A microscopic study of the effects of particle size and composition of atmospheric aerosols on the corrosion of mild steel

A novel approach to measure the corrosion effects of aerosols as a function of their aerodynamic size and chemical composition was used to study the effects of atmospheric aerosols on mild steel at a rural coastal site. The technique uses collocated micro-orifice uniform deposition impactor samplers to deposit ambient atmospheric particles on exposure steel coupons and collect aerosol samples for ionic analyses. Rusts were found on the coupons with aerosols but none on the blank coupons even the blanks were incubated at the same conditions. FTIR analysis shows that the composition of rusts changes gradually with the aerosol particle size.     

A new interpretation of the corrosion loss processes for weathering steels in marine atmospheres

Most available data sets for the long-term corrosion loss of various grades of weathering steel exposed to marine atmospheric environments are demonstrated to be consistent with the multi-phase corrosion model previously proposed for steels exposed to marine environments. This means that the early corrosion of weathering steels by oxidation is gradually inhibited by the build-up of corrosion products. These produce anoxic and sub-oxic conditions that may permit microbiological activity to govern the longer-term corrosion loss process. This new interpretation for the long-term corrosion of weathering steels may have implications for the design of such steels.     

Role of climatic conditions on corrosion characteristics of structural steels

Corrosion behaviour of low alloy (LASS) and plain carbon (PCSS) structural steels exposed in different types of climatic conditions and nature of rust formed on their surfaces have been studied after 2 years of exposures. The test sites were chosen to represent four types of environments who strongly influence the corrosion of metals and alloys. They include (a) humid-saline, (b) humid-saline-urban (c) humid-industrial and (d) plain dry-urban environments. Mass loss, Raman spectroscopy, scanning electron microscopy and electrochemical impedance spectroscopic studies have been performed to study the corrosion behaviour and characterise the nature of rusts formed on these steels. Mass loss measurement technique has been used to determine the loss of thickness of steels during their atmospheric and salt spray exposures. Results indicate that the corrosion rate of steels is strongly influenced by the climatic conditions prevailing at the exposure sites. The presence of SO₂ and salinity in the environments change the structure and protective properties of rust formed on the steels’ surface. Electrochemical impedance and cyclic polarisation studies of the steels in simulated environments have been performed to understand the mechanism of corrosion in different climatic conditions.     

Indoor atmospheric corrosion in Cuba. A report about indoor localized corrosion

Indoor weight loss of steel, chloride, sulphur compounds and dust deposition rate were determined in six storehouses having different characteristics. Relative humidity and temperature were determined in three storehouses. A model for indoor corrosion of steel depending on time of exposure and deposition of dust, sulphur compounds and chlorides is proposed. Dust deposition plays an important role indoors. The position of the sample has also a significant influence on corrosion. Indoor corrosion aggressivity in Cuban storehouses ranges in classification IC3 and IC4 according to the new ISO proposal of indoor aggressivity.A report about the presence of localized corrosion indoors (filiform like) using a special designed sample is made.     

Influence of chloride ion concentration and temperature on the corrosion of Mg-Al alloys in salt fog

The influence of temperature and chloride concentration on the corrosion behaviour of Mg-Al alloys exposed to salt fog was evaluated. Corrosion attack increased with decreasing aluminium content in the alloy and increasing Cl⁻ concentration and temperature. The effect of Al-Mn inclusions, which revealed several stoichiometries and were up to 300 mV more noble than the magnesium matrix, was only noticeable in the early stages of corrosion of the AZ31 alloy. Aluminium segregation and β-phase distribution were the main controlling factors for the AZ80 and AZ91D alloys, the latter being more susceptible to variations in the saline concentration.     

The atmospheric corrosion kinetics of low carbon steel in a tropical marine environment

The atmospheric corrosion kinetics of low carbon steel exposed for up to 36 months in marine and industrial sites was studied by weight loss measurements. The results show that the mechanism and kinetics of the atmospheric corrosion process presents transition behaviour in marine environments with high chloride ion content and high relative humidity, whereas no transition appears in industrial environment. The average corrosion velocity in marine site reaches a maximum during the period of transition and then fluctuates in a certain range; however, the instantaneous corrosion velocity follows different exponential functions before and after the period of transition.     

