Corrosion Science 58 (2012) 284290

Contents lists available at SciVerse ScienceDirect

Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Pourbaix diagrams for the nickel-water system extended to high-subcritical

and low-supercritical conditions
William G. Cook , Robert P. Olive
Department of Chemical Engineering, University of New Brunswick, P.O. Box 4400, Fredericton, NB, Canada E3B 5A3

a r t i c l e i n f o a b s t r a c t

Article history: One of the Generation IV nuclear reactor concepts is the supercriticalwater-cooled reactor (SCWR). To
Received 24 October 2011 assist with plant design and selection of potential construction materials, Pourbaix diagrams for the
Accepted 6 February 2012 nickel water-system slightly below and above the critical temperature at a pressure of 25 MPa have been
Available online 16 February 2012
developed. A revised HelgesonKirkhamFlowers model with parameters optimized to bunsenite solubil-
ity data was used to perform the necessary thermodynamic extrapolations. The third hydrolysis product
Keywords: (Ni(OH)3 ) was included in this study after careful review of new data. The diagrams revealed the need
A. Nickel
for strict water chemistry control to prevent transitioning to regions of active corrosion.
B. Electrochemical calculation
C. High temperature corrosion
2012 Elsevier Ltd. All rights reserved.
C. Oxidation
C. Pourbaix diagram.

1. Introduction
The supercritical water-cooled reactor (SCWR) is a Generation IV
reactor concept that will be able to realize thermodynamic efcien-
cies up to 50% by using water above its critical point (374 C,
22.1 MPa) as the coolant [1]. Compared to the current generation
of nuclear reactors, which typically have efciencies of approxi-
mately 33% [2], this will be a considerable improvement leading to
smaller, cheaper reactors with less fuel inventory. In Canada, a
reactor based upon the heavy water, pressure-tube design is being
developed as the logical evolution of the CANDU reactor. The
currently envisaged operating conditions for the CANDU-SCWR in-
cludes an operating pressure of 25 MPa and a core outlet tempera-
ture of 625 C [3]. Fig. 1 depicts the operating conditions for the
CANDU-SCWR relative to current light water reactors and the hea-
vy water CANDU reactors on a phase diagram for water. Because
the CANDU-SCWR will operate at such extreme conditions, the
selection of materials to be used in its construction will be
challenging.
A potential group of materials for application in the SCWR are the
nickel-based alloys. These alloys are highly corrosion resistant and
possess excellent high-temperature strength. The thin oxides that
do form on nickel-based alloys when exposed to SCW or high-
temperature steam are resistant to spalling, which is an undesirable
trait affecting the austenitic stainless steels. However, drawbacks to
the potential use of nickel-based alloys in SCWRs are that they have
been shown to be susceptible to irradiation-induced stress corrosion
Corresponding author. Tel.: +1 506 452 6318; fax: +1 506 453 3591.
E-mail address: wcook@unb.ca (W.G. Cook).
cracking [2] so that they are unsuitable for in-core applications due
to the potential for helium embrittlement, through neutron capture
followed by alpha decay. Although nickel-based alloys have been ex-
cluded for use as in core materials, nickel will undoubtedly be an
important alloying element in the alloys selected so knowledge of
the passive oxide phases that will form under reactor operating con-
ditions will give valuable information to the reactor designers.
The primary oxide that forms on nickel is bunesite, NiO, with
several studies available on its solubility in water over a range of
pH values and at temperatures up to 300 C [48].
Thermodynamic properties obtained from these studies allow
for the construction of Pourbaix diagrams, named after Marcel
Pourbaix, which are plots of electrochemical potential versus pH
for a given pressure, temperature, and dissolved ion concentration
[9]. Pourbaix diagrams are essentially thermodynamic maps show-
ing the regions of immunity, passivity, and corrosion for a particu-
lar metal-water system. Pourbaix diagrams for freely corroding
metals have traditionally been constructed at 10 6 mol/kg, which
is thought to represent the dissolved corrosion product concentra-
tion at the metal-solution interface, although some authors have
used a lower concentration of 10 8 mol/kg to represent the interfa-
cial concentration for the metals in the high purity water typically
used in power plant applications [10]. It is important to remember
that Pourbaix diagrams only display thermodynamic information
and provide no insight into the kinetic behavior of the system.
However, these diagrams are valuable because they show whether
corrosion is thermodynamically favorable in a given environment
and help facilitate the evaluation of corrosion mechanisms.
Using the bunesite solubility data obtained in previous studies
[4,6], Beverskog and Puigdomenech constructed Pourbaix diagrams

