QRS-1384J-1 v2.

1 Appendix F

Appendix F Corrosion of Stainless Steels

F.1 Introduction
Stainless steels are iron-based alloys that contain a minimum of 11-13 wt.% chromium
to provide corrosion resistance and to impart their "stainless" quality (Sedriks 1996).
At this minimum chromium content a stable Cr oxide/hydroxide a passive film forms
on the surface of the steel. The different classes of stainless steel take their name from
their predominant crystal structure (ASM 1987, 2005); namely: austenitic (face-centred
cubic (fcc)), ferritic (body-centred cubic (bcc)), martensitic (body-centred tetragonal or
bcc), or duplex alloys containing and approximately equal proportion of austenite and
ferrite. Stainless steels typically exhibit good resistance to general corrosion, although
the passive film can dissolve at low pH and/or high Cl- concentration. Localised
corrosion, such as pitting and crevice corrosion can occur in the presence of Cl- and
various S-containing species, but other anions such as carbonate, sulphate, and nitrate
are inhibitors. Some classes of stainless steel, particularly the austenitics, can be
susceptible to stress corrosion cracking (SCC) in the presence of Cl-.

The possible use of stainless steel as a canister material for the disposal of HLW or SF
has been investigated in a number of national programmes (Table F.1). Generally, the
focus has been on the austenitic alloys, particular the American Iron and Steel Institute
(AISI) 300-series, although NDA RWMD have recently reviewed the properties of
duplex alloys as part of the ILW Phased Geological Repository Concept programme
(King 2009a). A major study of the properties of stainless steels was carried out in the
Belgian programme in the 1990's. Various stainless alloys were considered for both
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 (Féron 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

1
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.

F.2 Stainless steels

Figure F.1 illustrates the compositional relationship between the main classes of
stainless steel (Sedriks 1996). Austenitic stainless steels contain varying quantities of
elements that stabilise the austenite phase, such as Ni, Co, C, N, Mn, and Cu. Other
elements, such as Cr, Si, Mo, V, Al, Nb, Ti, and W, stabilise δ-ferrite and form the basis
of the ferritic stainless steels.

Austenitic alloys represent the majority of the stainless steels that have been
considered for nuclear waste disposal canisters. Starting from the basic type 304
austenitic stainless steel, the addition of Mo to increase resistance to localised corrosion
produces type 316, with both available as low-C alloys (types 304L and 316L) to reduce
the possibility of sensitisation due to the precipitation of carbides (Cr23C6). An
alternative compositional strategy to prevent sensitisation is to add Ti (type 316Ti) to
precipitate C as a Ti carbide at a higher temperature than Cr23C6. Improved corrosion
resistance is offered by the so-called superaustenitic alloys (for example, types 904L
and 926, Table F.1), which contain increased Ni and Mo. High-temperature oxidation
resistance (and increased strength) is achieved by adding Cr and Ni to the basic type
304 formulation, as in types 309 and 309S. This improved high-temperature
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. The one ferritic alloy
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).

2
 QRS-1384J-1 v2.1 Appendix F

Table F.1: Compositions of Stainless Steels Considered for Use for the Disposal of ILW or HLW/SF1

UNS Number Common name Composition (wt.%)2 Other

Cr Ni C Mn Si P S

Austenitic alloys
S30400 304 18-20 8-10 0.08 2.0 1.0 0.045 0.030
S30403 304L 18-20 8-12 0.03 2.0 1.0 0.045 0.030
S30900 309 22-24 12-15 0.20 2.0 1.0 0.045 0.030
S30908 309S 22-24 12-15 0.08 2.0 1.0 0.045 0.030
S31600 316 16-18 10-14 0.08 2.0 1.0 0.045 0.030 Mo 2-3
S31603 316L 16-18 10-14 0.03 2.0 1.0 0.045 0.030 Mo 2-3
S31635 316Ti3 16.80 10.70 0.044 1.08 0.40 0.009 0.028 Mo 2.05, Ti 0.3
N08904 904L 19-23 23-28 0.02 2.0 1.0 0.045 0.035 Mo 4-5, Cu 1-2
N08926 9263 20.60 24.85 0.005 0.92 0.30 0.018 0.002 Mo 6.40, Cu 0.86, N 0.198

