QRS-1384J-1 v2.

1 Appendix E

Appendix E Corrosion of Nickel Alloys

E.1 Introduction
There is a wide range of Ni-based alloys that exhibit an equally wide range of corrosion
properties. Some alloys are designed for use in reducing acids, others in oxidising
acids, and others in alkalis. Nickel alloys are generally more-resistant to stress
corrosion cracking (SCC) in Cl- environments than austenitic stainless steels. Other
properties of Ni alloys include oxidation and sulphidation resistance and superior
mechanical properties in high-temperature applications. The breadth of corrosion and
mechanical properties is a result of the high solubility of other metals in Ni, resulting in
single-phase alloys. From a fabrication standpoint, Ni alloys are ductile, easily
formable, and can be welded using various techniques.

Nickel alloys have been considered as candidate HLW/SF canister materials in a

number of international programmes. AECL investigated the corrosion properties of
Hastelloy C-276 and Inconel 625 (Johnson et al. 1994). In Europe, Hastelloy C-4 has
been studied in the German (salt brine) and Belgian (Boom Clay) programmes, with
Inconel 625 and Hastelloy C-22 also considered in the latter (Kursten et al. 2004). In the
US Yucca Mountain Project, the Ni alloys considered include Alloys 625, 825, and 22
(Brossia et al. 2001).

E.2 Nickel alloys

Table E.1 lists the compositions of the various Ni alloys considered as canister
materials for the disposal of HLW/SF.

There are six major groups of Ni alloys, each characterised by the principal alloying
elements: Ni-Cu, Ni-Mo, Ni-Cr, Ni-Cr-Mo, Ni-Fe-Cr, and Ni-Fe-Cr-Mo alloys. All of
the alloys selected in the various international HLW/SF programmes belong to either
the Ni-Cr-Mo group (i.e., Alloys 625 and 22, Hastelloy C-4 and C-276) or the
Ni-Fe-Cr-Mo group (Alloy 825), primarily because of their resistance to corrosion
under both oxidising (due to the presence of Cr) and reducing (due to the presence of
Mo) conditions. Furthermore, Mo (and W in Alloy 22 and Hastelloy C-276) provides
improved resistance to localised corrosion. Silicon can improve the corrosion
performance under high-temperature oxidising conditions because of the formation of
protective Si-O films. Manganese is added as a deoxidant, but can increase the
susceptibility to localised corrosion because of the tendency for film breakdown to
occur at MnS inclusions.

1
 Table E.1: Composition of Selected Nickel Alloys.*

Alloy Alloy class Ni Cr Fe Mo C Si Mn Ti Other

Alloy 22 Ni-Cr-Mo 56.0 22.0 3.0 13.0 0.015 0.08 - - 3.0 W

Hastelloy C-4 Ni-Cr-Mo bal 140-18.0 3.0 14.0-17.0 0.015 0.08 1.0 0.70 2.0 Co. 0.03 S, 0.04 P

Hastelloy C- Ni-Cr-Mo bal 14.5-16.5 4.0-7.0 15.0-17.0 0.02 0.08 1.0 3.0-4.5 W, 2.5 Co, 0.35 V, 0.03 S,
276 0.03 P

Alloy 625 Ni-Cr-Mo 58.0 min 20.0-23.0 5.0 8.0-10.0 0.10 0.5 0.5 0.4 0.4 Al, 0.015 S, 3.15-4.15 Nb

Alloy 825 Ni-Fe-Cr-Mo 36.0-46.0 19.5-23.5 24-40 2.5-3.5 0.05 0.5 1.0 0.6- 1.5-3.0 Cu, 0.2 Al, 0.03 S
1.2

* wt.% max., unless stated otherwise.

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 QRS-1384J-1 v2.1 Appendix E

E.3 Corrosion modes for nickel alloys

E.3.1 General corrosion

The Ni-Cr-Mo and Ni-Fe-Cr-Mo alloys are protected from corrosion by a Cr-based
passive film. Both Cr(OH)3 (Figure E.1) and Cr2O3 exhibit similar ranges of stability in
water, spanning from acidic to highly alkaline pH and potentials below the H2O/H2
equilibrium line to values within several 100 mV of the O2/H2O equilibrium. The
stability of this film is partly the result of the very low solubility of Cr(III) (Figure E.2).
However, transpassive dissolution as Cr(VI) occurs at potentials more-negative than
those of some other passive materials, e.g., titanium (Figure D.2), resulting in a
tendency towards localised corrosion (Section E.3.2).