0010-938X/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2012.02.007
 W.G. Cook, R.P. Olive / Corrosion Science 58 (2012) 284290 285

Fig. 1. Phase diagram for water indicating the operating conditions for current Fig. 3. Heat capacity of water as a function of temperature.
nuclear reactors relative to those proposed for the CANDU-SCWR.

of the nickel-water system up to 300 C for concentrations of 10 6

and 10 8 mol/kg [10]. A later study by Saito et al. developed dia-
grams for the nickel-water system in supercritical conditions;
namely, 400 C and 450 C at 50 and 100 MPa [11]. The current
work arose to construct Pourbaix diagrams under conditions more
relevant to the potential operation of the CANDU-SCWR. These in-
clude diagrams constructed at 25 MPa, the currently envisaged
operating pressure for the reactor, in the both the high-subcritical
(350 C representing the reactor core inlet temperature) and low-
supercritical regions (400 C representing the upper limit of validity
of the HKF thermodynamic extrapolation model). This is the second
paper in a series of thermodynamic studies by the authors.

2. Properties of water

Water undergoes drastic changes in its physical properties as

temperature approaches and traverses the thermodynamic critical
point. At the critical point, the density of water vapor equals the li-
quid density (qv = ql = qc = 322 kg/m3) and a single phase exists.
Fig. 2 is a pressure versus density diagram for water illustrating
the existence of the critical point at the locus of the density curves.
The behavior of the heat capacity of water with increasing tem-
perature for a given pressure is shown in Fig. 3. For any given pres-
sure, the heat capacity reaches a maximum at what is known as the
pseudo-critical temperature. As illustrated in Fig. 3, increasing
pressure results in a decrease in the maximum heat capacity value
along with a shift in the maximum to a higher temperature.
Fig. 4 shows the effect of increasing temperature on the density
of water. As temperature increases, the amount of hydrogen bond-
ing in liquid water decreases. This results in the density decreasing
Fig. 4. Density of water as a function of temperature.
until the critical point is reached where it experiences a drastic
drop. Since the water molecules become closer in vicinity as pres-
sure is increased, the hydrogen bonding character will increase and
thus, increasing pressure lessens this effect.
As temperature is increased, the behavior of the dielectric con-
stant is analogous to density, as observed in Fig. 5 however, per-
haps not as drastic a transition at the critical point. In the
supercritical regime, the dielectric constant has low values. The
consequence of this is that substances that are normally soluble
in liquid water will no longer be so under supercritical conditions
while typically immiscible species, such as hydrocarbons and
organics, become highly soluble in supercritical water.

Fig. 2. Pressure-densitydiagram for water. Fig. 5. Dielectric constant of water as a function of temperature.
286 W.G. Cook, R.P. Olive / Corrosion Science 58 (2012) 284290

The effect of increasing temperature on the pH of neutral water

is illustrated in Fig. 6. The ion-product of water (Kw) formulation
used in this study is that proposed by Bandura and Lvov [12]as is
recommended by the International Association of Water and Steam
(IAPWS) [13]. The neutral pH of water at a given temperature and
pressure an important parameter in this work because the cur-
rently envisaged water chemistry for the CANDU-SCWR utilizes
pure, neutral water.

