Crevice Corrosion

N a r a s i Sridhar, 1 Darrell S. D u n n , 1 C. S. Brossia, 1 G u s t a v o A. Cragnolino, 1 a n d Jeffery R. Kearns 2

CREVICE CORROSIONOCCURSIN regions of a metal that are not directly exposed to an environment such as flanged joints, lap joints, and u n d e r corrosion deposits. The metals that undergo crevice corrosion are otherwise protected by a surface film. Mloys that are not protected by a surface film tend to corrode outside the crevice region where there is greater access to cathodic reduction reactions. In this regard, there are many similarities between pitting and crevice corrosion. Indeed, for some classes of materials, a case can be made that the same mechanism operates both phenomena. It must be emphasized that the crevice corrosion tendency is not the property of a particular alloy class; rather it is a function of the alloy's response to a given environmental condition. For example, carbon steels do not suffer crevice corrosion in acidic solutions because of the absence of a passive film, but do suffer crevice corrosion in alkaline solutions when there is a passive film. Similarly, some alloys suffer crevice corrosion in the presence of a corrosion inhibitor, whereas corrosion occurs outside the crevice in the absence of the inhibitor. Several tests have been developed over the years to determine the crevice corrosion resistance of alloys. The objectives of these tests include comparison of alloys, qualification of alloys for a given service, evaluation of the effects of fabrication processes on crevice corrosion resistance, quality control, and life prediction. This chapter will briefly describe the types of tests, and their applicability and limitations, with a focus on tests that have been or are now being considered by ASTM Committee G-1 on Corrosion of Metals. While these test principles are applicable to a wide variety of alloys, the information presented is focused on stainless and nickel-base alloys.

THE MECHANISMS OF CREVICE CORROSION

It was realized early on that crevice corrosion occurs because the protective film on the metal is somehow removed or made less protective. Mears and Evans [1] and Uhlig [2] suggested that oxygen depletion inside the crevice was responsible for the destabilization of the protective passive film. 1Southwest Research Institute, 6220 Culebra Road, San Antonio, TX 78238-5166. 2Previous Author of the chapter, Mcoa Technical Center, Alcoa Center, PA 15069-0001.
221

However, Rosenfeld and Marshakov [3] in the late 1950s conducted a detailed examination of processes occurring in the crevice that was a precursor to many experimental studies that are being conducted even today. They suggested that crevice corrosion occurs through a combination of reduction in oxygen or a corrosion inhibitor in the crevice, a reduction in pH, and shift in the potential within the crevice to a more negative value such that the potential is in the active regime. Since these early ideas, many conceptual models of crevice corrosion have been developed [4-39] that have elaborated one or more aspects of this model. Quantitative modeling crevice corrosion was first performed by Crolet and Defranoux [11], who considered only the effect of passive dissolution rate on pH reduction within the crevice and ignored the effect of transport of species in and out of the crevice. This was further improved by Galvele [12] and Oldfield and Sutton [14,15], who considered transport of species in and out of the crevice. These early models have since been improved considerably both in terms of the conceptual models and the numerical solutions [13,16-21]. The crevice corrosion process can be described in four stages: (1) deoxygenation, (2) increase of the salt and acid concentrations, (3) depassivation, and (4) propagation, as illustrated in Fig. 1. Crevice corrosion begins when discrete areas on a passive surface are physically isolated or occluded. Convection between the solution entrapped within an occluded area on a passive surface and the bulk environment is slow, so the dissolved oxygen in a crevice solution is rapidly depleted (Fig. 1, stage [a]). A localized galvanic cell is established due to the difference in the oxygen concentrations of the solutions within a crevice (anode) and the surrounding surface (cathode). The depletion of oxygen in the crevice solution shifts the corrosion potential for a passive surface in the active direction. Mthough "differential aeration" [1] is sufficient to induce crevice corrosion of certain metals and alloys, it only provides the initial driving force for the crevice corrosion of stainless alloys. As metallic dissolution continues within a crevice, the metal cations (e.g., Fe 2, Cr 3, A13, etc.) are concentrated in the stagnant solution within a crevice. They also react with water (called hydrolysis reaction) to generate acidity. Fe 2+ 2H20 :~ Fe(OH) 2 + 2H Cr 3+ 3H20 :~ Cr(OH) 3 + 3H+

(1)

Mobile anionic species (e.g., C1-) are attracted to the crevice and charge neutrality is maintained. The crevice solution

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CORROSION TESTS AND STANDARDS MANUAL

[a] Oxygen is consumed in the crevice in the crevice even at small applied potentials leading to current noise (Fig. 1, stage [d]), but above a critical potential, the dissolution rate increases steadily as pit stabilization occurs. The pit stabilization, in turn, is linked to formation of metal-chloride s a k films [38,39].

[d] Metastable pits nucleate and grow

Time

Distance into crevice

R E V I E W OF T E S T M E T H O D S F O R C R E V I C E CORROSION RESISTANCE
The tests can be classified into three general categories: (i) non-electrochemical tests, (ii) electrochemical tests under open-circuit conditions, and (iii) electrochemical tests under controlled potential or current conditions. Brief descriptions of the more established methods for evaluating crevice corrosion appear in Table 1 along with comments concerning limits of applicability. Details of each method can be found in the literature cited. The r e a d e r is also advised to consider one or more of the excellent reviews on test techniques for crevice corrosion [40-45, 76,114].

[c] Potential decreases from passive to active regime

[b] Acidification

and increase in
chloride concentration

L~

NON-ELECTROCHEMICAL TESTS
In these tests, specimens fitted with crevice-forming devices (artificial crevices) are exposed for varying lengths of time to environments containing an anionic species that promotes crevice corrosion (e.g., chloride) and an oxidizing agent to accelerate initiation of crevice corrosion (e.g., ferric ions). The crevice corrosion resistance is then measured by mass-loss and visual methods. ASTM G 483 (2000 version) involves four test methods. Methods A and C apply to pitting corrosion. Method B measures the crevice corrosion resistance at two fixed temperatures, whereas Method D measures the crevice corrosion resistance in terms of a critical crevice temperature. These two methods will be described in greater detail below, but the standards provide a comprehensive description of the methods.

Distance into crevice

Distance into crevice

FIG. l mProcesses leading to crevice corrosion.

becomes concentrated in metallic chlorides even when only small quantities of chloride anions are present in the bulk environment (Fig. 1, stage [b]). Active metallic dissolution occurs when the p H of the crevice solution is sufficiently low and the concentration of chlorides is high enough to break down the passive film. The development of a critical crevice solution is controlled by alloy composition, crevice geometry, and bulk solution chemistry [35,36]. The length of time (or incubation period) required to develop a critical crevice solution with a particular crevice geometry determines the effective crevice corrosion resistance of a stainless alloy. The critical crevice solution criterion has proven to be useful for ranking alloy performance [15,35,36]. Following Karlberg and Wranglen [8], m a n y investigators [22-29] have shown that a small potential gradient in the crevice can result in the shift of the electrochemical behavior from passive to active (Fig. 1, stage [c]) and thus result in high corrosion at an intermediate distance into the crevice. Once corrosion has been initiated, the reaction can proceed rapidly due to the unfavorable area ratio of the small, anodic crevice to the large, cathodic surrounding surface. For corrosion resistant alloys that do not exhibit a large active-passive slope at near-neutral pH, stages [b] and [c] are both required because an active-passive peak is not observed unless low pH values are attained [22,23,29]. Pits in crevices were reported early on by Karlberg and Wranglen [8]. An alternative mechanism was originally proposed by Stockert and Bohni [30] and later enhanced by Laycock et al. [37]. This suggests that pit nucleation occurs

A S T M G-48, M e t h o d B
Method B employs a 6 weight percent FeC13 solution (equivalent to 10 % FeC13 6H20 ), with an exposure period of 72 h at either 222 or 502C, or both. It involves the use of crevice formers (i.e., cylindrical TFE-fluorocarbon blocks) that are held tightly against the sample surface by two rubber bands. These methods produce localized corrosion of type 304L stainless steel at ambient temperature and can be used to r a n k other materials with respect to this stainless steel and to a lesser extent with respect to each other. The limited ability of Method B to rank a wide range of alloys stems from the limited temperatures used and the fact that the extent of localized corrosion at a given temperature, even if it can be measured accurately, is not often as important in materials selection as the initiation of localized corrosion. Method B employs two tetrafluoro ethylene (TFE) aStandard Test Methods for Pitting and Crevice Corrosion Resistance of Stainless Steels and Related Alloys by Use of Ferric Chloride Solution.