Ferritic alloys
S43000 430 16-18 - 0.12 1.0 1.0 0.040 0.030

Duplex alloys
S32304 SAF 2304 21.5-24.5 3-5.5 0.03 2.5 1.0 0.040 0.040 N 0.05-0.2, Mo 0.05-0.6
S31803 2205 21-23 4.5-6.5 0.03 2.0 1.0 0.030 0.020 N 0.08-0.2, Mo 2.5-3.5

1 After Sedriks (1996), except where noted

2 Maximum unless otherwise indicated, balance Fe.
3 Composition of alloy used by Druyts and Kursten (1999)

3
 Figure F.1: Compositional Relationship Between the Different Classes of Stainless
Steels (Sedriks 1996).

Although not formally considered as either a container material for HLW glass or as a
canister (or overpack) material for either HLW or SF, duplex stainless steels offer a
number of advantages over austenitic alloys (King 2009a). Duplex alloys contain
approximately equal proportions of austenite and δ-ferrite. As a consequence, the Ni
content (an austenite stabiliser) is lower and the Cr content (a ferrite stabiliser) is
higher than for the corresponding austenitic alloys. Table F.1 lists the composition of
two common duplex alloys, 2304 and 2205.

4
 QRS-1384J-1 v2.1 Appendix F

F.3 Corrosion modes for stainless steels

F.3.1 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 increases with increasing temperature

• the rate decreases with increasing pH, with corrosion rates generally
<0.1 µm/yr in alkaline pH representative of cement pore water

• the rate is higher in the presence of Cl-

• 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 µm/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

• the rate of atmospheric corrosion is generally low, with rates typically

<0.1 µm/yr at ambient temperature

5
 Table F.2: General Corrosion Rates of Types 304/304L and 316/316L Austenitic Stainless Steel in Alkaline and Near-neutral Solutions and
Under Atmospheric Conditions.

(a) Type 304/304L

Temperature [Cl-] Redox

Alloy pH Other Rate (µ
µm⋅⋅yr-1) Reference
(oC) (µ
µg⋅⋅g-1) conditions
12.8 200 days 0.0003
304 30, 45 Fujisawa et al. 1999
10.5 60 days 0.01
304 13.3 Ambient 18,400 Aerated 28 days 0.3 Mcdonald et al. 1995
30 0.06
304 13 50 Deaerated 0.18 Blackwood et al. 2002
80 0.82
10 0.009
Wada and Nishimura
304 12.5 50 Deaerated 230 days 0.0055
1999
13.5 0.0063
304 Ambient 90 7,000-43,000 Aerated 10 hrs 10-130 Morsy et al. 1979
304L Ambient 25-100 “Freshwater” Aerated 0.21 BSC 2004
27 11.4
304L Ambient “Saltwater” Aerated BSC 2004
90 5.82
25 0.2-0.96
Interstitial clay
304 Ambient 50 Aerated 0.22-0.23 Casteels et al. 1986
water
75 0.3-0.35
Urban, 5-15 yr <0.03
Urban, 5-15 yr 0.022 Johnson and Pavlik
304 - Ambient - Aerated
Marine, 5-15 yr 0.05-2 1982
Industrial/urban, 5-15 y 0.01
304 - Ambient - Aerated Industrial/urban 0.03-3 Kearns et al. 1984

6
 QRS-1384J-1 v2.1 Appendix F

(b) Type 316/316L

Temperature [Cl-] Redox Rate

Alloy pH Other Reference
(oC) (µ
µg⋅⋅g-1) conditions (µ
µm⋅⋅yr-1)
Mcdonald et al.
316 13.3 Ambient 18,400 Aerated 28 days 0.6
1995
316L >13 Ambient 10,000 Deaerated 0.1 MPa H2 0.03 Smart et al. 2004
8 yrs, Pacific Ocean Alexander et al.
316 Ambient Ambient 19,000 Aerated 4
seawater 1961
30 0.01
316L Ambient “Freshwater” Aerated BSC 2004
50-100 0.25
316L Ambient 27 “Saltwater” Aerated 1.94 BSC 2004
25 0.1-0.24
Interstitial clay Casteels et al.
316 Ambient 50 Aerated 0.1-0.34
water 1986
75 0.1-0.17
316 - Ambient - Aerated Various atmospheres 0.05 Dechema 1990

7
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
(Szklarska-Smialowska 2005). Chloride ions promote film breakdown, whereas other
species, such as OH-, CO32-, SO42-, and NO3- inhibit localised corrosion. Other species
result in pitting or crevice corrosion, most notably in the current context thiosulphate
(S2O32-) (Kursten and Druyts 2000), which can form from the oxidation of pyrite
minerals in the host rock or bentonite-based sealing materials.

