ORNL-TM-4174
POSTIRRADIATION EXAMINATION OF
MATERIALS FROM THE MSRE
H. E. McCoy
B. McNabb
AR
e
This report was prepared as an account of work sponsored by the United
States Government, Neither the United States nor the United States Atomic
Energy Commission, nor any of their employees, nor any of their contractors,
subcontractors, or their employees, makes any warranty, express or implied, or
assumes any legal liability or responsibility for the accuracy, completeness or
usefulness of any information, apparatus, product or process disclosed, or
represents that its use would not infringe privately owned rights.
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48
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ORNL-TM-4174
Contract No. W-7405-eng-26
METALS AND CERAMICS DIVISION
POSTIRRADIATION EXAMINATION OF MATERJIALS FROM THE MSRE
H. E. McCoy B.McNabb
DECEMBER 1972
} NOTICE
" This report was prepared ss an account of work
sponsored by the United States Government. Neither
* ; the United States nor the United States Atomic Energy
Commission, nor any of their employees, nor any of
their contractors, subcontractors, or their employees,
makes any warranty, express or implied, or assumes any
legal liability or responsibility for the accuracy, com-
pleteness or usefulness of any information, apparatus,
product or process disclosed, or represents that its use i
- would not infringe privately owned rights, l
f ;
OAK RIDGE NATIONAL LABORATORY fiy
Oak Ridge, Tennessee 37830
operated by
UNION CARBIDE CORPORATION
for the
U.S. ATOMIC ENERGY COMMISSION
~ PISTRIBUTION OF THIS DOCUMENT IS UNLI ITED
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CONTENTS
ADSIIACE . ot ittt ittt ittt it aa e e it et 1
Introduction . .............. @t e e et e e, 1
The MSRE and Its Operation .. ... ..c.ovuiiniiiininrnneneoeneeasosenenrasascasosoannsns 1
DS P O . L o ettt et it e i ie e e e 2
HStOTY « ot iee et et ie ettt aas it as i et 2
Examination of a Graphite ModeratorElement ........ ... ... ... il 6
Description of Graphite Elements ......... ..o oo 6
Visual Examination of Element 1184 . ...... e e et e e e 8
Chemical Analysis of the ModeratorElement .. ......... .. ..o, 10
Summary of ObServations .. ..........uneinitmiiiiinti it 14
Examination of the Graphite and INOR-8 Surveillance Specimens . .. ...............ocoiivinnn. 14
Examination of INOR-8 Control RodThimble ......... ... i iiiiiiiiiiiann. 15
Physical Description .. ........coiiiieiiininiiniinnannn e ittt 15
UndeformedSamples ...........oiiiiiiiieiiininnann, et etare e 18
Deformed Samples ... ..ovvttiii i i et 23
Summary of Observations . ............uururanniinnenneaoiiiiteteeeiiaaaaes 31
Examination of Freeze Valve 105 ... ... ittt ittt rrieectaonnansrtonnsnnns 31
Physical Description ..............c.ouann. e e e ee e e e 31
Visual and Metallographic Examination ... ..... ... oottt 31
Mechanical Property Tests .. .....ccuiiitiiiirnnnroieascientnnnntnrsoensaosaecsensas 39
Summary of Observations ..............ccceiviiirnnnn et eeesaiaeeceae e 44
Examination of the Sampler Assembly ... ..........oiiiiiiiiiiinon.ts e 44
Physical Description ........ S P 44
11 ) (3 o 021 S R R RN 47
Mist SHield .. .ovie ettt iii e iiettiaeeasaaeaaar st aaa e 54
Summary of Observations ................. Versanen e Cernesieetsanaacesaues 62
Examination of a Copper Sample Capsule ............ e ettt ieree it 65
Physical Description . ... ... e et P 65
Examination...........ccoiiiiiiiennones ettt ia et aanee e 65
Summary of Observations . ... ....uuuiiiniieentor oottt 69
Examination of the Primary Heat Exchanger ....................... I ... 69
Physical DesCrpPtON ... vvvves vt teninteeseneeenmersonsstrtaneranenaaateessuneanns 69
Examination......... e e e ettt et 70
Summary of ObServations .. .........iieeeirenreiae ittt 79
iii
Examination of the Coolant Radiator .................... e ettt iteiataea e 79
Physical Description . ... c.iiitiuiitiniiiii ittt ieatarettaratanrensaoasansnacnans 79
DS VAt OIS . o o v ottt eet e ittt ittt et e st e et e 80
Summary 0f Observations .. .....ciiiiiiiadaiieriititireetaataateacataanantrssaaanns 92
UMY L.ttt et ittt i ieseeeeeoaaaasocneasasosusnsnsosnnensnensasosensssnaasanss 92
Acknowledgment ... ... .. oo i i i e i it i e e s 95
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POSTIRRADIATION EXAMINATI'ON OF MATERIALS FROM THE MSRE
H.E.McCoy B.McNabb
- ABSTRACT
The Molten-Salt Reactor Experiment operated very successfully. The fuel loop was above 500°C
for 30,807 hr and contained fuel salt for 21,040 hr. A surveillance program was active during