CHAPTER 19--CREVICE CORROSION

223

TABLE 1--Comparison of tests for resistance to crevice corrosion. Test FeCl 3 Test, ASTM G 48, Method B [78,79] Summary (a) Non-Electrochemical Test Maximum corrosion depth perpendicular to the crevice plane and/or mass-loss are measured after exposure of creviced specimens to 22C, 50C, or both. Crevice device is a TFE block without serrations. The test can provide qualitative ranking of an alloy's resistance with respect to type 304L SS, but is not adequate in ranking a n u m b e r of corrosion resistant alloys. The rubber band holding the crevice blocks provide additional, uncontrolled crevice sites. A serrated TFE crevice block is used and critical crevice temperature is determined through a series of tests at 5C increments. The test can be used to rank alloys. Test is limited to 85C because of instability of FeC13. The pitting resistance equivalents used to determine starting temperature can be misleading because they do not consider synergism between alloying elements. Critical crevice temperature is dependent on specimen preparation, test time, and solution composition. A procedure similar to ASTM G 48 or ASTM G 78 should be followed. (b) Electrochemical Open-Circuit Potential Tests A sample with crevice block is electrically coupled to a larger open sample through a zero-resistance ammeter. The current flowing in the external circuit is an indicator of crevice activation and growth. It provides a more sensitive and continuous record of crevice initiation and growth processes, It simulates a real crevice condition. At present, there is no standard test procedure for this. Test time, area ratio of open to creviced sample are important factors. (c) Electrochemical Applied Potential/Current Tests The temperature is varied in steps or continuously while the potential is held at a constant value. The temperature at which a sustained increase in current is observed is noted as the critical temperature. While phenomenologically equivalent to ASTM G 48D, it provides greater freedom in choice of potential and sensitivity in current measurements. The potential can be scanned continuously or varied in a stepwise manner. The potential at which current increases during the upward scan or stepping of potential is called the initiation potential, Ecrev o r Ep. The potential at which current decreases to a low value during downward scan or stepping of potential is called repassivation potential, Ercre v o r Erp. The value of Ercre v is independent of prior growth of crevice corrosion provided a sufficient extent of growth is maintained. For corrosion resistant alloys, too high an initial potential at which crevice corrosion is initiated is can result in erroneous measurement of Ercre v. as a m a x i m u m of 0.038 m m d e p t h of p e n e t r a t i o n a n d m a x i m u m of 0.2 m g / c m a m a s s loss h a v e b e e n c o m m e r cially a c c e p t e d b y c e r t a i n m e t a l s p r o d u c e r s a n d users. As p r e v i o u s l y stated, m a n y i m p o r t a n t a s p e c t s of t h e t e s t t h a t i n f l u e n c e t h e result, s u c h as t h e m e t h o d of e x a m i n a t i o n a n d e v a l u a t i o n criteria, m u s t b e a g r e e d to b y t h e v e n d o r a n d u s e r of t h e p r o d u c t to b e tested.

FeC13 + HC1 Test, ASTM G 48, Method D [47,48,72, 77]

Other solutions Remote Crevice Assembly Test [87-89] ASTM G 71 can be used for guidance

Critical Temperature Tests

[48,50,64, 73-75, 79, 90-93]

Critical Potential Tests (ASTM G 61 and variants)

fluoropolymer blocks and either rubber band or o-rings to f a s t e n t h e b l o c k s to a flat s p e c i m e n a n d c r e a t e c r e v i c e s (Fig. 2, top). T h e r u b b e r - b a n d crevice a s s e m b l y is i n e x p e n sive, easy, a n d fast to a s s e m b l e , a n d p r o d u c e s u s e f u l r e s u l t s i n a r e a s o n a b l y s h o r t p e r i o d of time. H o w e v e r , t h e r u b b e r b a n d crevice a s s e m b l y h a s c e r t a i n d r a w b a c k s : 1. T h e t e s t is i n v a l i d if e i t h e r r u b b e r b a n d b r e a k s . 2. T h e c o m p r e s s i v e p r e s s u r e a s s o c i a t e d w i t h t h e r u b b e r b a n d is n o t u n i f o r m . 3. T h e r a t i o of t h e c r e v i c e d a r e a to t h e b o l d e x p o s e d a r e a r a t i o c a n n o t b e a c c u r a t e l y m e a s u r e d [66]. 4. T h e s u r f a c e f i n i s h of t h e T F E - b l o c k is n o t specified. 5. Crevice a t t a c k o f t e n i n i t i a t e s o n t h e edges of t h e s p e c i m e n in contact with rubber bands rather than under the TFE blocks. T h e edge a t t a c k m a y b e r e l a t e d to a c o m b i n a t i o n of crevice g e o m e t r y as well as m e t a l l u r g i c a l c o n d i t i o n (e.g., i n c l u s i o n s t r i n g e r s ) . T h i s m a y l e a d to u n c e r t a i n t i e s a b o u t c o r r e l a t i n g t h e t e s t r e s u l t s to service c o n d i t i o n s w h e r e e d g e s of p l a t e s / s h e e t s m a y n o t b e exposed. At t h e e n d of t h e test, t h e s a m p l e is e v a l u a t e d v i s u a l l y for signs of attack. ASTM G 46, 4 P r a c t i c e for E x a m i n a t i o n a n d E v a l u a t i o n of P i t t i n g C o r r o s i o n , c a n p r o v i d e guidelines for e v a l u a t i n g t h e e x t e n t of crevice c o r r o s i o n a f t e r t h e s a m p l e h a s b e e n r e m o v e d f r o m t h e test s o l u t i o n . A m a s s loss m e a s u r e m e n t is also r e c o m m e n d e d , b u t n o a c c e p t a n c e c r i t e r i a o r t e s t d a t a for v i s u a l o r g r a v i m e t r i c evaluations are presented in the standard. Criteria such

ASTM G 48, M e t h o d D
To o v e r c o m e t h e s e l i m i t a t i o n s , M e t h o d D m e a s u r e s t h e c r i t i c a l crevice c o r r o s i o n t e m p e r a t u r e , u s i n g a m u l t i p l e c r e v i c e a s s e m b l y (MCA). T h e t e s t s o l u t i o n is 6 wt. p e r c e n t FeC1 a a c i d i f i e d w i t h 1 wt. p e r c e n t HCI. T h i s t e s t m e t h o d is also r e f e r e n c e d i n A S T M G 1575 for e v a l u a t i n g t h e c o r r o s i o n p r o p e r t i e s of w r o u g h t i r o n - a n d n i c k e l - b a s e d c o r r o s i o n r e s i s t a n t alloys for t h e c h e m i c a l p r o c e s s i n d u s t r i e s . T h e m u l t i p l e crevice a s s e m b l y (MCA) c o n s i s t s of t w o "serr a t e d " w a s h e r s m a d e of T F E - f l u o r o c a r b o n b o l t e d t o g e t h e r t h r o u g h a h o l e drilled i n t h e s p e c i m e n , as i l l u s t r a t e d i n Fig. 2(b). The bolts, m a d e of a highly corrosion resistant alloy, are electrically i s o l a t e d f r o m t h e s p e c i m e n . T h e MCA elimin a t e s t h e crevices c r e a t e d w h e r e t h e r u b b e r b a n d c o n t a c t s t h e s p e c i m e n a n d facilitates t h e m e a s u r e m e n t of t h e c r e v i c e a r e a to b o l d l y e x p o s e d a r e a ratio. T h e a d v a n t a g e of t h e MCA is t h a t t h e c r e v i c e g e o m e t r y c a n b e m a d e v e r y severe b y 5Standard Guide for Evaluating the Corrosion Properties of Wrought Iron- and Nickel-Based Corrosion Resistant Alloys for the Chemical Process Industries.

