Beruflich Dokumente
Kultur Dokumente
Publications
NUMBER 1
1989
Book Number 481
and
The Institute of Metals
North American Publications Center
Old Post Road, Brookfield VT 05036
USA
1.-Ph. Berge
2 Corrosion Problems in Boiling Water Reactors and their Remedies
B. Rosborg
S . Leistikow
H.E. Evans
5 Corrosion Behaviour of Metallic Materials in the Cooling Gas 25
of High Temperature Reactors
V. Coen
I n 1 9 8 6 t h e EFC W o r k i n g P a r t y o n N u c l e a r
C o r r o s i o n was r e o r g a n i s e d w i t h t h e o b j e c t i v e
of c o n c e n t r a t i n g on n i n e t o p i c s o f r e l e v a n c e
t o t h e n u c l e a r power i n d u s t r y . The g r o u p o f
experts i n t h e Working P a r t y is d e d i c a t e d t o
collecting i n f o r m a t i o n on c o r r o s i o n i n t h i s
industry, t o t h e a n a l y s i s of t h e data
o b t a i n e d , and t o t r a n s f e r r i n g t h e i n f o r m a t i o n
t o s c i e n t i s t s and e n g i n e e r s i n t h e i n d u s t r y .
S u c c e s s e s i n overcoming p r o b l e m s and t h e need
f o r f u r t h e r r e s e a r c h w i t h also form p a r t of
t h e a c t i v i t i e s of t h e Working P a r t y .
T h e new s t r u c t u r e o f t h e W o r k i n g P a r t y i s
b a s e d on t h e f o l l o w i n g t o p i c s :
- P r e s s u r i s e d Water R e a c t o r s
- B o i l i n g Water R e a c t o r s
- Fuel Elements (Cladding)
- A d v a n c e d Gas R e a c t o r s
- High T e m p e r a t u r e R e a c t o r s
- L i q u i d Metal F a s t B r e e d e r s
- Fusion Reactors
- Reprocessing
- Waste Man ag em en t ( D i s p o s a l )
The f i r s t m e e t i n g o f t h e Working P a r t y
following t h e r e s t r u c t u r i n g was o n the
occasion of EUROCORR '87 i n Frankfurt.
R e p o r t s were p r e s e n t e d b y e x p e r t s o n t h e
m a j o r c o r r o s i o n p r o b l e m s i n a number of t h e s e
special topics, i.e. a 'state-of-the-art'
r e v i e w was made w i t h e m p h a s i s o n u n r e s o l v e d
problems needing a d d i t i o n a l research and
development.
T h e s e r e p o r t s were a v a i l a b l e as p r e p r i n t s
t o t h o s e a t t e n d i n g EUROCORR ' 8 7 w h e r e t h e y
were w e l l - r e c e i v e d . I t was t h e n g e n e r a l l y
recognised t h a t t h e information should be
made available to a wider readership through
a formal publication.
The p r e s e n t volume h a s t h e r e f o r e been
p r e p a r e d a n d r e p r e s e n t s Number One i n t h e
s e r i e s o f EFC p u b l i c a t i o n s .
Ph. B e r g e
Chairman of the Working Party
1 Corrosion in Pressurized Water Reactors
J. -Ph.' Berge
1
- Concentrated boric acid, even at room temperature, water in crevice locations, or t o decomposition of
can attack stainless steel pipe in the presence of trisodium phosphate used for secondary water
oxygen. Welds that are sensitized t o intergranular treatment.
corrosion are particularly susceptible t o this form
of deterioration - Localized chemical attack from acid phosphate
residues (wastage).
A further type of corrosion observed recently and
resulting in mostly transgranular cracks is currently - Buildup of magnetite in tube-to-tube support plate
under investigation in the laboratory. This form of annuli (denting) in cases where phosphate treat-
attack occurs in the presence of concentrated boric ment has been discontinued t o resolve previous
acid at temperatures of 100 t o 300' C, even though problems, giving rise t o concentrations of unbuffered
no other impurities, such as halogenated compound, acidic chloride solutions in crevices.
are present.
- Primary side stress corrosion cracking of the most
This phenomenon has been found to affect stainless widely used material, Inconel Alloy 600 containing
steels, high-nickel alloys and high-strength alloys. 70 % nickel. This phenomenon was reported in 1959
and was a subject of debate for almost 20 years
Further research, however, will be required to before the first serious consequences -cracking in
determine the exact conditions associated with this highly stressed regions of Alloy 600 tubes- were
type of corrosion and t o understand the mechanism observed
involved A relationship, however, has already been
shown t o exist between the combined presence of Most secondary side and support plate corrosion pro-
boric acid and chlorides and t h e occurence of blems can be resolved by stringent waterchemistry
cracking. control.
-
Alloy 601
C S
.I5O.OU
P
---
SijM
3.5 1.C
ASTM
B 163
Specifi- on aoiiaoa 0.50 1.1
cation 3
for EDF 050
-
A 376
-
a Desirable minimum value
- In plants built over the past ten years, the struc-
ture of Alloy 600 was improved and residual
b - Desirable maximum value stresses from bending and straightening operations
reduced by a final vacuum heat treatment for 15
The table above shows the materials of construction hours at about 700°C.
used by various vendors. The mechanical properties,
thermal characteristics and chemical composition of - In operating plants that experienced cracking in
these materials are described elsewhere ( P h Berge - regions subject t o high levels of residual stress,
J.R. Donati - Nuclear Technology - Vol. 5 5 Oct.81). such as small-radius bends and expanded tube-to-
In response t o potential corrosion risks or t o actual tubesheet joints, the former have undergone stress
corrosion problems, new materials and fabrication relieving heat treatment, while the latter have
processes have been adopted and system operating received a prestressing treatment by shot peening.
parameters adjusted accordingly, e.g. through water
chemistry control. A t the same t i m e , new causative Although the large number of cracked tubes in a
agents have been identified single component might seem t o constitute a threat
t o plant safety, examination of tube samples and
- Secondary side stress corrosion cracking, attribu- laboratory tests have shown that cracks in the roll
table typically t o a strongly alkaline environment transition at the upper surface of the tubesheet are
resulting from boiling of slightly contaminated axially oriented I t has also been demonstrated that,
2
even in the event of secondary side depressurization, cobalt-60 released into the reactor coolant system,
these cracks will result in primary-to-secondary since most hard facing alloys a r e cobalt-based
leakage before growing t o a size likely t o cause a During pickling or exposure t o borated water, cor-
significant tube failure. rosion can occur in zones depleted in chromium
Analyses are performed to determine exceptional through excessive carburizing when the hard facing
cases, where this "leak before break" criterion was deposited
might not apply because of fabrication anomalies,
and tubes are plugged accordingly as a preventive
measure. CORROSION PRODUCTS
To conclude, it seems probable that, thanks to A considerable research effort is currently being
R & D programs, f u t u r e reactors will be spared devoted t o determining optimum reactor coolant che-
the above corrosion problems, provided that mistry (injection of lithium hydroxide) when the
rigorous water chemistry control is maintained and concentration of boric acid is adjusted t o compensate
that the necessary material and design modifica- for core reactivity variations. A number of measures
tions are introduced. have been considered t o minimize the quantity of
oxides released by system components and t o avoid
As far as our understanding of the various corro- transport of corrosion products, which can become
sion mechanisms is concerned, tests in sodium activated by contact with fuel elements and accumu-
hydroxide solutions and pure w a t e r have demons- late at various locations in the system. These include
trated the significance of temperature and metallur- maintaining constant pH, selection of optimum pH,
gical structure. However, there are variations in and end-of-cycle pH adjustments. Water chemistry
behavior between the different alloys that are not specification must also cocsider the risk of damage
yet understood, and further investigation, particu- t o the fuel cladding, in the event of local boiling,
larly with respect t o grain boundary creep, will be and t o other system components.
required t o explain the effects observed and pre-
dict the behavior of other alloys. An understanding of transfer mechanisms, painsta-
king laboratory analyses, and comparison of detailed
reports from operating plants should indicate the best
BOLTING MATERIALS w a t e r chemistry specifications t o deal with this
problem. In addition, the elimination of cobalt alloys
Various types of bolting material corrosion have and a reduction of average t r a c e values of cobalt in
been observed under service conditions. structural materials should have a significant impact
on corrosion product activation problems.
- Corrosion of valve and seal assembly bolting due
t o boric acid buildup following reactor coolant
leakage.
CONCLUSION
Under these conditions, low alloyed steel bolting
is heavily corroded by boric acid, while stainless Over the 25 years since the first PWR nuclear po-
steels resist generalized corrosion But a compre- wer plants came into service, numerous corrosion
hensive study of the various materials with an problems have been encountered in various
austenitic matrix showed almost all of them t o components. Solutions t o d a t e have relied on an in-
be susceptible t o stress corrosion cracking at 300- creased understanding of the m echani s m s involved,
350' C in a 40 % solution of boric acid. This adherence t o good practice in material selection
phenomenon is very similar t o the stress corrosion and fabrication, and stringent compliance with
cracking of stainless steels in concentrated boric water chemistry specifications. Certain operators
acid discussed above. are still paying now for the failure t o observe these
principles in the past. In this domain, as in many
Here again, the corrosion mechanism is not yet others, numerous problems could have been avoided
fully understood and, in the absence of a reliable by closer collaboration between research laboratories
solution, the condition of bolting materials must and plant constructors or operators.
be monitored
B. Xosborg
The author is Manager of the Department for A prospective corrosion problem as judged from
Materials Technology at Studsvik AB, Sweden. literature references and one which relates to
plant life, is
5
-
Material-related remedies Materials low in P range, the mean load, and the frequency. Engineer-
and Si seem to have high resistance to cracking. ing codes, for example the ASME Boiler and
Pressure Vessel Code, provide means of evaluating
Environment-related remedy -
Laboratory testing any defect revealed by in-service inspection.
has shown that hydrogen water chemistry may be Within an International Cooperative Group on
favourable. Cyclic Crack Growth Kate a database has been
established, see below, which proposes new refer-
ence curves for the ASME Code as to corrosion
IGSCC IN HIGH-STRENGTH STAINLESS ALLOYS fatigue in pressure vessel steel.
3 DANKO, J C
CORROSION FATIGUE IN PRESSURE VESSEL STEEL Boiling water reactor research on pipe
cracking.
It has been stated that corrosion fatigue appears Materials Performance 24 (1985):5 p 14-17.
to be the primary subcritical crack growth mech-
anism in pressure vessel steel (9). However, no 4 HXNNINEN, H und AHO-MANTILA, I
current corrosion problems as to corrosion fatigue Umgebungsinduzierte Rissbildung bei Werkstoffen
in pressure vessel steel exist. Earlier incidents in druckfithrenden Bauteilen von Leichtwasser-
of BWR feedwater nozzle and control-rod-drive reaktoren.
return line nozzle cracking have been reported. Der Maschinenschaden 59 (1986):4 s 154-164.
These were, however, attributed to initiation of
cracks in the stainless steel cladding due to 5 Effects of Irradiation on Stress Corrosion
thermal fatigue, which then propagated a small Cracking.
distance into the pressure vessel steel until Results of the Research Assistance Task Force
they were discovered and ground away. Meeting, held June 3 and 4, 1986. EPRI NDE
Center, Charlotte, North Carolina, November
The environment has a major influence on corrosion 1986.
fatigue in pressure vessel steel at lower frequen-
cies. However, the role of oxygen in the reactor 6 EPRI 1986 Seminar on Countermeasures for Pipe
coolant is not yet clear, since high crack growth Cracking in BWRs.
rates can be obtained in both BWR and PWR simu- Palo Alto, California, November 1986.
lated environments, at least for steel with high
sulphur contents. 7 EPRI 1986 Seminar on BWR Corrosion, Chemistry,
and Radiation Control.
-
Material-related remedies Steels with low Palo Alto, California, November 1986.
sulphur contents (< 0.008 % S), and appropriate
sulphide morphologies, should be used for new 8 McILREE, A R
vessels. Degradation of high strength austenitic alloys
X-750, 718, and A-286 in nuclear power systems.
-
Stress-related remedies The corrosion fatigue Proc Inter Symp on Environmental Degradation of
crack growth rate is strongly dependent upon Materials in Nuclear Power Systems - Water
loading variables such as the stress-intensity Reactors, NACE, Houston 1984, p 838-850.
6
9 Proc Second IAEA Specialists' Meeting on
Subcritical Crack Growth.
NUREG/CP-0067, 1986.
7
,3 Zircaloy Fuel Cladding Corrosion Behaviour under Light
Water Reactor Operation and Accident Conditions
S. Leistikow
8
patches f o r m i n an o t h e r w i s e uniform-appearing - 155 b a r system pressure,
c o r r o s i o n l a y e r and reach l o c a l l y a much l a r g e r - a b a s i c a d d i t i v e ( u s u a l l y 1-2 ppm LiOH,
t h i c k n e s s t h a n t h e u n i f o r m oxide. sometimes NH40H) t o m i n i m i z e t h e c o r r o s i o n and
corrosion transpcrt o f primary c i r c u i t p l a n t
2. IN-REACTOR WATER CORROSION mater ia1s ,
- 0-1200 ppm HjBO3 as a d d i t i v e t o c o n t r o l
The i n - r e a c t o r c o r r o s i o n behavior o f Z i r c a l o y i s reactivity .
d i f f e r e n t from t h e e x - r e a c t o r behavior. Oxygen I n t h e p r i m a r y system of PWRs i n which t h e
c o n t e n t o f t h e p r i m a r y c o o l a n t i s one f a c t o r r a d i o l y t i c f o r m a t i o n of oxygen and o x i d i z i n g
which markedly i n f l u e n c e s t h e i n - p i l e behavior. r a d i c a l s i n t h e c o o l a n t i s suppressed by t h e
Under oxygenated system c o n d i t i o n s , f a s t n e u t r o n a d d i t i o n o f hydrogen t o t h e c o o l a n t , t h e
f l u x i s a c o n t r o l l i n g f a c t o r whereas under c o r r o s i o n of Z i r c a l o y was found t o be l e s s
reduced oxygen l e v e l s temperature may become more enhanced by i r r a d i a t i o n . The v i s u a l appearance o f
i m p o r t a n t . Other f a c t o r s which may a f f e c t i n - t h e i n - r e a c t o r o x i d e l a y e r s and t h e i r
r e a c t o r c o r r o s i o n i n c l u d e f u e l r o d power, c o o l a n t microstructure are very s i m i l a r t o t h e ex-reactor
c h e m i s t r y and pH, mass flow, crud, and p r i o r p r o d u c t s , i r r e s p e c t i v e of i r r a d i a t i o n and heat
oxidation h istory. f l u x conditions.
