SIandAII Ch6 Pitting Corrosion

Surfaces, Interfaces, and their Applications II
Pitting Corrosion
Pitting corrosion
For passive metals and alloys, uniform corrosion is rare or only possible in a very aggressive acidic (and alkaline for Aluminium) environments. In the presence of aggressive ions, microscopic local corrosion attacks can take place under certain conditions. Localized corrosion can manifest itself as pitting, crevice or intercrystalline (intergranular) corrosion, Fig. 6.1.
Figure 6.1: Manifestations of local corrosion: crevice corrosion (left), pitting (middle), intercrystalline (intergranular) corrosion (right) In the case of pitting corrosion, local corrosion attacks form at the passive surface. Crevice corrosion is to a large extent a geometrical problem (more intense attack in the crevices arising from stagnant media), and intercrystalline (intergranular) corrosion is a material problem (sensitization or non-noble grain boundaries which are preferentially attacked).
6.1
Introduction relevant factors for pitting corrosion attack
Definition: In order for a passive metal to be susceptible to pitting corrosion, two conditions have to be fulfilled: 1) Presence of aggressive anions (element: Cl, F, Br, I) inducing a local attack (dissolution) of the passive film 2) The equilibrium potential of the material must be higher than a material characteristic potential called Pitting potential
The characteristic appearance (Fig. 6.2) of the pit in the early stage of localized attack is: The attack has the form of geometrical features Very well delimited holes (sharp boundary) are found The material is absolutely intact next to the holes
Dr. Patrik Schmutz, Laboratory for Joining Technologies and Corrosion, EMPA Dbendorf, 2013
Pitting Corrosion
a)
b)
Figure 6.2: Optical appearance of pitting corrosion attack: (a) Pitting corrosion of Cr-Ni stainless steel in HCl solution, (b) cross-section through a typical semi-circular growing pit of a few hundred micrometres. The main reasons for localized corrosion failures are: Insufficient passive film stability (for stainless steel, insufficient chromium content cannot prevent chemical dissolution at the oxide-solution interface as discussed in the chapter 3 about passivation) Design errors: the presence of areas with stagnant solution will accelerate the generation of local aggressive conditions (defined later in chapter 6.2)
Inadequate surface preparation: the presence of deep scratches or defects during surface preparation can act as pit initiation sites.
In order to completely understand and assess the risk of a localized corrosion processes, it is necessary to clearly distinguish three different phases, Fig. 6.3: 1) Pit (hole) initiation During this incubation phase, aggressive ions destabilize locally the nm-thick passive oxide films or defects. It needs to be stated that the pit initiation stage extends to micrometer large dissolved holes. 2) Pit growth or 3) repassivation Even if sufficiently large dissolution occurred to form micrometer size pits, corrosion can still stops if a new oxide film forms on the hole surface. This situation is obtained when no local aggressive solution in the pit can be generated. If the chemical environment is getting so aggressive (acidic) that repassivation is thermodynamically impossible, the corrosion will locally propagate in depth by a dangerous autocatalytic process.
Pitting Corrosion
Figure 6.3: Schematic description of the different stages of a localized corrosion processes starting with an intact nm-thick oxide that is progressively dissolved. In the initial stage, active dissolution can be suppressed if an oxide film reforms (repassivation) before aggressive local chemistry is generated. Otherwise, a progressive in-depth pit growth occurs. The pits are geometric features that can be investigated in-solution from their very early stage of formation, Fig. 6.4. Missing atoms in crystalline passive films (example of Nickel oxide structure, Fig. 6.4a) and adsorption layer can be detected by electrolytic Scanning Tunneling Microscopy (STM) as well as nanoscale topographic changes related to pit formation, Fig. 6.4b.
a)
b)
Figure 6.4: Scanning Tunnneling Microscopy (STM) investigation of pit initiation process on a Nickel single crystal in NaCl solution: (a) Atomically resolved oxide structure showing missing atoms (white squares), (b) In-situ imaging of the growth of a nm-size pit
Dr. Patrik Schmutz, Laboratory for Joining Technologies and Corrosion, EMPA Dbendorf, 2013 3
Pitting Corrosion
a)
b)
Figure 6.5: Optical microscopic images of pits formed on Fe immersed in phthalate buffer solution (pH 5) with addition of: (a) 0.01KCl + 0.01 K2SO4, (b) only 0.01 KCl. Although, most of the pits grow as semi-circular shaped holes (Fig. 6.5a) because of the local diffusion processes, it is possible to generate crystallographic pits (for example hexagonal holes) like for Fe immersed in KCl containing phthalate buffer, Fig. 6.5b. Here, a combination of crystalline plane dependant adsorption for specific anions and orientation dependant dissolution rates is used to generate special pit geometries. Localized corrosion processes are not always detrimental and can also be used to structure surfaces when the corrosion mechanisms are well understood!
