Investigating effects of potential excursions and pH variations on cathodic protection using new electrochemical testing cells

Excursion from safe cathodic protection (CP) potentials occurs on buried steel pipelines due to various forms of electrical interferences such as stray currents. Variations in pH can also occur over some pipeline sections such as seashore and river crossing pipes. Currently, the exact effects of potential excursion and the pH on CP efficiency have not been sufficiently quantified preliminary due to difficulties in measuring these effects. In this work, these effects have been investigated using electrochemical cells designed to mimic the high resistivity and pH conditions observable over underground steel pipes, including a new electrochemical cell that has been designed to facilitate the effective simulation and control of pH, potential excursion and other CP testing parameters. The pH has been shown to be a key factor affecting the patterns of corrosion and CP efficiency. Localised corrosion has been found to be the dominating form of corrosion under potential excursions conditions.

The restoration of the passivity of stainless steel Weldments in pickling solutions observed using electrochemical and surface analytical methods

In this study, a solution containing ammonium fluoride (NH4F) and nitric acid (HNO3) was used as an alternative to the conventional highly toxic pickling solution HF/HNO3 for pickling weldments of selected stainless steels including Type 316 stainless steel (UNS S31600), duplex stainless steel 2205 (UNS S32205), and super duplex stainless steel 2507 (UNS S32750). Electrochemical and surface analytical methods were used to understand the effects of pickling on the stainless steel weldments. Cyclic potentiodynamic polarization (CPP) test results indicated that the restoration of passivity of stainless steel weldments could be achieved by pickling the weldments in both HF/HNO3 solution and NH4F/HNO3 solutions. Scanning electron microscopy observation of the UNS S32750 weldment surface revealed that both the HF/HNO3 solution and the NH4F/HNO3 solution could remove the heat tint on the weldment. X-ray photoelectron spectroscopy analysis indicated that treatment in these two pickling solutions produced passive films with similar characteristics. Thus, this work suggests that the NH4F/HNO3 solution is a promising alternative to HF/HNO3 solution for the pickling of stainless steel weldments, and that the CPP test approach can be used in conjunction with surface analytical methods for further development of safer and environmentally friendly picklingsolutions.

An ether-functionalised cyclic sulfonium based ionic liquid as an electrolyte for electrochemical double layer capacitors

A novel cyclic sulfonium cation-based ionic liquid (IL) with an ether-group appendage and the bis{(trifluoromethyl)sulfonyl}imide anion was synthesised and developed for electrochemical double layer capacitor (EDLC) testing. The synthesis and chemical-physical characterisation of the ether-group containing IL is reported in parallel with a similarly sized alkyl-functionalised sulfonium IL. Results of the chemical-physical measurements demonstrate how important transport properties, i.e. viscosity and conductivity, can be promoted through the introduction of the ether-functionality without impeding thermal, chemical or electrochemical stability of the IL. Although the apparent transport properties are improved relative to the alkyl-functionalised analogue, the ether-functionalised sulfonium cation-based IL exhibits moderately high viscosity, and poorer conductivity, when compared to traditional EDLC electrolytes based on organic solvents (propylene carbonate and acetonitrile). Electrochemical testing of the ether-functionalised sulfonium IL was conducted using activated carbon composite electrodes to inspect the performance of the IL as a solvent-free electrolyte for EDLC application. Good cycling stability was achieved over the studied range and the performance was comparable to other solvent free,
IL-based EDLC systems. Nevertheless, limitations of the attainable performance are primarily the result of sluggish transport properties and a restricted operative voltage of the IL, thus highlighting key aspects of this field which require further attention.

Exploring corrosion protection of Mg via ionic liquid pretreatment

We present the development of a 10–100 nanometer thick surface film upon pure Mg on exposure to an ionic liquid (IL) based on the bis(trifluoromethanesulfonyl)amide (TFSA) anion. This film formation is the result of the oxidative reactivity of the metal in the IL, with the subsequent effect of ultimately protecting the underlying metal from corrosion in aqueous chloride containing solution. Film formation was studied in the IL using an electrochemical droplet cell. It was seen that this film is adherent and subsequently facilitates appreciable protection against corrosion as judged by subsequent electrochemical testing in the form of potentiodynamic polarization and impedance spectroscopy, along with direct observation. The physical film morphology was studied by electron microscopy and focused ion beam.