C o r r o s i o n behavior appears t o be s t r o n g l y
2.1 BOILING WATER REACTOR (BWRI SYSTEMS dependent on t h e temperature a t t h e m e t a l - o x i d e
i n t e r f a c e . Under heat f l u x c o n d i t i o n s , t h i s
BWR exposure c o n d i t i o n s a r e temperature increases as t h e o x i d e l a y e r
- 280-3OO0C, thickens, f u r t h e r increasing t h e corrosion r a t e .
- 70 b a r system pressure, The temperature r i s e across t h e o x i d e depends on
- 0.2 ppm 02 (formed by r a d i o l y s i s ) , i t s thermal c o n d u c t i v i t y , which was found t o be
- h i g h p u r i t y water, no a d d i t i v e s , between 1,5-2,4 W/m*K f o r u n i r r a d i a t e d o x i d e and
- f a s t n e u t r o n f l u x 5-I013n/cm2s. t o be reduced by -30% due t o i r r a d i a t i o n /5/.
Under these c o n d i t i o n s , enhanced c o r r o s i o n A r e v i e w o f PWR f u e l r o d c o r r o s i o n r e s u l t s
of t h e Z i r c a l o y s i s observed, which t u r n e d o u t t o /6/ comes t o t h e f o l l o w i n g main conclusions:
be m a i n l y i n f l u e n c e d by t h e g i v e n f a s t n e u t r o n I n - p i l e corrosion i s characterized ( l i k e out-
flux. p i l e c o r r o s i o n ) by a p r e - t r a n s i t i o n and a
The growth r a t e of u n i f o r m o x i d e l a y e r s i n p o s t - t r a n s i t i o n regime w i t h c u b i c and l i n e a r
a BWR environment i s r a t h e r low due t o t h e low
system temperatures and can be n e g l e c t e d
kinetics respectively .
The p o s t - t r a n s i t i o n c o r r o s i o n i s i r r a d i a t i o n -
(Fig. 2 ) . Discussions and experimental programs enhanced a t l a y e r thicknesses 2 5pm. Compared
focus on n o d u l a r c o r r o s i o n , which increases w i t h t o t h e a p p l i e d b a s i c c o r r o s i o n law ( o u t - o f -
burnup according t o a power law -(BU)o.7. The p i l e ) , t h e enhancement amounts t o a f a c t o r
a x i a l p r o f i l e m a i n l y f o l l o w s t h e burnup ( f l u x ) close t o 4 f o r stress-re1 ief-annealed
p r o f i l e . Sensitively the nodular corrosion Zircaloy-4.
depends on t h e m a t e r i a l c o n d i t i o n s . Many r e s u l t s The e f f e c t o f t h e o x i d e l a y e r on t h e a c t u a l
p o i n t t o t h e s i z e and d i s t r i b u t i o n o f second c o r r o s i o n temperature i s o f h i g h importance; a
phase i n t e r m e t a l l i c p a r t i c l e s as composed of thermal c o n d u c t i v i t y o f 1.5 W/mK i s t a k e n i n t o
Z r ( N i , Fe) and Zr(Cr, Fe) as being t h e account. Nucleate b o i l i n g has no e x t r a e f f e c t
c o n t r o l l i n g parameters o f n o d u l a r c o r r o s i o n . It on t h e c o r r o s i o n behavior.
v a r i e s f r o m r e a c t o r t o r e a c t o r . Highest n o d u l a r The i n - p i l e c o r r o s i o n r e s u l t s o f a q u a n t i t y o f
c o r r o s i o n was found on m a t e r i a l s n o t 'p-quenched i d e n t i c a l m a t e r i a l can be c h a r a c t e r i z e d by an
d u r i n g t h e i r f a b r i c a t i o n , whereas @-quenched average value and a Gaussian d i s t r i b u t i o n .
m a t e r i a l s g e n e r a l l y showed an improved behavior The a b s o l u t e o x i d e t h i c k n e s s i s dependent on
/3/. For a c t u a l p r a c t i c e i t i s concluded t h a t an burn-up, t h e power h i s t o r y and t h e thermal-
a p p r o p r i a t e @ - t r e a t m e n t i s needed and temperature h y d r a u l i c c h a r a c t e r i s t i c s of t h e p l a n t .
t r e a t m e n t s o f t h e m a t e r i a l a f t e r i t s l a s t @- I n respect t o the allowable oxide thickness
quenching should s t a y w i t h i n a range i n which t h e o f PWR f u e l c l a d d i n g h i g h power experiments
d i s t r i b u t i o n o f t h e a l l o y i n g elements i s n o t showed a l o s s o f i n t e g r i t y o f t h e o x i d e l a y e r a t
affected.The reasons f o r t h e r e a c t o r - t o - r e a c t o r a c e r t a i n thickness r e s u l t i n g i n l o c a l
v a r i a t i o n s a r e s t i l l n o t w e l l known. I n - r e a c t o r d e g r a d a t i o n o f i t s thermal c o n d u c t i v i t y and l o c a l
n o d u l a r c o r r o s i o n does n o t depend on temperature p e r f o r a t i o n o f t h e c l a d d i n g w a l l . Experience w i t h
o r may even decrease w i t h i n c r e a s i n g temperature. t h i c k o x i d e l a y e r s showed a s t r o n g i n f l u e n c e o f
Therefore, t h e r e i s no e f f e c t o f t h e h e a t f l u x t h e h e a t f l u x ( F i g . 3) on t h e a l l o w a b l e o x i d e
and t h e o x i d e l a y e r i t s e l f on t h e c o r r o s i o n t h i c k n e s s /5/: A t a heat f l u x o f 70 W/cmP, Eddy
process. Oxide breakaway, b u t no d e f e c t s caused C u r r e n t (EC) s i g n a l s were d e t e c t e d a t f u e l r o d
by n o d u l a r c o r r o s i o n ( d i s r e g a r d i n g i n t e r a c t i o n p o s i t i o n s w i t h an average o x i d e l a y e r t h i c k n e s s
w i t h c r u d ) have been found. There i s s t i l l no o f > 115 pm around t h e circumference.
l i m i t known f o r t h e a l l o w a b l e degree o f nodular P e r f o r a t i o n s and s t r o n g EC s i g n a l s occurred o n l y
c o r r o s i o n /4/. a t p o s i t i o n s w i t h > 140 pm o x i d e t h i c k n e s s on
The hydrogen p i c k - u p f r a c t i o n i s low i n a c i r c u m f e r e n t i a l average, which corresponds t o >
BWR, and t h e r e i s no i n d i c a t i o n o f an i n c r e a s e a t 160 pm a t t h e l o c a l maximum.
h i g h e r l a y e r thicknesses. For instance, a H2 I n r e s p e c t t o hydrogen up-take i t can be
c o n c e n t r a t i o n o f o n l y 50 ppm was found i n a BWR concluded /5/6/ t h a t t h e amount o f hydrogen
f u e l r o d a t a burnup o f 45 GW d / t (U) and an absorbed by t h e c l a d d i n g s l o w l y increases
average o x i d e l a y e r t h i c k n e s s o f about 60 pm. s u p e r p r o p o r t i o n a l l y a f t e r h a v i n g reached o x i d e
l a y e r t h i c k n e s s as o f more t h a n 20 pm.
2.2 PRESSURIZED WATER REACTOR (PWR) SYSTEMS P r e c i p i t a t i o n o f z i r c o n i u m h y d r i d e s occurs a t
hydrogen c o n c e n t r a t i o n s above about 200 ppm,
Most PWR operate a t s t a r t i n g a t t h e c o l d e s t p o s i t i o n s . Such p o s i t i o n s
- about 350°C max. c l a d d i n g s u r f a c e temperature, are the outer r i m o f the cladding w d l l , t h a t
- a hydrogen overpressure ( d i s s o l v e d 2-4 ppm) t o s e c t i o n o f t h e circumference w i t h l o w e s t o x i d e
reduce t h e oxygen c o n t e n t i n t h e c o o l a n t , t h i c k n e s s , a x i a l gaps i n t h e f u e l column. and
9
combinations of these /6/. At an oxide scale 3.2 TEMPERATURE-TRANSIENT OXIDATION KINETICS IN
thickness o f 100 pm the average hydrogen- STEAM
concentration in the cladding reaches 500 ppm.
Under temperature-transient conditions the
3. OXIDATION UNDER ACCIDENT CONDITIONS IN oxygen uptake was mainly determined by the
STEAM duration and the temper ture of exposure.
Therefore, in a1 1 casestf transient temperature
Zircaloy-4 oxidation under accident conditions exposure, the results have shown that under the
was verified by experiments exposing fuel chosen reduced time-at-temperature conditions,
cladding tubes to steam at temperatures derived the extent of oxidation was lower than under
from calculated 1 oss-of -coolant (LOCA) trans1ents isothermal ones. A survey on all results of the
and those peaking at even higher temperatures and applied temperature transients in comparison to
causing severe fuel damage (SFD). The experiments our isothermal data and those of Baker-Just
evaluated by means of gravimetry and (Fig. 7 ) shows that the measured weight gain,
metallography were able to describe the kinetics when plotted as function of final plateau
of mass increase (mainly by oxidation) and temperature /9/, reveals obviously considerable
formation of oxygen-containing surface layers conservatisms in the currently used licensing
(Fig. 4). The simultaneously occuring effects - practice. Various experiments were performed in
as hydrogen and heat production, change of which - after having reached the critical
cladding tube dimensions and mechanical breakaway oxide scale thickness by isothermal
properties by oxidation, besides enhanced oxidation - slow heating or cooling ramps into/or
oxidation by creep deformation - equally were out of/or by avoiding the breakaway existence
determined. range were performed. The existence range of the
breakaway effect was found to correspond to the
3.1 ISOTHERMAL OXIDATION KINETICS prediction based on the isothermal investigation.
In respect to PWR loss-of-coolant accidents the 3.3 CREEP-RUPTURE BEHAVIOR IN STEAM
isothermal oxidation of Zircaloy-4 cladding
material has been investigated in steam within a By i sothermal-isobaric creep and creep-rupture
temperature range of 600-1300°C and an exposure testing of internally pressurized tube capsules
time of 2 15 min /7/. The kinetics of oxygen (600-1300", 5 150 bar) /IO/ which were externally
uptake, ZrOpscale, and a-Zr(0)-layer growth was exposed to steam, the interaction of creep
expressed by simple rate laws: (below 900°C) of deformation and oxidation was determined. The
cubic, (above 900°C) of parabolic time and experiments were interrupted and evaluated when
exponential temperature dependences. The either different states of creep deformation were
equations, deduced from these results describe attained or rupture occurred, or minor or
with good approximation the kinetics of oxygen major wall consumption by oxidation had taken
uptake (I), the growth of the oxide (y), ( a ) , and place.
of the oxide plus a-phase double layer (<). High-
temperature oxidation tests at 1350-1600°C /8/
have been performed under the aspect of accident One result in respect to the accident behavior of
conditions leading to severe fuel damage. By a Zircaloy-4 cladding indicates the existing
suitably controlled initial exposure to steam the limitation with respect to the creep strength of
specimen temperature could be stabi 1 ized at its the one-sided highly oxidized material. By one-
desired high level so that an evaluation with sided oxidation of tube capsules (1-360 min,
respect to oxidation kinetics became feasible. 1000°C, steam) the influence of oxide scale
During the extension of the tests from 15 growth on creep strength was elaborated by creep-
min to 25 h at 600-1600°C (Fig. 5) a special rupture tests in steam. It could be shown that
study of the so-called breakaway effect could be after having surpassed a temperature dependent
performed (Fig. 6). This term stands for the loss critical extent of oxidation, the initial
of protectiveness of an oxide scale due to its metal/oxide compound-related gain turns over to a
mechanical failure and consequently the total loss of strengtK and brittle fracture. The
transition to faster oxidation, expressed (as critical values-as shown also in Fig. 8- are
mentioned earlier) by a linear rate law. given in the following Tab.1.
Breakaway oxidation - when steam in surplus was
supplied - went along with strong hydrogen pick- Table 1: Conditions Leading to Instant Brittle
up.Within the range of medium test temperatures Rupture by Creep Testing in Steam
the initial oxidation kinetics are governed by
cubic to parabolic rate laws which change towards
linear functions after having reached the State o f Pre-Oxidation Test Conditions
critical oxide layer thicknesses. Within the
-
(a + p ) Zr temperature range the effect of the
breakaway on oxidation kinetics was found to be Ipml 1%1
moderate,. At 1050°C and above parabolic kinetics
persist. The metallic matrix under consumption i 350 227 30 1000 2 28
and th6 growing tetragonal/cubic oxides are
sufficiently plastic to accomodate one another ' 200 130 17 1200 2 18
(Fig. 6), thus avoiding the build-up of the
compressive oxide growth stresses which otherwise
induce the breakaway. Considerable changes in
tube dimensions have been observed: After total Beyond the above given test conditions the
wall oxidation by double-sided steam exposure internal pressure build-up leading to instant
during 6 h at 1200-1300°C an increase of the rupture drops below that of non-preoxidized tube
outer diameter by 12%, inner diameter by 8%, and material and finally to zero.In principle, these
wall thickness by 30-60% was measured. findings are in agreement with the Emergency Core
10
Cooling Criteria (ECCC), limiting the maximum /9/ S. Leistikow, G. Schanz, Werkst. Korr. 36
cladding surface temperature to 1200°C and the (1985) 105-116, Nucl. Engg. Des. 103 (1987)
maximum percentage of wall consumption to 17%=125 65-84
Pm. 1101 S. Leistikow et al., KfK-Rep. No. 2750
(1979) 4200148-70
4. CONCLUSIONS
The potential 1 imiting parameters for Zircaloy
claddiny corrosion in conditions of extended
burn up of LWR fuel have been considered. Under
PWR operation conditions there is no strong
argument against a moderately extended burnup in
spite of an at least linear increase o f corrosion
as consequence of increasing surface temperature
at the metal-oxide interface. Under BWR operation
conditions however nodular corrosion - as a
localized corrosion phenomenon - cannot yet be
suppressed by means of a suitable material
conditioning, making extrapolations to long-time
behavior complicated.
Its allowable degree is not yet clearly defined.
Additionally, considerations of extended burn-up
should take into account - besides waterside
corrosion - the extent of cladding oxidation
during a hypothetical LOCA which is limited by the ECC-
criteria to 17% = 125 pm of wall consumption.
This limitation was verified experimentally in
respect to brittle fracture when after exkswive
preoxidation Zircaloy tube capsules were creep-
rupture tested in steam.
5. ACKNOWLEDGEMENTS
Substantial help to summarize the experience on
Zircaloy water corrosion under LWR operation
conditions was given by Mr. F. Garzarolli from
Siemens KWU Erlangen and is gratefully
acknowledged.
