Professional Documents
Culture Documents
1 Appendix F
the HLW container and as an overpack material, including ferritic AISI 430 and two
austenitic alloys (AISI 309 and 316Ti) as container materials and the austenitic and
superaustenitic alloys AISI 316, 904L, and 926 as candidate overpack materials (Druyts
and Kursten 1999, Kursten and Druyts 2000, Kursten and Van Iseghem 1999).
However, the occurrence of thiosulphate from the oxidation of pyrite in the Boom clay
and the possibility of increased Cl- levels as a result of the evaporation of dilute clay
interstitial water lead to concern over the localised corrosion of stainless steels (Druyts
and Kursten 1999, Kursten and Druyts 2000) and resulted in the adoption of an
entirely different waste package design (Kursten and Druyts 2008). A stainless alloy
(AISI 309S) has also been selected for the container for HLW in the French programme
in argillaceous clay (Fron et al. 2009), but virtually all experimental studies have been
focussed on the corrosion behaviour of the unalloyed steel overpack. In Spain, the AISI
316L alloy has been investigated, along with a large number of other materials, as a
potential canister material for the disposal of HLW/SF in a granitic geological
formation (Kursten et al. 2004). Stainless steels were also briefly considered for use in
the Yucca Mountain repository (AISI 316L and the related Ni alloy 825, Dunn et al.
1996), until such time that uncertainty about the severity of the environment that could
form by evaporation of drips on the waste package surface caused the programme to
select more-corrosion-resistant alloys. Finally, there is much experience in the UK with
the use of austenitic stainless steels (AISI 304, 316 and their low-carbon equivalents
304L and 316L) for the disposal of ILW in cementitious grout (Smart and Wood 2004).
This brief review will focus primarily on the 300-series austenitic alloys, but mention
will also be made of the properties of corresponding duplex alloys which offer a
number of advantages but which have not yet been widely investigated as possible
canister materials.
An
performance is required, for instance, for the containers into which the molten HLW
will be poured.
Ferritic stainless steels contain no Ni (an austenite stabilizer) but contain varying
amounts of Cr to provide corrosion resistance. Superferritic alloys are obtained by
increasing the Cr content (up to 30 wt.%) and adding Mo.
considered for use as a container material for HLW (i.e., not an overpack material) is
the basic ferritic type 430 alloy containing 16-18 wt.% Cr (Table F.1).
21.5-24.5
21-23
SAF 2304
2205
S32304
S31803
16-18
430
S43000
18-20
18-20
22-24
22-24
16-18
16-18
16.80
19-23
20.60
304
304L
309
309S
316
316L
316Ti3
904L
9263
S30400
S30403
S30900
S30908
S31600
S31603
S31635
N08904
N08926
Cr
Common name
UNS Number
1.0
1.0
1.0
1.0
1.0
1.0
0.40
1.0
0.30
1.0
1.0
1.0
Austenitic alloys
8-10
0.08
2.0
8-12
0.03
2.0
12-15
0.20
2.0
12-15
0.08
2.0
10-14
0.08
2.0
10-14
0.03
2.0
10.70
0.044
1.08
23-28
0.02
2.0
24.85
0.005
0.92
Ferritic alloys
0.12
1.0
Duplex alloys
3-5.5
0.03
2.5
4.5-6.5
0.03
2.0
Composition (wt.%)2
Ni
C
Mn
Si
0.040
0.030
0.040
0.045
0.045
0.045
0.045
0.045
0.045
0.009
0.045
0.018
0.040
0.020
0.030
0.030
0.030
0.030
0.030
0.030
0.030
0.028
0.035
0.002
Other
N 0.05-0.2, Mo 0.05-0.6
N 0.08-0.2, Mo 2.5-3.5
Mo 2-3
Mo 2-3
Mo 2.05, Ti 0.3
Mo 4-5, Cu 1-2
Mo 6.40, Cu 0.86, N 0.198
Table F.1: Compositions of Stainless Steels Considered for Use for the Disposal of ILW or HLW/SF1
General corrosion
Stainless steels are protected from corrosion by a Cr-based passive film, the properties
of which are discussed in detail in Appendix E: Corrosion of Nickel Alloys. Both
Cr(OH)3 (Appendix E, Figure E.1) and Cr2O3 are thermodynamically stable over a wide
range of pH and for both reducing and, up to a few 100 mV below the O2/H2O
equilibrium, oxidising redox potentials. The stability of this film, however, decreases
with increasing acidity and temperature and in the presence of aggressive anions,
particularly Cl-.
