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Corrosion Science 53 (2011) 1670–1679

Corrosion Science 53 (2011) 1670–1679 Contents lists available at ScienceDirect Corrosion Science journal homepage:

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Corrosion Science

journal homepage: www.else vier.com/locate/corsci

Science journal homepage: www.else vier.com/locate/corsci Corrosion product analysis on crevice corroded Alloy-22

Corrosion product analysis on crevice corroded Alloy-22 specimens

P. Jakupi a , F. Wang b , J.J. Noël a , D.W. Shoesmith a ,

a Department of Chemistry, The University of Western Ontario, London, Ontario, Canada N6A-3K7 b Department of Physics, University of Science and Technology Beijing, Beijing 100083, PR China

article info

Article history:

Received 12 May 2010 Accepted 12 January 2011 Available online 25 January 2011

Keywords:

A. Alloy-22

A. Molybdenum

A.

Polymeric molybdates

C.

Crevice corrosion

A.

Nickel-based alloys

B.

Raman spectroscopy

abstract

Surface analytical techniques were applied to characterize corrosion products formed during the crevice corrosion of the Ni–Cr–Mo(W) Alloy-22 in 5 mol/L NaCl at 120 C. Micro-Raman spectroscopy demon- strated the formation of polymeric molybdates within the crevice corroded region where intergranular corrosion dominated. The location and chemical speciation of the Mo and W species formed was inves- tigated by Raman mapping. Crevice corrosion was found to propagate preferentially across the alloy sur- face rather than to penetrate deeply at localized sites, a feature which appears to be linked to the formation and build-up of polymeric molybdates.

2011 Elsevier Ltd. All rights reserved.

1. Introduction

Ni–Cr–Mo alloys are distinguished for providing corrosion resis- tance in extremely corrosive environments, and are consequently used in a wide range of corrosive industrial applications. The anti-corrosion and electrochemical properties of these alloys arise from the passive, thin (2–5 nm) protective oxide layer that covers the alloy, with the alloying components giving the oxide its unique properties. Ni-based alloys, in general, are more corrosion resistant than stainless steels due to their tolerance for extensive alloying. Cr and Mo are known to impart resistance against oxidizing and reducing acids, respectively [1,2] . In terms of passive corrosion and breakdown behavior, it has been suggested that Cr plays the key role in maintaining the passivity of the oxide [2] . Conse- quently, the breakdown potential is primarily influenced by the Cr content, while repassivation occurring after a breakdown event is influenced by the Mo content [3] . From a localized corrosion viewpoint, enhancing the passive nature of the oxide film should render the alloy immune to initiation. However, once initiation and subsequent propagation have occurred, a knowledge of how the surface composition evolves and affects repassivation is key to determining localized corrosion mechanisms. Although alloying with Mo is well known to increase the corro- sion resistance of iron and Ni-based alloys, the mechanisms are still not fully understood. It has been suggested that Mo locates

Corresponding author. Tel.: +1 519 661 2111x86366, fax: +1 519 661 3022. E-mail address: dwshoesm@uwo.ca (D.W. Shoesmith).

0010-938X/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi: 10.1016/j.corsci.2011.01.028

at defect sites that would otherwise preferentially dissolve [4,5] , leading to a modification of the rate of anodic dissolution due to the greater relative Mo–Mo bond strength found in alloys [6,7] . Lloyd et al. [2] observed, with increasing applied potential, segre- gation of the alloying elements, Ni–Cr to the inner alloy-oxide interface and Mo–W to the outer oxide–electrolyte interface for a

series of commercial Ni–Cr–Mo alloys. The greater the Mo content of the alloy, the greater the extent of segregation resulting in lower passive current densities. It has also been suggested that Mo is sta-

bilized at the oxide/electrolyte interface as MoO

steels [8,9] and gives the outer regions of the passive film a cation selective character that discriminates against the incorporation of

the aggressive Cl anion into the passive film. Bastidas et al. [10] observed the formation of Mo-chloro complexes on AISI 316 stain- less steels that may potentially decrease the free chloride concen- tration close to the alloy surface and further inhibit Cl ingress in the protective passive film. Inhibition of localized corrosion on stainless steels [11–14] and Ni-alloys [15,16] due to Mo has been studied extensively. In both alloys, the inhibiting effect of alloyed

Mo has been shown to be primarily due to the species MoO

when added as a salt to the electrolyte this species has been shown to increase corrosion resistance [15–17] . This study focuses on the crevice corrosion of the Ni–Cr–Mo–W Alloy-22 and especially the influence of Mo on propagation and repassivation. Crevice corrosion products have been studied primar- ily by Raman spectroscopy, although other surface analytical tech- niques were also used. To determine whether W behaved similarly to Mo, a few experiments were performed on the W-free Alloy- 2000. The nominal compositions of these alloys are given in Table 1 .

4 . Even

2

4 in stainless

2

P. Jakupi et al. / Corrosion Science 53 (2011)

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1671

Table 1 Elemental composition of Alloy-22 and Alloy-2000 (wt%).