6. LITERATURE
/
m -
Port-Transition
[linear) No Flaking
rm
x - Number of Rods
I
Weight
Gain Black
P r e -Transition 150
(Cubic I Locus 01 Constant
A h Transition
I
I
I
I
I lo(
tt
Exposure Time __*
Assembly Burnup
2 C o r r o s i o n o f Z i r c a l o y - 2 BWR Fuel Rods,
Produced 1965-1980 ( a f t e r Garzarol li and
Stehle /5/)
12
'T?1
1I,
O t a l COnSUmPtlOn (when double-sized oxidized) I I I I
13
Zr
I i3AKER-/JUSl~~/)im
lsot hermal - [pml
3L.7
- 26.1
/
/ - 17.L
LOCA- similar
T - transient
Experiments - 8.7
1
s
T
- 12m 1:
D[OCl
1,9-3 - I
- 'Oxide Scale Thickness Iprnl!
4 6 8 1 0 20 LO 60 80 100 200 400
8 Creep-Rupture Experiments o f Z i r c a l o y - 4
Tube Capsules i n Steam a t 1000 and 1200°C
a f t e r E x t e r n a l P r e o x i d a t i o n (1-360 min,
lOOO"C, Steam)
14
4 The Oxidation of Structured Stainless Steels and Fuel
Cladding in the Advanced Gas-Cooled Reactors
H. E. Evans
Berkeley Nuclear Laboratories, in other locations. The diverse alloys used vary
Central Electricity Generating Board, considerably in microstructure, composition and,
Berkeley, Gloucestershire, GL13 9PB. in some important aspects, in oxidation behaviour.
The most onerous exposure conditions exist for
SYNOPSIS fuel cladding and particular care must be taken in
assessing its behaviour during both normal
This paper surveys the oxidation behaviour of the operation and potential fault conditions.
whole range of stainless steels used in the
Advanced Gas-cooled Reactors (AGRs). The steels COMPOSITION ANTI PRINCIPAL USES
are categorised into: 18Cr varieties containing
between 9 and 12Ni which are used for structural The compositions of the various stainless steels
items and boiler tubes; 25Cr/20Ni steel used as employed in the AGRs are outlined in Table 1.
thermal insulation foils; 20Cr/25Ni alloys used as Some of the principal components made from these,
fuel element cladding. The maximum operating together with representative service conditions
temperatures vary from -423K for the structural are given in Table 2. In all cases the steels are
steels and insulation foils to -1143K for fuel exposed to the coolant gas (CO ,)1-1 .5v/oC0
cladding. containing smaller quantities of CHb, H 2 and H 0 )
An important feature which determines per- at 4.1 MNm-2 pressure, apart from Dungeness 'B ?
formance is the metal section lost due to oxid- which operates at d M N m - 2 pressure.
ation. To assess this, proper allowance must be Dwell periods and operating temperatures vary
made for localised as well as uniform attack and, considerably. The shortest dwell is seen by the
as a result, much emphasis is placed on the fuel cladding a: a m a x i m m of 40.000 hours but
ability of the steel to form healing oxide layers. this component also experiences the highest
Under normal operating conditions, no restrictions operating temperature of -1143K. On the other
are anticipated as a result of oxidation. A hand, structural steels must remain in situ for
detailed discussion is provided of the principal the reactor lifetime (-250,000 hours) but
postulated faults within the AGR system. The experience correspondingly lower operational
extent of clad oxidation under such circumstances temperatures (typically 4 2 3 K maximum). In
is an important factor in assessing fuel pin general, the more highly alloyed steels are used
integrity. where temperatures are high and/or dwell periods
long or where component redundancy I s limited.
INTRODUCTION The steels shown in Table 1 will be
categorised into 18Cr structural steels, 25Cr
Stainless steels have an important structural role insulation foils and boiler support items and the
vithin the circuit of the Advanced Gas-cooled 20Cr fuel cladding alloys. Their oxidation
Reactors (AGRs) and find duty as fuel element behaviour will be considered in this order.
cladding, insulation foils, within the boilers and
15
OXIDATION CHARACTERISTICS OF THE 18Cr STRUCTURAL conditions, in general, carbon becomes injected
STEELS into the steel from the C02-based oxidant and
precipitates as chromium-rich carbides. However,
General Kinetics provided that the component section thickness is
large (as w i l l be the case) negligible overall
The 18Cr steels given in Table 1 are here depletion of chromiuru within the bulk steel
described as a group with characteristics which occurs, and the ability to heal this form of
can be applied to both the wrought and cast forms. attack is not impaired. By contrast, contaminants
Previous reviews of the oxidation behaviour of such as chlorine and chloride ions can have a
these steels for AGR application have been major deleterious influence. These appear to
provided in references (1-4). The range of impair the ease with which healing layers can form
kinetics exhibited by these steels at their peak and encourage widespread development of duplex
operating temperature of 923K is depicted in oxidation. A result is that enhanced oxidation
Figure 1 and is divided into three broad types. rates can continue for many thousands of hours
Type 1 kinetics are portrayed by those exposure. Because of this, much care is taken to
components, mainly machined or cast, which have exclude chlorine-containing compounds from the
excellent oxidation resistance. The oxide formed reactor circuit.
is thin, uniformly distributed and chromium rich.
Type 2 kinetics are followed by the majority of Predictions of Behaviour in Reactor
reactor steels. They are characterised by a rapid
decrease of a high initial rate of attack to a In order to demonstrate the safe and reliable
final value comparable with those found in Type 1 operation of high-temperature structural compon-
kinetics. The oxide formed during these early ents, it is necessary to calculate the expected
stages is duplex in nature (Figure 2), composed of loss of metal section at end of service life
an outer layer of magnetite and an inner iron- (250,000 hours). To do this, the weight gain
chromium spinel containing 45w/o chromium. The kinetics, such as Type 1 and 2 of Figure 1, are
decrease in rate at longer times is associated expressed in a fractional power law of time to aid
with the formation of a c h r o m i w and silicon-rich extrapolation. From the weight gain, a uniform
healing layer at the base of the spinel (Fig. 2). oxide thickness is calculated and a maximuo value
Type 3 kinetics are an accentuated form of Type 2, of metal section loss by pitting estimated by
in that a healing layer eventually reduces the multiplying this by a factor in the range 1.3-2.4.
rate of duplex oxide penetration. The extended The mean metal loss values calculated at end of
period of duplex oxidation in this case is life (250,000h) at various exposure temperatures
achieved, however, by the introduction of an are shown in Figure 4 (ref. 4 ) for steels of
excessively large metal grain size or by artific- differing grain sizes. At those temperatures,
ially depleting the surface in chromium. Such e.g. 923,973K, at which healing layers readily
Type 3 kinetics are not characteristic of form, the metal loss predicted has a value similar
production reactor material. to the alloy grain size. This is consistent with
It can be appreciated from this discussion the metallographic evidence described above (e.g.
that the feature that differentiates betveen Figure 2) which shows that healing layers can form
kinetic type is the stage or depth into the steel at interior alloy grain boundaries. At lower
at which a healing layer is formed. For a given temperatures, the expected section loss increases
intrinsic rate of duplex oxidation, the ease of as it becomes more difficult to heal the duplex
healing is determined by the rate at which oxidation. The maximum rate of section loss is
chromium and silicon ions are supplied from the dependent on alloy grain size but occurs at an
metal to the oxideimetal interface. This intermediate temperature (e.g. at 873K for >80p
transport is aided by cold w r k (diffusion short grain size but at -793K for finer grains) within
circuiting by dislocations) and by a fine grain the operating range. At temperatures of 79313 and
size (grain boundary short circuiting). It is for less there is no effect of grain size.
this reason that cold worked steels, which The values of section loss shown in Figure 4
includes all cast components, and those with fine are, generally, very much less than the component
grains tend to display Type 1 kinetics or lie section and no potential problems or restrictions
towards the lower bound of Type 2. For those have been identified. The one exception is the
examples which do not form a chromium-rich layer case of insulation foils (which are of relatively
at the surface, duplex oxidation at 923K tends to thin section) for which the use of 18Cr steels has
be stopped at the first internal grain boundary been restricted to temperatures l e s s than 673K.
(e.g. Figure 2) due to rapid supply of chromium Confidence in the validity of these predictions is
and silicon to this interface. maintained by oxidation testing, which currently
At temperatures appreciably less than 923K extends to 100,00Oh, 1.e. well in advance of
(e.g. 800K) the rate of transport within the station operation. In addition, monitoring of the
steel is always insufficient to form healing behaviour of bolted, welded and dowelled joints is
layers even at grain boundaries. Because of this, undertaken to ensure that no anomalous behaviour
the metal l o s s rate increases with decreasing arises in such interfacial situations. These and
temperature to reach a maximum at around 790 to coupon samples are located both in the reactor
830K. This effect for relatively short exposure circuit and in on-site autoclaves ( 5 ) .
periods is shown in Figure 3(4).
As a final comment, iz should be noted that OXIDATION CHARACTERISTICS OF 25Cr STEELS
increasing silicon content of the alloy within its
specification range has a beneficial effect on the These steels, specifically as AIS1 Type 310, are
oxidation resistance (1). On the other hand, used as thermal insulation foils for the reactor
removal of a protective oxide by thermal vessel in locations where they will experience
spallation or mechanicai abrasion can trigger temperatures >673K and also as boiler structural
duplex oxidation of the chromium-depleted items. The thinnest foil sections are -1OOp. A
substrate in that region. Under duplex oxidation review of the oxidation properties of these steels
16
with reference to this AGR application is given in is relatively s m a l l ( 8 p ) SO that, at the temper-
ref. (6). atures of interest, & psotective chromia layer
The oxidation behaviour at the peak operating forms very rapidly: in -10h at 1023K and d h at
temperatures of 873-923K can be represented by the 1123K (7). Prior to loading into reactor, any U 0 2
Type 1 and Type 2 kinetics of Figure 1 provided contamination on the fuelled pin is removed by
that the right-hand ordinate axis is used. It can electrolytic cleaning in an aqueous nitric acid
then be appreciated that the rate of reaction is solution. This treatment also removes the
up to a factor 10 less than the equivalent rates deleterious effects of surface roughness which may
in the 18Cr steels. A greater propensity exists have been introduced during can machining (8).
for Type 2 kinetics to be followed at 923K than at The subsequent oxidation of these steels
873K. The highly protective Type 1 behaviour is occurs under a substantially protective oxide
associated with the formation of a chromia layer, which thickens according to parabolic kinetics,
whereas Type 2 reflects duplex oxidation but not e.g. Figure 5 (9). The rate of reaction is insen-
to the same extent as in the 18Cr steels. Never- sitive to the pressure of the oxidant in the range
theless, duplex oxidation is again associated with 0.1 to 4 M ~ m - ~also
, to CO content in the range
coarser-grained materials. 1 to 01'2 and to small additions of methane and
Using similar extrapolative techniques to water vapour (7). Whilst the oxide formed is
those used in the 18Cr steels, the predicted mean chromium-rich, it also contains appreciable
section loss at 250,000h due to the uniform amounts of manganese (as a spinel), particularly
surface oxide is only 3 . 5 ~at 923K and 1 . 0 ~at near the gas interface, and is separated from the
873K. Eowever, the principal loss of section metal by a thin (-10nm) layer of amorphous silica
found in ref. (6) was due to intergranular ( 1 0 , l l ) . With increasing exposure, especially at
oxidation below the uniform oxide. Such attack 1123-1173K, the iron content of the film Increases
was found under all but the most severe form of and the weight gain kinetics depart from para-
duplex oxidation. These penetrations were found bolic. Even so, the metal section loss due to the
to be chromium rich but their rate of growth formation of the uniform oxide is relatively small
decreased very rapidly with time. Work subsequent even at these high temperatures. Thus, an
to that reported in (6), (M.G. Angell, private exposure of 40,000h at 1143K will remove only
communication) suggested that these intrusions 4lp of metal (Table 3) and this loss poses no
represented rolling defects which had subsequently significant threat to the integrity of the .-.lad of
oxidised but did not propagate. Even so, assuming 3 8 0 p wall thickness. The application of i.nese
a non-zero growth rate of these penetrations gave out-of-reactor results to the high-flux reglon of
a predicted mean section loss after 250,000h at the reactor core is supported by experimental work
923K of -15p. This value also corresponds to the which shows negligible effect of neutron ani
section lost during severe duplex oxidation for fission fragment irradiation on oxidation rates at
which the intergranular attack was absent. In temperatures of current interest, e.g. 10738 (13).
either case, the predicted losses are appreciably The protective conditions described above result
less than the thickness of even the thinnest foils from the selective oxidation of chromium and
used. silicon to form surface layers. These are the
elements which have been identified earlier as
- 20Cr FUEL CLADDING being of similar importance to the structural
stainless steels. However, a consequence is that
Oxidation under Normal Operating Conditions the metal in the vicinity of the surface oxide
becomes depleted in these elements and,
Fuel cladding in the AGRs experience operating ironically, thereby increases the susceptibility
temperatures ranging from 673 to 1143K depending of the steel to severe localised oxidation.