4 S t a n d a r d Guide for Examination and Evaluation of Pitting Corrosion.

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CORROSION TESTS AND STANDARDS MANUAL

For Ni-base alloys: CCT( C ) = (1.5 x %Cr) + (1.9 x %Mo) + (4.9 x %Nb) + (8.6 x %W) - 36.2 For Iron-base alloys: CCT(C) = (3.2 x %Cr) + (7.6 x %Mo) + (10.5 %N) - 81.0 (Eq. 2) (Eq. 1)

(a)

Co)

7mm
0.5 mm dup

S--';k 12 IqatlMlu , 22mmq

1.....
2~4 m"

el

FIG. 2~tandardized crevice corrosion test specimen assemblies described in ASTM G 48 B (top) [25,44] and ASTM G 78 (bottom) [78,79], commonly referred to as the rubber band assembly and multiple crevice assembly (MCA), respectively. applying greater torque to the bolt and the multiple small contact points. A torque of 0.28 Nm is recommended by ASTM G 48, based on interlaboratory testing. Higher torque may be used, but creep of the crevice washer is an important concern. The depth and n u m b e r of crevice sites attacked u n d e r the washer are reported and can be statistically analyzed if desired, although statistical analysis is not required by ASTM G 48, Method D. Also shown in Fig. 2(c) is the multiple crevice assembly specified in ASTM G-786. Although the design and material of the crevice device are different, the underlying principle is the same in these crevice designs. The test consists of exposing the MCA in the FeC13 solutions at different temperatures to determine the temperature at which crevice corrosion can be observed when examined at a magnification of 20X. As a guidance to estimating the starting temperature, two multiple regression equations are suggested by ASTM G 48:

ASTM G 48 recommends that tests shall be started within 5C of the critical temperature estimated by the above equation. The m i n i m u m and m a x i m u m test temperatures are recommended to be 0C and 85C, respectively. Separate samples are to be used for each temperature and a test duration of 72 h is recommended. The m a i n limitation of Eqs 1 and 2 is that they do not recognize the interactive effects of some alloying elements and are regression estimates based on a limited n u m b e r of commercial alloys. For example, according to Eq 1, alloy C-276 (Ni-15.5%Cr16%Mo-4%W) would have a CCT of 52C, whereas alloy C-22 (Ni-22%Cr-13%Mo-3%W) would have a CCT of 47C, However, the observed CCT of alloy C-276 is significantly lower than that of alloy C-22. Critical temperature test values determined by various methods have been used for ranking and comparing the localized corrosion resistance of a large n u m b e r of commercial alloys and to develop new alloys [41,43,46-69]. Critical crevice temperature has been used as a convenient and quantitative measure of the relative ranking of various alloys. However, it must be used with caution in predicting the performance of an alloy in a given service. This is because the localized corrosion dependence on temperature is a function of the test technique, corrosion potential of the alloy in a given environment, and the concentration of chloride or other anionic species. For example, higher corrosion potentials, longer exposure time, and higher chloride concentrations have a tendency to lower the critical crevice temperature. However, the presence of inhibitive species such as nitrate can increase the critical crevice temperature. The Immersion Critical Pitting Temperature (ICPT) and Immersion Critical Crevice-Corrosion Temperature (ICCT) tests produce results that follow similar trends relative to alloy composition, as demonstrated by the well-known work of Garner (Fig. 3). Garner found that the ICPT values were approximately 20C higher than the ICCT values for a broad range of alloy compositions [47,70,71]. Crevice corrosion typically occurs at lower temperatures and in less time than pitting [71,73]. Consequently, a pitting test will typically take longer than a crevice test in the same test environment. However, since the problems associated with the geometry of the gap created by the crevice former are avoided, ICPT tests are more sensitive to differences in alloy composition [50, 74, 75] and are more reproducible (+2.5C for ICPT versus _+10C for ICCT) than are ICCT values [50,57]. The scatter in ICCT can be reduced by extending the test exposure period (e.g., from 24 to 72 h [76]) or testing more samples.

P r e c i s i o n in Critical T e m p e r a t u r e T e s t s
6Standard Guide for Crevice Corrosion Testing of Iron-Base and Nickel-Base Stainless Alloys in Seawater and Other ChlorideContaining Aqueous Environments. The variability of critical crevice temperature measurem e n t was originally addressed by Brigham [63]. The r o u n d

CHAPTER 19--CREVICE CORROSION

225

0 100
o

TABLE 3--Results of crevice corrosion tests in natural seawater

, , , i ' ' ' ' ' ' ' ' ~ ' ' ' ' I

i io

'

'

'

'

.................... i ..........

i ....................... i .....................
. . . . .

60 ..................i.....................
E

from the LaQue Center for Corrosion Technology, circa 1993 [77]. Percentage of 32 UNSNo. PRE~ Sites Resistan~ N06059 $32654 N08367 N10276 N08031 N08926 $31254 $32550 $31600 73 56 45 69 51 45 43 37 24 100 100 100 97 97 94 94 87 25

40 20
0 -2q 2
............. /
.............,.i__,..u..,_

.cci-

I 0
L,.

........... s " ;

i ................... {..................... }..................

...........................

........

E .... i .... i .... t 3 4 5 6 7 Molybdenum Content, wt%

apitting Resistance Equivalent = Cr + 3.3Mo + 16N. hEight different combinations of alloys and crevice-formers were tested.

FIG. 3---Immersion Critical Pitting Temperature (CPT) and Immersion Critical Crevice Corrosion Temperature (CCT) curves for molybdenum-bearing austenitic alloys. The dots represent, from left to right: UNS $31600, $31700, N08904, $31254, and N08366. Data are replotted from Refs 45,47,70.
suffers preferential attack. The bias of test results by edge attack is u n a c c e p t a b l e because, in general, p r o d u c t corrosion p e r f o r m a n c e is d e t e r m i n e d by the surface, not the through-thickness microstructure.

r o b i n test p r o g r a m using G 48, M e t h o d D is given in Table 2. The i n t e r l a b o r a t o r y test p r o g r a m f o u n d that the p o o l e d repeatability s t a n d a r d deviation and the 95 % c o n f i d e n c e limit for M e t h o d D w e r e 2C and 6C, respectively. The p o o l e d reproducibility s t a n d a r d deviation a n d 95 % confidence interval for M e t h o d D w e r e 6C a n d 16C, respectively. Previous studies [48, 70, 71] have established 10C as the v a r i a t i o n for i m m e r s i o n ICPT values above 40C. One significant difference in the results of ICPT and ICCT tests that use acidified ferric chloride (Table 2) versus straight ferric chloride is that the values o b t a i n e d are significantly l o w e r in the acidified solution. F o r example, the AL-6XN 4 alloy (UNS N08367) has an ICCT of 43C w h e n tested in c o n v e n t i o n a l ferric chloride but, as s h o w n in Table 2, it has a value of 30C in acidified ferric chloride. A l t h o u g h it is an a p p a r e n t l y insignificant part of ASTM G 48, the p r e p a r a t i o n of 2.5 by 5 c m (1 by 2 in.) c o r r o s i o n s p e c i m e n s f r o m sheet, strip, and, particularly, plate is a t i m e - c o n s u m i n g and costly part of p r o d u c t testing. M a n y c o r r o s i o n - r e s i s t a n t alloys are n o n m a g n e t i c , very tough, and, t h e r e f o r e expensive to m a c h i n e into c o r r o s i o n specimens. E v e n p r o p e r l y m a c h i n e d / p o l i s h e d c o u p o n edges are subject to preferential attack because e i t h e r (a) the r u b b e r bands h o l d i n g the c r e v i c e - f o r m e r o n the sample surface f o r m a v e r y tight c r e v i c e o n the s a m p l e edges, o r (b) a subsurface m i c r o s t r u c t u r a l c o n s t i t u e n t is exposed a n d

A p p l i c a t i o n s o f ASTM G 48 T e s t s
As n o t e d in Table 3 [77], the results of m u l t i p l e alloy tests in s e a w a t e r are correlated to the Pitting Resistance Equivalence (PRE) n u m b e r [47,48, 72, 77], w h i c h also correlates to alloy p e r f o r m a n c e in FeC13. A n d e r s o n [78] and S t r e i c h e r [79] u s e d MCA in s e a w a t e r tests to c o m p a r e alloy p e r f o r m a n c e . M o r e recently, a simple, flat, plastic (specifically, polym e t h y l m e t h a c r y l a t e , w h i c h is often r e f e r r e d to as "perspex") w a s h e r has b e e n successfully u s e d to evaluate a series of alloys in s e a w a t e r [77]. One application of the ASTM G 48 test has b e e n in s i m u l a t i n g leaking tube-to-tube sheet joints in s e a w a t e r h e a t exchangers and c o n d e n s e r s [81]. W h e n certain highly c o r r o s i o n - r e s i s t a n t alloys w e r e p a i r e d in a dissimilar m e t a l crevice (DMC) w i t h alloys t h a t w o u l d be e x p e c t e d to suffer crevice c o r r o s i o n in the p a r t i c u l a r test solution, the m o r e corrosion-resistant alloy was f o u n d to c o r r o d e due to the accelerating effects of the c o r r o s i o n p r o d u c t s f r o m the less resistant alloy. The results of DMC tests in ferric chloride w e r e c o n f i r m e d by l o n g - t e r m DMC exposures in s e a w a t e r [82].

