钢芯铝绞导线大气腐蚀产物层的结构及腐蚀机理

在模拟大气腐蚀环境中,采用干/湿NaHSO3+NaCl水溶液盐雾试验研究钢芯铝绞(ACSR)导线腐蚀产物的相组成及腐蚀层结构,讨论其腐蚀机理。结果表明:ACSR导线中单股铝线或镀锌钢芯线的腐蚀主要表现为点蚀,腐蚀产物组成复杂,主要为锌和铝的氢氧化物、硫酸盐与氯化物的复式盐;在腐蚀初期,内外层铝股线及钢芯线表面镀锌层开始形成点蚀坑,逐步形成连续的腐蚀层;由于镀锌层和内层铝股线之间构成原电池,因为牺牲阳极效应,镀锌层腐蚀速率最大;而内层铝股线受到保护,腐蚀速率最小,外层铝股线腐蚀速率居中。     

Adsorption characteristics of corrosion inhibitors from corrosion rate measurements

Corrosion rate data have been used for the determination of the adsorption parameters of the Frumkin isotherm in the system steel/acid solution/inhibitor. The inhibitors are derivatives of benzimidazole. The maximal amount of adsorbed inhibitor, the interaction parameter a and the equilibrium constant B of the isotherm are found simultaneously by using the SOLVER option of Excel. The statistical analysis of the results shows that this isotherm describes well the adsorption behaviour in the systems studied.     

Enhanced predictive corrosion modeling with implicit corrosion products

An advanced mathematical approach to describe the influence of corrosion products on the corrosion rate is presented here. The related model can be used as input equation for numerical predictive corrosion simulations or simply as an empirical model, to extrapolate experimental data of corrosion tests to longer times and to interpret the physical parameters behind. This semiempirical model assumes that a constant share of the dissolved metal precipitates on the surface and hinders the diffusion processes. Hence, the effective corrosion rate decreases exponentially with increasing dissolution. The explicit corrosion progress over time is derived by time integration on a newly developed, time dependent corrosion rate equation. The derived expression can be effortlessly implemented in existing for example finite element method, which is demonstrated for the uniform corrosion of a zinc surface. Furthermore, this approach is qualitatively compared with other empirical models for corrosion products and the validity is demonstrated by fitting of experimental data. A very good agreement between experiment and theory can be achieved for various materials and environments considering no change of the driving corrosion mechanism.     

Marine corrosion

Abstract

The accelerating effect of nitrates on the dissolution of tin sometimes observed in tinplate cans of acid products has been investigated by measurements of cathodic polarisation and by direct measurements of corrosion rate in oxygen-free solutions of sulphates and organic acids. The rate of reduction of nitrate, and hence the corrosion rate, increased as the corrosion potential of tin became more positive, possibly as a result of potential dependence of nitrate adsorption on tin. This finding may explain the known influences of pH, of dissolved tin and of the nature of the organic acids present, on the stimulation of corrosion produced by nitrate. The addition of anionic surface active agents created a negative shift of potential and inhibited corrosion but cationic agents caused a positive shift and stimulated corrosion. Sodium lauryl sulphate had a strong inhibitive effect at a concentration of 5 ppm and at 30 ppm almost completely suppressed the effect of nitrate.     

A new perspective on measuring the corrosion rate of localized corrosion

Many corrosion phenomena are nonuniform, which means that anodic and cathodic locations are spatially separated. An example is macrocell corrosion of steel in concrete. Under these conditions, determining the corrosion rate from polarization resistance measurements and using the Stern–Geary equation is fundamentally not possible. We present a novel theoretical approach for the interpretation of galvanostatic pulse measurements, to make them applicable as a method for corrosion rate measurements in situations of localized corrosion. Experiments show that it is important to consider that (a) only a fraction of the applied current flows through the anode of the macrocell, and (b) this current is not constant over time. We propose an approach to quantify and consider these two effects, based on information generally accessible in condition assessment of concrete structures. Our results show that galvanostatic pulse measurements are a robust method to determine the corrosion current. With the traditional empirical approach, the measurement error was generally below factor 3, and occasionally up to factor 10. With the novel approach, this error could be reduced to a factor of maximum 2 in all cases.     