on axial and radial location within the reactor Such local attack occurs when the surface
core. The maximum temperature of 1143K exists on oxides fail mechanically, either through cracking
only a small fraction of pins (< 1%) and then only or spalling. A result is that the chromium-
in a localised region on the pin. Even so, such depleted metal substrate becomes exposed to the
high temperature regions W i l l be sustained for a oxidant and rapidly develops iron-rich oxides in
significant fraction of fuel life and will de- the form of a localised pit (10). The pit pene-
crease mainly with fuel reactivity. A description trates into the steel at a rate many orders of
of the oxidation behaviour of 20/25/Nb cladding magnitude faster than that of the original pro-
with emphasis on its spallation behaviour has been tective oxide and constitutes a potent mechanism
given elsewhere (7). The present paper concen- for consuming metal. Fortunately, as the pit
trates on those aspects which relate directly to penetrates into the steel, the local chromium
fuel endurance under fault conditions. concentration at its base increases, simply
The oxidation characteristics of fuel cladd- because the extent of chromium depletion under the
ing tend to be of practical significance to pin original protective oxide decreases with depth
endurance only for operating temperatures >1023K into the metal. Eventually the pitting reaction
and it ia this domain of temperature which will be reaches a depth at which the local chromium con-
considered here. Most of the emphasis w i l l be on centration is sufficient to re-form a protective
the current standard Nb-stabilised 20Crt25Ni steel chromia layer. At this stage, the pit propagation
(Table 1) although a TIN-dispersion strengthened rate drops markedly and subsequent loss of section
alternative alloy is available for the system is negligible. An example of healed pits in the
should increased operational flexibility, such as standard cladding alloy is shown in Figure 6. The
load following, be required. larger of the two pits shown extends 4 O p into
In common with the'other stainless steels, the steel and is some 1 5 0 p in breadth. These
the ease of formation of the initial protective dimensions are considerably greater than the metal
chromia layer depends on the level of cold work grain size ( 8 p ) and demonstrate that this form of
and surface grain size. Since the clad steel is high-temperature pitting is not healed easily at
used in the annealed state, surface grain size internal metal grain boundaries as was the case
becomes the pre-eminent factor. This grain size for 18Cr steels at lower temperatures. This
17
difference arises because the rate of propagation :lad Behaviour during a Depressurisation Fault
of the pit is high (-1pdhour) and is too high
even for grain boundary transport of chromium to rhe most severe depressurisation fault is
be effective over long distances. envisaged to occur as a result of a major breach
Figure 6 also serves to show that a wide In the COq bypass circuit (e.g. ref. 14). As a
distribution of pit depths can exist on any zonsequcnce the gas coolant is lost at its fastest
particular specimen. This arises principally rate and the reactor is totally depressurired in
because pits are formed at different times during 30 minutes from the onset of the fault. Fuller
the exposure and propagate to depths characteris- Idetails of the post-fault sequences can be
tic of the chromium depletion profile at that time Dbtained from ref. (14). For present purposes,
(12). Measurements on healed pits indicate that the important point to note is that significant
healing occurs at a depth into the depletion pro- c o o l i n g ability is maintained during the depress-
file corresponding to -16W/oCr. This concentra- urisation sequence and, as a consequence, the clad
tion contour penetrates the steel approximately temperature increases by only 60 deg.K from that
parabolically with time and so shows that the which existed at the start of the fault.
maximum depth of pitting will also increase para- A result of the relatively lov clad temper-
bolically. The temperature variation of this atures experienced in the AGR depressurisation is
maximum depth will reflect the temperature that negligible oxidation occurs during the fault.
dependence of the chromium-depletion profile. The importance of the extent of clad oxidation
Best estimates of this maximum depth of pitting p d i c to the fault then lies in its effect on tube
attack are given in Table 3 for an exposure of rupture behaviour of pins during the fault. It is
40,000h at various temperatures. Also shown is when the reactor is fully depressurised and clad
the l o s s of section expected from protective temperatures are relatively high that pins accumu-
uniform oxidation only. late most creep damage. This arises simply
The important feature of this comparison is because the internal gas pressure within the pin
that even though pitting attack results in a exerts a nett tensile stress in the clad wall
significant loss of section, the maximum depths which is at a maximum when the circuit pressure is
predicted still constitute only 12% of the clad lowest. Prior oxidation is assumed to reduce the
section ever. at the highest operating temperature. load-bearing section of the clad uniformly by an
Extended exposures at temperatures higher than amount equal to the maximum pit depth predicted,
this, e.g. 1173K will lead to general loss of e.g. Table 3 . For the 20/25/Nb steel (cf. Table
protectivity of the surface oxide (NB. the incor- 1)) the pin rupture life varies as (wall thick-
poration of iron into the oxide layer as mentioned ness) 5, so that, for a given pin internal
above). A consequence is the development of pressure, a 5 0 p pit in the original 3 8 0 p wall
internal oxidation in the forms of silica intru- thickness is calculated to reduce rupture life by
sions with associated carburisation. This is the 3 factor 2. Thus, even the relatively modest
temperature range in which the steel begins to levels of attack predicted prior to the fault
suffer non-selective oxidation and within which (Table 3) can have a significant influence on
its oxidation resistance rapidly declines. The behaviour during the fault. Unlike structural
current aproach is to support the operation of steels, it is not sufficient to conclude simply
fuel cladding by advance laboratory testing in that satisfactory behaviour will obtain if the
order to ensure that such a breakdown regime is fraction of section lost under normal operation is
not entered. small. The behaviour of pins during the fault
The rate of uniform oxidation of the TIN- imposes a much more severe acceptance criterion
strengthened, alternative cladding alloy is and is a principal consideration when designing
similar to that found on the Nb-stabilised steel reactor output and fuel dwell period.
( 7 ) , as shown in Figure 5. However, the alloy One advantage of the TIN-strengthened
experiences a greater extent of localised oxid- alternative cladding is that its superior creep
ation and, overall, exhibits poorer oxidation properties result in far greater margins in this
properties than the standard cladding alloy. fault, even after allowing for its inferior
Nevertheless, oxidation under normal operation oxidation behaviour during normal operation, than
poses no threat to cladding integrity. exist with the standard steel.
This description has emphasised that both
the uniform and local l o s s of section experienced Clad Behaviour during a Pressurised Fault
by fuel cladding is insufficient to promote pin
failure by oxidation during normal operation. As The most severe pressurised fault envisaged
will be seen, however, the levels of attack pre- is the unintentional withdrawal of control rods
dicted are still significfnt under fault from the reactor core leading to rapid local rises
conditions and their effect must be taken into in reactivity and clad temperature. Details of
account in safety analyses. such faults and the protection systems used in the
AGR are given in ref. (14). It is emphasised in
Behaviour under Fault Conditions that paper that a conservative absolute limit on
maximum clad temperature permitted during the
fault, for even short periods, is 1623K (1350'C)
in order that clad melting does not occur. In
Postulated faults in the AGR system are categor- addition, the high temperatures involved could
ised into: (a) depressurised faults, which produce significant clad oxidation during the
involve either a complete or partial loss of fault, in contrast to the depressurisation fault
coolant; (b) pressur!sed faults, which take place discussed above. It is necessary to demonstrate
whilst the reactor coolant is at full pressure. that not only will clad not melt but that its
Numerous different faults exist within each
category but the most severe of each will be section lost due to oxidation w i l l not prejudice
considered in this section. The details apply the ability to maintain core cooling nor to remove
specifically to the Hinkley Point 'B' reactors but fuel from the core when the fault situation has
have relevance to other AGRs also. been terminated.
18
Studies of the oxidation properties of AGR Maximum operating temperatures for both the
cladding are currently being made in laboratory to 18Cr and 25Cr steels are around 923K (65OOC). At
temperatures of 1623K (135OOC) and initial results such temperatures their oxidation behaviour is
have recently been reported (15). The main obser- dominated by the ease with which chromium and
vation at these temperatures is that protective silicon-rich protective layers can form. Cold-
oxidation by the formation of chromium and worked or fine-grained structures readily display
silicon-rich layers is difficult to maintain and protective kinetics wish little section loss. On
that the oxidation reaction quickly degenerates the other hand, annealed, large-grained
into a non-selective form of attack in which iron structures, e.g. near welds, experience relatively
is also oxidised. An example of a section of clad non-protective duplex oxidation until a chromium-
tested in the laboratory and held at 1473K rich healing layer forms at the interface between
(1200'C) for 1 hour in notionally CO2/2'/0CO is oxide and metal. At temperatures of 923 and 873K,
shown in Figure 7. The oxide morphology is this generally occurs at the first metal grain
essentially the same aa that found at this temper- boundary and, as a consequence, end of life
ature by Leistikow(l6) for No.1.4970 stainless section losses are predicted to be little more
steel (15Cr/15Ni) tested in steam and by Ishida than the metal grain size. Because of
et a1.(17) for Type 304 steel, again tested in difficulties in forming healing layers at lower
steam. temperatures, the extent of attack maximises at
The experimentally observed kinetics of some intermediate temperature. Nevertheless,
oxidation obtained isothermally are used by inte- provided that contaminants, particularly halogens,
grating numerically through the temperature/time are avoided, no operational constraints are
transient of the fault. Clad section loss is then anticipated.
calculated as a first stage in assessing the The temperature range of operation of fuel
mechanical endurance of the fuel both during and cladding is much wider than for the structural
post fault. steels and extends to 1143K (87OOC). For purposes
As a demonstration of the ability of the clad of endurance assessments it is temperature in the
to maintain integrity during such transients, a range >1023K (750'C) that is of most significance.
severe pressurised fault was simulated in a series Within this range.protective oxidation conditions
of four experiments in the Windscale AGR using develop within a few hours with little subsequent
both new and previously irradiated fuel equipped uniform loss of section. However, mechanical
with thermocouples. A typical transient used is damage or spallation of the surface oxide results
shown in Figure 8 (18) and closely resembles the in localised oxidation and pit formation. It is
worst predicted for the commercial reactors (14). this local form of attack, vhich can penetrate
After each of the experiments, fuel mechanical many grain diameters into the steel, which is of
Integrity was preserved and the stringers were significance in a depressurisation (loss of
discharged routinely. Results of the examination coolant) fault. Assessment must be made in fuel
of the extent of clad oxidation are given by design of the effect of such pits on fuel-pin
Newbigging et a1.(19). They show that total depth rupture life during the fault. The AGR core may
affected varied from 14p for experiments 1 and 3 also experience pressurised faults where
which reached 1553K (1280'C) to 4 5 p for experi- reactivity insertions can cause rapid increases in
ment 2 which reached 1603K (133OOC). There was no clad temperatures. The extent of clad oxidation
apparent systematic difference between new and under such circumstances becomes an important
irradiated cladding and the extent of oxidation is factor in assessing fuel pin integrity.
broadly as expected from the recent laboratory
tests (R.C. Lobb, private communication). ACKNOWLEDGEMENT
Laboratory tests have also been undertaken on
the TiN-strengthened alloy at temperatures This paper was prepared at Berkeley Nuclear
relevant to the pressurised fault. Results are Laboratories and is published with permission of
presently limited but indicate a rignificant the Central Electricity Generating Board.
reduction in the rate of attack compared vfth the
standard clad for temperatures in excess of -1400K REFERENCES
(15). Such behaviour is consistent with obser-
vations (e.g. 20) on other dispersion-strengthened 1. S.J. Allan, J.F. Norton and L.A. Popple,
alloys. 'Corrosion of Steels in C 0 2 ' ,
An important conclusion to be drawn from this Br. Nucl. En. SOC., London, 1974, p284.
body of work is that the severity of a pressurised
fault transient depends on the integration of time 2. J.C.P. Garrett, S.K. Lister, P.J. Nolan and
at temperature. Thus, short durations at very J.T. Crook, 'Corrosion of Steels in C02',
high temperatures, approaching clad melt, Vi11 not Br. Nuc. En. SOC., London, 1974, p.298.
prejudice pin integrity for either cladding alloy
whereas longer times at lower temperatures could 3. J.C.P. Garrett, M.G. Angel1 and A. Whittaker,
be more damaging and result in greater section 'Gas-cooled Reactors Today', Br. Nuc. En.
lops due to oxidation. Soc. London, 1982, Vo1.2, p.231
19
7. P.W.G. Simpson and H.E. Evans, 'Nuclear Fuel
Performance', Br. Nuc. En. SOC., London,
1985, p.265.
8. K.C. Triparthi and J.E. Antill, Corros. Sci.,
-
10, (1970), 273.
20
Table 1
*
Subsequently nitrided to produce a through-
thickness dispersion of titanium nitride
particles
Operating Conditions
Alloy Type -Principal Components
Max.Temp. Duration
K('C) hrs.
Table 3
3 23
5 31
6 35
9 40
11 44
1 I I
21
0 io 15 20 25
Time kh
F i g u r e 1: Schematic c u r v e s showing Types 1,2 and
3 k i n e t i c s f o r l8Cr s t e e l s and Types 1
and 2 f o r 25Cr s t e e l s ( d e r i v e d from
r e f s . 3 and 6 . )
o 650'C
x 600'C
0 560'C
b 520 'C
o 480'C
Time kh
F i g u r e 2: The f o r m a t i o n of a h e a l i n g l a y e r F i g u r e 3: Weight g a i n k i n e t i c s f o r t h e o x i d a t i o n
b e n e a t h duplex o x i d e formed on l8Cr of 18Cr s t e e l s a t v a r i o u s t e m p e r a t u r e s
s t e e l s a t 923K ( 3 ) . (4)*
2oot
0
0
a O
8
1001 e
0
5
In
e e
X
8
50- X 0
-
-
-
R1 X Grain size
9 X 0 o 5-29p-n
A x 3~44prn
20- e 45-79 pm
0
>80pm
A Cast materials
1 I I
11 12 13
1000/7 K
I I I 1 I J
700 650 600 560 520 480
r T
Figure 4 : E x t r a p o l a t e d mean m e t a l loss a f t e r
250,000 h o u r s e x p o s u r e f o r 18Cr s t e e l s
of v a r i o u s g r a i n s i z e s ( 4 ) .
Figure 5 : Growth kinetics of the protective
oxide layer on 20Cr steels. Solid
lines are the best-fit parabola (9).
Exposure period. hr
800 -
I
!i
% 700 -
L
CI
W
E, 600
I-
500
400
3001 I I I I I I i I I I
0 2 4 6 8 10 12 14 16 18 20
Time from s t a r t o f transient-mins
24
5 Corrosion Behaviour of Metallic Materials i n the Cooling
Gas of High Temperature Reactors
The authors are i n Kernforschungsanlage Jiulich, Extensive test programmes have been carried out
I n s t i t u t fib- Reaktorwerkstoffe, P.O. Box 19 13, t o investigate the corrosion behaviour of the
5170 Julich, E'RG metallic materials i n the d i f f e r e n t service
environments i n order t o obtain the data which
can be extrapolated t o the envisaged service
SYNOPSIS l i v e s of the components (more than 100,000 h ) .
CONCLUSIONS
0.4
N
L1
'\ 95OoC
'\.
E
1-1
2.0
,/
,/
0
/'
Dl 95OoC /,'
€
,/'
W
- 2 ~ 0.8- ,/'
a
-w
n
,/'
,/'
-_----
7
0
0.4-
/'. '
/--
8 5 0 OC
-
/'p b)
o.o', , I , ! [ I [ &
0 2 4 b 8 10
time 1 1000 h F i g . 3: Scale formation of 1 " E L 617 i n ( a )
Fig. 2: Change i n carbon c o n t e n t of INCONEL 617 PNP helium a t 850 W , 4000 h , (b) PNP helium a t
d u r i n g exposure i n "PNP helium" w i t h ( a ) 0.15 Pa 950 OC, 2000 h and ( c ) PNP helium w i t h 0.01 Pa
and (b) 0.01 Pa H20 H20 a t 850 OC, 4000 h .
28
0.4 ,
P,
E -0.
\
-0.2 \
W
2L O f - \-
a
' CO = 1 . 5 Pa
a
+ -0.4- 't, FCH4 = 2 Pa
3
I
0 \'
-0. b -
0 '\\.