TABLE 2--Results of interlaboratory test program NOTE 1--Minimum temperature (C) to produce attack at least 0.025-mm (0.001-in.) deep on bold surface of specimen. Edge attack ignored. Method D--CCT Critical Crevice Corrosion Temperature (C) Method C---CPTCritical Pitting Corrosion Temperature (C)
Alloy/Laboratory 1 UNS $31603 UNS N08367 202020 UNS $44735 858585 80/80/80 UNS N06022 >85>85>85 >85/>85/>85 >85/>85/>85 >85/>85 >85/>85/>85 >85/>85 UNS $31603 <0/<0<0 <0/<0<0 <0/<0/<0 <0/<0 <0/<0/<0 <0/<0 UNS N08367 303030 25/25/25 25/30/30 34/34 UNS $44735 423542 35/35/^ 35/40/40 40/40 45/45/45 40/40 UNS N06022 50/^/50 50/55/55 55/60/60 67/67 55/55 75/^/^ 70/70/70 85/85/85 75/80 75/75/75 75/80

2
3 4 5 6

20/20/20
20/20/20 19/19 20/20/20 20/20

75/85/85
81/81 70/70/75 75/85

20/20/20
30/30

^Test run but no attack observed.

226

CORROSION TESTS AND STANDARDS MANUAL

The crevice can be formed in the same m a n n e r as for G 48, Method D. Care must be taken in exposing only the crevice with controlled gap. The crevice where electrical contact is made with the specimen is uncontrolled. This crevice area can be designed to be above the solution level. The choice of area ratio between cathode (non-creviced specimen) and anode (creviced specimen) depends upon the application. For example, in a low conductivity solution or an environment where a condensed water film controls corrosion, the cathode to anode area ratio is expected to be relatively small (less than 2:1). In flowing seawater systems, this ratio can be quite large. For example a ratio of 300:1 has been used [90]. Visual examination at the end of the test is essential in correlating the observed galvanic currents with degree of crevice corrosion. The open-circuit potential can be changed as in the non-electrochemical tests by changing the redox species or concentration. At present, there is no specific ASTM standard for his test. However, ASTM G 717 can be used as guidance.

ASTM G 78 Test
ASTM G 78 describes crevice corrosion testing using a number of specimen geometries. While the standard is primarily devoted to seawater testing, it can be adopted for other applications. In addition to variations of multiple crevice assembly, ASTM G 78 describes other geometries, including cylindrical pipe geometries with flexible polymeric sheaths as a crevice-forming device. The test method involves exposing the specimens to the applicable environment and evaluating the crevice corrosion susceptibility through mass-loss, measurement of the area of corrosion, and depth of penetration.

Other N o n - E l e c t r o c h e m i c a l T e s t s
Immersion tests have also been conducted in other environments, notably seawater. The test procedures for preparing the crevice samples can be similar to that in G 48, Method D. The results from seawater tests are shown in Table 3 [79]. It must be emphasized that natural seawater behaves quite differently than synthetic seawater in that the corrosion potential is often m u c h higher in natural seawater [83]. The FeC13 solution is not stable above about 85C, necessitating use of more aggressive environments for highly corrosion resistant alloys. On the other hand, the FeC13 solution can be too aggressive for some alloys, making it difficult to differentiate between alloys. Crevice corrosion tests in other oxidizing, chloride solutions have been reported in the literature [84]. Caution should be exercised in ranking alloys for their localized corrosion resistance in one oxidizing chloride solution based on their ranking in another chloride environment. For example, the ranking of alloys in FeCI3 solution has been found to be in variance with that in chlorine dioxide-containing solutions [85,86]. The localized corrosion resistance in chloride containing solutions may also not be an accurate indicator of their resistance to non-chloride environments.

ELECTROCHEMICAL TESTS UNDER APPLIED POTENTIAL/CURRENT

These techniques for evaluating crevice corrosion resistance involve holding (static) or incrementally changing (step or scan) the potential or current. Some of the more frequently used techniques for evaluating crevice corrosion resistance are listed below, following the definitions given in ASTM G 15: 1. Potentiostatic technique--Changes in current density are monitored for a sample maintained at a constant potential. The potential can be varied from sample to sample. 2. Galvanostatic technique---changes in potential are monitored for a sample m a i n t a i n e d at a constant current in a test solution. 3. Potentiostep or potentiostaircase technique--Changes in current density are monitored for a sample that is polarized in a series of potential increments or decrements. Typically, the time duration or potential steps in a crevice corrosion tests are not equal. 4. Potentiodynamic technique The potential is changed scanned) continuously at a predetermined rate (ASTM G 5). 5. Cyclic potentiodynamic technique--The potential is scanned forward from some low value to a high value and scanned backward to a predetermined potential or current value (ASTM G 61). 6. Galvanostep or galvanostaircase technique--Changes in potential are monitored for a sample that is polarized in a series of current increments or decrements. (For more information the reader is referred to a related standard, ASTM G 100, Method for Conducting Cyclic Galvanostaircase Polarization.)

ELECTROCHEMICAL TESTS UNDER OPEN-CIRCUIT CONDITIONS

Electrochemical tests are the most rapid way of detecting localized corrosion and measuring corrosion rates. With proper calibration and control, corrosion can be detected and quantified online and in real-time. Electrochemical tests can be conducted at open-circuit potential conditions by galvanically coupling a creviced specimen to an open (non-creviced) specimen and measuring the current flow using a zero-resistance ammeter [87-90]. Such an arrangement is called the remote crevice assembly. The area ratio between the creviced and non-creviced specimens can be varied depending upon the specific application. The advantage of this technique is the sensitivity with which early stages of crevice corrosion and later growth and repassivation can be measured, without perturbing the system away from its open-circuit potential. Care should be taken to minimize exposed (non-crevice) area in the anodic m e m b e r of the remote crevice assembly. The test specimen geometry can be designed to reproduce anticipated macroscopic crevice geometries in m a n y applications.

7Standard Guide for Conducting and Evaluating Galvanic Corrosion Tests in Electrolytes. The work of Qvarfort [51] represents a different approach to critical temperature testing that is intended to study pitting rather than crevice corrosion. See the previous chapter, Pitting, for a discussion of this approach.

CHAPTER 19--CREVICE CORROSION 2 2 7

These four basic techniques are used alone, combined, or in combination with other corrosion-accelerating factors such as increased temperature or chloride concentration. For example, ASTM F 746, Test Method for Pitting or Crevice Corrosion of Metallic Surgical Implant Materials, test involves alternatively controlling the potential until a specified current density is achieved and then following the current until a specified potential is achieved. One way of determining the critical crevice corrosion temperature is with a series of potentiostatic tests conducted at uniform increments of increasing temperature until a limit in current density is exceeded. In the electrochemical tests, it should be noted that some of the measured parameters are sensitive to crevice geometry. in a r a p i d increase in current density. Eventually, the change in current density is sustained at a level two or more orders of magnitude higher than the passive current level. The temperature at which this occurs is taken to be the electrochemical critical crevice corrosion temperature (ECCT) or electrochemical critical pitting temperature (ECPT), depending on whether a crevice-former was used. The transient surges of current density that occur below the ECT are usually ignored since such changes represent the initiation and rapid repassivation of pits. The results achieved by using the ECT technique have very good correlation with long-term exposure tests in brine as well as the same ranking as found in cyclic polarization work [55]. ECT test methods have been found to be very effective in detecting rather subtle differences in the composition and microstructure of stainless steels [95,96,103]. The most important aspect of ECT testing is that a wide range of alloys can be ranked by a single parameter. Another advantage of ECT testing over immersion testing is that different degrees of polarization can be used to simulate the corrosion potentials that are characteristic of various environments. If the corrosion potential (Ecorr) of an alloy in a service environment is known, a specimen of that alloy can be polarized to that potential in a simulated solution or to a value typically 200-600 mV more anodic than Ecorr in order to accelerate pitting or crevice corrosion. An extension of the ECT method described above that has been used to evaluate alloys for service on North Sea oil platforms [97,98] has been referred to as cyclic therm a m m e t r y [99]. The technique involves exposing a coupon fitted with an MCA to a test solution under an applied potential that simulates a process environment. The current density of the crevice specimen is monitored as the temperature of the test solution is slowly changed (e.g., 4C/24 h) in a cyclic m a n n e r up to a critical value and then back toward r o o m temperature. The test results are in the form of a curve (Fig. 5) that looks very much like a conventional anodic polarization curve [97] with the exception that temperature rather than applied potential is the independent variable. Values for a critical crevice corrosion

M e a s u r e m e n t o f Critical T e m p e r a t u r e
Electrochemical critical temperature (ECT) testing has been evolving for more than two decades [48,50,64,73-75,79, 91-94,101]. 7 The programmed changes in applied potential and temperature that constitute the ECT method are schematically illustrated in Fig. 4. (Note that the corresponding changes in current density are not illustrated in Fig. 4.) The periodic decreases in the applied potential and current density shown in Fig. 4 are due to the fact that the potential is not applied during the rise in temperature. Several workers have found that the continuous application of potential while temperature is increased continuously at a constant rate to be a more efficient and less complex method of testing [102]. The primary reason for preferring the intermittent or step method (the latter is illustrated in Fig. 4) over the continuous method of ECT testing is that the step method better simulates the conditions of the conventional immersion-type test, in which samples are removed from the test solution after exposure at each temperature and inspected, then reimmersed. Under some combination of elevated temperature and applied potential, localized corrosion will initiate and result

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FIG. 4~Schematic illustration of changes in test variables in the course of an intermittent type of ECT test [93].

