On-line corrosion monitoring in geothermal district heating systems. I. General corrosion rates

General corrosion rates in the geothermal district heating systems in Iceland are generally low, of the magnitude 1 μm/y. The reason is high pH (9.5), low-conductivity (200 μm/y) and negligible dissolved oxygen. The geothermal hot water is either used directly from source or to heat up cold ground water. The fluid naturally contains sulphide, which helps keeping the fluid oxygen-free but complicates the electrochemical environment. In this research on-line techniques for corrosion monitoring were tested and evaluated in this medium. Electrochemical methods worked well as long as frequency was kept low but ER worked better if oxygen was present.     

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.     

Passivation techniques to prevent corrosion of iron sulphides in roofing slates

The aim of the present study was to evaluate the efficacy of different methods of sulphide microencapsulation in terms of inhibiting sulphide oxidation in roofing slate. For this, a preliminary test was carried out with ground pyrite and the methods that provided the best results were applied to samples of roofing slate. Protection against oxidation was measured by the amount of iron released after enforced oxidation with H₂O₂ in the tests with pyrite, and by thermal cycle alteration, SO₂ and saline spray tests (EN 12326-2:2000 and EN 14147:2004) in the tests with the slate samples. The results indicate that treatments with potassium phosphate and potassium silicate, proposed for controlling acid mine drainage, were the most effective at protecting pyrite against oxidation, and that these methods are also effective when applied to slate.     

Effect of microcrystallization on pitting corrosion of pure aluminium

A microcrystalline aluminium film with grain size of about 400 nm was prepared by magnetron sputtering technique. Its corrosion behaviour was investigated in NaCl containing acidic solution by means of potentiodynamic polarization curves and electrochemical noise (EN). The polarization results indicated that the corrosion potential of the sample shifted towards more positive direction, while its corrosion current density decreased compared with that of pure coarse-grain Al. The EN analysis based on stochastic model demonstrated that there existed two kinds of effect of microcrystallization on the pitting behaviour of pure aluminium: (1) the rate of pit initiation is accelerated, (2) the pit growth process was impeded. This leads to the enhancement of pitting resistance for the microcrystallized aluminium.     

The influence of the cathodic process on the interpretation of electrochemical noise signals arising from pitting corrosion of stainless steels

The use of electrochemical noise (EN) measurements for the investigation and monitoring of corrosion has allowed many interesting advances in the corrosion science in recent years. A special advantage of EN measurements includes the possibility to detect and study the early stages of localized corrosion. Nevertheless, the understanding of the electrochemical information included in the EN signal is actually very limited. The role of the cathodic process on the EN signals remains uncertain and has not been sufficiently investigated to date. Thus, an accurate understanding of the influence of the cathodic process on the EN signal is still lacking. On the basis of different kinetics of the oxygen reduction it was established that the anodic amplitude of transients arising from pitting corrosion on stainless steel can be decreased by the corresponding electron consumption of the cathodic process. Therefore, the stronger the electron consumption, the weaker the anodic amplitude of the EN signal becomes. EN signals arising from pitting corrosion on stainless steel can be measured because the cathodic process is inhibited by the passive layer. This was confirmed by means of EN measurements under cathodic polarisation. Since the cathodic process plays a decisive role on the form of transients arising from pitting corrosion, its influence must be considered in the evaluation and interpretation of the EN signals.     

EN, EIS and polarization studies to evaluate the inhibition effect of 3H-phenothiazin-3-one, 7-dimethylamin on mild steel corrosion in 1 M HCl solution

The corrosion inhibition effect of 3H-phenothiazin-3-one, 7-dimethylamin as a new inhibitor was studied using different electrochemical and weight loss methods. It was found that this compound acts as a strong inhibitor for mild steel in 1 M HCl even at very low concentration (1 ppm). Results showed that this compound acts as a mixed type inhibitor. As the inhibitor concentration increased, the charge transfer resistance of mild steel increased and double layer capacitance decreased. The results of EN measurements after trend removal were in good agreement with other methods results. It was found that this inhibitor acts through adsorption on the metal surface. Also, adsorption obeys the Langmuir isotherm.     

Surface chemistry and corrosion behaviour of 304 stainless steel in simulated seawater containing inorganic sulphide and sulphate-reducing bacteria

Although many studies have been carried out regarding the role of sulphide anions in promoting microbial corrosion of various metal substrates, very little is known about the differences between inorganic sulphide and biogenically-derived sulphide by sulphate-reducing bacteria (SRB) and what the reasons for differing corrosion behaviour between the two types of sulphide may be towards common metals. In this study, various electrochemical and surface analytical techniques were employed to study the effect of the inorganic and biogenic sulphide (active SRB present) on the surface chemistry and corrosion behaviour of 304 stainless steels in a simulated seawater-based modified Baar’s (SSMB) medium. Clear differences in the surface chemistry of the sulphurised passive film by inorganic and biogenic sulphide (active SRB present) were quantified by X-ray photoelectron spectroscopy (XPS). The transformation of metal sulphides in abiotic and biotic sulphide solutions with the exposure time was correlated with different corrosion behaviour of 304 stainless steels.     