3. Calculation procedures and model optimization

Pourbaix diagrams are constructed from the Nernst equation,

which requires calculation of the standard cell potential (Eo) at
the required temperature and pressure. This is calculated from
the Gibbs energy of reaction, which requires knowing the Gibbs
energy of formation for all the species involved in the reaction at Fig. 7. Validity range for the R-HKF model used in this study as a function of
the temperature and pressure of interest. These values are typically pressure (including the range of assumed validity at 25 MPa).
determined by extrapolating tabulated values under standard con-
ditions (298 K, 0.1 MPa) to the required conditions by integration
For the nickel-water system, eight species were considered in
of the pure substances heat capacity and entropy functions. The
addition to the base metal: one uncharged aqueous species
reference standard state values for evaluation of the activity of a
(Ni(OH)2), three ionic species (Ni2+, NiOH+, and Ni(OH)3 ), and four
species are taken as unity (1 mol/kg for standard concentration,
oxides (NiO, Ni3O4, Ni2O3, and NiO2). The heat capacity of the solid
1 atm for standard fugacity) and the standard potential for the
species is well known over a wide temperature range and the
hydrogen evolution reaction is taken as zero at all temperatures.
extrapolated Gibbs energy of formation was found using tempera-
Unfortunately, for ions and aqueous species, relations of the tem-
ture-dependent heat capacity equations [19,20]. Extrapolations for
perature dependence of the heat capacity do not exist, thus
the ionic species were performed using the respective equations
semi-empirical extrapolation methods are used.
for charged species found in reference [11]. For the neutral, aque-
The revised HelgesonKirkhamFlowers (R-HKF) model is one
ous species, the thermodynamic extrapolation was employed as
method used for high temperature extrapolation of the thermody-
outlined in reference [16].
namic parameters of ions and uncharged aqueous species. This is a
The anionic species, Ni(OH)3 , has been included in this study
semi-empirical model that uses standard state thermodynamic
even though there is some doubt to its existence. Early bunsenite
properties along with ion or solute specic t parameters to gener-
solubility studies appeared to show that Ni(OH)3 was a signicant
ate the necessary Gibbs energy of formation values at the temper-
species at alkaline pH values [4,5]. However, a later study implied
ature and pressure of interest. Several sources have published the
that only the aqueous Ni(OH)2 species contributed to the solubility
equations used in the R-HKF model [11,1417]. The R-HKF model
in alkaline pH conditions, throwing into question the existence of
allows for thermodynamic extrapolation from 25 to 1000 C and
Ni(OH)3 under high temperature, alkaline conditions[7]. Most re-
from 0.1 to 500 MPa [17]. Unfortunately, this model is only vali-
cently, Palmer et al.[8] have published new measurements of buns-
dated for water densities higher than 350 kg/m3 [11] but by using
enite solubility up to 350 C and, from their analysis, they reafrm
a modication to the model proposed by Sue et al., a validated
the conclusion that only Ni2+ and Ni(OH)2(aq) are required to de-
extrapolation to water densities as low as 200 kg/m3 is possible
scribe the solubility of NiO. In order to rationalize our inclusion
[18]. With the above stipulations, the modied R-HKF model is va-
of both the Ni(OH)+ species and Ni(OH)3 in this work, Fig. 8a
lid for a temperature range of 250600 C and a pressure range of
and b show the three most relevant sets of NiO solubility data to
22.399.8 MPa. The Sue et al. modication has been incorporated
date at 300 C and 250 C respectively. As indicated by Palmer et
into the present work and assumed to be valid in the low supercrit-
al., the presence of Ni(OH)+ cannot be accessed from their current
ical regions examined here. Fig. 7 shows the valid temperature
results due to the overlap and errors associated with the measure-
range at various pressures of the R-HKF model using the Sue
ments in the acidic regions. Although they clearly show from their
et al. modication. The dotted line extending from the 25 MPa line
most recent work that the NiO solubility reaches a minimum and
on the graph is the region assumed to be valid in the present work.
levels out at a pHT of 7, they do not present their ndings from
their 250 C trial as shown in Fig. 8b. While the open diamonds
representing the new Palmer et al. data clearly show a minimum
and levelling out for the 300 C case (Fig. 8a), the 250 C data show
a denite increase in the NiO solubility at the highest pH used in
the tests (9.7), just within the top band of the error associated
with the 9.3 pH test, possibly showing evidence of the third hydro-
lysis product. Also, the Ziemniak data clearly shows a minimum
solubility around pH 89, however there were no measurements
reported at higher pH values that could clearly show whether
the solubility increases as did Tremaine and Leblancs. It should
be noted at all the experimental results are more-or-less within
the scatter of experimental error; thus, it is felt that the most com-
plete picture of NiO solubility is still displayed by the early work of
Tremaine and Leblanc and has been used as a self-consistent data-
set for the extraction of our HKF t parameters in this work.
The R-HKF parameters for the ionic and aqueous species were
Fig. 6. pH of neutral water as a function of temperature. determined by a tting procedure to the Tremaine and LeBlanc
 W.G. Cook, R.P. Olive / Corrosion Science 58 (2012) 284290
Fig. 8a. Speciation diagram for nickel at 300 C and 10 MPa (validation data from
Ref. [4], open circles; Ref. [7], open squares; Ref. [8], open diamonds).
Fig. 8b. Speciation diagram for nickel at 250 C and 10 MPa (validation data from
