Enhanced electrochemical oxidation of methanol on copper electrodes modified by electrocorrosion and electrodeposition

In this paper, we report a study of electrocatalytic oxidation of methanol on copper electrodes subjected to different surface treatments, either electrocorrosion or electrodeposition in the absence of strong hydrogen co-deposition. The surface morphology of treated electrodes was examined by Field Emission Scanning Electron Microscopy (FE-SEM). The effect of different treatment conditions and the methanol concentration dependence were evaluated by cyclic voltammetric technique. The results indicate that the oxidation of methanol can be enhanced by a suitable micro and nano structure generated by these treatments. This enhanced electrode activity is related to an increase of the effective surface area and/or to an increase of the surface concentration of electroactive molecules or intermediates.     

Neodymium conversion layers formed on zinc powder for improving electrochemical properties of zinc electrodes

Zinc powder, as active material of secondary alkaline zinc electrode, can greatly limit the performance of zinc electrode due to corrosion and dendritic growth of zinc resulting in great capacity-loss and short cycle life of the electrode. This work is devoted to modification study of zinc powder with neodymium conversion films coated directly onto it using ultrasonic immersion method for properties improvement of zinc electrodes. Scanning electron microscopy and other characterization techniques are applied to prove that neodymium conversion layers are distributing on the surface of modified zinc powder. The electrochemical performance of zinc electrodes made of such modified zinc powder is investigated through potentiodynamic polarization, potentiostatic polarization and cyclic voltammetry. The neodymium conversion films are found to have a significant effect on inhibition corrosion capability of zinc electrode in a beneficial way. It is also confirmed that the neodymium conversion coatings can obviously suppress dendritic growth of zinc electrode, which is attributed to the amelioration of deposition state of zinc. Moreover, the results of cyclic voltammetry reveal that surface modification of zinc powder enhances the cycle performance of the electrode mainly because the neodymium conversion films decrease the amounts of ZnO or Zn(OH)₂ dissolved in the electrolyte.     

Fabrication of Al and Al/Ti coatings on magnesium alloy by sputtering

Multi-magnetron sputtering was applied to prepare aluminum coating and aluminum/titanium multilayer coating on AZ31 magnesium alloy. FESEM, AFM and XRD were used to investigate the morphology and phase structure of these obtained coatings. Aluminum coating presented a (111) preferred texture and this texture was strongly strengthened with the Ti(002) plane as template in Al/Ti multilayer coating. The top surface of Al/Ti-coated sample took on a round roof-like morphology compared to the pyramid-like morphology of Al-coated sample. The result of polarization tests showed that both Al coating and Al/Ti multilayer coating could improve the corrosion resistance of AZ31 magnesium alloy in 3.5 wt.% NaCl solution.     

Mild steel corrosion inhibition in HCl by di-alkyl and di-1,2,3-triazole derivatives of uracil and thymine

The corrosion inhibition efficiency (IE) of four di-alkyl derivatives of uracil and thymine and six 1,2,3-triazole benzyl derivatives of uracil and thymine compounds was measured in the system: pipeline steel grade API 5L X52/1 M HCl using electrochemical impedance spectroscopy (EIS). The influence of the inhibitor concentration, 5–200 ppm, on the IE of all these compounds was determined. The results obtained showed that in all cases, the IE increased with increasing inhibitor concentration, and that, except for one of the di-alkyl derivatives of uracil, that was capable of attaining solely an IE of 84% at 200 ppm, the remainder displayed IEs greater that 90% at rather low concentrations, namely around 20 ppm. In this sense, the most remarkable inhibitor was one of the 1,2,3-triazole benzyl derivative of uracil, which gave 96% IE with merely 5 ppm. For all cases, it was found that these inhibitors follow a physisorption mechanism, which can be adequately described by the Langmuir isotherm. Moreover, it is shown that these compounds can affect both the anodic and cathodic processes, thus it can be classified as a mixed-type inhibitor capable of blocking both anodic and cathodic sites on the API 5L X52 steel surface immersed in HCl. The influence of the steel immersion time on their IE was also assessed in the corroding media for the two most efficient inhibitors. It is shown that even when the IE of both inhibitors diminished practically linearly as a function of time, both can provide adequate protection (IE > 88%) to the steel substrate even after 350 exposure hours to this highly corrosive media.     

