Prediction of Corrosion Behavior of Active-Passive Type Metals and Alloys in Specific Environments In principle, if the anodic polarization curve of a metal is known fora given environment and the cathodic reduction curves of reducible spe- cies in the environment are known, superposition of these curves should permit prediction of the corrosion behavior of the metal/environment system. This follows from the earlier discussion of the relationship of anodic and cathodic polarization curves to the net or experimentally de termined curves. The obvious limitation of the procedure isthe problem of establishing by experiment the individual anodic and cathodic polar- ization curves. The polarization curves for cathodic reactants such as dissolved oxygen, water, and hydrogen ions, which are inherent to all natural aqueous environments, as well as other species such as Fe, NO}, and Cr05, may be determined on inert surfaces such as platinum, ‘The extent to which these curves are applicable when the reactions oc: cur on active metal surfaces must be questioned. The exchange current densities will almost always be lower on the active metals and will dif fer depending on whether the surface of the metal contains a passive film, Theoretically, the limiting diffusion current density should be the same since the current limiting factor isthe diffusion rate of cathodic re- actant species through the boundary layer. This should be independent Of the metal substrate. However, corrosion product films may limit the diffusion rate, of oxygen, for example, and establish a lower limiting current density. In these circumstances, itis necessary to use qualitative estimates of the positions of the polarization curves. Itis more dificult to establish the individual anodic polarization curves since measure ments cannot always be made independent of species that are inherent to the aqueous environment, Careful deaeration can obviously remove or, atleast, significantly reduce the concentration of dissolved oxygen, However, the effect of pH on the anodic polarization curve cannot be determined independent of the coexistence of the hydrogen reduction reaction if the latver ean occur inthe potential range over which the mea- surements are being made ‘Some examples of how these predictions are made and some of the limitations and precautions that must be recognized are presented in this section Corrosion of Iron at pH = 7 in Deaerated and Aerated Environments and with Nitrite Additions A representative anodic polarization curve for iron in a buffered solu- tion of pH = 7 is shown in Fig. 5.41. Also shown are cathodic polariza- tion curves for dissolved oxygen and nitrite ions on platinum under aer-ated conditions (dissolved oxygen=8.5 ppm) and under deaerated conditions (dissolved oxygen = 1 ppb). Approximations also have been made to illustrate the effect of the formation of a corrosion product, layer (the FesO./Fe204 rust layer on iron) in shifting the oxygen reduc~ tion curve to lower current densities. The polarization curve for nitrite ion reduction is related to the reaction: NO} +8H' +603 NH} +2H,0 (£4 5.6) ‘The exact reaction involving the nitrite ion is uncertain, but the curve is the experimental result of polarizing a platinum electrode in a deaerated solution containing 1000 ppm NO3. The interscetion between the ap- propriate cathodic curves and the anodic curve for iron is identified by pairs of values of Esoer and icon The corrosion rates in terms Of icor for the three environments are: © Cl, aerated (clean surface): 500 mAfm? C2, aerated (rust surface): 60 3, deaerated: 5 C4, deaerated with nitrite ion: 2 C5, aerated with nitrite ion 14 1600 1400 1200 a 1) nase on © 1000 0) Goes sesen msn 800 (ci athodeenygen aucton 600 (oj amedc oxygen tatctn POTENTIAL, mV (S! 107 10° 10' 107 10° 10% 10% 10% CURRENT DENSITY, mA/m? Fig. 5.41 Avproximate anodic polarization curve for iton and cathodic polarization curves fo oxygen under several conditions al for nite ons. The polarization curves are used to estimate the eects of these en Yionmen's on corosion rate Estimated Ecorr and icorrfor the several envitor= ments ste Cl. clean siflace, aerated: C2, surace ith cowosion produc’, erated: 3, clean surface, deaerated; C4, clean surface, denerated pls nitite Suroce, aerated plus ite fons, passivated ions, passivated C5, ch‘The corrosion occurs in the active potential range of the anodic curve for both the aerated and deserated conditions without the nitrite ions. For the aerated environments, the major cathodic reaction is oxygen re- duction with the rate much lower when the surface is covered