Absolute values of instantaneous corrosion rates by faradaic rectification

Doss and Agarwal 1 discovered the "redoxokinetic effect" which is now familiarly known as faradaic rectification. Subsequently, the theory and applications of faradaic rectification due to a single electrode reaction have been developed by several workers 2-5. The theory and application of faradaic rectification in the case of a corrosion cell sustaining mixed electrode reactions on a corroding metal was reported recently 6"7. This led to the development of a new electrochemical method of corrosion rate determination. It was shown that changes in the instantaneous corrosion rates of a metal are readily evaluated by faradaic rectification measurements at the corrosion potential of the metal in a given medium. The aim of the present work is to show that absolute values of instantaneous corrosion rates may also be obtained by the new method under certain conditions. The practical advantages that arise from this development are pointed out.

The electrochemical corrosion behaviour of quaternary gold alloys when exposed to 3.5% NaCl solution

Lower carat gold alloys, specifically 9 carat gold alloys, containing less than 40 % gold, and alloying additions of silver, copper and zinc, are commonly used in many jewellery applications, to offset high costs and poor mechanical properties associated with pure gold. While gold is considered to be chemically inert, the presence of active alloying additions raises concerns about certain forms of corrosion, particularly selective dissolution of these alloys. The purpose of this study was to systematically study the corrosion behaviour of a series of quaternary gold–silver–copper–zinc alloys using dc potentiodynamic scanning in saline (3.5 % NaCl) environment. Full anodic/cathodic scans were conducted to determine the overall corrosion characteristics of the alloy, followed by selective anodic scans and subsequent morphological and compositional analysis of the alloy surface and corroding media to determine the extent of selective dissolution. Varying degrees of selective dissolution and associated corrosion rates were observed after anodic polarisation in 3.5 % NaCl, depending on the alloy composition. The corrosion behaviour of the alloys was determined by the extent of anodic reactions which induce (1) formation of oxide scales on the alloy surface and or (2) dissolution of Zn and Cu species. In general, the improved corrosion characteristics of alloy #3 was attributed to the composition of Zn/Cu in the alloy and thus favourable microstructure promoting the formation of protective oxide/chloride scales and reducing the extent of Cu and Zn dissolution.

The influence of pH on the corrosion of medium strength aerospace alloys 8090, 2091 and 2014

The influence of pH on the corrosion behaviour of two aluminium-lithium-copper-magnesium-zirconium (8090 and 2091) alloys was studied and compared with a standard aircraft alloy, 2014 (Al-4.4% Cu) and 99.9% pure Al. In constant exposure and potentiodynamic polarization studies conducted in 3.5% NaCl solution having different pH values, all the alloys exhibited high corrosion rates in acidic and alkaline environments, with a minimum in less hostile environments close to neutral pH. The pitting potentials for aluminium-lithium alloys were slightly lower than those for 2014 and pure Al. The effect of pH on the passive current density was also less for aluminium-lithium alloys.

Corrosion of 310 stainless steel in H2 H2O-H2S gas mixtures; studies at constant temperature and fixed oxygen potential

Corrosion of SAE 310 stainless steel in H2-H2O-H2S gas mixtures was studied at a constant temperature of 1150 K. Reactive gas mixtures were chosen to yield a constant oxygen potential of approximately 6 × 10-13 Nm-2 and sulfur potentials ranging from 0.19 × 10-2 Nm-2 to 33 × 10-2 Nm-2. The kinetics of corrosion were determined using a thermobalance, and the scales were analyzed using metallography, scanning electron microscopy, and energy dispersive X-ray analysis. Two corrosion regimes, which were dependent on sulfur potential, were identified. At high sulfur potentials (P S 2 ± 2.7 × 10-2 Nm-2) the corrosion rates were high, the kinetics obeyed a linear rate equation, and the scales consisted mainly of sulfide phases similar to those observed from pure sulfidation. At low sulfur potentials (P S 2 ± 0.19 × 10-2 Nm-2) the corrosion rates were low, the kinetics obeyed a parabolic rate equation, and scales consisted mainly of oxide phases. Thermochemical diagrams for the Fe-Cr-S-O, Fe-Ni-S-O, Cr-Ni-S-O, and Si-Cr-S-O systems were constructed, and the experimental results are discussed in relation to these diagrams. Based on this comparison, reasonable corrosion mechanisms were developed. At high sulfur potentials, oxide and sulfide phases initially nucleate as separate islands. Overgrowth of the oxide by the sulfide occurs and an exchange reaction governs the corrosion process. Preoxidation at low oxygen potentials and 1150 K is beneficial in suppressing sulfidation at high sulfur potentials.

