Counteraction of pitting in copper water pipes by bicarbonate dosing

Copper pipes are extensively used for tap water installations and generally perform well. Exceptionally, however, copper pipes are perforated due to pitting. Three main types of pitting (I, II and III) have been identified, but as for the causes and the mechanisms these have not yet been fully clarified. Through case studies, model experiments, thermodynamic calculations, and service tests, evidence has been obtained that waters having a pitting propensity for copper pipes can be made less corrosive by an increase of the HCO content. On water treatment the following water composition should be aimed at:

• – a pH value of at least 7
• – an HCO content of at least 70 mg/l, preferably 100 mg/l
• – as low SO content as possible, or at least lower than the HCO content (both in mg/l).

     

Atmospheric corrosion rates,time-of-wetness and relative humidity

The effect of relative humidity (RH) on atmospheric corrosion rates r has been studied in laboratory experiments for rust covered steel in air and air + 1 ppm SO₂. The expression: describes the experimental results, where r_crit is the corrosion rate at the critical relative humidity RH_crit and b″ is the normalized corrosion rate at RH = 100%. While a large effect of NaCl impurities in rust was found, no effect of SO₂ was observed. Time-of-wetness was determined in outdoor exposure using the previously described atmospheric corrosion monitor (ACM). It was found that for exposure at a site in Thousand Oaks, California, the time-of-wetness corresponds to RH > 40%.     

Determination of the polarization resistance from impedance measurements

Four different methods for determining the polarization resistance R from impedance data are discussed. These methods are suitable for online corrosion monitoring. Their use is illustrated for iron in tapwater and in neutral, aerated Na₂SO₄ containing various inhibitors. R-values obtained with the CIRFIT-method are compared with R which is obtained from a linear sweep through E_corr. The integration method has the advantage of computation speed.     

Evaluation of corrosion inhibitors for cooling water systems operating at high concentration cycles

The present work aimed at evaluating AISI 1020 carbon steel corrosion resistance of a 6:4:1:1 (MoO/HEDP/PO/Zn²⁺) inhibitor mixture present in a solution which simulates an industrial cooling water system operating at high concentration cycles (1050 ppm Cl⁻ and 450 ppm Ca²⁺). High concentration cycles are desirable, because system purge and treated water consumption are decreased. On the other hand, a high number of concentration cycles can increase the concentration of salts and dissolved impurities, causing corrosion, incrustations, and deposits inside the pipes, heat exchangers, and cooling towers. Thus, the chloride (Cl⁻) and calcium (Ca²⁺) ions aggressiveness was studied on the proposed inhibiting mixture, at the temperatures of 40 and 60 °C, through electrochemical techniques like open circuit potential measurements, anodic and cathodic polarization, and weight loss. The results showed that the inhibitor mixture conferred adequate protection to carbon steel in low concentrations, even in high aggressive media.     

Evaluation of localized corrosion phenomena with electrochemical impedance spectroscopy (EIS) and electrochemical noise analysis (ANA)

The use of electrochemical impedance spectroscopy (EIS) and electrochemical noise analysis (ENA) for non-destructive evaluation of corrosion processes is illustrated for three model systems. EIS can be used to detect and monitor localized corrosion of Al alloys and determine pit growth laws which can be used for lifetime prediction purposes. Electrochemical potential and current noise data can be analyzed in the time and the frequency domain. A comparison of noise data obtained for Pt and an Al 2009/SiC metal matrix composite (MMC) exposed to 0.5 N NaCl has shown that the use of potential noise data alone can lead to erroneous conclusions concerning corrosion kinetics and mechanisms. The electrochemical noise data have been evaluated using power spectral density (PSD) plots in an attempt to obtain mechanistic information. The system Fe/NaCl has been used to determine the relationship between the polarization resistance R_p obtained from EIS data and the noise resistance R_n determined by statistical analysis of potential and current noise data. Potential and current noise can be recorded simultaneously allowing construction of noise spectra from which the spectral noise resistance R can be obtained as the limit for zero frequency. Good agreement between R_P, R_n and R has been observed for iron exposed to NaCl solutions of different corrosivity. For polymer coated steel exposed to 0.5 N NaCl for five months analysis of EIS data allows to draw conclusions concerning the degree of disbonding of the coating and the decrease of the coating resistivity with exposure time. R_n and R obtained from electrochemical noise data for an alkyd coating on cold rolled steel agree with each other and show the same time dependence as R_p and the pore resistance R_po determined from EIS data, but are significantly lower than R_p and R_po. The relationships of derived noise parameters such as R_n and R to coating properties and to the remaining lifetime of a polymer coating are not clear at present.     