6.2
Pitting corrosion mechanisms
The pitting corrosion susceptibility of a material can be assessed and discussed based on electrochemical potentiodynamic polarization measurements, Fig. 6.6. A passive material will usually show a very low current density (A/cm2) up to the water dissociation potential or to the chromium transpassive dissolution for steel in absence of aggressive anions. The occurrence of a localized corrosion (pitting) process is evidenced on the electrochemical measurement by a drastic reduction of the potential range for passivity and a rapid current increase when the critical value for the pitting potential Epit is exceeded. For a given material, the higher the pitting potential is, the more corrosion resistant it will be. The polarization potential is giving the driving force for anodic dissolution and will help stabilizing a localized corrosion process (spontaneously with the cathodic reduction or externally with a potentiostat). When the potential is decreased below the repassivation potential Erep , the driving force for dissolution is reduced and the attacked sites are deactivated by formation of an oxide film in the pit.
On Figure 6.6, a schematic view of an anodic potentiodynamic polarization curve with the different relevant parameters is given. Ideally, materials with Erep close to Epit will be more corrosion resistant than if Erep is very low because when the two potentials are close together, any potential drop in the pit will shut down its growth (current decrease). When a very low repassivation potential is measured on a material, this means that every initiated localized attack will growth. Stable pitting condition: Existing pits have repassivated at: E > Epit E < Erep
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Pitting Corrosion
Figure 6.6: Schematic description of electrochemical anodic potentiodynamic polarization measurements (typical for stainless Steel) obtained with and without aggressive chloride anions.
6.2.1
Pit initiation
The first stage of the pitting process called pit initiation is related to the breakdown of the protecting passive oxide. Different mechanisms (Fig. 6.7) have been proposed for the various passive materials depending on the thickness of their oxides and also on the chemical stability at the oxide-solution interface (see chapter 3). A further aspect related to the passive oxide has been discussed in the chapter 5 and is the very high potential drop (up to 107 V/cm) accommodated in the film that will favour ion migration. It is possible to distinguish between: 1) The penetration mechanism: the Cl- ions (or other halides anions) are integrated instead of OH- and migrate through the passive film inducing hole formation at the metal-oxide interface. This type of initiation process is typical of corrosion resistant material with very thin thermodynamically stable oxides like Chromium. 2) The island adsorption mechanism: the Cl- ions (or other halides anions) adsorbs locally on the surface replacing OH- and decreases the stability of the oxide surface. The passive layer dissolves faster until the metal surface is exposed. This process is typical of less corrosion resistant materials such as stainless steels where the passive oxide is in an dynamic formation-dissolution state (see Quartz Crystal Nanobalance results in the Passivation chapter) 3) The oxide cracking mechanism: in this case, the surface oxides (hydroxides) film cracks open due to stresses (internal or applied). This initiation mode is rarer and implies as prerequisite a poorly passivating surface (thicker oxide) or the presence of a thick anodized layer for example. Magnesium in the alkaline domain would be such an example of a material able to passivate but forming a thick oxide layer that can crack in presence of chlorides.
Pitting Corrosion
Figure 6.7: Schematic presentation of the three initiation mechanism often found
In industrially produced materials, there are other factors increasing the pit initiation probability such as inclusions and defects, Fig. 6.8. Typically for stainless steel, the manganese sulphide particles are dissolving very easily (they are not passivating, Fig.6.8a) and generating very detrimental crevices where aggressive electrolyte can be trapped, Fig. 6.8b. Sulphur addition is necessary to improve machinability of steels so that defect engineering (size, shape, composition) is necessary to reduce the localized corrosion susceptibility of these defects. For this reason, it has been necessary to develop dedicated local electrochemical methods, suitable to perform corrosion resistance assessment on single material defects. The electrochemical Microcell setup presented in detail in section 6.4 is currently the most powerful one and has been widely used to elucidate the role of inclusion in corrosion susceptibility of stainless steel.
