Observation of corrosion behavior of stainless steels in a salt manufacturing plant environment using the multichannel electrode method

Crevice corrosion of four kinds of stainless steel, SUS316L, NAS64, NAS185N and NAS254N, in saturated NaCl solution at temperatures up to 100 °C was investigated using the multichannel electrode method. In this method, a pile of five individual working electrodes (WEs) of stainless steel sheet were embedded in epoxy resin and a small hole penetrating through the five WEs was treated as an artificial crevice. Time transition and distribution of the coupling current between the five WEs were measured as a function of crevice depth, kind of stainless steel, temperature and concentration of dissolved oxygen (DO). Anodic or cathodic coupling current on the five WEs of SUS316L changed depending on their corroding state. On the other hand, NAS64, NAS185N and NAS254N showed that the WE outside the crevice contributed as a cathode and that WEs inside the crevice contributed as an anode. The coupling current on SUS316L was strongly affected by concentration of DO, while the coupling current on NAS64, NAS185N and NAS254N was not affected by DO, probably due to the establishment of a passive state inside the crevice.     

Current distribution during galvanic corrosion of carbon steel welded with type-309 stainless steel in NaCl solution

Galvanic corrosion of carbon steel welded with type-309 stainless steel in NaCl solution was tentatively evaluated with a newly developed multi-channel electrode technique in which the welded specimen was divided into nine working electrodes (WEs), reconstructed in resin, and connected individually to an imaginary ground level of an electric circuit via relay switches. This allows the WEs to join a galvanic couple and simultaneous measurement of participating current or open circuit potential of each WE. WEs were immersed together in 5.1 × 10² mol dm⁻³ or 2.1 × 10⁻⁴ mol dm⁻³ NaCl solutions, and spatial distribution of participating currents and open circuit potentials were monitored as a function of immersion time. The WE of the weldment acted as a cathode throughout the immersion period, while the other WEs of base steel became anodes or cathodes depending on their location, immersion time and concentration of the electrolyte solution. The ability of zinc-rich paint to protect the welded specimen as sacrificial anode was also investigated.     

Determination of electrochemical parameters and corrosion rate for carbon steel in un-buffered sodium chloride solutions using a superposition model

Corrosion of carbon steel in un-buffered NaCl solutions was studied applying linear potential sweep technique to a rotating disk electrode. Current-potential curves were obtained from linear potential sweep at a rate of 1 mV s⁻¹ in solution with concentrations in the range 0.02-1 M NaCl and rotation rates in the range 170-370 rad s⁻¹, at 22 °C. Potential sweeps, which were conducted in the potential range −700 to −100 mV/SHE, were started from the cathodic limit in order to approach the measurement of corrosion under rust-free conditions. Polarization curves were analyzed with a superimposition model developed ad hoc and implemented in a computer program, which enabled determining the corrosion rate and kinetics parameters of the underlying anodic and cathodic sub-processes. The anodic sub-process, dissolution of iron, was well described in terms of a pure charge transfer controlled reaction, while the cathodic sub-process, oxygen reduction on iron, was well described in terms of mixed mass transfer and charge transfer control. Increase of electrode rotation rate increases the limiting current of oxygen reduction, which results in an enhanced corrosion rate of carbon steel. Increase of NaCl concentration has a dual effect: the limiting current of oxygen reduction decreases as a result of the influence of NaCl concentration on solution viscosity and the anodic dissolution of iron increases due to the influence of NaCl on pitting formation. However, this last mechanism predominates and a net increase in carbon steel corrosion rate is observed in this case.     

