The Synergistic Impurities Effect on the Candu

Steam Generator Corrosion

DUMITRA LUCAN1*, LUCIAN VELCIU1, GHEORGHITA JINESCU2*
1
Institute for Nuclear Research Pitesti, 1 Campului Str., 115400, Mioveni, Romania
2
Politechnica University of Bucharest,1-7 Gh. Polizu Str., 011061, Bucharest, Romania

The concentration of the impurities and deposits formation on the steam generator structural materials can
cause several types of corrosion. The failure of the steam generator as a result of tubing and tubesheet
degradation by corrosion has been a major cause of Pressurized Water Reactor (PWR) plant unavailability.
Steam generator problems have caused major economic losses in terms of lost electricity production
through forced unit out ages and, in cases of extreme damage, as additional direct cost for large-scale repair
or replacement of steam generators. Steam generator materials (especially the tubes material) are
susceptible to failure by a variety of mechanisms, the most majority of which are related to corrosion in the
presence of deposits containing aggressive impurities. The feedwater that enters the steam generators
under normal operating conditions is extremely pure, but nevertheless contains low levels (generally in the
g/l concentration range) of impurities such as iron, chloride, sulphate, silicate, etc. When water is converted
to steam, the non-volatile impurities are left behind. As a result the concentrations of different impurities in
the water from the bulk steam generator are considerably higher. Nevertheless, the concentrations of
corrosive impurities are still low and therefore the bulk water is not significantly aggressive towards steam
generator materials. The excellent performance of CANDU steam generators can be attributed, in part, to
their design and performance characteristics, which typically involve higher recirculation ratios and lower
heat fluxes and temperatures than other PWR steam generator. The purpose of this paper consists in
assessment of corrosion behavior of the tubesheet material (carbon steel SA508 class 2) at the normal
secondary circuit parameters. The testing environment was the demineralized water containing silicon
compounds, sulfates and chlorides at pH=9.5 regulated with morpholine and cyclohexylamine (All Volatile
Treatment AVT). The paper presents the results of metallographic examinations and the results of
electrochemical measurements. The experimental results allowed us to establish the contribution of the
impurities concentration on the evolution of the corrosion processes.
Keywords: steam generator tubesheet, corrosion, carbon steel SA 508 cl.2, water chemistry, impurities
concentration

Silicon compounds are abundant both in the steam

generator deposits removed from operating plants and in
the hideout return analyses performed during plant
operation.
High concentration of SiO2 in the crevices may react
with the impurities forming different polymerized species
of silicates that show retrograde solubility at the operating
temperature of steam generator, which, in turn, precipitate,
leaving free SiO2 and/or impurities in the solution.
In the case of the low fluid flow rate or at the change of
flow direction it generates the deposits containing silicon
compounds.
The effect of the silicon compounds on the behaviour of
the steam generator materials has never been considered
adequately. The information available is contradictory, and
it is possible to encounter in the literature old results that
indicate an inhibition or an aggressive effect of silicon
compounds in caustic environment. Lack of understanding
of the role played by silicon compounds may be caused by
the complexity of their chemistry which complicates
laboratory testing and interpretation of the analyses of the
deposits.
The inhibition effect of silicon compounds was shown
in the corrosion tests. Under all corrosion tests conditions,
the material of the steam generator tubesheet (SA 508