operation to follow the property changes of the graphite moderator and the INOR-8 structural
material. After operation was discontinued in December 1969, several components were removed for
examination. These included a graphite moderator element from the core, a control rod thimble,
freeze valve 105, the sample cage and mist shield from the fuel salt pump bowl, a copper sampler
capsule, tubes and a portion of the shell of the primary heat exchanger, and tubes and two
" thermocouple wells from the air-cooled radiator,
Examination of these materials showed excellent mutual chemical compatibility between the
salts, graphite, and INOR-8. The INOR-8 exposed to fuel salt formed shallow intergranular cracks
believed to be due to the ingress of the fission product tellurium. The INOR-8 was also embnttled by
exposure to thermal neutrons, and this was attributed to the formation of helium by the ! B(n,a) Li
transmutation. ‘
INTRODUCTION
The Molten-Salt Reactor Expenment was a unique fluid- fuel reactor' It operated at temperatures
around 650°C for more than 30 ,000 hr between 1965 and December 1969. Operation was terminated in
1969 because the technical feasibility and promise of molten salt systems had been demonstrated, and the
operating funds were needed for development work associated with advanced concepts of molten-salt
reactors. ' S |
Surveillance samples of graphite and INOR-8 were removed periodically during operation of the MSRE,
and these were examined in detail. After operation, parts of several components were examined. The details
of the examinations of the various sets of INOR-8 surveillance samples were reported, 25 and some of the
observations made on the various components were discussed in a topical report® dealing with intergranular
crackmg of INOR-8. The present report consolidates the observations made on the surveillance samples and
the components. The components include a control-rod thimble from the core, a freeze valve that isolated
the reactor vessel and a fuel drain tank, the salt sampler cage and mist shield from the fuel salt pump bowl,
a portlon of the shell and several tubes from the primary heat exchanger; two thermocouple wells from the
coolant circuit, and several tubes from the air radiator i in the coolant c1rcu1t :
* THE MSRE AND ITS OPERATION
The MSRE and an account of most of its history are described by Haubenreich and Engel,! and Robert-
son’ has described in detail all components and systems. Because these references are widely available, the
1. P. N. Haubenreich and J. R. Engel, “Experience with the MSRE,” Nucl. Appl. Technol. 8, 118 (1970).
-2, H. E. McCoy, An Evaluation of the Molten-Salt Reactor Experiment Hastelloy N Surveillance Specimens — First
Group, ORNL-TM-1997 (November 1967).
- 3. H. E. McCoy, An Evaluation of the Molten-SaIt Reactor Expenment Hastelloy N Surveillance Specimens — Second
Group, ORNL-TM-2359 (February 1969).
4, H. E. McCoy, An Evaluation of the Molten-Salt Reactor Expenment Hastelloy N Survetllance Specimens — Third
Group, ORNL-TM-2647 (January 1970).
5. H. E. McCoy, An Evaluation of the Molten-Salt Reactor Experiment Hastelloy N Survetllance Specimens — Fourth
Group, ORNL-TM-3063 (March 1971).
6. H. E. McCoy and B. McNabb, Intergranular Cracking of INOR-8 in the MSRE, ORNL-4829 (November 1972).
7. T. C. Robertson, MSRE Design and Operations Report, Part I — Description of Reactor Design, ORNL-TM-728
(January 1965)..
description here is restricted to that necessary for the reader to understand the function of each component
- and the significance of the postoperation examination.
Descnptron
The parts of the MSRE with which we will be concerned are included in the flowsheet in Fig. 1. The
- MSRE consisted basically of the primary circuit mcludmg the reactor vessel, a fuel pump, and an
intermediate heat exchanger a coolant circuit including the tube side of the intermediate heat exchanger, a
coolant pump, and an air radiator; and several auxiliary components associated with fuel and coolant salt
storage and fission gas- processing. Al metallic parts that contacted salt were made of a nickel-base alloy
known as INOR-8 and now available commercially under the trade names of Hastelloy N and Allvac N. This
alloy, developed at Oak Ridge National Laboratory® specifically for use in fluoride salts, has the nominal
' composition Ni—16% Mo—7% Cr—5% Fe—0.05% C. The graphite moderator was made of a special
low-porosity graphite, grade CGB, to exclude salt from the. graphite pore structure.’ The graphite was
produced in the form of bars 2.5 in. square by 72 in. long. These were machined to 2 in. square with a
channel on each face for fuel salt flow.