Table F.2 contains a summary of selected rates for the general corrosion of types
304/304L and 316/316L austenitic stainless steel (King 2009a). Various conclusions can
be drawn from these data, including:
a wide range of rates have been reported, reflecting not only a variation in
environmental conditions but also of the experimental technique
the rate decreases with increasing exposure time (due to the formation of an
ever-thickening passive film)
the rate decreases with increasing pH, with corrosion rates generally
<0.1 m/yr in alkaline pH representative of cement pore water
the presence of high Cl- concentrations (of the order of 10,000's mg/L) can
negate the beneficial effect of elevated pH, leading to corrosion rates that
approach 1 m/yr in saline alkaline solution
although the data are sparse, there is no apparent different in the rate of general
corrosion of the regular C and low C alloys or between types 304 and 316
Ambient
304
304
304
Ambient
304L
304
304
304L
13
12.8
10.5
13.3
pH
10
12.5
13.5
Ambient
Ambient
304
304
304
Alloy
Ambient
Ambient
90
25-100
27
90
25
50
75
50
Ambient
30
50
80
30, 45
Temperature
(oC)
Aerated
Aerated
Aerated
Interstitial clay
water
Aerated
Aerated
Aerated
Deaerated
Deaerated
Aerated
Redox
conditions
Saltwater
7,000-43,000
Freshwater
18,400
[Cl-]
(
gg-1)
10 hrs
230 days
200 days
60 days
28 days
Other
Urban, 5-15 yr
Urban, 5-15 yr
Marine, 5-15 yr
Industrial/urban, 5-15 y
Industrial/urban
0.0003
0.01
0.3
0.06
0.18
0.82
0.009
0.0055
0.0063
10-130
0.21
11.4
5.82
0.2-0.96
0.22-0.23
0.3-0.35
<0.03
0.022
0.05-2
0.01
0.03-3
Rate (
myr-1)
BSC 2004
Reference
Table F.2: General Corrosion Rates of Types 304/304L and 316/316L Austenitic Stainless Steel in Alkaline and Near-neutral Solutions and
pH
13.3
>13
Ambient
Ambient
Ambient
Ambient
Alloy
316
316L
316
316L
316L
316
316
30
50-100
27
25
50
75
Ambient
Ambient
Ambient
Ambient
Temperature
(oC)
Aerated
Aerated
Interstitial clay
water
-
Aerated
Aerated
Aerated
Deaerated
Aerated
Redox
conditions
Saltwater
Freshwater
19,000
10,000
18,400
[Cl-]
(
gg-1)
Various atmospheres
0.1 MPa H2
8 yrs, Pacific Ocean
seawater
28 days
Other
0.01
0.25
1.94
0.1-0.24
0.1-0.34
0.1-0.17
0.05
0.03
0.6
Rate
(
myr-1)
Dechema 1990
Casteels et al.
1986
BSC 2004
BSC 2004
Mcdonald et al.
1995
Smart et al. 2004
Alexander et al.
1961
Reference
F.3.2
Localised corrosion
Localised corrosion occurs due to breakdown of the passive film leading to either
pitting
of
exposed
surfaces
or
crevice
corrosion
of
occluded
regions
(1)
(2)
or
respectively.
The pitting potential is a function of alloy composition, Cl- concentration (and the
concentration of other aggressive or inhibitive species), temperature, pH, and various
metallurgical parameters, such as surface finish, degree of sensitisation, etc. Figure F.2
shows the characteristic decrease in EP with the logarithm of the Cl- concentration, as
well as the decrease with increasing temperature. Figure F.3 more clearly shows the
temperature dependence of EP for austenitic alloys Type 304 and 316 and for the ferritic
Type 430 alloy. The Mo-containing Type 316 alloy exhibits the most-positive pitting
potential and, for the same value of ECORR, would be the least susceptible to pitting
corrosion.
The most susceptible of the three alloys is the ferritic Type 430 alloy.
Figure F.4 shows the variation of EP with pH for the same three alloys.
The
dependences shown in the figure suggest the existence of a threshold pH above which
the pitting potential rapidly increases, with that threshold increasing in the order
Type 316 < Type 430 < Type 304.
Figure F.2: Dependence of the Pitting Potential for Type 304 Stainless Steel on
Chloride Concentration for Various Temperatures (Szklarska-Smialowska 2005).
As noted above, thiosulphate ions also induce pitting of stainless steels. The data in
Figure F.5 suggest a decrease in EP of 100-200 mV due to the presence of thiosulphate at
a [Cl-]:[S2O32-] ratio of 17.
susceptibility of both Type 316L and 904 austenitic alloys in the presence of
thiosulphate, although the latter alloy which contains approximately double the
amount of Mo as Type 316L was significantly more resistant, as indicated by a 200400 mV difference in EP. Interestingly, Kursten and Druyts (2000) noted that S2O32affected pit initiation but not pit growth.
Other anions inhibit localised corrosion. Figure F.6 shows the effect of sulphate on the
crevice corrosion of Types 304 and 316 austenitic stainless steels in chloride solutions.
