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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta
a r t i c l e
i n f o
Article history:
Received 14 February 2013
Received in revised form 28 March 2013
Accepted 28 March 2013
Available online 8 April 2013
Keywords:
Nickel alloys
Bicarbonate
Carbonate
pH
XPS
AES
a b s t r a c t
The depletion of Cr and Mo in the passive lms grown on commercial NiCrMo(W) alloys in carbonate/bicarbonate solutions has been studied potentiodynamically and by X-ray photoelectron and Auger
spectroscopy. Depletion in these two key alloying elements occurs at lower potentials than expected on
all the alloys studied. It has been shown that the key feature leading to this behavior is the buffering
of surface pH to >8.6, when the surface deposition (or retention) of insoluble protective Mo(VI) species
does not occur as would be expected under the acidic local conditions generated by Cr(VI) and Mo(VI)
dissolution. The presence of a small solution concentration of Mg2+ ions leads to the accumulation of a
Mg(OH)2 deposit when the surface pH is maintained sufciently alkaline.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
NiCrMo alloys having an optimum concentration of Cr and
Mo demonstrate excellent corrosion resistance in both oxidizing and reducing environments [14]. A NiCrMoW alloy, C-22
(Ni22Cr13Mo3W), has been studied as a candidate material for
nuclear waste containers in the proposed Yucca Mountain (Nevada,
USA) repository [5]. The exposure conditions under which this alloy
may be susceptible to localized corrosion (especially crevice corrosion) have been studied extensively [612], with a primary focus
on the acidic conditions likely to prevail within an active crevice.
In the last ten years many studies have been performed to understand the inuence of various parameters, such as, pH, potential
and temperature, on the passive lm behavior of NiCrMo alloys
[2,3,10,1316]. However, the effects of solution composition have
not been studied in detail.
In Part I of this study [17] it was demonstrated that, in the
presence of bicarbonate ions, the passive lm on the Hybrid-BC1
alloy undergoes barrier layer degradation at an unexpectedly low
potential. Electrochemical studies show that when the potential is
increased above this apparent breakdown value, an anodic peak,
329
Table 1
Nominal chemical compositions of the relevant alloys (wt.% of major alloying element).
Alloying element
C-22
UNS
N06022
Hybrid-BC1
UNS
N10362
Alloy 59
UNS
N06059
Alloy 625
UNS
N06625
Alloy 686
UNS
N06686
Cr
Mo
W
Fe
Ni
22
13
3
3
56
15
22
<2
62
23
16
<1
59
21
9
5
62
21
16
4
1
58
analyses were performed with a Kratos Axis Ultra XPS at Surface Science Western (SSW) employing monochromatic Al K
(1486.8 eV) radiation. The binding energy was calibrated to give
a Au 4f7/2 line position at 83.95 eV. XPS spectra were corrected for
charging by taking the C 1s spectrum for adventitious carbon to be
at a binding energy of 284.8 eV. Survey spectra were recorded on
all samples followed by high resolution XPS spectra for Ni 2p, Cr
2p, Mo 3d, C 1s and O 1s spectral regions. The XPS spectra were
analyzed using the commercial CasaXPSTM software.
Auger data were obtained using a PHI 660 Auger electron spectrometer (AES) with an excitation energy of 5 keV. Depth proles
were measured using an Ar+ ion sputtering beam. A survey scan
was acquired for each sample and during depth proling the
intensity for Ni, Cr, Mo, Mg and O were monitored as a function of sputtering time. To convert sputtering times to analyzed
depths, a reference sputtering prole was obtained on a specimen
of the Hybrid-BC1 alloy under similar conditions. The sputtering
rate obtained for this reference specimen was 28 nm/min. It was
assumed that the sputtering rate for a surface covered with an
electrochemically grown oxide was similar to that of the reference
specimen.
3. Results
3.1. Effect of alloying elements
Fig. 1 shows the potentiodynamic scans recorded on different
alloys in a 1 M NaCl + 0.1 M NaHCO3 (pH = 8.2) solution at 60 C.
Despite the differences in Cr, Mo and W content of these alloys,
they all exhibit similar polarization behavior, the current increasing
at E > 200 mV (vs SCE) leading to a current peak around 400 mV
followed by a region of secondary passivation prior to complete
1000
800
600
E vs SCE/mV
2. Experimental
400
200
Hybrid-BC1
Alloy 625
Alloy 59
Alloy 686
C-22
0
-200
-400
-600
-800
-8
-7
-6
-5
-4
-3
-2
-2
log (j/A cm )
Fig. 1. Potentiodynamic scans recorded on different NiCrMo (W) alloys in 1 M
NaCl + 0.1 M. NaHCO3 solution at 60 C.
