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ORNL-TM-1437.txt
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ORNL-TM-1437.txt
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—
L
ra
Contract No. W-7405feng-26 :
METALS AND CERAMICS DIVISION
A STUDY OF LEAD AND LEAD-SALT CORROSION IN
- THERMAL-CONVECTION LOOPS
' @, M, Tolson and A. Taboada
,
7
- APRIL 1966
Fa
~OAK RIDGE NATIONAL LABORATORY
~ "0k Ridge, Tennessee |
.. - operated by
ON. CARBIDE CORPORATION
Sowa s for the o
U.S, ATOMIC ENERGY COMMISSION
\ -
CFSTI PRICES
ORNL-TM-1437
A,
it
4
’
'ufi%f
b et
fi‘&: ’ -
-\*‘«—* &ii
»
A STUDY OF LEAD AND LEAD SALT CORROSION IN
THERMAL - CONVECTION LOOPS
G.vM. Tolson and A, Taboada
ABSTRACT
Thermal-convection loop tests of several structural
~alloys were operated using circulating molten lead.
Screening tests were run to evaluate Croloy 2 1/4 Cr,
~ carbon steel, AISI-type 410 stainless steel, and
No—1% Zr at conditions described in Teble l Two of the
"~ test loops contained surge tanks in which fluoride salts,
Nb—1% Zr alloy, and graphite were placed in contact with
the lead to determine the compatibility of these
materials in a direct-cooled lead system.
A1l of the steel loops tended to plug in the cold
regions because of formation of dendritic crystals of -
" iron and chromium. . The hot-leg attack consisted of
general surface removal with a few large pits extending
to a greater depth. The Nb—1% Zr alloy showed no
measurable attack; however, niobium -crystals were found
| in the cold leg of a loop which operated 5000 hr at
o 1400°F with a AT of 400°F. |
INTRODUCTTON
Liquid 1ead has béen’proposed as'a coolant-for molten-salt'breeder
? reactors. In one reactor des1gn, lead is in direct contact with salts
| _at temperatures up to llOO°F thus eliminating a heat exchanger and
| resulting in superlor heat transfer and thermal efficiencies. In another
Ndesign, the lead extracts heat from the salt in. a salt-lead heat exchanger.
- The materials commonly used in‘reactors at these temperatures, such as’
’,,300 series stainless steels, Inconels, or Hastelloys, cannot be used in
contact with lead because of the high solubility levels of nlckel in
'lead that result in excessive mass transfer.‘ The refractory'metals
“1offer very good corros1on resistance but are difficult to fabricate and
7 _are too expensive for a complete reactor system. Carbon steels offer
B good ‘corrosion resistance to- liquid lead but are very marginal with
_ respect to both strength and oxidation resistance, Since Croloys (steel
materials. o . : o
'solution attack but do not adequately'measure rass transfer. In addition, ¥
‘although the attack rate for Inconel at 1100°F was reported as
U‘v
with 1 1/4 to 9% Cr and 1/2 to 1% Mo) and 400 series stainless steels
have good oxidation resistance, adequate strength, and contain no nickel,
these appeared to be the most promising material for this‘appiication.
Consequently, the primary effort was expended in evaluating these
LITERATURE SURVEY
A great portion of the liquid lead corrosion tests'deseribed in
the literature involves capsule tests that demonstrate the occurrence of {“
no standard test procedure was used from one test to the hext., Test
specimens were contained in a variety of capsule materlals such as
graphite, quartz, and the specimen material itself. Inhibitors were
frequently used, and a variety of methods were used to prevent oxidation..
The maximum test time was approximately 500 hr.
Results in these isothermal tests generally indicated that iron,
carbon steels, low-chromium steels, and chromium stainless steels
(nickel-free) had good resistance to corrosion by lead at temperatures
up to 1400°F. Austenitic stainless steels were geod to 1000°F. Tan-
talum, niobium, and molybdenum were not attacked by lead at 1800°F,
Nickel and nickel-base alloys had poor resistance to attack by lead,
0.38 mils/year.l Other nonferrous alloys of Cu, Pt, Au, W, Sn, Zn, Mn, | o
Zr, and Ti behaved poorly or were not recofimended Carbon demonstrated ‘_ _ _ :r‘
poor resistance to attack by lead at 1800°F but good resistance at
935°F., ‘
In addition to the above, other experimentation has been done - 3
using thermal-convectlon loops to study mass transfer. As in the static
work, no standard test design existed, making comparlson'of data diffi-
cult, The effect of impurities in lead are not well understood.’ Oxygen 'fi
- has been reported to increase corrosion in lead. Some research indicates
1L. R, Kelman, W, D. Wilkinson, and F. I. Yaggee, Resistance of (:)I
Materials to Attack by Liquid Metals, ANL-4417 (July 1950). ‘
fy
»
{
-l Y
P
. h\»‘?é\ N
4},".319—23 (March 1960).