cl.2) demonstrates a corrosion resistance when compared

to its behaviour in other impurities (NaCl, Na2SO4). The
information obtained from this work was not sufficient to
appreciate if the corrosion behaviour observed in the
solutions containing silicon compounds was caused by
the incorporation of silicon in the oxide layer, making the
latter more protective or simply that it had a barrier effect
preventing contact between the solution and the surface
of the material. Supplementary it is important to consider
the significant synergistic effect of the mixture of impurities
like SiO2, NaCl, Na2SO4, [1-12]. The present work studies
the effect of silicon compound, such as silica (SiO 2),
sodium sulphate (Na2SO4) and natrium chloride (NaCl)
used together, on the corrosion susceptibility of steam
generator tubesheet material, carbon steel SA 508 cl.2.
Experimental part
The corrosion experiments included in the present paper
have been carried out by autoclaving at the specific
parameters for the secondary circuit of the CANDU steam
generator: temperature 260 oC, pressure 5.1MPa. The
preoxided samples for 10 days were from carbon steel
SA508 cl.2, the structural material of the steam generator
tubesheet, which was sectioned on the 15x20x2 mm

email: dumitra.lucan@nuclear.ro; jinescu_gheorghita@yahoo.com

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Fig.1. Aspect of the sample (a),

superficial layer (b) and surface
morphology ((c) and (d)- slight
grinding) for the SA508 sample
preoxided 10 days and then
tested 30 days in solution I

pieces. The testing solutions, with pH 9.5 regulated with

morpholine and cyclohexylamine, had the composition:
I.1g/l NaCl+1g/L Na2SO4+1g/L SiO2
II. 2g/l NaCl+2g/L Na2SO4+2g/L SiO2
III.5g/l NaCl+5g/L Na2SO4+5g/L SiO2
The testing time was 10 days, 20 days, 30 days and 40
days for every condition and the specific parameters for
the steam generator secondar y circuit. The postexamination testing has made by metallographic analysis
with the optical microscope Olympus GX71, and by
electrochemical measurements using the potentiodynamic method with the PAR 2273 overall electrochemical potentiostat galvanostat.

surface morphology it observes that the initially developed

layer influences the formation of nonuniform deposits
regarding the thickness and the composition too. There
are portions of the surface where the layer initially formed
during pre-oxidation missing and there are portions where
it formed randomly appreciable deposits whose
composition can be investigated by complementary
methods, (fig.1c). After a slight grinding of samples
exposed in the above conditions it shall observe the pitting
having a maximum diameter between 90 m and 101m,
(fig.). The smaller pits are present while, in addition, there
is a significant generalized corrosion over the entire surface
of the sample.

Results and discussions

SA 508 tested in solution containing 1g/L NaCl+1g/L
Na2SO4+1g/L SiO2 [I]
The sample of carbon steel SA 508 cl.2 preoxided for 10
days, tested 30 days in the solution I, (fig.1a), presents on
the surface a layer formed from a deposit that includes
many corrosion products and impurities from the testing
solution. The oxide layer previously formed gives the
possibility of a good adhesion, but in the same time
contributes to the development of the channels and even
to the diffusion of elements from the base alloy to the
surface layer and to the diffusion from the solution to the
base alloy. The superficial layer having a thickness of 6.5m
is shown in figure 1b. The mixed layer composed from
oxides, silicon and sodium compounds has a thickness
greater than in the previous cases and manages to maintain
the continuity despite its lack of uniformity. From the

SA 508 tested in solution containing 2g/L NaCl+2g/L

Na2SO4+2g/LSiO2 [II]
The SA 508 sample preoxided for 10 days, tested 30
days in solution II, (fig. 2a) shows the surface layer with a
non-uniform deposition notice which is based on this initial
deposition of magnetite. The formed superficial layer having
a thickness of 4 m5.5m is shown in figure 2b. The
mixed layer composed of oxides, silicon compounds and
sodium has a thickness greater than in previous cases and
manages to maintain its continuity. The surface
morphology observed that the initially formed layer
influences the formation of deposits both on the uneven
thickness and on the composition. There are portions
where the surface remains only with the layer initially
formed during pre-oxidation and portions where there are
formed randomly appreciable deposits whose composition
will be investigated by complementary methods, (fig.2c).
By investigating the thickness of the layer, there are

Fig.2. Aspect of the sample (a),

superficial layer (b) and surface
morphology ((c) and (d)- slight
grinding) for the SA508 sample
preoxided 10 days and then tested 30
days in solution II

