Professional Documents
Culture Documents
ORNL-2055
.
LEGAL NOTICE
T h i s report
WOI
nor the Commission, nor any person octing o n beholf of the Commission:
A.
Mokes
ony warronty
completeness,
any
01
or representation, express
OT
implied,
informotion, apporatus,
p r i v a t e l y owned rights;
method,
or process disclosed
of
As used i n the obove, "person a c t i n g on behalf of the Commission" includes any employee or
contractor of the Commission t o the extent that such employee or contractor prepares, hondles
OT
distributes,
or provides o c c c s s to,
w i t h the Commission.
CLASSIFIED
ORNL-2055
Contract
No. W-7405-eng-26
METALLURGY DIVISION
W. D. Manly
DATE ISSUED
CLASSIFIED
3 Y 4 5 b 0350095 7
UNGLASS IFIE0
ORNL-2055
1. C. E. Center
2, Biology Library
3. Health Physics Library
-5, Central Research Library
& Reactor Experimental
Engineering Library
7-26. Laboratory Records Department
27. Laboratory Records, ORNL R.C.
28. A. M. Weinberg
29. L. B. Emlet (K-25)
30. J. P. Murray (Y-12)
31. J. A. Swartout
32. E, H. Taylor
33. E. D. Shipley
34. M. L. Nelson
35. W. H. Jordan
36. C. P. Keim
37. J. H. Frye, Jr.
38. R. S, L i v i n g s t o n
39. R. R. Dickison
40. S. C. L i n d
41. F. L. Culler
4 2 A. H. h e l l
43. A. Holl aender
44. M. T. Kelley
45.
46.
47.
48.
49.
50.
51.
52.
53-75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
K. 2. Morgan
J. A. Lane
T. A. Lincoln
A. 5. Householder
C. S. Harrill
C. E. Winters
D. S. Billington
D. W. Cardwell
W. D. Manly
E. M. King
A. J. Miller
D. D. Cowen
R. A. Charpie
M. L. Picklesimer
M. J. Skinner
G. E. Boyd
C. J. McHargue
P. U Reyling
G. C. Williams
N. J. Grunt (consultant)
E. Creutz (consultant)
T. S. Shevlin (consultant)
ORNL - -12 Technical Library,
Document Reference Section
EXTERNAL DISTRlBUTlQN
category
UNCLASSI FlED
iii
.........
D. Manly
ABSTRACT
The corrosion of structural metals or alloys i n liquid metal i s for the most part due
t o the dissolving of the various constituents of the metals or alloys by the liquid metal.
The manner i n which t h i s dissolution proceeds gives r i s e to many types of attack,ranging
from a simple solution-type attack t o a deep intergranular attack with the preferential
leaching of one constituent of an ~ l l o y , Examples of the many types of corrosion experienced with solid-metal-liquid-metal systems are illustrated. The role of impurities
on the corrosion i s discussed.
In n static one-metal system the solution step stops when the solubility l i m i t i s
reached; however, in more complex systems the corrosion of metals can be continued
because of removal of the dissolved materials from the liquid metal by a temperature
gradient and/or by dissimilar-metal transfer.
Thus the transfer of metal froni the hot
region of a plumhing system and i t s subsequent deposition in the cold zone, and the
transfer of material from one part of the system and i t s alloying with a metal of different
Composition in another part of the system w i l l greatly increase the corrosion as compared t o the results obtained in static systems. Examples of temperature-gradient mass
tronsfer and dissimilar-metal transfer are reviewed, and factors governing the occurrence
of these phenomenu are outlined.
i n the amount of attack over that expected t o saturate the liquid metal because of the mass transfer
of material under the driving force of the temperature gradient or the concentration gradient.
In the short time that interest hos existed i n
the corrosion characteristics of liquid metals, many
testing methods have been developed t o determine
the interaction between liquid metals and solid
metals. These methods range from the very simple
static capsule test t o the expensive and camplicated forced-circulation loop tests which carefully
reproduce the operating conditions. The tests and
the manner in which data are derived from them
have been previously described.2
Several types of corrosive attack of solid metals
by liquid metals have been ~ b s e r v e d . ~ In t h i s
discussion the types of liquid-metal attack w i l l
be arranged into the following cotegories:
1. simple solution,
2. alfoying between liquid metal and solid metal,
3. intergranular penetration,
4. impurity reactions,
5.
6.
occur in o static system as a result of simple solut i o n by examining the solubility l i m i t of the solid
metal in the liquid metal at the operating temperature.
However, there would be no conception of
the rate a t which the solubility l i m i t was achieved.