In a given environment, localised corrosion occurs at a characteristic electrochemical

potential (E). The characteristic potential can either be based on the value at which
film breakdown occurs (EP or ECREV for pitting and crevice corrosion, respectively) or
that at which a propagating pit or crevice re-passivates (ERP or ERCREV, respectively).
The criterion for pitting or crevice corrosion is that the corrosion potential (ECORR)
exceeds either the film breakdown or re-passivation potentials, i.e.,

ECORR > EP, ECREV (1)

or

ECORR > ERP, ERCREV (2)

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.

8
 QRS-1384J-1 v2.1 Appendix F

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. Kursten and Druyts (2000) also reported increased
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 200-
400 mV difference in EP. Interestingly, Kursten and Druyts (2000) noted that S2O32-
affected 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.

9
 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
 QRS-1384J-1 v2.1 Appendix F

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 Cl-
concentrations 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 re-
passivation 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
 QRS-1384J-1 v2.1 Appendix F

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
 Table F.3: Literature Data on Pitting of Type 304/304L Stainless Steels.

Temperature [Cl-] EP or ERP

Type Other Reference
(oC) (µ
µg⋅⋅g-1) (mVSCE)
304 80 19,000 Synthetic seawater +50 (EP) Haruki et al. 1991
With additions of Na2S2O3 (EP)
0 mol⋅dm-3 +30*
4 x 10-4mol⋅dm-3 -20
1 x 10-3 mol⋅dm-3 +40
2 x 10-3 mol⋅dm-3 -130
304 20 34,500 Szklarska-Smialowska 2005 (Fig 7.15)
4 x 10-3 mol⋅dm-3 -205
0.01 mol⋅dm-3 -195
0.1 mol⋅dm-3 -135
0.4 mol⋅dm-3 -95
1.0 mol⋅dm-3 -65
With additions of Na2S2O3 (EP)
0 mol⋅dm-3 -65*
1 x 10-4 mol⋅dm-3 -65
304 80 34,500 4 x 10-4mol⋅dm-3 -255 Szklarska-Smialowska 2005 (Fig 7.15)
1 x 10-3 mol⋅dm-3 -265
0.01 mol⋅dm-3 -260
0.1 mol⋅dm-3 -190
25 +415 (EP)
40 +320
304 17,000 With addition of 0.1 mol⋅dm-3 NaHCO3, pH 8 Szklarska-Smialowska 2005 (Fig 12.2)
60 +155
90 +65
100 -55 (EP)
304 345 Sensitized 304 Szklarska-Smialowska 2005 (Fig 12.5)
150 -240

14
 QRS-1384J-1 v2.1 Appendix F

Table F.3: Literature Data on Pitting of Type 304/304L Stainless Steels (Continued).

Temperature [Cl-] EP or ERP

Type Other Reference
(oC) (µ
µg⋅⋅g-1) (mVSCE)
20 EP = 750 – 152 log [Cl-]
40 Range 100- EP = 628 – 140 log [Cl-] Szklarska-Smialowska 2005
304
60 20,000 EP = 554 – 144 log [Cl-] (Fig 12.6)
80 EP = 500 – 145 log [Cl-]
Szklarska-Smialowska 2005
304 Ambient 34,500 +232 (EP)
(Fig 18.4)
304 3,450 With addition of 0.1 mol⋅dm-3 NaHCO3 -70 (EP) Sedriks 1996 (Table 4.3)
+50 µg⋅g-1 SO42-, 2 µg⋅g-1 Cu2+ (EP)
Base metal +390
304 30 660 Sedriks 1996 (Table 4.10)
Weld HAZ +190
60% cold work +210
-51 (EP)
304L 30 142,000 pH 9.3 Sridhar et al. 1993
-216 (ERP)
pH 3 -5 (EP)
pH 4 +10
pH 5 +15
pH 6 +25
pH 7 +40
304 18,400 Sedriks 1996 (Fig. 4.38)
pH 8 +50
pH 9 +60
pH 10 +70
pH 11 +80
pH 12 +400

