Steps towards highly-efficient water splitting and oxygen reduction using nanostructured ß-Ni(OH)2.

ß-Ni(OH)2 nanoplatelets are prepared by a hydrothermal procedure and characterized by scanning and transmission electron microscopy, X-ray diffraction analysis, Raman spectroscopy, and X-ray photoelectron spectroscopy. The material is demonstrated to be an efficient electrocatalyst for oxygen reduction, oxygen evolution, and hydrogen evolution reactions in alkaline media. ß-Ni(OH)2 shows an overpotential of 498 mV to reach 10 mA cm-2 towards oxygen evolution, with a Tafel slope of 149 mV dec-1 (decreasing to 99 mV dec-1 at 75 °C), along with superior stability as evidenced by chronoamperometric measurements. Similarly, a low overpotential of -333 mV to reach 10 mA cm-2 (decreasing to only -65 mV at 75 °C) toward hydrogen evolution with a Tafel slope of -230 mV dec-1 is observed. Finally, ß-Ni(OH)2 exhibits a noteworthy performance for the ORR, as evidenced by a low Tafel slope of -78 mV dec-1 and a number of exchanged electrons of 4.01 (indicating direct 4e--oxygen reduction), whereas there are only a few previous reports on modest ORR activity of pure Ni(OH)2.

Effectiveness of Epoxy Coating Modified with Yttrium Oxide Loaded with Imidazole on the Corrosion Protection of Steel.

The search for highly effective corrosion protection solutions to avoid degradation of the metallic parts is enabling the development of polymeric organic coatings. Of particular relevance, polymeric nanocomposite coatings, modified with corrosion inhibitors, have been developed to provide enhanced surface protection. In this work, yttrium oxide nanoparticles loaded with corrosion inhibitor (Imidazole), used as additives in the formulation of epoxy for coated on the steel substrate. The loading of Y2O3 with imidazole was confirmed by field emission scanning electron microscopy (FE-SEM) and Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and Brunauer-Emmett-Teller analysis. UV-Vis analysis demonstrated the pH-sensitive behavior of the imidazole that helps in self-release when necessary. Electrochemical impedance spectroscopy (EIS) of the coated samples revealed that the coating modified with Y2O3/IMD provides better corrosion protection compared to coatings containing only Y2O3. XPS analysis validated the presence of an imidazole protective film on the steel substrate that enhanced the corrosion resistance of the coated samples.

Enhancement of mechanical and corrosion resistance properties of electrodeposited Ni-P-TiC composite coatings.

In the present study, the effect of concentration of titanium carbide (TiC) particles on the structural, mechanical, and electrochemical properties of Ni-P composite coatings was investigated. Various amounts of TiC particles (0, 0.5, 1.0, 1.5, and 2.0 g L-1) were co-electrodeposited in the Ni-P matrix under optimized conditions and then characterized by employing various techniques. The structural analysis of prepared coatings indicates uniform, compact, and nodular structured coatings without any noticeable defects. Vickers microhardness and nanoindentation results demonstrate the increase in the hardness with an increasing amount of TiC particles attaining its terminal value (593HV100) at the concentration of 1.5 g L-1. Further increase in the concentration of TiC particles results in a decrease in hardness, which can be ascribed to their accumulation in the Ni-P matrix. The electrochemical results indicate the improvement in corrosion protection efficiency of coatings with an increasing amount of TiC particles reaching to ~ 92% at 2.0 g L-1, which can be ascribed to a reduction in the active area of the Ni-P matrix by the presence of inactive ceramic particles. The favorable structural, mechanical, and corrosion protection characteristics of Ni-P-TiC composite coatings suggest their potential applications in many industrial applications.

Antagonist biocompatibilities of Zn-based materials functionalized with physiological active metal oxides.