FIG. 5~Cyclic thermammetry plot for N08367 alloy exposed in a crevice assembly to aerated 3 wt% NaCI under an applied potential of 600 mV (SEE). The temperature was changed by 4C/24 h; data from Ref 97.

228

C O R R O S I O N TESTS AND STANDARDS MANUAL

increases significantly when the potential is raised from a lower value either in a stepwise or continuous fashion. The E ~ v or E~ is the potential at which the current decreases to a low value when the potential is decreased (Fig. 7). However, there has been considerable debate about the validity of these parameters for determining the long-term performance of a given alloy and their dependence on measurement techniques [39,103-107]. It is well known that the Ep and Ecr~v, the potential at which the current increases from a low passive value to a high active value, depends on the scan rate [104], among other factors. Another reason cited against the use of critical potential as a measure of the localized corrosion resistance is the observation made by Wilde and Wilde and Williams [106,107] that the E~p decreased with the extent of prior pit growth. Since then, a n u m b e r of studies [39,108-110] have shown that the Ercrev and E~p attain a lower b o u n d value beyond a certain pit or crevice corrosion depth (Fig. 8). Longer-term, potentiostatic tests have also shown that the Erp measured for deep pits is a reasonable p a r a m e t e r to predict long-term localized corrosion occurrence [39,108]. The techniques for measuring the repassivation potential have not been standardized, although existing methods can be adapted. For alloys that exhibit low to moderate resistance to localized corrosion, the ASTM G 61 method is adequate in defining the repassivation potential, provided sufficient growth in crevice corrosion is assured. F o r highly corrosion resistant alloys, the use of cyclic, potentiodynamic polarization method (ASTM G 61) can lead to misleading results. F o r example, hysteresis between the forward and backward scans has traditionally been used as an indicator of localized corrosion. In highly corrosion resistant alloys, such a hysteresis can be observed without any visual appearance of crevice corrosion (Fig. 9a and b). This is because the initiation of crevice corrosion in the forward scan is monitored by the magnitude of current density. In highly corrosion resistant alloys high currents can be attained during continuous scanning by polarizing to high potentials (above 1 V SCE) where transpassive dissolution takes place. The fact that this is not crevice corrosion is

temperature (CCT) and a repassivation temperature (TR) can be determined from a cyclic t h e r m a m m e t r y curve, as indicated in Fig. 5 [98].

Bias in ECT Tests

The current limit for the ECT, like mass loss or crevice depth, is crucial in establishing a value for the ECT. No criteria for ECT have yet been established by any internationally recognized standards writing organization. A limited survey of the literature yielded test parameter values ranging from 0.01-1.8 mA/cm 2, depending on test environment and sample configuration. One method for establishing the current limit for an ECT test that has been used by several workers involves conducting a series of cyclic potentiodynamic polarization tests (after ASTM G 615) at various temperatures to determine the current density associated with the pitting potential. The influence of the rate of temperature increase in an ECT is analogous to that of potential scan rate in cyclic potentiodynamic polarization test. Figure 6 shows that lower rates of temperature increase result in lower ECCT values. With regard to intermittent versus continuous ECT test, intermittent tests generally produce higher ECT values than do continuous tests. The reason is that metastable pits are more likely to stabilize and propagate in a continuous test; intermittent tests pits or crevices can repassivate during the intervals when the specimen is illowed to return to open circuit potential.
Measurement of Critical Potentials

Critical potentials are important in determining the resistance of a metal to localized corrosion because they have a mechanistic underpinning and they are rapid measurements. Two potentials have been used as a measure of the crevice corrosion resistance---crevice/pit initiation potential (E .... or Ep) and crevice/pit repassivation potential (Er~rev or Erp). The Ecrev or Ep is the potential at which the current

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FIG. 6~Effect of the rate of temperature increase on the anodic current density for welded $31254 in natural seawater at an applied potential of +400 mV (SCE). The solution temperature was increased continuously at the cited rates. Data from Ref 99.

10-10 10-9 10-8 10-7

I I I I 10-6 10-5 104 10.3 10-2

Current Density, A/cm 2 FIG. 7--Cyclic potentiodynamic polarization curve for type 316L SS showing hysteresis and crevice corrosion.

CHAPTER 19--CREVICE CORROSION 229

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2 10-2 254SMO 24 g/L C! O.8 g/I. SO4 5 0 OC 10-3 10~ ~"

Alloy825

the overall characteristics of the polarization curve, followed by potentiostep technique is r e c o m m e n d e d for highly corrosion resistant alloys.

Precision in Measuring Critical Potentials

ASTM G 61 shows the precision in these measurements. The scatter in the Ep and Ecrev is m u c h larger than the scatter in Erp or E ..... [39,108-110]. Limited experimental data [108] indicate a scatter in the Ercrev values of about 100 mV.
Measurement of Depassivation pH

FIG. 8 ~ T h e repassivation potential as a function of prior crevice corrosion and pit depth showing a bounding value less sensitive to penetration depth [3gJ.

0.g-0.4-

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' I 2 I ' I 4 6 Time, Hours ' '

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17

Following a n u m b e r of crevice corrosion modeling approaches [11,12,14], another measure of the crevice corrosion resistance of an alloy was established in terms of the depassivation pH, pH d. This is the pH below which an alloy does not exhibit any passivity and thus represents the conditions at an active crevice corrosion site. It must be noted that in some of the experimental investigations criteria are adopted that may not always result in complete depassivation. For example, Oldfield and Sutton [14] assume a certain current density under potentiostatic conditions as the criterion for depassivation. The pH a values have been measured for a n u m b e r of alloys [36,113]. The pH d can be measured either by generating polarization curves in various simulated crevice solutions with decreasing pH using ASTM G 5 or G 61 method or by monitoring the potential of a specimen u n d er galvanostatic conditions while simultaneously decreasing the pH by the addition of HC1. There is no standard procedure established for this measurement.

-0.S lO-a

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REFERENCES %
[1] Mears, R. B. and Evans, U, R., "Corrosion at Contact with Glass," Transactions of the Faraday Society, Vol. 30, 1934, pp. 417-423. [2] Uhlig, H. H., "Pitting of Stainless Steels," Transactions of AIME, Vol. 140, 1940, pp. 387-432. [3] Rosenfeld, I. L. and Marshakov, I. K., "Mechanism of Crevice Corrosion," Corrosion, Vol. 20, No. 4, 1964, pp. 115t-125t. [4] Schafer, G. J. and Foster, P. K,, "The Role of the Metal-Ion Concentration Cell in Crevice Corrosion," Journal of the Electrochemical Society, Vol. 106, No. 5, 1959, p. 468. [5] Schafer, G. J., Gabriel, J. R., and Foster, P. K., "On the Role of the Oxygen Concentration Cell in Crevice Corrosion and Pitting," Journal of the Electrochemical Society, Vol. 107, No. 12, 1960, pp. 1-1. [6] Bombara, G., "Stress-Corrosion Cracking and Crevice Corrosion in Passivable Alloys," Corrosion Science, Vol. 9, No. 7, 1969, pp. 519-533. [7] Brown, B. F., "Technical Note: Concept of the Occluded Corrosion Cell," Corrosion, Vol. 26, No. 8, 1970, pp. 249-250. [8] Karlberg, G. and Wranglen, G., "On the Mechanism of Crevice Corrosion of Stainless Cr Steel," Corrosion Science, Vol. 11, 1971, pp. 499-510. [9] Picketing, H. W. and Frankenthal, R. P., "On the Mechanism of Localized Corrosion of Iron and Stainless Steel I. Electrochemical Studies," Journal of the Electrochemical Society, Vol. 119, No. 10, 1972, pp. 1297-1304. Uo] Picketing, H. W. and Frankenthal, R. P., "On the Mechanism of Localized Corrosion of Iron and Stainless Steel II. Morphological Studies." Journal of the Electrochemical Society, Vol. 119, No. 10, 1972, pp. 1304-1310.