330
1000
800
E vs SCE/mV
600
0
30 C
0
45 C
0
60 C
0
75 C
400
200
0
-200
-400
-600
-800
-8
-7
-6
-5
-4
-3
-2
-1
-2
log (j/A cm )
Fig. 2. Potentiodynamic scans recorded on the Hybrid-BC1 alloy in 1 M NaCl + 0.1 M
NaHCO3 solution at different temperatures.
transpassive behavior at potentials above 750 mV. The HybridBC1 alloy has a higher passive current and lower ECORR value than
the other alloys, which probably reects the lower Cr content of this
alloy and the relatively short period on open circuit before applying
the potentiodynamic scan. However, irrespective of composition,
all these alloys exhibit an identical apparent breakdown potential
and similar anodic peak potential (425 mV) values.
The similarity in barrier layer degradation potentials, irrespective of compositional differences, indicates that the increase in
current beyond the apparent breakdown potential is not a result
of localized corrosion. This was demonstrated for the Hybrid-BC1
alloy using cyclic potentiodynamic polarization studies in Part I
of the study [17]. Since the passive layer composition on these
alloys is likely to be very similar it is not surprising that the potential at which the onset of this barrier layer degradation process
commences is independent of the substrate alloy composition. It is
anticipated, as previously demonstrated for the Hybrid-BC1 alloy in
chloride/bicarbonate solution, that above the apparent breakdown
potential all the studied alloys form a thick Ni oxide/hydroxide layer
depleted in Cr, Mo and W, which accounts for the secondary partial
passivation in the potential range 400750 mV. These results conrm that the apparent breakdown and the appearance of an anodic
peak are independent of the concentration of Cr, Mo or W and other
minor alloying elements. Similar behavior for different commercially available Cr-containing Ni-based alloys has been reported by
others [18].
331
counts/a.u.
Ni 2p
O 1s
Cr 2p
Mg KLL
C 1s
Mo 3d
1200
1000
800
600
400
200
Binding Energy/eV
Fig. 5. XPS survey spectra for the lms grown at 0 mV (SCE) in chloride and chloride/carbonate solution.
-4.0
1M NaCl + 0.1 M Na2CO3
1M NaCl + 0.1M NaHCO3
-4.5
-2
log (j/A cm )
-5.0
-5.5
-6.0
-6.5
0
log(t/s)
Fig. 6. Log(I) log(t) plots recorded on the Hybrid-BC1 alloy in chloride/carbonate
and chloride/bicarbonate solution at 0 mV (SCE).
332
100
1000
90
800
Mg
Ni
80
600
E vs SCE/mV
70
at. %
60
50
40
400
200
0
-200
30
-400
20
-600
10
-800
-8
0
0
100
200
300
400
-7
-6
Fig. 7. Film cation composition as a function of potential recorded on the HybridBC1 alloy in 0.1 M NaCl + 0.1 M Na2 CO3 solution.
O
Ni
Mg
Cr
Mo
90
80
70
at. %
60
50
40
30
20
10
0
0
50
100
150
200
250
300
350
-4
-3
-2
-2
E vs SCE/mV
100
-5
log (j/A cm )
400
depth/nm
Fig. 8. AES depth prole recorded on the Hybrid BC1 alloy after anodic lm growth
at 200 mV (Fig. 4a) in 1 M NaCl + 0.1 M Na2 CO3 solution.
800
600
E vs SCE/mV
400
1000
800
600
400
E vs SCE/mV
1000
200
0
-200
-400
200
1M NaCl + 0.1M NaHCO3
-400
-600
-800
-800
-7
-6
-5
-4
-3
-2
-2
-200
-600
-1000
-8
333
-1000
-8
-7
-6
-5
log (j/A cm )
Fig. 10. Potentiodynamic scans recorded on the Hybrid-BC1 alloy at 60 C in chloride/hydroxide solutions containing various amounts of added NaOH. The pH values
measured before and after the experiments are shown in brackets.
-4
-3
-2
-1
-2
log (j/A cm )
Fig. 11. Potentiodynamic scans recorded on the Hybrid-BC1 alloy at 60 C in chloride/bicarbonate and chloride/hydroxide solutions. The horizontal dashed lines
show the potentials at which lms were grown and analyzed by XPS.
counts/a.u.
3.0x10
2.5x10
2.0x10
1.5x10
NiO
Ni(OH)2
1.0x10
870
865
860
855
1400
NiO
Ni(OH)2
counts/a.u.
850
Binding Energy/eV
1000
800
600
400
870
865
860
855
850
Binding Energy/eV
Fig. 12. High resolution deconvoluted XPS spectra for the Ni 2p peak recorded
on oxide lms grown on the Hybrid-BC1 at 60 C at a potential of 335 mV
(SCE) and 425 mV (SCE) (Fig. 11) in (a) chloride/hydroxide solution and (b) chloride/bicarbonate solution respectively.
334
4. Discussion
5. Conclusions
(1)
(2)
Acknowledgements
This research was funded by the Canadian Natural Sciences and
Engineering Research Council (NSERC). The authors also acknowledge Haynes International, ThyssenKrupp and Special Metals for
providing the samples. Special thanks go to Dr. Sridhar Ramamurthy and Dr. Mark Biesinger at Surface Science Western (SSW)
for their assistance on analytical techniques employed in this study.
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