The corrosion inhibition mechanism of new rare earth cinnamate compounds — electrochemical studies

A combination of linear polarisation resistance (LPR) and cyclic potentiodynamic polarisation (CPP) measurements demonstrated that the lanthanum-4 hydroxy cinnamate compound could inhibit both the cathodic and anodic corrosion reactions on mild steel surfaces exposed to 0.01 M NaCl solutions. However, the dominating response was shown to vary with inhibitor concentration. At the concentrations for which the highest level of protection was achieved, both REM-4 hydroxy cinnamate (REM being lanthanum and mischmetal) displayed a strong anodic behaviour for mild steel and their inhibition performance, including their resistance against localised attack, improved with time.

Electrochemical impedance spectroscopy (EIS) measurements and modelling were carried out so as to propose a simple electrical model and correlate the extracted parameters to the inhibition mechanism put forward for REM-cinnamate based compounds. The results supported the high corrosion inhibition performance of the compounds as well as the build-up of a protective film with time. Based on a two-layer model the results suggested that the upper layer of the inhibitor film seemed to offer less resistance to the diffusion of electrochemically active species than the highly resistive inner layer at the film/metal interface.

N-methyl-N-alkylpyrrolidinium nonafluoro-1-butanesulfonate salts : Ionic liquid properties and plastic crystal behaviour

A series of N-methyl-N-alkylpyrrolidinium nonafluoro-1-butanesulfonate salts were synthesised and characterised. The thermophysical characteristics of this family of salts have been investigated with respect to potential use as ionic liquids and solid electrolytes. N-Methyl-N-butylpyrrolidinium nonafluoro-1-butanesulfonate (p_1,4NfO) has the lowest melting point of the family, at 94 °C. Electrochemical analysis of p_1,4 NfO in the liquid state shows an electrochemical window of ~6 V. All compounds exhibit one or more solid–solid transitions at sub-ambient temperatures, indicating the existence of plastic crystal phases.

Electrochemical performance of polyaniline nanofibres and polyaniline/multi-walled carbon nanotube composite as an electrode material for aqueous redox supercapacitors

Polyaniline (PANI) nanofibres are synthesized by interfacial polymerization and their electrochemical performance is evaluated in an aqueous redox supercapacitor constituted as a two-electrode cell. The initial specific capacitance of the cell is 554 F g−1 at a constant current of 1.0 A g−1, but this value rapidly decreases on continuous cycling. In order to improve the cycleability of the supercapacitor, a composite of polyaniline with multi-walled carbon nanotubes (CNTs) is synthesized by in situ chemical polymerization. Its capacitive behaviour is evaluated in a similar cell configuration. A high initial specific capacitance of 606 F g−1 is obtained with good retention on cycling. In both supercapacitors, the effect of charging potential on cycling performances is investigated.

Nanorods of vanadium compounds: synthesis, characterisation, and application in electrochemical energy storage

The synthesis and characterisation of nanorods of vanadium pentoxide, V(2)O(5), vanadium trioxide, V(2)O(3), vanadium dioxide, VO(2)(B), and vanadium nitride, VN, are presented, and their application in electrochemical supercapacitors and lithium-ion batteries is outlined. Specifically, a novel method for the preparation of V(2)O(5) nanorods is discussed. It involves ball milling as a first step and controlled annealing as a second step. Nanorods of V(2)O(5) can be converted into those of other vanadium-related phases by simple chemical reduction treatments. Such chemical transformations are pseudomorphic and often topotactic, that is, the resulting nanorods belong to a different chemical phase but tend to retain the original morphology and preferential crystal orientation dictated by parent V(2)O(5) crystals.

The corresponding properties of nanorods for their prospective application in electrochemical energy storage (lithium-ion batteries and electrochemical supercapacitors) are discussed. The synthesised V(2)O(5) nanorods possess a stable cyclic behaviour when they are used in a cathode of a lithium-ion battery and are suitable for use in an anode. VN nanorods synthesised by NH(3) reduction of V(2)O(5) were found to possess pseudocapacitive properties in aqueous electrolytes.