A [SO42-]:[Cl-] ratio of 1.2 (on a molar basis) is sufficient to inhibit the crevice corrosion
of Type 304 and a [SO42-]:[Cl-] ratio of as little as 0.4 is sufficient for the more-resistant
Type 316 alloy.
Figure F.3: Dependence of the Pitting Potential on Temperature for Types 304 and
316 Austenitic and Type 430 Ferritic Stainless Steels in 3% NaCl Solution (from
Sedriks 1996).
Figure F.4: Dependence of the Pitting Potential on pH for Types 304 and 316
Austenitic and Type 430 Ferritic Stainless Steels in 3% NaCl Solution (from Sedriks
1996).
10
Figure F.5: Effect of Thiosulphate on the Pitting Potential of Type 316L Stainless
Steel as a Function of Chloride Concentration at 80oC (Sedriks 1996).
Figure F.6: Inhibitive Effect of Sulphate on the Crevice Corrosion of Types 304 and
316 Stainless Steel in Chloride Solutions (from Sedriks 1996).
11
Figure F.7: Map of the Dependence of Crevice Corrosion and Pitting on Potential
and Chloride Concentration (from Szklarska-Smialowska 2005).
Crevice corrosion occurs under less-aggressive conditions than pitting because the
restricted mass transport of species into and out of the occluded region promotes the
development of the critical chemistry required to sustain stable pit or crevice growth.
Thus, crevice corrosion will occur at more-negative potentials and/or at lower Clconcentrations than pitting, as illustrated in Figure F.7 for Type 304L stainless steel.
As indicated by Equations (1) and (2), it is not the value of EP/ERP or ECREV/ERCREV that
determines the susceptibility to localized corrosion, as such, but the difference between
ECORR and the critical potential. This criterion is illustrated in Figure F.8 which shows
the dependence of the pitting and pit re-passivation potentials for Type 316L stainless
steel on Cl- concentration at 95oC and the corresponding values of ECORR in aerated and
deaerated solutions. Based on the criteria in Equations (1) and (2), therefore, pitting
would only occur in aerated solution and then only on the basis of the pit repassivation criterion and not on the film breakdown criterion. Localised corrosion
would not occur at all in deaerated solution.
Tables F.3 to F.8 provide data with which to assess the susceptibility to localised
corrosion of Types 304/304L and 316/316L austenitic stainless steels. These tables are
not an exhaustive review of all of the data in the literature, but do provide a significant
database for assessing localised corrosion susceptibility. Tables F.3 and F.4 summarize
pitting and pit re-passivation potentials for Types 304/304L and 316/316L,
respectively. Corresponding data for the crevice and crevice re-passivation potentials
are given in Tables F.5 and F.6 for Types 304/304L and 316L, respectively. Finally,
12
Figure F.8: Comparison of the Pitting (EP) and Re-passivation (ERP) Potentials for
Type 316L Stainless Steel as a Function of Chloride Concentration at 95oC and the
Corresponding Values of the Corrosion Potential (ECORR) in Aerated and Deaerated
Solutions (Dunn et al. 1996).
Tables F.7 and F.8 list various measurements of the corrosion potential under various
environmental conditions for Types 304/304L and 316L, respectively. There are few
corresponding values for the other alloys in Table F.1.
There are two other commonly used methods for assessing the susceptibility to
localised corrosion of stainless steel. First, the effect of alloy composition on pitting (or
crevice corrosion) susceptibility can be compared based on the pitting resistance
equivalent number (PREN) approach. The PREN is given by
PREN = %Cr + a% Mo + b% N
(3)
where the values of a and b vary for pitting and crevice corrosion.
13
14
304
304
80
304
25
40
60
90
100
150
20
Temperature
(oC)
80
304
304
Type
Sensitized 304
345
Synthetic seawater
With additions of Na2S2O3
0 moldm-3
4 x 10-4moldm-3
1 x 10-3 moldm-3
2 x 10-3 moldm-3
4 x 10-3 moldm-3
0.01 moldm-3
0.1 moldm-3
0.4 moldm-3
1.0 moldm-3
With additions of Na2S2O3
0 moldm-3
1 x 10-4 moldm-3
4 x 10-4moldm-3
1 x 10-3 moldm-3
0.01 moldm-3
0.1 moldm-3
Other
17,000
34,500
34,500
[Cl-]
(
gg-1)
19,000
(EP)
-65*
-65
-255
-265
-260
-190
+415 (EP)
+320
+155
+65
-55 (EP)
-240
(EP)
+30*
-20
+40
-130
-205
-195
-135
-95
-65
EP or ERP
(mVSCE)
+50 (EP)
Reference
304
30
304L
18,400
142,000
660
30
304
34,500
Range 10020,000
[Cl-]
(
gg-1)
3,450
Ambient
Temperature
(oC)
20
40
60
80
304
304
304
Type
pH 3
pH 4
pH 5
pH 6
pH 7
pH 8
pH 9
pH 10
pH 11
pH 12
pH 9.3
Other
-70 (EP)
(EP)
+390
+190
+210
-51 (EP)
-216 (ERP)
-5 (EP)
+10
+15
+25
+40
+50
+60
+70
+80
+400
+232 (EP)
EP or ERP
(mVSCE)
EP = 750 152 log [Cl-]
EP = 628 140 log [Cl-]
EP = 554 144 log [Cl-]
EP = 500 145 log [Cl-]
Table F.3: Literature Data on Pitting of Type 304/304L Stainless Steels (Continued).