Effect of heat treatment on H2S corrosion of a micro-alloyed C–Mn steel

The H₂S corrosion resistance of a C–Mn pipeline steel with three different microstructures has been evaluated using electrochemical techniques with a 3% wt. NaCl solution at 50 °C. Microstructures included martensite, ferrite, and ferrite + bainite. Electrochemical techniques included potenthiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR), and electrochemical noise (EN) measurements. Most of the tests lasted 24 h. All techniques showed that the highest corrosion rate corresponded to the steel with a martensitic microstructure; up to one order of magnitude higher than the corrosion rate for steels with a ferritic + bainitiic microstructure, whereas the steel with the ferritic microstructure showed the lowest corrosion rate. EIS tests showed that the corrosion process was under charge transfer control, whereas EN results indicated that the three steels exhibited a clear tendency towards a localized type of corrosion. However, for longer immersion times, the steel with a martensitic microstructure tended to exhibit a mixture of uniform and localized attack. Results were discussed in terms of grain size, grain boundary energy, amount and distribution of particles found in each steel.     

Detection of corrosion degradation using electrochemical noise (EN): review of signal processing methods for identifying corrosion forms

Electrochemical noise (EN), as one of the most promising in situ electrochemical methods in corrosion and electrochemical science, has been developing rapidly in recent years with the advancements in instrumentation and signal processing methods. One advantage of EN is its application in long-term or early stage corrosion process monitoring because it instantly detects corrosion rate and corrosion forms. Investigators have applied various mathematical methods to extract characteristic parameters from EN. In this paper, identifying corrosion forms using parameters obtained from time domain, frequency domain and time–frequency domain is reviewed, and the correlation between parameters and corrosion forms is discussed. Finally, other in situ techniques are recommended to be employed synchronously with EN measurement in order to obtain reliable analyses.     

Application of LPR and EIS techniques for on-site corrosion monitoring at the geothermal plant in Central Poland

Corrosion monitoring station was installed at ‘Geotermia Mazowiecka’ geothermal plant in Poland. Linear polarisation resistance and electrochemical impedance spectroscopy techniques were applied to estimate the corrosion rate and the surface changes of K55 carbon steel, L80-13CR and 316 stainless steels directly in the geothermal water flux. The enhanced corrosion of K55 carbon steel and corrosion rate of L80-13CR and 316 stainless steels was observed. The formation of biofilm increased the resistivity of the surface.     

Evaluation of a fractal analysis technique for corrosion studies

Corrosion tests were performed to obtain electrochemical noise (EN) data during general and pitting corrosion in NaCl solutions for type 316 and 403 stainless steels. The data were analyzed by the Hurst parameter (HP) based on the rescaled range analysis. A correlation of the HP with the noise resistance was found in general corrosion, and the variability in published HP data is in part due to the difference in the value of noise resistance. The variability is also attributed to the difference in the amount of high frequency components in EN data. The HP is, however, a useful parameter for assessing the effectiveness of an inhibitor based on the characteristics of EN spectra, but not for identifying changes in the mode of corrosion in the case where the level of EN is low.     

In situ study of dew point corrosion by electrochemical measurement

Dew point corrosion (DPC) is an electrochemical process in a dynamic electrolyte layer, which makes it difficult to carry out conventional electrochemical measurements and thus is not conducive to corrosion mechanism study. In situ electrochemical measurements including electrochemical impedance spectroscopy (EIS) and electrochemical noise (EN) are realized by a novel DPC simulation set-up and special electrode arrangements in this work. DPC of carbon steel is studied by in situ test method and ex situ test method, respectively. Different corrosion mechanisms are obtained from two methods. Thus, it is significant to study DPC by in situ test method so as to understand DPC essentially.     

Electrochemical study of the corrosion of different alloys exposed to deaerated 80 °C geothermal brines containing CO2

Corrosion of metallic engineering materials accounts for problems during geothermal operation in the Upper Rhine Graben (URG). Herein, we study the electrochemical behaviour of various metal alloys in an 80 °C simulated geothermal environment by using potentiodynamic polarisation and open-circuit potential measurements. Two different natural geothermal waters from URG geothermal sites were used for the experiments. The measurements reveal spontaneous passivation to be a key process for all alloys. This ennoblement protects more noble alloys from significant corrosion (e.g. titanium gr. 2, alloy 625) and brings less noble alloys to failure, mostly due to pitting corrosion (e.g. 316L).     

Evaluation of cavitation erosion–corrosion degradation of mild steel by means of dynamic impedance spectroscopy in galvanostatic mode

Cavitation erosion and corrosion of mild steel was studied by means of a vibratory facility in 3% w/w NaCl solution. Dynamic Electrochemical Impedance Spectroscopy (DEIS) measurements were carried out in the galvanostatic mode to allow on-line monitoring of impedance parameters in cavitation failure. The results, based on an analysis of instantaneous impedance spectra, correspond to degradation under the influence of cavitation erosion–corrosion. It has been shown that a change of pseudo-capacitance corresponds to an increase in sample roughness, while the charge-transfer resistance determines changes in the corrosion rate under the combined mechanical and electrochemical factors.     