a)
b)
Figure 6.8: Influence of inclusions on pitting corrosion susceptibility: (a) weaker or absence of passive film on MnS inclusions in stainless steel, (b) dissolution of the inclusion (imaged by Focussed Ion Beam FIB) cut inducing the formation of microcrevices on a corrosion resistant stainless steel The pitting potential is defined by the threshold potential at which the measured current rapidly increases because of the growth of a stable localized attack. Pit formation can however already occur at potentials lower than the pitting potential. In this potential domain (E < Epit), these local events are often very numerous (Fig. 6.9a), but solution aggressivity for stable growth is not achieved. We are in presence of metastable
Pitting Corrosion
pitting events. The hole formation process for the metastable pitting process is measurable as a dissolution current transient, Fig. 6.9b. When local dissolution occurs and the current starts to increase, the polarization in the hole in formation will be automatically decreased because of the ohmic drop U=RI effect. The concept that solution resistance is slowing down the reaction rate has already been discussed in relation with galvanic coupling. In the case of a localized attack, it means that as soon as the current locally increased, the driving force (potential) for dissolution is decreased at the pit bottom and passivation can be re-established. But during, the dissolution phase, local solution aggressivity is also increasing and once a given threshold passed charge is reached, one of the metastable pit will transfer in a stable growing pit.
Figure 6.9: Electrochemical characterization of metastable pits: (a) complete polarization curves with current transients in presence of chlorides, (b) Enlargement of a single current transient corresponding to one initiation event
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b)
Figure 6.10: Scanning Electron Microscopy (SEM) characterization of metastable pitting corrosion event on stainless Steel in NaCl: (a) before removing the passive film remnant, (b) after removal of the cover passive film to show the real pit size
Pitting Corrosion
Note: A metastable pit, even before being in a stable growth condition is already a large microscopic attack as can be seen on Fig. 6.10. It is however important, for a correct assessment of the localized corrosion susceptibility of a material/structure, to determine if you are in presence of metastable events that will not result in safety relevant damages or if dangerous stable pits are growing. Sometimes, the effective size is not seen because of the presence of the passive film, but once the cover is removed, metastable pit size of a few micrometer are found, Fig. 6.10b. 6.2.2 Pit growth
Once a metastable pit reached stabilized growth, in-depth propagation will occur. The question is now why a localized attack can be so detrimental. The answer becomes clear when considering the electrochemical reactions involved. Following reaction steps are found during pit growth processes, Fig. 1) Dissolved metallic ions are hydrolyzed (see equation below). As a result, large amount of protons (H3O+) are formed and the pH will drop quickly in the pit.
2) This hydrolysis process induces a local excess of positive charge (H3O+). The electroneutrality in the local pit solution volume has to be achieved at any time so that fast Cl- migration in the pit will occur producing locally more aggressive HCl solutions.
3) The diffusion of O2 is more difficult in the occluded pit area resulting in local O2 depletion. Obtaining stable passivation equilibrium condition is difficult with small O2 diffusion current as shown in Figure 6.12 so that constant activation of the pit is guaranteed. When an active-passive transition is present for the passive material, a decrease of the pH will result in an increase of the critical current density (icrit), Fig. 6.13. The repassivation process is therefore even more hindered. The combination of all these phenomena induces an autocatalytic process for the localized attack where the dissolution rate is accelerating during a first phase. If the pH drops below a value of 4, it is also necessary to take into account an additional cathodic reaction taking place only in the pit, the hydrogen reduction (H-type corrosion process). This cathodic reaction is charge transfer controlled so that it can induce very high dissolution rate in the pits and acidification will accelerate the pit growth rate.
2H+ + 2e-
= H2
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Pitting Corrosion
For a passive metal, an active passive element (microgalvanic coupling) is furthermore created and maintained during the pit growth phase: Active anode (pit) Passive cathode (intact passive layer around the pit)
Concerning the galvanic coupling conditions, the area ratio is catastrophic with a small anode surrounded by a very large cathode. If the electrolyte conductivity is good and the passive film supports oxygen reduction, then the pits will grow very fast !
Figure 6.11: The different processes occurring during the pit growth process generating very acidic local environment and autocatalytic acceleration of the dissolution
a)
b)
Figure 6.12: Equilibrium situation that can be spontaneously obtained for the corrosion reaction: (a) stable passivation outside of the pit in aerated neutral solution, (b) active corrosion in acid pit media with higher icrit and lower O2 diffusion current
Pitting Corrosion
Figure 6.13: Increase of icrit with decreasing pH stabilizing active corrosion in presence of O2 reduction reaction
6.3
Pitting susceptibility of Materials
Due to the fact that oxygen is almost always present in the environment, and that equilibrium conditions up to its reversible potential can be established: E rev, O2 = 1.23 SHE - 0.059 pH most of the industrially relevant materials will spontaneously suffer from localized corrosion attacks if their pitting potential does not surpass the Erev, O2. Fig. 6.14 schematically presents this situation with the dangerous pitting potential domain extending up to the blue point.
Figure 6.14: Potentiodynamic polarization curve of metal that can be passivated in the absence and activated in the presence of pitting inducing anions.