Protective properties of hexacyanoferrate containing polypyrrole films on stainless steel

The protective properties of polypyrrole coatings containing hexacyanoferrate anions are presented. The composite coatings were electrodeposited galvanostatically on stainless steel from the aqueous solutions containing pyrrole monomer and potassium hexacyanoferrate(II) together with traces (10 μmol dm⁻³) of free CN⁻ ions. The protective properties of the resulting coatings were investigated in the highly aggressive medium of 0.1 mol dm⁻³ HCl and 0.4 mol dm⁻³ NaCl. Diagnostic experiments included measurements of open circuit potential with time of exposure, chronoamperometric (current-time) examination of the steel samples at a selected constant potential of 0.5 V and potentiodynamic measurements. To get insight into the dynamics of the steel dissolution at open circuit potential and at the selected anodic potential, changes of concentrations of iron and chromium in the test solution as a function of exposure time were determined using atomic absorption spectrometry. Morphology of the composite film was examined using scanning electron microscopy.     

Effect of cathodic protection on corrosion of pipeline steel under disbonded coating

In this work, a test rig was developed to study the effect of cathodic protection (CP) on corrosion of X70 pipeline steel in the crevice area under disbonded coating through the measurements of local potential, solution pH and dissolved oxygen concentration. Results demonstrated that, in the early stage of corrosion of steel, CP cannot reach the crevice bottom to protect steel from corrosion due to the geometrical limitation. Corrosion of steel occurs preferentially inside crevice due to a separation of anodic and cathodic reaction with the depletion of dissolved oxygen in the crevice solution. The main role of CP in mitigation of sequential corrosion of steel in crevice under disbonded coating is to enhance the local solution alkalinity. With the increase of distance from the open holiday, a high cathodic polarization is required to achieve appropriate CP level at crevice bottom. A potential difference always exists between the open holiday area and inside crevice, reducing the CP effectiveness.     

Stable pit formation on AA2024-T3 in a NaCl environment

Scanning vibrating electrode (SVE), particle induced X-ray emission spectroscopy (PIXE) and standard electrochemical measurements were used to study the establishment of stable pits on AA2024-T3 in neutral sodium chloride solution (0.1 M NaCl). Pits were allowed to develop until hydrogen evolution was observed. Typical current at the mouth of the pits were in the vicinity of 1 mA. PIXE maps revealed the intermetallic (IM) particle distributions in the surface as well as significant chloride buildup around the pits. A significant fraction of the small selection of pits examined here appeared to have an S-phase particle (or remnant) within 20 μm of a AlCuFeMn type IM particle suggesting a coupling between the two. The electrochemistry of the coupling between different IM particle types was further investigated using potentiodynamic scans in 0.1 M aqueous NaCl solution of macroscopic electrodes made according to the IM particle compositions. Current densities at the open circuit potential of AA2024-T3 were largest, typically (0.2 up to 1 mA/cm²) for phases that were anodic with respect to AA2024-T3. Coupling of the IM particles was examined by comparing the degree of clustering around chloride attack sites to the average particle density for each map. There were significantly higher number of IM particles surrounding pit sites than the average IM particle densities indicating that local clustering played an important role in pit initiation.     

Behaviour of crevice corrosion in iron

Crevice corrosion was investigated in iron exposed to a strong-buffered acetate solution (0.5 M CH₃COOH + 0.5 M NaC₂H₃O₂), pH = 4.66. The current and the potential gradient within the crevice were measured at crevice depth (L) = 7.35, 8, 10, and 15 mm, for a crevice that was positioned facing the electrolyte in a downward position. A remarkable shift in potential (>1.2 V) in the active direction was measured inside the crevice cavity, when the potential at the outer surface was held at 800 mV(SCE). Experimentation showed that there is a critical depth value, above which little changes occur on the transition boundary between passive and active regions on the crevice wall, x_pass, and below which x_pass location shifts sharply towards the crevice bottom. Steeping of the potential gradient occurred with time indicating enhancement of crevice corrosion, which was seen by the gradual increase in the current. These findings were in close agreement with the IR voltage theory and related mathematical model predictions. Morphological examination showed an intergranular attack around the active/passive boundary (x_pass) on the crevice wall.     