0 500 1000 1500 2000 -0.8 I I I I I I I I
Time / h
Fig. 4: Creep curves for alloy INCONEL 617 in
different environments showing the deleterious
effect of decarburization on creep strength /5/.
29
3
5 2-
.., ...* . Carbide
depleted zone
\ IO2 = _.-*
InternaI
z 7- .
6 oxidation
-w
Q
5-- L.
aJ ,Y*
d 3- m'
.
c Ox i de
2-
.-0
In
.
.(
';., scale
..
0.
IO1 - 1
!-
0
0 br- a) -
.'
A1
2
4 1 1 1 1 I I 1 I l l l l l I
-
N 7-
€
- Carbur i zat i on
u 5-
6€7 4-
\ 3-
b 103 2 3 4 5 lo4 2 3
time / h
F i g . 7: C o r r o s i o n k i n e t i c s of INCONEL 617 a t
950 OC i n He-H20/H2/CH4/CO-0.15/50/1/10 Pa
30
6 Corrosion in Fast Breeder Reactors
H. U. Borgstedt is in the Institute of Materials the primary and secondary systems have their
and Sol id State Research, Kernforschungszentrum specific corrosion problems which are dependent
Karlsruhe, Fed. Rep. of Germany; on the temperature and flow velocity of the
L. Champeix is head of the Liquid Metals sodium, the choice of materials and their
Division, Centre d'Etudes Nuclbaires de combination in a cooling circuit and of chemical
Cadarache, France parameters.
1. INTRODUCTION 2. CORROSION CAUSED BY FLOWING SODIUM
Breeder reactors need fast neutrons for breeding Corrosion by flowing sodium is caused by the
and fission. Water is not suitable for the solubility of metals in the liquid metal or by
cooling of the fuel elements. The high density of chemical reactions of constituents of materials
energy requires a coolant with a very good with impurities in the sodium. The reactions may
thermal conductivity. Liquid sodium is such a cause the formation of more or less adherent
medium, and it is liquid between 100-1000°C at a layers or the loss of the reaction products due
pressure below four bars. Its viscosity is to solution or spalling off by the flowing
comparable to that of water and its compatibility liquid. Alloys as autenitic CrNi steels are
with several materials is fairly satisfactory. Its corroded in both ways. The combined processes of
neutron-physical properties lead to relative high dissolution and chemical reactions create typical
breeding ratio. The activation of sodium corrosion phenomena. Phenomena and corrosion
according to rates are dependent on parameters as temperature,
flow velocity, down-stream position, purity of
sodium in respect to oxygen and carbon, and the
presence of materials acting as sinks for
requires shielding of the primary cooling dissolved elements.
system. The hazards caused by sodium-water
reactions in a sodium-heated steam generator are 2.1. CORROSION OF CORE COMPONENTS AND FUEL-
separated from the activated primary system by ELEMENT CLADS
the use of a secondary sodium system transferring
the heat generated in the core via a sodium heat Since the core components - fuel-element clads,
exchanger to the steam generator or superheater wrapper tubes, distance holders, etc. - are
of the water circuit. exposed to the coolant at the highest temperature
Though there are no hazards that activated level, their materials tend to lose constituents
sodium might be exhausted into the atmosphere by to the flowing sodium. The loss of material
means of a violent sodium-water reaction, there depends on the temperature according to equation
are still problems to be solved which are due to (1) valid for a cladding tube at down-stream
the material optimization in the steam generator position zero and a sodium velocity of 3-5 m/s
and the secondary sodium circuit itself. Thus, [ll
31
18000
logloS[~rn/al= 3,845+1,5 log[Ol --
4,604. T
(1) crystals tend to diffuse into the matrix of the
structural material.
Carbon exchange seems to be of lower
Equation (1) is developed for stainless steel importance at the lower temperature level o f the
AISI 316 or 304; it has also been proved for primary tubing of a fast reactor. The diffusion
several stabilized austenitic steels 121. The being much slower does not affect very thick
loss of wall thickness S is calculated from zones of the tube walls. An effect of
weight loss measurements. The chemical attack of carburization on the creep-rupture behaviour of
sodium is, however, not uniformly distributed. A the steel AISI 304 is observed. As far as it is
part of the weight loss is caused by the only shortening the tertiary creep region, it is
selective leaching of alloying elements. Thus, a less important for the creep life time of
small loss of thickness occurs. Grain boundary components. Decarburization o f the structural
grooving indicates faster dissolution processes material may cause a slight reduction of its
at these parts of the surfaces, and the surface high-temperature strength [61. Not all steels are
layers are changed in their chemical composition sensitive to such effects. It does not seem that
due to losses of chromium, nickel, and manganese
[l-41. The chemical changes may lead to sodium of 550°C influences the fatigue life of
structural changes,/ferritic zones at the surface stainless steels, though some effects on the
and grain boundaries are created. Fig. 1 shows an fracture mode are known. The exchange of nitrogen
example of a cladding tube of steel X8 CrNiMoVNb between steels and sodium generates similar
16 13 exposed 5000 h to flowing sodium at 700°C effects as does the carbon exchange.
151. 2.3 CORROSION OF STEAM GENERATOR MATERIALS
The formation of cavities at triple grain
boundaries is observed in surface layers of some
o f the steels. Thus, one has to conclude that the Materials to be used in steam generators are the
ferrite layer does not contribute to the strength austenitic alloy X 10 NiCrAlTi 32 20 (Incoloy
of the tubes. 800) and ferritic steels as 2,25 Cr 1Mo since
The steels tend to exchange carbon with the these materials are less sensitive to local
liquid metal. At 700°C the diffusion rate of attack from the water side 171. While the
carbon in steel is fast enough to cause changes austenite has a higher Ni content than the
of carbon concentrations in significant parts of structural steels AISI 304 or AISI 316, the
the cladding tubes. While unstabilized steels are ferritic steels do not contain considerable
decarburized at this high temperature, stabilized amounts of nickel. Thus, the use of these
steels pick-up carbon from sodium. The materials can give rise for some mass transfer o f
carburization affects the whole wall thickness of nickel. Incoloy 800 acts as a source for nickel
cladding tubes as is demonstrated in Fig. 2 15;. in the sodium circuit, the ferritic steels as
The uptake of carbon influences the sinks.
microstructure, since carbides precipitate in the The steam generators are, however, the heat
region of the highest concentrations. On the sinks in the secondary sodium circuit. Thus, they
inner side, where carburization remains limited, should rather act as traps for dissolved
the 0-phase occurs after long exposure at 700°C. materials than as components to be corroded by
The changes of carbon concentrations are the flowing sodium. Incoloy 800 may partly suffer
important for the mechanical properties of the some depletion of nickel, the effects, however,
cladding tubes, carburization increases the should be very limited. It has been found that at
strength and reduces the ductility of the steels. temperatures 5 600°C the formation of internal
High carbon contents are detected by means of iffusion layers can nearly be neglected [81, the
microhardness measurements. losses of material are lower than 100 g/m2.a or
An aspect related to safety and reliability 10 pm/a [71.
of the system is the leaching of activated Though carbon transfer between ferritic
elements in corrosion processes, thus activating 2,25Cr 1Mo steel and austenitic steel 316 L is
the cooling systems. Such active isotopes are favored by thermodynamics, no loss of carbon of
51Cr, 60~0,54Mn, and 58Co. While chromium and the ferrite occurs up to a temperature of 475"C,
manganese have the tendency to migrate through which is the maximal temperature in the steam
the sodium circuits (from the core to the heat generator of the PHENIX reactor 191. Ferritic
exchanger), cobalt remains in the high- steels with higher chromium contents (up to 9 wt-
temperature region. Activation of components %) do not suffer decarburization even at higher
(pumps, heat exchanger, etc.) &r costs of the temperatures.
maintenance and the shielding of the primary
system. 2.4 CORROSION UNDER ACCIDENT CONDITIONS
2.2 CORROSION OF STRUCTURAL MATERIALS Accidents may cause a rise of the temperature in
the core. Thus, the materials of the core
The materials of the tank and primary piping of a components may be exposed to sodium at higher
fast reactor are exposed to sodium at a lower than the normal temperature level. Corrosion
level of the temperature than the core rates are known to be temperature dependent
components. Their position is down-stream to the according to equation (1). Experimental
temperature maximum at the core exit. Thus, measurements have been made up to a temperature
dissolution and loss of material does not seem to of 760°C. The equation may be used to this
be of concern for the life time of the temperature, and extrapolated up to the boiling
components. Many regions of the system are temperature of sodium (- 880°C) Heating of the
effected by material deposition. The deposits sodium to 760 resp. 880°C would increase the
cover the surfaces of the tubes, since they form corrosion rates to 0,Ol resp. 0,03 pm/d. The
dense surface layers of non-metal1 ic (oxidic or effect of such excursions of the operation
carbidic) material. Chromium is enriched in these temperature is negligible since the duration o f
layers. They also contain some crystals of such events has to be considered to be short.
metallic appearance, in which nickel and The increase in temperature may however,
manganese are enriched. The constituents of these generate high stress on the cladding tubes. This
32
high stress is not harmful if inealstic P.A. Baque, L.J. Champeix and E.T.
beformation of the material does not occur. If it Honnorat, in: Chemical Aspects of Corrosion
occurs, a limited sodium effect might be observed and Mass Transfer in Liquid Sodium, Ed.
at surface grain boundaries. The effects need Sa.A. Jansson, The Metallurgical SOC. of
some time to develop deterioration of the AIME, New York 1973, 299-316
materials, since all these deteriorations are P. Baque, L. Champeix, A. Lafon and E.
based on diffusion processes. Sermet, in: Liquid Alkali Metals, The
Accidents may increase the impurity levels British Nuclear Energy SOC., London 1973,
of the coolant by leakage, which allows water or 223-231
air to enter the system. Sodium hydroxide is 51 H.U. Borgstedt and W. Dietz, Report KfK
found to cause stress corrosion of austenitic 2516, Kernforschungszentrum Karl sruhe, 1977
steel AIS1 316 L, if the concentration of NaOH, 61 H. Huthmann, G. Menken, H.U. Borgstedt and
the temperature and the stress are high enough H. Tas, in: 2nd Internat. Conf. on Liquid
[ 101. A more detailed study has been made on the Metal Technology in Energy Production, J.M.
behaviour of Incoloy BOO in sodium-sodium Dahlke (Ed.), NTIS, Springfield, Va., 1980,
hydroxide mixtures under applied stresses[71. As Vol. 2, Chapter 19, p. 33
is indicated in Fig. 3, the occurrence of stress 71 L. Champeix, in: ALLOY 800, W. Betteridge
corrosion depenas on the hydroxide concentration et al., eds., North Holland Publ. Comp.,
and the stress level. If a certain stress at a Amsterdam 1978, 283-289
given concentration of hydroxide is exceeded, H.U. Borgstedt, G. Frees, A. Marin, in:
intergranular stress corrosion of the material is ALLOY 800, W. Betteridge et al., eds.,
observed. At a temperature below 42OoC, hydroxide North Holland Publ. Comp., Amsterdam 1978,
is not stable in contact with liquid sodium. In 291-295
the lower temperature region the effects are P. Baque, M. Besson, L. Champeix, J.R.
therefore less pronounced. Donati, C. Oberlin and P. Saint-Paul, in:
Internat, Conf. on Liquid Metal Te-hnology
3. CONCLUSIONS in Energy Production, M.H. Cooper (Ed.),
NTIS, Springfield, Va., 1976, Vol. 2, 834-
Sodium corrosion effects are small compared to 840
effects in gaseous circuits operated at high L. Champeix, P. Baque, and C. Chairat, in:
temperatures. It is, however, necessary to keep 2nd Internat. Conf. on Liquid Metal
the conditions of operation within a range such that Technology in Energy Production, J.M.
corrosion is limited to a low level to prevent an Dahlke (Ed.), NTIS, Springfield, Va., 1980,
activation of the system with long life radioactive Vol. 1, Chapter 8, p. 49
corrosion products.
Several materials are suitable for ,use
in liquid sodium reactors, among them ferritic
and austenitic and high temperature alloys with
up to 32 wt% nickel contents. The designers have,
however, to consider the mass transfer between
naterials of different compositions. The exchange
and transfer of non-metallic elements, such as
carbon or nitrogen, has to be taken into account.
Safety and reliability of sodium cooled
reactors are almost unaffected by sodium
corrosion. Leakages may occur if a component or
tube contains weak points at which stresses are
concentrated or weldments are not properly
performed. Thus, the design and construction has
to be checked thoroughly.
Mass transfer causes deposition or
precipitation of material. It has never been
observed that such precipitations have been able
to block a sodium system. Precipitated layers,
however, decrease the heat conduction and
increase the pressure drop of tubes or channels.
Ferritic surface layers, on the other hand,
interfere with magnetic fields of flow meters and
pumps.
Some more severe sodium effects may occur
after accidents which cause increases of the
temperature and the impurity contents of the
liquid metal. They may be limited by a
restriction o f the unusual parameters to short
periods of time.
REFERENCES
[l] A.W. Thorley and C. Tyzack, in: Liquid
Alkali Metals, The British Nuclear Energy
SOC., London 1983, 257-274
121 H.U. Borgstedt, in: 2nd Internat. Conf. on
Liquid Metal Technology in Energy
Production, J.M. Dahlke, Ed., NTIS,
Sorinafield. Va.. 1980. 7.1-10
33
Fig. 1
I i t
0
0 100 200 300 pm 5 10 15
Na side fuel side CONC. N a O H ( w t - % )
cladding tube w a l l
Fig. 2 : Carburization of a cladding tube of steel X8 Fig. 3 : Sensitivity t o intergranular crack corrosion of
CrNiMiNb 16 16 in sodium of 700°C after an lncoloy 800 in Na/NaOH mixtures
exposure of 5000 hrs
34
7 Corrosion Problems in Nuclear Fusion Reactors
V. Coen
nr. Coen is with the Materials Science Division one envisaged for probable utilization in the
of the Joint Research Centre of the Commission near future is the D-T reaction
of the European Communities at Ispra ( V A ) Italy.