Element

Ni

Cr

Mo

W

Fe

Co

Mn

Si

C

S

Cu

Alloy-22

Bal.

22

13

3

3

2.5

0.5

0.08

0.01

0.02

Alloy-

Bal.

23

16

3

2

0.5

0.08

0.01

0.01

1.6

2000

2. Experimental procedure

Crevice corrosion experiments were conducted using an elec- trochemical cell built within a Teflon (PTFE)-lined Hastelloy pres- sure vessel [18] . A homemade Ag/AgCl (saturated KCl) reference electrode [19] was used to measure the potential of the working electrode. All potentials reported in this study are quoted against this electrode unless stated otherwise. The working electrode was cut from an Alloy-22 plate which was 0.317 cm (1/8 00 ) thick. The alloy composition is given in Table 1 . The Alloy-22 specimen was machined and bent into a V-shape to ensure that only one cre- vice was formed in contact with the electrolyte solution, . The cre- vice assembly was held together with threaded Alloy-22 bolts and nuts. The crevice former was a small Teflon wafer sandwiched be- tween the flat metal surface of the working electrode and a poly- sulfone coupon. This assembly defined a creviced area of 4 cm 2 . The working electrode had a threaded tapped hole in one end to accept a nickel alloy welding rod used to make electrical contact to external circuitry. Udel (Polysulfone) bushings were placed be- tween the working electrode and the metal bolts and nuts to insu- late the bolts and any additional creviced areas at these locations from the working electrode. The crevice-forming face of the work- ing electrode was grinded with a series of wet silicon carbide pa- pers (320, 600, 800, 1000, and 1200 grits). All parts of the crevice assembly were degreased by sonication in methanol and de-ion- ized water, and then rinsed with de-ionized water, and air dried. Prior to assembly, the V-shaped crevice electrode and Teflon cre- vice former were submerged in the electrolyte solution to be used, to ensure wetting of the crevice interior. The crevice tightness was adjusted using a Teflon ‘‘feeler’’ strip cut from the same sheet as the Teflon crevice former. A 5 mol/L NaCl solution prepared using de-ionized (DI) Milli- pore water (18.2 M X cm) and reagent grade sodium chloride from Caledon Chemicals (99.0% assay) was used in all experiments. The solution was naturally aerated by agitation in air. To prevent boil- ing of the electrolyte, the cell was pressurized to 414 kPa with ultra high purity argon gas. The temperature was controlled at 120 C in all experiments. During heat-up, the corrosion potential of the creviced specimen was measured using a Solatron model 1284 potentiostat. Once the desired temperature was reached ( 6 h), crevice corrosion was initiated and propagated under constant cur- rent (galvanostatic) control. As discussed previously [20], this was

Udel bushing working electrode Teflon crevice
Udel bushing
working
electrode
Teflon crevice

electrolyte

level

Alloy-22 nuts

and bolts

Udel block

former

Fig. 1. Schematic of the creviced working electrode (not to scale).

necessary since all attempts to initiate and propagate crevice cor- rosion using an Alloy-22 creviced electrode galvanically coupled to a counter electrode of the same alloy under the same conditions were unsuccessful. On completion of each experiment, the creviced specimen was rinsed with de-ionized water and methanol and then dried and stored in a desiccator prior to surface analysis. The specimens were photographed and examined with an optical microscope (Olym- pus, IX70). A Hitachi S-4500 field emission Scanning Electron Microscope (SEM) equipped with an EDAX™ energy dispersive X- ray (EDX) system was used to examine the surface topography of the creviced specimens. X-ray photoelectron spectroscopic (XPS) analyses were per- formed using a Kratos Axis Ultra XPS. Spectra were analyzed using the commercial CasaXPS software, v. 2.2.107 [21] . XPS spectra were corrected for charging by taking the C 1s spectrum for adven- titious carbon to be at a binding energy of 284.8 eV. High resolu- tion spectra were fitted with a mixed Gaussian/Laurentian function using the parameters published by Biesinger et al. [22] . Confocal Raman spectroscopy was performed under ambient conditions with an Alpha SNOM, (WITec). A linearly polarized YAG laser (Verdi 5, Coherent Inc.) with a wavelength of 532 nm was used for Raman excitation. A 50 objective lens was used to focus the laser beam onto chosen regions of the specimen. Raman spectra were recorded at each image pixel by an air-cooled back- illuminated CCD camera. A typical image consisted of 50 50 pix- els that made up a total of 2500 spectra. Raman images of the cor- roded specimens were constructed by integrating the intensities of the characteristic Raman bands within the scanned area in the X–Y orientation. A laser power of 10 mW was used to enhance Raman scattering. Creviced specimens were checked after analysis to en- sure no damage had occurred due to surface heating by the laser.