Zinc coated with nanostructured ZnO flowers has received increasing attention as a versatile biomaterial for medical applications. Whatsoever, the potential of these materials to meet specific medical requirements must be explored. Despite in its infancy, surface functionalization is the key strategy to achieve this goal. The functionalization, successfully achieved with cooper (Cu), iron (Fe) or manganese (Mn) oxides (Ox), was highly dependent on the presence of the flowered structures, with the deep physicochemical characterization of these new surfaces revealing specific metal oxide distributions. The functionalization with these metal oxides resulted in distinct biological and in vitro behaviours. The biological response, assessed by fibroblast viability, hemocompatibility, and chick chorioallantoic membrane (CAM), further supported by the in vitro degradation studies, evaluated by immersion and electrochemical techniques, revealed that the deleterious role of CuOx functionalization brought potential for anti-cancer applications; with an antagonist behaviour, the functionalization with MnOx, and in a less extent with FeOx, can be used to favour wound healing in traumatic processes. Despite the possible correlation between biocompatibility and hydroxyapatite precipitation, no correlation could be drawn with the corrosion activity of these surfaces. Overall, the minor addition of relevant physiological as Cu, Fe or Mn oxides resulted in antagonist in vitro responses that can be used as expedite strategies to modulate the behaviour of Zn-based materials, contributing in this way for the design of anti-cancer or wound healing therapies.

Microbiologically influenced corrosion mechanism of 304L stainless steel in treated urban wastewater and protective effect of silane-TiO2 coating.

Microbiologically influenced corrosion (MIC) of bare and silane-TiO2 sol-gel coated stainless steel (SS) was studied in treated urban wastewater (TUWW). Combining the electrochemical impedance spectroscopy (EIS) and the scanning vibrating electrode technique (SVET) showed that SS surface colonization occurs, at earlier stages, by iron-oxidizing bacteria (IOB), and later by sulphate-reducing bacteria (SRB). The SVET results showed that chemical corrosion process and bacterial respiration led to the depletion of dissolved oxygen, creating a differential aeration cell and thus a localized corrosion phenomenon. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) showed that the growth of a bacterial biofilm on 304L SS was a dynamic process, stimulating the localized oxidation of SS. To improve corrosion protection, a silane-TiO2 sol-gel coating for SS is proposed. SEM showed that the coating reduced bacterial adhesion and EIS study demonstrated that the coating improved the barrier properties and corrosion resistance of 304L SS in TUWW over a short period of immersion.

Potential anti-cancer and anti-Candida activity of Zn-derived foams.

Zinc (Zn)-derived foams have been prepared from an alkaline electrolyte solution by galvanostatic electrodeposition under different conditions. A detailed physico-chemical characterization was performed by Raman spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM). A pioneer application of these foams in medical implant-related applications was investigated. The in vitro behaviour of these Zn-derived foams in simulated physiological conditions was studied. The results revealed that the presence of zinc oxide was important enough to change the in vitro behaviour of these materials. The potential of these Zn-derived foams in inhibiting bone cancer cell proliferation - osteoscarcoma cells - and important pathogenic fungi responsible for implant-related infections -Candida albicans- was examined. Furthermore, the foams were evaluated for cytocompatibility with normal human osteoblasts. The results obtained allowed us to conclude that Zn-derived foams have an interesting potential for anti-cancer and anti-Candida activity, targeted for bone-related implant applications, suggesting that this novel material may have potential for further clinical studies.

Large-scale synthesis of free-standing N-doped graphene using microwave plasma.

Direct assembling of N-graphene, i.e. nitrogen doped graphene, in a controllable manner was achieved using microwave plasmas at atmospheric pressure conditions. The synthesis is accomplished via a single step using ethanol and ammonia as carbon and nitrogen precursors. Tailoring of the high-energy density plasma environment results in a selective synthesis of N-graphene (~0.4% doping level) in a narrow range of externally controlled operational conditions, i.e. precursor and background gas fluxes, plasma reactor design and microwave power. Applying infrared (IR) and ultraviolet (UV) irradiation to the flow of free-standing sheets in the post-plasma zone carries out changes in the percentage of sp2, the N doping type and the oxygen functionalities. X-ray photoelectron spectroscopy (XPS) revealed the relative extension of the graphene sheets π-system and the type of nitrogen chemical functions present in the lattice structure. Scanning Electron microscopy (SEM), Transmission Electron microscopy (TEM) and Raman spectroscopy were applied to determine morphological and structural characteristics of the sheets. Optical emission and FT-IR spectroscopy were applied for characterization of the high-energy density plasma environment and outlet gas stream. Electrochemical measurements were also performed to elucidate the electrochemical behavior of NG for supercapacitor applications.