Figure E.1: Potential-pH (Pourbaix) Diagram for the Cr-H2O System Assuming
Cr(OH)3 is the Stable Solid (Pourbaix 1974).

3
 Figure E.2: Solubility of Chromium(III) Solids in Water at 25oC (Pourbaix 1974).

As a result of this passivity, the general corrosion rate in aerobic and anaerobic
environments is very low. The passive current density (which is the electrochemical
equivalent of the passive corrosion rate) decreases with increasing Cr content of the
alloy. Thus, Alloys 625 and 22 would be expected to have lower corrosion rates than
the Hastelloys (Table E.1). The mean corrosion rate of Alloy 22 in a range of simulated
concentrated Yucca Mountain pore waters at a temperature of 60oC is 5-10 nm/y (DOE
2008), based on 5- and 10-year exposure tests. The corrosion rate is independent of the
concentration and composition of the aqueous phase (except for the presence of F-),
and is moderately temperature sensitive with an activation energy of 26 kJ/mol.
Under the more-aggressive Q-brines studied in the German programme, 3-year mean
corrosion rates ranged from 200 nm/y at 90oC to 900 nm/y at 200oC. As in the Yucca
Mountain Project, the corrosion rate was found to decrease continuously with exposure
time as the passive film thickens and becomes more protective.

The question for the use of any passive alloy is whether the alloy will maintain
passivity for the entire service life of the canister. For Ni alloys, one mechanism that
has been identified that could compromise the integrity of the passive film is the
anodic segregation of sulphur at the metal-film interface (Marcus 1995). Sulphur
accumulates at the metal-film interface as the alloy dissolves and, once it reaches a
sufficient concentration can form a non-protective Ni3S2 film resulting in an increase in
the dissolution rate. Both Cr and Mo are beneficial as they promote dissolution of the

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

sulphide film and formation of the oxide. The question is whether this Ni3S2 film is
stable or whether it spalls from the surface, permitting the Cr(III) passive film to re-
form. In the latter case, it is unlikely that there will be a significant impact on the long-
term corrosion rate. A similar effect is possible due to S species in solution.
Regardless, there are clearly advantages to specifically an alloy with low S and high Cr
and Mo contents.

E.3.2 Localised corrosion

As noted above, Ni-Cr-Mo and Ni-Fe-Cr-Mo alloys are subject to film breakdown and
transpassive dissolution. Unlike Ti alloys, for which the pitting potential is extremely
positive, Ni alloys do exhibit both pitting and crevice corrosion. However, because
crevice corrosion occurs under milder conditions (i.e., lower potentials, lower
temperature, and/or lower chloride concentration) and because there will inevitably be
occluded regions on the canister surface, crevice corrosion has received the most
attention in various national programmes.

Various approaches have been taken to the study of crevice corrosion. In the chemical
industry it is common to refer to a Critical Crevice Temperature above which there is
a visible indication of localised attack on a standard-type specimen in a standard,
generally highly aggressive, environment. This approach has been used in some
national programmes, but using a simulated GDF environment instead of the standard
acidic-oxidising solution usually used. Whilst this approach is useful for ranking
different alloys and, given extensive field experience, for judging whether a particular
alloy will be suitable for service in a given environment, it provides no mechanistic
insight that can be used to make predictions over very long periods of time.

In the qualification of Ni alloys for use as a HLW/SF canister material, the approach
often taken has been to determine the chemical and electrochemical conditions for the
propagation of localised corrosion. The criterion generally adopted is that the
corrosion potential (ECORR) must exceed the re-passivation potential for a creviced
sample (ERCREV). Mathematically, this criterion can be expressed as

ECORR - ERCREV > 0 (E-1)

This in itself is a conservative indicator of crevice initiation, since ERCREV is actually the
potential at which a propagating crevice ceases to grow.