D + T -- He4 + n t 17.58 MeV (1)
SYNOPSIS
T has a h a l f life of only 12.3 years, it is not
In order to produce Tritium by neutron found naturally in useful concentrations and
iri,;idiation in a fusion reactor the use of Li must be produced.
or of Lithium bearing material is essential. Lithium is the breeding material for T, it can
The Breeding materials most commonly considered absorb a neutron and produce T and He according
a r e liquid metals o r alloys (Li, Pb-17Li) and to the following reactions:
ceramics (Li20, L i A l O Li Si0 Li Si0
2’ 2 3’ 4 4’ 4
Li ZrO ) . Li6 + n - - + H e (2)
2 3
The coolants are H 0, the liquid metals o r
alloys (self cocle8 concepts) or He. The
structural materials envisaged comprise Li7 + n - T + He4 + n ’ (3)
austenitic stainless steels (AIS1 316, Cr-Mn
steels), ferritic or martensitic steels (HT9, If neutron multipliers as Be and Pb (n, 2n) are
1.4014). present the breeding ratio will be adequately
In this paper the main corrosion/compatibility increased.
effects are deecribed and the results obtained In a fusion reactor (exemplified in Fig. 1) a D
critically reviewed. Special emphasis is placed ard T plasma is confined at a very high
on the compatibility between liquid metal or temperature ( m y 08 K ) for a specific length of
alloy and structural materials relevant to NET time; the neutrons resulting from the fusion
(Next European Torux) . reaction breed tritium and release their energy
to the blanket producing heat that is conducted
1 . INTRODUCTION away via a coolant.
Two kinds of confinements are studied the
In miclear fusion nuclei of two light elements magnetic (Tokomaks and Mirrors) and inertial.
join together to produce a heavier nuclei with Presently fusion reactors are still at the
a ccntemporaneous emission of energy. stage of Conceptual Design Studies and the
While many fusion reactions are possible the Tokamak concept is the one most studied. This
35
is especially so in Europe, where the NET (Next ration (wall thinning, flow restrictions,
European Torus) is the main fusion device which accumulation of radioactive material, loss of
according, to the European fusion energy mechanical integrity) of the system studied,
development strategy, will follow JET (Joint and this depends on parameters peculiar to each
European Torus) and provide the basis for specific material-liquid metal system.
designing a DEMO (Demonstration Reactor). Important factors affecting the corrosion are,
In this paper we will concentrate on the for instance:
materials compatibility problems related to the
Tokamak type reactor. The first wall, as its the purity of the liquid metal (interstitial
name explicitly indicates, is the first barrier content)
interfacing with the plasma; candidate the composition and microstructure of the
structural materials f o r the first wall are: containment material
austenitic stainless steels and especially AISI operating temperature
316 (on account of the large data base on the ti r.e
fission reactor performance of this alloy) j temperature gradient in the system
ferritic (martensitic) steels such as HT-9 flow velocity.
(Fe-12Cr-lMo,VW), DIN 1.4914 (Fe-lO.SCr,MoNbV),
Fe-9Cr-1Mo and the low activation Vanadium Of course, some of these parameters, especially
based alloys. The two NET reference materials the last two, depend on the use of the liquid
are AISI 316 L and DIN 1.4914. metal. If it is used only as a tritium breeder,
In direct contact with the first wall is the it can be semi-stagnant and thus with only
blanket which has to breed tritium for the fuel small temperature gradients in the system. If
cycle, convert the fusion energy into heat and it is also used as a coolant, high flow
conduct that heat away to an energy producing velocities and l a r g e O T will be present, with
system. The blanket consists of the structure, an jncrease in the mass transfer problems.
breeder and coolant. The candidate structural The corrosion tests which are usually carried
materials are the same as for the first wall. out include :
The breeders are, of course, liquid or solid
lithium compounds. The most commonly proposed - isothermal static tests (in capsules or pots)
are for the liquids: pure Li and the eutectic to determine the basic mechanisms of reaction
Pb-17Lij for the solids: Li 0, LiAlO Li Si@ between the components of the system inclu-
2 2’ 2 3’ ding impurities and interstitialsj
Li ZrO Li ZrO
2 3’
The separate ctblants are: H 0 or He. In the - the study of corrosion and mass transfer in
2
self cooled concepts, naturally, Li and Pb-17Li non-isothermal systems. This is usually
are also considered. To a lesser degree, the carried out in loops. In the case of semi-
use of liquid Na and molten salts has also been stagnant tritium breeding blankets, thermal
envisaged. convection loops (TCL) with low flow velocity
The NET options are: (a) for the liquid and small temperature gradients are
breeder, Pb-17Li (H 0 cooled) and (b) for the sufficient while where higher velocities and
2
solid breeder concept: all the above mentioned T are required, forced convection loops (FCL)
oxides (He cooled). Most of the corrosion are necessary.
compatibility problems encountered in a fusion
reactor concern the blanket-coolant combina- 2.2. Lithium
tions. It will be attempted to examine them in
detail, concentrating on the NET priorities. It is only during a limited number of years that
It must however be stressed that, in none of litliium compatibility studies have been
the tests carried out, the severe fusion directed towards experimental conditions
reactor environement (14 MeV neutron radiation corresponding to the requirements of the fusion
and high magnetic field) is completely reactor conceptual designs. Most of the tests
reproduced. carried out previously have the disadvantage of
dubious purity of the liquid metal as wellbf
2. CORROSION CAUSED BY INTERACTION BETWEEN THE the handling procedure so that data are often
FIRST WALL/BLANKET STRUCTURAL MATERIAL AND contradictory and not easy to evaluate. Good
LIQUID BREEDING/COOLANT MATERIALS. rexiew papers exist on the pre-fusion era of
lithium technology /1,2,3,4/. Nearly all of the
2.1. General consideration of corrosion by recent studies are mainly on austenitic steels
liquid metals (Ni or Mn rich) and to a much lesser degree on
the ferritic-martensitic steels.
Corrosion of materials by liquid metals may
occur by different mechanisms: dissolution,
mass transfer due to thermal gradients, inter-
stitial element transfer and intergranular
penetration. Usually, more than one of these, Two main phenomena characteri.ze the action of
if not all of them, contribute to the deterio- Li on these steels: dissolution and grain
36
boundary attack: the relative effects depend pressure, no grain boundary penetration could
largely on the experimental conditions. Ni, Mn be observed under the same experimental condi-
and to a lesser degree Cr are dissolved from tions in which it had previously been detected
the steels. The dissolution rates in flowing Li (Fig. 6-7).
increase with an increase in the thermal As far as oxygen is concerned, it does not
gradient or flow velocity in the system. No appear to have any influence on the attack of
systematic correlation is however available. As steels! the surface oxides are reduced by Li
a result of Ni or Mn depletion a porous with formation of Li 0. No increase in disso-
2
ferritic layer is developed on the surface of lution rates has been reported.
the steels. The thickness of the ferrite layer, In Fig. 8 the main features of the corrosion
which corresponds to the depth of penetration mechanisms for the Li/austenitic stainless
when no grain boundary attack is evident, o r steel couple are schematically summarized.
the weight loss are usually used to express the
corrosion rates. 2 . 2 . 2 . Ferritic-Martensitic steels:
...........................
Nitrogen present as Li N in the Li o r dissolved
in the steel plays ad important role in the There is far less information on the mechanism
corrosion phenomenon. It provokes a grain of corrosion of these steels in lithium. In
boLndary attack and increases the dissolution static tests /15/, with pure lithium, specimens
rate of Cr. Both phenomena are linked to the of 2 l/qCr-lMo steel were decarburized whereas
formation of a Li-N-Cr compound. Grain boundary steels with higher chromium content (HT-9) did
attack was first reported /5/ in AISI 316 at not appear to be decarburized. This decarburi-
lo89 K (1-2 wt.% Lj. N) then in AISI 304 L zation phenomenon is strictly dependent on the
3
( 2 wt.% Li N) /6-7/ and in nitrogen saturated exposure temperature and on heat treatment, so
364 L. Tie nucleation of grain boundary that it can certainly be minimized. In tests
cartides preceding penetration was suggested. carried out in non-isothermal, flowing lithium
It was shown /8/ by microanalytical techniques it would seem /16/ that after a relatively
that 316 exposed to Li, containing nitrogen at large weight loss (associated vith Cr
unit activity at 923 K was subject to depletion) during the initial 500 h exposure to
Substantial Li penetration along grain I,i the weight l o s s in HT-9 and Fe-9Cr-lMo
boundaries, (Fig. 2 ) and the formation of a steels follows a linear behaviour with time and
surface corrosion product of the type Li CrN yields constant dissolution rates; the
9 5
was postulated. By studying the grain boundary dissolution rates for HT-9 and Fe-9Cr-1Mo
penetration (Fig. 3-4) of Li in nitrogen alloyed steels increase by a factor of 10 when the
Cr-Mn steels /9-10-11/ it was clearly shown temperature increases from 673 to 823 K, and an
that at. 873 K the M C carbides, formed prior increase in nitrogen in Li increases the
23 6
to the Li penetration, rearrange and change dissolution rates. This, again, may be linked
their composition in the presence of Li. to the formation of the Li-Cr-N compound.
Coherent twin boundaries (in which carbides are Weight change measurements indicate for 12 Cr -
not precipitated) are not penetrated by Li The 1 Mo VW steel, exposed to thermally convective
presence of a Li-Cr-N compound corresponding Li between 873 and 733 K for 7000 h, a dissolu-
probably to Li CrN has also been evidenced in tion rate of 3.0 mg/m .h.
the grain bounr?aric?s by the SEM technique (Fig. In the temperature range 77$-623 K the weight
5 ) . As far as dissolution is concerned it is loss was only 0.7 mg/m .h. This large
reported /l5/ that in an FCL (Forced Conveztion difference is explained /17/ by assuming that
Loop) greater Cr depletion and weight loss were weight changes reflect the competition between
encountered in 316 with Li containing 250 ppm N the following phenomena: dissolution/deposition
than in Li with e100 ppm N. On the other hand, of steel constituent, soluble reaction product
it seems that in a TCL (Thermal Convection formation and soluble surface reaction
Loop) /3/ similar changes in Nitrogen content products. At higher temperatures thermal
cause no effect on corrosion. It must be gradient elemental transfer would tend to
stressed that the experimental conditions may dominate such that a relatively large net
have been different (possibility of N weight l o s s might result at T max. Such tempera-
gettering?). It is clear that additional data tures may be above the temperature range of
are required to establish the actual effect of stability of the surface product or
nitrogen on corrosion and mass transfer in preferential dissolution of Cr at this higher
flowing Li systems. Since the intergranular temperature may significantly reduce its
penetration of Li and the formation of Li CrN activity at the surface. As the temperature
is apparently linked to carbide precipita?ion,
5
range of a loop experiment is lowered the
it is possible that in the temperature range in relative importance of thermal gradient mass
which no carbide precipitation occurs for transfer decreases and corrosion product
relatively long times this attack could be reaction can make a large contribution to the
avoided. It has been shown /l4/ that when the measured net weight changes and radically
carbon content of the steel was lowered, by change the slope of the mass change profile.
working in presence of a hydrogen partial
37
particularly interesting as an alternative to
liquid Li /24/. The Li-Pb phase diagram is
------- reported in Fig. 10. The immediately obvious
Although the experimental data are not advantage is the fact that breeder and neutron
sufficient to clarify the influence of the multiplier are combined in one and the same
various system parameters on the phenomena material. Moreover, the eutectic does not show
involved in the corrosion of steels by Li, a vigorous chemical reactions with air or water
qualitative assessment of the operating which is an important criterion in the choice
temperature limits can be made by comparing of breeder materials. Only a few data exist on
data obtained in the different laboratories the physical acd chemical properties of Pb-17Li
that have carried out experiments in flowing as well as on the corrosion and mass transfer
Li. Fig. 9 is a simplified version of the curve behaviour of this alloy. The main reason is
presented in /18/ to which data from C.E.N. Mol that up to now it had no commercial application
/l9/ have been added and corresponds to an (it is not even found in commerce). Most of the
Arrhenius plot of corrosion rates (sound metal studies carried out in the recent years related
l o s s ) for types 316 (including 304 values) and to the structural material-breeding/coolant
HT-9 in flowing Li. compatibility concern mainly AISI 316. In
It is clearly apparent that in FCL (representa- Europe the experiments were ca.rried out in
tive of Li used also as the coolant) the static and TCL conditions /19,25,26,27,28/
dissolution rates for type 316 are an order of while in the U.S.A. an FCL was also operated
magnitude greater than in TCL systems (represen- and some data on the behaviour of ferritic
tative of Li used as breeding blanket only). steels (HT-9, Fe-9Cr-1Mo) are also available
Dissolution rates for the Ferritic steel HT-9 /18,29,30,31/. The corrosion mechanism of AISI
in TCL and FCL are identical and similar to 316 316 in Pb-17Li is characterized by a strong Ni
in TCL. depletion and penetration of Pb and Li into the
If the limits of 5 um/y loss rates associated matrix (Fig. 11) /25/. A porous ferrite layer
with radioactive transport and 20 um/y associa- is developed and in some cases it is very weak
ted with plugging are accepted /18/, it would and spalls either during exposure to the
appear that in circulating Li AISI 316 could be lithium lead eutectic (especially in FCL tests)
used in the range 723-773 K, while if Li is o r during cleaning of the specimens. It is very
semi-stagnant it could be used in the tempera- difficult to remove the residual Pb-17Li from
ture range 823-873 K. This upper temperature the corrosion samples. The different techniques
range would apply to HT-9 in both cases. adopted include dissolution in Li o r Hg or
h’a+NH followed by washing in alcohol and water.