15
 Table F.3: Literature Data on Pitting of Type 304/304L Stainless Steels (Concluded).

Temperature [Cl-] EP or ERP

Type Other Reference
(oC) (µ
µg⋅⋅g-1) (mVSCE)
H2 atmosphere 0.076 µg⋅g-1 O2 -50 (EP)
N2 atmosphere 0.460 µg⋅g-1 O2 -20
304 25 34,500 Sedriks 1996 (Table 4.16)
Ar atmosphere 0.057 µg⋅g-1 O2 +50
O2 atmosphere 30.1 µg⋅g-1 O2 +65
304 30 18,400 +60 (EP) Sedriks 1996 (Fig. 4.42)
304 25 17,000 pH 5 +200 (EP) Sedriks 1996 (Table 4.15)
345 +565 (EP)
Mean values, dEP/dlog[Cl-] = 127 mV
304 20 3,450 +460 Laycock et al. 2005
1000 grit
34,500 +315
345 +495 (EP)
Mean values, dEP/dlog[Cl-] = 137 mV
304 20 3,450 +385 Laycock et al. 2005
220 grit
34,500 +220
0 +360 (EP)
30 +190
304 3,450 Park et al. 2002
60 +60
90 -20

16
 QRS-1384J-1 v2.1 Appendix F

Table F.4: Literature Data on Pitting of Type 316/316L Stainless Steels.

Temperature [Cl-] EP or ERP

Type Other Reference
(oC) (µ
µg⋅⋅g-1) (mVSCE)
316L 80 19,000 Synthetic seawater +150 (EP) Haruki et al. 1991
With additions of Na2S2O3 (EP)
0 mol⋅dm-3 +180*
1 x 10-4mol⋅dm-3 +110
2 x 10-3 mol⋅dm-3 +125
4 x 10-3 mol⋅dm-3 +125 Szklarska-Smialowska 2005
316L 20 34,500
0.01 mol⋅dm-3 +140 (Fig 7.15)
0.04 mol⋅dm-3 -50
0.1 mol⋅dm-3 -25
0.4 mol⋅dm-3 +5
1.0 mol⋅dm-3 +50
With additions of Na2S2O3 (EP)
0 mol⋅dm-3 +55*
1 x 10-4mol⋅dm-3 +55
2 x 10-3 mol⋅dm-3 +85 Szklarska-Smialowska 2005
316L 80 34,500
4 x 10-3 mol⋅dm-3 0 (Fig 7.15)
0.01 mol⋅dm-3 -135
0.04 mol⋅dm-3 -115
0.1 mol⋅dm-3 -100
Seawater (EP/ERP)
18 ECORR = -155 mVSCE (8 mm crevice corrosion) +505/+2
30 ECORR = -346 mVSCE (25-30 mm CC) +274/-166 Szklarska-Smialowska 2005
316L 19,000
40 ECORR = -393 mVSCE (25-30 mm CC) +156/-274 (Table 13.2)
50 ECORR = -365 mVSCE (10 mm CC, 0.025 mm pit) +155/-215
60 ECORR = -362 mVSCE (40 mm CC, 0.021 mm pit) +28/-142

17
 Table F.4: Literature Data on Pitting of Type 316/316L Stainless Steels (Continued).

Temperature [Cl-] EP or ERP

Type Other Reference
(oC) (µ
µg⋅⋅g-1) (mVSCE)
316 17,000 With addition of 0.1 mol⋅dm-3 NaHCO3 +140 (EP) Sedriks 1996 (Table 4.3)
316 31,000 Oxygenated solution, 0.4-2 wt.% Mn +210-245 (EP) Sedriks 1996 (Table 4.27)
40 +275 (EP)
50 +220
316L 21, 500 Sedriks 1996 (Fig. 4.36)
60 +135
70 +70
-48 (EP)
316L 30 142,000 pH 9.3 Sridhar et al. 1993
-237 (ERP)
pH 3 +285 (EP)
pH 4 +285
pH 5 +285
pH 6 +285
pH 7 +285
316 18,400 Sedriks 1996 (Fig. 4.38)
pH 8 +290
pH 9 +305
pH 10 +350
pH 11 +460
pH 12 +585
35 +115 (EP)
316L 80 345 NaCl solutions only -5 Sedriks 1996 (Fig. 4.41)
3450 -105
35 +45 (EP)
345 -180
316L 80 Cl-/S2O32- mixtures, [Cl-]:[S2O32-] = 17 Sedriks 1996 (Fig. 4.41)
3450 -215
34,500 -275
316 30 18,400 Effect of temperature +230 (EP) Sedriks 1996 (Fig. 4.42)

18
 QRS-1384J-1 v2.1 Appendix F

Table F.4: Literature Data on Pitting of Type 316/316L Stainless Steels (Concluded).