Various factors affect the value of ERCREV. Chloride promotes film breakdown
(Figure E.3), whereas other anions, most notably nitrate, but also sulphate and
carbonate, inhibit both initiation and propagation of localised corrosion. Increasing
temperature leads to a decrease in ERCREV (Figure E.4). In a similar fashion to stainless

5
Figure E.3: Crevice Re-passivation Potential for Alloy 625 as a Function of Chloride
Concentration at 60oC and 95oC (Cragnolino et al. 1999)

Figure E.4: Temperature Dependence of the Crevice Re-passivation Potential of

Alloy 22 in Various Chloride Solutions (Cragnolino et al. 1999).

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 QRS-1384J-1 v2.1 Appendix E

Figure E.5: Crevice Re-passivation Potential as a Function of Chloride Concentration

for Various Ni-based Alloys (Brossia et al. 2001).

steels, the resistance to crevice corrosion can be related to the Cr and Mo contents of
the alloy (Figure E.5).

An important aspect of the crevice corrosion of Ni alloys is their tendency to re-

passivate following initiation. This process, sometimes referred to as stifling, may
result from a number of factors, including:

o iR (potential) drop down the crevice

o mass-transport effects

o loss of critical crevice chemistry by catalysis of H+ reduction

o loss of critical crevice chemistry by the reduction of inhibiting anion, e.g., NO3-
in NO3-:Cl- mixtures

o negative shift in ECORR upon the initiation of localized corrosion

7
Figure E.6: Re-passivation of Single Propagating Pit for Alloy 825 (Dunn et al. 1996).

Figure E.6 shows the re-passivation of a single artificial pit on Alloy 825 as a function
of potential. The pit was initiated at a potential of +0.6 VSCE and the propagation
kinetics determined for various potentials. Below a potential of 0 VSCE the pit growth
slows and eventually stops. Similar effects are observed during crevice corrosion (Mon
et al. 2005).

E.3.3 Environmentally assisted cracking

Compared with austenitic stainless steels, Ni alloys are resistant to stress corrosion
cracking (SCC). Nickel alloys are much less-susceptible than austenitic stainless steels
to cracking in Clbased groundwaters, but can be susceptible in the presence of
sulphur species and lead. Figure E.7 shows the dependence of the threshold stress
intensity factor (KISCC) in hot chloride solutions as a function of the Ni content of the
alloy. The earlier data of Speidel (1981) suggest immunity to cracking for a Ni content
>30 wt.%, whereas the later data of Roy and Flemming (1998) and McCright (1998)
suggest a benefit of increasing Ni content, but not complete immunity. On the basis of
the Speidel (1981) data, all of the alloys in Table E.1 would be immune to SCC.

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 QRS-1384J-1 v2.1 Appendix E

Figure E.7: Dependence of the Susceptibility of Nickel Alloys to Stress Corrosion

Cracking as a Function of Nickel Content(Cragnolino et al. 1999). KISCC is the
threshold stress intensity factor for SCC. Measurements in 5 wt,% and 22 wt.% NaCl
solutions at temperatures of 90-120oC.

Experience from various national programmes supports the suggestion that the Ni
alloys in Table E.1 are immune to cracking in Cldominated GDF environments.
Hastelloy C-4 U-bend specimens did not exhibit cracking in Q-brine between
temperatures of 90oC and 200oC (Kursten et al. 2004). Alloy 22 has proven to be
immune to cracking in a range of concentrated brines solutions at 90oC under severe
constant extension rate testing (DOE 2008). Cracking was observed in some tests, but
only at applied potentials 200-300 mV more-positive than ECORR (King et al. 2008).

Nickel alloys are susceptible to SCC and hydrogen embrittlement in certain aggressive
conditions, including: elevated temperatures (>150-200oC), pH <4, presence of H2S, and
presence of lead (ASM 1987). Of these conditions, the low pH and high temperature
will either not exist or can be avoided by appropriate GDF design. Sulphide species
may be present in the host rock and/or in the groundwater. The susceptibility of the
canister to SCC would need to be determined based on the expected interfacial
concentration of sulphide, elemental S, and thiosulphate. Similarly, if Pb were to be
used as a metal-matrix material, the concentration of Pb(II) at the canister surface due
to dissolution from a prematurely failed canister would need to be determined.