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REV.CHIM.(Bucharest) 67No. 4 2016

Fig.3. Aspect of the sample (a),

superficial layer (b) and surface
morphology ((c) and (d)- slight grinding)
for the SA508 sample preoxided 10 days
and then tested 30 days in solution III

Fig.4. The influence of the testing

solution on the layer thickness

highlighted pits whose maximum depth is 3m. Analyzing

a sample surface exposed in the above conditions after a
slight grinding it shall reveal the presence of pitting
corrosion, consisting in pits with extremely varied
dimensions, the diameter values were between 29m and
162m, (fig..2d).
On the sample from carbon steel SA 508, preoxided for
10 days and then tested 40 days in the solution II, one can
observe a thickness layer having 4 m6 m, this initial
oxide contributing in the obtaining of the deposits with
pronounced unevenness. The surface morphology
highlights covering almost entirely with deposits containing
impurities and corrosion products. On the sample surface
were observed the presence of pits having a maximum
diameter between 195 and 215m. The intensity of pitting
corrosion is influenced in this case by the testing time and
the aggressiveness of the solution.

SA 508 tested in solution containing 5g/L NaCl+5g/L

Na2SO4+5g/L SiO2 [III]
The sample of SA 508 preoxided for 10 days and then
tested 30 days in the testing solution III, (fig.3a), shows on
the surface a layer having a non-uniform thickness,
probably due to a strong and adherent oxide layer which
was previously formed and created good conditions, but
at the same time contribute to the diffusion grooves and
even some elements of the base alloy to the surface layer.
The superficial layer developed had a thickness between
323.5m shown in figure 3b. A mixed layer composed of
oxides, silicon and sodium compounds has a thickness
greater than in previous cases and manages to maintain
the continuity. From the surface morphology it can be
observed that the initially formed layer influences the
formation of deposits with uneven thickness and
REV.CHIM.(Bucharest)67 No. 4 2016

composition. There are portions in which the surface

remains only with the layer initially formed during preoxidation and portions where are formed randomly
appreciable deposits whose composition will be
investigated by complementary methods, (fig. 3c). Pitting
corrosion is present in this case and the maximum
diameter of pits had value between 18 and 88m, (fig.3d).
For the sample of SA 508 preoxided for 10 days and then
tested 40 days in solution III one can observe an irregular
layer incorporating oxides and corrosion products having
the thickness between 3 and 50m. There are shown
similar surface morphology pitting corrosion, pits having a
maximum diameter between 18 and 28m, being isolated
or joined together.
Figure 4 9 show the influence of the type of solution
and of the testing time on the thickness of the layer
incorporating oxides and corrosion products, the maximum
diameter and density of the pits. Thus in figure 4 and figure
5 one can observe that the considerable thicknesses of
the layers are obtained when the samples were tested in
solution I and solution II for an exposure time of 20 days,
30 days and 40 days respectively. The high layer thickness
is obtained for testing in solution III for 40 days (~50m).
Pitting corrosion was assessed both by the maximum
estimated diameter of pits and by determining the
approximate number of pits per unit area (density pits),
(fig.6 and fig.7). The observed maximum diameter of pits
has a maximum value (215m) in the case of the exposure
for 40 days in solution II.
When the samples were tested in solution III for 40 days,
one can observe the highest density of pits (123 pits/mm2),
(fig.8 and fig.9).
Besides the examination by metallographic method, the
results of which were discussed above, the electro-

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Fig.5 The influence of testing time on the layer

thickness

Fig. 6. The influence of testing solution

on the pitts maximum diameter

Fig.7. The influence of testing time on the

pitts maximum diameter

Fig.8. The influence of testing solution

on the pitts density

chemical methods were also used in the pursuit of

thorough investigations of the reaction to corrosion of the
material tubesheet of the steam generator in the presence
of aqueous solutions containing chlorides, sulphates and
silicon compounds at the chemical parameters specific to
the steam generator secondary circuit. The samples with
the same initial state, preoxided for 10 days, tested the
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same period of time (30 days) in the three solutions (I, II,
III) are compared by electrochemical testing, (fig.10).
There are significant differences in the corrosion
behaviour when the test is made with the potentiodynamic
method in demineralised water adjusted to pH 9.5 in the
sense that the aggression of the testing solution determines
the increase of corrosion when repeating the operation.