by & cor rosion product layer that reduces access of oxygen to the surface. In the deaerated environment, the major eathodie reaction is the direct reduc tion of water. The thermodynamics and kinetics of the nitrite ion reac- tion are such that the polarization curve for the reduction of this ion tersects the iron curve only in the passive region. The combined effect of the nitrite and oxygen is to move the corrosion potential into the pas- sive range. The iron is, therefore, passivated by the nitrite ion, which is, referred to as a passivating type inhibitor. It should be noted, however that its use in inhibiting corrosion is significant only in the aerated envi- ronment where the rate is reduced by a factor of about 43 over the aer- ated environment with corrosion product layer. In the deverated envi ronment, the rate is already sufficiently small so as not to require the nitrite inhibitor to usefully decrease the rate. Additions of the order of 100 ppm chloride ion to the aerated nitrite environment will cause the corrosion potential to decrease into the active range and the corrosion rate fo increase. In the presence of chloride ions, the anodic polarization curve in the vicinity of i,q, is increased. The net cathodic curve now in- tersects the anodic curve in the active range and at a higher current den- sity than in the absence of the nitrite ion, in which ease addition of ni- trite increases rather than inhibits corrosion. Corrosion of Iron, Nickel, Chromium, and Titanium in Sulfuric and Nitric Acids The approximate anodic polarization curves for iron, nickel, chro- ‘mium, and titanium in 1 N H3SQg are shown in Fig. 5.42. The cathodi reactions are for the environments shown and are representative of curves obtained on platinum, Since they may be displaced significantly when the reactions occur on the other metal surfaces, particularly the shift of the oxygen curves to lower potentials and current densities, the following discussion is qualitative. The conclusions drawn, however, are consistent with observations on the actual metal/environment sys~ tems. In deaerated 1 N HySO, (pH = 0.56), hydrogen-ion reduction is the cathodic reaction with the cathodic polarization curve intersecting the iron, nickel, and chromium curves in the active potential region. Hence, active corrosion occurs with hydrogen evolution, and the corrosion rates would he estimated by the intersections of the curves. ‘The curves predict that the titanium will be passivated. However, the position of the cathodic hydrogen curve relative to the anodic curves for titanium and chromium indicates that if the exchange current density for the hydro-gen reaction were higher (e.g., 10 mA/m*), both titanium and chromium ‘would exist in the passive state with low corrosion rates. Conversely, if the exchange current density were lower (e.g.,.0.01 mA/m*), both met- als would corrode in the active state with the rate being much larger for chromium. As a consequence, the corrosion behavior of these metals can be very sensitive to small changes in the environment, metal com position, and surface condition, all of which may influence the ex- change current density for the hydrogen reaction. This sensitivity has been demonstrated by showing that small additions of platinum to both titanium and chromium result in large decreases in corrosion rate in boiling sulfuric acid (Ref 37). The platinum increases the hydrogen ex- change current density and brings about the decrease in corrosion rate as just described. Limited information is available on the anodic polarization of the four metals in Fig. 5.42 in nitric acid. As an approximation, the behavior in sulfuric acid is assumed to apply in nitric acid, The overall reaction for the reduction of nitric acid is 2H* + NO3 +2e + NO3 +H30 (Bq 5.7) 1800 1600 1400 1200 1000 800 600 400 200 0 -200 -400 “600 pedee 800 107 10 POTENTIAL, mV (SHE) a 6 1o' 10° 10° 10% 10° 10 CURRENT DENSITY, mA/m? larization curves for ion, nickel, chromium, and tion in TN H,50q. Approximate cathodic po curvesforreduction of niticacid dissolved oxygen, and hysrogen ions, planation for predicting corrosion behawor based on intersection 0 aa Sid eather curves am bu fina Fig. 5.42 Appoxin‘The sequence of reactions involved in the overall reduction of nitrie acid is complex, but direct measurements confirm that the acid has a high oxidation/reduction potential, ~940 mV (SHE), a high exchange current density, and a high limiting diffusion current density (Ref 38), The cathodic polarization curves for dilute and concentrated nitric acid in Fig. 5.42 show these thermodynamic and kinetic