MITIGATION OF CAUSTIC STRESS CORROSION CRACKING OF

STEAM GENERATOR TUBE MATERIALS

BY BLOWDOWN - A CASE STUDY

Anu Dutta, I. A. Patwegar, S.K.Chaki, V. Venkat Raj

Reactor Safety Division

Bhabha Atomic Research Centre
Trombay, Mumbai 400 085

1. INTRODUCTION

The vertical U-tube steam generators are among the most important equipment in nuclear power
plants as they form the vital link between the reactor and the turbogenerator. Over thirty five
years of operating experience of water cooled reactor has demonstrated that steam generator
tubes are susceptible to various forms of degradation. This degradation leads to failure and
outages of the power plant. A majority of these failures have been attributed to concentrated
alkali attacks in the low flow areas such as crevices in the tube to tube sheet joints, baffle plate
location and the areas of sludge deposits. Free hydroxides can be produced by improper
maintenance of phosphate chemical control in the secondary side of the steam generators and
also by the thermal decomposition of impurities present in the condenser cooling water which
may leak into the feed water through the condenser tubes. The free hydroxides concentrate in
the low flow areas. This buildup of free hydroxide in combination with residual stress leads to
caustic stress corrosion cracking. In order to mitigate caustic stress corrosion cracking of Inconel
600 tubes, the trend is to avoid phosphate dosing. Instead All Volatile Treatment (AVT) for
secondary water is used backed by full flow condensate polishing. In German installations, on
the other hand, Incoloy 800 is being used as tube material with well controlled phosphate
chemistry in the secondary water coupled with adequate blowdown to limit the concentration of
free alkali within safe limit. Condensate demineraliser, while preventing the scale forming and
alkali forming chemicals, present in the cooling water, from getting into the feed cycle can still
pose problems due to the reported leakage of sodium ions from the demineraliser beds,
especially towards the end of the exhaustion cycle. This sodium ion can give rise to free alkali in

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the boiler water. Hence, sodium hydroxide concentration is now being considered as the basis
for steam generator blowdown.

A methodology has been established for determining the blowdown requirement in order to
mitigate caustic stress corrosion cracking in the secondary side of the vertical U-tube natural
circulation steam generator. A case study has been carried out for zero solid treatment (AVT
coupled with full flow condensate polishing plant) water chemistry. Only continuous blowdown
schemes have been studied based on maximum caustic concentration permissible in the
secondary side of the steam generator. The methodology established can also be used for
deciding concentration of any other impurities.

2. DESCRIPTION OF METHODOLOGY

2.1 Effect of residual stress and caustic concentration

No ready figures are available to specify the tolerable free hydroxide limits in the steam
generator secondary side water. However, some laboratory studies on caustic corrosion cracking
of Inconel 600 and Incoloy 800 have been reported and an attempt is made here to arrive at the
limit for free hydroxide indirectly. Incoloy 800 appears to be extremely resistant to caustic stress
corrosion cracking in caustic concentration less than or equal to 40 gm/litre[1]. However, at this
caustic concentration stresses in Inconel 600 should be limited to 170 MPa. to prevent caustic
stress corrosion cracking [2]. Thus it is apparent that both residual stress and caustic
concentration are important parameters with reference to caustic stress corrosion cracking. In
Kraft Work Union (KWU) and later B&W/AECL designs, tubes of alloy 800 are used. The mill
annealing conditions vary among the manufacturers. B&W/AECL have used stress relieved (677
o
C/8 hr) tubing for their alloy 600 tubed steam generators. Some of the most recent designs using
alloy 600 tubing have thermally treated tubing (704 oC/15 hr) to improve resistance to stress
corrosion cracking.

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2. 2 Permissible level of free alkali
For establishing the level of free alkali permissible in the secondary side of steam generator, we
shall assume a concentration of 30 gm/litre only instead of reported 40 gm/litre. This is the
concentration limit for free alkali in the areas prone to caustic attack, namely, crevices and other
low flow areas. Concentration factor > 104 has been postulated [3] to occur in these areas,
consequently the sodium hydroxide that has entered the steam generator through the feed water
(at ppb level) can build up locally to several weight percent. This can give rise to stress corrosion
cracking of Inconel tubing, especially in the hot leg side of the U-tube steam generator, where
the temperature differential between the primary and secondary coolants is the greatest. For the
present study, assuming a concentration factor of 105 , the concentration limit of free hydroxides
in the bulk water in the steam generator which will form the control limit for blowdown
considerations can be arrived at.