9
E.3.4 Microbiologically influenced corrosion

Although, unlike Ti alloys, it is not possible to claim that Ni alloys are immune to
microbiologically influenced corrosion (MIC) (Little et al. 1991), the susceptibility to
microbial attack appears to be limited (King 2009, Lloyd et al. 2004). Even in the
presence of large quantities of nutrients, Farmer et al. (2000)) only reported a doubling
of the general corrosion rate. This lack of susceptibility has been attributed to the wide
range of stability of the passive film (Figure E.1) (Lloyd et al. 2004).

As with other candidate canister materials, the key to predicting the long-term MIC
behaviour of a Ni alloy canister is to have an understanding of where and when the
microbial activity occurs (King 2009). Provided that microbial activity at the canister
surface can be avoided by appropriate GDF design, MIC should have a minimal effect
on the service life of the canister. However, if microbial activity at the surface cannot
be avoided and a biofilm forms on the canister, then MIC could impact the service life
because of enhanced general corrosion, localised attack, and/or SCC, especially as
induced by sulphate-reducing bacteria.

E.3.5 Galvanic corrosion

In their passive state, Ni alloys are relatively noble. In any galvanic couple with a
more-active material, such as Fe, Mg, Al, Zn, the Ni alloy would act as the cathode
with the active material preferentially corroding. In contact with other passive
materials, Ni alloys may be active or passive, but the driving force for corrosion (i.e.,
the difference in potential between the two passive materials) will be small and any
effect minimal.

E.3.6 Anthropogenic analogues

As for stainless steel and Ti alloys, there is a relatively short history of the use of Ni
alloys and, as a consequence, few analogues for the long-term performance of Ni-based
HLW/SF canister materials. Cragnolino et al. (2003), however, did study the
electrochemical characteristics of josephinite, a mineral containing a naturally
occurring Ni-Fe alloy as an analogue for Alloy 22. Although there are few similarities
between the composition and metallurgy of Alloy 22 and that of joephinite, the study
did report interesting data regarding the anodic characteristics and susceptibility to
localised corrosion of the mineral. For example, josephinite was more passive at high
pH than a cast Ni3Fe alloy, but was more susceptible to pitting corrosion.

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 QRS-1384J-1 v2.1 Appendix E

E.4 Corrosion behaviour of nickel alloys

E.4.1 Effect of redox conditions

Due to the presence of Cr and Mo in the Ni-Fe-Cr-Mo and Ni-Cr-Mo series of alloys,
the alloys in Table E.1 exhibit good corrosion resistance under both aerobic and
anaerobic conditions. The Cr oxide film provides much of the thermodynamic
stability, with Mo providing additional stability under acidic reducing conditions
through the formation of MoO2. Under oxidising conditions, Cr(III) is converted to
Cr(VI) at redox potentials (EH) equivalent to those present initially in the GDF due to
the trapped atmospheric O2, but dissolution of the canister material is determined by
the corrosion potential which is many hundreds of mV more-negative than EH due to
the kinetic limitations. In the absence of localised film breakdown, therefore, Ni-Cr-Mo
alloys offer good corrosion resistance over the entire range of redox potentials expected
within the GDF.

However, due to the presence of Cl- and of occluded regions or film defects, localised
corrosion in the form of crevice corrosion or pitting is possible under aerobic
conditions. Once all of the O2 has been consumed, ECORR will drop below the re-
passivation potential and any propagating pits or crevices will cease to grow. (Stifling
of pits or crevices may occur before the consumption of O2 due to the metallurgical or
other factors described in Section E.3.2). They key issue is whether the pit or crevice
has propagated through the canister wall prior to the transition to anaerobic
conditions. This answer to this question depends on a number of factors, including the
GDF design, the time-dependence of the environmental conditions, and the alloy
selected as a canister material.

E.4.2 Effect of chloride

The Cl- concentration affects both the general and localised corrosion behaviour of Ni
alloys. The solubility of Cr(III) increases in the presence of Cl- (Pourbaix 1974),
resulting in higher a passive current density and a higher rate of passive corrosion. In
aerated solutions at temperatures of 60oC and 90oC, however, there is little dependence
of the corrosion rate of Alloy 22 on Cl- concentration over the range 70 mg/L to
178,000 mg/L, with a mean rate of ~5 nm/y. (DOE 2008). In aggressive Q-brines,
higher corrosion rates are observed, in the range of 100s of nm/y (Kursten et al. 2004).