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REV.CHIM.(Bucharest) 67No. 4 2016

Fig.9. The influence of testing time

on the pits density

Fig.10. Potentiodinamics curves for the SA508 sample in

demineralized water, pH=9.5 (AVT),
initially preoxided 10 days and then tested 30 days
in solution I, II and III

The corrosion intensity increases with the increasing of

the impurities concentration in the testing solution.
Conclusions
On the surface of metallic materials tested in dilute
solution of silica acid at high temperatures forms a
protective film containing crystalline corrosion products
consisting in magnetite and combinations of the
compounds of silicon mixed with iron and other elements
that make up the majority of corrosion alloys tested.
Rapid nucleation and growth of the magnetite layer in
oxidizing conditions was observed, if the temperature and
/ or silica acid concentration grow to an approximate value
of 0.33ppm.
It was established that a reaction occurs or complexing
ligand that is formed between silica acid and metal surface
formed by the reaction of ferrous ion and hydroxyl ion anode
cathodic reaction formed by playing a significant role in
the coating.
Corrosion testing was done to the carbon steel SA 508
cl.2 samples in three solutions containing different amounts
of NaCl, Na2SO4 and SiO2.
When testing the carbon steel SA 508 in the solution I,
after performing metallographic analysis is seen as
superficial layer thickness increases with exposure time
from 10 to 20 days and one can observes lower values of
thickness later 1m, 4m respectively. For 30 days of
testing, the sample of SA 508 shows on the surface a layer
consisting of a deposit which includes corrosion products
and impurities contained in the test solution, the layer
thickness being 6.5m. For 40 days form a 25.5m layer
which shows considerable nonuniformity. In this case
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characterized by localized corrosion developed pits with a

depth of 12m and a diameter of 175m.
For a sample from carbon steel SA 508, preoxidated 10
days, testated 10 days in solution II, the aspect of the
surface is influenced by the concentration of the impurities
in the testing solution. The maximum thickness of the oxide
and corrosion products layer is 2.8m. It highlights the
presence of corrosion pitting, the maximum diameter of
the pits being between 65 and 72m.
The sample SA 508 preoxided 10 days and then tested
20 days in solution II shows a surface layer having a
thickness of 24m. This is evidenced for pitting attack a
maximum size of a pit diameter equal to 198m. They are
present simultaneously on the tested surface too the
smaller pits having the diameters between 12 to 33m.
The surface of the sample tested 30 days shows a
thickness layer of 4 5.5m. Analyzing a surface sample
exposed in the above conditions we can observe the
presence of pitting corrosion, consisting in the pits with
average depth of 3m and diameter dimensions of
extremely varied between 29 and 162m. For a sample
tested 40 days, The thickness layer is 46m and the
diameters of the pits are between 195 and 215m.
For the SA 508 sample preoxided 10 days, tested 10
days in solution III, the aspect of the surface is greatly
influenced by the presence of the impurities and their
concentrations in the testing solution. The maximum
thickness of the oxide and corrosion products layer is 2
and 4.5m. It highlights the presence of corrosion pitting,
the maximum diameter of the pits being between 63 and
93m. The SA 508 sample preoxided 10 days and then
tested 20 days in solution III shows a surface layer having
a thickness of 2 17.5m. The sample tested for 30 days

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shows on the surface a layer with a thickness of 323.5m.