Eigenschaften von Elektrolyt-Filmen bei der atmosphärischen Korrosion

Properties of electrolyte films formed through atmospheric corrosion An investigation has been carried out into the composition of the electrolyte films which are formed on non-metallic materials (glass) as well as on metals (Cu, Zn, Fe) in an atmosphere containing SO₂. Fresh as well as pre-corroded specimen were used. It was found that the SO₂ absorbed in the solution is very rapidly oxidized into SO if the electrolyte film contains dissolved particles of the corrosion products. With 1 to 55 ppm SO₂ in the atmosphere, the change in the pH value of the electrolyte is but small and does not vary with the SO₂ partial pressure.     

Inhibierung der Lochbildung und des Lochwachstums bei Aluminium

Inhibition of pit initiation and pit growth on aluminum Under potentiostatic conditions over 40 organic and inorganic compounds have been investigated in order to determine their inhibiting effect on the pitting corrosion of aluminum in 0.01 molar NaC1 solutions. The concentration dependent inhibitor efficiency decreases in the order: Na-oleate, NO ? WO > IO, MoO, BrO, Na-benzoate > CrO > NO, Na-tartrate. SO, ClO and the other organic compounds tested accelerate the pit growth as well as too low concentrations of inhibiting ions. The accelerating effect depends directly on the conductivity of the electrolyte. The inhibitor efficiency depends on the potential and is deteriorated by non inhibiting ions such as ClO or SO. The minimum concentration required to inhibit completely the pit initiation and the pit growth is often not identical. This fact explains partly the inconsistent data found in the literature. The phenomena observed are explained on the basis of the Temkin isotherm.     

Influence of the sulphate reducing bacteria on API‐X70 steel corrosion

The corrosion behaviour of API X70 immersed in a specific medium with a strain of thermophilic sulphate reducing bacteria (SRB) was analysed. Anaerobic corrosion test was carry out for 32 days at 50 °C. During the exposure time, pH, sulphate (SO) and hydrogen sulphide (H₂S) concentration were measured. Corrosion potential, linear polarization resistance and potentiodynamic polarization curve were used in order to get the influence of the SRB in the corrosion phenomenon. Scanning electron microscopy was used to determine corrosion morphology. Results show that the SRB activity influenced the overall corrosion process. The anodic branches in the polarization curves show a passivity feature, whereas, the cathodic branches were not affected. A localized corrosion attack was found.     

Über das Verhalten einiger CrNiMo-Stähle beim Einsatz im chemischen Betrieb

The behaviour of some CrNiMo steels in use at chemical plants A report is given about the behaviour of some highly alloyed CrNiMo steels in use in inorganic-chemical plants. The observations are supported and supplemented by results of potentiostatic tests. In the presence of mixed acids, the corrosion resistance of the steels greatly depends, e.g., on the SO: Cl^? ion ratio. In the presence of Cl^? ions and at higher temperatures, exceeding about 70°C, the resistance is largely influenced by the specifically orientated analytical and structural pattern of the steels. Attention is drawn to the detrimental influence, especially in cast metals and welds, of the concomitant element, silicon, which — if encountered in increasing quantitities — favours the segregation of several corrosion-promoting phases. Examinations of case of damage in practical operation, supported by potentiostatic tests with CrNiMo steels, with and without copper contents, have shown that the presence of copper is apt to reduce the corrosion resistance in media containing hydrochloric acid or chlorine ions. On the other hand, a copper content may be beneficial in sulphate solutions free from chlorine ions.     

Corrosion of pretreated aluminium after cathodic electrodeposition of paint

Cathodic deposition of paint (CDP) is Well introduced for the industrial coating of primers onto steel since nearly two decades. Epoxy resins provide optimum results. There is an increasing demand to apply the same technique for aluminium, especially for mixed constructions Fe/Al in motor car bodies. However, this metal may be attacked by the OH^?-ions, generated by the cathodic electrolysis of water according to: H₂O + e^? → ½ H₂ + OH^?. The Al₂O₃ · xH₂O protecting layer may dissolve slowly as aluminate and Al-metal then reacts rapidly with water to generate the threefold volume of hydrogen under the reestablishment of the oxide layer. Thus, the overall reaction for this cathodic corrosion of Al is given by: Al + 2H₂O + e^? → AlO + 2H₂. It can be foreseen, that the changes at the phase boundary Al, AlOOH/paint and the accumulation of hydrolysed aluminate in the coating may influence, among other, the corrosion protection behavior of the paint layers. A systematic study of the influence of four different industrial epoxy resins from BASF Lacks & Farben AG (1)–(4) with their individual pigment systems, the one for paint (3) to be free of lead silicate, was undertaken. Seven different aluminium (alloy) substrates were employed. Their pretreatment modes were mostly due to zincphosphatation. Three standard corrosion tests for conventional corrosion, (CC) and one for filiform corrosion (FFC) were employed and evaluated, as usual. The accelerated open air corrosion test lasted 360 days. It was found, that for CC the corrosion protection capability was predominantly influenced by the resin, and it decreased in the following order: The effect of the substrate was not very pronounced, but a relative optimum could be seen with Al Mg 0.4 Si 1.2-chromate pretreatment and Bonazinc 2000® and with Al Mg 1.5 Si 0.5 Cu 4.0-chromate pretreatment (with one exception). The ranking for FFC changed to: , and zincphosphated Al Mg 3 was superior over all the other substrates. The analytically determined rate of cathodic corrosion for unpigmented paints did not correlate to these results, and this may be indicative for specific pigment effects. In conclusion, this systematic study reveals, on the basis of practical systems and corrosion test methods, a way for the optimization of CDP on aluminium.     