?
l\
that many elements may'act_as corrosion inhibitors. These.inhibitors
could act to form a protective, film in the case of titanium and zir-
conium (ref. 2), to decrease the solubility of the container material in
lead as may be the case of nickel, or to remove oxygen from the system
in- the case of magnesium.
In one of the 1nvest1gations the relative resistance to mass
transfer in liquid lead of 24 metals and alloys was measured3 at 1472°F
‘maximm loop temperature and 300°F AT, The tests were run in quartz
thermal—cdnvection loops with the alloy being_studled formed-lnto tubes
‘which were inserted into the hot leg and cold lég. In these tests
niobium and molybdenum exhlbited no mass transfer after 500 hr of test.
Nickel—base alloys and austenitic stainless steels were hlghly susceptible
to mass transfer and plugged the loops within 100 hr. Intergranular
attack was noted in the hot region.- The pure metals, Fe, Cr, Co, Ti,
and Ni, all plugged W1thin 100 hr The .400. serles stainless steel
(chromlum) and molybdenum-bearlng alloys showed llttle evidence of mass
transfer after approximately 500 hr. There was some evidence of prefer-‘
ential leaching of chromium by'lead.in,thls type alloy, - Several inves-
tigators have studiedfithe reslstanoe-of ste61s to corrosion by lead, /
bismuth, andxleadAbismutn.alloys-were found to be more corrosive than '
lead,.%he literatureTindicafies-that they all result in the same general
behavior.patterns,_"The corrosion of steels in uninhibited lead was
reported* to be about 1/40 of that noted in uninhibited bismuth under,
comparable conditions (1472°F maximum temperature with 212°F AT). The
most sophisticated work with 1ead and lead-bismuth alloys was done by
-'e_BNL in conjunetion with the LMFR Program.5 Although only one lead 1oop
N ~ e ;=; ST
20, F. Kammerer et al., Trans. ATME 212 20—25 (1958)
3J. V. Cathcart and W. D. Manly3 Corrosion 12 43~48 (February 1956)
43, A, James and J. Troutman, J. Iron Steel I Inst. CLondon) 1%,
5A. J. Romano, C. J Klamut and D. H, Gurinsky, The Investigation
- of Container Materials for Bi and Pb Alloys. Part I; Thermal Convection
- Loops, BNL-811 (T-313) (July 1963).
4 c - | -
was operated; many bismuth and lead-bismuth.loop tests were conducted;
iIn'general, the low-alloy steels and low-chromium steels exhibited the
best corrosion resistance to bismuth and lead-bismuth; however, titanium
and zirconium additions were required to obtain goodlcorrosion resistance
in loops that operated above 752°F. The authors concluded that titanium
and zirconium inhibited corrosion by forming\ZrN, TiN, and TiC on the
walls in the hottest regidns of the loops. No corrbsion occurred in
inhibited loops that operated for 10,000 hr at temperatures as high as
1022°F in bismuth and temperatures as high as 1202°F in lead-bismuth
eutectic, A single Croloy 2 1/4 steel loop containing‘zifconium—ifihibiteq | L
lead was operated for over 27,000 hr with a i022°F hotlleg and approxi- +
mately 212°F AT, Although the zirconium additions had been made, the
zirconium was not detected by chemical analysis of the solution. . The
lead also contained about 250 ppm of magnesium, which had been added to
prevent loss of zirconium by oxidation, and it may have héd an inhibiting
effect.