The fuel salt composition was LiF-BeF, -Z1F 4 -UF,4 (65-30-5<1 mole %); the coolant was LiF—34 mole
% BeF, . At full power the 1200-gpm fuel stream normally entered the reactor vessel at 632°C and left at
654°C; the maximum outlet temperature at which the reactor operated for any substantial period of time
was 663°C (1225°F). When the reactor was at low power, the salt systems were usually nearly isothermal at
about 650°C. During extended shutdowns the salt was drained into tanks, where it was kept molten while
the c1rculat1ng loops were allowed to cool. Plugs of salt frozen in flattened sections of pipe (“freeze
valves™) were used to isolate the drain tanks from the loop. The liquidus temperature of the fuel salt was
about 440°C and that of the coolant salt was 459°C, so the loops were heated to 600 to 650°C with
external electric heaters before the salt was transferred from the storage tanks Hehum (sometlrnes argon)
was the cover gas over the fuel and coolant salts.
~ During operation, samples of fuel salt were obtained by lowering small copper buckets (capsules) into
the pool of salt in the pump bowl. The pump bowl served as the surge space for the loop and also for
separation of gaseous fission products from a 50-gpm stream of salt sprayed out into the gas space above
the salt pool. To protect the sample bucket from the salt spray in the pump bowl, a spiral baffle of INOR-8
extended from the top of the bowl down into the salt pool. A cage of INOR-8 rods inside the spiral baffle
guided the sample capsule in the pump bowl. | o
The fuel system was contained in a cell in which an atmosphere of nitrogen containing from 2 to 5%
oxygen was maintained. This containment atmosphere was recirculated through a system that provided
cooling for the control rods and the freeze valves. Most of the coolant piping was exposed to air.
History
‘The history of the MSRE during the four years in which it operated at significant power is outlined in
Fig. 2. Construction was finished and salt was charged into the tanks late in 1964. Prenuclear testing,
including 1100 hr of salt circulation, occupied January through May 1965. During nuclear startup
experiments in May through July 1965, fuel salt was circulated for 800 hr. The salt was dreined_, and final
H. E. McCoy, “The INOR-8 Story,” ORNL Review 3(2), 35 (1969).
8 .
9. H. E. McCoy and I. R. Weir, Materials Development for Molten- Salt Breeder Reactors, 0RNL-TM-1854 p. 46 (June
1967).
-
«)
N
ORNL-DWG 65- 114108
LEGEND
" FUEL SALT
— COOLANT SALY
sevsnsencsnss HELIUM COVER GAS
RADIOACTIVE OFF -GAS
i ——
i
!
-1
. OFF-GAS A
N T A It DT Y (R LR
ABSOLUTE
FILTERS
BLDG.
ra’vtmurm
STACK FAN b emrtfimetsans 0
: : X FROM ! FREEZE VALVE (TYP)
~tign COOLANT ; . L g
F" SYSTEM t"
¢ __.fi;r;-:
i -
. y ¥ o
1 1 ABSOLUTE
g -
P o WATER STEAM Zo_ b #o FILTERS
WATER STEAM L : s
t i goerdliesd
ODOLANT
DRAIN
TANK
Fig. 1. Design flowsheet of the MSRE.
INVESTIGATE
OFFGAS PLUGGING
REPLACE WALVES
AND FILTERS
RAISE POWER
REPAR SAMPLER
ATTAN FULL POWER
CHECK CONTAINMENT
FULL ~POWER RUN
=— MAIN BLOWER FALURE
‘REPLACE MAIN BLOWER
MELY SALT FROM GAS LINES
REPLACE CORE SAMPLES
TEST CONTAINMENT
RUN WITH ONE BLOWER
> WNSTALL SECOND BLOWER
ROD QUT OFFGAS LINE
CHECK CONTAINMENT
30-doy RUN
AT FULL POWER
}REFLEEARLNE
- DISCONNECTS
- SUSTAINED OPERATION
AT HIGH POWER
REPLACE CORE SAMPLES
© TEST CONTAINMENT
02 4868 89
POWER {Mw)
Fig. 2. Qutline of the four years of MSRE power operation.