The effect of Cl- concentration on the initiation of localised corrosion is more apparent.
Over the range 0.01 mol/L to 1 mol/L, the crevice re-passivation potential for
Alloys 625 and 825 decrease by ~100 mV per decade change in the Cl- concentration
(Figure E.5). Selection of the appropriate material requires a knowledge of the

11
susceptibility of the alloy as a function of Cl- concentration, potential and temperature,
as well as a knowledge of how these parameters change with time at the canister
surface.

E.4.3 Effect of temperature

The most important effects of temperature are on the localised and SCC behaviour of
the alloys. There is a modest effect of temperature on the general corrosion rate of Ni
alloys, with rates increasing from 0.20 m/y at 90oC to 0.90 m/y at 200oC in Q-brine
(Kursten et al. 2004). The general corrosion of Alloy 22 in synthetic brine solutions
exhibits an activation energy of 25-60 kJ/mol (DOE 2008).

Increasing temperature increases the susceptibility of Ni alloys to localised corrosion.

A common method for comparing the susceptibility of different alloys is to determine a
threshold temperature in a standard solution, often an acidic ferric chloride solution.
In this aggressive environment, the critical crevice temperatures (CCT) for Hastelloy C-
276 and Alloy 22 are 55oC and 80oC, respectively (ASM 2005). In GDF-type
environments, the equivalent CCT would be significantly higher. The CCT can be
viewed as the temperature at which ECORR exceeds ERCREV in that particular
environment. The effect of temperature on ERCREV can be seen from Figure E.4.

The susceptibility of Ni alloys to SCC increases significantly with increasing

temperature. Susceptibility increases at temperatures above 150oC and particularly
above 200oC (ASM 1987).

High temperatures can also impact the microstructure of Ni alloys and, hence, the
mechanical and corrosion properties. Rebak et al. (2000) considered the effect of
thermal aging on the microstructure, mechanical properties, and corrosion resistance of
Alloy 22. Thermal aging can induce long-range ordering (LRO) and the formation of
brittle tetrahedrally close-packed (TCP) phases. Based on time-temperature-transition
(TTT) relationships, it can be shown that LRO and TCP formation will not occur over
GDF timescales, even for a maximum canister temperature of 250oC.

E.4.4 Effect of pH

The passive film on Ni-Cr-Mo and Ni-Fe-Cr-Mo alloys becomes more soluble with
decreasing pH. Many Ni alloys are, however, used successfully to handle concentrated
acid solutions (ASM 1987, 2005).

For the expected range of pH for the generic GDF designs (neutral to alkaline), Ni
alloys will exhibit good corrosion resistance. Nickel alloys would be suitable for use
with cementitious backfill of a concrete overpack, but these alloys exhibit sufficient

12
 QRS-1384J-1 v2.1 Appendix E

corrosion resistance without the need to condition the environment through the use of
concrete.

E.4.5 Effect of sulphur species

Nickel alloys do exhibit some susceptibility to sulphide, elemental sulphur, and

oxysulphur anions (ASM 2005). Adsorption of S on Ni inhibits passivation because of
the formation of a Ni3S2 layer (Marcus 1995). A critical S surface coverage of 0.7-
0.8 monolayers is required to suppress passivation. This surface coverage can arise
from the anodic segregation mechanism discussed in Section E.3.1 or from S species in
the environment. The relationship between the onset of S-assisted de-passivation and
the concentration or rate of supply of S species to the (canister) surface has not be
adequately determined. For Ni alloy canisters in a bentonite-backfilled GDF, it is
possible that the rate of supply of S species would be too slow to induce de-
passivation, but would need to be studied in more detail.

Enhanced crevice corrosion, increased rate of general corrosion, and a susceptibility to

pitting was observed on Hastelloy C-4 when 25 mg/L H2S was added to Q-brine
solution at 150oC (Kursten et al. 2004).

E.4.6 Effect of other anions and cations

There are few adverse effects on the corrosion behaviour of Ni alloys of anions or
cations other than Cl- or S species. Instead, a beneficial effect of sulphate, carbonate,
and, especially of nitrate, on the crevice corrosion of Ni alloys has been reported (DOE
2008).