properties. Their position relative to the anodic curves indicate that all four metals should be passivated by concentrated nitric acid, and this is observed, In fact, iron appears almost inert in concentrated nitric acid with a corrosion rate of about 25 um/year (1 mpy) (Ref 8). Slight dilution causes a vio~ lent iron reaction with corrosion rates >25 x 10° um/year (10° mpy). Nickel also corrodes rapidly in the dilute acid. In contrast, both chro- ‘ium and titanium are easily passivated in dilute nitric acid and corrode with low corrosion rates, Corrosion of Type 304 Stainless Steel in Sulfuric Acid ‘Type 304 stainless stee! is basically an alloy of 18 to 19 wt% Cr and 8 to 10 wt% Ni. Its corrosion behavior in sulfuric acid is sensitive to both alloy composition and the sulfuric acid environment. Variables with re- spect to alloy composition include whether the Cr and Ni concentra- tions are high or low within the allowed range and the concentrations of residual elements such as sulfur, phosphorus, copper, and molybdenum. Thermal and mechanical treatments are also variables but are not con- sidered in the following. Important variables with respect to the sulfuric acid environment include degree of seration and agitation (velocity ef- fect) and small concentrations of species such as nitric acid, cupric ions, and ferric ions. The net influence of these variables is to find corrosion rates varying from <25 jum/year (1 mpy) to >2500 kim/year (100 mpy) (Ref 39). ‘This wide range of corrosion behavior can be understood by analyz ing how the positions of the individual anodic and cathodic polarization curves lead (o significant differences in Esore and igor. Figure 5.43 is an approximate representation of the individual polarization curves of re- actions to be considered in an analysis of the corrosion behavior. The peaks of the anodic curves (L. and H) are representative of the limits, {gu that have been observed for type 304 stainless steels in deaerated | Nosulfuric acid, Values range from 100 to 30,000 mA/m* (Ref 40). High values have been associated with alloys having abnormally high sulfur concentrations with the sulfur concentrated in nonmetallic inclusions ‘These inclusions dissolve to give high local concentrations of sulfide ions that increase the active-peak current density as discussed in rela tion to Fig. 5.34, The hydrogen-ion reduction curve is representative of IN 280s (pH ~ 0.6), and the oxygen reduction curve is representative of this acid saturated with air, Under deaerated conditions, the onlycathodic reaction is hydrogen-ion reduction, Under aerated conditions, the effective cathodic curve is the sum of the oxygen and hydrogen-ion reduction curves; this sum curve is shown by the crosses and is used in the analysis of corrosion under aerated conditions. Intersections of anodic and cathodic polarization curves define the electrochemical parameters, Ecoor and icowr, fot corrosion. In Fig, 5.43, four intersections occur; two occur between the cathodic hydrogen re- duction curve and the anodic curves, (L) and (H), and two between the cathodic sum curve and each of the wo anodic curves. The former two intersections apply to deaerated conditions and the latter to aerated con- ditions. Figure 5.44 shows the two polarization curves predicted for the two alloys under deaerated conditions, The shift in the active-peak, cur- rent-density maximum results in a change in intersection of the anodic and cathodic curves such that alloys with the high ica have a lower Ecore and a higher ico. These differences correlate with direct measurements of corrosion potentials and corrosion rates of stainless steels. It is im- portant to recognize that in the deaerated acid, corrosion occurs in the active range of the polarization curve for alloys of both low and high an- odie-peak current density. Figure 5.45 shows the two polarization curves predicted for the (wo alloys under aerated conditions, The solid curve is predicted for the al- oy with the higher (H) anodic-peak current density, and the curve de- fined by the crosses is predicted for the alloy with the lower (L) anodic- 1200 1000 ua Z sof 5 600 teducion X= Oxygen + hydrogen > 400 = 200 Zo = Fee rodueton “400 Fs. Loner arate pst fuer danse eee 600 F fiche ancor peck -800 f” eument genet curve 1000 0 5 498 10’ 10? 10° t0* 10 CURRENT DENSITY, mV/m2 10" 10 10 Fig, 5.43 Schematic polarization curves for type 304 stainless steel in 1 H,S0,.{ (low and H (high) distinguish the effects that minor ‘composition variables can have on the position of the active peak current den sity ri the stainless steel polarization curve.