Temperature [Cl-] EP or ERP

Type Other Reference
(oC) (µ
µg⋅⋅g-1) (mVSCE)
345 +317 (EP)
3,450 +205
316 20 120 grit finish, aerated solution Laycock and Newman 1997
10,300 +170
34,450 +98
3,450 Mean values, dEP/dlog[Cl-] = 206 mV +630 (EP)
316 20 Laycock et al. 2005
34,450 1000 grit +415
345 +750 (EP)
Mean values, dEP/dlog[Cl-] = 220 mV
316 20 3450 +500 Laycock et al. 2005
220 grit
34,500 +335

19
 Table F.5: Literature Data on Crevice Corrosion of Type 304/304L Stainless Steels.

[Cl-] ECREV or ERCREV

Type Temperature (oC) Other Reference
(µ
µg⋅⋅g-1) (mVSCE)
17,000 +131 (ECREV)
304 Szklarska-Smialowska 2005 (Fig 18.4)
34,500 +10
10 -120 (ERCREV)
20 -140
30 -150
40 -155
304L 19,000 Seawater, pH 8.2 Tani et al. 2008
50 -175
60 -175
70 -200
80 -210
304 80 19,000 Synthetic seawater -10 (ECREV) Haruki et al. 1991

20
 QRS-1384J-1 v2.1 Appendix F

Table F.6: Literature Data on Crevice Corrosion of Type 316L Stainless Steel.

Temperature [Cl-] ECREV or ERCREV

Type Other Reference
(oC) µg⋅⋅g-1)
(µ (mVSCE)
10 -80 (ERCREV)
20 -95
30 -110
40 -120
316L 19,000 Seawater, pH 8.2 Tani et al. 2008
50 -140
60 -155
70 -155
80 -165
ERCREV = -301.5 – 3.7([Cl-]-15) – 15.3([SO42-]-2.1)
–188.7([S2O32-]-0.4) – 2(T-36.5)
6,000- 0-800 µg⋅g-1 S2O32-, –0.047(([Cl-]-15)([SO42-]-2.1)
316L 23-50 Sridhar et al. 2004
24,000 800-3,400 µg⋅g-1 SO42- + 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
316L 80 19,000 Synthetic seawater +80 (ECREV) Haruki et al. 1991

21
 Table F.7: Literature Data on Corrosion Potential of Type 304/304L Stainless Steels.

Temperature [Cl-] Redox ECORR

Grade pH Other Reference
(oC) (µ
µg⋅⋅g-1) conditions (mVSCE)
24 -90
30 -90
50 -120
304L 8.2 19,000 Aerated Seawater Tani et al. 2008
60 -140
70 -155
80 -210
304L 9.3 30 142,000 Deaerated -488 Sridhar et al. 1993
304 5 25 17,300 Deaerated -464 Sedriks 1996 (Table 4.15)
Szklarska-Smialowska 2005
304 34,500 Aerated -63
(Fig 18.4)
304 4.5 3,450 Aerated -14 Sridhar et al. 2004

22
 QRS-1384J-1 v2.1 Appendix F

Table F.8: Literature Data on Corrosion Potential of Type 316L Stainless Steel.

Temperature [Cl-]
Grade pH Redox conditions Other ECORR (mVSCE) Reference
(oC) (µ
µg⋅⋅g-1)
316L 9.3 30 142,000 Deaerated -685 Sridhar et al. 1993
7 -117
316L 10 0.32 µg⋅g-1 O2 0.5 m Na2SO4 -119 Sridhar et al. 2004
12 -145
24 -80
30 -85
50 -105
316L 8.2 19,000 Aerated Seawater Tani et al. 2008
60 -120
70 -140
80 -165
10-1,000 µg⋅g-1
316L 95 6-1,000 Deaerated NO3-, 2 µg⋅g-1 F-, -739 to -454 Sridhar et al. 1993
20-1,000 µg⋅g-1 SO42-
10 +70
316L 12.6 22 177,000 Aerated -80 Cui and Sagues 2003
13.6 -125
316L 12.6 22 Aerated -100 Cui and Sagues 2003
1,000 -125
316L 95 Aerated Dunn et al. 1996
200,000 -330
0.45 µg⋅g-1 O2 -86
2.6 µg⋅g-1 O2 -44
316L 19,000 Sridhar et al. 2004
7.6 µg⋅g-1 O2 -18
34.7 µg⋅g-1 O2 +47

23
 Figure F. 9: Correlation between the pitting resistance equivalent number and
pitting potential for various austenitic, duplex, and superaustenitic stainless steels
(Malik et al. 1996).