Biofunctional composite coating architectures based on polycaprolactone and nanohydroxyapatite for controlled corrosion activity and enhanced biocompatibility of magnesium AZ31 alloy.

In this work a biofunctional composite coating architecture for controlled corrosion activity and enhanced cellular adhesion of AZ31 Mg alloys is proposed. The composite coating consists of a polycaprolactone (PCL) matrix modified with nanohydroxyapatite (HA) applied over a nanometric layer of polyetherimide (PEI). The protective properties of the coating were studied by electrochemical impedance spectroscopy (EIS), a non-disturbing technique, and the coating morphology was investigated by field emission scanning electron microscopy (FE-SEM). The results show that the composite coating protects the AZ31 substrate. The barrier properties of the coating can be optimized by changing the PCL concentration. The presence of nanohydroxyapatite particles influences the coating morphology and decreases the corrosion resistance. The biocompatibility was assessed by studying the response of osteoblastic cells on coated samples through resazurin assay, confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). The results show that the polycaprolactone to hydroxyapatite ratio affects the cell behavior and that the presence of hydroxyapatite induces high osteoblastic differentiation.

Surface studies on acrylic bone cement.

Poly(methyl methacrylate) (PMMA) is used to fill the gap between the prosthesis and the surrounding bone in cemented arthroplasties. Biocompatibility problems related to bone cement application limit the clinical success of these cemented arthroplasties. Being the cement surface in close connection with the living bone, it is reasonable to assume that surface properties such as, surface composition and surface energy, will play a role in the biomaterial performance. X-ray photoelectron spectroscopy (XPS) analysis and surface energy studies were carried out during 4 months, in order to assess a possible correlation between aging time and surface changes. The aging of PMMA, in a biological model fluid, strongly influences the composition and wettability of the cement surface. These changes may be explained through the hydrolysis of PMMA ester groups and the subsequent hydrogen bonding. Although our study does not exactly reproduce the in vivo environment surrounding a prosthesis, it suggests that the changes in the composition and wettability of the surface may modulate the host response towards the implant, thus contributing to its loosening.

The effect of ethanol on acrylic bone cement.

Prosthesis loosening is a major problem associated with the use of poly(methyl methacrylate) (PMMA) bone cement that may be related to a peri-implant vacuolisation commonly observed at bone-cement interface. Methyl methacrylate (MMA) monomer may be one of the cement components partly responsible for the mentioned vacuolisation due to a cytotoxic effect associated to this compound. Alcoholism has been related to bone necrosis in predisposed individuals. Furthermore, ethanol has been shown to clean material with adherent cement debris during cleaning procedure in laboratory. Consequently, we have decided to study whether ethanol will also be related to an increased liberation of MMA from the polymer matrix. 'In vitro' release studies using PMMA plates were conducted to access the role of ethanol on the liberation of the monomer. Contact angle measurements and surface tension estimation were also carried out in order to find a possible effect of ethanol on surface cement properties. Results suggest that ethanol, even in small quantities, enhances the leaching of the monomer from the polymer matrix, but does not considerably change the wettability properties of the cement surface.

Corrosion resistance of a composite polymeric coating applied on biodegradable AZ31 magnesium alloy.

The high corrosion rate of magnesium alloys is the main drawback to their widespread use, especially in biomedical applications. There is a need for developing new coatings that provide simultaneously corrosion resistance and enhanced biocompatibility. In this work, a composite coating containing polyether imide, with several diethylene triamine and hydroxyapatite contents, was applied on AZ31 magnesium alloys pre-treated with hydrofluoric acid by dip coating. The coated samples were immersed in Hank's solution and the coating performance was studied by electrochemical impedance spectroscopy and scanning electron microscopy. In addition, the behavior of MG63 osteoblastic cells on coated samples was investigated. The results confirmed that the new coatings not only slow down the corrosion rate of AZ31 magnesium alloys in Hank's solution, but also enhance the adhesion and proliferation of MG63 osteoblastic cells, especially when hydroxyapatite nanoparticles were introduced in the coating formulation.

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.