Effect of sulphide on corrosion of copper in seawater

The corrosion of ETP copper in natural seawater and putrid seawater has been studied. The corrosion rates and the sulphide content were monitored at regular intervals. In the absence of oxygen in the putrid media, the presence of sulphide favoured a reduction in the corrosion rate.

Corrosion behaviour of steel in beach soil along Bohai Bay

Research on corrosion of steel structures in various marine environments is essential to assure the safety of structures and can effectively prolong their service life. In order to provide data for anticorrosion design of oil exploitation structures in the Bohai Bay, the corrosion behaviour and properties of steel in beach soil, using typical steel samples (Q235A carbon steel and API 5Lx52 pipeline steel) buried 0.5, 1.0 and 1.5 m deep under typical beach soils in Tanggu, Yangjiaogou, Xingcheng, Yingkou and Chengdao for 1-2 years were studied. The carbon steel and pipeline steel were both corroded severely in the beach soil, with the form of corrosion being mainly uniform with some localised attack (pitting corrosion). The corrosion rate of the carbon steel was up to 0.16 mm/year with a maximum penetration depth of 0.76 mm and that of the pipeline steel was up to 0.14 mm/year, with a maximum penetration depth of 0.53 mm. Compared with carbon steel, the pipeline steel generally had better corrosion resistance in most test beach soils. The corrosion rates and the maximum corrosion depths of carbon steel and pipeline steel were in the order: Tanggu>Xingcheng>Chengdao>Yingkou>Yangjiaogou with corrosion altering with depth of burial. The corrosion of steel in the beach soil involves a mixed mechanism with different degrees of soil aeration and microbial activity present. It is concluded that long term in situ plate laying experiments must be carried out to obtain data on steel corrosion in this beach soil environment so that the effective protection measures can be implemented.

Study on steel corrosion in different seabed sediments

A series of simulation experiments on carbon steel (A(3) steel) and low alloy steel (16 Mn steel) in marine atmosphere (MA), seawater (SW) and seabed sediment (SBS) including rough sea sand, fine sea sand and seabed mud were carried out indoors for a year or so by means of individually hanging plates (IHP) and electrically connected hanging plates (ECHP). The corrosion of steels in SBS was mainly due to the macrogalvanic cell effect. The steel plates at the bottom of SBS, as the anode of a macrogalvanic cell, showed the heaviest corrosion with a corrosion rate of up to 0.12 mm/a, approximately equal to that of steel plates in marine atmosphere. The test results showed that the corrosion rates of A(3) and 16 Mn steel in marine environment were in the order: MA > SW > SBS by the IHP method; and MA > SBS > SW by the ECHP method. The corrosion rates of steels in the water/sediment interface were directly proportional to the grain size of the SBS by the ECHP method, but those of steels in the water/sediment interface did not vary with the grain size of SBS by the IHP method. The corrosion rate of low-alloy steel was a little higher than that of carbon steel. The results of this study have important applications for design of offshore steel structures such as oil platform, pier, and port.

Alloy elements' effect on anti-corrosion performance of low alloy steels in different sea zones

The corrosion rate of low alloy steel in different sea zones has close correlation with the content of the alloy element. From the field data of steel corrosion rates in atmospheric zone, splash zone and immersion zone, regression analysis was used to study the correlation between the corrosion rate of steels and the amount of added alloy elements. Three regression equations were obtained in different sea zones. Based on the equations, the anti-corrosion performance of the alloy elements can be deduced which can be used to screen out low alloy steel with good anti-corrosion performance. (C) 2007 Elsevier B.V. All rights reserved.