The pigment influence on the anticorrosive performance of some alkyd films

This paper presents the results regarding the pigments effect on the protective properties of alkyd films in 3% natrium chloride solution. The films were realized on carbon steel substrate from an alkyd resin using the pigments of metallic, mineral and organic type. Dry films thickness in 30–35 μm range was obtained. Electrochemical techniques (electrochemical impedance spectroscopy (EIS) and stepwise polarization) were used. The interpretation of the impedance spectra (Nyquist and Bode diagrams) with the immitance analysis Equivcrt. Programme established two electrical equivalent circuits (with two and four time constants) for the carbon steel/alkyd film systems in electrolyte solution, fitted to the experimental data. The electric capacitance and resistance of the alkyd films were monitored with the immersion time to establish the water and ions permeability of these paint films. The electrochemical parameters of alkyd coated carbon steel from the anodic potentiostatic polarisation curves were determined. The correlation of all experimental results established that the tested pigments except the green organic pigment increase the protective performances of alkyd coatings. Best protection of the carbon steel was found for the alkyd film with aluminum powder pigment.     

Direct electrochemical formation of alloyed AuPt nanostructured electrocatalysts for the oxidation of formic acid

The formation of highly anisotropic AuPt alloys has been achieved via a simple electrochemical approach without the need for organic surfactants to direct the growth process. The surface and bulk properties of these materials were characterised by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX) and electrochemically by cyclic voltammetry to confirm alloy formation. It was found that AuPt materials are highly active for both the model hydrogen evolution reaction and the fuel cell relevant formic acid oxidation reaction. In particular for the latter case the preferred dehydrogenation pathway was observed at AuPt compared to nanostructured Pt prepared under identical electrochemical conditions which demonstrated the less preferred dehydration pathway. The enhanced performance is attributed to both the ensemble effect which facilitates CO_(ads) removal from the surface as well as the highly anisotropic nanostructure of AuPt.     

Effect of zirconia sol in electrolyte on the characteristics of microarc oxidation coating on AZ91D magnesium

The microarc oxidation coatings were prepared on AZ91D magnesium alloy in a Na₂SiO₃-KOH electrolyte with and without zirconia sol, respectively. The effect of zirconia sol as an additive in the electrolyte on the surface morphologies, compositions, structures, and corrosion resistances of the coatings were investigated. It was found that the coating formed in the Na₂SiO₃-KOH electrolyte with zirconia sol has more uniform morphology, less micropores and cracks than that formed in an electrolyte without zirconia sol. The phase compositions of the coatings also varied after addition of zirconia sol in the electrolyte, owing to the participation of zirconia sol in the reaction and its incorporation into the oxide coating, and Zr existed in the form of Mg₂Zr₅O₁₂. The results of potentiodynamic polarization analysis show that the coating formed in the electrolyte with zirconia sol increases significantly corrosion resistance for magnesium alloy.     

Biocorrosion resistance of coated magnesium alloy by microarc oxidation in electrolyte containing zirconium and calcium salts

The key to use magnesium alloys as suitable biodegradable implants is how to adjust their degradation rates. We report a strategy to prepare biocompatible ceramic coating with improved biocorrosion resistance property on AZ91D alloy by microarc oxidation （MAO） in a silicate-K2ZrF6 solution with and without Ca（H2PO4）2 additives. The microstructure and biocorrosion of coatings were characterized by XRD and SEM, as well as electrochemical and immersion tests in simulated body fluid （SBF）. The results show that the coatings are mainly composed of MgO, Mg2SiO4, m-ZrO2 phases, further Ca containing compounds involve the coating by Ca（H2PO4）2 addition in the silicate-K2ZrF6 solution. The corrosion resistance of coated AZ91D alloy is significantly improved compared with the bare one. After immersing in SBF for 28 d, the Si-Zr5-CaO coating indicates a best corrosion resistance performance.     

Deformation behavior of nanostructured ZnO films on glass

Nanostructured ZnO films on glass substrate were studied by nanoindentation, scanning electron and atomic force microscopy. The films were obtained by a straightforward mechanoactivated oxidation method. The morphology of the obtained films was grained with a grain size in the range 50-100 nm and the thickness was approximately 2 μm. A detailed deformation behavior of ZnO films, critical parameters and indentation induced plastic deformation mechanisms were determined in correlation to bulk ZnO, Si single crystal and commercial ZnO films. In comparison to a single crystal ZnO, nanostructured films exhibit increased hardness (9 GPa); however, the Young's modulus is decreased (120 GPa). A directly detectable evidence of brittleness, “pop-in” and “pile-up” phenomena in ZnO films was not observed. The ZnO/glass interface is stable and exhibits high adhesion, no signs of delamination or presence of brittleness cracks were detected (even at load P_max > 2 N). The role of grain boundaries on the properties of deformation behavior of ZnO nanostructured films has been discussed.     