3. Results

3.1. Surface analytical results within propagated region

Fig. 2 shows the creviced region of an Alloy-22 specimen on which crevice corrosion was galvanostatically initiated and propagated at 200 l A. Corrosion damage is conspicuous near the edge (i.e. mouth) of the creviced region and appears to have prop- agated laterally across the surface much more rapidly than it pen- etrated into the alloy. An optical magnification ( Fig. 3 ) reveals that the crevice corroded region is decorated with pits and preferential

teflon crevice former propagated region creviced region

teflon crevice former

teflon crevice former propagated region creviced region

propagated region

teflon crevice former propagated region creviced region

creviced region

Fig. 2. Alloy-22 specimen on which crevice corrosion was initiated and propagated galvanostatically at an applied current of 200 l A.

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P. Jakupi et al. / Corrosion Science 53 (2011) 1670–1679

corrosion

product

corrosion product intergranular corrosion

intergranular

corrosion

Fig. 3. Optical micrograph of the Alloy-22 specimen in Fig. 1 . This magnified image was taken within the crevice corroded region to show the preferred attack on the grain boundaries and the resulting.

corrosion along the grain boundaries. Intergranular corrosion (IGC) was shown to dominate the damage morphology for crevice corro- sion via galvanostatic control on Alloy-22. Fig. 4 shows the mea- sured potential of the creviced specimen at the applied constant current of 200 l A: For the first 50 s the measured potential in- creases rapidly before decreasing to a steady state value for the duration of the experiment (>300 s). As discussed in more detail previously [20,23], the steady-state potential indicates the occur- rence of crevice propagation and reflects both the development of aggressive chemistry and a resulting IR drop within the active region of the crevice. The steady-state potential observed, as well as the lack of potential excursions and transients associated with it, indicates that once initiation and stabilization of an active loca- tion has occurred, no new corrosion sites initiate. This suggests that propagation involves the growth of a single (or very small number) of initiated sites. Since the area damaged by propagation increases with time under constant current conditions, the current density must decrease, at least at some locations within the cre- vice. This implies that the spread of corrosion damage is more readily achieved than the accumulation of damage at deep local sites. If the critical conditions for propagation are to be maintained, then the current density and hence critical chemistry, must be maintained at the spreading edges of the damaged area, strongly suggesting that the current density decreases at the already dam- aged locations left behind. It seems likely that these trailing loca- tions undergo repassivation. Fig. 3 shows that corrosion products are present within the creviced area and tend to accumulate on the grain surfaces. During dismantling of the creviced specimen once the experiment was

   

0.6

    0.6  
 
 

0.4

 
   

0.3

 

E (V)

E

Ag/Cl )

0.2

 
 

0.0

V

E (V

   
 

-0.3

 

0.0

 

0

100

200

300

400

400

500

500

600

600

700

700

 

Time (s)

 
 
 
 

-00.22

 

0

10000

 

20000

30000

 

40000

 

Time (s)

 

Fig. 4. Potential measured on a creviced Alloy-22 specimen corroded at an applied constant current of 200 l A.

completed, the corrosion products appeared to have stayed intact on the alloy surface even after rinsing and drying. Similar behavior is observed over the applied current range, 20–200 l A. To characterize the corrosion products within the creviced re- gions, a variety of surface analytical techniques were applied. Figs. 5 and 6 show SEM images and corresponding EDX maps of IGC areas and grain surfaces, respectively, for a specimen corroded at an applied current of 200 l A. The elemental analyses show similar trends in both areas. EDX signal intensities for Mo, W, and O were all greater on the corroded grain boundaries and for the corrosion products on the grain surfaces compared to the bare grain surfaces. By contrast, the signal intensities for Ni and Cr were depleted in these regions relative to the bare grain surface. To further examine the chemical nature of the corrosion products within the corroded regions Raman spectroscopy was employed. Fig. 7 shows optical images and the corresponding Raman maps recorded within the corroded region, specifically at locations where IGC had occurred and corrosion products had accumulated. Contrast in the Raman signal intensities recorded at grain bound- aries and on grain surfaces was clearly observed. Also, a distinctive signal contrast was observed between bare grain surfaces and those covered by corrosion products. The signal intensities in Fig. 7 are the integration of the total Raman signals observed with- in the spectrum. Low-resolution Raman spectra ( Fig. 8 ) of the mapped regions in Fig. 7 show similar signals for areas subjected to IGC and those where corrosion products accumulated on the grains, indicating the accumulation of corrosion products has also occurred within the corroded grain boundaries. Peaks were observed and centered at 355, 835, and 965 cm 1 . The peaks observed at 350 and 835 cm 1 were consistently broader than the sharper peak at 965 cm 1 . Depth profiles and 3D Confocal Laser Scanning Micros- copy (CLSM) images [24] also show the accumulation of corrosion products within the corroded grain boundaries, which have been previously shown to be locations of preferential attack on creviced specimens [25] . In a multi-component alloy such as Alloy-22 ( Table 1 ) care should be taken in assigning Raman peaks to specific chemical spe- cies. According to the Critical Crevice Solution (CCS) model, crevice propagation is characterized by accelerated oxidation and dissolu- tion, and the subsequent hydrolysis of metal cations leading to a low pH and an increase in chloride content within the creviced re- gion [26,27]. Precise pH measurements within the creviced region are not practical due to the constricted geometry however, acidic values (<3) are undoubtedly expected during propagation [28,29]. From the elemental surface analyses ( Figs. 5 and 6 ) the rel- ative EDX signal intensities for Mo, W, and O were enhanced at cor- roded sites and in corrosion products within the corroded region,

suggesting that the Raman signals observed from the mapped images are due to a mixture of these species formed within an acidic environment.