15
Szklarska-Smialowska 2005
(Fig 18.4)
Sedriks 1996 (Table 4.3)
Szklarska-Smialowska 2005
(Fig 12.6)
Reference
25
30
25
20
20
0
30
60
90
304
304
304
304
304
304
16
Temperature
(oC)
Type
3,450
18,400
17,000
345
3,450
34,500
345
3,450
34,500
34,500
[Cl-]
(
gg-1)
pH 5
Other
EP or ERP
(mVSCE)
-50 (EP)
-20
+50
+65
+60 (EP)
+200 (EP)
+565 (EP)
+460
+315
+495 (EP)
+385
+220
+360 (EP)
+190
+60
-20
Table F.3: Literature Data on Pitting of Type 304/304L Stainless Steels (Concluded).
Reference
316L
80
316L
18
30
40
50
60
20
Temperature
(oC)
80
316L
316L
Type
19,000
34,500
34,500
[Cl-]
(
gg-1)
19,000
Synthetic seawater
With additions of Na2S2O3
0 moldm-3
1 x 10-4moldm-3
2 x 10-3 moldm-3
4 x 10-3 moldm-3
0.01 moldm-3
0.04 moldm-3
0.1 moldm-3
0.4 moldm-3
1.0 moldm-3
With additions of Na2S2O3
0 moldm-3
1 x 10-4moldm-3
2 x 10-3 moldm-3
4 x 10-3 moldm-3
0.01 moldm-3
0.04 moldm-3
0.1 moldm-3
Seawater
ECORR = -155 mVSCE (8 mm crevice corrosion)
ECORR = -346 mVSCE (25-30 mm CC)
ECORR = -393 mVSCE (25-30 mm CC)
ECORR = -365 mVSCE (10 mm CC, 0.025 mm pit)
ECORR = -362 mVSCE (40 mm CC, 0.021 mm pit)
Other
(EP)
+55*
+55
+85
0
-135
-115
-100
(EP/ERP)
+505/+2
+274/-166
+156/-274
+155/-215
+28/-142
(EP)
+180*
+110
+125
+125
+140
-50
-25
+5
+50
EP or ERP
(mVSCE)
+150 (EP)
17
Szklarska-Smialowska 2005
(Table 13.2)
Szklarska-Smialowska 2005
(Fig 7.15)
Szklarska-Smialowska 2005
(Fig 7.15)
Reference
316L
80
30
316L
316
18
80
316L
316
30
316L
Temperature
(oC)
40
50
60
70
316
316
Type
35
345
3450
35
345
3450
34,500
18,400
18,400
142,000
21, 500
[Cl-]
(
gg-1)
17,000
31,000
Effect of temperature
pH 3
pH 4
pH 5
pH 6
pH 7
pH 8
pH 9
pH 10
pH 11
pH 12
pH 9.3
Other
EP or ERP
(mVSCE)
+140 (EP)
+210-245 (EP)
+275 (EP)
+220
+135
+70
-48 (EP)
-237 (ERP)
+285 (EP)
+285
+285
+285
+285
+290
+305
+350
+460
+585
+115 (EP)
-5
-105
+45 (EP)
-180
-215
-275
+230 (EP)
Table F.4: Literature Data on Pitting of Type 316/316L Stainless Steels (Continued).
Reference
Temperature
(oC)
20
20
20
Type
316
316
316
[Cl-]
(
gg-1)
345
3,450
10,300
34,450
3,450
34,450
345
3450
34,500
Mean values, dEP/dlog[Cl-] = 220 mV
220 grit
Other
EP or ERP
(mVSCE)
+317 (EP)
+205
+170
+98
+630 (EP)
+415
+750 (EP)
+500
+335
Reference
Table F.4: Literature Data on Pitting of Type 316/316L Stainless Steels (Concluded).
19
20
304
304L
304
Type
10
20
30
40
50
60
70
80
80
Temperature (oC)
19,000
19,000
[Cl-]
(
gg-1)
17,000
34,500
Synthetic seawater
Seawater, pH 8.2
Other
ECREV or ERCREV
(mVSCE)
+131 (ECREV)
+10
-120 (ERCREV)
-140
-150
-155
-175
-175
-200
-210
-10 (ECREV)
Reference
Table F.5: Literature Data on Crevice Corrosion of Type 304/304L Stainless Steels.