Synthesis of carbon films containing diamond particles by electrolysis of methanol

Carbon films containing diamond particles were deposited onto a Si (100) substrate by electrolysis of methanol under a direct current potential of 1200 V, with a current density of about 52 mA/cm², at atmospheric pressure and in the temperature range of 50-55 °C. The surface morphology, microstructure and crystalline structure of the deposited films were characterized by scanning electron microscopy (SEM), Fourier transformation infrared (FTIR) spectroscopy, Raman spectroscopy and transmission electron microscopy (TEM) respectively. The SEM images show that the films are formed by particle clusters and a surrounding glassy phase. The Raman spectra of the films indicate that the particle clusters are composed of diamond and that the glassy phase is composed of amorphous carbon. The FTIR measurements suggest the existence of hydrogen which is mainly bonded to the sp³ carbon in the films. The transmission electron diffraction patterns further indicate that the particles in the films consist of single-crystalline diamond. Both TEM and Raman measurements have confirmed unambiguously the formation of diamond crystals in the deposit, although the particles are not uniformly distributed on the entire surface.     

Corrosion resistance of biomimetic calcium phosphate coatings on magnesium due to varying pretreatment time

Calcium phosphate coatings were prepared on magnesium substrates via a biomimetic coating process. The effects of a magnesium hydroxide pretreatment on the formation and the ultimate corrosion protection of the coatings were studied. The pretreatment layer was found to affect the amount of defects present in the coatings. Corrosion resistance of the coatings was studied in vitro using two simulated body fluids, 0.8% NaCl and Hanks solution. In NaCl, the resistance to corrosion of all samples decreases with time as corrosion proceeded through cracks and other defects in the coatings. Samples with no pretreatment displayed the highest corrosion resistance as these samples had the fewest defects in the coating. However, in Hanks solution, corrosion resistance increased with time due to additional nucleation of calcium phosphate from the fluid on to the substrate. In this solution, additional pretreatment time was beneficial to the overall corrosion resistance.     

Synthesis of nano-sized biphasic calcium phosphate ceramics with spherical shape by flame spray pyrolysis

Nanometer size biphasic calcium phosphate (BCP) powders with various Ca/P molar ratios satisfied with appropriate phase ratios of HA/β-TCP were prepared by high temperature flame spray pyrolysis process. The BCP powders had spherical shapes and narrow size distributions irrespective of the ratios of Ca/P. The mean size of the BCP powders measured from the TEM image was 38 nm. The composition ratio of Ca/P was controlled from 1.500 to 1.723 in the spray solution, and required phase ratios of HA/TCP are controlled systematically. The calcium dissolution of the pellets obtained from the BCP powders directly prepared by flame spray pyrolysis in buffer solution increased with the decrease of Ca/P ratios except with the Ca/P ratio of 1.713. The pellet surface with Ca/P ratio of 1.500, which consisted of β-TCP, was eroded dramatically for 7 days. On the other hand, the pellet surface with Ca/P ratio of 1.667 was stable and did not disintegrate after immersion in Tris–HCl buffer solution based on the SEM observation.     

Facile synthesis of Ag dendrites on Al foil via galvanic replacement reaction with [Ag(NH3)2]Cl for ultrasensitive SERS detecting of biomolecules

Symmetric silver dendrites have been synthesized on commercial aluminum foil via galvanic replacement reaction with [Ag(NH₃)₂]Cl. This process is facile and environmentally friendly, without the use of any templates, surfactants or oxidants, and also avoiding the introduction of fluoride anions as a strong toxicity resulting in hypocalcemia. The products were characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM) and X-ray diffraction (XRD). SEM characterizations and electrochemical measurements including an electrochemical direct current polarization method and OCP-t technique demonstrate that chloride has proven to be the key factor to the formation of well-defined dendritic shape. The as-prepared Ag dendrites are developed as a surface-enhanced Raman scattering (SERS)-active platform for detection of folic acid, DNA and RNA with well resolved bands and high Raman intensities. The detection concentration for the three biomolecules reaches the level of 10⁻¹² M, and thus the symmetric silver dendrites can potentially be employed as effective SERS sensors for label-free and ultrasensitive biomolecule detection.     

