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North-Holland, Amsterdam
207
The basis for a recently initiated program on the chemical decontamination of nuclear reactor components and the possible
impact of decontamination on extended-life service is described. The incentives for extending life beyond the present 40-year
limit are discussed, and the possible aging degradation processes that may be accentuated in extended-life service are
summarized. Chemical decontamination processes for nuclear plant primary systems are reviewed with respect to their
corrosive effects on structural alloys, particularly those in the aged condition. Available experience with chemical cleaning
processes for the secondary side of pressurized water reactor (PWR) steam generators is also considered. Overall, no severe
materials corrosion problems have been found that would preclude the use of these chemical processes, but concerns are raised
with respect to corrosion-related problems that may develop during extended service.
1. Introduction
208
materials, and radiation-induced embrittlement and intergranular stress-corrosion cracking (IGSCC) of reactor internal components.
It has been recognized only relatively recently that
sensitization of stainless steels can occur after prolonged exposures (of the order of years) to temperatures
of 400C or less [7,8]. This process, known as low-temperature sensitization, generally requires an initial brief
exposure to higher temperatures (600-800C) to
nucleate the carbide particles that subsequently grow at
lower temperatures. Just as with conventional sensitization, this precipitation process depletes the grainboundary regions of Cr and leaves them more susceptible to intergranular corrosion. Low-temperature sensitization is of concern in nuclear plant coolant piping and
reactor internals operating at temperatures of
250-288C, particularly under conditions of extendedlife operation.
Another aging phenomenon, sometimes known as
475C embrittlement, can occur in ferritic and cast
duplex stainless steels. When these steels are exposed
for extended periods of time to temperatures in the
range from 300 to 500C, the Cr-rich a' phase precipitates within the ferrite, resulting in severe embrittlement. It now appears that a similar series of time-dependent precipitation phenomena may occur at light
water reactor (LWR) operating temperatures in the
ferrite phase of cast duplex stainless steels such as CF-3
and CF-8, which are used to fabricate nuclear plant
primary coolant piping as well as valve and pump
casings [9]. Again, this very slow aging process is of
greatest concern under conditions of extended-life operation.
Carbon steel piping materials, particularly in boihng
water reactors (BWRs), are subject to time-dependent
low-cycle fatigue damage caused primarily by thermal
cycling. The American Society of Mechanical Engineers
(ASME) Boiler and Pressure Vessel Code Section III
includes fatigue design curves to deal with this problem,
but these curves do not allow for the deleterious effects
of the operating environment [10]. Experimental studies
have suggested that the safety factors built into the
ASME Code design curves may be inadequate for
structural carbon and low-alloy steels in a BWR environment [11,12]. Since this environmental fatigue
damage accumulates with length of service, it is included here as an aging phenomenon. Recent work
indicates that the problem may be related to the sulfur
content of steel [13].
The embrittlement of reactor pressure vessels and
internal components due to neutron irradiation may
also be considered to be an aging phenomenon of sorts.
3. Chemical decontamination
3.1. General background
3.1.1. Nature of contaminant oxides
The radioactive contamination presents on the
surfaces of nuclear reactor cooling circuit components
consists of a complex mixed oxide made up primarily of
transition-metal spinels. The principal radionuclides
present in this film include 58C0, 6C0, SlCr, 55Fe, 59Fe,
54Mn, 63Ni, and 65Zn. Of these, 6C0 is the most
important, since it accounts for approximately 80% of
the exposure received by U.S. nuclear plant workers
during operation, inspection, and maintenance activities
[151.