The pitting potential values of common materials measured versus the Standard Hydrogen Electrode (SHE) in 0.1M NaCl solution is presented in Tab. 6.1. It is obvious that materials like Aluminium are very susceptible to pitting initiation (very low pitting potential). The
Pitting Corrosion
different Cr-Ni stainless steels and Nickel show better pitting corrosion resistance but can all spontaneously fail in aerated media. Chromium and Titanium with pitting potential higher than 1 Volt are immune against pitting corrosion in this chloride containing media. For chromium, it must not be forgotten that the material surface will experience transpassive dissolution at higher potential, but the detected current increase is not related to a localized corrosion attack. Table 6.1: Pitting potentials for different metals and alloys Metal Aluminium Nickel 18/8 CrNi steel 12% Cr steel 30% Cr steel Chromium Titanium Epit ( versus SHE, 0.1 N NaCl) -0.37 0.28 0.26 0.20 0.62 > 1.0 > 1.0 (1 N NaCl)
For high-alloyed steel, the resistance against pitting increases with higher chromium and molybdenum content, Fig. 6.15. It is worth noticing that in order to obtain a significant increase in pitting corrosion resistance, very large amount of chromium are necessary because chromium is needed to stabilize efficiently the passive film on stainless steel that is first in a very dynamic state of constant formation-dissolution from 12% Cr up to approximately 30% Cr. This aspect needs to be checked for any new alloy development because the alloying element concentration necessary for passivation and for pitting corrosion resistance of the passive film can be very different. For Molybdenum, the situation is different. If sufficient amount of Chromium is present in order to guarantee passivation, addition of small amount of Molybdenum (a few percent) is sufficient to obtain similar pitting corrosion resistance, Fig.6.15b.
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b)
Figure 6.15: Influence of alloying element of stainless Steel on the pitting potential increase in NaCl solutions
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Pitting Corrosion
Molybdenum acts in a different way on the localized corrosion process. Addition of Mo will decrease the critical current density for the active-passive transition in very acidic media, Fig. 6.16. The influence of small Mo addition in obtaining order of magnitude current decrease is shown in Fig. 6.16b. One first beneficial effect is that pits can repassivated because even with low oxygen contents in the pits, the only possible equilibrium is in the passive domain, Fig. 6.16a. Molybdenum has a second very beneficial effect that is related to the dissolved molybdate ions that can act as a buffering agent in the pit. The pH drop is smaller and obviously the hydrogen reduction rate can also be kept low.
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b)
Figure 6.16: Potentiodynamic polarization measurement and critical current density as function of Molybdenum content
Figure 6.17 shows an example of the pitting potential change with the alloy composition. Three steel types with different compositions (Tab. 6.2) were potentiodynamically polarized in neutral NaCl of LiCl solutions. Fig. 6.17 shows that steels with the highest Ni and Mo content possesses the highest pitting potential.
a)
b)
Figure 6.17: Potentiodynamic polarization measurement of different steels (see Tab 6.2 for composition) in: (a) 0.1M NaCl and (b) 6M LiCl
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Pitting Corrosion
Table 6.2: Some steel and nickel qualities sorted in groups with increasing pitting and crevice corrosion resistance; depending on the qualities, alloys indicated in brackets can be present in different groups. The second part of the table indicate where the different group of alloys can be used group I II III IV V VI materials 1.4301, 1.4303, 1.4306, 1.4541, 1.4543 1.4401, 1.4404, 1.4406, 1.4429, 1.4435, 1.4436, 1.4438, 1.4571 1.4439, 1.4462, 1.4503, (1.4539) (1.4539), 1.4563 1.4529, 1.4565, Avesta 254 SMO, (2.4856) 2.4602, 2.4610, 2.4819, (2.4856)
The localized corrosion resistance of stainless steels against pitting (and crevice corrosion) is positively influenced by the already mentioned elements chromium (Cr), molybdenum (Mo), and nitrogen (N), and negatively influenced by the elements sulphur (S), manganese (Mn, together with sulphur), and carbon (C). The elements that have a positive effect are summarized in the PRE (Pitting Resistance Equivalent). To calculate the PRE, the following equation is used: PRE = a %Cr + b %Mo + c %N. For the constants, a = 1, b = 3.3 und c = 0 30 are used. The PRE has no strict scientific meaning. Nevertheless, it is a suitable guideline to a comparative evaluation of the resistance of solution annealed / quenched stainless steel (and nickel alloys). Impurities, inclusions,
Pitting Corrosion
degree of deformation, previous heat treatments and the surface condition of the steel are not considered in the PRE. Regarding their resistance to pitting and crevice corrosion, stainless steels can be roughly divided into groups (Tab. 6.2). This division into groups of alloys provides only a general rule for corrosion resistance but should avoid that alloys with low pitting corrosion resistance are used in completely wrong environment. This can represent a major safety issue. In specific cases, the material impurities (Mn and S content, see Fig. 6.17) and especially the surface quality (ground, brushed, polished, honed) can play an important role. Lower classified steel with better surface quality behaves in a more resistant way than higher classified steel with bad surface (rough, grooves, scratches).