3
As far as the effects of interstitial, nitrogen
2 . 2 . 4 . Mechanical Property Degradation:
______-_________---------------
an.d oxygen on the properties of Pb-17Li are
Only limited information exists on the effect concerned, j . t has been shown /32/ that while
of Li on the mechanical properties of the former is absolutely inocuous, the latter
austenitic steels and even less on the is quite deleterious: it enhances the corrosion
ferritics. Most of the data come from static of AISI 316 and is able to extract Li from the
experiments. It would seem that Liquid Metal eutectic alloy. The results for nitrogen were
Emhrittlement (L.M.E.) does not occur in the Li confirmed by a study /33/ in which it is repor-
environment /20-21/ and that for austenitic ted that 316 steel is corroded by nitrogen in
stainless steels tensile and creep properties Pb-17Li only at pressures above 10l2Pa.
are not altered by the Li environment /20-22- The mechanism of corrosion of AISI 316 in Pb-
23/. The creep strength of austenitic and 17Li in presence of oxygen was studied by
ferritic steels, in flowing Li, is lower than carrying o7.it tests with and without added
in static Li o r argon /16/. This is due to the oxygen //34/.
formation of a weak ferrite layer on the These experiments have shown that oxygen
austenitic steels and decarburization of enhances the corrosion of 316 steel by
ferritic steels. While fatigue life is not increasing the depth of the ferritic corrosion
influenced by pure Li it is significantly layer (Fig. 12) and the extent of chromium
reduced in flowing Li containing<lOOO p.p.m. N depletion within the layer. Tests using lithium
/18/ on account of intergranular attack of the lead alloys with compositions between Pb-17Li
material. Tests in flowing Li, of known purity and Pb-11Li and in pure Pb showed no change in
are necessary to establish a clear relation the depth of the ferritic zone with composition
between corrosion and degradation of mechanical of the alloys but a significant increase for
properties. pure lead. Measurements of the solubility of
nickel in Pb-17Li and Pb-1OLi showed the
2.3. Pb-17Li sclubility to be similar for both compositions
and to be much less than that previously
It is only since about 1980 that the lithium measured in pure Pb. The solubility may be
lead eutectic containing 87 at% Pb and 17 at% expressed by the equations:
Li (referred to herein as Pb-17Li) has appeared
38
981.2 potential structure or cladding material. The
log S(wppm)
10
= 4.832 - -for Pb-17Li thermodynamic stability of the oxides
T(K) considered: Li 0, LiAlO , Li Si0 , Li Si0
Li ZrO indicate 2 that tiey s ? o u l d not 4react
4'
1162
logloS (wppm) = 5.148 - -
T(K)
for Pb-1OLi
2
direct3y with Fe-Cr alloys. The main problem
concerns the impurities present in these
materials mainly LiOH o r Li CO introduced
The increase in ferrite zone formation, in the during fabrication or resulting 2from3 oxygen and
presence of oxygen, cannot, therefore, be due hydrogen partial pressures of the environmental
to increased Ni solubility caused by a change atmosphere. Tests carried out in closed systems
in composition of the alloy. A study of the at 873-1000 K /37,38,39/ have revealed that
reactions of oxides with Pb-17Li has shown that Li 0 is more reactive with steels than LiAlO
Cr may interact with oxygen to form the ternary 2 2'
Li Si0 The reaction products detected were
oxide LiCr0 Liii-0 3 ' and LiFeCrO More recently
2'
In contrast to Li no grain boundary attack has was s own that the 4'
/40/ 'it Li5Fe06! reaction of Li 0
been evidenced in presence of Pb-17Li. with AISI 316 in the temperature range 773-953
In Fig. 13 the main features of the corrosion K could be avoided after scrupulous re-purifi-
mechanisms for the couple Pb-l7Li/austenitic cation of Li 0 with Li to remove all traces of
steels are schematically summarized. 2
LjOH. Lately /41/, tests were carried out to
Notwithstanding the paucity of the available investigate (always in a closed system) the
results an Arrhenius plot of the up to date compatibility of various Li based oxides with
corrosion rates of AISI 316 (304) is presented AISI 316 and the ferritic-martensitic steel
in Fig. 14. Owing to the uncertainty of the 1.4914, in the temperature range 773-1073 K for
weight changes. The values taken into considera- times up to 500 h, in the presence of various
tion are those where the thickness of the amounts of H 0 o r NiO as initial contaminants.
ferritic layer is mentioned; where more than 2
It appears that, in addition to temperature and
one value is given the highest has been taken. time, the chemical interaction between solid
breeder materials and the Cr-Ni steels depend
2.3.1. Operating Limits for Steels in Pb-17Li on the moisture content o r oxygen partial
......................................
pressure in the system.
If, as in the case for Li the limits of 5 um/y The extent of cladding attack caused by NiO is
loss associated with radioactive transport/ and comparable to that caused by H 0; it is thus
2
20 um/y associated with plugging are accepted stated that "the formation of LiOH does not
/ operating limits of AISI 316 in Pb-17Li
the play the decisive role but the presence of
would be in the range 623-673 K. The very few reactive oxygen introduced by H 0 o r NiO". When
data on ferritic steels (HT-9, Fe-9Cr-lMo) a sufficiently high oxygen potential is
show, as in the case for Li, an increase in the present, which results in the formation of Cr
temperature range of about 100 K. and Fe oxides or spinels the latter react with
the Li compound. The attack of the cladding is
stronger for Li 0 followed sequentially by
Li Si0 Li Si0 2 LiAlO
. and Li ZrO Fig. 15
The very few data available on the influence of 4' 2this
ilfustrates . 3'trend. %f a claiding3'attack of
the lithium-lead eutectic on the mechanical 200 um after 10 000 h (H 0 content 1 mole % per
properties of the steels seems to show that / Li 0) is acceptable,
1 xole 2 the following provi-
AISI 316 L, AMCR (a Cr-Mn steel) and DIN 1.4914 sional maximum
2 . cladding temperatures are given
are not subject to Liquid Metal Embrittlement for both AISI 316 and 1.4914 steels: Li Si0
(LME) in the presence of Pb-17Li at 523 or 1173 KjLi Si0 1063 K j Li 0, 993 K. Tests2 in . 3'a
573 K ('3!,/, (the melting poing of the 4 environment
flowing gas 4' witi controlled H 0 par-
embrittler is 508 K) . tial pressure still have to be performed. 2 It
Stress corrosion tests carried out on tensile should also be mentioned that sulphidisation of
specimens of AISI 316 L, in Pb-17Li for 2500 h AISI 316 has been observed /26/ in contact with
at 723 K with constant loads corresponding to LiAlO containing sulphate impurities.
2
80 and 60 % of the ultimate stress have not
revealed any influence of stress on corrosion
/35/. Equivalent rasults are reported /36/
after 6000 h at 673 K with constant uniaxial REFERENCES
-
stress of 134 MPa.
1. UCRL-50647.
2.4. Corrosion caused by interaction between 2 . HEPL-TME 78-15-UC 20, April 1978
-_
the first wall/blanket structural material 3. ANL 8001, March 1973
and solid lithium compounds. 4. ORNL/TM-4927, January 1976
5 . E.E. Hoffman, ORNL-2924 (1960)
There are limited data on the compatibility of 6. R.A. Patterson, R.S. Schlager, O.L.Olson,
the candidate solid breeding materials with J . Nucl. Mat. 57 (19751, 312
39
7 . D.L. Olson, G.M. Reser, D.M.Matlock, NACE, 26. P.Fauvet, J.Sannier, G.Santarini, Procee-
35 (1980) dings of the 13th SOFT, 1984, Pergamon Press
8. M.G. Barker, S.A. Franklin, P.G.Gadd, D.R. 27. H.U.Borgstedt, G.Frees, G. Drechsler, to be
Moore, Material Behaviour & Physical published in J. Nucl. Mat.
Chemistry in Liq. Metal Systems, Ed. H.U. 28. M.Broc, P.Fauvet, T.Flament, J.Sannier, to
Borgstedt (Plenum N.Y. 1982) p.113 be published in J. Nucl. Mat.
9. E. Ruedl, V. Coen, T.Sasaki, H.Kolbe, J. 29. O.K.Chopra, D.L.Smith, J. Nucl. Mat. 122 &
Nucl. Mat. 110 (1982), 28 123 (19841, 1219
10. E. Ruedl, T. Sasaki, J. Nucl. Mat. 116 30. F.Tortorelli, J.H.Devan, to be published in
(19831, 112 J. Nucl. Mat.
11. E. Ruedl, V. Coen, T.Sasaki, H.Kolbe, J. 31. O.K.Chopra, D.L.Smith, to be published in
Nucl. Mat. 123, Nosl-3, May 1984, 1247 J. of Nucl. Mat.
12. O.K.Chopra, D.L.Smith, to be published in 32. V.Coen, A.T. Dadd, H.Kolbe, L.Orecchia,
J. Nucl. Mat. Proc. 3rd Int. Conf. on Liq. Met. Eng. and
13. J.H.Devan, J. Nucl. Mat. 85&86 (1979), 249 Technology, Oxford (April 1984) The British
14. V.Coen, H.Kolbe, L.Orecchia, T.Sasaki, J . Nucl. SOC. London, Vol.1 p.347
Nucl. Mat. 85&86 (1979), 271 33. W.R.Watson, R.J.Pulham, ibid. Vol. 3, p. 99
15. P.F.Tortorelli, J.H.Devan, R.M.Yonco, J. 34. M.G. Barker, V. Coen, J.A. Lees, H. Kolbe,
Mat. for En. Syst. V01.2, March 1985, 5 L. Orecchia and T. Sample, to be published
16. O.K.Chopra, D.L.Smith, J. of Nucl. Mat. in J. of Nucl. Mat.
133&134 (1985), 861 35. V.Coen, H.Kolbe, L.Orecchia, to be pu-
17. P.F. Tortorelli, Personal Communication, blished in J. of Nucl. Mat.
work to be published in J. of Nucl. Mat. 36. M.Broc, T.Flament, P.Fauvet, J.Saunier,
18. ANL/FPP-84-?, Vol .2, ch.6 Personal Communication, work to be
19. H.Tas, J.A. Dekeyser, F.Casteels, J. published in J . of Nucl. Mat.
Walnier, F .Deschutter, FT/Mol/T86-04 37. T.Kurasawa, H.Takeshita, S.Muraoka, S.Nasu,
20. O.K.Chopra, J. Nucl. Mat. 115 (1983), 223 M.Miyake, T.Sano, J. Nucl. Mat. 80 (1979),
21. M.Grundmann, H.U. Borgstedt, KFK 3819, Oct. 48
1984 38. P.A.Finn, S.R.Breon, N.R.Chellew, J. Nucl.
22. P.Fenici, V.Coen, J.Arrighi, H.Kolbe, T. Mat. 103&104 (1981), 561
Sasaki, E.Rued1, J. of Nucl. Mat. 85886 39. O.K.Chopra, D.L.Smith, J. Nucl. Mat. 103 &
(1979), 277 104 (1981), 555
23. P.Fenici, V.Coen, E.Rued1, H.Kolbe, T. .
40. R.J .Pulham, W.R .Watson, J .J .Collinson, J
Sasaki, J. of Nucl. Mat. 103&104 (1981), 689 Nucl. Mat. 122&123 (1984), 1243
24. V.Coen, J. Nucl. Mat. 133&134 (1985), 46 41. P.Hofmann, W.Dienst, to be published in J.
25. V.Coen, P.Fenici, H.Kolbe, L-Orecchia, T. Nucl. Mat.
Sasaki, J. Nucl. Mat. 110 nO1, Sept. 1982,
108
40
SCHEMATIC DIAGRAM OF TYPICAL
NUCLEAR FUSION REACTOR CYCLES
/ Breeding
exchanger
Fig. 1 Schematic diagram o f typical nuclear
fusion reactor cycles.
41
Fig. 4 Cross section of Carpenter 18/18 Plus
heat treat d in Li at 873 K f o r 1500 h .
Secondary 'Li+ ion image as obtained in
probe microanalyser. Primary ions
2'
Fig. 5 SEM micrograph of cross-section of
Nitronic 32 heat treated at 873 K in Li
f o r 1000 h. Note formation at the grain
boundaries of the Li-Cr-N compound.
42
Li / AUSTENITIC S.S.
Ferritic layer
Less Ni I
Less Mn
Less Cr if N %
lo-’ 1 1 I I ( I I
43
Fig. 1 1 SEM micrograph of crosssection of
sample of AIS1 316 L heat treated in
Ph-17Li at 873 K for 750 h showing Pb
and Li penetration.
a ) DEI composition
Ferritic layer
Pb, Li penetration Dissolution attack
Less Ni
Less Mn
Less Cr if OP
Austenitic structu
45
Tern perature"C Annealino temperature "C
lo4 -
-
-
600 550 500 450 400 350
I l l I I
W E N MOL
I
4
lo3
-
1 I I I I I I
Fig. 14 Arrhenius plot of corrosion rates for Fig. l j Chemical reactions of Li-based oxide
austenitic stainless steels in Pb-17Li ceramics containing 1 mol%H 0 o r 1
2
deduced from the papers presented at mol%Ni@ per 1 mol Li 0 with various
the 2nd International Conference on stainless steels (ll-l?%Cr) normalized
Fusion Reactor Materials. April 13-17, to an annealing time of 100 h o u r s , from
1986 (Chicago) . Ref. 41.
46
8 Corrosion Resistance of Metallic Materials for Use in
Nuclear Fuel Reprocessing
. +
v i t r i f i c a t i o n o f f g a s t r e a t m e n t ( 6 N HN03
F e (111) + C r ) When t h e medium b e c o m e s o x i d i z i n g e n o u g h
s o as t o b r i n g t h e material i n t o t h e
I n c o m p a r i s o n w i t h Magnox f u e l s , t h e repro- transition between t h e p a s s i v e and
c e s s i n g o f PWRl BWR a n d i n p a r t i c u l a r f a s t trans-passive s t a t e s o r even r i g h t i n t o
breeder f u e l s w i t h much h i g h e r b u r n - u p s , the transpassive range, in which
y i e l d s l a r g e amounts of dissolution fines accelerated general corrosion also
made up o f p l a t i n o i d s such a s platinum, occurs.
r u t h e n i u m and r h o d i u m : t h e s e e l e m e n t s may
enhance s t a i n l e s s steel c o r r o s i o n p o s s i b l y i n In concentrated boiling n i t r i c acid, IGA
t h e t r a n s p a s s i v e s t a t e by l o c a l g a l v a n i c o c c u r r i n g e v e n on f u l l y a n n e a l e d m a t e r i a l is
c o u p l i n g i n c o n c e n t r a t e d n i t r i c a c i d on h o t a l l t h e more d e l e t e r i o u s s i n c e t h e c o r r o s i o n
s p o t areas. p r o d u c t s such a s Fe and C r (susceptible to
o x i d a t i o n t o C r '+) c a n b u i l d u p a n d e x e r t a
Furthermorer f a s t breeder f u e l dissolution s e l f - a c c e l e r a t i n g e f f e c t on t h e a t t a c k .
p r o d u c e s h i g h e r p l u t o n i u m c o n t e n t s and a l s o
by p a r t i a l c o r r o s i o n o f t h e s t a i n l e s s s t e e l I n f u e l r e p r o c e s s i n g , I G A i s e v e n more l i k e l y
h u l l s corrosion products such as Fe3, Cr%: t o o c c u r as a c i d c o n c e n t r a t i o n , process
t h e s e i o n s may t h e n e n h a n c e t h e c o r r o s i v i t y temperature and w a l l t e m p e r a t u r e (increased
of the dissolution liquors particularly in by h e a t f l u x ) a r e h i g h e r a n d o x i d i z i n g i o n s
t h e f i n a l s t a g e s of a b a t c h p r o c e s s . s u c h a s C r (VI), Pu ( V I ) a n d h i g h e r c o n c e n -
t r a t i o n s of Fe can be produced.