Thus, in looking at the F e - L i phase diagram in
Fig, 4, it can be seen that the amount of attack
of iron by lithium should be quite small i n a static,
isothermal system; and corrosion tests have proved
this.
Therefore, in simple-solution type attack
the amount of damage the solid metal w i l l receive
depends on the ratio of surface area t o volume of
the system, but the rate at which the attack occurs
9
1
Fig. 1.
Even-Surface Removal from Titanium
Specimen After 40 hr in L e a d at 1000C.
1OOX.
Reduced
33.5%.
Reduced 33%.
UNCLASSIFIED
ORNL-LR-DWG
14457
4 200
V
e io00
W
W
OI
5k
800
600
400
200
2.
40
Attack After
hr of Type
Li
(0
Fig.
1
20
LITHIUM (SOLIDI
30
40
50
+ IRON (SOLID)]
60
70
80
90
Fe
IRON ( w t %)
14%.
UNCLASSI FlED
ORNL-LR-DWG (4458
SILVER ( a t % )
50 60
70
IO 20 30 40
1000
80
90
900
I400
-2
W
1200 Ej
1000
?I
800
600
Pb
IO
20
30
400
40
50
SILVER ( w t
60
70
80
90
. 1
Ag
%I
uNCLASS1FI ED
Y-7067
-.
"61
Y- 144?7
'
c
ii
01
A
b
Fig. 8. Copper Capsule-Sodium T e s t a t 18OOOF for 100 hr. Sodium penetration into s o l i d copper at
t h e grain boundaries with the resultant formation of an intermetallic compound.
32.5%.
Fig. 12. Hot L e g of a 75% Ni-25% Mo ThermalConvection L o o p Operated for 200 hr with L e a d at
800C and with a Temperature Gradient of 300OC.
150X. Reduced 35%.
Ioop.
..
UNCLASSIFIEI
y-na6
1
'
alloy^.^
comprising the
1954).
U NCLASSI FlED
ORNL-LR-DWG
14459
40
LEAD ( a t %1
20
40 50 6070 90
30
2000
1800
1600
LL
1400
3
n
1200
1000
w
n
800
al
600
Fig. 16.
P l u g from an Inconel-Lead ThermolConvection Loop That Operated for 125 hr at 800OC
with a Temperature Gradient o f 200'C.
3.5X. Reduced 11%.
CU
10
Fig.
20
18.
30
40
50
60
70
80
90
Pb
400
LEAD ( w t %I
ORNL-LR-OW6
5W3
HOT LEG
MELLAR LAYER
COLD LEG
SUPERSATURATION
HUCLEATION
1000C.
200X.
5J. V. Cathcart
and W.
D.
P ~ o p e r t i e s of
The greater the difference in the chemical pot e n t i a l s of A and of 6 i n the two solid phases,
the greater w i l l be the driving force for the occurrence of mass transfer. The rate of mass transfer i s dependent on the temperature since an i n crease i n temperature will, of course, increase
the diffusion rate i n both the l i q u i d and the solid
phases. A high s o l u b i l i t y of metal A in 6, or 6
i n A, or both, w i l l also f a c i l i t a t e mass transfer.
Y-1216
ONE
IRON C A P S U L E WITH L U M P S i IN L i .
T R I P L I C A T E TEST AT 4 0 0 0 C FOR 4 hr.
APPROX. 2 5 % Si, 75% L i ; 1 4 - I L
OF
UNCLASSI
.. - . .- Fl
. ED
7
.c :,
..
. .
-...
e
0
.
Fig.
j
010
22. The Effect o f Type of Container on the Corrosion of Type 304 Stainless Steel i n L i t h i u m at
UNCLASSIFIED
OWL-LR-DWG
5642
METAL
A
ION
METAL
MOVE
OR
DIFFUSION INTO
METAL B AND
ALLOY FORMATION
10
rate-controlling step for the various types of liquidmetal corrosion has not been determined. For the
successful containment of the l i q u i d metals, the
amounts of impurities, such as oxygen, nitrogen,
and carbon, should be carefully controlled. Future
work in the f i e l d of liquid-metal corrosion must
be directed toward increasing the understanding
of the rate-controlling steps of dissimilar-metal
transfer and temperature-gradient mass transfer.
When this has been accomplished, corrective measures can then be taken t o keep these types of
corrosion to a minimum.
ACKNOWLEDGMENTS
The author would l i k e t o acknowledge the assistance of J. V. Cathcart, E. E. Hoffman, and other
members of the Oak Ridge National Laboratory
working in the f i e l d of liquid-metal corrosion. The
metallographical work used i n t h i s paper was performed by a group under the direction of R. J. Gray.