Micromorphological effect of calcium phosphate coating on compatibility of magnesium alloy with osteoblast

Abstract

Octacalcium phosphate (OCP) and hydroxyapatite (HAp) coatings were developed to control the degradation speed and to improve the biocompatibility of biodegradable magnesium alloys. Osteoblast MG-63 was cultured directly on OCP- and HAp-coated Mg-3Al-1Zn (wt%, AZ31) alloy (OCP- and HAp-AZ31) to evaluate cell compatibility. Cell proliferation was remarkably improved with OCP and HAp coatings which reduced the corrosion and prevented the H₂O₂ generation on Mg alloy substrate. OCP-AZ31 showed sparse distribution of living cell colonies and dead cells. HAp-AZ31 showed dense and homogeneous distribution of living cells, with dead cells localized over and around corrosion pits, some of which were formed underneath the coating. These results demonstrated that cells were dead due to changes in the local environment, and it is necessary to evaluate the local biocompatibility of magnesium alloys. Cell density on HAp-AZ31 was higher than that on OCP-AZ31 although there was not a significant difference in the amount of Mg ions released in medium between OCP- and HAp-AZ31. The outer layer of OCP and HAp coatings consisted of plate-like crystal with a thickness of around 0.1 μm and rod-like crystals with a diameter of around 0.1 μm, respectively, which grew from a continuous inner layer. Osteoblasts formed focal contacts on the tips of plate-like OCP and rod-like HAp crystals, with heights of 2–5 μm. The spacing between OCP tips of 0.8–1.1 μm was wider than that between HAp tips of 0.2–0.3 μm. These results demonstrated that cell proliferation depended on the micromorphology of the coatings which governed spacing of focal contacts. Consequently, HAp coating is suitable for improving cell compatibility and bone-forming ability of the Mg alloy.     

The corrosion behavior of Ti-6Al-3Nb-2Zr-1Mo alloy: Effects of HCl concentration and temperature

Investigation about the corrosion behavior of Ti alloys in different ambient environment is of great significance for their practical application.Herein,we systematically investigate the corrosion behavior of a newfound Ti-6Al-3Nb-2Zr-1 Mo (Ti80) alloy in hydrochloric acid (HCI) ranging from 1.37 to 7 M,and temperature ranging from 25 to 55 ℃,by means of electrochemical measurements,static immersion tests and surface analysis.Results manifest that increasing either HCI concentration or temperature can accelerate the corrosion of Ti80 alloy via promoting the breakdown of native protective oxide film and then further facilitating the active dissolution of Ti80 matrix.According to potentiodynamic polarization curves,Ti80 alloy displays a spontaneous passive behavior in 1.37 M HCI at 25 ℃,compared to a typical active-passive behavior under the other conditions.As indicated by cathodic Tafel slope,the rate determining step for cathodic hydrogen evolution reaction is likely the discharge reaction step.The apparent activation energies obtained from corrosion current density and maximum anodic current density for Ti80 alloy in 5 M HCI solution are 62.4 and 55.6 kJ mol-1,respectively,which signifies that the rate determining step in the corrosion process of Ti80 alloy is mainly determined by surface-chemical reaction rather than diffusion.Besides,the electrochemical impedance spectroscopy tests demonstrate that a stable and compact oxide film exists in 1.37 M HCl at 25 ℃,whereas a porous corrosion product film forms under the other conditions.Overall,the critical HCI concentration at which Ti80 alloy can maintain passivation at 25 ℃ can be determined as a value between 1.37 and 3 M.Furthermore,the corroded surface morphology characterization reveals that equiaxed α phase is more susceptible to corrosion compared to intergranular β3 phase due to a lower content of Nb,Mo,and Zr in the former.     

Experimental and theoretical investigations on the inhibition of mild steel corrosion in the ground water medium using newly synthesised bipodal and tripodal imidazole derivatives

Two new imidazole derivatives, namely 1,4-bis(N-imidazolylmethyl)-2-5-dimethoxybenzene (BIDM) and 1,3,5-tris(N-imidazolylmethyl)-2,4,6-trimethoxybenzene (TITM), were synthesised and their effects on the inhibition of mild steel corrosion in ground water medium are reported. The study was carried out using gravimetric and electrochemical techniques in order to determine the corrosion inhibition efficiencies of the bipodal and tripodal structured imidazoles. Further, the quantum chemical calculations using density functional theory (DFT) gave a profound insight into the inhibitory action mechanism of BIDM and TITM and their calculation parameters, such as E_HOMO, E_LUMO and ΔE were in good agreement with the results of the experimental studies. BIDM and TITM exhibited lowest corrosion current densities of circa 7.5 μA cm⁻² and 4.1 μAcm⁻² at the optimum concentrations of 0.67 and 0.49 mM, respectively. All measurements thus confirmed that both BIDM and TITM behaved as good inhibitors for mild steel corrosion in ground water medium.     