104 1.2 0.8 0.4 0 i0 "5 a

10~ ~ 0 ' I ' I ' I '

2 4 6 Time, Hours
10-7

-0.4

FIG. 9--Cyclic potentiodynamic polarization curve for alloy 254 SMO showing a large hysteresis, but no crevice corrosion (a). If potentiostep tests were performed with the initial potential value at 1.2V SCE, no crevice corrosion is initiated upon subsequent growth at 0.8 V SCE, as noted by lack of current increase (b). If the initial potential was held at 1.0 V SCE, then crevice corrosion growth occurred at 0.8 V SCE subsequently as noted by the current increase (c).

seen in Fig. 9b, where the potential is held at 0.8 V SCE after initiating corrosion at 1.2 V SCE. The current in this case does not increase even after relatively long time periods. In such a case, backward scanning will indicate a misleading value for repassivation potential. On the other hand, if the corrosion is initiated at a lower potential, the current increases and crevice corrosion is observed visually. Therefore, a combination of cyclic polarization test to determine

230

CORROSION TESTS AND STANDARDS MANUAL

Corrosion, H. S. Isaacs, U. Bertocci, J. Kruger, and S. Smialowska, Eds., National Association of Corrosion Engineers, Orlando, FL, 1-5 June 1987, 1990, Vol. NACE-9, pp. 467-473. [31] Sridhar, N. and Dunn, D. S., "Effect of Applied Potential on Changes in Solution Chemistry Inside Crevices on Type 304. Stainless Steel and Alloy 825," Paper 347, NACE CORROSION/94, NACE International, Baltimore, MD, 1994. [32] Ogawa, H., Denpo, K., and Miyasaka, A., "Criteria for Passivity Breakdown of High Alloy Materials in Relation to Crevice Corrosion Nucleation," Corrosion Science, Vol. 31, No. 1, 1990, pp. 459-464. [33] Sato, N., "Some Concepts of Corrosion Fundamentals," Corrosion Science, Vol. 27, No. 5, 1987, pp. 421-433. [34] Sato, N., "Toward a More Fundamental Understanding of Corrosion Processes," Corrosion, Vol. 45, No. 5, 1989, pp. 354-368. [35] Crolet, J. L., Defranoux, J. M., Seraphin, L., and Tricot, R., "Electrochemical Characterization of the Crevice Corrosion Resistance of Stainless Steels," Memoires Scientifiques Revue Metallurgie, Vol. 71, No. 12, 1974, pp. 797-805. [36] Crolet, J. L., Seraphin, L., and Tricot, R., "Influence of Chloride Content on the Depassivation pH of Stainless Steels," Memoires Scientifiques Revue Metallurgie, Vol. 73, No. 1, 1976, pp. 1-8. [37] Laycock, N. J., Stewart, J., and Newman, R. C., "The Initiation of Crevice Corrosion in Stainless Steels," Corrosion Science, Vol. 39, No. 10-11, 1997, pp. 1791-1809. [38] Isaacs, H. S., "The Behavior of Resistance Layers in the Localized Corrosion of Stainless Steel," Journal of the Electrochemical Society, Vol. 120, No. 11, 1973, pp. 1456-1462. [39] Sridhar, N., Dunn, D. S., Brossia, C. S., and Cragnolino, G. A., "Stabilization and Repassivation of Localized Corrosion," Research Topical Symposium on Localized Corrosion, G. S. Frankel and J. R. Scully, Ed., Houston, TX, NACE International, 2001, pp. 1-29. [40] Oldfield, J. W. and Sutton, W. H., "Crevice Corrosion of Stainless Steels--II. Experimental Studies," British Corrosion Journal, Vol. 13, No. 3, 1978, pp. 104-111. [41] Isseling, F. P., "Electrochemical Methods in Crevice Corrosion Testing: Report Prepared for the European Federation of Corrosion Working Party 'Physico-Chemical Testing Methods of Corrosion," British Corrosion Journal, Vo]. 15, No. 2, 1980, pp. 51-69. [42] Kruger, J. and Rhyne, K., "Current Understanding of Pitting and Crevice Corrosion and Its Application to Test Methods for Determining the Corrosion Susceptibility of Nuclear Waste Metallic Containers," Nuclear and Chemical Waste Management, Vol. 3. No. 4, 1982, pp. 205-227. [43] Postlethwaite, J., "Electrochemical Tests for Pitting and Crevice Corrosion Susceptibility," Canadian Metallurgical Quarterly, Vo]. 22, No. 1, 1983, pp. 133-141. [44] Oldfield, J. W., "Test Techniques for Pitting and Crevice Corrosion Resistance of Stainless Steels and Nickel Base Alloys in Chloride Containing Environments," International Materials Reviews, Vol. 32, No, 3, 1987, pp. 153-170. [45] Kain, R. M., "Evaluation of Crevice Corrosion," Corrosion, Vol. 13, L. J. Korb and D. L. Olson, Eds., ASM, Materials Park, OH, 1988, p. 405. [46] Streicher, M. A., "Development of Pitting Resistant Fe-Cr-Mo Alloys," Corrosion, Vol. 30, No. 3, 1974, pp. 77-91. [47] Garner, A., "Crevice Corrosion of Stainless Steels in Seawater: Correlation of Field Data with Laboratory Ferric Chloride Tests," Corrosion, Vol. 37, No. 3, 1981, pp. 178-184. [48] Nagaswami, N. S. and Streicher, M. A., "Accelerated Laboratory Tests for Crevice Corrosion of Stainless Alloys," Paper 7l, NACE CORROSION/83 Conference, NACE, Anaheim, CA, 1983. [49] Hibner, E. L., "Modification of Critical Crevice Temperature Test Procedures for Nickel Alloys in a Ferric Chloride Environment," Materials Performance, Vol. 26, No. 3, 1987, pp. 37-40.

[11] Crolet, J. L. and Defranoux, J. M., "Calculation of Incubation Times in Crevice Corrosion of Stainless Steels," Corrosion Science, Vol. 13, No. 7, 1973, pp. 575-585. [12] Galvele, J. R., "Transport Process and the Mechanism of Pitting of Metals," Journal of the Electrochemical Socie~,
Vol. 123, No. 4, 1976, pp. 464-474.

[13] Gravano, S. M. and Galvele, J. R., "Transport Processes in Passivity Breakdown - IIL Full Hydrolysis Plus Ion Migration Plus Buffers," Corrosion Science, Vol. 24, No. 6, 1984, pp. 517-534. [14] Oldfield, J. W. and Sutton, W. H., "Crevice Corrosion of Stainless Steels--I. A. Mathematical Mode," British Corrosion Journal, Vol. 13, No. 1, 1978, pp. 13-22. [15] Turnbull, A., "Chemistry Within Localized Corrosion Cavities," in Advances in Localized Corrosion, H. S. Isaacs, U. Bertocci, J. Kruger, and S. Smialowska, Eds., National Association of Corrosion Engineers, 1990, Vol. NACE-9, pp. 359-373. [16] Alkire, R. C. and D. Siitari, "Initiation of Crevice Corrosion - II, Mathematical Model for Aluminum in Sodium Chloride Solutions," Journal of the Electrochemical Society, Vol. 129, No. 3, 1982, pp. 488-496. [17] Sharland, S. M., "A Mathematical Model of the Initiation of Crevice Corrosion in Metals," Corrosion Science, Vol. 33, No. 2, 1992, pp. 183-201. [18] Watson, M. K. and Posflethwaite, J., "Numerical Simulation of Crevice Corrosion," Corrosion, Vol. 46, No. 8, 1990, pp. 522-530. [19] Gartland, P. O., "Modeling Crevice Corrosion of Fe-Ni-Cr-Mo Alloys in Chloride Solutions," 12th International Corrosion Congress, NACE International, 1993, Vol. 3B, pp. 1901-1914. [20] Walton, J. C., "Mathematical Modeling of Mass Transport and Chemical Reaction in Crevice and Pitting Corrosion," Corrosion Science, Vol. 30, No. 8/9, 1990, pp. 915-928. [21] Walton, J. C., Cragnolino, G. A., and Kalandros, S. K., "A Numerical Model of Crevice Corrosion for Passive and Active Metals," Corrosion Science, Vol. 38, No. 1, 1996, pp. 1-18. [22] Lillard, R. S. and Scully, J. R., "Modeling of the Factors Contributing to the Initiation and Propagation of the Crevice Corrosion of Alloy 625," Journal of the Electrochemical Society, Vol. 141, No. 11, 1994, pp. 3006-3015. [23] Lillard, R. S., Jurinski, M. P., and Scully, J. R., "Crevice Corrosion of Alloy 625 in Chlorinated ASTM Artificial Oceanwater," Corrosion, Vol. 50, No. 4, 1993, pp. 251-265. [24] Nisancioglu, K. and Holtan, H., "Correlation of the Protection Potential and the Ohmic Potential Drop," Electrochimica Acta, Vol. 23, No. 3, 1978, pp. 251-253. [25] Picketing, H. W., "The Limiting IR Voltage within Electrolyte in Cavities During Localized Corrosion and Hydrogen Charging of Metals," Corrosion and Corrosion Protection, R. P. Frankenthal and F. Mansfeld, Eds., The Electrochemical Soc., Inc., Pennington, NJ, 1981, p. 85. [26] Picketing, H. W., "The Significance of the Local Electrode Potential within Pits Crevices and Cracks," Corrosion Science, Vol. 29, No. 2/3, 1989, pp. 325-341. [27] Xu, Y. and Picketing, H. W., "A Model of the Potential and Current Distribution within Crevices and Its Application to the Iron-Ammoniacal System," Critical Factors in Localized Corrosion, G. S. Frankel and R. C. Newman, Eds., The Electrochemical Society, Pennington, NJ, 1992, pp. 389-406. [28] Shaw, B. A. and Moran, P. J., "The Role of Ohmic Potential Drop in the Initiation of Crevice Corrosion on Alloy 625 in Seawater," Corrosion Science, Vol. 32, No. 7, 1991, pp. 707-719. [29] Kehler, B. A., Ilevbare, G. O., and Scully, J. R., "Crevice Corrosion Behavior of Ni-Cr-Mo Alloys: Comparison of Alloys 625 and 22," Research Topical Symposium on Localized Corrosion, G. S. Frankel and J. R. Scully, Eds., Houston, TX, NACE International, 2001, pp. 30-64. [30] Stockert, L. and Boehni, H., "Metastable Pitting Processes and Crevice Corrosion on Stainless Steels," Advances in Localized

