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.

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.

Corrosion properties of a RF-magnetron-sputtered TiN coating deposited on 316L stainless steel

The effect of rf-power in the range from 100 to 200 W on the electrochemical properties of TiN coatings deposited on 316L stainless steel was investigated by using various electrochemical techniques in a 3.5-wt\% NaCl solution. Surface analyses were also conducted to analyze the coating characteristics. X-ray diffraction (XRD) and atomic force microscopy (AFM) analyses confirmed that increasing the rf-power led to a preferred orientation of the TiN(200) microstructure and decreased the surface roughness. The potentiodynamic test results confirmed the passive behavior of all of the specimens with low passive current densities and demonstrated that the effective pitting resistance of the TiN coatings increased with increasing rf-power. The electrochemical impedance spectroscopy (EIS) tests showed that the TiN films deposited with high rf-power had excellent corrosion resistance during an immersion time of 720 h due to their high total resistance and low porosity.

Effect of aluminum on the corrosion resistance of low-alloy steel in 10wt% sulfuric acid solution

The aqueous corrosion behavior of low-alloy steel with aluminum contents was examined in a 10 wt% H₂SO₄ (pH 0.13) solution using electrochemical techniques and surface analyses. The corrosion resistance of the new alloy steel was evaluated in terms of electrochemical parameters, such as passive current density, film, and charge transfer resistances. The results showed that a high Al content in the steel imparted better passivation behavior resulting in a lower corrosion rate. It related to the enrichment of iron carbonate and hydrocarbon by the dissolution of the carbide phase.

Corrosion properties of plasma-polymerized methylcyclohexane films using electrochemical methods

Three types of methylcyclohexane (MCH) coating were deposited as interlayer dielectrics on copper using plasma-enhanced chemical vapor deposition (PECVD) at three different RF plasma power levels. The coating performance was then evaluated by an electrochemical im pedance spectroscopy (EIS) and a potentiodynamic polarization test in 3.5 wt.% NaCl solution. An atomic force microscopy (AFM) and Fourier transform infrared reflection (FT-IR) spectroscopy were also conducted to analyze the coatings. The MCH coatings showed a lower corrosion rate than the copper substrate in the potentiodynamic tests. The EIS results showed that the corrosion resistance of the coatings increased with an increasing plasma power. Thus, the MCH films with an increasing plasma power improved the corrosion resistance due to the formation of a low-porosity coating, the enhanced formation of C−H, C−C, and C≡C stretching configurations, and the improved smooth surfaces.

Electrochemical behavior of CrN coating for polymer electrolyte membrane fuel cell

CrN films on a bipolar plate in polymer electrolyte membrane fuel cells have several advantages owing to their excellent corrosion resistance and mechanical properties. Three CrN samples deposited at various radio frequency (RF) powers by RF magnetron sputtering were evaluated under potentiodynamic, potentiostatic and electrochemical impedance spectroscopy conditions. The electrochemical impedance spectroscopy data were monitored for 168 h in a corrosive environment at 70 °C to determine the coating performance at +600 mV_SCE under simulated cathodic conditions in a polymer electrolyte membrane fuel cell. The electrochemical behavior of the coatings increased with decreasing RF power. CrN films on the AISI 316 stainless steel substrate showed high protective efficiency and charge transfer resistance, i.e. increasing corrosion resistance with decreasing RF power. X-ray diffraction confirmed the formation of a CrN(200) preferred orientation at low RF power.

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.

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.

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.

Potentiostatic control of ionic liquid surface film formation on ZE41 magnesium alloy