On corrosion behaviour of magnesium alloy AZ31 in simulated body fluids and influence of ionic liquid pretreatments

This paper reports on the corrosion of Mg alloy AZ31 in simulated body fluid (SBF) using static immersion tests and electrochemical impedance spectroscopy. A preliminary study on the effect of flowing SBF on the corrosion behaviour of AZ31 has also been carried out. Low toxicity ionic liquids (ILs) trimethyl(butyl)phosphonium diphenyl phosphate P1444DPP and trihexyl(tetradecyl)-phosphonium bis-2,4,4trimethylpentyl-phosphinate [P66614][ i(C8) 2PO2] have been used to provide corrosion protection for AZ31 in SBF. Time dependent immersion tests indicate that under static conditions, AZ31 suffers severe localised corrosion in SBF, with pits developing predominantly beside the Al-Mn intermetallic phase in the α matrix. At longer immersion times, the corrosion product eventually precipitates and covers the entire specimen surface. When exposed to SBF under flowing conditions with a shear stress of 0·88 Pa, more uniform corrosion was observed. The optical profilometry results and electrochemical impedance spectroscopy analysis suggest that both P
1444DPP and [P66614][i(C8)2PO2] pretreatments can increase the corrosion resistance of AZ31 in SBF, in particular by decreasing the number of deeper pits found on the alloy surface. Cytotoxic test shows that the presence of the ILs P
1444DPP and [P66614][i(C8)2PO2] in cell culture media slightly inhibits the growth of human coronary artery endothelial cells in comparison with the good cell viability around the treated specimen. A pretreatment with IL is used in order to improve the corrosion resistance of this alloy in SBF. © 2012 Institute of Materials, Minerals and Mining.

Microstructures, mechanical properties and in vitro corrosion behaviour of biodegradable Mg-Zr-Ca alloys

The microstructures, mechanical properties, corrosion behaviour and biocompatibility of the Mg-Zr-Ca alloys have been investigated for potential use in orthopaedic applications. The microstructures of the alloys were examined using X-ray diffraction analysis, optical microscopy and scanning electron microscopy. The mechanical properties of Mg-Zr-Ca alloys were determined from compressive tests. The corrosion behaviour has been investigated using an immersion test and electrochemical measurement. The biocompatibility was evaluated by cell growth factor using osteoblast-like SaOS2 cell. The experimental results indicate that the hot-rolled Mg-Zr-Ca alloys exhibit much finer microstructures than the as-cast Mg-Zr-Ca alloys which show coarse microstructures. The compressive strength of the hot-rolled alloys is much higher than that of the as-cast alloys and the human bone, which would offer appropriate mechanical properties for orthopaedic applications. The corrosion resistance of the alloys can be enhanced significantly by hot-rolling process. Hot-rolled Mg-0.5Zr-1Ca alloy (wt %) exhibits the lowest corrosion rate among all alloys studied in this paper. The hot-rolled Mg-0.5Zr-1Ca and Mg-1Zr-1Ca alloys exhibit better biocompatibility than other studied alloys and possess advanced mechanical properties, corrosion resistance and biocompatibility, suggesting that they have a great potential to be good candidates for orthopaedic applications. © 2012 Springer Science+Business Media New York.

