhancement of active corrosion protection via combination of inhibitor-loaded nanocontainers.

The present work reports the synthesis of layered double hydroxides (LDHs) nanocontainers loaded with different corrosion inhibitors (vanadate, phosphate, and 2-mercaptobenzothiazolate) and the characterization of the resulting pigments by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The anticorrosion activity of these nanocontainers with respect to aluminum alloy AA2024 was investigated by electrochemical impedance spectroscopy (EIS). The bare metallic substrates were immersed in dispersions of nanocontainers in sodium chloride solution and tested to understand the inhibition mechanisms and efficiency. The nanocontainers were also incorporated into commercial coatings used for aeronautical applications to study the active corrosion protection properties in systems of industrial relevance. The results show that an enhancement of the active protection effect can be reached when nanocontainers loaded with different inhibitors are combined in the same protective coating system.

Novel inorganic host layered double hydroxides intercalated with guest organic inhibitors for anticorrosion applications.

Zn-Al and Mg-Al layered double hydroxides (LDHs) loaded with quinaldate and 2-mercaptobenzothiazolate anions were synthesized via anion-exchange reaction. The resulting compounds were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy/energy-dispersive X-ray spectroscopy. Spectrophotometric measurements demonstrated that the release of organic anions from these LDHs into the bulk solution is triggered by the presence of chloride anions, evidencing the anion-exchange nature of this process. The anticorrosion capabilities of LDHs loaded with organic inhibitors toward the AA2024 aluminum alloy were analyzed by electrochemical impedance spectroscopy. A significant reduction of the corrosion rate is observed when the LDH nanopigments are present in the corrosive media. The mechanism by which the inhibiting anions can be released from the LDHs underlines the versatility of these environmentally friendly structures and their potential application as nanocontainers in self-healing coatings.