Permissible concentration of hydroxide in crevice = 30 gm / l

Concentration factor = 105
Permissible concentration of hydroxide in bulk water = 30/ 105 gm / l = 300 ppb.

It should however be remembered that this figure of 300 ppb has been arrived at by interpolating
reported laboratory data. Therefore the concentration of free alkali in the steam generator water
should be kept much below the limit of 300 ppb by resorting to appropriate blowdown. This is
necessary in order to keep the caustic concentration below the safe level, so that in any case, it
can not exceed the above mentioned critical limit of 300 ppb.

2.3 Sodium ion leakage from the condenser demineraliser

The main source of sodium ions is the condenser demineraliser resin. The sodium leakage from
the resin is expected to result in a concentration of 0.5 ppb with a corresponding free hydroxide
concentration of 0.87 ppb (or ~1 ppb). But in practice this may at times exceed to 2 ppb due to
the malfunction of demineraliser plant. With water evaporation in steam
generator, this concentration will keep increasing in the steam generator. Blow down is resorted
to so that the concentration is kept well below 300 ppb.

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2.4 Mathematical formulation
Removal of dissolved and suspended impurities can be done in two ways viz. organized removal
of impurities which is effected by blowdown and non-organized unwanted removal which occurs
when deposits are formed on the internal surface of the equipment and as leakage losses of
coolants. Deposits can form on internal surface when the limit of solubility of a particular
substance in water has been exceeded, say on an increase of temperature (the solubility of most
substances decreases with increasing temperature) or due to an increase in the concentration of a
substance on evaporation. The general equation of mass balance of impurities can be derived
from the following consideration. A change in the quantity of impurities in the water of a plant
system with time can be written as V(dc/dt) where, V is the hold up of the plant system and dc/dt
is the time variation of concentration of impurities. This variation is determined by: (i) the
amount of impurities entering with feed water, i.e. Wf.Cf, and with blowdown return water, i.e.
Wb.Cf (it is assumed that blowdown water is purified to a quality not inferior to that of feed
water); (ii) the quantity of surface corrosion products, S.wc; (iii) the amount of impurities
removed with blowdown water, i.e. Wb.Cb and with steam, i.e. Wf.Cs and by the liberation of
impurities on the formation of deposits, i.e. S.wd.
Thus,
V(dc/dt) = Wf(Cf-Cs) + S(wc-wd) - Wb(Cb-Cf) (1)

If we assume negligible corrosion of structural material in view of excellent water chemistry

then wc = 0 . Also when Zero Solid Water Chemistry is used then wd is negligible. The rate of
blowdown as determined by the condition of absence of corrosion and deposits is

V(dc/dt) = Wf(Cf-Cs) - Wb(Cb-Cf) (2)

The dissolved and suspended solids enter the steam generator with feed water and get
concentrated as steam is generated. Finally a point may be reached beyond which operation
becomes unsatisfactory, due to exceeding of the limits on suspended solids, silica content,
alkalinity etc. To keep within the specified limits, some of the water with concentrated impurities
can be removed by blowdown. In case of phosphate treatment, phosphate is added to the coolant
to maintain the desired pH. It reacts with scale forming impurities to produce soft phosphate

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sludge . The phosphate sludge is removed, along with other impurities in the steam generator
coolant, by blowdown.

2.5 Discretization :
Equations (1) and (2), given above are applied to steam generators of nuclear power stations.
Fig. 1 shows a typical steam generator used in PWR and PHWR systems. The steam generator is
divided into two zones for the analysis, viz. tube bundle zone where impurities are concentrated
because of steam generation and steam dome where mixing of feedwater and recirculated water
takes place. Separate mass balance equations are written for these two zones and are solved
simultaneously in order to obtain the changes in caustic concentration with time.

3. CASE STUDY :

The total secondary side hold up of the steam generator considered for analysis is 26 tonnes. The
free hydroxide concentration in feedwater is 1 ppb. ZST (Zero Solid Treatment) water chemistry
is assumed so that control limit for blowdown is caustic concentration. Continuous blowdown
has been considered as it automatically keeps the steam generator water chemistry within the
desired limit. The blowdown rates considered are 0.3% and 1%. For the present case study, it is
assumed that the blowdown is started when the caustic concentration in the steam generator is
either 50 ppb or 250 ppb.