23-50
80
316L
Temperature
(oC)
10
20
30
40
50
60
70
80
316L
316L
Type
Synthetic seawater
6,00024,000
19,000
Seawater, pH 8.2
Other
19,000
[Cl-]
gg-1)
(
ECREV or ERCREV
(mVSCE)
-80 (ERCREV)
-95
-110
-120
-140
-155
-155
-165
ERCREV = -301.5 3.7([Cl-]-15) 15.3([SO42-]-2.1)
188.7([S2O32-]-0.4) 2(T-36.5)
0.047(([Cl-]-15)([SO42-]-2.1)
+ 3.83([Cl-]-15)([S2O32-]-0.4)
0.75([Cl-]-15)(T-36.5) + 0.35([Cl-]-15)2
T in oC, concentrations in g/L
+80 (ECREV)
Table F.6: Literature Data on Crevice Corrosion of Type 316L Stainless Steel.
Reference
21
22
3,450
4.5
142,000
17,300
304
9.3
5
304L
304
19,000
[Cl-]
(
gg-1)
34,500
8.2
304L
Temperature
(oC)
24
30
50
60
70
80
30
25
304
pH
Grade
Aerated
Aerated
Deaerated
Deaerated
Aerated
Redox
conditions
Seawater
Other
-14
-63
ECORR
(mVSCE)
-90
-90
-120
-140
-155
-210
-488
-464
Table F.7: Literature Data on Corrosion Potential of Type 304/304L Stainless Steels.
Reference
8.2
316L
316L
316L
316L
316L
316L
10
12.6
13.6
12.6
9.3
7
10
12
316L
316L
pH
Grade
95
22
22
95
24
30
50
60
70
80
Temperature
(oC)
30
19,000
1,000
200,000
177,000
6-1,000
19,000
[Cl-]
(
gg-1)
142,000
0.45 gg-1 O2
2.6 gg-1 O2
7.6 gg-1 O2
34.7 gg-1 O2
Aerated
Aerated
Aerated
Deaerated
Aerated
0.32 gg-1 O2
Deaerated
Redox conditions
10-1,000 gg-1
NO3-, 2 gg-1 F-,
20-1,000 gg-1 SO42-
Seawater
0.5 m Na2SO4
Other
+70
-80
-125
-100
-125
-330
-86
-44
-18
+47
-739 to -454
-685
-117
-119
-145
-80
-85
-105
-120
-140
-165
ECORR (mVSCE)
Table F.8: Literature Data on Corrosion Potential of Type 316L Stainless Steel.
23
Reference
The correlation between the PREN and the pitting potential for various austenitic,
duplex, and superaustenitic stainless steels is shown in Figure F.9.
Of the alloys
considered for use as ILW or HLW/SF (Table F.1), the duplex alloy 2205 provides the
higher pitting resistance (or, at least, most-positive EP value), followed by the
superaustenitic Type 904L, and the austenitic 316L and 304L alloys.
Another method for characterizing the resistance to localised corrosion is the critical
pitting (CPT) and critical crevice (CCT) temperature. These critical temperatures are
determined in an aggressive solution using exposed and creviced samples. The actual
CPT and CCT values depend on the nature of the environment, but are typically
measured in acidified ferric solutions. Figure F.10 shows the Cl- concentration
dependence of the CPT and CCT for a number of austenitic, duplex, and
superaustenitic stainless steels and indicates the same order of corrosion resistance as
the PREN data in Figure F.9.
24
Figure F.10: Corrosion map illustrating critical pitting and crevice corrosion
temperatures as a function of chloride concentration for various austenitic, duplex,
and super-austenitic stainless steels (ASM 2005). Critical conditions for pitting and
crevice corrosion indicated by solid and dashed lines, respectively.
F.3.3
25
Figure F.11: Ranges of pH, Chloride Concentration and Temperature for the Pitting
and SCC of 304 Stainless Steel (Jones 1992).
The microstructure and elemental composition also affect the susceptibility to SCC.
The -ferrite microstructure of ferritic stainless steels is inherently less susceptible to
cracking than the austenite structure; a difference which is responsible for the
precipitous increase in the time-to-failure at low Ni contents shown in Figure F.13.
Ferritic steels, however, are not immune to immune to SCC (Sedriks 1992). Figure F.14
also shows the effect of Ni content on the SCC susceptibility (in this case based on the
threshold stress intensity factor for cracking1), with the susceptibility of specific alloys
indicated.
This figure clearly shows the superior SCC resistance of both the
The threshold stress intensity factor KISCC is the value of KI, the linear-elastic fracture
mechanics stress intensity factor, below which SCC crack growth is not observed.