Effect of iron-containing intermetallic particles on the corrosion behaviour of aluminium

The effect of heat treatment on the corrosion behaviour of binary Al-Fe alloys containing iron at levels between 0.04 and 0.42 wt.% was investigated by electrochemical measurements in both acidic and alkaline chloride solutions. Comparing solution heat-treated and quenched materials with samples that had been subsequently annealed to promote precipitation of Al₃Fe intermetallic particles, it was found that annealing increases both the cathodic and anodic reactivity. The increased cathodic reactivity is believed to be directly related to the increased available surface area of the iron-containing intermetallic particles acting as preferential sites for oxygen reduction and hydrogen evolution. These particles also act as pit initiation sites. Heat treatment also causes depletion in the solute content of the matrix, increasing its anodic reactivity. When breakdown occurs, crystallographic pits are formed with {1 0 0} facets, and are observed to contain numerous intermetallic particles. Fine facetted filaments also radiate out from the periphery of pits. The results demonstrate that the corrosion of aluminium is thus influenced by the presence of low levels of iron, which is one of the main impurities, and its electrochemical behaviour can be controlled by heat treatment.     

Galvanic corrosion between the constituent phases in duplex stainless steel

The exclusive single-phase with the exact chemical composition of the constituent phase in 2205 duplex stainless steel (DSS) could be prepared using selective dissolution method. The respective electrochemical behavior of each constituent phase could then be measured. The experimental results showed that the two distinct peaks in the active-to-passive transition region of the polarization curve determined in 2 M H₂SO₄ + 0.5 M HCl mixed solution were actually corresponded to the respective anodic peaks of the single austenite and ferrite phases. A polarity reversion was found between austenite and ferrite phases in mixed H₂SO₄ + HCl solution and HNO₃ solution. Galvanic current measurements also revealed that austenite was anode in HNO₃ solution, but became cathode when exposed in 2 M H₂SO₄ + 0.5 M HCl mixed solution.     

Critical pitting temperature for Type 254 SMO stainless steel in chloride solutions

The variation with time of the open circuit potential of high molybdenum containing stainless steel (Type 254 SMO) was measured in 4% sodium chloride solution in the temperatures range 30-100 °C. The plot of steady state potentials as function of temperature showed an inflection at 50 °C, attributed to the decrease of oxygen solubility in test solution above 50 °C. Potentiodynamic cycling anodic polarization technique was used to determine the critical pitting potential (E_pit) and the critical protection potential (E_prot) of the steel in 4-30% NaCl solutions at temperatures between 30 and 100 °C. By plotting the two values versus solution temperature, the corresponding critical pitting (CPT) and the critical protection (CPrT) temperatures were determined. Both parameters decreased with increasing chloride content. Above the CPT, E_pit and E_prot decreased linearly with log[Cl⁻]. The addition of bromide ions to the solution shifted both E_pit and E_prot towards positive values. In 4% NaCl, E_pit increased linearly with pH in the range 1-10. The combined effect of chloride ion concentration and pH on the morphology of the pits was examined by scanning electron microscopy (SEM) following potentiodynamic cycling anodic polarization.     

Depassivation current transients measured between identical twin microelectrodes in open circuit

Current transients between identical twin titanium microelectrodes have been measured in open circuit. The electrodes showed transient breakdown of passivity in 1.5 M HCl although the potential is far below the pitting potential. Measurement of the current between the twin microelectrodes in sodium sulphate solution containing no chloride showed no detectable breakdown transients above the background noise. The current transients represent the breakdown of passivity and associated nucleation of corrosion pits. Some of the open circuit breakdown events show evidence of brief metastable pit propagation in the titanium surface.     