4. RESULTS

Fig. 2 shows the increase in caustic concentration when there is no blowdown. Time required to
reach 300 ppb from the initial caustic concentration of 1 ppb is approximately 13 hrs. Though
the blowdown rate is zero, water in the form of moisture which contains sodium hydroxide in the
steam leaves the steam generator. The concentration of sodium hydroxide in the moisture is
assumed to be same as that in the steam dome water.
Fig. 3 shows the change in caustic concentration with time for 0.3% and 1% blowdown. It is
clear that as the blowdown rate is increased the caustic concentration in the steam generator for
the steady state is reduced. The stabilized caustic concentration indicates that the total amount of

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sodium hydroxide entering through feedwater and blowdown make up water is same as that
leaving through blowdown and steam. The caustic concentration in the steam generator can be
maintained below 100 ppb if the blowdown rate is 1% of steam flow rate. If permissible level of
sodium hydroxide is kept above 100 ppb, then blowdown rate can be decreased, thus saving the
energy. For blowdown rate of 0.3%, the stabilized state is reached when the sodium hydroxide
concentration is little above 200 ppb.

If the initial caustic concentration in the steam generator at the start of the blowdown is 250 ppb
then the amount of sodium hydroxide leaving the steam generator through blowdown (say 1% of
steam flow rate) and moisture in steam is higher than the amount of sodium hydroxide entering
through water (sodium hydroxide concentration is 1 ppb and water flow rate is equal to steam
flow rate plus blowdown rate). As the amount of sodium hydroxide leaving the steam generator
is higher than that entering through feedwater, the caustic concentration in the steam generator
gradually decreases and approach the steady state value when the amount of sodium hydroxide
entering and leaving the steam generator is same . If the concentration of sodium hydroxide at
the beginning of the blowdown is 50 ppb, then the amount of sodium hydroxide leaving the
steam generator is lower than the amount of sodium hydroxide entering. This leads to a gradual
increase in caustic concentration in the steam generator until the steady state value is reached. As
the amount of sodium hydroxide entering the steam generator is fixed for a given feedwater
quality and flow rate, this has to match with the amount of sodium hydroxide leaving the steam
generator at the stabilized condition. Once the blowdown rate is fixed (say 1% of steam flow
rate), then matching can occur only at a particular sodium hydroxide concentration inside the
steam generator, irrespective of the sodium hydroxide concentration at the beginning of the
blowdown. However, the time required to reach the stabilized condition is dependent on the
initial caustic concentration at which blowdown starts.
It may be noted that during blowdown, apart from sodium hydroxide, other impurities will also
be simultaneously removed and remain below their critical concentration.

5. CONCLUSION :

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A methodology has been developed for determining the blowdown requirement of vertical
natural circulation steam generators used in nuclear reactors so that the appropriate sodium
hydroxide concentration in the secondary side of the steam generator can be maintained. A case
study has been carried out for ZST chemistry. The methodology developed has been applied to a
case study of continuous blowdown. However, same methodology can be employed to study
batch blowdown operation also.

NOMENCLATURE :
Cb Concentration of impurities in blow down water, g/kg
Cf Concentration of impurities in feed water, g/kg
Cs Concentration of impurities in steam, g/kg
wc Rate of liberation of corrosion products in water from unit surface of structural
material in contact with fluid, g/sq. m s
wd Rate of formation of deposits, g/sq. m s
Wb Blow down rate, Kg/s
Wf Feed flow rate, Kg/s
S Surface area, internal, of plant system, sq. m

6. REFERENCES :
1. “Tubes for PWR steam generators” by D. Vuillaume, Vallourec Industries, Power
Generation Division, Paris.
2. “Stress Corrosion Cracking of steam generator tube materials in sodium hydroxide solutions”
by R. S. Pathania and S. A. Chitty, Corrosion, Vol. 34, No. 11, Nov., 1978.
3. “Corrosion of steam generator tubing in operating PWRs “ by John. R. Weeks, Materials
Engineering Branch, Directorates of Licensing, USAEC.

steam
outlet nozzle

driers

7 steam drum
 FIG. 1 U-Tube Steam Generator

Fig 2. Caustic build up in tube bundle zone of steam generator

300
ntration in ppb

250

200 8
 Fig 3. change in caustic concentration with time

250
Caustic concentration in ppb

blow down rate = 0.3% of steam flow rate

200

150

blow down rate = 1% of steam flow rate

100

50

10 20 30 40 50
Time in hr