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
 QRS-1384J-1 v2.1 Appendix F

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 Environmentally assisted cracking

Stainless steels exhibit different susceptibilities to environmentally assisted cracking

(EAC). By far the most common form of EAC for stainless steels is the Cl- stress
corrosion cracking (SCC) of austenitic alloys. Cracks often initiate from pits and, for
this reason, the SCC susceptibility is related to the pitting susceptibility (Figure F.11).
The susceptibility to SCC (and pitting) clearly increases with increasing temperature
and Cl- concentration and decreasing pH.

There is evidence for a threshold temperature and, possibly, Cl- concentration below
which SCC does not occur. Based on the data in Figure F.12, the threshold temperature
for SCC is of the order of 60oC and the threshold Cl- concentration is somewhat less
than 1 mg/L. Although useful as a general guide, care should be taken in the use of
such "thresholds" since they are based on industrial timescales, rather than the
extended timescales of interest for ILW/HLW/SF disposal. This caution is especially
so for any threshold Cl- concentration since evaporation will concentrate surface liquid
films.

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 δ-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
superaustenitic Type 904L and the ferritic Type 444 alloy.

1 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
 QRS-1384J-1 v2.1 Appendix F

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).

The Mo content also affects SCC susceptibility (Figure F.15). The increased SCC
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
 Figure F.13: Effect of Ni content on the susceptibility of 18-20 wt.% Cr stainless
steels in boiling magnesium chloride solution at 154oC (after Sedriks 1992).

28
 QRS-1384J-1 v2.1 Appendix F

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 Microbiologically influenced corrosion

Like most engineering materials, stainless steels are susceptible to microbiologically

influenced corrosion (MIC) (Little et al. 1991). Apart from the inherent susceptibility of
the material(s), any assessment of the potential for MIC of stainless steel HLW/SF
canisters also needs to take into account the effect of the GDF environment on the
location and duration of microbial activity (King 2009b).

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
 QRS-1384J-1 v2.1 Appendix F

• localised corrosion due to the formation of thiosulphate (discussed above),

• preferential attack of welds, and

• 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.

F.3.6 Anthropogenic Analogues

Stainless steels have a history of less than one hundred years. Therefore, there is
relatively little experience with these alloys compared to materials such as copper and
C-steel. Smart and Wood (2004) have reviewed a number of case histories from the
architecture, transportation, and infrastructure industries demonstrating good
corrosion resistance to atmospheric conditions and immersion in seawater for periods
exceeding 60 years. King (2009a) has reviewed a number of cases of the use of duplex
stainless steels for architectural purposes and bridge construction. These
anthropogenic analogues provide support for values for the rate of the long-term
atmospheric corrosion of stainless steels.

2 The shift in ECORR to more-positive values.

31
F.4 Corrosion behaviour of stainless steels

F.4.1 Effect of redox conditions

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. It is clear from the discussion in
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 more-
negative 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
 QRS-1384J-1 v2.1 Appendix F

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. This change in the temperature dependence of the
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

Increasing pH promotes passivation and counteracts the effects of aggressive anions,

such as Cl-. The beneficial effects of increasing pH on the rate of general corrosion is
evident from the data in Table F.2. Under alkaline conditions (pH > 10), rates of
general corrosion are typically of the order of 0.01 µm/y, whereas rates are generally 1-
2 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). The
environmental conditions necessary for cracking shift to higher Cl- 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. Provided the [OH-]:[Cl-] is above this value then localised corrosion is
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 Effect of sulphur species

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
 QRS-1384J-1 v2.1 Appendix F

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 Effect of other anions and cations

In addition to the inhibitive effect of sulphate on the localised corrosion of stainless

steels in Cl- solutions, certain other anions, such as carbonate and nitrate, also act as
inhibitors (Szklarska-Smialowska 2005). Nitrate, in particular, is an effective inhibitor,
possibly due to the consumption of protons in the reduction of NO3- to either NH3 or
N2, thus raising the pit or crevice pH. Carbonate would be expected to have a similar
effect on the pH of the occluded chemistry.