Electrochemical pitting corrosion behaviour of α-brass in LiBr containing solutions

The potentiodynamic anodic polarization curve of α-brass (70% Cu-30% Zn) in 1 M LiBr solution showed an initial active region of the alloy dissolution followed by two well defined anodic current peaks then a narrow passivation region before the pitting potential (E_pit) is reached. The initial active anodic region exhibited Tafel slope with 90 mV dec⁻¹ attributed to the formation of CuBr₂⁻ complexes. The anodic current peaks were attributed to the formation of CuBr and Cu²⁺ ions, respectively. The change of pH values of LiBr solution did not affect the anodic polarization curves of α-brass. Increasing the solution temperature from 30 to 90 °C changed the corrosion type from pitting to general one. The addition of 10⁻² M benzotriazole (BTAH) to 1 M LiBr solution is completely inhibited the pitting corrosion at 30 °C while it did not inhibit the pitting at 90 °C. The inhibition effect was attributed to the adsorption of BTAH molecules on the alloy surface, which obeys Langmuir isotherm. The presence or absence of pitting corrosion was confirmed by using SEM.     

Effects of alternating current on corrosion of a coated pipeline steel in a chloride-containing carbonate/bicarbonate solution

In this work, the alternating current (AC)-induced corrosion of a coated pipeline steel was studied in a chloride-containing, concentrated carbonate/bicarbonate solution, which simulated the trapped high pH electrolyte under coating, by potentiodynamic polarization measurements, immersion tests and surface characterization technique. It was found that an application of AC resulted in a negative shift of corrosion potential of the steel, caused an oscillation of anodic current density, and degraded the steel passivity developed in the solution. With the increase of AC current density, the corrosion rate of the steel increased. At a low AC current density, a uniform corrosion occurred, while at a high AC current density, pitting corrosion occurred extensively on the steel electrode surface. At individual applied AC, there was a higher electrochemical dissolution activity of the coated steel electrode containing a 1 mm defect than that of the electrode containing a 10 mm defect.     

Temperature effect in the corrosion resistance of Ni-Fe-Cr alloy in chloride medium

The corrosion susceptibility of alloy 33 in 0.5 mol/L sodium sulphate solutions containing or not 0.1 mol/L sodium chloride was tested at three different temperatures: 22 °C, 40 °C and 60 °C. Electrochemical studies were performed using corrosion potential measurements (E_corr) as well as potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. Corrosion potential measurements showed that alloy 33 was passivated by a previously air formed film which was not destroyed during immersion in both solutions. No corrosion was observed during these tests although the temperature affected the film. Potentiodynamic polarization experiments showed that at high anodic potentials the previous film was broken up, and localized corrosion occurred in both solutions and at the three temperatures tested. Electrochemical impedance spectroscopy tests confirmed the presence of a stable passive film on the alloy surface at open circuit potential. Mott-Schottky analysis indicated that the passive film is an n-type semiconductor due to the presence of point defects of donor species, such as oxygen vacancies and interstitial metallic cations. As the potential increases the Cr(III) present in the barrier layer oxidizes producing Cr(VI) soluble species. The dissolution creates metallic cation vacancies that are acceptor species and the film changes from n-type to p-type semiconductor. The passive film rupture and the following localized attack are related to the drastic oxidative dissolution of the film at high anodic potentials, independent of its p-nature, chloride presence or increased temperature.     

Corrosion resistance properties of glow-discharge nitrided AISI 316L austenitic stainless steel in NaCl solutions

Glow-discharge nitriding treatments can modify the hardness and the corrosion resistance properties of austenitic stainless steels. The modified layer characteristics mainly depend on the treatment temperature. In the present paper the results relative to glow-discharge nitriding treatments carried out on AISI 316L austenitic stainless steel samples at temperatures ranging from 673 to 773 K are reported. Treated and untreated samples were characterized by means of microstructural and morphological analysis, surface microhardness measurements and corrosion tests in NaCl solutions. The electrochemical characterization was carried out by means of linear polarizations, free corrosion potential-time curves and prolonged crevice corrosion tests. Nitriding treatments performed at higher temperatures (>723 K) can largely increase the surface hardness of AISI 316L stainless steel samples, but decrease the corrosion resistance properties due to the CrN precipitation. Nevertheless nitriding treatments performed at lower temperatures (?723 K) avoid a large CrN precipitation and allow to produce modified layers essentially composed by a nitrogen super-saturated austenitic metastable phase (S-phase) that shows high hardness and very high pitting and crevice corrosion resistance; at the same polarization potentials the anodic current density values are reduced up to three orders of magnitude in comparison with untreated samples and no crevice corrosion event can be detected after 60 days of immersion in 10% NaCl solution at 328 K.     

