Passivation region

The titanium oxide film consists of mtile or anatase (31) and is typically 250-A thick. It is insoluble, repairable, and nonporous in many chemical media and provides excellent corrosion resistance. The oxide is fully stable in aqueous environments over a range of pH, from highly oxidizing to mildly reducing. However, when this oxide film is broken, the corrosion rate is very rapid. Usually the presence of a small amount of water is sufficient to repair the damaged oxide film. In a seawater solution, this film is maintained in the passive region from ca 0.2 to 10 V versus the saturated calomel electrode (32,33). 

Titanium is susceptible to pitting and crevice corrosion in aqueous chloride environments. The area of susceptibiUty for several alloys is shown in Figure 7 as a function of temperature and pH. The susceptibiUty depends on pH. The susceptibiUty temperature increases paraboHcaHy from 65°C as pH is increased from 2ero. After the incorporation of noble-metal additions such as in ASTM Grades 7 or 12, crevice corrosion attack is not observed above pH 2 until ca 270°C. Noble alloying elements shift the equiUbrium potential into the passive region where a protective film is formed and maintained. 

Anodic Protection On the reverse anodic scan there will be a low current region (LCB) in the passive range. The passive potential range of the LCB is generally much narrower than the passive region seen on a forward slow scan. In anodic protection (AP) work the midpoint of the LCB potential is the preferred design range. This factor was verified for sulfuric acid in our laboratory and field studies. 

Note also that a galvanic couple can be established between passive regions and active regions of the same stainless steel component. For... 

Figure 2-13 shows the potential dependence of the corrosion rate in the passive region (Fig. 2-2) for the system Fe/H2S04. kiU < = 0.8 V, the transition... 

Although thermodynamics can predict the region of pH and potential in which solid oxides, hydroxides and other compounds are stable, it can provide no other information thus on the basis of these considerations alone a metal in the passive region should be completely converted to a solid compound by reacting with water with a consequent loss of properties. 

Cid etal. studied the corrosion resistance of Ni, 5% Fe-Ni and 10% Fe-Ni alloys in the trans-passive region in sulphuric acid. For a given acid concentration the addition of iron reduced the corrosion rate. It was concluded that the addition of small percentages of Fe was doubly beneficial, decreasing both general and intergranular corrosion. 

In de-aerated 10sulphuric acid (Fig. 3.45) the active dissolution of the austenitic irons occurs at more noble potentials than that of the ferritic irons due to the ennobling effect of nickel in the matrix. This indicates that the austenitic irons should show lower rates of attack when corroding in the active state such as in dilute mineral acids. The current density maximum in the active region, i.e. the critical current density (/ ii) for the austenitic irons tends to decrease with increasing chromium and silicon content. Also the current densities in the passive region are lower for the austenitic irons... 

Similar curves determined in 50 Vo sodium hydroxide solution at 60°C show (Fig. 3.46) that the austenitic irons exhibit more noble active dissolution and also lower current densities in the active and passive regions than the ferritic irons the current densities in both regions decrease markedly with increasing nickel content (Fig. 3.47). 

Fig. 3.47 Current densities in active and passive regions for ferrite and austenitic cast irons...

Active region Max. c.d. prior to passivation, i, Potential of passivation, Ep C.d. in passive region, /p Passive region... 

An interesting illustration of the effect that quite small alloying additions may sometimes have on anodic behaviour is seen in Fig. 4.27 from a comparison of the Ni-30Cu alloy Alloy 400 with its age-hardening variant Alloy K500, which contains 2-7% A1 and 0-6% Ti. The presence of these elements in the latter alloy is responsible for a well-defined passive region, whereas the former alloy shows only a slight tendency to passivate in acidic... 

The significance of the Flade potential Ef, passivation potential pp, critical current density /pn, passive current density, etc. have been considered in some detail in Sections 1.4 and 1.5 and will not therefore be considered in the present section. It is sufficient to note that in order to produce passivation (a) the critical current density must be exceeded and b) the potential must then be maintained in the passive region and not allowed to fall into the active region or rise into the transpassive region. It follows that although a high current density may be required to cause passivation ) only a small current density is required to maintain it, and that in the passive region the corrosion rate corresponds to the passive current density (/p, ). 

Another contribution of the potentiostatic technique to s.c.c. studies has been the report that cracking prevails essentially at two potential levels for metals showing an active-passive transition. These potentials are located near the top and bottom of the passive region. Along the same lines, Uhlig and his co-workers have determined critical ranges of potential for s.c.c. , although their theoretical interpretation differs from that of the other references cited. 

Critical Pitting Potential the most negative potential required to initiate pits in the surface of a metal held within the passive region of potentials (it varies with the nature of solution, temperature, time, etc.). 

In the third case, the transpassive state appears at a more noble potential than the passive state, where the dissolution current that was suppressed at the passive region again increases. The boundary potential... 

---