Characterisation and impedance spectroscopy of substituted Li1.3Al0.3Ti1.7(PO4)3−x(ZO4)x (Z=V, Nb) ceramics*1

Lithium ion conducting ceramics based on the lithium aluminium titanium phosphate (LATP) NASICON structure have been prepared with various substitutions of the phosphorous. The effect of the processing method has been shown to be the key factor in determining the conductivity, both bulk and grain boundary, as well as the conductivity trends observed as a function of substitution.

Use of electrochemical impedance spectroscopy for study of CO2 corrosion prevention by batch treatment inhibitor films

Electrochemical impedance spectroscopy (EIS) was used to study and evaluate commercial batch treatment inhibitors which are used for protecting oil wells, gas wells, and pipelines from CO2 corrosion, focusing on the evaluation of inhibitor film persistency. It was found that theformation and deterioration of batch treatment inhibitor films were accompanied by typical impedance spectral changes. During the formation of inhibitor films, electrode impedance showed a rapid increase and the Bode phase angle plots also showed a sudden change. Thus, the formation of inhibitor film was a very fast process. During the deterioration of inhibitor films, electrode impedance showed a gradual decrease and the Bode phase angle plots showed changes which characterised the three stages of the inhibitor film deterioration process. The relationships between EIS and corrosion rate are discussed, including comparisons with weight loss measurements. Based on the experimental findings in the present work, a method is suggested for estimating the persistency of inhibitor films by monitoring the characteristic changes in the Bode phase angle plots and by measuring electrochemical charge transfer resistance at the second and third stages of the inhibitor film deterioration process.

Electrochemical impedance spectroscopy and surface characterization techniques to study carbon dioxide corrosion product scales

Electrochemical impedance spectroscopy (EIS) was used to study carbon dioxide (CO2) corrosion product scales and their effects on further CO2 corrosion. Objectives were to determine the suitability of EIS for studying corrosion scales and to investigate the influence of environmental factors on scale formation. EIS provided useful information about protective abilities and electrochemical properties of corrosion scales. CO2 corrosion scales formed at high-temperature and pressure provided better protection than those formed at low-temperature and pressure. The level of protection of the scale formed at higher temperature and pressure increased with exposure time. EIS results were compared with coupon weight-loss measurements. Scales were analyzed using a combination of Fourier transform infrared (FTIR) analysis, x-ray diffraction (XRD), and electron microscopy.

Studies of CO2 corrosion product scales using electrochemical impedance spectroscopy and surface characterisation techniques

Electrochemical impedance spectroscopy (EIS) was used to study carbon dioxide (CO2) corrosion product scales and their effects on further CO2 corrosion. Objectives were to determine the suitability of EIS for studying corrosion scales and to investigate the influence of environmental factors on scale formation. EIS provided useful information about protective abilities and electrochemical properties of corrosion scales. CO2 corrosion scales formed at high-temperature and pressure provided better protection than those formed at low-temperature and pressure. The level of protection of the scale formed at higher temperature and pressure increased with exposure time. EIS results were compared with coupon weight-loss measurements. Scales were analyzed using a combination of Fourier transform infrared (FTIR) analysis, x-ray diffraction (XRD), and electron microscopy

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.

Sodium ion dynamics in a sulfonate based ionomer system studied by 23Na solid-state nuclear magnetic resonance and impedance spectroscopy

A poly(2-acrylamido-2-methyl-1-propane-sulphonate) (PAMPS) ionomer containing both sodium and quaternary ammonium cations functionalised with an ether group, has been characterised in terms of its thermal properties, ionic conductivity and sodium ion dynamics. The ether oxygen was incorporated to reduce the Na+ association with the anionic sulfonate groups tethered to the polymer backbone, thereby promoting ion dissociation and ultimately enhancing the ionic conductivity. This functionalised ammonium cation led to a significant reduction in the ionomer Tg compared to an analogue system without an ether group, resulting in an increase in ionic conductivity of approximately four orders of magnitude. The sodium ion dynamics were probed by 23Na solid-state NMR, which allowed the signals from the dissociated (mobile) and bound Na+ cations to be distinguished. This demonstrates the utility of 23Na solid-state NMR as a probe of sodium dynamics in ionomer systems.

Electrochemical impedance spectroscopy as a tool to measure cathodic disbondment on coated steel surfaces: capabilities and limitations

The disbondment of protective organic coatings under excessive cathodic protection potentials is a widely reported coating failure mechanism. Traditional methods of evaluating cathodic disbondment are based on ex situ visual inspection of coated metal surfaces after being exposed to standard cathodic disbondment testing conditions for a long period of time. Although electrochemical impedance spectroscopy (EIS) has been employed as an effective means of evaluating various anti-corrosion properties of organic coatings; its application for assessing the cathodic disbondment resistance of coatings has not been sufficiently exploited. This paper reports an experimental study aimed at developing EIS into a tool for in situ measurement and monitoring of cathodic disbondment of coatings. A clear correlation between EIS parameters and the disbonded coating areas has been confirmed upon short term exposure of epoxy-coated steel electrodes to cathodic disbondment conditions; however the degree of this correlation was found to decrease with the extension of exposure duration. This observation suggests that EIS loses its sensitivity with the propagation of coating disbondment, and that in order to achieve quantitative determination of the coating cathodic disbondment localized EIS measurements are required to measure the parameters related to local disbonded areas.

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.

An electrochemical impedance study of ionic liquid film formation and aqueous corrosion of magnesium alloy ZE41

Ionic liquid surface treatments are proposed as a method of controlling corrosion processes on magnesium alloys. An important magnesium alloy, ZE41 (nominally 4% Zn and 1% rare earth), was treated with the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate (P₆₆₆₁₄DPP). Impedance spectra were acquired at intervals during the treatment, indicating the development of a film and allowing a measure of the film formation process to be obtained over time. Mechanically polished and electro-polished surfaces were prepared; these surfaces, treated and untreated, were subsequently exposed to 0.1 M NaCl aqueous solutions. The corrosion behavior of the prepared surfaces were assessed using impedance spectroscopy and optical microscopy. The results indicated a significant role for the method of surface preparation used and, in both cases, the ionic liquid treatment produced a more corrosion-resistant surface.