The radioactive oxides can divided into two types,
"deposited" and "grown-on" [16]. The deposited oxides
are produced when non-radioactive surface oxides
formed on components upstream from the core are
released into the circulating coolant by corrosion or
erosion processes as suspended particles or dissolved
ions. Some of these particles or ions deposit or precipi-
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210
Table 1
Summary of experience with chemical decontamination of commercial nuclear power reactors in the United States
Date
Plant
Process
Components
decontaminated a
6/76
4/77
9/77
10/79
5/80
3/81
4/81
10/81
12/81
4/82
4/82
5-8/82
12/82
4/83
3-4/83
10/83
10/83
1/84
3/84
4/84
4/84
5/84
7/84
7-8/84
9/84
11/84
12/84
1984
10/85
11/85
5/86
6/86
7/86
11/86
12/86
Dresden 1
Peach Bottom 3
Peach Bottom 2
Vermont Yankee
Brunswick 2
Nine Mile Point
Brunswick I
Vermont Yankee
Brunswick 1
Peach Bottom 2
Nine Mile Point
Nine Mile Point
Hatch 1
Peach Bottom 3
Vermont Yankee
Quad Cities 2
Dresden 3
Pilgrim
Monticello
Quad Cities I
Brunswick 2
Millstone 1
Peach Bottom 2
Pilgrim
Dresden I
Dresden 2
Cooper
Quad Cities 2
Vermont Yankee
Dresden 3
Quad Cities I
Oyster Creek
Brown's Ferry 1,2,&3
Quad Cities 2
Dresden 2
NS-1 (conc.)
NS-1 (conc.)
NS-1 (cone.)
CAN-DECON
CAN-DECON
CAN-DECON
CAN-DECON
CAN-DECON
CAN-DECON
CAN-DECON
CAN-DECON
CAN-DECON
CAN-DECON
CAN-DECON
CAN-DECON
CAN-DECON
CAN-DECON
NS-1 (dilute)
LOMI
CAN-DECON
Citrox
CAN-DECON
CAN-DECON
NS-1 (dilute)
NS-1 (cone.)
NS-1 (dilute)
Citrox (dilute)
CAN-DECON
LOMI
LOMI
CAN-DECON/LOMI
LOMI
7 processes compared
LOMI
LOMI
1964
1976
9/82
11/82
4/83
8/83
8/84
5/85
1985
1/86
6-8/86
1986
Shippingport
Surry
Surry 2
Surry 2
Girma
Millstone 2
Palisades
Millstone 2
Indian Point 3
Connecticut Yankee
H.B. Robinson
Millstone 2
Turco 4502/4521
NS-1 (conc.)
CAN-DECON
LOMI
CAN-DECON
OZOX
CAN-DECON
Citrox A
LOMI
CAN-DECON
LOMI
OZOX-A
Years since
startup
16
3
3
7
4
4
4
9
5
8
12
12
7
8
10
11
12
11
13
12
8
14
10
12
24
14
10
12
13
14
14
17
9-12
14
16
PCRS
Evaporator
Channel head (cold leg)
Channel head (hot leg)
Channel heads
Channel heads
Channel heads
Channel heads
Channel heads
Channel heads
Isolated primary pump
Channel heads
7
3
9
9
13
8
13
10
9
18
15
11
Application
Primary coolant piping
Primary coolant piping
Corrosion-resistant
cladding on pressure
vessels and piping
Primary coolant piping;
valve and pump casings
Carbon steels
A285; A515, Grade 60; A570
211
4. CAN-DECON process
212
injected into the circulating coolant to achieve a concentration of approximately 0.1 wt%. The organic acids
attack and dissolve the contaminant oxide film, and the
metal ions released combine with the chelating agent.
Continuous on-line regeneration of the decontaminating
solution is accomplished by passing a side stream of
active solution through a filter and cation resin column
to remove particulate and dissolved ions. The decontamination treatment is typically performed at a
coolant temperature of 120C, although decontaminations have successfully been carried out at temperatures
from approximately 80 to 135 o C [24]. Decontamination
times normally range from 24 to 100 h [25].
The higher-Cr oxide films formed on contaminated
PWR components are not soluble in the LND-101A
reagent and its modifications, since the Cr is present in
these films as insoluble Cr 3+. An alkaline potassium
permanganate (AP) solution designated LND-104 has
therefore been developed to oxidize the Cr 3 ions to the
soluble Cr 6 state. In decontaminating a PWR, the
reducing LND-101A treatment described above is typically preceeded by or are alternated with one or more
oxidizing LND-104 treatments.