26
Figure F.12: Corrosion map for the susceptibility of various austenitic and duplex
stainless steels to stress corrosion cracking in aerated chloride environments as a
function of temperature (Sedriks 1996).
resistance of alloys such as Type 904L results in part from the increased resistance to
pitting which acts as a necessary precursor for crack initiation.
Both austenitic and duplex stainless steels are susceptible to SCC in sulphide- and
thiosulphate-containing environments. The severity of cracking of Types 304L and
316L have been shown to increase with decreasing pH and with increasing
thiosulphate and/or chloride concentrations (Smart 2000).
27
28
Figure F.14: Effect of Ni content on the threshold stress intensity factor for SCC for a
range of Fe-Cr-Ni alloys (after Sedriks 1992).
F.3.4
29
Figure F.14: Dependence of the threshold stress intensity factor for SCC on the Mo
content of Fe-Cr-Ni-Mo alloys in aerated 22% NaCl solution at 105oC (after Sedriks
1992).
When intimately exposed to active microbial communities and biofilms, stainless steels
are subject to various forms of MIC. In common with other materials, stainless steels
will undergo corrosion due to the formation of reduced S species (produced by the
action of sulphate-reducing bacteria) and organic acids (produced by a range of
bacteria and fungi) (Little et al. 1991). In addition to the common forms of MIC,
however, stainless steels are susceptible to other specific forms of attack, including:
30
ennoblement of ECORR.2
Various mechanisms have been proposed for the ennoblement of ECORR, including the
production of H2O2 within the biofilm and the catalysis of O2 reduction by MnO2.
Ennoblement could increase the probability of localised corrosion, especially if it is
accompanied by the formation of thiosulphate elsewhere in the biofilm.
Of crucial importance, however, is where and when microbial activity is possible in the
GDF (King 2009b). As described elsewhere in this report, if microbial activity is only
possible at locations away form the canister surface, for example, due to the use of
highly compacted bentonite or cementitious backfill, then the possible damage due to
MIC will be much reduced.
F.3.5
Galvanic corrosion
As with Ni alloys, stainless steels are relatively noble in their passive state. In any
galvanic couple with a more-active material, such as Fe, Mg, Al, Zn, stainless steel
would act as the cathode with the active material preferentially corroding. In contact
with other passive materials, the driving force for corrosion (i.e., the difference in
potential between the two passive materials) will be small and any effect minimal.
These
anthropogenic analogues provide support for values for the rate of the long-term
atmospheric corrosion of stainless steels.
As for other passive materials, the evolution of redox conditions in the GDF will affect
both the rates of general and localised corrosion. Although the evidence from the rates
summarised in Table F.2 is sparse, general corrosion rates in aerated environments are
typically higher than those under deaerated conditions.
More importantly, the evolution of redox conditions will affect the probability of
localised corrosion and SCC of stainless steels.
Section F.3.2 that pitting and crevice corrosion are primarily of concern under aerobic
conditions when ECORR is most likely to exceed the film breakdown or re-passivation
potentials. Indeed, the evidence from Figure F.8 indicates that pitting of Type 316L
stainless steel will not occur in Cl- solutions at 95oC under anaerobic conditions.
However, as indicated in Figure F.5, the presence of thiosulphate shifts EP to morenegative values, making pitting more likely even as the redox conditions in the GDF
shift from aerobic to anaerobic.
The probability of SCC is also linked to the evolution of redox conditions. Stress
corrosion is closely linked to conditions under which pitting occurs, so the probability
of cracking can similarly be expected to diminish as redox conditions become
anaerobic.
F.4.2
Effect of chloride
Of the groundwater and/or porewater species that may be present in the GDF,
chloride ions are the species most likely to affect the corrosion of the canister. Chloride
ions affect the stability of the passive film. Even in the absence of localised film
breakdown, Cl- ions degrade the stability of the passive film through an increase in the
solubility of Cr(III) (Pourbaix 1974), resulting in higher rates of general corrosion in
saline solutions (Table F.2).
As discussed in detail above, however, the most significant effect of Cl- is the impact on
the localised corrosion and SCC behaviour of the canister. Increasing Cl- concentration
shifts the pitting and crevice potentials to more negative values (Figures F.2, F.5, F.7,
F.8, F.10, and F.11). Increasing Cl- concentration also increases the probability of SCC
(Figures F.11 and F.12).
32
F.4.3
Effect of temperature
Increasing temperature affects the rate of general corrosion and the probability of both
localised corrosion and SCC. Increasing temperature typically results in higher rates of
general corrosion (Table F.2), although not all of the studies in which the effect of
temperature has been studied show a consistent trend with temperature. However, the
data of Blackwood et al. (2002) in alkaline solution do exhibit a monotonic increase
with temperature and suggest an activation energy of 47 kJ/mol.