Figure 6.17: Microstructural observation of the MnS inclusions distribution in a Stainless steel as function of the nominal Sulphur content in the alloy. Higher chloride concentrations (more aggressive conditions) shift the pitting potential to more negative values (Fig. 6.18). This effect is however relatively marginal compared to the corrosion resistance changes that can be obtained by modifying and alloy or changing the materials.
Figure 6.18: Pitting potentials of different metals depending on the Cl- concentrations
Pitting Corrosion
Finally, it needs to be mentioned that pitting corrosion is only an issue as long as the material is passive and the surface is protected. Reducing the chloride concentration in neutral environments will result in slow passive film dissolution process (left-bottom conditions of Fig. 6.19). In presence of higher chloride concentration in neutral to slightly acidic HCl media will induce severe localized attack (middle part of the graph) until passivation cannot be obtained typical at pH around 0 (right part of Fig. 6.19).
Figure 6.19: Pitting versus uniform corrosion of stainless steel as function of chloride concentration and pH
6.4
6.4.1
Local electrochemistry - the Microcell technique

Introduction
The durability of technical passive alloys (e.g., stainless steels or aluminium alloys) is often limited by chemical or structural heterogeneities. Inclusions play a key role in being potential initiation sites of pitting and crevice corrosion, Fig 6.17. Many electrochemical methods to study localized corrosion are based on large-scale experiments with exposed areas in the square millimetre to square centimetre range. To understand the mechanisms of pit initiation and propagation, it is useful to also study the corrosion processes at the micro- and nanometre ranges. Such investigations often provide a better insight into the initiation mechanism of localized corrosion. The electrochemical techniques for localized corrosion tests in microscopic and nanoscopic dimensions can be divided into two major groups: 1. Scanning techniques: Immersed samples (immersed area is in the square millimetre to square centimetre range) are scanned using microelectrodes or ultramicroelectrodes. These methods allow obtaining information about the local distribution of one or several parameters during corrosion experiments. The experiments might be performed under open-circuit conditions or under potential or current control. Depending on the particular technique, a lateral resolution down to a few nanometres is possible. However, many scanning methods do not allow measuring of local corrosion currents. The potentiostat controls the current flow of the whole immersed surface area.
Pitting Corrosion
2. Small-area techniques: By decreasing the size of the exposed area, it is possible to localize the electrochemical process. This can be achieved by thin embedded wires, photoresist techniques, a droplet cell, or small glass capillaries touching only small areas of the specimen surface, Fig. 6.20. These techniques allow, in contrast to the scanning methods, polarization of the microscopic surface areas. All common electrochemical techniques, for example, potentiostatic or potentiodynamic measurements, galvanostatic measurements, and cyclic voltammetry, can be applied. Local corrosion currents can be evaluated directly. With a high-resolution potentiostat, corrosion processes on a molecular level can be recorded, even if the small-area techniques do not show such a high lateral resolution as the scanning methods.
Figure 6.20: Different examples electrochemical reaction rates
of
methods
allowing
local
determination
of
6.4.2
Electrochemical Microcell principle
The setup for microelectrochemical investigations based on the microcapillary is shown schematically in Figure 6.21a. The entire setup is mounted on a microscope, allowing for precise positioning of the capillary. The fully assembled microcell is shown in Fig. 6.21b. The microcell basically consists of a pulled microcapillary filled with electrolyte. The tip diameter of the capillary can be varied from about 1 to 1000 m depending on the experimental requirements. Between the front end of the microelectrode and the surface of interest, a layer of silicone rubber is applied as sealant. The microcell is fixed at the revolving nosepiece replacing an objective, and the specimen is mounted on the microscope stage. This arrangement enables the search for a site with different magnifications before switching to the microcapillary measurement. In this way, simple, precise, and fast positioning of the microcell is possible. A reference and counter electrode are connected to the capillary allowing electrochemical control of the investigated surface.