-peak current density. The curves indicate that the alloy with the lower anodic peak would be passivated by the aeration; the anodic and cath- odie polarization curves cross in the passive potential range of the alloy’ 1200 1000 800 600 400 200 0 -200 -400 -600 -800 “1000 10" 10° 10' 107 10? 10% 108 108 CURRENT DENSITY, mA/m? POTENTIAL, mV (SHE) Fig, 5.44 Schematic polarization curves ior type 304 stainless steel in deaeraed N H:50, | ou) and H hgh) distinguish thetic. that minor composition variables can have onthe posifan a the active peak Cerent density i nthe stainless ste! potanzation cave. Estimated coro- Son potentials ani cortosioncurtent densities are shown 200 4009 een Se ma Z eto eee = «0 ee et = 0 femetey site = 200 = -400 3 sco ‘0 000 10" 10° 10’ 10? 10° 104 10% 10° CURRENT DENSITY, mA/m? Fig. 5.45 Schematicpolarization curves for type 0 stainless steel in er acd T NH,SD, low! ane High eating the fit that minor composition variables an have nm the postion of the active pent cure ‘ent density ei inthe tants tel polarization curve. Estinated coosion potentials and corasion eurent densities ae shawn. tn partcula, rote hat Eorrosion can occur in he active or passive potential range depending on the postion aieThe result is « corrosion rate of about 10 mA/m?, ioe (L). In contrast, the alloy with the higher anodic peak would not be passivated. The po- larization curves cross inthe active potential range ofthe alloy resulting in an active corrosion rate corresponding to about 250 mA/m?, ‘This analysis provides explanations of observations that slight creases in oxidizing power of the environment can significantly de- crease the corrosion rate by changing the corrosion mode from active to passive, For example, increasing the amount of dissolved oxygen in the ‘eavironment or increasing fluid velocity to increase the limiting-diffu- sion current density can move the cathodic curve beyond the an- ‘odie-peak current density. Other examples are the decrease in corrosion rate with small additions of nitric acid, ferric ions, and cupric ions to the environment, all of which result in a net cathodic curve at higher current onsities, thereby placing the alloy in the passive state Chapter 5 Review Questions 1. a, Sketch an anodic polarization curve (E versus log i) for an ac tive-passive metal, starting at E’, i. Identify ian, Epps and ip b. In developing a new corrosion-resistant, active-passive alloy, discuss why itis desirable to have values of int, Ep and ip a8 low as possible. (Hint: Consider the intersections of anodic and cath odie polarization curves.) 2. Based on the data presented in Fig. 5.42, for each element/electro- lyte listed below, state whether active or passive corrosion occurs and give the corrosion current density, icoz. In each situation, as- sume the worst-case condition, a. Fe in concentrated nitric acid b. Fe in dilute nitric acid ¢. Ni in aerated neutral solution d. Cr in aerated neutral solution . Cr in aerated acidic (pH = 0.56) solution f. Crin deacrated acidic (pH = 0.56) solution g. Tiin aerated acidic (pH = 0.56) solution h. Tin deaerated acidic (pH = 0.56) solution 3. With reference to the polarization curves in Fig. 5.42: ‘4, Determine the values of ict, Epp, and ip for iron. b. Give the approximate potential ranges for active, passive, and transpassive corrosion of chromium, Could an increase in fluid velocity for an aerated acid solution at pH = 0.56 tesult in the passivation of either iron or chromium? Explain,4d. Does the contribution of dissolved oxygen to the corrosion of iron change significantly when the acidity is decreased from pH 0f 0.56 to 7.0 Explain. When ferric chloride (FeCl) is progressively added to deaerated ‘water in contact with stainless steel, the following observations are made: (a) for small additions, the corrosion rate increases; (b) for intermediate additions, the corrosion rate suddenly decreases; and (©) for larger additions, pitting corrosion occurs. Use appropriate polarization curves to explain these observations. A stainless steel undergoes pitting corrosion in a chloride-ion-con- taining environment, If the oxidizing potential of the environment could be changed, should it be increased or decreased in order to minimize or eliminate the pitting corrosion? Explain. When pitting corrosion is a problem with type 304 stainless steel, the problem can frequently be solved by changing to type 316 stain less steel, which contains molybdenum. To explain this effect, which of the following would represent the major influence of mo: lybdenum: decreases ice, decreases ip, or increases Epp? Explain,