4.2. Corrosion studies on C A N - D E C O N
213
tions lowered their corrosivity, it also appeared to promote IGA. Adding 70-90 ppm ferric ion as ferric
citrate to the citric acid/oxalic a c i d / E D T A solutions
reduced I G A to insignificant levels. However, similar
ferric ion additions to citric acid/oxalic acid solutions
(no EDTA) can increase or decrease surface attack,
depending upon the initial concentration of oxalic acid
present. Citric a c i d / E D T A solutions caused negligible
damage with or without ferric ion additions. These
results thus support London Nuclear's contention that
I G A can be controlled by ferric ion additions to CANDECON LND-101A (i.e. the reformulated Rem-E-D)
or by removing the oxalic acid (LND-107). They do not
explain the enhanced IGSCC seen by General Electric
researchers in Inconels 600, 182, and X-750 exposed to
LND-101A with ferric ion additions.
Overall, the experimental corrosion data obtained on
the CAN-DECON process present a somewhat confused picture. The observed general corrosion rates appear to be acceptable for most alloys tested, although
corrosion inhibitor additions may be required to protect
carbon and low-alloy steels. Early work conducted by
General Electric clearly implicated CAN-DECON in
the I G A and IGSCC of sensitized type 304 SS, but later
London Nuclear and Ontario Hydro studies found that
these effects could be eliminated through ferric ion
additions. Recent results obtained by Chalk River on
generic solutions related to CAN-DECON LND-101A
support this finding, at least for sensitized type 304 SS.
However, additional experiments carried out by General Electric have found that the CAN-DECON treatment can accelerate crack growth in several alloys, even
with ferric ion additions. N o data are available on the
effects of CAN-DECON on alloys subjected to prior
long-term aging.
5. LOMI process
214
During the development of the LOMI decontamination process, corrosion studies were conducted by the
CEGB-Berkeley Nuclear Laboratories [36]. Alloys included EN 2 carbon steel, several stainless steels, Inconels 600 and 800, Zircaloy 2, and several stainless steel/
carbon steel weldments. Corrosion rates were found to
be negligible for all but the carbon steel, the type 410
SS, and the weldments. The type 410 SS corroded at a
rate of 0.47-0.66 # m / h , and the rate for the weldments
was less than 0.005 # m / h . The carbon steel corroded
only when the reducing capacity of the reagent had
been exhausted, i.e. when all of the V 2 ions had
oxidized to V 3+. The observed average corrosion rates
for the carbon steel over the entire 3.2-h exposure were
0.31 to 0.72/~m/h.
Additional corrosion tests of the LOMI solution
were conducted by Pacific Northwest Laboratories
(PNL) under EPRI sponsorship [37]. Prefiimed type 304
SS specimens were exposed to simulated BWR (NP,
LOMI, and N P / L O M I ) and PWR (NP, LOMI, A P / N P ,
N P / L O M I , and A P / N P / L O M I ) decontamination
treatments. Prefilmed Inconel 600 specimens were exposed only to the simulated PWR treatments. The extent of general corrosion observed was very small in all
cases. The greatest observed thickness losses for both
alloys, of the order of 0.2 /~m, were produced by the
N P / L O M I and A P / N P / L O M I processes. No differences were observed between samples not rinsed and
stored wet for 14 days after decontamination and those
rinsed and stored dry.