DESCRIPTION OF TESTS
Six uninhibited thermal-convection loop tests were performed at
ORNL to explore the compatibility of materials with lead under cofiditions
expected in molten salt reactors. ‘One additional loop test was also
verformed to evaluate the performance of a newly designed thermal- -
convection loop. A description of the loop and the results are presented
in the Appendix. The operating conditions for all the loops are summarized -
in Teble 1. |
Two of the loops (type 410 stainless steel and 2-1/4 Cr steel) had
Nb—1% Zr alloy liners in the surge tanks. Molten Salt Reactor Experiment
fuel salt® floated on the lead surface in the surge tanks as shown in
Fig. 1. These loops also contained a graphite specimen in the surge tank
which was exposed to both the salt and the lead at the lead-salt inter-
face. The maximum temperature in the loops was about 1200°F and the AT
was 300°F,
; | o
67,9% UF,, 7.6% ThF,, 29.2% F1Fs, 37.1% LiF, and 18.2% ZrF,.
_- A 'PROBE LINE TO DETERMINE
» . LIQUID LEVEL -
- B W - el 8 — STOP TO HOLD LINER
\ | A - ] | "IN PLACE
) | i Ryl e N Loy LéAD SALT INTERFACE|
~
o - . Fig. 1l.. Section Through the Surge: Tank ‘Used on the 410 Loop.
- Notice the salt is floating on the lead and the only metal which :
; B j contacts the salt is the Nb—-1% Zr liner. The graphite specimens were -
o .. suspended from the small wire extending 1nto the salt and cannot be
- . seen in the picture, - T - S - ;
Table 1. Operating Conditions of Thermal-Convection
' Loop Tests Using Lead as a Coolant '
Loop Maximum
Material : Temperature AT - Operated
- | (°F) -~ (°F) - (hr)
Croloy 2 1/4 1210 300 266
AISI-type 410 11210 300 1346
stainless steel o ‘ _ - -
Croloy 2 1/4 f 1100 200 5156
ASTM type A-106 1100 200 5064
No-1% Zr clad with 1400 400 385~
type 446 stainless ' '
steel ‘ ‘ |
Nb—1% Zr clad with 1400 - 400 5280
type 446 stainless o
steel o
aLoop containing salt shut down due to instrument
malfunction. o _
Two other loops which did not contain salt or graphite operated at
1100°F with a 200°F AT, One of these loops was constructed of 2 1/4 Cr
~ steel, the other of low-carbon steel. A third set of,leop-tests was
operated to investigate the compatibility of nidfiium with lead both with
‘and without MSRE salt. These loops were fabricated from niobium clad
with type 446 stainless steel. o
A cleaning charge of lead was used in all the iron-base loops.
The charge was run isothermally at the maximm operating temperature of
the loop overnight (ebout 12 hr) and then dumped. The lOops'were then
refilled with clean lead and pufi into operation. This was not done with
the Nb—1% Zr loop because of the difficulty in attaching a drain line.
o
loop Showed about 1 mil of3attack, as can be seen in Fig. 3.
sion was observed on the Nb—l% Zr liner, as demonstrated by the photo-
REsULTs OF TESTS _
Of the two steel loops that contained salt the 2 1/4 Cr steel
?plugged after only 288 hr and the type 410 stainless steel plugged after
1346 hr, ‘As shown in Fig. 2, the plugs were made up of dendritic
crystals, which were determined to be iron and chromium by x-ray diffrac-
tion and wet chemical analysis. The maximum-depth of attack on the type
- 410 stainless steel piping in the hot leg was 2 mils, as determined by
The pitting in the hot leg of the 2 1/4 Cr
No corro-
metallographic examinetion.
micrograph shown in Flg. 4.
SR Y.58172
Dendritic crystals of Iron and Chromium Which Formed in
Fig.' 2.
200x%,
Ethe Cold Leg of a 2 1/4 Cr Lead Loop After 266 hr, Unetched
Y.58161
Fig. 3. Corroded Section of Hot Leg From 2 1/4 Cr Lead Loop
Operated at 1200°F for 266 hr. Unetched. 500x. .
Fig. 4. Nb=1% Zr Liner Exposed to Lead and Salt for 1349 hr at
1200°F in 2 1/4 Cr Lead Loop. 200x.
Je
rate since plugging time is not a function of corrosion rate.
After 648 hr of operation, the cold leg of the 2 1/4 Cr Loop,
which contained no salt or graphite, began to plug as indicated by
In order %o’ determine 1f the hot leg
was being selectively attacked the lead was dumped from the loop and
decrea51ng cold-leg temperature.
the hot leg was radlographed Several areas were noted where the lead
had wet the metal and had not drained from the loop, thus indicating
' selective dttack,” The lead that was dumped from the. loop was examined
and found to contain crystals of iron and chromium which had‘floated to
the top surface during cboling; The loop was then refilled with new
lead, restarted, and operated for 5156 hr.
tion without plugging does not necessarily mean'a decrease in corrosion
' Post-
test metallographic examination of the cold-leg region showed the
The increased time of opera-
presence of a large amount of dendritic crystals, as revealed in Fig. 5.