CHAPTER 19--CREVICE CORROSION [50] Brigham, R. J., "Temperature as a Crevice Corrosion Criterion," Corrosion, Vol. 30, No. 11, 1974, pp. 396-398. [51] Qvarfort, R,, "New Electrochemical Cell for Pitting Corrosion Testing," Corrosion Science, Vol. 28, No. 2, 1988, pp. 135-140. [52] Qvarfort, R,, "Critical Pitting Temperature Measurements for
Stainless Steels with an Improved Electrochemical Method," Corrosion Science, Vol. 29, No. 8, 1989, pp. 987-993. [53] Dean, S. W., "Electrochemical Methods for Corrosion Testing in the Process Industries," Electrochemical Corrosion Testing with Special Consideration of Practical Applications: Papers and Discussions of an International Workshop, J. C. Rowlands and F. Mansfeld, Eds., VCH, Deerfield Beach, FL, Ferrara, Italy, 1985, pp. 1-15. [54] Schofield, M. J. and Kane, R. D., "Critical Review of Corrosion Test Methods for Duplex Stainless Steels," Paper 90572, CORROSION/90, NACE International, Las Vegas, NV, 23-27 April 1990. [55] Bardal, E., Drngli, J. M., and Gartland, P. O., "Behavior of Corrosion-Resistant Stainless Steels in Seawater: A Review," Corrosion Science, Vol. 35, No. 1-4, 1993, pp. 257-267. [56] Streicher, M. A., "Pitting Corrosion of 18Cr-8Ni Stainless Steel," Journal of the Electrochemical Society, Vol. 103, No. 7, 1956, pp. 375-389. [57] Renner, M., Heubner, U., Rockel, M. B., and Wallis, E., "Temperature as a Pitting and Crevice Corrosion Criterion in the FeCl3," Werkstoffe und Korrosion, Vol. 37, No. 4, 1986, pp. 183-190. [58] Lizlovs, E. A., "Crevice Corrosion of Some High Purity Ferritic Stainless Steels," Localized Corrosion--Cause of Metal Failure, ASTM STP 516, ASTM International, West Conshohocken, PA, 1972, pp. 201-209. [59] Bond, A. P. and Dundas, H. J., "Resistance of Stainless Steels to Crevice Corrosion in Seawater," Materials Performance, Vol. 23, No. 7, 1984, pp. 39-43. [60] Bond, D. P., Dundas, H. J., Ekerot, S., and Semchyshen, M., "Stainless Steels for Seawater Service," Stainless Steel'77, Climax Molybdenum Co., Ann Arbor, MI, 1977, p. 197. [61] Tsujikawa, S., Kudo, K., Ogawa, H., et al., "A New Test for Predicting Pitting Corrosion Resistance of CRA's in Sour Environments," Paper 65, NACE CORROSION/88 Conference, NACE International, St. Louis, MO, 1988. [62] Wallen, B., Bergqvist, A., and Olsson, J., "Testing of Three Highly Alloyed Stainless Steels According to the MTI Corrosion Tests," E., Risbergs, Ed., l l t h Scandinavian Corrosion Congress, Swedish Corrosion Institute, Stockholm, Sweden, Stavanger, Norway, 1989, pp. 1-9. [63] Brigham, R. J., "On the Variability of Crevice Corrosion Initiation in Ferric Chloride Exposure Tests," Corrosion, Vol. 37, No. 10, 1981, pp. 608-609. [64] Brigham, R. J. and Tozer, E. W., "Localized Corrosion Resistance of Mn-Substituted Austenitic Stainless Steels: Effect of Molybdenum and Chromium," Corrosion, Vol. 32, No. 7, 1976, pp. 274-276. [65] Christie, D. W., "Effect of Post-Weld Cleaning on Corrosion Resistance of Austenitic and Duplex Stainless Steel Weldments in Bleach Plant Service," NACE Western Canadian Region Conference, NACE, Edmonton, Canada, 1992, pp. 1-14. [66] Degerbeck, J., "On Accelerated Pitting and Crevice Corrosion Tests," Journal of the Electrochemical Society, Vol. 120, No. 2, 1973, pp. 175-182. [67] Kolts, J. and Sridhar, N., "Temperature Effects in Localized Corrosion," Corrosion of Nickel-Base Alloys, R. C. Scarberry, Ed., ASM International, Metals Park, OH, 1985, pp. 191-198. [68] Lagerberg, S., Bernhardsson, S., and Lau, P., "Electrochemical Testing Methods for the Study of Localized Corrosion," 10th Scandinavian Corrosion Congress, Swedish-Corrosion Institute, Stockholm, Sweden, 1986, pp. 271-277.

231

[69] Lau, P. and Bernhardsson, S., "Electrochemical Techniques for

the Study of Pitting and Crevice Corrosion Resistance of Stainless Steels," Electrochemical Techniques for Corrosion Engineering, R, Baboian, Ed., NACE International, Houston, TX, 1977, pp. 281-286. [70] Garner, A., The Effect of Autogenous Welding on Chloride Pitting Corrosion in Austenitic Stainless Steels," Corrosion, Vol. 35, No. 3, 1979, pp. 108-113. [71] Garner, A., "Materials Selection for Bleached Pulp Washers," Pulp & Paper Canada, Vol. 82, No. 12, 1981, pp. 109-120. [72] Strandmyr, O. and Hagernp, O., "Field Experience with Stainless Steel Materials in Seawater Systems," Corrosion/98, Paper 707, Houston, TX: NACE International, 1998. [73] Brigham, R. J., "Pitting and Crevice Corrosion Resistance of 18% Cr Stainless Steel," Materials Performance, Vol. 13, No. 11, 1974, pp. 29-31. [74] Brigham, R. J. and Tozer, E. W., "Effect of Alloying Addition on the Pitting Resistance of 18%Cr Austenitic Stainless Steel." Corrosion, Vol. 30, No, 5, 1974, pp. 161-166. [75] Brigham, R. J. and Tozer, E. W., "Temperature as a Pitting Criterion," Corrosion, Vol. 29, No, 1, 1973, pp. 33-36. [76] Rockel, M. B. and Renner, M., "Critical Review of Laboratory Methods Testing the Resistance of High Alloyed Stainless Steels and Nickel Alloys Against Localized Corrosion in Chloride Solutions," 8th European Congress of Corrosion, Vol. 1, Centre Francais de la Corrosion, Societe de Chimie Industrielle, F75007 Paris, France, Nice, France, 19-21 November 1986. [77] Kain, R. M., "Seawater Testing to Assess the Crevice Corrosion Resistance of Stainless Steel and Related Alloys," 12th International Corrosion Congress, NACE International, Vol. 3B, 1993, pp. 1889-1900. [78] Anderson, D. B., "Statistical Aspects of Crevice Corrosion in Seawater," Galvanic and Pitting Corrosion~Field and Laboratory Studies, ASTM STP 576, ASTM International, West Conshohocken, PA, 1976, pp. 231-242. [79] Streicher, M. A., "Analysis of Crevice Corrosion Data from Two Sea Water Exposure Tests in Stainless Alloys," Materials Performance, Vol. 22, No. 5, 1983, pp. 37-50. [80] Kain, R. M., "Crevice Corrosion Testing in Natural Seawater Significance and Use of Multiple Crevice Assemblies," Journal of Testing and Evaluation, Vol. 18, No. 5, 1990, pp. 309-318. [81] Kearns, J. R., Johnson, M. J., and Grubb, 3. F., "Accelerated Corrosion in Dissimilar Metal Crevices," Paper 228, NACE CORROSION/86 Conference, NACE, Houston, TX, 1986. [82] Maurer J. R., "Long-Term Exposure of Dissimilar Metal Crevice in Filtered Seawater," Materials Performance, Vol. 33, No. 4, 1994, pp. 51-54. [83] Gallagher, P., Malpas, R. E., and Shone, E. B., "Corrosion of Stainless Steels in Natural, Transported, and Artificial Seawater," British Corrosion Journal, Vol. 23, No. 4, 1988, pp. 229-233. [84] Manning, P, E., "Comparison of Several Accelerated Laboratory Tests for the Determination of Localized Corrosion Resistance of High-Performance Alloys," Corrosion/82, Paper No. 176, Houston, TX: NACE International, 1982. [85] Wensley, D. A., Reid, R. C., and Dykstra, H., "Corrosion of Nickel-Based Alloys in Chlorine Dioxide Washer Service," Corrosion/90, Paper 537, Houston, TX: NACE International, 1990. [86] Nadezhdin, A. and Wensley, D. A., "Composition Factors Affecting Resistance of Ni-Cr-Mo-N Alloys to Crevice Corrosion," Materials Performance, Vol. 31, No. 11, 1991, pp. 57-59. [87] Lee, T. S., "A Method for Quantifying the Initiation and Propagation Stages of Crevice Corrosion," Electrochemical Corrosion Testing, ASTM STP 727, F. Mansfield and U. Bertocci, Eds., ASTM International, West Conshohocken, PA, 1981, pp. 43-68.