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Figure 6.21: (a) Schematic description of the Microcell system and (b) photographic view of the mounted setup
a)
b)
Figure 6.22: (a) Glass microcapillary with silicone sealant used and (b) measurement principle with positioning of the capillary precisely on different locations of a heterogeneous structure. Thin microcapillaries are obtained by heating borosilicate glass tubes and pulling them when they reach the glass temperature. For sealing, the glass capillaries are dipped in a onecomponent silicone lacquer. A stream of ethanol is pressed through the micropipette in order to flush out the silicone inside the capillary without destroying the fine tip. Very thin layers of silicone are applied to the capillary tip by repeating this process many times. The hardening process proceeds at a slow rate, which allows the silicone surface to energetically minimize under the effect of surface tension, resulting in smooth and dense coatings, Fig. 6.22a. This process allows production of capillaries with tip diameters below 1m.The quality of the silicone sealant is a most critical factor, as it determines to a high degree the quality of an electrochemical experiment.
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Figure 6.23: Different examples of application directly of final products (implants, machined watch components, electrical circuit)
Measurement of the local electrochemical response and corrosion susceptibility of metallic materials can be performed on curved substrates or complex shaped components because of the sealing at the end of the capillary, Fig. 6.23.
6.4.3
Pitting corrosion mechanisms information obtained
The first information that is of interest for a heterogeneous material is the distribution of pitting corrosion susceptible areas on a surface. For this purpose, the influence of the size of the exposed area on pit initiation can be investigated by means of microcapillaries of decreasing sizes. Figure 6.24 shows how the pitting potential might change if the exposed area is decreased. Local polarization curves were measured at random sites on the low sulphur 1.4301 (Fig, 6.17; also called 304 SAE Grade) plate in 1M NaCl. The diameter of the microcapillaries varied from 50 to 1000 m. Common large-scale measurements show a pitting potential of about +300mV (SCE). Measurements performed with 1000 m microcapillaries show similar pitting potentials. Diminishing the exposed surface to an area of 50 m in diameter led to an increase of the pitting potential to about +1200mV (SCE). Microelectrochemical experiments revealed that the pitting potential is an area dependent value. Additional measurements showed that the increase of the pitting potential is caused by a decrease of the number of weak points when the exposed area is diminished.
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Figure 6.24: Pitting potentials of a 1.4301 plate (0.003% S) as a function of the diameter of the microcell. The polarization curves were measured at random sites in 1M NaCl
Figure 6.25 shows a polarization curve measured on the medium-sulphur 1.4301 rod. A capillary with a tip diameter of about 100 m was used to select a single MnS inclusion. The electrolyte was 1M NaCl. The curve reveals onset of pitting at +300mV (SCE). Large-scale measurements showed stable pitting at a similar potential, so that it can be stated that this type of inclusion represent the most susceptible defect in the alloy. Microelectrochemical measurements performed on areas without MnS inclusion did not indicate pitting at potentials below the onset of oxygen evolution. Figure 6.25b shows the SEM picture of the inclusion after the corrosion experiment. It indicates that the inclusion/bulk interface is mainly attacked.
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b)
Figure 6.25: Pitting behaviour of a single MnS inclusion on an 1.4301 rod (0.017% S): (a) Polarization curve measured in 1M NaCl and (b) SEM picture of the attacked MnS inclusion taken after the corrosion experiment
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Getting even more local with smaller capillaries, Figure 6.26 shows polarization curves measured on the high-sulphur 1.4301 plate. A capillary with a tip diameter of about 2.5 m was chosen to study the corrosion behaviour of different zones of a single MnS inclusion in 1M NaCl. The investigated spots are indicated with white circles on the SEM picture taken before the corrosion. The electrochemical experiments were discontinued at a current limit of 10 nA (corresponding to a current density of about 200 A/cm2). After a measurement, the capillary was positioned on the next spot. The polarization curves of the 3 spots provide information on the pitting behaviour of different zones of the inclusion. The measurements performed on the adjacent bulk matrix indicate no pitting at potentials below +1000mV (SCE). The current fluctuations in the passive range were probably caused by activation and repassivation processes. The measurements performed on the inclusion/bulk interface show that pit initiation occurred in the potential range between +100 and +300mV (SCE). Curves measured on the interface showed numerous current fluctuations caused by pit nucleation processes. The pitting potentials of the polarization curves measured on the MnS inclusion are shifted to values about 200mV more positive compared to the interface. The fact that the centre part of a MnS inclusion shows active behaviour only at higher potentials supports the hypothesis that MnS inclusions are covered by an oxide film. The oxide film shows most defects at the interface inclusion/bulk due to the change of the crystallographic structure. This might explain why different polarizations are necessary to activate the interface and the centre part of an inclusion.