Ligas Ti-Al-Nb como biomaterial: elaboração, caracterização, modificação eletroquímica da superfície e estudo da biocompatibilidade utilizando culturas primárias de células da medula óssea humana

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Corrosion behaviour of magnesium in ethylene glycol

Corrosion of magnesium engine components by coolant is an important issue in the automotive industry where magnesium alloys may be used. It is of significance to understand the corrosion behaviour of pure magnesium in ethylene glycol solutions, as this can provide a basis for developing new coolants for magnesium alloy engine blocks. In this paper, through corrosion and electrochemical tests, it was found that the corrosion rate of magnesium decreased with increasing concentration of ethylene glycol. Individual contaminants, such as NaCl, NaHCO3, Na2SO4 and NaCl can make aqueous ethylene glycol solution more corrosive to magnesium. However, in NaCl contaminated ethylene glycol, NaHCO3 and Na2SO4 showed some inhibition effect. The solution resistivity played an important role in the corrosion of magnesium in ethylene glycol solutions, and the competitive adsorption of ethylene glycol and the contaminants on the magnesium surface was also responsible for the observed corrosion behaviours. The corrosion of magnesium in ethylene glycol can be effectively inhibited by addition of fluorides that react with magnesium and form a protective film on the surface. (C) 2003 Elsevier Ltd. All rights reserved.

Corrosion resistance of aged die cast magnesium alloy AZ91D

The corrosion behaviour of die cast magnesium alloy AZ91D aged at 160degreesC was investigated. The corrosion rate of the alloy decreases with ageing time in the initial stages and then increases again at ageing times greater than 45 h. The dependence of the corrosion rate on ageing time can be related to the changes in microstructure and local composition during ageing. Precipitation of the beta phase (Mg17Al12) occurs exclusively along the grain boundaries during ageing. The beta phase acts as a barrier, resulting in a decreasing corrosion rate in the initial stages of ageing. In the later stages, the decreasing aluminium content of alpha grains makes the alpha matrix more active, causing an increase in the corrosion rate. Electrochemical testing results also confirm the combined effects of the changes in alpha and beta phases on the corrosion resistance of the aged die cast AZ91D alloy. (C) 2003 Elsevier B.V. All rights reserved.

An assessment of novel biodegradable magnesium alloys for endovascular biomaterial applications

Magnesium alloys have been widely explored as potential biomaterials, but several limitations to using these materials have prevented their widespread use, such as uncontrollable degradation kinetics which alter their mechanical properties. In an attempt to further the applicability of magnesium and its alloys for biomedical purposes, two novel magnesium alloys Mg-Zn-Cu and Mg-Zn-Se were developed with the expectation of improving upon the unfavorable qualities shown by similar magnesium based materials that have previously been explored. The overall performance of these novel magnesium alloys has been assessesed in three distinct phases of research: 1) analysing the mechanical properties of the as-cast magnesium alloys, 2) evaluating the biocompatibility of the as-cast magnesium alloys through the use of in-vitro cellular studies, and 3) profiling the degradation kinetics of the as-cast magnesium alloys through the use of electrochemical potentiodynamic polarization techqnique as well as gravimetric weight-loss methods. As compared to currently available shape memory alloys and degradable as-cast alloys, these experimental alloys possess superior as-cast mechanical properties with elongation at failure values of 12% and 13% for the Mg-Zn-Se and Mg-Zn-Se alloys, respectively. This is substantially higher than other as-cast magnesium alloys that have elongation at failure values that range from 7-10%. Biocompatibility tests revealed that both the Mg-Zn-Se and Mg-Zn-Cu alloys exhibit low cytotoxicity levels which are suitable for biomaterial applications. Gravimetric and electrochemical testing was indicative of the weight loss and initial corrosion behavior of the alloys once immersed within a simulated body fluid. The development of these novel as-cast magnesium alloys provide an advancement to the field of degradable metallic materials, while experimental results indicate their potential as cost-effective medical devices.^

An Assessment of Novel Biodegradable Magnesium Alloys for Endovascular Biomaterial Applications

Magnesium alloys have been widely explored as potential biomaterials, but several limitations to using these materials have prevented their widespread use, such as uncontrollable degradation kinetics which alter their mechanical properties. In an attempt to further the applicability of magnesium and its alloys for biomedical purposes, two novel magnesium alloys Mg-Zn-Cu and Mg-Zn-Se were developed with the expectation of improving upon the unfavorable qualities shown by similar magnesium based materials that have previously been explored. The overall performance of these novel magnesium alloys has been assessesed in three distinct phases of research: 1) analysing the mechanical properties of the as-cast magnesium alloys, 2) evaluating the biocompatibility of the as-cast magnesium alloys through the use of in-vitro cellular studies, and 3) profiling the degradation kinetics of the as-cast magnesium alloys through the use of electrochemical potentiodynamic polarization techqnique as well as gravimetric weight-loss methods. As compared to currently available shape memory alloys and degradable as-cast alloys, these experimental alloys possess superior as-cast mechanical properties with elongation at failure values of 12% and 13% for the Mg-Zn-Se and Mg-Zn-Se alloys, respectively. This is substantially higher than other as-cast magnesium alloys that have elongation at failure values that range from 7-10%. Biocompatibility tests revealed that both the Mg-Zn-Se and Mg-Zn-Cu alloys exhibit low cytotoxicity levels which are suitable for biomaterial applications. Gravimetric and electrochemical testing was indicative of the weight loss and initial corrosion behavior of the alloys once immersed within a simulated body fluid. The development of these novel as-cast magnesium alloys provide an advancement to the field of degradable metallic materials, while experimental results indicate their potential as cost-effective medical devices.