P
- 7Brookhaven previonsly had found that areas of selective attack
could be identified in mercury systems in this manner because of the
increased wetting action of the liquid metal.
Y-62845 -
.008
. Figo 5.
- Leg of the 2 1/4 ‘Cr Lead Loop Which Ran for 5156 hr at llOO°F with a AT
of 200°F , —
Dendritlc Crystals of Iron and Chromlum Found in the Cold -
10
The approximate depth of hot-leg attack as determined by the change in
wall thickness averaged 5 mils and could have been as deep as 8 mils,
The uncertainty in the depth of attack is due to the pitting nature of
the attack and the variation in the wall thickness, Analysis of the
crystals ih the cold leg showed about the same Fe/Cr/Mo ratio as that
existing in the original loop piping alloy. A black film found floating
on the lead in the top of the surge tank was identified as MnO by x-ray
diffraction and spectrographic analysis, The manganese was probably
preferentially leached from the hot leg and then deposited in the surge
tank as it scavenged oxygen from the rest of the system materials.
The carbon steel loop, constructed of large-diameter pipe, operated
for 5000 hr before shutdown. Prior to shutdown, the loop was begimning
to show some signs of restricted flow. ‘Subsequent measurements of the
wall thickness of the loop piping showed a meximum of 10 and an‘average
of 7 mils of attack similar to that found in the 2 1/4 loops (see Fig. 6).
V62846 §|
0.045 INCHES
N 100X
| Y
Fig. 6. Section Through Hot Leg of 2 1/4 Cr Lead Loop Which
Operated for 5156 hr with a Hot-Leg Temperature of 1100°F and a AT of
' 200°Fo
The attack consisted of uniform surface removal.
P8
c;;iz
»
. | - 7 o o
2 o , | I | .
| 1ii3t* . . The 1oops constructed of wal% Zr clad with type 446.stainless
steel were shut down after only 385 hr of operatlon due to a faulty
'relay in the controlrsystem; The loop that contained salt could not be
restarted prdbably due to separation of a hlgh-meltlng constltuent of
the salt upon coollng. The 1oop ‘that contained only lead was restarted
. | and operated 5280 hr, Posttest metallographic examination showed no
signiflcant hot-leg attack, as indlcated by the photograph shownt in
Fig. 7. .Some mass transfer crystals were found in this loop, as shown
in Fig} 8. The crystals were found to be 90 to- 100% Nb by electron
probe as shown in Fig. 9, Nicbium mass transfer has not been reported
by any other investlgators.,
En
g, Hallerman and R.'S;'Crouse; personai communication, Nov. 9, 1965,
- . ’
. . - .
B Y.66685
o I - Fig. 7. Section Through Hot Leg of Nb—l% Zr LOOp Which Operated
f "iJ - Over 5000 hr with a Cold-Leg Tbmperature of l400°F and a AT of 400°F.
f Unetched. 750x. - , .
ay -
12
Fig. 8. Nicbium Crystals Found in Cold Leg of Nb-1% Zr Loop Which
Operated Over 5000 hr at 1400°F and a AT of 400°F. Unetched. 250x%.
Y-67208
Fig. 9. Optical and Niobium Ly X-Ray Image Taken of the Niobium
Crystels Formed in the Cold Leg of a Niobium Thermal Convection Loop
Which Operated 500 hr at 1400°F and a AT of 400°F. 250x. (a) Light
optics. (b) Niobium Lg X-Ray Image. | ‘ -
.
_‘ (“h
€
o>
w!
13 -
© CONCLUSIONS AND RIECOMMENDATTONS
The results of the tests are given in feble 2 along with a
Brookhaven loop to use as a comparison. The poor performance of the
| ferritic materials described here: suggests that these materials are
unsuitable to contain,lead{at the conditions_investigated. This is
'surpriSing-in light of the 27,795-hr Brookhaven loop;_ The 78°F 4if-
ference in hot-leg'temperature between our 5156<hr loop and the
Brookhaven 1oop'is'not'great enough to-explain the several orders of
magnitude difference in the corrosion, ‘The difference could‘be due to
-the_inhibiting effect of the magnesium, used as a debxident in the
Brookhaven loop. Previously‘ cited literature describing the benefit
to be derived by inhibitors“offers a possible remedy. The most promising
inhibitor for our System wouldibe titanium since it is also compatible
with the salt, ? It is therefore recommended that several tests be per-
- formed to evaluate the effect of titanium and/or magnesium as inhibitors
in a steel-liquid 1ead system.