a)
b)
Figure 6.26: Corrosion behaviour of different zones of a single MnS inclusion on a 1.4301 plate (0.026% S) in 1M NaCl: (a) Polarization curves measured on different spots of the MnS inclusion using a microcapillary with a tip diameter of about 2.5m, (b) SEM picture of a MnS inclusion taken before the corrosion measurements
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Modification of the microcells allows the evaluation of various parameters during a corrosion experiment or performing of corrosion measurements under different stress parameters (temperature, mechanical loading and flow) pH measurements: A 25-m tungsten wire insulated with 5mm polyimide can be used to measure the pH at variable positions over the sample surface during corrosion experiments (26). The wire, with a freshly cut tip, is inserted into the microcapillary and positioned with a fine threaded micrometer screw with a resolution of +2m. Prior to an experiment the tungsten wire is calibrated in different buffer solutions to check the reproducibility. Only the results of measurements with reproducibility better than 0.5pH units are usually accepted. The experimentally determined response time of the tungsten wire is in the order of 1 sec, which is about 10 times longer than the time of the diffusion of the hydrogen ions to the probe. Measurements with temperature control: A Peltier element is used to control the temperature of the sample during a corrosion experiment. The Peltier element allows varying of the temperature between 0 C and 100 C. A special temperature control unit with a linear control characteristic was developed in order to avoid interference with low current measurements. Measurements with applied mechanical stress: A special sample holder is used for experiments with applied stress. For constant deflection tests, thin samples are used as specimens. Stress is applied to the specimen by holding it down at the border and bending it over a centred screw. The amplitude of the applied stress is calculated. The calculations are verified with the help of the minimum deformation which led to indications of plastic deformation after relaxation of the applied stress. Measurements with friction: A rotating aluminium oxide tube inside the microcapillary allows corrosion measurements with friction. This modification allows testing of the behaviour of a metal probe in an electrolyte under rubbing conditions on the micrometre scale. Rotational speed, load, and applied electrochemical potential or current can be varied so that it is possible to analyse the corrosion rate during rubbing at various controlled conditions. In order to quantify the tribocorrosion, profilometer measurements of the treated zone were performed. An accuracy of 10% was found. With this microtribometer the testing object could be directly placed on the sample holder without any particular pretreatment. Measurements with flow: An additional microcapillary inside the microcell enables testing of the vertical fluid flow. The bottleneck shape of the microcapillary allows application of very high flow rates. The inner capillary is positioned with a fine threaded micrometer screw with a resolution of +2 m. Measurements with sensors pH
A coated 25 m tungsten wire was used to determine the pH before and after pit initiation at a MnS inclusion in 1M NaCl, Fig. 6.28. A capillary with a tip diameter of about 100 m was used to select a single MnS inclusion on the high-sulphur 1.4301. Before each polarization experiment, a cathodic potential of -500mV (SCE) was applied for 2 min. The pretreatment led to a pH of about 9.5 because of the cathodic reduction reaction. During the polarization experiment the pH decreased slowly back to the value of the bulk electrolyte. A value of pH 5 was measured during the dissolution of the MnS inclusion and a pH value around 2 after the
Pitting Corrosion
onset of stable pitting. Diffusion calculations were performed to estimate the pH inside the pit nucleation site. The results showed that a measured pH of 2 correlated with a pit pH of 1.5 and a measured pH of 5 correlated with a pit pH of 4.5.
Figure 6.27: Schematic representation of the different sensors that can be implemented in the microcapillary.
a)
b)
Figure 6.28: (a) Polarization curve and pH values measured on a single MnS inclusion of a 1.4301 plate (0.026% S) in 1M NaCl, (b) Polarization curves measured on single MnS inclusions of a 1.4301 rod (0.017% S) in 1M Na2SO4 at different temperatures
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Temperature
Figure 6.28b shows polarization curves measured in 1M Na2SO4 on the medium sulphur 1.4301 plate at different temperatures. A capillary with a tip diameter of about 70 m was chosen to study the dissolution behaviour of single MnS inclusions in 1M Na2SO4 at elevated temperature. In sodium sulphate, MnS inclusions are active, but the 1.4301 alloy does not pit. Dissolution of the Mns inclusion starts at lower potentials when the temperature is increased Mechanical Stress
Microelectrochemical corrosion measurements were performed at single large MnS inclusions in order to evaluate the influence of applied mechanical stress on the pitting behaviour of stainless steels at room temperature. The rolling process of the high-sulphur 1.4301 plate leads to stretched inclusions. Depending on their orientation, different corrosion behaviour is observed. Experiments on unstressed specimens with single shallow MnS inclusions showed metastable pitting in 1M NaCl, whereas stable pitting was initiated at deep inclusions. Figure 6.29a shows the polarization curves for sites with single large and shallow MnS inclusions measured in 1M NaCl without stress and with an applied stress equal to 80% of the yield strength. The curve for an inclusion without applied stress indicates MnS dissolution between +300 and +550mV (SCE). Large current peaks were observed 100mV after the onset of MnS dissolution. The curve indicates metastable corrosion, but not stable pitting. SEM pictures (Figure 6.29b) showed several small corrosion sites at the inclusion/bulk interface. The MnS inclusion did not dissolve completely in 1M NaCl; it dissolved just partly.