3.2. Assigning Raman peak signals to molybdates and tungstates

Molybdates and tungstates are known to aggregate to form polynuclear species in low pH solutions [30,31] . At near-neutral

. Within

is

4 via the proton-consuming

known to co-exist with MoO equilibrium:

the range 4.5 < pH < 6.5 the paramolybdate species Mo 7 O

pH, in oxic solutions the stable molybdate species is MoO

2

4

6

24

2

7MoO

2

4

þ

8H þ ¡Mo 7 O

6

24

þ

4H 2 O

ð 1Þ

Larger aggregates such as the octamolybdate anion Mo 8 O 26 4 are known to be formed upon further acidification into the pH range 2.9 to 1.5,

P. Jakupi et al. / Corrosion Science 53 (2011) 1670–1679

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Jakupi et al. / Corrosion Science 53 (2011) 1670–1679 1673 Fig. 5. SEM image and corresponding

Fig. 5. SEM image and corresponding EDX maps of a crevice corroded region on Alloy-22 specimen.

EDX maps of a crevice corroded region on Alloy-22 specimen. Fig. 6. SEM image and corresponding

Fig. 6. SEM image and corresponding EDX maps of the corrosion products accumulated on the grain surfaces of a crevice corroded Alloy-22 specimen.

8MoO

2

4

þ

12H þ ¡Mo 8 O 4 þ 6H 2 O

26

ð 2Þ

and, for pH < 1.5 (i.e. the conditions anticipated within a propagat- ing creviced region), further aggregation may lead to the polymo- lybdate [31–33] anion, Mo 36 O 112 8 . At pH 0.9, molybdate is known to reach its isoelectric point and form molybdic acid (MoO 3 H 2 O), and on further acidification, positively charged species such as MoO , MoO 4+ and HMo 2 O 4 þ have all been reported [34,35]. To study the inhibitive effect of nitrates on Alloy-22 corrosion under acidic conditions, Gray et al. [36] utilized in situ Raman spec- troscopy to characterize transpassive dissolution products. Signifi- cant Raman peaks were observed at 321 and 349 cm 1 , which were attributed to the Mo–O bond stretching mode and the Mo(2)–O bond bending mode, respectively. The Raman spectra reported clo- sely matched the spectra for Mo(V) chloride solution standards, but the authors reported the detected species as MoO 4 . No evi- dence for Mo-polymerization was observed. In this study a broad peak is observed spanning the wavenumber region 175–570 cm 1 , but centered at 355 cm 1 . According to lit- erature values, this broad feature can be assigned to the r Mo–O bending mode characteristic of MoO 2 and MoO 3 oxides [36–39]. Two distinct peaks are also observed at 835 and 965 cm 1 , with the latter usually being the most intense of the three observed peaks

þ

2

6

in the spectra. Although sharper than the broad peak at 355 cm 1 , these peaks are still much broader than the sharp peaks observed for pure crystalline materials [37,40] . Published studies [39,41,42] sug- gest that the peak observed at 835 cm 1 is due to the asymmetric

stretch of Mo–O–Mo bonds, characteristic of MoO

4 . However, this

peak was observed to be relatively weak compared to the peak ob- served at 897 cm 1 , which is primarily used to characterize

MoO 2

4 . Dieterle and Mestl [37] observed significant peaks at 835

and 843 cm 1 and attributed them to the bridging Mo–O 2 vibrations of the intermediate molybdenum oxide, Mo 4 O 11 . Cross and Schrader [43] also observed a sharp peak at 834 cm 1 , which they attributed to the oxide intermediate Mo 4 O 11 formed upon heating MoO 3 thin films. In a Raman study of aqueous molybdates [44] as a function of pH, no peaks in the wavenumber region 830–850 cm 1 were ob- served for a near-neutral pH of 6.6, while acidification of the aqueous solution to pH 2.2 and pH 0.95 led to the appearance of Raman peaks at 844 and 835 cm 1 , respectively. It was suggested these peaks could be due to the formation of the highly aggregated molybdate species, Mo 36 O 112 8 . Acidification of aqueous molybdates to pH 2.2 also led to the appearance of a broad peak at 363 cm 1 attributed to the octamolybdate anion Mo 8 O 4 The sharpest and most intense peak observed in the Raman spec- tra ( Fig. 8 ) at 965 cm 1 has been assigned to the symmetrical

2

26 .