E.4.7 Effect of gamma radiation

Nickel alloys do exhibit some sensitivity to gamma radiation at high absorbed dose
rates. An extensive series of tests was performed for the German programme in
irradiated Q-brine solutions at a temperature of 90oC (Kursten et al. 2004). There was
no apparent effect of irradiation on the behaviour of Hastelloy C-4 at a dose rate of
1 Gy/h, but an increase in the rate of general corrosion and a susceptibility to pitting
was observed for dose rates of between 10 Gy/h and 1000 Gy/h. However, this
observation should not be interpreted as indicating a general threshold to radiation
effects in all environments, since the passive region is particularly narrow (in terms of
potential) in this aggressive environment and it does not require much additional
(radiolytic) oxidant to drive the system into the transpassive region. In less-aggressive
environments, where the passive region is wider, the threshold for the effect of
irradiation, if any, would be expected to be higher.

13
E.4.8 Effect of unsaturated conditions and atmospheric
exposure

Nickel alloys provide the same excellent corrosion resistance in unsaturated conditions
as in bulk solution (ASM 1987, 2005). The major difference between the two
environments is that the rate of mass transport of aggressive species to the canister
surface could be higher in the absence of a backfill material.

E.5 Lifetime predictions

The only formal lifetime prediction for a Ni alloy HLW/SF canister material is that for
Alloy 22 canisters in the Yucca Mountain GDF (DOE 2008). Under the permanently
aerobic conditions of this unsaturated GDF, the canisters were considered to be
susceptible to a combination of: general corrosion, localised (crevice) corrosion, MIC,
and, if subject to mechanical damage from falling rocks, SCC. The extent of general
corrosion was estimated from the time-temperature history and temperature-
dependent weight-loss corrosion rates measured from 5-year exposure tests. Crevice
corrosion only affects that small fraction of the canisters for which the accompanying
drip shield has failed prior to the end of the thermal transient, and is not a significant
cause of canister failure. MIC was assumed to occur at all times, despite arguments
that the onset of microbial activity at the canister surface will be delayed for some time
because of the inhospitable near-field environment (Lloyd et al. 2004, King 2009). The
extent of MIC damage was estimated on the basis of a multiple of the general corrosion
rate of a factor of between 1 and 2, based on laboratory observations. Although SCC
was considered possible if the canister shell experienced extensive residual stress due
to rock loading, it was argued that it would not result in canister failure as the
tortuous, corrosion-product-filled crack would not provide a pathway for
radionuclides to exit the canister. The 20-mm-thick canisters were predicted to have
lifetimes of >500,000 years (DOE 2008).

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 QRS-1384J-1 v2.1 Appendix E

E.6 Critical conditions

Table E.2 summarises the sensitivity of Ni alloys to the various environmental
conditions discussed above. There are no truly critical conditions for which the use
of a Ni alloy canister would not be recommended. However, there are a number of
conditions that could lead to issues, including:

o Sulphur species Ni alloys are susceptible to de-passivation, enhanced general

corrosion, SCC, and localised corrosion in the presence of H2S, elemental S,
and/or oxysulphur species. The key question is whether the concentration or
flux of S species at the canister surface is high enough to cause adverse effects.
This, in turn, is dependent on the repository design as much as the nature of the
host rock.

o Chloride ions - Cl- will induce the localised corrosion of Ni alloys. The
threshold Cl- concentration is alloy dependent.

o Lead Ni alloys are susceptible to SCC in the presence of lead. Lead is only
likely to be present in the system if it is used as a matrix material inside the
canister. In this event, the potential for common-mode-failure of the canisters
due to lead leaching from an initially defected canister would need to be
assessed.

15
 Table E.1: List of Critical Conditions for HLW/SF Canisters Manufactured from Nickel-based Alloys

Parameter Critical Comment

condition

Host rock High sulphide A high sulphide mineral content in the host rock could induce de-passivation, enhanced general
mineral content corrosion, pitting, and SCC if H2S or other S sulphur species contact the canister surface. It is not
possible to define an unacceptable sulphide mineral content since the canister susceptibility
depends on the interfacial concentration or flux of S species, which in turn is dependent on the
design of the GDF, in particular the nature of any backfill material.