a)
b)
c)
Figure 6.29: Schematic Dissolution and pitting behaviour of single shallow MnS inclusion in 1M NaCl without and with applied stress: (a) Polarization curves measured on single shallow MnS inclusions of a 1.4301 plate (0.026% S) in 1M NaCl, (b) SEM image of the shallow MnS inclusion after the electrochemical experiment without applied stress, (c) SEM image of the shallow MnS inclusion after the electrochemical experiment with applied stress.
23
Pitting Corrosion
Weld joints are often a major target of corrosion. The welding process often results in decreased material properties in the heat affected zone and the weld itself. The microcell technique has been successfully used to test welds of stainless steels. Local measurements of different areas of welds have indicated that different zones suffer corrosion attack depending on the type of weld. The measuring technique proved easy to handle and apply. Unlike immersion tests, which may take several days, it yields a reliable judgment of the quality of a weld in only a few minutes. In many applications, it is required that the corrosion resistance of the entire construction is tested. The microcell technique allows also a non-destructive testing of welds. The corrosion resistance of laser welds was evaluated to optimize a new laser welding process to join 1.4301 sheets. Figure 6.30a shows SEM pictures of a laser weld. The production pieces with the laser weld were tested as received in 1M NaCl solution. In Figure 6.30b, an example of polarization curves measured on different spots of the laser welding is shown. It is clear that the corrosion resistance of the matrix and the zone adjacent to the weld trench is significantly higher than that of the weld trench itself. The bottom of the trench showed a low corrosion resistance. It was found that the holes at the bottom of the trench (Figure 6.30a) significantly decreased the corrosion resistance. Too high laser intensity caused these holes. This meant that the process parameters had to be optimized.
a)
b)
Figure 6.30: Microelectrochemical testing of a laser weld on a 1.4301: (a) SEM pictures of the laser weld and (b) polarization curves and pitting potentials of different zones of the laser weld measured in 1M NaCl
24
Pitting Corrosion
Summary
General In order to evaluate correctly the failure risks related to localized corrosion processes, it is important to consider that the bulk solution chemistry is often irrelevant and that propagation rate is completely determined by the very aggressive local chemistry that can establish in a pit, Fig. 6.31. Local microcell measurements have shown that pHs down to a value lower than 2 can be found. At this pH, most of the metals cannot passivate properly. Geometry of defects also plays a crucial role: deep microcrevices generated by defect dissolution (Fig 6.31 right: dissolved MnS) or inadequate surface preparation can stabilize a growing pit on material that would otherwise not suffer from pitting corrosion.
Figure 6.31: Schematic description of the critical parameters in pitting corrosion Microcell technique
The microelectrochemical technique using microcapillaries as microcells is an elegant method to study local phenomena on metal surfaces. Due to the enhanced current resolution down to picoamperes and femtoamperes, local processes in the nanometer range can easily be measured. Incorporation of microsensors into the microcapillary cell generates additional chemical parameters such as pH values simultaneously with electrochemical measurements. This provides important analytical information especially, with respect to nonstationary processes. The results of localized corrosion experiments on stainless steels in 1M NaCl clearly showed that in moderately concentrated solutions, the presence of MnS inclusions is of primary importance for pit initiation, whereas the size and geometry as well as the amount of chlorides and the temperature are critical for the transition from metastable to stable pit growth. Pit initiation studies at MnS inclusions on 1.4301 stainless steels were performed at different scales. Electrochemical experiments using a capillary with a tip diameter in the range of 100 m allowed evaluation of the corrosion behaviour of areas with one single inclusion. Electrochemical measurements using a capillary with a tip diameter in the range of 1m allowed investigation of different spots of a single inclusion. Hence, the corrosion behaviour of the weakest zone could be determined.
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SIandAII Ch6 Pitting Corrosion

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Surfaces, Interfaces, and their Applications II

Introduction relevant factors for pitting corrosion attack

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Pitting corrosion mechanisms

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Pitting susceptibility of Materials

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Local electrochemistry - the Microcell technique

Surfaces, Interfaces, and their Applications II

Figure 6.20: Different examples electrochemical reaction rates

Electrochemical Microcell principle

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Pitting corrosion mechanisms information obtained

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

Surfaces, Interfaces, and their Applications II

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