Crystal structure and electrochemical properties of rare earth non-stoichiometric AB(5)-type alloy as negative electrode material in Ni-MH battery

The La0.85MgxNi4.5Co0.35Al0.15 (0.05less than or equal toxless than or equal to0.35) system compounds have been prepared by are melting method under Ar atmosphere. X-ray diffraction (XRD) analysis reveals that the as-prepared alloys have different lattice parameters and cell volumes. The electrochemical properties of these alloys have been studied through the charge-discharge recycle testing at different temperatures and discharge currents. It is found that the La0.85Mg0.25Ni4.5Co0.35Al0.(15) alloy electrode is capable of performing high-rate discharge. Moreover, it has very excellent electrochemical properties as negative electrode materials in Ni-MH battery at low temperature, even at -40degreesC.

Structure and electrochemical characteristics of RENi3 alloy

The RENi3 (RE = La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Y) series compounds have been prepared by arc melting constituent elements under Ar atmosphere. X-ray diffraction (XRD) analysis reveals that the as-prepared alloys have different lattice parameters and cell volumes, depending on different rare earth (RE) element. The electrochemical characteristics, including the electrochemical capacity, P-C isotherms, high rate chargeability (HRC) and high-rate dischargeability (HRD), of these alloys have been studied through the charge-discharge recycle testing at different temperatures, charge currents and discharge currents. The results show that YNi3 has the largest cell volume, smallest density, and moreover, it shows more satisfactory electrochemical characteristics than other alloys, including discharge capacity, HRC, HRD and low temperature dischargeablity.

AN INTEGRATED CALCIUM-FLUORIDE CRYSTAL IR THIN-LAYER CELL AND ITS APPLICATION TO IDENTIFICATION OF ELECTROCHEMICAL REDUCTION PRODUCT OF BILIRUBIN

An integrated CaF2 crystal optically transparent infrared (ir) thin-layer cell was designed and constructed without using any soluble adhesive materials. It is suitable for both aqueous and nonaqueous systems, and can be used not only in ir but also in uv-vis studies. Excellent electrochemical and spectroelectrochemical responses were obtained in evaluating this cell by cyclic voltammetry and steady-state potential step measurements for both ir and uv-vis spectrolectrochemistry with ferri/ferrocyanide in aqueous solution, and with ferrocene/ferrocenium in organic solvent as the testing species, respectively. The newly designed ir cell was applied to investigate the electrochemical reduction process of bilirubin in situ, which provided direct information for identifying the structure of the reduction product and proposing the reaction mechanism.

Fabrication and testing of a doped lanthanum gallate electrolyte thin-film solid oxide fuel cell

A supported lanthanum gallate (LSGM) electrolyte thin-film solid oxide fuel cell with Ni-YSZ cermet anode and strontium-doped lanthanum manganite (LSM)-yttria stabilized zirconia (YSZ) composite cathode was, for the first time, fabricated and tested. The cell was prepared by an unconventional approach, in which an LSGM thin film (about 15 mum thick) was first deposited on a porous substrate such as a porous YSZ disk by a wet process and sintered at a high temperature (above 1400degrees C). NiO was then incorporated into the porous substrate by a carefully controlled impregnation process and fired at a much lower temperature. In this way, the severe reaction between LSGM and NiO at a high temperature, which is required for the full densification of LSGM film, can be avoided. A strontium-doped LaMnO3 (LSM)-YSZ composite cathode was screen printed on the surface of the LSGM film and then fired at 1250degrees C. The electrolyte resistances of the SOFC single cells fabricated by this approach are much lower compared to those of thick LSGM film supported cells. A maximum output power density of over 0.85 W/cm(2) at 800degreesC with H-2 as fuel and air as oxidant for a fabricated cell was achieved. (C) 2002 The Electrochemical Society.