Inhibition treatment of the corrosion of lead artefacts in atmospheric conditions and by acetic acid vapour: use of sodium decanoate

The efficiency of linear sodium decanoate, CH₃(CH₂)₈COONa (noted NaC₁₀), as corrosion inhibitor of lead was determined by electrochemical techniques in two corrosive mediums: ASTM D1384 standard water and acetic acid-enriched solutions. Best results were obtained with 0.05 mol l⁻¹ of NaC₁₀ solution. In these conditions, the inhibition efficiency can be estimated of 99.9%. The corrosion inhibition effect was confirmed by cyclic atmospheric tests in a climatic chamber in two different conditions: water saturated vapour, and acid acetic enriched vapour simulating the atmosphere in the wooden displays in museums. Surface analyses by SEM and X-ray diffraction indicate that the metal protection is due to the formation of a protective layer mainly composed of lead decanoate Pb(C₁₀)₂ (metallic soap). This inhibition treatment was applied on objects of metallic cultural heritage: gallo-roman sarcophagus in lead. Electrochemical methods confirm the efficiency of treatment on archaeological materials. In conclusion, this inhibitor treatment seems to be very promising against the atmospheric corrosion and the corrosion by organic acid vapour in museums.     

The effects of Cl ion concentration and relative humidity on atmospheric corrosion behaviour of PCB-Cu under adsorbed thin electrolyte layer

The effects of Cl⁻ ion concentration and relative humidity on atmospheric corrosion behaviour of PCB-Cu under adsorbed thin electrolyte layer were investigated by cathodic polarization curves and electrochemical impedance spectroscopy. Results indicated that the cathodic process of PCB-Cu corrosion was dominated by the reduction of oxygen and corrosion products. The cathodic current density increased with increasing relative humidity and Cl⁻ ion concentration. The corrosion rate was initially dominated by oxygen reduction, but at the later stage of corrosion, the anodic process began to affect the corrosion rate due to the accumulation of corrosion products.     

EIS monitoring study of atmospheric corrosion under variable relative humidity

Electrochemical impedance spectroscopy (EIS) technique was used to investigate atmospheric corrosion in laboratory simulated environments with variable relative humidity (RH) and fixed Cl⁻ content. The results show the suitability of EIS for analyzing electrochemical corrosion behaviour at 5-100% RH. At 5-30% RH, EIS spectra reflected the character of the electrode, whereas at 40-100% RH, the model of EIS spectra was established with the help of surface analysis. From 70% RH, the film resistance (R_r) reflects the degree of corrosion and the charge transfer resistance (R_t) provides quantitative representation of the corrosion rate, which were verified by weight loss tests.     

The influence of the microstructure on the atmospheric corrosion behaviour of magnesium alloys AZ91D and AM50

Even though magnesium, as a structure metal, is most commonly used in an atmospheric environment, most investigations of magnesium are performed in solution. In the present work the atmospheric corrosion of two commonly used magnesium alloys, AZ91D and AM50, has been investigated from the initial stages up to the most severe forms of corrosion. A detailed investigation of the morphology of a corrosion attack and its development over time shows that the atmospheric corrosion mechanism is similar for the two alloys. Based on these findings a schematic model of the initial atmospheric corrosion attack on AZ91D is presented and discussed.     

Atmospheric corrosion of historical organ pipes: The influence of environment and materials

The corrosion of lead-rich pipes in historical organs in different parts of Europe has been investigated. The influence of the environment and the composition and microstructure of the pipe metal was studied. Pipe corrosion was documented by visual inspection (boroscope). The corrosion attack and the composition and microstructure of the metal were characterized by OM, SEM, XRD, IC and FAAS. It is shown that the degree of corrosion of the pipes is correlated to the concentration of gaseous acetic and formic acid in the organ. The organic acids are emitted by the wood from which the wind system is built. It is also shown that pipe corrosion decreases with increasing tin content in the range 0-4% (wt). Possible conservation strategies are discussed.     