Increasing temperature shifts the pitting potential to more-negative values (Figures F.2
and F.3). Based on the data in Tables F.3 and F.4, the decrease in EP/ERP is of the order
of -3.4 to -7.0 mV/oC for Types 304 and 316L, although there is evidence that ERP for
Type 316L reaches a minimum value at ~40oC and then shifts to more-positive values
with increasing temperature.
pitting characteristics of Type 316L is also evident in Figure F.3, where the decrease in
EP with increasing temperature appears to level off at temperatures above 70oC. This
improved film stability at higher temperatures could be due to the presence of Mo in
the passive film and its inherent greater thermal stability. Based on a single report, the
temperature dependence of the crevice re-passivation for Types 304L and 316L is
somewhat smaller, decreasing by about -1.2 mV/oC (Tables F.5 and F.6).
The influence of temperature on the localised corrosion behaviour is only partly
described by the temperature dependence of EP/ERP and ECREV/ERCREV.
It is also
necessary to take into account the temperature dependence of ECORR, since it is the
difference between the critical potential and ECORR that determines the probability of
localised corrosion. The corrosion potential also shifts in the active direction with
increasing temperature, but at a slower rate. Again based on a single study, the
temperature dependence of ECORR for Types 304L and 316L stainless steel in aerated
solution containing 19,000 mg/L Cl- is -2.0 mV/oC and -1.5 mv/oC, respectively
(Tables F.7 and F.8). The fact that the critical potential decreases more rapidly with
increasing temperature than the value of ECORR indicates that localised corrosion
becomes more likely with increasing temperature and is one explanation for the
observation for the critical pitting and crevice corrosion temperatures discussed earlier.
F.4.4
Effect of pH
general corrosion are typically of the order of 0.01 m/y, whereas rates are generally 12 orders of magnitude higher at near-neutral pH.
33
Pitting is more likely to occur at lower pH (Figure F.11), which is partly explained by
the effect of pH on ECORR (which will shift to more-positive values with decreasing pH)
and partly by the effect of pH on the critical potential for localised corrosion
(Figure F.4). As noted earlier, there is evidence for a threshold pH above which EP
shifts to significantly higher values. This threshold pH is a function of the alloy, with
values of pH 10, 11, and 11.5 for Types 316, 430, and 304, respectively. The resistance
of stainless steels to localised corrosion in alkaline solutions typical of the pore water in
cement grout is confirmed by tests performed in the Nirex/NDA program. Smart
(2002) reports no pitting of 304, 304L, 316, or 316L austenitic stainless steels in cements
containing up to 10 wt.% Cl-.
The solution pH also clearly affects the probability of SCC (Figure F.11).
environmental conditions necessary for cracking shift to higher
Cl-
The
concentrations
and/or higher temperature as the pH increases. The susceptibility of 304L and 316L
austenitic stainless steels to SCC has been determined in simulated cementitious
environments containing chloride and/or thiosulphate ions for the Nirex/NDA
program (Smart 2002). The severity of cracking increased with decreasing pH and
with increasing thiosulphate and/or chloride concentrations.
The beneficial effect of increasing pH can be expressed as a [OH-]:[Cl-] ratio, above
which the probability of localised corrosion or SCC is significantly diminished. Based
on the apparent threshold pH values for EP in Figure F.4, this "threshold" [OH-]:[Cl-]
would corresponds to 2 x 10-4 for Type 316, 2 x 10-3 for Type 430, and 6 x 10-3 for
Type 304.
unlikely. These values are consistent with the absence of pitting reported by Smart
(2002) for 304, 304L, 316, or 316L austenitic stainless steels in cements containing up to
10 wt.% Cl-, for which the [OH-]:[Cl-] would have been in the range 4 x 10-3 to 4 x 10-2
for an assumed pH range of pH 12-13.
F.4.5
Sulphur species have both beneficial and detrimental effects on the corrosion
behaviour of stainless steels, depending upon the oxidation state of sulphur. In the
fully oxidised +6 state, sulphate inhibits the crevice corrosion of Type 304 and 316 in
Cl- solutions (Figure F.6). A [SO42-]:[Cl-] molar ratio of 1.2 and 0.4 is sufficient to inhibit
the crevice corrosion of Types 304 and 316, respectively.
In the +4 oxidation state, thiosulphate ions increase the susceptibility to both pitting
and crevice corrosion (Figure F.5, Tables F.3, F.4, and F.6) and to SCC (Smart 2002).
Indeed, the concern over the increased susceptibility to cracking and localised
corrosion (Kursten and Druyts 2000, Kursten et al. 2004) lead to the change in the
34
Belgian programme from stainless steel as the candidate canister (overpack) material to
a cementitious C-steel supercontainer design (Kursten and Druyts 2008).
Stainless steels are also susceptible to SCC and accelerated general corrosion in the
presence of sulphide (ASM 1987, 2005).