Redox conditions None The passive film on Ni-Fe-Cr-Mo and Ni-Cr-Mo alloys provides equal protection under aerobic and
anaerobic conditions.

Temperature >250oC Thermal aging effects would require a sustained temperature of >250oC to induce microstructural
changes in Alloy 22. The corresponding temperature and/or time for other Ni alloys is not known.

>150oC There is an increased susceptibility to SCC at temperatures greater than 150oC.

Gamma radiation >1-10 Gy/h In aggressive Q-brine solutions at 90oC, an increase in the rate of general corrosion and a
susceptibility to pitting is observed at an absorbed dose rate in the range 1-10 Gy/h. In less-
aggressive environments, the threshold dose rate is likely to be significantly higher.

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

Backfill material and None There is no apparent benefit to a cementitious backfill or overpack, but it is unlikely to be
near-field mass detrimental to the canister performance. In an un-backfilled GDF, the canister would need to be
transport protected from S species.

Under sufficiently aggressive conditions, most Ni alloys are susceptible to localised corrosion in Cl-
Chloride Alloy
environments. The combination of Cl- concentration, temperature, and electrochemical potential
concentration dependent determine whether localised corrosion will initiate. The threshold Cl- concentration is alloy
dependent.
Other ground water None There are no adverse effects of other groundwater species. Species such as nitrate, sulphate, and
species (sensitivity to carbonate can inhibit the effects of Cl- on the localised corrosion of Ni alloys. Ni alloys are
Pb) susceptible to SCC in the presence of Pb which, although not a ground water species, could be
present if Pb is used as a matrix material.

Sulphur species H2S, elemental Sulphur species can lead to de-passivation, enhanced general corrosion, SCC, and localised
S, corrosion of Ni alloys. The important factor is the concentration or flux of S species at the canister
surface.

Microbial activity Minimal The passive film on Ni-Fe-Cr-Mo and Ni-Cr-Mo alloys appears to be relatively resistant to MIC,
although some effect may be observed if microbial activity occurs at the canister surface.

Residual stress and None Ni alloys are susceptible to SCC under severe environmental conditions. It is accepted that a tensile
external load stress sufficient to cause SCC may exist on the canister surface at some stage.

GDF saturation time None Ni alloys exhibit the same corrosion resistance under unsaturated conditions as in bulk solution.

17
E.7 Advantages and disadvantages of nickel alloys
as a canister material
The advantages of a Ni alloy canister include:

o Excellent corrosion resistance in the passive state, offering the possibility of

very long canister lifetimes.

o Resistance to SCC, except at elevated temperature or in the presence of lead or

sulphur species.

o Good industrial experience with joining and inspection of Ni alloys, aided by

the likely thin-wall design.

o Minimal impact on other barriers.

o Resistance to MIC.

o Ni containers are suitable for use with bentonite or cementitious backfill or in

un-backfilled GDF designs.

The disadvantages of a Ni alloy canister include:

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

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

and/or localised corrosion.

o Susceptibility to localised corrosion in Cl- environments, but this can be

minimised through proper alloy selection.

o Little international experience in design and licensing of a Ni alloy canister.

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

References for Appendix E

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.

Brossia, S., L. Browning, D.S. Dunn, O.C. Moghissi, O. Pensado, and L. Yang. 2001.
Effect of environment on the corrosion of waste package and drip shield
materials. Center for Nuclear Waste Regulatory Analysis Report, CNWRA
2001-03.

Cragnolino, G., D.S. Dunn, C.S. Brossia, V. Jain, and K.S. Chan. 1999. Assessment of
performance issues related to alternate engineered barrier system materials and
design options. Center for Nuclear Waste Regulatory Analysis Report,
CNWRA 1999-003.

Cragnolino, G.A., Y.-M. Pan, F. Turner, and E. Pearcy. 2003. Natural analogs of high-
level waste container materials experimental evaluation of josephinite. Center
for Nuclear Waste Regulatory Analysis Report, CNWRA 2003-XX.

DOE. 2008. Yucca Mountain Reposiotry license application. U.S. Department of

Energy, DOE/RW-0573.