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P. Jakupi et al. / Corrosion Science 53 (2011) 1670–1679

P. Jakupi et al. / Corrosion Science 53 (2011) 1670–1679 Fig. 7. Optical images (a and

Fig. 7. Optical images (a and c) and the corresponding Raman maps (b and d) of crevice corroded regions on an Alloy-22 specimen. Spectra were recorded in region s (outlined in dash-line) showing IGC (a and b) and accumulated corrosion products on grain surfaces (c and d).

stretching of the Mo–O bond [39] . Commonly for molybdates, the Raman bands observed in the ranges 950–1006 and

918–945 cm 1 are characteristic of octahedrally and tetrahedrally coordinated compounds respectively, and are key in accurately identifying molybdate species, since the Raman peaks are usually the most intense within these frequency ranges [39,45–47] . Shifting of these peaks is linked to the molybdate chain length; for example, symmetrical t (Mo–O) stretching increases from 897 to 943 to 965

, and

cm 1 , characteristic of the molybdate species MoO

Mo 8 O 4 , respectively [45] . Aqueous molybdate studies [40,41,44]

4

,

Mo 7 O

24

2

6

26

have shown that the Raman band located at 897 cm 1 , which is char-

acteristic of the species MoO

with the appearance of Raman bands centered within the range 950–1000 cm 1 when the pH is decreased. In this study ( Figs. 8 and 9 ), the sharp asymmetric peak has been consistently observed

4 , decreases in intensity concomitantly

2

within the region 915–970 cm 1 , which is assigned to the polymeric Mo 8 O 4 (965 cm 1 ) species [39,40] . The shoulder on the low fre- quency side of the peak suggests that stretching modes for other

polymeric molybdate species [40], such as Mo 7 O

(940 cm 1 ) and

Mo 3 O 2 (950 cm 1 ) may also contribute to this peak. Broadening of the peak centered at 355 cm 1 , may also be attributed to a combi- nation of Raman active species, specifically the oxides MoO 2 and MoO 3 and the Mo 8 O 4 species formed at low pH.

26

10

6

24

26

The broadness of the peaks ( Figs. 8 and 9 ) suggests a lack of crystallinity and order of the Raman-active species. Also, Raman bands arising from tungstate species [42,44] with similar stretching frequencies to those of molybdates may also contribute to the broadness of the peaks in Figs. 8 and 9 . For comparison the commercial alloy, Alloy-2000, which con- tains an increased Mo content, but no W, was also analyzed to

 

(a)

  (a) (b)  

(b)

 

400

400   400
400   400
 

400

400   400

Intensity (Arbitrary Units)

Intensity (Arbitrary Units)

300

300 300
300 300

300

(Arbitrary Units) Intensity (Arbitrary Units) 300 300   200   200   200 200 400 400
(Arbitrary Units) Intensity (Arbitrary Units) 300 300   200   200   200 200 400 400
 

200

 

200

 

200

200

400

400

600

600

800

800

ν (cm -1 )

1000

1000

1200

1200

 

200

200

400

400

600

600

800

800

ν (cm -1 )

1000

1000

1200

1200

Fig. 8. Low-resolution Raman spectra of areas exhibiting (a) IGC and (b) corrosion product accumulation recorded on crevice corroded Alloy-22 at an applied current of 200 l A.

P. Jakupi et al. / Corrosion Science 53 (2011) 1670–1679

1675

40000 Alloy-2000 (without W) Alloy-22 (with W) 30000 20000 1000010000 0 250 250 500 500
40000
Alloy-2000 (without W)
Alloy-22 (with W)
30000
20000
1000010000
0
250
250
500
500
750
750
1000
1000
1250
1250
1500
1500
-1
ν
ν cm
cm
Relative Intensity (arbitrary units)

Fig. 9. High-resolution Raman spectra comparing the spectra recorded on corrosion products on crevice corroded Alloy-22 (with W) and Alloy-2000 (without W) crevice corroded at an applied current of 200 l A to an accumulated charge of 3 C.

determine whether W played a similar role to Mo. Fig. 9 shows high-resolution spectra recorded on corroded grain boundaries for both Alloy-22 and Alloy-2000. Only minor differences, such as minor peak shifts and variations in broadness, especially for the

peak centered at 838 cm 1 , were observed. A full spectral decon- volution would be required to accurately locate and determine whether there was any significant effect of W on the spectra. As

, is known to be the predomi-

for molybdates, the tungstate, WO

nant species at near-neutral pH and further acidification leads to polymerization (Reaction (3)) and then dimerization [31] (Eq. (4)).