In vitro studying corrosion behaviour of biocorrodible Mg alloys

The idea of bioabsorbable/biocorrodible stents has gained increasing attention in the last decade. Permanent coronary stents, traditionally made from 316L grade stainless steel, are routinely used for the treatment of blocked arteries. However, these stents can cause complications such as restenosis, thrombosis and the need for the patient to undergo prolonged antiplatelet therapy. Biodegradable metal stents provide an opportunity for the stent to remain in place for a period to ensure restoration of function and then degrade through a carefully controlled bio-corrosion process. Among the number of potentially suitable materials, Magnesium alloys have shown great promise as a stent material due to their non-toxicity [1] and the corrosion rates attainable in biological environments. However, a carefully controlled corrosion process is essential in order to avoid hyper hydrogen generation and the fatal consequences that follow. In addition uniform corrosion is a basic requirement to maintain the mechanical integrity and load bearing characteristics. Work being undertaken in our laboratories focuses on controlling the corrosion behaviour of magnesium in a simulated biological environment in the presence of protein. In the investigation reported here the Mg alloy has been examined using Scanning Electrochemical Microscope (SECM) to visualize the corrosion process and identify the corrosion pattern. Complementary bulk electrochemical techniques (EIS and potentiodynamic polarization) have been used to acquire kinetic and mechanistic information. Early results obtained by SECM have revealed the tendency towards pitting corrosion in the early stages which subsequently develops in to filiform corrosion.

Characterization of decamethylferrocene and ferrocene in ionic liquids : Argon and vacuum effect on their electrochemical propertiesce

The electrochemistry of decamethylferrocene (DmFc) has been studied in organic solvent systems and proven to be a superior internal reference redox standard to ferrocene (Fc). However, the electrochemical information on this redox couple in ionic liquids is still limited. Therefore, the voltammetric and amperometric behaviour of DmFc was investigated under argon and vacuum conditions in six different ionic liquids and compared to that of Fc under the same experimental conditions. Consequently, the concentration, the heterogeneous electron-transfer rate constant (k0), volatility, and diffusion coefficients (D) of Fc and Fc+, as well as the solubility, k 0, and D values for DmFc and DmFc+ were determined under argon and vacuum conditions by fitting the experimental chronoamperometric and voltammetric data with numerical and digital simulations. The rate of mass transport of ferrocene and decamethylferrocene was observed to decreases between 6-37% by changing the working atmosphere from argon to vacuum. The D Fc/DFc+ ratios are in the range 1.31-2.01 in the different ILs. Importantly, the DDmFc/DDmFc+ ratio is ≈ 1 in 1-methyl-3-butylimidazolium bis(trifluoromethylsulfonyl)amide, 1-methyl-1-butylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, and 1-methyl-3-ethylimidazolium tris(pentafluoroethyl)trifluorophosphate. The experimental mid-point potential and half-wave potential of Fc0/+ vs. DmFc0/+, as well as the formal potential obtained after correction for inequality in the respective diffusion coefficients of both redox processes are presented. Even though DmFc is not freely soluble in the different ILs, the results presented in this work suggest that the DmFc0/+ redox process is less dependent than Fc on the IL nature. This is a very relevant finding for the application of this transition-metal sandwich complex as an internal reference redox system in IL solutions. © 2014 Elsevier Ltd.

Evaluating the corrosion behaviour of magnesium alloy in simulated biological fluid by using SECM to detect hydrogen evolution

Scanning electrochemical microscopy (SECM) in surface generation/tip collection mode is investigated as an assessment tool for studying the corrosion behaviour of magnesium in simulated biological fluid. The technique provides a local map of hydrogen (H2) evolution which alone can be used as a direct measure of corrosion. The H2 generated during corrosion of magnesium is oxidized at the probe(i.e. a Pt ultra micro-electrode);with the magnitude of the current generated due to oxidation being indicative of the intensity of H2 evolution at a local scale on the magnesium surface. This method was calibrated using a cathodically polarized Pt disk to simulate H2 evolution in a controlled condition on a homogeneous surface. Potential interference from dissolving Mg or high local pH was also investigated. The technique was implemented for studying H2 evolution at the surface of AZ31 as a model Mg alloy.SECM results combined with SEM-EDX and profilometry data revealed that local domains of higher H2 evolution on the surface of AZ31 are in close proximityof the observed pitting sites.