3. RELEVANT MATERIALS: EVALUATION OF THEIR
CORROSION RESISTANCE A d v e n t o f low i m p u r i t y g r a d e s
48
too corrosive for the improved stainless design improvements to avoid crevice
steel grades susceptible to transpassive effects, unrenewed volumes, unfavorable
corrosion, or when silicon rich steels would condensate effects and location of
display prohibitive general corrosion rate sensitive junctions (for example
(11, 18, 201, i.e. in the strongly oxidizing zirconium/stainless steels) in high
and acid media as shown in Table 11. temperature processes:
49
(16 A . KRATZER, B. PIEGER, H. TISCHNER, E.M. HORN, (20 H. CHAUVE, J. DECOURS, R. DEMAY, M. PELRAS,
Proceedings 9th ICMC, 2, 465, Toronto J. SIMONNET, G. TURLUER, Paper TC 580-9,
(USA), June ( 1 9 8 4 ) AIEA Technical Committee Meeting on
(17 R.R. KIRCHHEINER, F. HOFMAN, Th. HOFFMANN, materials reliability in the back end
G. RUDOLPH, Corrosion 86, Paper 120, NACE, of the nuclear fuel cycle, Vienna (Austria),
Houston (USA) ( 1 9 8 6 ) Sept. ( 1 9 8 6 )
( 1 8 TAWLMURA, K. ARKAWA, Y. MORIGUSHI, The ( 2 1 J.A. BEAVERS, J.C. GRIESS, W . K . BOYD,
Science Technology and Application of Corrosion, 36, 5, 292 ( 1 9 8 1 )
titanium, R. Jaffee Editor, Pergamon Press, ( 2 2 T.L. YAU, Corrosion, 39, 5, 168 ( 1 9 8 3 )
Oxford (Great Britain) ( 1 9 7 0 ) ( 2 3 ) T.L. YAU, 4th ASTM Symposium on Industrial
*
(19) F. FURUYA, H. SATO, K. SHIMOGORI and al., Applications of Titanium and Zirconium,
Proceedings ANS Meeting on Fuel Repro- Philadelphia, Pa. (USA) ( 1 9 8 4 )
cessing and Waste Management, Jackson
Wy. (USA) ( 1 9 8 4 )
TABLE I
Materials and typical composition in weight %
MATERIALS Nb
W n' 1 . 4 3 0 6 s l r 6 f . 101
-
Zr+Hf Hf Fe+Cr Sn Nb Cu C H N 0
min. IMX. mx. max. mx. max. mx.
Ti Ta Fe H N 0
TABLE I1
Comparison of typical mean general corrosion rates
in 4 boiling nitric acid solutions of increasing oxidizing power ;
weight loss in mg.dm-'.day-' (mdd)
[(IGA) when observed = intergranular attack]
5 N HN03 5 N HN03
MATERIALS 5 N HN03 14.4 N HN03
+ 1 Ml-I PU + 1 a.1-l cr
rm.year-1 mdd vm.year - 1 mdd vm.year -1 mdd vm.year - 1
~ ~~ ~~
Quench-annealed s t a i n l e s s steels
I
Titanium 240 20 160 < 2 <16 ( 2 < 16
Zirconium grade 7 0 2 <3 a . 5 (3 < 2 (10 < 0.5 ( 3
50
-- ---- ' -- -- -1
r-
I tritiated -I r------l
t r i t i a t e d 1- 4 1r-
oxalic mother I
I acid recovery I I acid recovery 1i quor
I evaporator J
L- -- --
-- -- --
II i. n t e r c y c 1 e - l
1 concentrator I
L- --
i-- --I
(H"J3) (TBP) (TBP) 1
1 1 2
mechanical
treatments
1u t pu - extraction IJ t pu and pu 5
-
Pu purification
by
u + ~u t F d c , a r i f i c a t i o n W
---J
solvant -. parti tion
JyPurification -
t
(TBP)
5 u
dissolution uranyl
1' rr fine nitrate 8
storage concentrator
-
1 uranyl
t nitrate
IIIII
I I " ' l ' l '
I 1 I I I I 1 I 1 1 1
'E
5
A
110 INTERGRANULAR
ATTACK
,-A
M IMTERGRMUUR
I I
I I
I I
I I
I I
I
Sulzer Brothers Ltd. , be effective for from lo3 to loe years. This
Winterthur, Switzerland, requirement could be fulfilled by a container.
Corrosion specialists must forecast the behaviour
of the container materials over these time
SYNOPSIS periods; a task which is surely unique in the
history of corrosion science.
Nuclear power produces a range of waste
types which require safe disposal. Most countries A relatively small amount of HLW is
have set themselves the task of disposing of produced per unit of nuclear generating power.
nuclear waste in repositories on their own soil. A 1000 MW(e) power plant produces around 4 m3
(10 tonnes) , conditioned (vitrified) HLW per
The aim of all projects is to prevent year. The HLWs are mixtures of short- and long-
radionuclides from entering the biosphere. Most lived radionuclides. The radiotoxicity initially
concepts for the disposal of high level waste decays rapidly - more than 99% reduction in the
(HLW) require that the technical barriers should first 1000 years - and then more slowly at longer
be effective for from lo3 to loe years. This periods, before finally reaching levels similar to
requirement could be fulfilled b y a container. those found in naturally occurring minerals.
Corrosion specialists must forecast the behaviour
of the container materials over these time The stages typical for most waste disposal
periods. projects are shown in table 1. All final
disposal concepts for HLW include a series of
INTRODUCTION complimentary engineered and natural barriers.
The barriers going out from the waste are:
Atomic energy is an important source of 1. The waste form, e.g. the glass matrix of
electric power in many industrialised nations ; vitrified waste:
the operation of a nuclear power plant produces a 2 . The container:
range of nuclear waste types which require safe 3 . The backfill, i.e. the material used to fill
disposal. Most countries have set themselves the the space around the container. (Not present
task of disposing of the nuclear waste produced in all concepts.)
in repositories on their own soil. There is 4 . The geological formation in which the
considerable international cooperation on points repository lies.
of common interest. 5. The remaining path from the chosen geological
The aim of all projects is to prevent formation to the biosphere; this includes
radionuclides from entering the biosphere. Most the surrounding geological formations, the
concepts for the disposal of high level waste hydrogeological situation i.e. the rate of
exchange of groundwater with water in the
(HLW) require that the technical barriers should
biosphere.
52
The container is important in that it is a for lifetimes of up to ca. 1000 years. The life
high integrity barrier, most of the other barriers is attained by providing sufficient corrosion
are retardation and/or dilution barriers. The allowance. The Swiss container design for
radionuclides can not migrate as long as the instance has a 250 mm wall thickness, 50 mm of
container remains intact. The integrity of which is the corrosion allowance, the remaining
the container should be retained during the wall thickness is required to sustain the
operational phase of the repository, and pressures at depths of 1200-1500 metres. The
preferably until well after the perturbations experimental evidence is that the average
of conditions in the geological formation due to corrosion rate in a range of groundwater
the working of the repository and the thermal salinities is under 20 p / y r in the low oxygen
energy from the waste have dissipated. The .
conditions expected in deep repositories [ 11
thermal phase lasts about 1000 years. The main problem is whether this attack is
The surface temperature of the container uniform. Pitting rates producing forecast
depends on the concept and can range up to penetrations of 200 mm in 1000 years exposure
25OOC after the repository is sealed. have been observed in carbonate/ chloride
Most of the first choice container types in solutions which favour pitting [ 2,3]. The high
the disposal concepts are metallic, although in initial pitting rates necessary for these high
several countries the alternative of a ceramic penetration depths have not been observed in
container is still being pursued. anaerobic natural or synthetic groundwaters
The metal containers can be divided into two [1,3,41*
types, the 'consumable' type where the lifetime is Titanium alloys grade 1 2 and Ti-0.2% Pd are
attained by providing sufficient wall thickness the most favoured of the high corrosion resistant
(e. g. carbon steel) and the 'non-consumable' materials. These alloys are less sensitive to
type where only a few millimeters of corrosion pitting than the N i - C r types and are also more
resistant material are necessary (e. g. passive resistant to pitting at higher temperatures than
materials or thermodynamically stable metals) . pure titanium [ 5 , 6 ] .
The corrosion resistant layer is applied externally Copper is thermodynamically stable in
to a pressure vessel; the underlying material is oxygen free crystalline groundwaters; the long
credited with no corrosion resistance. life expectancy of copper containers is based on
this fact. The slight corrosion expected is due
NATIONAL SOLUTIONS to residual oxygen in the repository and the
production of other corrodants e.g. sulphide from
Table 2 gives a summary of the geological microbial action [ 71.
formations chosen in selected national Stress assisted cracking of these materials
programmes , the materials under closest under repository conditions has also been
consideration, and the Lifetime requirement investigated [ 2 , 6 ,81 . Although environmental
for the container. assisted cracking of the candidate materials
There are three basic types of repository is thought unlikely, carbon steels (e.g. in
which give three fundamentally different carbonate solutions) and the titanium alloys
corrosion media, these are: (hydrogen embrittlent) may suffer stress assisted
1 . crystalline rock formations, cracking in corrodants present in the ground-
2 . dry salt formations, waters. It is not clear, however, whether
3. clay formations. conditions in a repository are sufficiently severe
for environmentally induced cracking to occur.
Repositories in dry rock formations above
the water table have been proposed, thereby Repositories in rock salt.
avoiding corrosion and transport of radionuclides
by ground waters. Rock salt formations are dry, but for the
purposes of safety analyses the ingress of water
Repositories in crystalline formations. as concentrated brines is postulated. Various
brine solutions have been used in corrosion
Most crystalline rock formations under investigations for materials for rock salt
consideration are saturated with groundwater. repositories. The brines are either saturated
There is a suggestion to site a repository in sodium chloride with small additions of potassium,
granite above the normal groundwater level (UK) magnesium and calcium chloride or sulphate or
and the tuff' repository (Table 2) is also of the magnesium chloride based such as Q-brine [ 9 ] :
'dry' type. The waters expected in these hard 1 . 4 wt% NaC1,
rock repositories are similar in type but vary 4.7 wt% KC1,
greatly in salinity, all are saturated in silicate. 26.8 wt% MgC1.
Sea water is often used as a high salinity 1 . 4 wt% MgSO,.
comparison medium. Some sample analyses of Corrosion rates quoted for the lower pH
waters featured in the various programmes are magnesium brines are given in Table 5 .
given in Table 3. The general and pitting corrosion resistance
The corrosion behaviour of some of the of Ti-O.Z%Pd and titanium grade 12 as well as
candidate materials in crystalline groundwaters Hastelloy C-4 are acceptable. The titanium alloys
and sea water is summarized in table 4 . have been shown to be susceptible to crevice
As can be seen in Table 4, there is corrosion and Hastelloy to pitting under gamma
considerable interest in carbon steels, (and radiation (oxidising conditions) [9,10].
cast irons) cast or wrought for HLW containers
53
Carbon steels are possible candidate 6. Long-Term Performance of Materials Used for
materials as consumable containers provided High-Level Waste Packaging. NUREGICR-
they are not exposed to temperatures in excess 4379 Vol.1. First Quarterly Report, Year 4,
of around 150OC. A container of this type is 1985. Battelle, Columbus. Compiled by
proposed for salt repnsitories [9]. D.Stah1, N.E. Miller.
7. Final storage of spent nuclear fuel - KBS 3.
Repositories in clay formations. SKBFl KB S , Sweden.
8. Stress Corrosion Testing of Pure OFHC-
The containers will be placed in supported
Copper in Simulated Groundwater
galleries in clay formations. These galleries are
Conditions. Report YJT-84-21, Nuclear Waste
likely to collapse after the operational phase and
Commission of the Finnish Power Companies.
the containers will be contacted by the clay or if
Nov. 1984. P. Aaltonen, H. Hanninen, M.
a backfill is used by interstitial clay water. The
Kemppainen.
composition of this water was 121 :
Water A: expected composition 9. Corrosion Behaviour of Container Materials
13.9 g / l Na,SO,, for the Disposal of High-Level Waste in Rock
0.87 g / l K,SO,, Salt Formations.
19.2 g / l MgSO,, Commission of the European Communities,
3.6 g / l CaSO, Luxembourg 1986 10040 EN. E. Smailos,
Water B: a possible intrusion waIer W. Scharzkopf, R . Koster.
39.8 mgll Na,SO,, 10. Waste Package Reference Conceptual Designs
15.0 mg/l MgSO,, for a Repository in Salt. BMIIONWI-517
10.1 mg/l NaF, Technical Report, Feb. 1986.
74.2 mg/l Na,CO,, 11. Corrosion of metals in Tropical
39.4 mg/l KC1, Environments.
19.9 mg/l NaC1. Materials Performance, July 1976.
The corrosion rates measured at 90°C in waters A C.R. Southwell, J.D. Bultman,
and B are given in table 6. .
A. L Alexander.
The results for clay and crystalline 12. Engineered Waste Package Conceptual
environments are similar; both Hastelloy C-4 and Design, Spent fuel (Form I) Disposal in
Ti-O.2%Pd were concluded to be suitable candidate Salt.
materials; corrosion rates on carbon steels varied AESD-TME-3087, Mar. 81. Westinghouse.
between 2 and 300 p l y r depending mainly on
the amount of oxygen available [ 21.
CONCLUSION
REFERENCES
Table 1 Time scales involved in nuclear waste disposal and safety analyses.
(** Times vary according to concept)
Geological
Formation
Clay Titanium-O.2%Pd
..................................................................................
Tuff 1. Stainless steel (316) 1000 USA
min. 300
55
Table 3. Compositions of crystalline rock groundwaters considered in
some of the corrosion programmes.
56
European Federation of Corrosion
-
Series Introduction
The EFC, incorporated in Belgium, was founded The Working Parties function in various ways, e.g.
in 1055 with the purpose of promoting European by preparing reports, organising symposia, conduct;
co-operation in the fields of research into ing intensive courses, and producing instryctional
Membership is based upon participation by The activities of the Working Parties are co-ord-
corrosion societies and committees in technical inated, through a Science and Technology Advisory
delegates to Working Parties, whose membership is The administration of the EFC is handled by three
also expanded by co-option of other individuals. Secretariats: Dechema in the Federal Republic of
The activities of the Working Parties cover Germany, the Societe de Chimie Industrielle in
c'arrosion topics associated with inhibition, France, and the Institute of Metals in the United
education, reinforcement.in concrete, microbial Kingdom, These three Secretariats meet at the
effects, hot gases and combustion products, Board of Administrators of the EFC.
environment sensitive fracture, marine environ- There is an annual General Assembly at which
ments, surface science, physico-chemical methods delegates from all member societies meet to deter-
of measurement, the nuclear industry, and computer mine and approve EFC policy.
based information systems. Working Parties on News of EFC activities, forthcoming conferences,
other topics are established as required. courses etc. is published in a range of accredited
corrosion and certain other journals throughout EFC Secretariats are located at:
The output of the EFC takes various forms. Papers The Institute of Metals
London, UK FRANCE