Ref. [4], open circles; Ref. [7], open squares; Ref. [8], open diamonds).
solubility data for NiO at 300 and 250 C with a bias on the lower
band of their experimental errors [4]. To begin, the standard Gibbs
energies of formation and entropies were taken Palmer et al. [21].
Then, the R-HKF parameters were adjusted until the desired t
through the experimental data was obtained. It should be noted
that, as described in the paper by Beverskog and Puigdomenech,
the heat capacity of the dissolved ionic and aqueous species is
essentially a tting parameter and may have little to no physical
or chemical signicance [10].
This study also includes the three oxides Ni3O4, Ni2O3, and NiO2.
Beverskog and Puigdomenech questioned their existence in pas-
sive lms based on earlier experimental studies and denoted the
higher oxides as beta phase and gamma phase due to uncer-
tainties in their stoichiometries [10]. The decision to include the
oxides in this study was made because of their well-dened heat
capacities over a wide temperature range along with the fact that,
regardless of what the area is labeled on the Pourbaix diagram, it is
ultimately a passive thermodynamic region.
Finally, it is known that bunsenite undergoes a solid phase
transformation from a rhombic to cubic structure at approximately
247 C [7]. However, because the optimization of the R-HKF
parameters used in this study was performed at 300 and 250 C,
this transformation is presumed to not be of concern in this work.
4. Results
Fig. 8a is a speciation diagram illustrating the results of the t-
ting procedure of the HKF parameters to the Tremaine and Le-
287
Blanc bunsenite solubility data at 300 C and 10 MPa. The
abscissa is the pH calculated at temperature. The hollow circles
on the diagram denote the Tremaine and LeBlanc data set while
the hollow diamonds represent the Palmer et al. data from their
2011 study and the hollow squares denote the Ziemniak and Goy-
ette data from their 2004 study. It should be noted that the Ziem-
niak et al. data was obtained between 301.7 and 302.4 C rather
than at 300 C although this slight difference should have mini-
mal effect. While Ziemniak et al. argue that their data does not
provide evidence of the anionic Ni(OH)3 species, a measurement
was not taken at as a pH above 9 as did Tremaine and LeBlanc
who clearly show an increase in solubility in the alkaline regions
eluding to the presence of an anionic species and, as described
above, the recent dataset of Palmer et al. may not be entirely as
conclusive as believed.
To further optimize our parameters, a t was done to the Tre-
maine and LeBlanc data at 250 C and 10 MPa. The results of this
are shown in Fig. 8b. There is a reasonably good t of the total dis-
solved nickel through the data points, except at low pH values, and
it should be pointed out that fewer data points exist under these
conditions than at 300 C. A summary of the optimized heat capac-
ity and other thermodynamic data used in this study is compared
to the Beverskog and Puigdomenech data and presented in Table 1.
However, a direct comparison of the parameters is not overly use-
ful since their study did not include the Sue et al. modication to
the R-HKF model. All water properties used in constructing the
Pourbaix diagrams in this study were calculated according to the
IAPWS-IF 97 guidelines. For solid species, an activity of unity was
assumed in all Nernst equation and equilibrium constant calcula-
tions. The activity of water above the critical point was taken as
its fugacity coefcient at the indicated temperature and pressure
[22]. Below the critical point, waters activity was assumed to be
unity. The electrochemical potential on the ordinate axis of every
Pourbaix diagram in this study is relative to the standard hydrogen
electrode (zero at all temperatures). Each diagram contains two
sloping dashed lines that denote the stability of water. The lower
line corresponds to the hydrogen evolution reaction while the
upper line is the oxygen reduction reaction. Additionally, a vertical
dashed line is drawn on each diagram representing the pH of neu-
tral water at the temperature and pressure in question. This is the
operating pH for SCWRs using pure water.
To validate our approach, two diagrams were developed to
compare results with those constructed by Beverskog and Puigdo-
menech at 300 C and 10 MPa [10]. Fig. 9a is the diagram for
10 6 mol/kg while Fig. 9b is for 10 8 mol/kg. The diagram at
10 6 mol/kg compares very well with that of Beverskog and Puig-
domenech with the stability region of bunsenite ending at slightly
more acidic and alkaline pHs in the current study. As previously
mentioned, there were differences in the choice of species included
between the two studies; however, the regions of immunity, pas-
sivity, and corrosion are nearly the same for both diagrams.
Fig. 9b reveals differences between the two studies. At 10 8 mol/
kg, the current work reveals a stability region for NiOH+ between
the Ni2+ and NiO regions that is not present in the earlier work. It
should be noted that their region of Ni2+ extended further and thus
the overall thermodynamic areas of corrosion, immunity, and
passivity were roughly the same. The differences between the dia-
grams can be attributed to the tting optimization of the HKF
parameters and the incorporation of the Sue et al. modication into
the present study.
With the validation completed, Pourbaix diagrams were con-
structed for conditions just below the critical point. A pressure of
25 MPa was chosen for the diagrams because it is the envisaged
operating pressure for the SCWR. For a temperature below the crit-
ical point, 350 C was chosen as being representative of the reactor
core inlet temperature. Fig. 10a is Pourbaix diagram for a dissolved
288 W.G. Cook, R.P. Olive / Corrosion Science 58 (2012) 284290