The behaviour of praseodymium 4-hydroxycinnamate as an inhibitor for carbon dioxide corrosion and oxygen corrosion of steel in NaCl solutions

Praseodymium 4-hydroxycinnamate (Pr(4OHCin)3) was investigated as a novel corrosion inhibitor for steel in NaCl solutions, and found to be effective at inhibiting corrosion in both CO2-containing and naturally-aerated systems. Surface analysis results suggest that the corrosion inhibition ability of Pr(4OHCin)3 in the naturally-aerated corrosion system could be attributed to the formation of a continuous protective film. For the CO2-containing system, the corrosion inhibition efficiency of Pr(4OHCin)3 was predominantly because of formation of protective inhibiting deposits at the active electrochemical corrosion sites, in addition to a thinner surface film deposit. © 2013.

Studying the cathodic disbondment of coatings using electrochemical impedance spectroscopy

The disbondment of protective organic coatings is a widely reported pipeline coating failure mode in the oil and gas industry. Traditional methods of evaluating cathodic disbondment of pipeline coatings are based on visual inspection of pipeline conditions, and laboratory testing of cathodic disbondment resistance (CDR) using standard methods such as ASTM G8. Although some other laboratory-based techniques, such as scanning kelvin probe and scanning acoustic microscopy have been used to study the cathodic disbondment (CD) of coatings, these are often difficult to apply in practical testing. Over the past decade, electrochemical impedance spectroscopy (EIS) has been employed as a potential method for measuring CD. This paper reports preliminary results from an EIS study designed to characterise CD behaviour of epoxy coatings under excessive cathodic protection. EIS data correlated well with the area of disbonded coating. Analysis of EIS data can provide valuable information on the initiation and rates of CD.

New insights into the thermal behaviour of organic ionic plastic crystals: magnetic resonance imaging of polycrystalline morphology alterations induced by solid-solid phase transitions

Organic ionic plastic crystals (OIPCs) show strong potential as solid-state electrolytes for lithium battery applications, demonstrating promising electrochemical performance and eliminating the need for a volatile and flammable liquid electrolyte. The ionic conductivity (σ) in these systems has recently been shown to depend strongly on polycrystalline morphology, which is largely determined by the sample's thermal history. [K. Romanenko et al., J. Am. Chem. Soc., 2014, 136, 15638]. Tailoring this morphology could lead to conductivities sufficiently high for battery applications, so a more complete understanding of how phenomena such as solid-solid phase transitions can affect the sample morphology is of significant interest. Anisotropic relaxation of nuclear spin magnetisation provides a new MRI based approach for studies of polycrystalline materials at both a macroscopic and molecular level. In this contribution, morphology alterations induced by solid-solid phase transitions in triisobutyl(methyl)phosphonium bis(fluorosulfonyl)imide (P1444FSI) and diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate (P1224PF6) are examined using magnetic resonance imaging (MRI), alongside nuclear magnetic resonance (NMR) spectroscopy, diffusion measurements and conductivity data. These observations are linked to molecular dynamics and structural behaviour crucial for the conductive properties of OIPCs. A distinct correlation is established between the conductivity at a given temperature, σ(T), and the intensity of the narrow NMR signal that is attributed to a mobile fraction, fm(T), of ions in the OIPC. To explain these findings we propose an analogy with the well-studied relationship between permeability (k) and void fraction (θ) in porous media, with k(θ) commonly quantified by a power-law dependence that can also be employed to describe σ(fm).

Well-controlled preparation of evenly distributed nanoporous HOPG surface via diazonium salt assisted electrochemical etching process

Evenly distributed nanoporous highly oriented pyrolytic graphite (HOPG) surfaces with controllable pore size were successfully prepared via diazonium salt assisted electrochemical etching method. The porous HOPG was investigated by atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) Raman spectroscopy and X-ray diffraction. The size of these pores can be tuned by manipulating the electrochemical etching time. These porous HOPG substrates also demonstrated the enhanced electrocatalytical behaviour and were employed as benign arena for the immobilization of Ru(bpy)32+ for electrochemiluminescence (ECL) sensing applications.