Der Einfluß von CO2 auf die Korrosionskinetik von Zink in Modellwässern

Influence of CO₂ on the corrosion kinetics of zinc in water Mechanism and kinetics of Zn and Zn/Fe corrosion in water containing various contents of CO₂ is studied by impedance spectra completed by gravimetric corrosion measurements. Electrode impedance is clearly found to be a function of P, the diffusion parameter is of essential importance. A_d as a function of P yields the same curves as the rest potential dependence on CO₂ and moreover the gravimetrically measured corrosion velocity rises linearly with CO₂. –Determination of corrosion velocity according to STERN-GEARY cannot be realized in the systems under investigation. –Experimental results lead to the conclusion that the main corrosion reaction takes place at the metal/layer-phase. The corrosion mechanism is discussed.     

Inhibitoren der Korrosion 17(1) Die Bedeutung des „Hart-Weich-Konzepts”︁ von Pearson für die Erkennung von Struktur-Wirkungsbeziehungen von Inhibitoren bei der Korrosion des Eisens in NaCl-Lösungen bei Gegenwart von Sauerstoff

Corrosion inhibitors 17 The importance of pearson's “hard-soft-concept” with respect to the recongnition of relationship between structure and activity of inhibitors of the corrosion of iron in sodium chloride solutions in the presence of oxygen On the base of a previously published postulate according to which Pearson's hard-soft-concept may form the base for finding inhibitors for specific applications it is shown with the aid of model inhibitors with “hard” functional groups that it is indeed feasible to derive defined relations between the structure and the activity of inhibitors. The hard groups used were the phosphoryl ?P(O)O and the carbonyl ?C?O groups. It has been shown that such compounds are able to form very stable and protective surface layers on iron and that the efficiency of the inhibitors clearly increases with increasing length of the aliphatic chain. As has been shown by eletrochemical measurements these acids have a bearing on the rest potential as well as on the current-potential behaviour; this fact points to rather variable compositions of the surface layer. In the case of polyfunctional acids sterical factors may have a bearing on inhibitor efficiency, too.     

A mechanistic study of initial atmospheric corrosion kinetics using electrical resistance sensors

This paper describes a novel experimental approach to the study of atmospheric corrosion of iron and zinc, utilising electrical resistance sensors that are sensitive to corrosion losses of the order of one atomic monolayer. Using such devices, a mechanistic study of the initial stages in the atmospheric corrosion of iron and zinc was performed in a rectangular flow cell using controlled relative humidity (RH), temperature and gas flow rate. Additionally, the effects of SO₂ contamination in the gas phase and prior NaCl contamination of the metal surface were studied. It was found that the initial corrosion kinetics of iron and zinc are, not unexpectedly, dominated by the development of surface corrosion product films, but that the growth kinetics vary with metal, humidity, etc. Specifically, in the presence of gas-phase SO₂, activation energies and kinetic and chemical rate orders were consistent with control of the atmospheric corrosion process by solution-phase oxidation of sulphite–sulphate ion. For iron, this implies that the well-known sulphate-nest theory is inoperative at least during the early stages of atmospheric corrosion. In contrast, for chloride–contaminated zinc, the data were consistent with a rate-controlled diffusion of a species, probably water vapour or oxygen, through a thickening corrosion product film. Finally, the kinetic and chemical rate orders for corrosion of chloride–contaminated iron precluded a diffusion-controlled mechanism, but were consistent with a rate-controlling process involving some regeneration of chloride: e.g. as in metal–ion hydrolysis in a pit or similar localised corrosion events.     

