Austenitic stainless steels passivity passivation

Fig- 7.65 Schematic EPR (electrochemical potentiokinetic reactivation) curves for three amounts of sensitization of an austenitic stainless steel. Passive film formed at (1). Downscans pass through maximum attack at (2). Environment 1 N H2S04 + 0.01 M KSCN at 30 °C. Curve (3) is observed if passive film continues to form on downscan. Source Ref 93... 

It is known that the common austenitic stainless steels have sufficient corrosion resistance in sulfuric acid of lower concentrations (<20%) and higher concentrations (>70%) below a critical temperature. If with higher concentrations of sulfuric acid (>90%) a temperature of 70°C is exceeded, depending on their composition, austenitic stainless steels can exhibit more or less pronounced corrosion phenomena in which the steels can fluctuate between the active and passive state [19]. 

Stainless steel 316L material used for piping and equipment shows considerable corrosion resistance because of the beneficial effect of molybdenum on the surface properties. It is also observed that the surface treatment (pre-reduced, polished, passivated and chemically treated surfaces) of stainless steel equipment and piping reduces the corrosion process in seawater applications. The corrosion resistance of stainless steel in seawater applications can also be enhanced by bulk alloying the stainless steel with nitrogen, chromium, molybdenum and nickel by converting the stainless steel into super austenitic stainless steel. From leaching studies it is also observed that the release of iron, chromium and nickel from the super austenitic stainless steel to seawater is considerably... 

Austenitic stainless steels are generally regarded as being spontaneously passive in aerated, near-neutral aqueous solutions, but surface treatment has a significant... 

Localized biological corrosion of stainless steels. There are three general sets of conditions under which localized biological corrosion of austenitic stainless steel occurs (Figure 6.29). These conditions should be examined for metals that show active-passive corrosion behavior. Microbiological corrosion in austenitic steel weldments has been documented. (Wahid)61, (Krysiak)14... 

Passivation is usually part of a chemical cleaning process using a sodium nitrite solution. (Chromates, once used extensively, are now considered to be too toxic.) Austenitic stainless steels are usually passivated in air after pickling and neutrahzation. Pickling is a chemical process to descale or clean new stainless steel. (See ASTM A380 for recommended procedures.) For heavily oxidized materials, the pickling process removes the chromium-depleted surface beneath the layer of scale. The acid solutions used contain sufficient nitric acid (a good oxidizer) so that a subsequent passivation step is unnecessary. 

Stress corrosion cracking is a form of localized corrosion, where the simultaneous presence of tensile stresses and a specific corrosive environment prodnces metal cracks [157, 168]. Stress corrosion cracking generally occnrs only in alloys (e.g., Cn-Zn, Cu-Al, Cu-Si, austenitic stainless steels, titaninm alloys, and zirconinm alloys) and only when the alloy is exposed to a specific environment (e.g., brass in ammonia or a titaninm alloy in chloride solutions). Removal of either the stress on the metal (which must have a surface tensile component) or the corrosive environment will prevent crack initiation or cause the arrest of cracks that have already propagated. Stress corrosion cracking often occurs where the protective passive film breaks down. The continual plastic deformation of the metal at the tip of the crack prevents repassivation of the metal surface and allows for continued localized metal corrosion. 

The Tafel constant was b = 0.20 V decade-1 for iron electrodes [55] and b = 0.20 V decade-1 for austenitic stainless steels [54] in acid solution. It is noticed that these Tafel constants are greater than those (0.03-0.1 V) usually observed with general dissolution of metals in acid solution. The other mode of localized corrosion is the active mode of corrosion that prevails in the potential range less positive (more cathodic) than the passivation potential, EP, in which potential range the localized corrosion is mainly controlled by the acidity of the occluded pit solution. In the potential range of active metal dissolution, the anodic dissolution current density is also an exponential function of the electrode potential, except for diffusion-controlled dissolution. 

Multiwall carbon nanotube (MWCNT)-reinforced hydroxyapatite composite coatings (80% HAp/20% MWCNT) were deposited on austenitic stainless steel AISI 316L by laser surface alloying (LSA) with a 2.5-kW CW Nd YAG laser (Kwok, 2007). EIS of unprotected AISI 316L and HAp/MWCNT-coated steel obtained at open circuit potential are shown in Figure 7.60 after immersion in 0.9% NaCl solution for 2 h. The Bode plot shows that the total impedance Z has noticeably increased for the steel substrate coated with HAp/MWCNT. While the thin passive oxide film on the stainless steel surface was rendered less protective... 

An interesting aspect of the expression (10) concerns the case of metals and passive alloys because the real polarization potential exhibits a discontinuity around the zone of transition from active to passive state. In fact, if Ip denotes the passivity current density, the value of the discontinuity is of the same order of magnitude as R,IpS because during this transition the current intensity falls very rapidly. The discontinuity may be very pronounced because the values of Ip, which depend on the type of metal, the environment and temperature, may be very high. In the case of the AISI 321H titanium-stabilized, austenitic stainless steel in 1 M HCIO4 -1- 0.3 M NaCl solutions at 25 °C, the value of Ip depends on the thermal history of the specimen [50]. In meiny instances it was found to be about 10 mAcm . ... 

For some material-environment combinations it has been shown that accelerated anodic dissolution of yielding metal is the significant mechanism. This is the case for austenitic stainless steels in acidic chloride solutions. In these steels, plastic deformation is characterized by a dislocation pattern giving wide slip steps on the surface. For such systems, Scully [7.50] has proposed a model for initiation and development of stress corrosion cracks, which has been supported by other scientists [7.51]. The model in its simplest form is illustrated in Figure 7.52. A necessary condition is that flie surface from the beginning is covered by a passivating film (A). 

In ferritic and austenitic stainless steels, crevice corrosion is almost always initiated by local activation. This can be induced in a crevice by oxidant depletion, if necessary supplemented by halides. The passivity then breaks down. The access of oxidants to the material surface, and hence the passivity, may also be hindered by local deposits. 

As discussed in Section 19.2.4, stainless steels are best employed under fully aerated or oxidizing conditions, which favor the passive state. Whether used in handling chemicals or exposed to the atmosphere, the alloy surface should always be kept clean and free of surface contamination. Otherwise, crevice corrosion may cause pitting and localized rusting. Austenitic stainless steels cooled too slowly through the sensitizing temperature zones tend to rust in the atmosphere. 

---