Localised effects of macrofouling species on electrochemical corrosion of corrosion resistant alloys

Abstract

Interactions between macrofouling and corrosion have been studied on two duplex stainless steels (UNS S31803 and UNS S32760), an austenitic stainless steel (UNS S31354), a nickel base alloy (UNS N06625), and a cobalt base alloy (UNS R30006) in long term tests conducted in natural sea water off the west coast of Scotland. After an 18 month exposure period, the specimens were heavily fouled primarily with barnacles and mussels and all the materials exhibited crevice corrosion at the specimen/resin interface, although this was less extensive on the nickel base alloy. Localised corrosion was observed under the base of live barnacles on UNS S31603 stainless steel. Direct current electrochemical anodic polarisation tests undertaken after the 18 month exposure period yielded unusually high currents in the range of potentials between the free corrosion value and the breakdown potential. However, long term exposure and associated macrofouling had little effect on the overall breakdown of general surface passivity as indicated by values of the breakdown potential. The higher currents were associated with the appearance, after the anodic polarisation, of black sulphide corrosion products at the specimen/resin crevices, around barnacles, and around mussel byssus threads.     

Novel images of the evolution of stress corrosion cracks from corrosion pits

SCC in turbine disc steels exposed to simulated steam-condensate tends to nucleate preferentially from corrosion pit precursors. The evolution of these cracks is not straightforward and not well understood. In this work, unique three-dimensional X-ray microtomographic images have confirmed that cracks develop predominantly at the shoulder of the pit, near the pit/surface interface, for specimens stressed to 50–90% σ_0.2. In support of this observation, FEA of model pits indicate that strain is a maximum on the pit wall just below the pit mouth. Implications of these observations for the pit-to-crack transition and predictive-modelling of crack nucleation and growth are discussed.     

Anodic polarisation measurements of corrosion and corrosion inhibition of Steel in concrete

Abstract

Anodic polarisation experiments were carried out on steel in concrete. The effects of surface treatment of the steel, medium of curing, as well as durations of curing were investigated.

Corrosion of steel in concrete due to the presence of the corroding chloride ions, either added to the mixing water or diffusing from the external attacking medium, was also investigated. The chloride ions when present in the mixing water are more effective in destroying the passivation of steel than when present in the outside medium. In the former case a minimum concentration of 1 % is required for this action, while in the latter case 4% is required.

Anodic corrosion inhibitors like nitrite, chromate, phosphate, benzoate and silicate were tried in order to suppress the action of the corrodent. The minimum concentration required of the inhibitor to stifle the corrosion is generally lower in the case when it is added to the mixing water of concrete. Possible mechanisms of corrosion and corrosion inhibition are discussed in the light of the current views on both processes.     

AC corrosion. Part 2: Parameters influencing corrosion rate

Pipelines and AC power transmission lines frequently share corridors leading to AC interference corrosion problems, as documented by pipeline failures that have occurred in the USA, Canada and Europe, even when cathodic protection is applied. In order to investigate these phenomena, weight loss tests on carbon steel samples were performed in soil-simulating conditions (aerated and de-aerated sulphate solutions) at various AC current densities from 10 to about 900 A/m². Tests on freely corroding samples showed that the corrosion rate increased as AC current density increased; the effect of AC on corrosion rate was also detected at current densities lower than 30 A/m². The results obtained are analyzed and discussed together with polarization test results, which were presented in a previous paper by Goidanich et al. (submitted for publication) [1].     

Study on corrosion of steels in marine environment by corrosion simulation device

Three kinds of steels were studied using electrically connected hanging specimen in the corrosion simulation device and offshore long scale hanging specimen. The experimental results obtained by the two methods show that the device can better reflect the offshore corrosion environment. A Ni‐Cu‐P steel specimen was studied through analysis of the specimen's corrosion products and corrosion types. The surface of the samples before and after the removal of the rust layer produced by these two methods were observed and compared after some experiments. The microstructure of the corrosion products under different marine environments were analyzed and compared through IR. It indicated good correlation between the electrically connected hanging specimen method and the long scale hanging specimen method.     