It highlights the presence of corrosion pitting consisting in
the pits with highly variable diameter sizes between 18m
and 88 m. For a sample tested 40 days the thickness
layer is 3 50m and diameter of the pits is between 18
and 28m.
The corrosion behaviour of the samples after they have
been exposed in solutions containing a complex
combination of impurities investigated by electrochemical
measurements, performed in aqueous medium with
specific parameters of the secondary circuit steam
generator reveals that the deposits formed after testing
allow the access of the solution to the alloy surface and
developing a significant corrosion. This is due mainly to
the synergistic effect of the three impurities present
simultaneously.
The corrosion susceptibility is in turn relates to the
impurity concentration in solution and testing time.
In general, the chlorides and the sulphates cause pitting
corrosion but where the simultaneous presence of two
compounds and SiO2 has revealed the emergence of a
particularly intense pitting corrosion characterized by depth,
maximum diameter and density pits assessed for each
test condition.
The presence of the chloride and sulphate together with
silicon compounds contributes to enhanced corrosion and
the deposition of the corrosion products on the SA 508
carbon steel surfaces.
The concentration of silicon compounds has to be
monitored carefully and strictly maintained below 1 ppm
into the steam generator because in the contrary case they
lead to the formation of hardness deposits as tough
consisting in blocking of flow orifices and local overheating
appearance.
The tests of the experimental program were made in
terms of aggressiveness high testing solutions that can be
found rarely in the steam generator after long periods of
operation, the main aim being to enable specialists to judge
this type of processes when the technical expertise of the

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components extracted from equipment operated in a NPP

is necessary.
Chemical parameters of cooling water must be
maintained at the optimal values to ensure minimum
corrosion even in the most vulnerable areas of the corrosion
such as the regions with restricted circulation in the steam
generator.
References
1. FUJITA N., MATSUURA C., ISHIGURE K., Corrosion, 45, no.11, 1989.
2.NAVAS M., GOMEZ-BRICENO D., GARCIA-MAZANO M., MCLLREE A.R.,
Corrosion NACE, July, 1999.
3.LUCAN D., FULGER M., JINESCU GHE., International Symposium on
Nuclear Energy SIEN 2003, Bucharest, 2003, CD-ROM Proceedings.
4.LUCAN D., FULGER M., SAVU GH., VELCIU L., International Congress
on Advances in Nuclear Power Plants, Cordoba, Spain, May 4-7, 2003,
CD-ROM Proceedings.
5.LUCAN D., FULGER M., SAVU Gh., VELCIU L., International Congress
on Advanced Nuclear Power Plants, May 15-19, Seoul, KOREA, 2005,
CD-ROM Proceedings.
[6]. LUCAN D., Power Plant Chemistry Journal of All Power Plant
Chemistry Areas, Germany, 8, no.6, 2006, p. 361.
7.LUCAN D., FULGER M., JINESCU GHE., Rev. Chim.(Bucharest), 58,
no.12, 2007, p.1182.
8.LUCAN D., FULGER M., JINESCU GHE., Rev. Chim.(Bucharest), 59,
no.9, 2008, p.1026.
9. LUCAN D., Nuclear Engineering and Design, 241(1), 2011, p.1007.
10.LUCAN D., FULGER M., ASTEFANESEI D., Nuclear 2010, Third Annual
International Conference on Sustainable Development through Nuclear
Research and Education, Pitesti, Romania, 2010, CD-ROM Proceedings.
11. LUCAN, D., VELCIU, L., MIHALACHE, M., DINU A., 2-nd International
Conference on Asian Nuclear Prospects, Mamallapuram, Chennai,
India, 2010, CD-ROM Proceedings.
12. LUCAN D., VELCIU L., MIHALACHE M., DINU A., FULGER M.,
ASTEFANESEI D., Journal of Nuclear Research and Development,
Institute for Nuclear Research, no.1, 2011, p.27
Manuscript received: 6.10.2015

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