Dunn, D.S., G.A. Cragnolino, and N. Sridhar. 1996. Localized corrosion initiation,
propagation, and repassivation of corrosion resistant high-level nuclear waste
container materials. In Proc. CORROSION/96, NACE Intenrational (Houston,
TX), paper no. 97.

Farmer, J., D. McCright, G. Gdowski, F. Wang, T. Summers, P. Bedrossian, J. Horn, T.

Lian, J. Estill, A. Lingenfelter, and W. Halsey. 2000. General and localized
corrosion of outer barrier of high-level waste container in Yucca Mountain.
Proc. Transportation, Storage, and Disposal of radioactive Materials 2000,
PVP-Vol. 408 (American Society of Mechanical Engineers, New York, NY),
pp. 53-69.

Johnson, L.H., J.C. Tait, D.W. Shoesmith, J.L. Crosthwaite, and M.N. Gray. 1994. The
disposal of Canadas nuclear fuel waste: engineered barriers alternatives.
Atomic Energy of Canada Limited Report, AECL-10718, COG-93-8.

19
King, F. 2009. Microbiologically influenced corrosion of nuclear waste containers.
Corrosion 65, 233-251.

King, F., M. Kolar, J.H. Kessler, and M. Apted. 2008. Yucca Mountain engineered
barrier system corrosion model (EBSCOM). J. Nucl. Mater. 379, 59-67.

Kursten, B., E. Smailos, I. Azkarate, L. Werme, N.R. Smart, G. Santarini. 2004.

COBECOMA, State-of-the-art Document on the COrrosion BEhaviour of
COntainer Materials. European Commission, Contract N FIKW-CT-20014-
20138 Final Report.

Little, B., P. Wagner and F. Mansfeld. 1991. Microbiologically influenced corrosion of

metals and alloys. Int. Mater. Rev. 36, 253-272.

Lloyd, A.C., R.J. Schuler, J.J. Nol, D.W. Shoesmith, and F. King. 2004. The influence
of environmental conditions and passive film properties on the MIC of
engineered barriers in the Yucca Mountain Repository. In Scientific Basis for
Nuclear Waste Management XXVIII, J.M. Hanchar, S. Stroes-Gascoyne, and
L. Browning (eds.), Mat. Res. Soc. Symp. Proc. 824 (Materials Research Society,
Warrendale, PA, 2004), pps. 3-9.

Marcus, P. 1995. Sulfur-assisted corrosion mechanisms and the role of alloyed

elements. In Corrosion Mechanisms in Theory and Practice, P. Marcus and J.
Oudar (eds), Marcel Dekker (New York, NY), p. 239-263.

McCright, R.D. 1998. Engineered materials characterization: corrosion data and

modeling update for the Viability Assessment. Lawrence Livermore National
Laboratory Report No. UCRL-ID-119564, Volume 3, Revision 1.1.

Mon, K.G., G.M. Gordon, and R.B. Rebak. 2005. Stifling of crevice corrosion in
Alloy 22. Proc. 12th Int. Conf. Environmental Degradation of Materials in
Nuclear Power System Water Reactors, T.R. Allen, P.J. King, and L. Nelson
(eds.), The Minerals, Metals & Materials Society (Warrendale, PA), p. 1431-1438.

Pourbaix, M. 1974. Atlas of Electrochemical Equilibria in Aqueous Solutions, 2nd.

edition. NACE International, Houston, TX.

Roy, A.K. and D.L. Fleming. 1998. Stress corrosion cracking of Fe-Ni-Cr-Mo and Ni-
Cr-Mo and Ti alloys in 90oC acidic brine. In Proc. CORROSION/98, NACE
International (Houston, TX), paper no. 157.

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

Rebak, R.B., N.E. Koon, J.R. Dillman, P. Crook, and T.S.E. Summers. 2000. Influence of
aging on microstructure, mechanical properties, and corrosion resistance of a
Ni-22Cr-13Mo-3W alloy. In CORROSION/2000, NACE International (Houston,
TX), paper no. 00181.

Speidel, M.O. 1981. Stress corrosion cracking on stainless steels in NaCl solutions.
Metallurgical Transactions 12A, 779-789.

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