232

CORROSION TESTS AND STANDARDS MANUAL

Corrosion Congress, NACE International, Vol. 3A, 1993, pp. 1477-1490. [102] Kane, R. D., Wilhelm, S. M., and McIntyre, D. R., "Application of the Critical Pitting Temperature Test to the Evaluation of Duplex Stainless Steel," Corrosion Testing and

[88] Kain, R. M. and Lee, T. S., "Recent Developments in Test Methods for Investigating Crevice Corrosion," Laboratory Corrosion Tests and Standards, ASTM STP 866, G. S. Haynes
and R. Baboian, Eds., ASTM International, West Conshohocken, PA, 1985, pp. 299-323. [89] Kain, R. M., "Electrochemical Measurement of the Crevice Corrosion Propagation Resistance of Stainless Steels: Effect of Environmental Variables and Alloy Content," Materials Perfornmnce, Vol. 23, No. 2, 1984, pp. 24-30. [90] Steinsmo, U., Rogne, T., and Drugli, J., "Aspects of Testing and Selecting Stainless Steels for Seawater Applications," Corrosion, Vol. 53, No. 12, 1997, pp. 955-964. [91] Brigham, R. J., "The Initiation of Crevice Corrosion on Stainless Steels," Materials Performance, Vol. 24, No. 12, 1985, pp. 44-48. [92] Bernhardsson, S., Mellstr6m, R., and Brox, B., "Limiting Chloride Contents and Temperatures with Regard to Pitting of Stainless Steels." Paper 85, NACE CORROSION/80 Conference, Anaheim, CA, 1980. [93] Bernhardsson, S. and Mellstr6m, R., "Performance of a Highly Alloyed Stainless Steel in Marine Environments," Anti-Corrosion, 1985, p. 7. [94] Davis, G. O. and Streicher, M. A., "Initiation of Chloride Crevice Corrosion of Stainless Alloys," Paper 205, NACE Corrosion/85 Conference, Boston, 1985. [95] Davison, R. M., "Characterization of Stailaless Steel Plates for Paper Machine Headbox Applications," Paper 90542, CORROSION/ 90, NACE International, Las Vegas, NV, 23-27 April 1990. [96] Alfonsson, E. and Qvarfort, R., "Investigation of the Applicability of Some PRE Expressions for Austenitic Stainless," Materials Science Forum: Electrochemical Methods in Corrosion Research (EMCR) 4, Vol. 111-112, 1992, pp. 483-491. [97] Steinsmo, U., Rogne, T., Drngli, J. A., and Gartland P. O., "High Alloyed Stainless Steels for Chlorinated Seawater Applications--Critical Crevice Temperatures," Engineering Solutions to Industrial Corrosion Problems, NACE International, Sandefjord, Norway, 1993. [98] Gartland, P. O., Steinsmo, U., Drugli, J. M., and Solheim, P., "High, Alloyed Stainless Steels for Chlorinated Seawater Applications: A Summary of Test Results for Eleven Austenitic and Duplex Materials," Paper 646 NACE CORROSION/93, NACE Nashville, TN, 1993. [99] Martinchek, G. A. and Yaffe, M. R., CMS 110 Critical Pitting Test System Operator's Manual, GAMRY Instruments, Inc., Langhorne, PA, 1992. [100] Drngli, J. M. and 3ohnsen, R., "Corrosion Testing of Stainless Steel Weldments in Seawater, NaC1- and FeC13 Solutions," Paper 410, NACE CORROSION/88, St. Louis, MO, 1988. [101] Arvig, P. O. and Davison, R. M., "Measuring Corrosion Resistance of Stainless Steels Using the 'Avesta Cell'-Experiences and New Applications," 12th International

Evaluation: Silver Anniversary Volume. ASTM STP 1000,

R. Baboian and S. W. Dean, Eds., ASTM International, West Conshohocken, PA, 1990, pp. 289-302. [103] Thompson, N. G. and Syrett, B. C., "Relationship between Conventional Pitting and Protection Potential and a New, Unique Pitting Potential," Corrosion, Vol. 48, No. 8, 1992, pp. 649q559. [104] Szldarska-Smialowska, Z., "Pitting Corrosion of Metals," Houston, TX: NACE International, 1986. [105] Rogne, T., Drngli, J. M., and Johnsen, R., "Testing for Initiation of the Crevice Corrosion of Welded Stainless Steel in Natural Seawater," Materials Performance, Vol. 26, No. 9, 1987, pp. 29-34. [106] Wilde, B. E., "A Critical Appraisal of Some Popular Laboratory Electrochemical Test for Predicting the Localized Corrosion Resistance of Stainless Alloys in Seawater," Corrosion, Vol. 28, No. 8, 1972, pp. 283-291. [107] Wilde, B. E, and Williams E., "The Use of Current/Voltage Curves for the Study of Localized Corrosion and Passivity Breakdown on Stainless Steels in Chloride Media," ElectrochimicaActa, Vol. 16, No. 11, 1971, pp. 1971-1985. [108] Dunn, D. S., Cragnolino, G. A., and Sridhar, N., "An Electrochemical Approach to Predicting Long-Term Localized Corrosion of Corrosion-Resistant High-Level Waste Container Materials," Corrosion, Vol. 56, No, 1, 2000, pp. 90-104. [109] Tsujikawa, S. and Okayama, S., "Repassivation Method to Deter-mine Critical Conditions in Terms of Electrode Potential, Temperature and NaC1 Concentration to Predict Crevice Corrosion Resistance of Stainless Steels," Corrosion Science, Vol. 31, No. 1, 1990, pp. 441-446. [110] Tsujikawa, S., "Critical Depth for Initiation of Growing Crevice Corrosion," Critical Factors in Localized Corrosion, G. S. Frankel and R. C. Newmans, Eds., The Electrochemical Society, Pennington, NJ, 1992, pp. 378-388. [111] Syrett, B. C., "Technical Note: PPR Curves--A New Method of Assessing Pitting Corrosion Resistance," Corrosion, Vol. 33, No. 6, 1977, pp. 221-224. [112] Imai, H., Fukumoto, I., and Masuko, N., "Repassivation Potential for Crevice Corrosion of Austenitic SUS304 Stainless Steel with Teflon Ball Crevice," Corrosion Engineering, Vol. 36, 1987, pp. 461-466. [113] Okayama, S., Tsujikawa, S., and Kikuchi, K., "Effects of Alloying Elements on Stainless Steel Depassivation pH," Corrosion Engineering, Vol. 36, 1987, p. 631. [114] Betts, A. J. and Boulton, L. H., "Crevice Corrosion: Review of Mechanisms, Modeling, and Mitigation," British Corrosion Journal, Vol. 28, No. 4, 1993, pp. 279-295.