CH.7.

P ITTING

AND

CREVICE CORROSION

Pitting g Corrosion

Initiated by localized breakdown of passive film, usually on MnS by ClDifficult to detect pits because of their small size Pitting requires an extended initiation period. Once started, a pit penetrates the metal at an increasing rate Growth mechanism of pit is identical to that of crevices

Localized Corrosion: Cl- Effects

Process of Pitting g Corrosion

Film breakdown metastable pitting (pit initiation vs. vs repassivation) stable pitting: pit growth

Models on Passivity y Breakdown by y ClPenetration Model Adsorption p Model

Growth mechanism of pitting corrosion Autocatalytic nature of pitting corrosion

Pitting corrosion occurs by the breakdown of passive film. f l Cl l- is detrimental d l in breaking b k the passive film. Mixing electrolytes in the pit with bulk solution is highly restricted ; major concentration difference is built up; low pH and high [Cl-]. Large cathode area(external surface) and small s a a anode ode a area(pit). ea(p t) External surface is generally passivated due to high O2 + high pH or cathodically protected. Within a pit ; i) Rapid metal dissolution(anodic dissolution). ii) Increase in [Cl-] iii) Hydrolysis reaction by cation leads to acidification of solution
ClClClM+Z CleH+ H2 M+Z H+ H+ M+Z Salt Film eIR drop OH-

OH-

O2

O2

Evaluation of Tendency y to Pitting g

Film breakdown potential or pitting potential Critical pitting temperature. temperature Minimum [Cl-] causing pitting. Measurements of the number and the depth of pits in a suitable standard solution solution. (Fig. (Fig 7.3) 7 3)

Pitting g Potential, , Epit

Potentiodynamic Method Measure the current density with changing the

potential t ti l gradually d ll at t a constant t t scanning i rate t and determine the critical potential (Epit) at which the current density increases abruptly due to film breakdown. Protection potential for pits or a repassivation potential for pits is obtained when the measurements are done in reverse direction. If no pitting occurs, the curve traces the same path on reversing. On the other hand, if the alloy has undergone d pitting, i i then h we will ill get a hysteresis h i loop due to the film breakdown and pit formation. With reducing the potential, repassivation of pits starts and finishes until we reach the potential Erp when the pits have been repassivated. repassivated

Epit Erp

a. b.

c.

E<Epit : Pits nucleation occurs. Erp<E<Epit : New pits can not be formed, but the h existing i i pits i may propagate E<Erp : the metal remains passive.

log i

A metal in which Ecorr is lower than Erp would not undergo pitting corrosion. The area in the hysteresis loop under identical conditions(i.e, conditions(i e potential sweep reversal at the same applied current density) is directly related to the resistance of the alloy to the propagation of crevice corrosion. The difference in sweep rate can vary the value Epit; Higher the sweep rate, the Eb increases. increases

Effect of Chloride Concentration

Dependence of Epit on [Cl-] Epit = A log [Cl-] + B Epit = 0.168 - 0.88 log [Cl-] (304 SS) Epit= 0.05 - 0.124 log [Cl-] (Al)

Minimum conc. of [Cl-] necessary for pitting Alloy Fe 5.6Cr-Fe 11.6Cr-Fe 20 Cr-Fe Cr Fe 24.5Cr-Fe 29.4Cr-Fe 18.6Cr-9.9Ni-Fe 18.6Cr 9.9Ni Fe Cl (N) 0.0003 0.017 0.069 01 0.1 1.0 1.0 0.1

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Effect of Inhibitor on Pitting g

Pitting corrosion depends not only on the [Cl-], but also on the concentration of unaggressive anions. In general, unaggressive anions produce three different effects on pitting; Increase in Epit

Many anions present in the solution containing Cl- ions act as inhibitors, ie.,

SO42-, OH-, CO32-, NO3- , all of these anions shifts Epit to more p positive values. As the potential of passive metal is shifted in the noble direction, the amount of Cl- adsorbed on the surface is increased. The anions inhibit the adsorption of Cl- by a competitive adsorption on the surface of passive film. The minimum [Cl-] necessary for pitting in 18 18-8 8 stainless steel are given by; log[Cl-] = A log [ inhibitor ] + B

log[Cl-] l [Cl-] log[Cl log[Cl-] log[Cl-]

= = = =

1.62 1.88 88 0.85 0.83

log[OH-] + 1.84 3 ] +1.18 l [ O3log[NO 8 log[SO42-] - 0.05 log[ClO4-] - 0.44

The efficiency of inhibitor decreased in the order; OH-< NO3- < SO42- < ClO411

 Decrease in the number of pits

a) Deaerated SO42-

Environmental effects on corrosion behavior of stainless steels.

M+

H2
Neutral electrolyte (No Cl-) (

Active Dissolution b) Aerated SO42EOH-/O2 ECORR,B Epit

inhibitor ClC

MxOy
Metal-Passive c) ) Aerated SO42- + Cl-

ECORR,C

Ecorr > Epit MxOy

Metal-Pitting

EH+/H2 EM+/M A

ECORR,A

d) Aerated SO42+ Cl- + inhibitor

log i

MxOy
Metal-Passive
12

Effect of Alloying y g Elements

Ni C r
S, Mn, Al

PRE = %Cr + 3.3 (%Mo + 1/2 %W)+ 16~30 %N

Cr, Ni, W, Ti

Mo, V

Ni Mo Ni, Mo, Cu

C r

Cr, Ti
C Ni Cr, Ni, Mo, Cu, Nb, Ti

S, Mn

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Influence of Solution Temperature p

Increasing the solution temperature causes Epit to shift in the active direction, indicating an increased tendency toward pitting. Critical pitting temperature (CPT) CPT is determined by measuring anodic current of an alloy with increasing the solution temperature either at open circuit or at a selected potential applied to the given i alloy. ll At CPT, CPT the th current t density d it i increases abruptly. b tl Lower L CPT implies i li greater t susceptibility.

900 E ( V) (mV) 100 30

No Pitting

Increasing Mo in 18Cr-8Ni Stainless Steel

Pitting

5% 0% 3%

Temperature (0C) 65
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Mechanism of Crevice Corrosion

Anodic reaction : M M+ + eeCathodic reaction : O2 + 2H2O + 4e- 4OHe-

Hydrolysis reaction of metal ion in crevice : M+Cl- + H2O MOH + H+ ClLow pH, high ClCl- conc., depassivation and IR drop lead to an accelerating or autocatalytic corrosion in the crevice.

e-

e-

15

Crevice Corrosion on LNG Ship p

16

Crevice Corrosion Test Assembly y

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Mitigation g of Crevice Corrosion

Do not form crevices. Use alternative joining technology such as welding or brazing. Use sealants to avoid moisture penetrating into the crevice. Design to remove stagnant areas where moisture and deposits can collect Design in drains which permit full draining of the system collect. with no residual moisture. No materials which will hold moisture near the metal surface. Increase maintenance to include removal of deposits by high pressure washing, etc.

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References

KAIST , http://corrosion.kaist.ac.kr Comprehensive Treatise of Electrochemistry, Vol. 4., Electrochemical Materials Science, Plenum Press, 1981.

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