2

4

6WO

2HW 6 O

2

4

þ

5

21

7H þ ¡HW 6 O

5

21

þ 3H 2 O

þ 4H 2 O¡W 12 O 36 ð OHÞ 10

10

ð 3Þ

ð

4Þ

However, the kinetics of reactions (3) and (4) are known to be slower than the formation of the polymerized molybdates [31,46], via reactions (1) and (2). Raman peaks similar to those in Fig. 9 have been observed for aqueous polymeric tungstate solu-

tions (as a function of pH [46] ) at 838 and 960 cm 1 and attributed

to WO

significant differences in the spectra recorded on Alloys-22 and 2000 are observed, Fig. 9 , and it is likely that the polymeric molyb- dates dominate the corrosion product content within the corrosion damaged region since the Mo content of the alloys is considerably

higher than the W content. Fig. 10 shows Raman images of the corroded grain boundary shown in Fig. 7 b. The image intensities were integrated and sepa- rated into the wavelength ranges characteristic for the three Ra- man bands in an attempt to determine the distribution of Raman-active species within the damaged area. Based on intensity (yellow being the most intense), it appears that the Raman bands

residing in the 940–985 cm 1 ( Fig. 10 c), attributed primarily to the species Mo 8 O 4 (discussion above), dominate the damaged areas followed by the band in the region 325–364 cm 1 , also prob- ably attributable to Mo 8 O 4 . Fig. 10 does not necessarily imply these species are the most concentrated, but rather, shows how these species are qualitatively distributed across the damaged region. In general, the Raman active species observed in the 820–856 cm 1 range was always the least distributed, i.e. most localized. Quantifying these species would be difficult due the complexities of in situ measurements within the constricted geom- etry of a crevice.

4 and the polymeric species in Eqs. (3) and (4) . However, no

2

26

26

3.3. Corrosion products outside the corrosion-damaged region

Fig. 11 shows micrographs of the solid corrosion products formed just outside the damaged region on an Alloy-22 specimen crevice corroded at 70 l A. These were optically different in size and color from the corrosion products observed within the dam-

aged area. In this study the corroded region is defined as the area

In this study the corroded region is defined as the area Fig. 10. Raman images constructed

Fig. 10. Raman images constructed from Raman signals recorded within the wavenumber ranges: (a) 325–364 cm 1 , (b) 820–856 cm 1 , and (c) 940–985 cm 1 on the corroded grain boundary regions shown in Fig. 6 b.

crevice mouth

c r e v i c e m o u t h propagated region (a) (b)

propagated region

(a)

(b) outside corroded region/stained region
(b)
outside corroded
region/stained region

Fig. 11. (a) Alloy 22 specimen on which crevice corrosion was initiated and propagated galvanostatically at a constant applied current of 70 l A: (b) the area just outside the crevice corroded region.

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P. Jakupi et al. / Corrosion Science 53 (2011) 1670–1679

(a)

Intensity (Arbitrary Units)
Intensity (Arbitrary Units)

(b)

400

300

200

1000 2000 3000 4000
1000
2000
3000
4000

ν (cm -1 )

Fig. 12. (a) Raman intensity map of the creviced area immediately outside the corrosion damaged region; (b) the corresponding spectrum for an intense signal ( yellow) area. (For interpretation of the references in color in this figure legend, the reader is referred to the web version of this article.)

in which corrosion damage is clearly observed. Upon disassembly and rinsing of the creviced specimen, the corrosion products observed in Fig. 11 b stayed intact on the alloy surface and were consistently observed outside the crevice corroded location on specimens galvanostatically corroded at a variety of applied cur- rents. The corrosion products were a greenish brown in color, and cracked. The organization of the insoluble corrosion products suggest that it was once a uniform layer and that cracking occurred during drying. Fig. 12 a shows a Raman intensity (yellow being most intense) map of the corrosion products. The intensity is not uniform across the insoluble layer and the resulting spectrum, Fig. 12 b, taken from a location of high intensity, showed similar peaks to those observed within the damaged region, Fig. 8 ,

although they were not as sharp. This, and the observation that the Raman intensity decreases with distance from the damaged re- gion, suggests that Mo corrosion products were transported out of the damaged region onto the non-corroded region. SEM/EDX was used to determine the elemental contrast in alloying components in this region. This analysis, Fig. 13 , shows there is an enhancement of chromium and a depletion of nickel on the region of the surface covered with corrosion product flakes ( Fig. 13 b) and vice versa for a region where the bare alloy surface is exposed ( Fig. 13 c). Subse- quent XPS analysis ( Fig. 14 ) showed that the chemical content of the flakes is predominantly chromium, in particular the species, Cr(OH) 3 ( 95%). A small amount of Cr 2 O 3 and Cr was also observed. Both chromium(III) compounds are Raman active [48,49] but have

chromium(III) compounds are Raman active [48,49] but have Fig. 13. SEM micrograph showing (a) the area

Fig. 13. SEM micrograph showing (a) the area just outside the crevice corroded region and the corresponding EDX spot analyses for the region covered with flakes (b) and the uncovered region (c).

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7000 Cr 2p 3/2 6000 Cr(OH)3 5000 4000 3000 575 580 Binding Energy (eV) intensity
7000
Cr 2p
3/2
6000
Cr(OH)3
5000
4000
3000
575
580
Binding Energy (eV)
intensity (Arbitrary Units)

Fig. 14. The Cr 2p 3/2 XPS band measured on the corrosion products shown in Fig. 12 a. The dashed line shows the fit for Cr(OH) 3 .

a low Raman scattering cross-section and are known to exhibit significant spectral broadness [50] . Mo(VI) was the predominant molybdenum species observed in the XPS spectrum, which is con-

, and Mo 8 O 4 species identified

sistent with the presence of MoO by Raman spectroscopy.