Influence of micro and macro cracks due to sustained loading on chloride-induced corrosion of reinforced concrete beams

Chloride-induced corrosion of steel is one of the most commonly found problems affecting the durability of reinforced concrete structures in both marine environment and where de-icing salt is used in winter. As the significance of micro-cracks on chloride induced corrosion is not well documented, 24 reinforced concrete beams (4 different mixes - one containing Portland cement and another containing 35% ground granulated blastfurnace slag at 0.45 and 0.65 water-binder ratios) were subjected to three levels of sustained lateral loading (0%, 50% and 100% of the load that can induce 0.1 mm wide cracks on the tension surface of beam - F_0.1) in this work. The beams were then subjected to weekly cycles of wetting with 10% NaCl solution for 1 day followed by 6 days of drying at 20 (±1) °C up to an exposure period of 60 weeks. The progress of corrosion of steel was monitored using half-cell potential apparatus and linear polarisation resistance (LPR) test. These results have shown that macro-cracks (at load F_0.1) and micro-cracks (at 50% of F_0.1) greatly accelerated both the initiation and propagation stages of the corrosion of steel in the concrete beams. Lager crack widths for the F_0.1 load cases caused higher corrosion rates initially, but after about 38 weeks of exposure, there was a decrease in the rate of corrosion. However, such trends could not be found in 50% F _0.1 group of beams. The extent of chloride ingress also was influenced by the load level. These findings suggest that the effect of micro-cracking at lower loads are very important for deciding the service life of reinforced concrete structures in chloride exposure environments. © 2014 4th International Conference on the Durability of Concrete Structures.

Corrosion by sulfate reducing bacteria that utilize nitrate

16S rRNA gene sequencing was used to identify a sulfate-reducing bacterium (SRB) from a Danish North Sea oilfield water injection system. This species was cultivated, purified and subsequently identified as being >97% similar to Desulfovibrio gracilis. Like some other Desulfovibrio species this SRB, strain OP102, could reduce nitrate as an electron acceptor and produce ammonia in the absence of sulfate. In addition, in the presence of sulfate, when nitrate was dosed at 100 mg/l it was again reduced by the bacterium, with some ammonium production. Therefore, this mechanism could be important in oilfield systems where nitrate is applied to prevent sulfide generation by SRB which leads to reservoir souring. In static tests the influence of this Desulfovibrio on corrosion was assessed using carbon steel coupons, in the presence of sulfate and in the presence of sulfate with 100 mg/l nitrate. Corrosion rates were less than 1.5 mpy when coupons were incubated in the same water, with sulfate and with nitrate. Furthermore, the occurrence of pitting corrosion was fairly low under all circumstances.

Monitoring pitting-crevice corrosion using the WBE-noise signatures method

An electrochemically integrated multi-electrode array namely the wire beam electrode (WBE) and noise signatures analysis have been applied in novel combinations to study crevice corrosion behaviour in the presence of pits. Characteristic electrochemical noise signatures were found to correlate with characteristic changes in WBE current distribution maps, which indicate corrosion rates distributions, corrosion patterns and the degree of pitting and crevice corrosion. Specifically, two characteristic noise patterns were observed: (i) the characteristic noise pattern of quick potential changes towards more negative direction with no recovery (termed noise signature I) was found to correspond with the initiation and stabilization of the anode inside crevice; and (ii) the characteristic noise pattern of the cyclic potential oscillation at a constant frequency (termed noise signature II) was found to correspond with the stable anodic dissolution in the occluded cavity site in WBE current distribution maps. A new parameter namely the localization parameter (LP) has been proposed to describe the degree of localization. The LP for crevice corrosion was found to be low compared to that for pitting corrosion.

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.

Review of critical issues in carbon dioxide corrosion testing and monitoring techniques

This paper presents a brief review of major techniques applied in carbon dioxide corrosion testing and monitoring. The focus is on the advantages and disadvantages of variously designed testing apparatus and monitoring devices for localized corrosion detection and assessment. Critical factors affecting the reliability and accuracy of major corrosion testing techniques are briefly discussed. It is concluded that major reasons that lead to reporting of inaccurate corrosion rates and patterns include: (i) limitations in conventional electrochemical and nonelectrochemical methods for localized corrosion measurements, and difficulties in data interpretation; (ii) challenges in simulating localized corrosion mechanisms and their changes with the extension of corrosion testing. Underdeposit corrosion testing is presented as a case to illustrate challenges in simulating localized corrosion processes and mechanisms. Experiment data have been presented to show potential difficulties of the artificial pit electrode method in evaluating underdeposit corrosion and its inhibitors. The wire beam electrode method has been used to study underdeposit corrosion with and without inhibitor present. Several interesting corrosion mechanisms have been revealed at different stages of underdeposit corrosion processes.