On the atmospheric corrosion of thin copper films

Sputtered and electrodeposited copper specimens were exposed to the laboratory atmosphere for 18 months, after which the corrosion products were analysed by electrochemical methods and reflectance spectra. The formation of corrosion products takes place in three stages: initially cuprous oxide is formed, followed by the growth of cuprous sulphide, and finally cuprous oxide is converted to cuprous sulphide. The presence of water is essential for these corrosion reactions to occur.     

Laboratory scale investigation into the corrosion of copper in a sulphur-containing environment

The effect of temperature and gas composition on the corrosion rate and corrosion by-product of copper foil was studied by exposing it to sulphur (S₂), S₂ + hydrochloric acid (HCl) and hydrogen sulphide. The temperature was varied from 80 to 140 °C. Copper foil reacted with S₂ to form CuS, Cu₉S₈ and Cu_1.8S. Corrosion rates ranged from 9.6 μm/h at 110 °C to 0.5 μm/h at 140 °C. The presence of HCl caused pitting and enhanced the corrosion rate above 112 °C. Cu₂S formed when copper was exposed to hydrogen sulphide gas. Sulphide scale that formed was friable and non-adherent.     

Electrochemical noise during non‐stationary corrosion processes

In the present work, electrochemical noise (EN) was measured in three different types of experimental set‐ups in order to obtain and compare various types of corrosion. Simultaneously with EN measurements, a parallel technique was used, regarding the type of experimental set‐up: a computer visualization system combined with optical microscopy, or measurements of mechanical changes. In order to distinguish between these corrosion types and to assess corrosion rate, the measured EN signals were analysed by two different techniques: spectral and statistical. On the basis of estimated significant spectral parameters (power spectral densities of current and voltage noise, spectral noise resistance) and statistical parameters (standard deviation, localisation index and noise resistance), the passive state, localized corrosion types and uniform corrosion can be recognized. However, by these parameters it is not possible to distinguish between certain localized corrosion processes: metastable pitting, initiation and growth of stable pits, stress‐corrosion cracking. It was ascertained that these corrosion processes exhibit unstable nature, and consequently generated EN signals are usually non‐stationary. Since stationarity is required for spectral and statistical analysis, the unstable nature of these processes was recognized as the main reason for unreliable results. It is believed that these types of signal analysis give poor information about corrosion processes which can be easily identified from EN signal itself: transient corrosion processes and transitions between different corrosion processes.     

A novel experimental arrangement for corrosion study of X60 pipeline steel weldments at turbulent flow conditions

Electrochemical noise (EN) measurements were carried out to study the effect of turbulent flow conditions on corrosion kinetic of API X60 pipeline steel weld immersed in synthetic seawater. In order to control the hydrodynamic conditions, two rotating cylinder electrodes were used. The EN data were analysed by three different statistical methods: currents transients, noise resistance and localisation index (LI). On the other hand, the spectral method was used in order to get the noise impedance. The superficial analysis using a scanning electron microscopy was carried out. According to EN analyses, the current transients indicate that the aggressiveness of the corrosion increased as the rotation speed also increased. The highest corrosion rate values were obtained at turbulent flow conditions. In the superficial analysis, a localised corrosion form was found in all corrosion processes; these results are agreed with the results obtained by LI.     

腐蚀在线监测系统在青岛石化常减压装置的应用

通过在青岛石化安装腐蚀在线监测系统对常减压装置腐蚀在线监测系统的机理、功能进行了实验分析,结果表明,对常减压装置工艺防腐起到指导作用为加工高硫原油装置的防腐提供了有效的方法及对策.     

H2S and O2 influence on the corrosion of carbon steel immersed in a solution containing 3 M diethanolamine

Aqueous solutions with 3 mol L⁻¹ (M) diethanolamine (DEA) concentration are extensively used in the gas processing industry to remove acid gases. However, the degradation of the DEA and the formation of heat-stable salts (HSS) lead to severe corrosion problems. Even worse, equipment corrosion can be magnified by the unavoidable presence of sulphide acid and dissolved oxygen as a result of hydrocarbon (natural gases and crude oil) processing. The aim of this work is to study the combined corrosion effects of DEA, sulphide acid and oxygen on carbon steel. Electrochemical methods revealed that in the 3 M DEA medium without oxygen, corrosion processes are modulated by adsorbed DEA film formation. Furthermore, it was shown that the addition of oxygen and 15 × 10⁻³ mol L⁻¹ (15 mM) H₂S produced the formation of an adherent film on the carbon steel surface. Chemical analyses by EDAX revealed a homogeneous film of corrosion products composed of iron oxide and sulphide formed in DEA solution containing O₂ and H₂S, respectively. Equivalent circuits were used to estimate the parameters associated with ion diffusion through the formed corrosion films. The results showed that the presence of H₂S induced the formation of thin iron sulphide films that provide protective properties to the metal. It is concluded that the presence of oxygen in a sweetening plant should be avoided as DEA degradation can be produced with the subsequent decrease in chelating process efficiency and the increase in corrosion problems.