Studies on the initial stages of zinc atmospheric corrosion in the presence of chloride

A four-year exposure program was carried out in Taiwan in which 23 test sites with different climatic and pollution conditions were chosen and evaluated according to ISO standards 9223-9226. Examination of the results indicated that most of the tests sites were very corrosive to zinc specimens and there was a severe white rust problem for freshly galvanized items stored in high humidity outdoors environments. In addition, the initial stages of zinc atmospheric corrosion in the presence of chloride were studied quantitatively in a non-aqueous electrolyte (methanol) using ex situ electrochemical impedance spectroscopy (EIS) to determine polarization resistance (R_p). The samples were exposed to the synthetic atmospheres with careful controlled relative humidity, temperature, and contaminating salts. It was observed that a change of R_p was accompanied by a change in the corrosion product on the zinc surface, and that the R_p increased with relative humidity (RH) during pre-exposure. Furthermore, the corrosion products of zinc were analyzed qualitatively by grazing-angle X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. Zinc hydroxycarbonate (Zn₅(CO₃)₂(OH)₆) and zinc oxide (ZnO) in this surface layer were found to provide protection against chloride contaminants.     

The atmospheric corrosion of quaternary bronzes: The leaching action of acid rain

The effect of leaching rain on the corrosion behaviour of bronze UNSC83600 was investigated as to the influence of alloying elements (Cu, Sn, Zn, Pb) through dropping tests simulating a severe runoff condition with a solution reproducing natural acid rain. Corrosion was followed with time monitoring both samples and leaching solutions (up to 30 days) by SEM, EDS, Raman spectroscopy, XRD, AAS. The bronze patina behaves as a porous layer enriched in stable tin compounds allowing uniform dissolution of Cu, Zn and partly of Pb. Laboratory results are in good agreement with field studies of outdoor bronzes in unsheltered condition.     

The effects of temperature and electric field on atmospheric corrosion behaviour of PCB-Cu under absorbed thin electrolyte layer

The effects of temperature and electric field on atmospheric corrosion behaviour of PCB-Cu under absorbed thin electrolyte layers were investigated by cathodic polarization and electrochemical impedance spectroscopy. Results indicate that the cathodic current density increases with increasing temperature, but decreases with increasing intensity of electric field. Electric field reduces the corrosion rate of PCB-Cu due to the aggressive ions migrating out from PCB-Cu electrode surface under the effect of electric field. When the ions can not freely migrate out from PCB-Cu electrode surface, local enrichment of aggressive ions under the electric field will cause serious localized corrosion of PCB-Cu.     

Pitting of zinc: Observations on atmospheric corrosion in tropical countries

A five-nation study has investigated the mechanisms and rates of the atmospheric corrosion of zinc and steel in tropical regions in Australia, Thailand, Indonesia, Vietnam and The Philippines. For the study, 18 exposure sites encompassing severe marine, marine, severe industrial, industrial, marine/industrial, urban and highland environments were established across the countries. At each location, zinc and steel plates were exposed for periods of three months and one year, and measurements were taken of a wide range of surface-response and climatic parameters, including gaseous SO_x and NO_x, airborne salinity, relative humidity (RH) and temperature, rainwater composition, surface temperature and time of wetness (TOW). Exposed plates were used to determine mass loss, the nature of corrosion products (using FTIR and SEM-EDS) and the morphologies of corrosion layers (via SEM-EDS). Regression analysis indicated that the prime factors controlling zinc corrosion rate were climate (temperature and rainfall) and surface-response (TOW), and surprisingly not pollutant levels, despite significant variation in SO_x levels across the sites. SEM studies indicated the presence of pitting below the oxide layers on zinc, particularly those plates exposed at marine and other sites with relatively low SO_x levels. In contrast, no pitting was observed (or pits had very low aspect ratios) in the specimens exposed at sites with high SO_x levels. The possible processes leading to the observed damage patterns are discussed.     

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.     

Pitting corrosion mechanism of Type 304 stainless steel under a droplet of chloride solutions

Pitting corrosion of Type 304 stainless steel under drops of MgCl₂ solution has been investigated to clarify the rusting mechanism in marine atmospheres. A pitting corrosion test was performed under the droplets with various combinations of the diameter and thickness (height) by exposure to a constant relative humidity. Probability of occurrence of pitting corrosion decreased with decreasing the diameter and thickness. Pitting corrosion progressed only when the [Cl⁻] exceeded 6 M (RH < 65%). In almost cases, there was a small hole (∼10 μm diameter) in the center of a single pit, which may be the trace of an inclusion particle like MnS dissolved out. The pitting corrosion mechanism of Type 304 under droplets containing chloride ions has been proposed.     

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.     