Conversely, cations that can be hydrolysed to form acidic solutions (e.g., Mg2+, Ca2+)
would be expected to have an adverse impact on the localised corrosion susceptibility.
These latter species are of particular concern if present as precipitated salts on the
canister surface, since they deliquesce at low relative humidities (see Section F.4.8).

F.4.7 Effect of gamma radiation

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:

• The corrosion potential in 0.018 mol⋅dm-3 NaCl increased substantially when a

radiation field (104 Gy/hr) was introduced, but no increase in general corrosion
rate or initiation of pitting was observed.

• Radiation appears to inhibit pitting, probably due to defect annealing in the

passive oxide film.

• 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.

• Crevice propagation can be maintained at 103 Gy/hr, but not at 10 Gy/hr.

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 200-
300 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 Effect of unsaturated conditions and atmospheric

exposure

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. These conditions present an ideal opportunity for the
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. Surface corrosion took the form of pitting at isolated salt
crystals formed by the evaporation of seawater and which subsequently deliquesced
when exposed to a humid atmosphere. These pits could serve as locations for the
initiation of SCC, an area of active research by NDA RWMD (A.J. Cook and S.B. Lyon,
unpublished work).

F.5 Lifetime predictions

No formal lifetime predictions have been made for stainless steel HLW/SF canisters.
The reluctance to adopt stainless steels for this purpose results from their sensitivity to
the effect of Cl- ions and the heat-generation from the waste. Thus, even if the Cl-
concentration in the groundwater or backfill pore water is low, it is difficult to
guarantee that evaporative concentration will not lead to higher concentrations. Given
the ubiquitous nature of Cl- in deep groundwaters and the inevitable elevated
temperature at the canister surface, it is difficult to justify the use of stainless steels in
the absence of a cementitious backfill.

In the presence of a cementitious backfill, however, stainless steels are likely to provide
containment for the duration of the alkaline phase. Thus, elevated pH (defined here as
pH > 10-11) inhibits the effects of Cl- ions on the rate of general corrosion, the initiation
of localised corrosion, and SCC. The beneficial effect of the alkaline pH will, of course,
only last as long as the pore-water pH is influenced by leaching of alkalis and

36
 QRS-1384J-1 v2.1 Appendix F

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.

F.6 Critical conditions

Table F.9 discusses each of the environmental factors considered in this report and lists
a number of critical conditions for which the use of stainless steel canisters would
either not be recommended or which would require detailed investigation in order to
develop a sufficiently justifiable prediction of the long-term corrosion behaviour.

There are a number of critical conditions for stainless steel canisters in a bentonite-
backfilled or non-backfilled GDF, including:

• The presence of sulphide minerals in the host rock or backfill materials -

thiosulphate formation during the aerobic phase could induce localised
corrosion or SCC.

• Elevated temperature - localised corrosion and SCC occur at temperatures at or

slightly above 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 is likely to be <100oC
unless highly corrosion-resistant alloys are selected.

• Chloride ions - stainless steels are subject to localised corrosion and SCC in Cl—
containing environments, especially at elevated temperature.

• Sulphur species - thiosulphate produced by the partial oxidation of pyrite

impurities in clay-based sealing materials or the host rock could induce
localised corrosion and SCC of the canister. Sulphide present naturally in the
groundwater or produced by sulphate-reducing bacteria could lead to
accelerated general corrosion or SCC.

• 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
 Table F.1: List of Critical Conditions for HLW/SF Canisters Manufactured from Stainless Steel

Parameter Critical condition Comment

The presence of sulphide minerals in the host rock or backfill materials would be of concern
Presence of sulphide
Host rock because of the possibility of thiosulphate formation during the aerobic phase. Thiosulphate
minerals
could then induce localised corrosion or SCC of stainless steel canisters.

The passive film on stainless steels provides good protection against general corrosion under
Redox conditions None both aerobic and anaerobic conditions. However, the propensity for film breakdown and
localised corrosion or SCC is greatly enhanced under aerobic conditions.

The probability of localised corrosion or SCC increases significantly with increasing

<100oC (in absence of temperature. Localised corrosion and SCC can occur at temperatures at or slightly above
Temperature 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
is likely to be <100oC unless highly corrosion-resistant alloys are selected.