Characterization of AISI 4340 corrosion products using Raman spectroscopy

Most of the currently available corrosion product characterization techniques require extensive samples preparation methods and cannot be employed under aqueous conditions. Raman spectroscopy possesses the advantage of characterization of the corrosion products under practical operation conditions, including aqueous, without any sample preparation procedures. The present study examines the corrosion characteristics of AISI-4340 steel at aqueous and atmospheric environments using Raman spectroscopy. FeO, Fe₂O₃, and Fe₃O₄ were observed as the main corrosion products. The measured oxides thicknesses ratio were compared to the theoretic value obtained from Tammann equation.     

Effect of cations on corrosion of zinc and carbon steel covered with chloride deposits under atmospheric conditions

The effect of sodium, calcium, and magnesium chlorides deposited on zinc and carbon steel surfaces was studied under atmospheric conditions. The cations strongly affected the corrosion rate of zinc, whereas they had a significantly lower impact on the corrosion of carbon steel. The corrosivity of cations of chloride salts for zinc increased in order of Mg²⁺ < Ca²⁺ < Na⁺. The higher corrosion resistance of zinc treated with calcium and magnesium chlorides was connected to prevention of formation of hydrozincite during zinc exposure in wet air. It was observed that zinc weight loss and the carbonate to simonkolleite ratio in corrosion products were correlating. The principal protective effect of bivalent cations can be seen in the decrease of pH of the surface electrolyte, which was caused by hydrolysis of such cations and subsequent formation of simonkolleite that blocked the cathodic sites.     

Long-term immersion corrosion of steels in seawaters with elevated nutrient concentration

Data from a variety of field exposure programs is used to quantify the effect of concentration of dissolved inorganic nitrogen (DIN) on long-term seawater immersion corrosion loss of structural steels. A linear correlation model that asymptotes the long-term part of the previously proposed bi-modal corrosion loss model is used. It allows for average seawater temperature. Model parameters and their variability are determined and reported. The model permits prediction of long-term corrosion loss in nutrient polluted waters of known average temperature. An example shows that anthropological pollution of seawater potentially is a major hazard for corrosion of steel infrastructure.     

Modelling immersion corrosion of structural steels in natural fresh and brackish waters

The multi-phase mean-value model previously proposed for modelling the marine immersion corrosion of low carbon and low alloy structural steels is examined for application to fresh and brackish waters. Use is made of field data for brackish and fresh waters available in the literature, supplemented with data or estimates for water temperature, pH, hardness and nutrient levels. It is shown that the data exhibits consistency with the model and that it is a function of average water temperature. Corrosion in brackish and fresh waters corrosion depends on water hardness, pH and nutrient levels, with higher pH levels and lower water hardness associated with higher aerobic levels of corrosion but these are not significant for anaerobic corrosion. In the anaerobic phases 3 and 4 of the model, the available data and associated trends are interpreted as showing that elevated levels of nutrients produce higher rates of corrosion. Conversely, these phases showed very low rates of corrosion for fresh waters with very low nutrient levels. Consistent with basic corrosion theory and with laboratory observations, salinity by itself is not a clear distinguishing characteristic. The model provides a new approach to interpreting the available data for corrosion in fresh and brackish waters. It permits plausible explanations for previous apparently inconsistent observations for corrosion in brackish waters. Finally, it reinforces the need for full and detailed reporting of corrosion testing programs, including details of precise timing, location, orientation and environmental conditions including means and variations in water temperatures, DO, salinity, pH, water hardness, carbonates and various nutrients.     

Differences between corrosion products formed on copper exposed in Tokyo in summer and winter

We analyzed the copper corrosion products that formed during a month in summer and a month in winter at three sites in Tokyo using several analytical techniques. The X-ray diffraction patterns revealed that cuprite Cu₂O and posnjakite Cu₄SO₄(OH)₆·H₂O formed on copper exposed in summer. By contrast, only cuprite was found in winter exposed copper. The X-ray fluorescence results indicated that the amounts of sulfur and chlorine on the copper plates exposed in summer were much greater than those in winter. This could be explained by the change in particulate sulfate and sea salt concentrations. Depth profiling analysis by Auger electron spectroscopy revealed that the oxide layer formed in summer was thicker than that in winter. This difference in oxide layer thickness could have been due to the differences in temperature, relative humidity, and the amount of sulfur and chlorine on the copper plate.     