Monitoring corrosion and corrosion control of iron in HCl by non-ionic surfactants of the TRITON-X series - Part I. Tafel polarisation, ICP-AES and EFM studies

The corrosion inhibition characteristics of non-ionic surfactants of the TRITON-X series, known as TRITON-X-100 (TX-100), TRITON-X-165 (TX-165) and TRITON-X-305 (TX-305), on iron in 1.0 M HCl solution were studied. Measurements were conducted in 1.0 M HCl solutions without and with various concentrations of the three selected surfactants using chemical (ICP-AES method of analysis of dissolved cations) and electrochemical (Tafel polarisation and EFM) techniques at 25 °C. These measurements were complemented with SEM and EDX examinations of the electrode surface. Polarisation data showed that the non-ionic surfactants used in this study acted as mixed-type inhibitors with cathodic predominance. The protection efficiency increased with increase in surfactant concentration. Maximum protection efficiency of the surfactant was observed at concentrations around its CMC. From their molecular structure, these surfactants may adsorb on the metal surface through two lone pairs of electrons on the oxygen atoms of the hydrophilic head group.     

Galvanic corrosion of titanium coupled to welded titanium in LiBr solutions at different temperatures

The galvanic corrosion generated between the titanium-welded titanium pair has been studied in heavy brine LiBr solutions at 25, 50 and 100 °C under open circuit conditions using a zero-resistance ammeter (ZRA). The results showed that welded titanium was the anode of the pair, so that its corrosion resistance decreases due to the galvanic effect. However, the extremely low galvanic current densities registered by the pair reveal the poor severity of the coupling under the studied conditions. Furthermore, it was observed that the electrodes were in the passive state, increasing the probability of localized corrosion with temperature.     

Investigating corrosion processes in the micrometric range: A SVET study of the galvanic corrosion of zinc coupled with iron

The galvanic corrosion of an iron/zinc pair immersed in aqueous 0.1 M Na₂SO₄ solution has been investigated by using the scanning vibrating electrode technique (SVET). In this way, investigations in the micrometer range of the progress of the electrochemical reactions involved in galvanic process were performed. The anodic oxidation process is observed to be initiated on the zinc sample in a localized manner, whereas the cathodic reaction involving the electroreduction of dissolved oxygen is homogeneously distributed over the iron sample. This later process is the rate determining step in the overall corrosion process, as demonstrated by the changes in the ionic and galvanic currents measured in the system when the area of the iron specimen is varied relative to that of zinc. The occurrence of coupled chemical reactions in the solution phase involving the products of the corrosion reactions could also be deduced from the integration of the ionic currents measured for each half-reaction during a SVET scan. Thus, the corrosion processes involved in the galvanic coupling of iron and zinc have been further understood by using this microelectrochemical technique appropriately, helping to better interpret large scale measurements.     

Electrochemical characteristics of zirconium oxide treated Type 304 stainless steels of different surface oxide structures in high temperature water

Electrochemical polarization analyses were conducted to investigate the impact of different oxide structures on corrosion resistance of ZrO₂-treated Type 304 stainless steel specimens in high temperature water. All specimens were pre-oxidized in high temperature water containing either 300 ppb dissolved oxygen or 50 ppb dissolved hydrogen, followed by a hydrothermal deposition treatment with ZrO₂ nanoparticles. Experimental results revealed that the corrosion potentials and corrosion current densities on the ZrO₂-treated specimens were lower than those on the untreated ones, and the decreases in these parameters were more distinct on the ZrO₂-treated specimens with oxides developed under dissolved oxygen condition.     

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.