The Nb—1% Zr in these tests had better compatibility at higher :
temperatures than the ferritic‘materials. Although it is expensive and
at present difficult to fabricate, Nb-1% Zr could possibly be used in the
.~ high-temperature portion Ofga bimetal system, It is therefore suggested
that the effects of MSRE salt in & Nb—l% Zr-lead system be further
investigated _ _ o
‘The loops that. were used in this investigation were run for
'iscreening purposes and were not designed to obtained a maximum amount of
~ data. Corros1on rates on the 1oops could only be determined metallo-‘
"-ugraphically.- Since the attack occurs as uniform surface removal, the
7 :'depth of attack could- only be determined by wall thickness differences,
7_;fan inaccurate method due to the variation in original pipe wall thick-
'ness.r Consequently, a new loop de51gn has been develcped and is des- N
““.cribed in the Appendix._ The new 1oop gives better control of the loop
‘Variables and provides for improved methods of analysis. : -
Table 2. Operating Conditions and Results of Thermal-Convection
Loop Tests Using Lead as a Coolant
‘ - Maximum : Maximum Depth Average Depth .
Loop Material - Temperature AT Operated of Attack of Attack Inhibitors
o~ (°F) (°F) (hr) (in.) . (in.)
Croloy 2 1/4 1210 300 266 0.001.% None
AISI-type 410 1210 300 1,346 0,002% None
stainless steel | |
Croloy 2 1/4 | 1100 200 5,156 0.008" -~ 0.006° None
ASTM-type A-106 1100 200 5,064 0.010° 0.007" None
Nb—1% Zr clad with type 1400 400 385° ' . None
446 stainless steel | |
Nb—1% Zr clad with type - 1400 400 5,280 None® None" None
446 stalnless steel : , '
Croloy 2 1/4° 1022 221 27,765 None Nome 250 ppm Mg +
_ | Zr
®Determined metallographically by thickness of corrosion layer.
bDetermined metallographically by wall-thickness change.
cLoop containing salt shut down due to instrument malfunction.
fldNo measurable hot-leg attack however, crystals of niobium were formed in the cold
Brookhaven Loop.
4w ' o »
leg.
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15
- APPENDIX
In an effort.to%inCreaSe the value of thermal -convection loop tests,
a new test loop was developed (see Fig. 10) incorporating the folIOW1ng
features:
1. Removable hot-leg samples for both weight-change measurements and
metallographic analysis. Samples can be removed w1thout contacting
the salt. | | '
- 2. Temperature control by'a'thermocouplehlocated in the lead. The
'thermocouple is movable 80 that a temperature profile of the hot
i leg can also be obtained.
3. MSRE salt floating on 1ead in contact with both the Nb—l% Zr liner
‘and graphite in the surge tank,
4. Miniaturized de51gn to. facilitate sectioning or radiographing of the
complete loop. |
5. Sampling of both the 1ead and salt
6. A method by which the 1oop may be drained and refilled without
removing the salt so that the hot leg can be radiographed to find
selective attack and so that mass transfer crystals may'be removed
by gravity separation. ) f
7. Improved control of theJCOld-leg temperature.
A.prototype loop of the new design was run to_test_the'temperature ,
distribution and the sample removal=and'cleaning techniques, = The loop
-operated with a hot-leg temperature of 1100 and 1200°F and a maximum
AT of 230°F The sample cleaning techniques that were developed con-
‘sisted of amalgamation of- the 1ead with mercury and then removal of the
_- amalgamate with concentrated nitric acid Control specimens . processed
'7_-along with the loop specimens showed no significant weight change. One
of the removable samples used in the loop was zirconium. It did not
"1ose or gain any weight. Since the loop plugged after 1848 hr of opera-
tion end showed & maximum of 4. 5 mils of attack, it is apparent that the
., “presence of z1rconium did not signlficantly affect the corr051on behavior
~ in the system.
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