2

4

26

4. Discussion – corrosion product impact on crevice corrosion propagation

Crevice corrosion studies on Alloy-22 conducted by Shan and Payer [51] showed a similar distribution of alloying elements as observed in this study. Despite observing congruent dissolution in the active region, corrosion products in the corroded region were rich in O, Mo, and W and depleted in Ni and Cr. This was attributed to a difference in solubilities of corrosion products at low pH. Also, dark green deposits similar to those observed in Fig. 11 were found on the uncorroded metal surface around the crevice contacts. Corrosion products such as H 2 gas and insoluble deposits formed within the active region have been shown to promote ini- tiation and subsequent propagation [52,53] by decreasing the cre- vice gap and increasing the crevice electrolyte resistance R, allowing the IR drop criterion to be satisfied [54] . Lillard et al. [16] compared the corrosion resistance of commer- cial Ni-alloys in terms of their Mo content: Alloy-276 (15–17 wt% Mo), Alloy-625 (8–10 wt% Mo), and Alloy G-3 (6–8 weight% Mo). They demonstrated that the corrosion resistance decreased in the order Alloy-276 > Alloy-625 > Alloy G-3, which corresponds to the decreasing Mo content. Alloying with Mo was shown to de- crease the passive current density and lower the anodic dissolution rate in the alloy’s active polarization region, consequently, decreas- ing crevice corrosion propagation rates. It was shown for a series of Ni–Cr–Mo alloys (in 0.1 M H 2 SO 4 + 1 M NaCl) that alloying with Mo

suppresses dissolution [2] . Lillard et al. [16] attributed the inhibit-

, but were still

ing affects of Mo to the dissolution product MoO

unclear as to the exact mechanism. Addition of sodium molybdate (Na 2 MoO 4 ) to the creviced alloy’s bulk electrolyte even caused a delay in crevice initiation and a significant decrease in propagation

rates [11,15–17] . To ensure the inhibiting effect of MoO

4 was not

simply due to competitive migration with Cl into the creviced re- gion, Lillard et al. [16] , for comparison, added Na 2 SO 4 in a separate

did not display the same

inhibiting effects as MoO

. Many hypotheses have been proposed

crevice experiment and showed that SO

2

4

2

2

4

2

4

including that it is

thermodynamically unstable with respect to Mo polymeric species

at low pH, reactions (1) and (2). It has also been proposed that salt

films, such as MoO 2 Cl 2 , contribute to the inhibiting behavior [15] .

The bi-polar film model proposes that the passive film is com-

posed of an inner anion-selective and an outer cation-selective

layer. Alloying with Mo [55] , as well as the addition of MoO

4 into

the electrolyte [17] was shown to enhance the inner barrier layer and to improve the corrosion resistance of the Fe–19Cr–9Ni alloy.

This effect was attributed to the cation selective property of MoO

and its ability to deprotonate Cr(OH) 3 thereby facilitating the

formation of the stable Cr 2 O 3 inner barrier layer. Also, the outer

molybdate layer was shown to hamper the ingress of Cl and

OH effectively eliminating rehydration of this barrier layer.

Although this role has not been verified explicitly for the polymeric molybdates identified in this study, it is plausible that the in-

creased negative charge on these species would enhance cation selectivity and inhibit ingress of anions into the outer film. Addi-

tionally, the thermodynamic instability of MoO

at low pH with

respect to Mo polymeric species comes at the expense of H + con- sumption, reactions (1) and (2), which would reinforce the ten- dency for an active site within the creviced region to repassivate. This study suggests the inhibiting nature of alloyed Mo on active

crevice propagation is due to the formation of insoluble polymeric

molybdates, Mo 7 O

as a polymeric gel during crevice corrosion and then dried into so- lid form upon dismantling and drying of the crevice, Fig. 3 .

Experimental evidence suggests that Mo has a greater impact on the transpassive state then the passive state of Ni–Cr–Mo oxi- des. On Alloy-22, the protective barrier layer has been character- ized primarily as Cr 2 O 3 [2] , and with increasing applied potential, from 200 to 500 mV (versus 0.1 M KCl, Ag/AgCl) in acidic solution the oxide showed an increase in segregation resulting in an inner Cr–Ni layer and an outer Mo–W layer consistent with a stronger influence of Mo and W at more positive potentials. In studies on Al- loy-22 under open-circuit conditions in acidic chloride environ- ments [56,57], the impedance response indicates that the composition of the oxide changes with pH and exposure time and, in a complimentary study, the authors characterized the ma- jor transpassive dissolution product as Mo [36] . These studies sug- gest that once the integrity of the oxide is threatened, in acidic solutions and at positive potentials the influence of Mo becomes more pronounced. Although the presence of Mo containing corrosion products has been demonstrated, there is still uncertainty as to the exact Mo