环保型镁合金微弧氧化工艺的研究

对比了电解液中不含Cr^6＋、F和PO4^3-的环保型微弧氧化工艺和一美国专利的成膜效果。新工艺氧化膜表面光滑，孔的分布不太均匀，一个大孔中包含几个小孔；美国专利氧化膜的孔为圆形，非常均匀，孔与孔之间的距离非常小。两种工艺氧化膜成分不同，新工艺中含有Mg、Si和Al；美国专利中含有Mg、Al、Si和F。另外，美国专利得到的氧化膜厚度只有61μm，仅为新工艺膜厚的一半。两种工艺氧化得到的样品，经过336h盐雾实验后，新工艺能更好地提高基体耐蚀性。不同氧化工艺所得氧化样品耐蚀性的差异可以归因于各工艺所用电解质组成及其浓度不同，导致氧化膜性能如表面形貌、组成、厚度等方面不同，最终使得氧化膜耐蚀性不同。     

Annealed microstructure dependent corrosion behavior of Ti-6Al-3Nb-2Zr-1 Mo alloy

Corrosion resistance of titanium(Ti)alloys is closely connected with their microstructure which can be adjusted and controlled via different annealing schemes.Herein,we systematically investigate the specific effects of annealing on the corrosion performance of Ti-6 Al-3 Nb-2 Zr-1 Mo(Ti80)alloy in 3.5 wt.%NaCl and 5 M HCl solutions,respectively,based on open circuit potential(OCP),potentiodynamic polarization,electrochemical impedance spectroscopy(EIS),static immersion tests and surface analysis.Results indicate that increasing annealing tempe rature endows Ti80 alloy with a higher volume fraction ofβphase and finerαphase,which in turn improves its corrosion resistance.Surface characterization demonstrates thatβphase is more resistant to corrosion thanαphase owing to a higher content of Nb,Mo,and Zr in the former;additionally,the decreased thickness of a phase alleviates segregation of elements to further restrain the micro-galvanic couple effects betweenαandβphases.Meanwhile,the influential mechanisms of environmental conditions on corrosion of Ti80 alloy are discussed in detail.As the formation of a highly compact and stable oxide film on surface,annealed Ti80 alloys exhibit a low corrosion current density(10^-6A/cm²)and high polarization impedance(10⁶Ω·cm²)in 3.5 wt.%NaCl solution.However,they suffer severe corrosion in 5 M HCl solution,resulting from the breakdown of native oxide films(the conversion of TiO₂to aqueous Ti³⁺),active dissolution of substrate Ti to aqueous Ti³⁺and existence of micro-galvanic couple effects.Those findings could provide new insights to designing Ti alloys with high-corrosion resistance through microstructural optimization.     

Green approach to corrosion inhibition of mild steel in hydrochloric acid and sulphuric acid solutions by the extract of Murraya koenigii leaves

The inhibition of the corrosion of mild steel in hydrochloric acid and sulphuric acid solutions by the extract of Murraya koenigii leaves has been studied using weight loss, electrochemical impedance spectroscopy (EIS), linear polarization and potentiodynamic polarization techniques. Inhibition was found to increase with increasing concentration of the leaves extract. The effect of temperature, immersion time and acid concentration on the corrosion behavior of mild steel in 1 M HCl and 0.5 M H₂SO₄ with addition of extract was also studied. The inhibition was assumed to occur via adsorption of the inhibitor molecules on the metal surface. The adsorption of the extract on the mild steel surface obeys the Langmuir adsorption isotherm. The activation energy as well as other thermodynamic parameters (Q, ΔH^*, and ΔS^*) for the inhibition process was calculated. These thermodynamic parameters show strong interaction between inhibitor and mild steel surface. The results obtained show that the extract of the leaves of M. koenigii could serve as an effective inhibitor of the corrosion of mild steel in hydrochloric and sulphuric acid media.