U-bend and CERT tests were conducted on both
alloys in both the lightly and heavily sensitized conditions after various prefilming and LOMI, N P / L O M I ,
and A P / N P / L O M I treatments. No IGA or SCC was
seen under any of the test conditions. Scanning electron
microscope (SEM) examinations of non-decontaminated, decontaminated, and post-filmed type 304
SS specimens indicated that film removal and some
minor uniform corrosion occurred in the case of the
A P / N P / L O M I treatment. However, the surfaces appeared to repassivate during post-filming. Slight pitting
was observed on one of the Inconel 600 specimens after
ondary side [38]. These corrosion products form primarily as a result of impurity ingress owing to condenser
in-leakage and can seriously damage steam generator
components. Feed train corrosion products enter the
steam generator as particulates (typically Fe and Cu
corrosion products) or as dissolved ions. In the steam
generator, they react chemically or agglomerate to form
sludge deposits on the tube surfaces and tube support
system. These deposits, in turn, impair heat transfer and
form effective sites for localized corrosion. A related
problem occurs at carbon steel tube support plates,
where the accumulation of corrosion products can cause
deformation (denting) of the steam generator tubes. In
some severe cases, these corrosion phenomena have
necessitated total replacement of steam generators.
Mechanical methods for sludge removal from PWR
steam generators have not proven entirely satisfactory,
and alternative chemical cleaning methods are of considerable interest. The Steam Generators Owners Group
(SGOG), under EPRI sponsorship, has conducted research on this problem for approximately the past 10
years [39,40]. As a result of this effort, non-proprietary
chemical solutions utilizing EDTA (diammonium salt),
i.e. E D T A - ( N H 4 ) 2 , as the active ingredient have been
developed for the removal of iron- and copper-bearing
sludge deposits.
6.2. Corrosion studies on chemical cleaning
215
216
The CAN-DECON process can produce non-uniform corrosive surface attack, including I G A and pitting, under at least some conditions in sensitized type
304 SS, sensitized Inconel 600, and tempered Inconel
X-750. In the case of sensitized type 304 SS, the observed I G A has been linked to subsequent enhanced
IGSCC. Minor pitting of sensitized Inconel 600 has also
been observed after N P / L O M I and A P / L O M I treatment. Such non-uniform attack is of concern because it
creates sites for subsequent SCC or, in extreme cases,
may of itself lead to significant penetration.
None of the tests described above was carried out on
material subjected to prior long-term aging, where lowtemperature sensitization and related precipitation phenomena may further facilitate non-uniform corrosion.
In addition, Inconel 82 and 182 weld filler metals have
not been thoroughly tests for non-uniform corrosion
effects, and no tests have been conducted on the cast
duplex stainless steels. The latter alloys are suspect
because their duplex austenite-ferrite microstructure
creates the potential for differential corrosion rates of
the two phases or accelerated attack at the phase
boundaries through galvanic effects. These concerns are
supported by corrosion studies showing that the ferritic
stainless steels typically have significantly higher general corrosion rates than the austenitic stainless steels in
decontamination solvents.
The carbon and low-alloy steels are not, in general,
susceptible to I G and SCC in LWR environments.
However, a number of carbon and low-alloy steels have
exhibited significant general corrosion rates in the
CAN-DECON LND-101A reagent and, to a lesser extent, in the NP-LOMI and AP-LOMI solutions. In
LWR systems commonly subject to chemical decontamination, these alloys, when present, are frequently clad with a more corrosion-resistant alloy. This
creates the possibility for accelerated localized corrosion
8. Summary
In summary, experimental data and experience with
the chemical decontamination and chemical cleaning of
nuclear reactor components indicate no severe materials
corrosion problems that would preclude the use of these
techniques. However, no data are available on materials
subjected to prior long-term aging, and concerns exist in
several areas, particularly with respect to aged materials. These areas of concern include: (1) possible enhanced pitting, IGA, and I(3SCC in aged alloys; (2)
non-uniform corrosion effects in aged case duplex stainless steel; (3) possible unacceptable general corrosion
rates of carbon and low-alloy steels; (4) localized corrosion at flaws in clad carbon and low-alloy steels; (5)
possible enhanced irradiation-assisted IGSCC in aged
BWR core components; and (6) the limited corrosion
data available on the high-strength Ni-based and other
alloys used for core structural applications.
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