Gamma radiation >1-10 Gy/h There is no evidence for adverse effects of irradiation at does rates <1 Gy/h.

Given the ubiquitous nature of Cl- ions in groundwaters and the heat generation by the
Backfill material and HLW/SF, the use of stainless steel canisters would not be recommended without the use of a
Requires
near-field mass cementitious backfill.
cementitious backfill
transport

38
 QRS-1384J-1 v2.1 Appendix F

Stainless steels are subject to localised corrosion and SCC in Cl—containing environments,
Chloride Dependent on nature especially at elevated temperature. Given the ubiquitous nature of Cl- ions in groundwaters
concentration of backfill and alloy 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.
The presence of Ca2+ and Mg2+ in the groundwater could lead to the generation of acidic
Other ground water
None environments, but the use of stainless steel would not be recommended without a cementitious
species
backfill which should maintain an alkaline near-field pH.

Thiosulphate produced by the partial oxidation of pyrite impurities in clay-based sealing

Thiosulphate, materials or the host rock could induce localised corrosion and SCC of the canister. Sulphide
Sulphur species
sulphide present naturally in the groundwater or produced by sulphate-reducing bacteria could lead to
accelerated general corrosion or SCC.

As with other canister materials, microbial activity remote from the canister presents a minimal
Significant if biofilms threat to the canister lifetime. However, surface microbial activity and biofilm formation could
Microbial activity
formed lead to ennoblement of ECORR and the possibility of localised corrosion and the possibility of
preferential weld attack.

Austenitic and duplex stainless steels are susceptible to SCC in the presence of Cl- and a
Residual stress and Dependent on nature
sufficient applied or residual tensile stress. Ferritic alloys are less susceptible, but are not
external load of backfill and alloy
immune to Cl—induced SCC.

Stainless steels exhibit good corrosion resistance under atmospheric conditions. The non-
GDF saturation time None uniform wetting of surface salt contaminants could lead to spatial separation of anodic and
cathodic sites and the possibility of localised corrosion and/or SCC.

39
F.6 Advantages and disadvantages of stainless steel
as a canister material
The advantages of stainless steels as a canister material include:

• UK experience in design of a stainless steel canister for ILW.

• Extensive experience in fabrication, welding, and inspection of stainless steel

vessels.

• Excellent corrosion resistance in cementitious environments.

• Minimal impact on other barriers in terms of gas production or alteration of

bentonite.

The disadvantages of stainless steel as a canister material include:

• Stainless steel canisters are only suitable for use with a cementitious backfill,
thus limiting the flexibility of the GDF design.

• Susceptibility to localised corrosion and SCC in the presence of Cl- ions,

especially at elevated temperature.

• The need for an internal structural element, thus complicating the canister
design.

• The need to make long-term predictions of the passive corrosion behaviour

and/or localised corrosion.

• No international experience in design and licensing of a stainless steel canister

for HLW/SF.

40
 QRS-1384J-1 v2.1 Appendix F

References for Appendix F

Alexander, A.L., C.R. Southwell, and B.W. Forgeson. 1961. Corrosion of metals in
tropical environments, part 5 – stainless steel. Corrosion 17, 345.

ASM. 1987. Metals Handbook, Ninth edition, Volume 13, Corrosion. American
Society for Metals International, Metals Park, OH.

ASM. 2005. ASM Handbook, Volume 13B, Corrosion: Materials. American Society for
Metals International, Metals Park, OH.

Blackwood, D.J., L.J. Gould, C.C. Naish, F.M. Porter, A.P. Rance, S.M. Sharland, N.R.
Smart, M.I. Thomas, and T. Yates. 2002. The localised corrosion of carbon steel
and stainless steel in simulated repository environments. AEAT/ERRA 0318,
Dec 2002.

BSC (Bechtel SAIC Company). 2004. Aqueous corrosion rates for waste package
materials. Prepared for US DOE, ANL-DSD-MD-000001, Oct 2004.

Casteels, F., G. Dresselaars, and H. Tas. 1986. Corrosion behaviour of container

materials for geological disposal of high level waste. Commission of the
European Communities Report, EUR 10398 EN, p. 3-40.

Cui, F. and A. Sagüés. 2003. Corrosion performance of stainless steel clad rebar in
simulated pore water and concrete. In Proc. CORROSION/2003, NACE
International (Houston, TX), paper no. 03310.

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