Korrosionsverhalten feuerverzinkter Baustähle in überwiegend sandhaltigen Böden

Corrosion behaviour of galvanized steel in mainly sandy grounds In mainly sandy grounds with different portions of fine parts < 0,06 mm (2,5–20,4%) specimens of ungalvanized and galvanized steel were stored outside and in the laboratory. Besides the composition of the ground, the salinity and the temperature of the ground were varied too. The corrosion rate and, for ungalvanized specimens, the behaviour to pitting corrosion were determined. Furthermore the factors characterising the corrosion behaviour such as specific resistance of soil and corrosion potential were investigated continuously. The loss in weight of metal was much greater for ungalvanized than for galvanized specimens and increased for ungalvanized specimens with an increasing portion of fine parts in the ground. Additions of salt at the beginning of the tests produced an increased amount of metal wastage, but for galvanized specimens they only had an influence upon initial corrosion. The increased removals of material started since contents of 3 · 10^?3 MolCl^? + SO/kg. If salts were added to the ground after 2 years (after the formation of a surface layer), they increased the wastage of material for ungalvanized but not for galvanized specimens. Apart from ungalvanized bars in the soil with a fineness portion of 20,4%, corrosion, after an acceleration at the beginning, slowed down owing to the formation of a surface layer. Ungalvanized specimens were attacked by a strong pitting corrosion and that more in aerated than in dense and, thus, water-containing grounds. The additions of salt accelerate more an uniform corrosion of material than a pitting corrosion. As for galvanized specimens after a local removal of zinc under extreme conditions the steel base had been hardly corroded away. The parts free of zinc were protected cathodically by the still existing zinc. The corrosion of steel depends upon the temperature: by increasing the temperature from 4 to 20°C increases of corrosion up to 100% were stated. As for galvanized surfaces temperature has only a small influence upon corrosion.     

The corrosion inhibition of copper in hydrochloric acid solutions by a tripeptide compound

The efficiency of glutathione as a non-toxic corrosion inhibitor for copper in 0.5 M HCl has been studied by using the weight-loss technique, cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. Maximum protection efficiency reaches about 92.7% for glutathione at 10 mM concentration level. Results obtained from potentiodynamic polarization and impedance measurements are in good agreement. The adsorption of glutathione on copper surface follows Langmuir isotherm. The adsorption free energy of glutathione on copper (−32 kJ mol⁻¹) reveals a strong physical adsorption of the inhibition on the metal surface.     

Effect of Si on the Corrosion behaviour of Fe-B and Fe-Ni-B glassy alloys

The effect of substituting Si for B on the electrochemical behaviour of the glassy alloy families Fe-B and Fe-Ni-B has been investigated in solutions with pH ranging from 4 up to 8.4. The influence of the aggressive ions (Cl^? and SOu) has also been studied. AES and XPS have been used to further characterize the alloys in order to interpret their behaviour in the various solutions.     

The influence of an isobutane-SO2 pollutant system on the earlier stages of the atmospheric corrosion of metals

Whilst much research upon atmospheric corrosion has involved SO₂, the pollutant smoke aerosol and associated sorbed hydrocarbons have been largely ignored. As a preliminary study, the present work concerns the corrosivity of air-based atmospheres containing 50 vpm isobutane and/or 3.5 ppm SO₂ at 78 % r.h. It was found that, relative to a clean air atmosphere, isobutane inhibited the corrosion of iron and nickel whilst having rather less effect upon zinc, aluminium and copper. isobutane inhibited the corrosivity of SO₂ to iron, whilst conversely enhancing the corrosivity of SO₂ to aluminium, copper, nickel and zinc. In order to account for these results, proposed explanations involve the molecular dipole polarization of isobutane, its adsorption and coordination association at anodic and cathodic sites, affecting electrochemical reactions both directly and indirectly by mass transfer limitations, and its interference with maintenance repair reactions on surface layers.     

The influence of copper upon the atmospheric corrosion of iron

The atmospheric corrosion of pure iron and the binary alloy Fe-0.5Cu has been analyzed by a simultaneous measurement of the anodic current density of the metal dissolution and the cathodic current density of the O₂ reduction reaction during several wet/dry cycles using a magnetic and a gas volumetric technique, respectively. The results show three typical stages of the atmospheric corrosion: stage 1 (wetting of a dry surface): rapid corrosion with rust reduction as cathodic process; stage 2 (wet surface): slow corrosion with O₂ reduction as cathodic process; and stage 3 (drying out of the surface): very rapid corrosion with O₂ reduction as the cathodic process during critical wetting of the surface. The effect of copper is restricted to stage 3, where the corrosion rate is much smaller for the Fe-0.5Cu alloy than for pure iron. Two models are discussed to explain these results.