Ex-situ and in-situ X-ray diffractions of corrosion products freshly formed on the surface of an iron-silicon alloy

Ex-situ X-ray diffraction measurements of a small amount of samples extracted from wet corrosion products freshly formed on a pure iron and iron-2 mass% silicon surfaces have been conducted using synchrotron radiation for clarifying the formation process of corrosion products. The results showed that γ-FeOOH was formed on the outer side of wet corrosion products formed on the surface of the pure iron by sodium chloride solution, while γ-FeOOH, α-FeOOH, Fe₃O₄, and green rusts were formed on the inner side. On the other hand, in comparison to the case of the pure iron, a significant formation of β-FeOOH was observed in the iron-silicon alloy. Influences of silicon alloying on corrosion products formed by aqueous solution containing sulfate ions were also observed. Furthermore, in-situ diffraction measurements by a conventional X-ray source were conducted for analyzing corrosion products formed on the pure iron and iron-silicon alloy surfaces by cyclic exposure to wet and dry atmospheres. The results obtained by the in-situ diffraction and ex-situ diffraction measurements on the corrosion products were consistent.     

Atmospheric corrosion of carbon steel in Colombia

The corrosion behaviour of carbon steel at six test sites in Colombia and its relationship with exposure time and environmental characteristics of each site were investigated. The corrosion products were characterized by XRD, SEM and EDS. It was found that in Barranquilla, the most aggressive site, corrosion depends mainly on chlorides. Furthermore, in the more aggressive environments there was a greater tendency to formation of protective corrosion products. Lepidocrocite and goethite were found as major constituents of rust. A structure not reported in the literature was found, corresponding to strings of several hundred micrometers long and consisting of lepidocrocite plates.     

The effect of synthetic zinc corrosion products on corrosion of electrogalvanized steel. II. Zinc reactivity and galvanic coupling zinc/steel in presence of zinc corrosion products

The reactivity of zinc under synthetic zinc patinas and the galvanic coupling in steel/patina/Zn are studied. Zn₅(OH)₆(CO₃)₂ and Na₂Zn₃(CO₃)₄⋅3H₂O inhibit zinc anodic dissolution in NaCl, while Zn₅(OH)₈Cl₂ H₂O and Zn₄(OH)₆SO₄ nH₂O do not. The galvanic current in steel/patina/NaCl/Zn is smaller as compared to steel/NaCl/Zn. The inhibiting effect decreases with time for Na₂Zn₃(CO₃)₄⋅3H₂O or Zn₄(OH)₆SO₄ nH₂O due to the transformation into Zn(OH)₂. In NaHCO₃, the polarity between zinc and steel can reverse. The effect of confinement on the cathodic current is stronger than the initial effect of patina which is explained by the instability of the patinas under rapid pH-increase.     

Steam oxidation resistance of new 12%Cr steels: Comparison with some other ferritic steels

The oxidation resistance in pure steam at the 600-650 °C temperature range of a newly developed 12%Cr steel has been investigated for long-term exposures (224 days = 5,376 h). The laboratory and industrial heats were tested in comparison with other ferritic 9-13% chromium steels. Corrosion rates were determined by direct measurements of mass losses obtained after a reducing descaling process. Weight loss and metallographic results confirm the good corrosion resistance in steam of the new steel and allow classing the tested steels in 2 families: one classical with average oxidation behaviour, “T91-type” and another one with low mass losses, varying very slightly with the temperature and the exposure time increasing. To have a better understanding of the observed phenomena, the possible influences of the main alloying elements (Cr, Si, Mn, Mo, W) of steels mentioned by different authors were reviewed and compared to the results obtained for the ten 9-13%Cr studied steels. It appears that the alloying elements cannot be considered separately: as a matter of fact they have not only a specific influence but also a joint influence on the steam corrosion behaviour of the 9-13%Cr ferritic steels.     