F.4.6
F.4.7
Shoesmith and King (1999) have reviewed the available information on the effects of
radiolysis on the corrosion of stainless steels. Among the observations reported are:
Results on crevice corrosion ( in 10 mg/L Cl-) are ambiguous. A dose rate of 2.8
Gy/hr may be sufficient to initiate crevice corrosion, but the availability of a
large cathode may be more important.
Marsh et al. (1986) studied the effect of gamma radiation on the potential and localised
corrosion behaviour of Type 304L stainless steel in aerated solutions containing
300 mg/L Cl-. At a dose rate of 2 x 103 Gy/hr, the value of ECORR increased by 200300 mV. Although this would suggest an increased probability of localised corrosion,
the oxidising radiolysis products responsible for the positive shift in ECORR also
35
inhibited film breakdown, although they had no effect on the re-passivation of existing
pits.
Overall, and in common with other materials (Shoesmith and King 1999), no
measurable effect of irradiation is observed on stainless steels at absorbed dose rates of
less than 1 Gy/hr.
F.4.8
Smart (2000) has reviewed the atmospheric behaviour of stainless steels waste
containers. Corrosion can occur when salt contaminants on the surface of the canister
absorb moisture (deliquesce) from the air forming small volumes of highly
concentrated solutions.
establishment of spatially separated anodic and cathodic processes and the initiation
and propagation of localised corrosion and SCC.
Recently, Tani et al. (2008) have compared the behaviour of austenitic and duplex
stainless steels exposed to humid atmospheres following contamination by salts
contained in seawater.
portlandite/CSH gels present in cement. Prediction of the lifetime of the canister then
becomes a matter of predicting the time evolution of the pH of the cement backfill.
The presence of sulphide minerals in the host rock or backfill materials thiosulphate formation during the aerobic phase could induce localised
corrosion or SCC.
Chloride ions - stainless steels are subject to localised corrosion and SCC in Cl
containing environments, especially at elevated temperature.
External load and residual stress - austenitic and duplex stainless steels are
susceptible to SCC in the presence of Cl- and a sufficient applied or residual
tensile stress. Ferritic alloys are less susceptible, but are not immune to Cl
induced SCC.
Many or all of these critical conditions could be obviated by the use of a cementitious
backfill. Stainless steels should provide adequate performance for the period that the
backfill pore-water pH is maintained at a value >pH 12.
37
38
transport
near-field mass
Gamma radiation
Temperature
Redox conditions
Host rock
Parameter
temperature. Localised corrosion and SCC can occur at temperatures at or slightly above
both aerobic and anaerobic conditions. However, the propensity for film breakdown and
The passive film on stainless steels provides good protection against general corrosion under
because of the possibility of thiosulphate formation during the aerobic phase. Thiosulphate
The presence of sulphide minerals in the host rock or backfill materials would be of concern
Comment
cementitious backfill
Requires
>1-10 Gy/h
cementitious backfill.
HLW/SF, the use of stainless steel canisters would not be recommended without the use of a
Given the ubiquitous nature of Cl- ions in groundwaters and the heat generation by the
There is no evidence for adverse effects of irradiation at does rates <1 Gy/h.
cementitious backfill) ambient, depending upon the aggressiveness of the environment and the alloy composition. In
the absence of a cementitious backfill, the threshold temperature for localised corrosion or SCC
None
minerals
Presence of sulphide
Critical condition
Table F.1: List of Critical Conditions for HLW/SF Canisters Manufactured from Stainless Steel
Dependent on nature
of backfill and alloy
None
external load
formed
Significant if biofilms
sulphide
uniform wetting of surface salt contaminants could lead to spatial separation of anodic and
Stainless steels exhibit good corrosion resistance under atmospheric conditions. The non-
sufficient applied or residual tensile stress. Ferritic alloys are less susceptible, but are not
Austenitic and duplex stainless steels are susceptible to SCC in the presence of Cl- and a
lead to ennoblement of ECORR and the possibility of localised corrosion and the possibility of
39
threat to the canister lifetime. However, surface microbial activity and biofilm formation could
As with other canister materials, microbial activity remote from the canister presents a minimal
materials or the host rock could induce localised corrosion and SCC of the canister. Sulphide
environments, but the use of stainless steel would not be recommended without a cementitious
The presence of Ca2+ and Mg2+ in the groundwater could lead to the generation of acidic
Stainless steels are subject to localised corrosion and SCC in Clcontaining environments,
especially at elevated temperature. Given the ubiquitous nature of Cl- ions in groundwaters
and the heat generation by the HLW/SF, the use of stainless steel canisters would not be
recommended without the use of a cementitious backfill.
Thiosulphate,
Microbial activity
Sulphur species
species
None
concentration
Dependent on nature
Chloride
Stainless steel canisters are only suitable for use with a cementitious backfill,
thus limiting the flexibility of the GDF design.
The need for an internal structural element, thus complicating the canister
design.
40
1987.
American
Commission of the
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44