The effects of mechanical stress, environment and cathodic protection on the degradation and failure of coatings: An overview

Organic coatings have been used in conjunction with cathodic protection as the most economical method of corrosion protection by the oil and gas pipeline industry. In a bid to prolong the life of the pipelines, the degradation and failure of pipeline coatings under the effects of major influencing factors including mechanical stress, the environmental corrosivity and cathodic protection have been extensively investigated over the past decades. This paper provides an overview of recent research for understanding coating degradation under the effect of these factors, either individually or in combination. Electrochemical impedance spectroscopy remains the primary and the most commonly used technique of studying the degradation of organic coatings, although there have been attempts to use other techniques such as electrochemical polarization (both dynamic and static), electrochemical noise, Scanning Kelvin Probe, Fourier Transform Infrared Spectroscopy, Differential Scanning Calorimetry and Dynamic Mechanical Analyser. Major knowledge and technological gaps in the investigation of the combined effects of mechanical stress, environmental corrosivity and cathodic protection on coating degradation have been identified.

An overview of methods for simulating and evaluating pipeline corrosion

Steel pipelines, buried under the soil and protected by the combination of protective coatings and cathodic protection (CP), are used for oil and gas transportation. These pipelines are one of the critical infrastructures for energy transportation and therefore became lifelines of modern society. The deterioration of the external surfaces of transmission pipelines is a serious problem and is caused mainly by coating and/or CP failure leading to the loss of integrity of pipelines. To avoid such damage, there is a need of techniques which are able to locate active corrosion sites, monitor corrosion, and evaluate corrosion damage. Fundamental understanding of such processes occurring on coated pipelines (with various types of defects in coatings as well as pipe) in complex soil environment is necessary for the development of such techniques. Numerous laboratory techniques, i.e., electrochemical impedance spectroscopy based, polarisation measurements based, mathematical simulations, direct observation etc. have been used to develop fundamental understanding, simulate and evaluate corrosion occurring in oil and gas pipelines under various operating conditions. Given the complex nature of the pipeline corrosion, application of these laboratory techniques in field measurements as well as in understanding the corrosion mechanisms is lacking. This paper presents an overview of investigations, based on electrochemical techniques, for simulation and evaluation of pipeline corrosion in laboratory.

Quantifying the effects of major factors affecting the effectiveness of cathodic protection of pipelines

electrical interference signals on CP and steel corrosion using newly designed electrochemical corrosion cells; as well as to monitoring cathodic disbondment of coatings using electrochemical impedance spectroscopy. Typical results from using these new techniques for measuring stray current corrosion and for probing the cathodic disbondment of pipeline coatings have been briefly discussed.

Environment friendly hydraulic lubricants – properties & performance.

 The present study aims to undertake research to improve the properties of vegetable oil based biodegradable lubricants for hydraulic oil applications. Different approaches were explored and adopted to investigate the thermo-oxidative stability, tribological property and corrosion behaviour of biodegradable basestocks as per the ISO 15380 specification.

Experimental and theoretical investigation on corrosion inhibition of AA5052 aluminium alloy by l-cysteine in alkaline solution

The corrosion inhibition of l-cysteine on AA5052 aluminium alloy in 4 mol/L NaOH solution was investigated by hydrogen gas evolution experiment, polarisation curve, galvanostatic discharge, electrochemical impedance spectroscopy measurements and quantum chemical calculations. The adsorption of l-cysteine on aluminium alloy surface obeyed the amended Langmuir's adsorption isotherm. The polarisation curves indicated that l-cysteine acted as a cathodic inhibitor to inhibit cathodic reaction. The inhibition mechanism was dominated by the geometric covering effect. The galvanostatic discharge shows that the additives restrain the hydrogen evolution and increase the anodic utilization rate. Quantum chemical calculations indicated that l-cysteine molecules mainly interacted with on the carboxyl groups on the aluminium alloy surface. A strong hybridization occurred between the s-orbital and p-orbital of reactive sites in the l-cysteine molecule and the sp-orbital of Aluminium.

Effects of Mg17Sr2 Phase on the bio-corrosion behavior of Mg-Zr-Sr alloys

The effect of the second phase Mg17Sr2 on the biocorrosion behavior of Mg5ZrxSr (x = 0, 2, 5 wt%) alloys before and after solution treatment was investigated. Electrochemical impedance spectroscopy, cathodic polarization and hydrogen evolution were used to evaluate the biocorrosion of Mg5ZrxSr. We found that Mg17Sr2 precipitated on boundary zones and enhanced the galvanic effect, leading to a severer corrosion of the Mg matrix adjacent to Mg17Sr2. The corrosion subsequently spread gradually from the regions adjacent to the Mg17Sr2 to the central Mg matrix. However, a high volume fraction of Mg17Sr2 could also form a continuous network, isolate the Mg matrix and act as a barrier of corrosion.