An exploratory study of the corrosion of Mg alloys during interrupted salt spray testing

A first systematic investigation was carried out to understand the corrosion of common Mg alloys (Pure Mg, AZ31, AZ91, AM30, AM60, ZE41) exposed to interrupted salt spray. The corrosion rates were also evaluated for these alloys immersed in 3 wt.% NaCl by measuring hydrogen evolution and an attempt was made to estimate the corrosion rate using Tafel extrapolation of the cathodic branch of the polarisation curve. The corrosion of these alloys immersed in the 3 wt.% NaCl solution was controlled by the following factors: (i) the composition of the alpha-Mg matrix, (ii) the volume fraction of second phase and (iii) the electrochemical properties of the second phase. The Mg(OH)₂ surface film on Mg alloys is probably formed by a precipitation reaction when the Mg²⁺ ion concentration at the corroding surface exceeds the solubility limit. Improvements are suggested to the interrupted salt spray testing; the ideal test cycle would be a salt spray of duration X min followed by a drying period of (120-X) min. Appropriate apparatus changes are suggested to achieve 20% RH rapidly within several minutes after the end of the salt spray and to maintain the RH at this level during the non-spray part of the cycle. The electrochemical measurements of the corrosion rate, based on the “corrosion current” at the free corrosion potential, did not agree with direct measurements evaluated from the evolved hydrogen, in agreement with other observations for Mg.     

Erosion resistance of CO2 corrosion scales formed on API P110 carbon steel

The erosion resistance of CO₂ corrosion scales formed on carbon steel was investigated in water–sand two-phase flow utilizing weight loss test, scanning electron microscopy, and X-ray diffraction. The effects of CO₂ partial pressure, stirring speed, test time, and grain size on the erosion resistance of the scales were analysed. Results show that several characteristics of CO₂ corrosion scales are key factors affecting erosion resistance. Cubic polynomials are used to fit the erosion rate data, and effectively evaluate the ability of CO₂ corrosion scales to resist erosion. An erosion mechanism, based on fluid dynamics and CO₂ corrosion scales characteristics, is discussed.     

Pitting corrosion of spray formed Al-Li-Mg alloys

The pitting corrosion behaviour of two new spray formed alloys, designated OX24 and OX27, has been compared with spray formed AA7034 and more corrosion resistant AA5083 by polarisation tests. The new alloys have been designed for use in the aerospace industry where good corrosion resistance and specific mechanical properties are required. OX24 and AA5083 had good corrosion resistance; OX27 pitted immediately showing poor corrosion resistance. However, both OX24 and OX27 show better corrosion resistance than AA7034. Scanning electron microscopy showed that corrosion was associated with intermetallic particles, except in OX24 where initiation appeared not to be associated with the Zr-rich intermetallics.     

A study on the initial corrosion behavior of carbon steel exposed to outdoor wet-dry cyclic condition

The initial corrosion behavior of carbon steel subjected to outdoor wet-dry cyclic exposure and exposure under natural environments have been investigated. The weight loss results indicate a transition from corrosion acceleration to deceleration during the early stage of corrosion of carbon steel under both conditions. The corrosion kinetics under both conditions follow empirical equation D = Atⁿ. Outdoor wet-dry cyclic exposure significantly promoted the initiation but the rate of corrosion was about three times as fast. The morphology of corrosion surfaces and cross-section of rust layer have been examined using SEM and the compositions have been analyzed using XRD and EPMA.     

Characterisation of initial atmospheric corrosion carbon steels by field exposure and laboratory simulation

The early stages of the evolution of atmospheric corrosion of carbon steels exposed in both a laboratory simulated and a natural atmosphere environment in Shenyang have been observed by in situ scanning electron microscopy. In the case of laboratory cyclic wet-dry tests, even though the chloride content level is very low, filiform corrosion is initiated in the early stage. The filiform corrosion grows in random directions, forming a network of ridges. White nodules nucleate and grow on the ridges during continued corrosion and eventually connect with each other to form the initial corrosion scale. Pits were also found on the surface beneath corrosion products. In the case of a natural atmospheric environment, both filiform corrosion and other localized corrosion, such as pitting and inter-granular attack take place in the initial stage. It is obvious that there is variety of localized corrosion in the initial stage of atmospheric corrosion.