Modelling of reinforcement corrosion – geometrical effects on macrocell corrosion

Reinforcement corrosion is still the most frequent reason for damage of concrete structures. It can be caused by carbonation or the ingress of chlorides. In cases of localized contaminations with chlorides, macrocells with very high corrosion rates can be established. Thereby the resulting macrocell current is dependent on many different boundary conditions like driving voltage, concrete resistivity and the geometrical arrangement of anode and cathode. In order to investigate macrocell corrosion, the herein presented research work was carried out by laboratory experiments and additionally by numerical analyses. First the numerical simulations were calibrated by laboratory measurements and thereafter, a numerical parameter study was carried out to increase the available database and identify the impact of changes in single parameters. As the focus is on geometrical effects, all laboratory specimens and numerical models were designed to represent practical conditions with diverse geometrical arrangements, e.g., slabs or beams with localized depassivations. In addition, parameters like concrete resistivity, driving voltage and cathode to anode surface area ratios have been varied. Thereafter, all results were used to derive cell factors for a simple macrocell current estimation. The present status of the project will be presented and discussed.     

Monitoring corrosion rates and localised corrosion in low conductivity water

Monitoring of low corrosion rates and localised corrosion in a media with low conductivity is a challenge. In municipal district heating, quality control may be improved by implementing on-line corrosion monitoring if a suitable technique can be identified to measure both uniform and localised corrosion. Electrochemical techniques (LPR, EIS, crevice corrosion current) as well as direct measurement techniques (high-sensitive electrical resistance, weight loss) have been applied in operating plants. Changes in the corrosion processes are best monitored in non-aggressive, low conductivity media with sensitive electrical resistance technique and crevice corrosion current measurements.     

Antibacterial drugs as corrosion inhibitors for corrosion of aluminium in hydrochloric solution

The corrosion behavior of aluminium in 2 M HCl solution in the absence and presence of four compounds of antibacterial drug was investigated using hydrogen evolution, weight loss, and potentiostatic polarization techniques. It was found that, the inhibition efficiency of these compounds depends on their concentration and chemical structure. The inhibitive action of these compounds was discussed in terms of blocking the electrode surface by adsorption of the molecules through the active centers contained in their structure. The adsorption process follows Langmuir adsorption isotherm. The effect of temperature on the rate of corrosion in the absence and presence of these compounds was also, studied. Some activated thermodynamic parameters were computed.     

Co-operative corrosion phenomena

The corrosion of aluminium alloy 2024-T3 (AA2024-T3) was studied as a function of immersion time from 2.5 to 120 min in 0.1 M aqueous NaCl solution. At immersion times as short as 5 min, rings of corrosion product of 100 to 200 μm diameter, containing smaller domes of corrosion product, were observed using SEM. The domes of corrosion product had greater chloride concentrations than elsewhere on the surface and represented sites of anodic attack. As the immersion time was increased, significant grain boundary attack was observed within the rings of corrosion product. Analyses of Particle Induced X-ray Emission (PIXE) maps of the corroded surfaces showed a significantly higher number of IM particles around the chloride attack sites than the average particle density for the maps, indicating clustering of IM particles. These results suggest a co-operative corrosion effect as a result of clustering of the IM particles. A mechanism for the generation of the corrosion rings is discussed.     

The role of rusts in corrosion and corrosion protection of iron and steel

The processes of atmospheric corrosion of iron and steel and the properties of corrosion products (rusts) are modeled based on a quantitative evaluation of the chemical reactions pertaining to corrosion to elucidate the conditions with which corrosion-protective rust films form. Based on the model, it is suggested that in the initial stage of corrosion, in the rusts, the pH of the aquatic system is maintained at 9.31 owing to an equilibrium with iron(II) hydroxide and the rate of air-oxidation at this pH is very fast, and that dense, self-repairing rust films form, protecting the underlying iron and steel. However, after corrosion stops, the rust film deteriorates due to the dissolution and shrinkage by aging, and the deteriorated rust film separates the anode and cathode reaction products (Fe²⁺ and OH⁻ ions) to cause crevice corrosion. The air-oxidation of iron(II) in anode channels without the presence of OH⁻ ions results in strongly acidic solutions (pH 1.41), causing acid-corrosion. It is proposed that good catalysts (e.g. copper(II) and phosphate ions) accelerate the air-oxidation at low pH, delaying the crevice- and acid-corrosion stages. Further, it is argued that iron compounds with negative charges due to the non-stoichiometric proportions of the lattice oxide ions and metal ions (solid oxoanions of iron) exhibit stable cation-selective permeability even with a drop in pH. Rust films including such compounds would stop the passage of aggressive anions and act to protect iron and steel.