The generation of potentially corrosion-resistant films on light metal alloys of magnesium have been investigated. Magnesium alloy, ZE41 [Mg−Zn−Rare Earth (RE)-Zr, nominal composition 4 wt % Zn, 1.7 wt % RE (Ce), 0.6 wt % Zr, remaining balance, Mg], was exposed under potentiostatic control to the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate, denoted [P_6,6,6,14][DPP]. During exposure to this IL, a bias potential, shifted from open circuit, was applied to the ZE41 surface. Electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA) were used to monitor the evolution of film formation on the metal surface during exposure. The EIS data indicate that, of the four bias potentials examined, applying a potential of −200 mV versus OCP during the exposure period resulted in surface films of greatest resistance. Both EIS measurements and scanning electron microscopy (SEM) imaging indicate that these surfaces are substantially different to those formed without potential bias. Time of flight-secondary ion mass spectrometry (ToF-SIMS) elemental mapping of the films was utilized to ascertain the distribution of the ionic liquid cationic and anionic species relative to the microstructural surface features of ZE41 and indicated a more uniform distribution compared with the surface following exposure in the absence of a bias potential. Immersion of the treated ZE41 specimens in a chloride contaminated salt solution clearly indicated that the ionic liquid generated surface films offered significant protection against pitting corrosion, although the intermetallics were still insufficiently protected by the IL and hence favored intergranular corrosion processes.

The effect of potential bias on the formation of ionic liquid generated surface films on Mg alloys

An electrochemical approach to the formation of a protective surface film on Mg alloys immersed in the ionic liquid (IL), trihexyl(tetradecyl)phosphonium–bis 2,4,4-trimethylpentylphosphinate, was investigated in this work. Initially, cyclic voltammetry was used with the Mg alloy being cycled from OCP to more anodic potentials. EIS data indicate that, under these circumstances, an optimum level of protection was achieved at intermediate potentials (e.g., 0 or 0.25 V versus Ag/AgCl). In the second part of this paper, a small constant bias was applied to the Mg alloy immersed in the IL for extended periods using a novel cell design. This electrochemical cell allowed us to monitor in situ surface film formation on the metal surface as well as the subsequent corrosion behaviour of the metal in a corrosive medium. This apparatus was used to investigate the evolution of the surface film on an AZ31 magnesium alloy under a potential bias (between ±100 mV versus open circuit) applied for over 24 h, and the film evolution was monitored using electrochemical impedance spectroscopy (EIS). A film resistance was determined from the EIS data and it was shown that this increased substantially during the first few hours (independent of the bias potential used) with a subsequent decrease upon longer exposure of the surface to the IL. Preliminary characterization of the film formed on the Mg alloy surface using ToF-SIMS indicates that a multilayer surface exists with a phosphorous rich outer layer and a native oxide/hydroxide film underlying this. The corrosion performance of a treated AZ31 specimen when exposed to 0.1 M NaCl aqueous solution showed considerable improvement, consistent with electrochemical data.

Corrosion inhibition of 7000 series aluminium alloys with cerium diphenyl phosphate

Cerium diphenyl phosphate (Ce(dpp)3) has previously been shown to be a strong corrosion inhibitor for aluminium-copper magnesium alloy AA2024-T3 and AA7075 in chloride solutions. Surface characterisation including SEM and ToF-SIMS coupled with electrochemical impedance spectroscopy (EIS) measurements are used to propose a mechanism of corrosion inhibition which appears to involve the formation of a complex oxide film of aluminium and cerium also incorporating the organophosphate component. The formation of a thin complex film consisting of hydrolysis products of the Ce(dpp)3 compound and aluminium oxide is proposed to lead to the observed inhibition. SEM analysis shows that some intermetallics favour the creation of thicker deposits predominantly containing cerium oxide compounds.

A single-step synthesized cobalt-free barium ferrites-based composite cathode for intermediate temperature solid oxide fuel cells

Cobalt-free perovskite cathode with excellent oxygen reduction reaction (ORR) properties below 800 °C is a key material toward wide implementation of intermediate-temperature solid oxide fuel cells. This work reports the phase structure, microstructure and performance of such cathode based on the composite phases of triclinic Ba0.9Bi0.1FeO3-δ, cubic BaFeO3 and orthorhombic BaFe2O4 prepared by sol–gel route. The resultant barium ferrites composite cathode exhibits uniform particles, pores and elements distribution. In particular, favorable ORR properties of this cathode is demonstrated by very low interfacial resistance of only 0.036 and 0.072 Ω cm2 at 750 and 700 °C and maximum power density of 1295 and 840 mW cm−2 at 750 and 700 °C.