dissolution product. Since MoO

at pH < 3 [58] it is unlikely that this species is the major dissolution

4 is thermodynamically unstable

[16] to explain the inhibiting nature of MoO

2

4

2

2

4

2

4

6

24

and Mo 8 O 4 . It is likely these species existed

26

2

product during crevice propagation. Wanklyn [11] demonstrated that crevice corrosion of stainless steels (Type 430 and 316) and the Ni-alloy, Inconel 625, were inhibited only when Mo 6+ , rather than Mo 3+ and Mo 4+ were added to the crevice electrolyte. It has been suggested [16] that during passive dissolution within the

creviced region, MoO

would be formed and eventually exert an

inhibiting effect once a decrease in pH and crevice propagation oc- curs. Additionally, it was shown that Mo 6+ could be formed by ano- dic dissolution of MoO 2 grown oxides at pH 2.4 [11] ,

2

4

MoO 2 þ 2H 2 O ! MoO

2

4

þ 2H þ þ 2e

ð 5Þ

However, the above reaction suggests that Mo is dissolved from a barrier layer which is unlikely for Ni–Cr–Mo alloys which have been shown to have predominantly Cr barrier layers. This would

then suggest that the Raman signal at 355 cm 1 observed in this study would only be attributable to the oxide MoO 3 , and the poly- meric species, Mo 8 O 4

26 .

Fig. 15 summarizes the distribution of alloying elements ob- served in the present study. The SEM micrograph depicts a region

1678

P. Jakupi et al. / Corrosion Science 53 (2011) 1670–1679

P. Jakupi et al. / Corrosion Science 53 (2011) 1670–1679 Fig. 15. SEM micrograph of a

Fig. 15. SEM micrograph of a crevice corroded Alloy-22 specimen showing: (1) the corrosion-damaged region with corroded grain boundaries containing polymeric molybdates; (2) insoluble chromium hydroxides consistently found just outside region 1; and (3) the non-corroded creviced region still showing polishing marks.

just outside the corrosion damaged region of the creviced speci- men shown in Fig. 11 , and shows three distinct regions: (1) a dam- aged/corroded region decorated with intergranular corrosion; (2) a region covered with insoluble chromium hydroxide flakes; and (3) a region, still underneath the crevice former, that resembles the freshly polished passive alloy. Based on the pH and its influence on the solubilities of the major alloying components, Ni, Mo, and Cr, we can say that Fig. 15 illustrates the consequences of a pH gra- dient stretching from the crevice corrosion-damaged region 1, with low pH and concentrated in insoluble polymeric molybdates, through region 2 covered by chromium hydroxides insoluble at higher pH, to region 3, which remains unaffected by crevice corro- sion. Given the pH dependence of the solubility of chromium(III) [58] , its precipitation as an insoluble corrosion product would be expected after only a small increase in pH. Also, as suggested by the CCS model [26,27], extremely low pH values are required to maintain the localized active site. Therefore the location of the insoluble chromium hydroxides delineates the extent of the cor- roded region, as shown in Fig. 15 .

5. Conclusions

Insoluble corrosion products were shown to accumulate within the corroded regions of creviced Alloy-22 and Alloy-2000 speci- mens, especially within corroded grain boundaries. The damaged regions were more concentrated in Mo and O (and to a lesser de-

gree, W, in the case of Alloy-22) relative to the non-damaged re- gions, while Ni and Cr were depleted. The Mo-containing compounds were identified via Raman spectroscopy as the oxide

MoO 3 , as well as the polymeric species Mo 7 O

lished literature suggests that the Raman peak centered at 835 cm 1 could be attributed to the oxide Mo 4 O 11 and/or the poly-

meric species Mo 36 O 112 8 . However, this study alone could not re- solve whether these species coexisted with the identified polymeric species. For Alloy-22, analogous tungstate compounds may also have been formed within the corroded region, but similar Raman signals for Alloy-22 and Alloy-2000 (no W content) could not easily be de-convoluted to verify this. Polymeric species were formed within the corroded region as a result of the relative ther-

for Alloy-22)

modynamic instability of MoO

at low pH suggesting that alloying Mo plays a significant role in controlling crevice propagation on Ni–Cr–Mo alloys.

and Mo 8 O 4 . Pub-

6

24

26

4

(and possibly WO

4

2

2

Acknowledgements

The authors thank the Science and Technology Program of the Office of the Chief Scientist (OCS), Office of Civilian Radioactive Waste Management (OCRWM), and the United States Department of Energy (DOE) for support. The work was performed under the Corrosion and Materials Performance Cooperative, DOE Coopera- tive Agreement No. DE-FC28-04RW12252. The views and opinions of the authors expressed herein do not necessarily state or reflect those of the United States Department of Energy. The authors would also like to acknowledge Zhifeng Ding for use of the Raman apparatus and Surface Science Western for the use of their facilities.

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