Supported silver nanoparticle and near-interface solution dynamics in a deep eutectic solvent

Type III deep eutectic solvents (DES) have attracted significant interest as both environmentally friendly and functional solvents that are, in some ways, advantageous to traditional aqueous systems. While these solvents continue to produce remarkable thin films and nanoparticle assemblies, their interactions with metallic surfaces are complex and difficult to manipulate. In this study, the near-surface region (2-600 nm) of a carbon surface is investigated immediately following silver nanoparticle nucleation and growth. This is accomplished, in situ, using a novel grazing transmission small-angle X-ray scattering approach with simultaneous voltammetry and electrochemical impedance spectroscopy. With this physical and electrochemical approach, the time evolution of three distinct surface interaction phenomena is observed: aggregation and coalescence of Ag nanoparticles, multilayer perturbations induced by nonaggregated Ag nanoparticles, and a stepwise transport of dissolved Ag species from the carbon surface. The multilayer perturbations contain charge-separated regions of positively charged choline-ethylene and negatively charged Ag and Cl species. Both aggregation-coalescence and the stepwise decrease in Ag precursor near the surface are observed to be very slow (∼2 h) processes, as both ion and particle transport are significantly impeded in a DES as compared to aqueous electrolytes. Altogether, this study shows how the unique chemistry of the DES changes near the surface and in the presence of nanoparticles that adsorb the constituent species.

Applications of scanning electrochemical microscopy (SECM) for local characterization of AZ31 surface during corrosion in a buffered media

Different modes of scanning electrochemical mapping (SECM) such as surface generation/tip collection (SG/TC), amperometry, AC-SECM and potentiometry were employed to characterize the active/passive domains, hydrogen gas (H2) evolution and local pH on a corroding surface of AZ31 in simulated biological fluid (SBF). It was found that the main domains of H2 evolution are associated with lower insulating properties of the surface as well as higher local pH. The near surface pH was found to be highly alkaline indicating that, even in a buffered solution such as SBF, the local pH on a corroding AZ31 surface can be significantly different to the bulk pH. © 2014 Elsevier Ltd.

Stoichiometric changes in lithium conducting materials based on Li1+xAlxTi2−x(PO4)3: impedance, X-ray and NMR studies

The lithium fast-ion conductor, Li_1+xAl_xTi_2−x(PO₄)₃ (LATP) has been modified via changes in stoichiometry during the processing steps. The resultant changes have been followed using ²⁷Al MAS NMR, X-ray powder diffraction and impedance spectroscopy. The most important changes were those of the form Li_1.3+4yAl_0.3Ti_1.7−y(PO₄)₃. It was possible to remove the AlPO₄ phase (both tridymite and berlinite polymorphs), as monitored by X-ray diffractograms and ²⁷Al NMR spectra. Consequently, these changes appear to result in increased grain boundary conductivity of the LATP material.

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.

Proton transport in choline dihydrogen phosphate/H3PO4 mixtures

Mixtures of the plastic crystal material choline dihydrogen phosphate [Choline][DHP] and phosphoric acid, from 4.5 mol% to 18 mol% H₃PO₄, were investigated and shown to have significantly higher proton conductivity compared to the pure [Choline][DHP]. This was particularly evident from the electrochemical hydrogen reduction reaction and the proton NMR diffusion measurements, in addition to ionic conductivity measured from the impedance spectroscopy. The ionic conductivity was observed to increase by more than an order of magnitude in phase I (i.e. the highest temperature solid phase in [Choline][DHP]) reaching up to 10⁻² S cm⁻¹. The multinuclear NMR spectroscopy data suggest that, at least on the timescale of the NMR measurement, the H⁺ cations and [DHP] anions are equivalent in both phases. The pulsed field gradient NMR diffusion measurements of the 18 mol% acid sample indicate that all three ions are mobile, however the H⁺ diffusion coefficient is an order of magnitude higher than for the [Choline] cation or the [DHP] anion, and therefore conduction in these materials is dominated by proton conductivity. The thermal stability, as measured by TGA, is unaffected with increasing acid additions and remains high; i.e. no significant mass loss below 200 °C.