Long-term atmospheric corrosion of zinc

A great deal of information is available on the short- and mid-term atmospheric corrosion of zinc: corrosion rate data as a function of atmosphere type, corrosion mechanisms, effect of environmental variables, effect of surface orientation, damage functions, etc. However, very little information has been published on the atmospheric corrosion of zinc over long time periods (10-20 years), despite its great usefulness. On the other hand, many studies have analyzed the nature of corrosion products formed on zinc in a wide range of atmospheric environments, using different experimental techniques, but few have focused on the morphology of corrosion product layers. This paper reports the characteristics—mainly composition and morphology—of corrosion products formed on zinc panels after long-term exposure (13-16 years) in various types of atmospheres in Spain: rural, urban, industrial, mild marine and severe marine.     

Experimental investigation on the short-term impact of temperature and moisture on reinforcement corrosion

In this study, reinforced concrete specimens with and without mixed-in chlorides were conditioned at different relative humidities and subsequently subjected to varying temperatures. Results of the study confirmed that neither temperature nor moisture content have a major impact on the corrosion state and rate of passively corroding reinforcement. For actively corroding reinforcement, a temperature and moisture dependent corrosion rate was observed. The temperature dependency could be described by the Arrhenius equation with moisture dependent activation energies of approximately 10 kJ/mol at 75% RH and 35–40 kJ/mol above 85% RH.     

The atmospheric corrosion of quaternary bronzes: The action of stagnant rain water

The corrosion behaviour of a quaternary bronze UNS C83600 exposed to stagnant acid rain was examined through wet-dry tests. During the tests, parallel monitoring was performed to determine the evolution of both the bronze surface and the weathering solution composition. The results show that the kinetics of bronze oxidation is governed by diffusion through a two-layer patina: an inner Sn-rich layer and an external Cu and Pb-rich layer. The corrosion rate of the alloy decreases with time, but the dissolution of individual metals (Cu, Zn and Pb) in the environment increases with different trends, showing progressive patina destabilisation.     

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.     

Effect of direct current electric field on atmospheric corrosion behavior of copper under thin electrolyte layer

A thin layer electrochemical cell was successfully developed to study the atmospheric corrosion behavior of copper film in printed circuit board (PCB-Cu) under thin electrolyte layer (TEL) and direct current electric field (DCEF) by electrochemical impedance and electrochemical noise analysis. The electrochemical measurements and SEM morphologies after corrosion test indicate that DCEF decreases the corrosion of PCB-Cu under TEL. The corrosion rate and probability of pitting corrosion of PCB-Cu under DCEF decrease due to the electric migration of aggressive Cl⁻ ion out of working electrode surface.     

Use of inkjet printing to deposit magnesium chloride salt patterns for investigation of atmospheric corrosion of 304 stainless steel

Inkjet printing was used to deposit MgCl₂ salt patterns on 304 stainless steel foils to investigate atmospheric corrosion. Results were found to be more consistent if initial hydration (1 h at ∼90% RH) of the printed salt pattern was carried out. The pit diameter following exposure at 45% RH and 300 K for 24 h was found to increase with the diameter of the original salt deposit, which is consistent with the idea of cathodic limitation of the pit current. For a constant deposition area, the pit diameter increases with increased salt deposition density, which may be associated with a lower ohmic drop resulting from a higher droplet, or could be influenced by enhanced corrosion during the initial hydration stage.     

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 effect of acetic acid on the stress corrosion cracking of 3.5NiCrMoV turbine steels in high temperature water

The effects of acetic acid on the stress corrosion cracking (SCC) susceptibility of ASTM A470/471 turbine disk/rotor steels (3.5NiCrMoV) were evaluated. Thus, this study investigated the possibility of corrosion damage to turbine components due to acidified, early condensates containing acetic acid, which is a common impurity in steam cycle systems. Constant extension rate tests (CERTs) were carried out in aqueous solutions containing acetic acid at various concentrations (pH 3-5) at 150 °C to ascertain the susceptibility in terms of strain to failure and reduction in area upon fracture. Acetic acid significantly affects the SCC susceptibility of the turbine steels with the susceptibility increasing with increasing acetic acid concentration, except at the very highest concentration at which excessive dissolution led to crack blunting. The SCC susceptibility test results were analyzed using the CEFM (Coupled Environment Fracture Model), and it is shown that this model accounts for the experimentally-observed relationships between the SCC growth rate and the concentration of the acetic acid in terms of the conductivity of the solution.