Table 1
Comparison of standard thermodynamic data for the nickel-water system. (data from Ref. [10]).

Beverskog and Puigdomenech This Study

o 1 o 1 1
Species DfG (kJ mol ) S (J mol K ) Cpo (J mol 1
K 1
) DfGo (kJ mol 1) So (J mol 1
K 1
) Cpo (J mol 1
K 1
)
Ni2+ 46.3 132.2 41 43.9 176.6 45
NiOH+ 227.2 49.7 200 227.15 140.8 280
Ni(OH)2 406.0 71 100 388.17 50.3 320
Ni(OH)3 586.5 133 300 578.28 100.6 260

species concentration of 10 6 mol/kg under these conditions. The
lower concentration of 10 8 mol/kg is depicted in Fig. 10b.
Comparing Fig. 10a to Fig. 9a (both at 10 6 mol/kg) reveals the
diagrams are similar but the bunsenite stability region is slightly
larger at the higher temperature and pressure. The same trends
are present in comparing the lower concentration (10 8 mol/kg)
diagrams. In Fig. 10b, the bunsenite region is slightly larger than
in Fig. 9b at the expense of the Ni(OH)3 and the NiOH+ region is
slightly larger as well.
To complete the study, three diagrams at different dissolved
concentrations were constructed just above the critical point at
400 C and 25 MPa. Fig. 11(ac) depict concentrations of
10 6 mol/kg, 10 8 mol/kg and 10 14 mol/kg, respectively. At a con-
centration of 10 6 mol/kg, the diagram is dominated by the immu-
nity region and passive areas with no active corrosion regions
present (Fig. 11a). Decreasing the concentration by two orders in
magnitude reveals the corrosion regions forming at low pH
(Fig. 11b). It is not until the concentration is decreased to
10 14 mol/kg that bunsenite is no longer thermodynamically sta-
ble as shown in Fig. 11c. However, while bunsenite does not appear
at these conditions, the higher oxides are still present.
5. Discussion
Nickel is quite resistant to corrosion in subcritical conditions
with neutral pH at 350 C and 25 MPa. In both Fig. 10a and b, the
immunity region for the base metal extends above the hydrogen
evolution line for all pH values from slightly below the neutral
pH of water to very alkaline pHs. This implies that nickel will
not corrode in the absence of oxygen in the system. At 350 C,
25 MPa, and 10 6 mol/kg, as depicted in Fig. 10a, nickel transitions
to the passive bunsenite region in the presence of oxygen at neu-
tral pH as depicted by the dashed vertical line. However, if the con-
centration is reduced by two orders of magnitude to 10 8 mol/kg
as shown in Fig. 10b, while nickel still transitions to the passive re-
gime as the electrochemical potential increases, a slight shift to a
lower pH results in the transition to NiOH+ instead. This has

6
Fig. 9a. Nickel Pourbaix diagram at 300 C, 10 MPa and 10 6
mol/kg. Fig. 10a. Nickel Pourbaix diagram at 350 C, 25 MPa and 10 mol/kg.

8 8
Fig. 9b. Nickel Pourbaix diagram at 300 C, 10 MPa and 10 mol/kg. Fig. 10b. Nickel Pourbaix diagram at 350 C, 25 MPa and 10 mol/kg.
 W.G. Cook, R.P. Olive / Corrosion Science 58 (2012) 284290
6 8
Fig. 11a. Nickel Pourbaix diagram at 400 C, 25 MPa and 10 mol/kg.
implications for the SCWR if it is operated at neutral pH conditions
and contains low levels of dissolved corrosion products. If the pH of
the system becomes slightly more acidic (due to impurity ingress
for example), nickel transitions to an active corrosion regime. Dia-
grams such as Fig. 10b at low concentrations are relevant to SCWR
design because of the desire to maintain low concentrations of dis-
solved corrosion products to minimize in-core deposition. The fact
that the NiO to NiOH+ transition is so close to the operating pH
indicates the possibility of rapid degradation of nickel-based alloys
if they were to be used in the highest temperature regions of the
SCWR feedtrain. Also, the fact that the nickel to bunsenite
transition is just slightly above the hydrogen evolution line has
implications for stress corrosion cracking as this phase transition
is often implicated in cracking mechanisms for nickel alloys in
the presence of dissolved oxygen or other oxidizing agents
(hydrogen peroxide for example) [23,24].
In the supercritical regime (Fig. 11ac), the observed trend is
that as the dissolved corrosion product concentration decreases,
the corrosion regions increase in size. The 10 6 mol/kg diagram
is not of much relevance to SCWR applications as the concentration
of nickel in the coolant should never be that high. Fig. 11b depicts a
situation of more interest because the coolant entering the reactor
core would have a concentration near the solubility limit in the
cold leg of 10 8 mol/kg. Under neutral water conditions, only
passive lms are stable in Fig. 11b; however, as described above,
the nickel to bunsenite transition is very close to the hydrogen line
and oxidizing conditions present in the coolant could lead to
stress-corrosion cracking of the nickel-based alloy. This is in fact
seen as a drawback of nickel-based alloy use in supercritical water
systems as many alloys (Inconel 600, 625, 690, etc.) have demon-
strated high propensity for SCC in supercritical water [2,25,26].
Fig. 11c depicts the rst order-of-magnitude decrease in
concentration where bunsenite does not form. Therefore, it is con-
cluded that the solubility of bunsenite is between 10 14 mol/kg
and 10 13 mol/kg at 400 C and 25 MPa. Dissolved corrosion prod-
uct concentrations of 10 14 mol/kg are possible because of the
sharp decline in both density and the dielectric constant of water
above the critical point as demonstrated in Figs. 4 and 5. The drop
in the dielectric constant means that ions and aqueous species typ-
ically soluble in water will no longer be so. Hence, one expects the
concentration of dissolved species to drop considerably above the
critical point. This also results in the undesirable operational con-
dition of having the corrosion products depositing along the reac-
tor core. It should be noted that the higher oxides still form at these
conditions but are separated from the immunity region by the
active corrosion areas.
It is re-emphasized that the density of water at 400 C and
25 MPa is 167 kg/m3. From Fig. 7, this is outside of the validated
289
Fig. 11b. Nickel Pourbaix diagram at 400 C, 25 MPa and 10 mol/kg.
14
Fig. 11c. Nickel Pourbaix diagram at 400 C, 25 MPa and 10 mol/kg.
range for the Sue et al. modication but is assumed in this study
to still be valid. It is hoped that future work will focus on validating
the R-HKF model to the lower densities at higher temperatures and
pressures.
As of the present, there is no solubility study of bunsenite above
the critical point. Because of this, there is no way to validate any
thermodynamic extrapolation against data obtained in the super-
critical regime. Despite this limitation, the diagrams presented here
are a rst step in developing Pourbaix diagrams in the high-subcrit-
ical and low-supercritical regimes for the nickel-water system.
6. Conclusion
Pourbaix diagrams were developed for the nickel water system
in high-subcritical and low-supercritical conditions at 25 MPa,
conditions representative of the operational conditions in a
CANDU-SCWR. The dissolved species chosen for use in this study
included the rst and third hydrolysis species, Ni(OH)+ and
Ni(OH)3 , although recent work questions their existence. From
assessment of all the relevant data, we feel there is still reason to
believe the Ni(OH)3 anion is present in high-temperature alkaline
water and have chosen to include it in this study. The Pourbaix
diagram at 350 C and 10 8 mol/kg revealed the need for a strict
water chemistry control program for SCWR operation. In the high
purity water typically used in power plants(10 8 mol/kg or less),
nickel can transition to an active corrosion region in the presence of
oxygen if the pH becomes slightly more acidic than neutral. As a re-
sult, a more alkaline chemistry may be needed to insure the passive
bunsenite region forms and is maintained. The diagrams above the
critical point at 400 C show that decreasing dissolved corrosion
290 W.G. Cook, R.P. Olive / Corrosion Science 58 (2012) 284290

product concentration results in increasing the corrosion areas
while decreasing the size of the passive regions. Bunsenite does
not form at concentrations of 10 14 mol/kg, indicating its solubility
is between 10 14 mol/kg and 10 13 mol/kg at 400 C and 25 MPa.
Acknowledgements
The authors thank the NSERC/NRCan/AECL Generation IV Tech-
nologies Program for the funding necessary to carry out this work
and useful conversations with Dave Guzonas (AECL) and Peter Tre-
maine (University of Guelph).
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