SALT N
FUEL LOOP POWER
S
—
ORNL~DWG 69-.T253R2
XENON STRIPPING
INSPECTION AND
REPLACE CORE SAMPLES
TEST AND MODIFY
FLUORINE DISPOSAL
PROCESS FLUSH SALT
PROCESS FUEL SALT
LOAD URANIM -233
REMOVE LOADING DEVICE
233y 7ERO -POWER
PHYSICS EXPERMENTS
INVESTIGATE FUEL
SALT BEHAVIOR
CLEAR OFFGAS LINES
REPAR SAMPLER ANO
CONTROL ROD DRIVE
233, DYNAMCS TESTS
INVESTIGATE GAS
W FUEL LOOP
HIGH-POWER OPERATION
10 MEASIRE B3y o /e,
INVESTIGATE COVER GAS,
XENON, AND FISSION
PRODUCT BEHAVIOR
ADD PLUTONIUM
IRRADIATE ENCAPSULATED U
MAP F.P. DEPOSITION WITH
GAMMA SPECTROMETER
MEASURE TRITIUM,
SAMPLE FUEL
REMOVE CORE ARRAY
PUT REACTOR IN STANDBY
%, .
)
ORNL-DWG T0-2164
120
Ho
100
8
CHROMIUM (ppm)
3
40
30
RUN 8 1
FLUSH & ¢ tie 2
DJFMAMJJASONDJFMAMJJASONDJFMAMJJASONDJFMAMJJASOND
19€9
1966 1967 1968 -
Fig. 3. Corrosion of the MSRE fuel circuit in 235y and 233y power operations, as measured by chromium
concentration in the fuel salt.
preparations for power operations were made in the fall of 1965. Low-power experiments in December led
into the history covered in Fig..2 (see Haubenreich and Engel’° and MSR Program semiannual progress
reports for more detail).
The nuclear fuel was 33%-enriched 23U, and the UF, concentration in the fuel salt was 0.8 mole %
until 1968. Then the uranium was removed by fluorination and 2*2UF, was substituted. The UF,
concentration required with 223U was only 0.13 mole %. The composition of the fuel salt was observed by
frequent sampling from the pump bowl.!! Aside from the 23U loading and periodic additions of small
increments of uranium or plutonium to sustain the nuclear reactivity, the only other additions to the fuel
salt were more or less routine small (~10-g) quantities of beryllium and, in two or three experiments, a few
grams of zirconium and FeF,. The purpose of these additions was to adjust the U(III)/U(IV) ratio, which
affects the corrosion potential and the oxxdatlon state of corrosmn-product iron and nickel and fission
product niobium. '
The primary corrosion mechanism in the fuel salt system was selective removal of chromium by
-
2UF, + Cr(in alloy) = 2UF; + CrF,(in salt) ,
and the concentration of chromium in salt samples was the primary indicator of corrosion. Figure 3 shows
chromium concentrations observed in the MSRE fuel over the years of power operation. The step-down in
chromium concentration in the salt in 1968 was effected by processing the salt after the 235U fluorination.
The total increase in chromium in the 4700-kg charge of fuel salt is equivalent to leaching all of the
chromium from the 852 ft*> of INOR-8 exposed to fuel salt to a depth of about 0.4 mil.
Since the coolant salt did not contain uranium, the corroslon rate was extremely low. During operation,
the chromium content of the coolant salt remained at 32 ppm, w1th1n the accuracy of the analysis.
10. P. N. Haubenreich and J, R. Engel, “Experience with the MSRE,” Nucl. Appl. Technol. 8, 118 (1970).
11. R. E. Thoma, Chemical Aspects of MSRE Operation, ORNL-4658 (Decembér 1971).
EXAMINATION OF A GRAPHITE MODERATOR ELEMENT
Description of Graphite Elements
The properties of the grade CGB graphite used to fabricate the moderator elements are given by McCoy
and Weir.!2 It is basically a petroleum needle coke that was bonded with coal-tar pitch, extruded to rough
shape, and heated to 2800°C. High density and low permeability were achieved through multiple
impregnations and heat treatments. The product was well graphitized and highly anisotropic. |
The graphite was produced as bars 2.5 in. square by 72 in. long. These bars were machined to several
configurations, but most of them had the geometry shown in Fig. 4. These elements were assembled as
shown in Fig. 5 to form the core. The elements fit together to form channels for salt flow. Four moderator
blocks were left out to leave spaces for three control rod thimbles and a surveillance assembly. The five
elements “enclosed” by the four spaces had INOR-8 lifting lugs so that they could be easily removed for
examination.
12. H. E. McCoy and J. R. Weir; Materials Debelo_pment for Moiten-Salt Breeder Reactors, ORNL-TM-1854, p. 46
(June 1967). - ' :
ORNL~LR-DWG 56874 R
TYPICAL MODERATOR STRINGERS
SAMPLE PIECE
NOTE: NOT TO SCALE
Fig. 4. Typical graphite stringer arrangement.
@
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Fig. 5. Reactor core block assembly plan, drawing D-BB-B-40416.
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S-IN SINTH ROW FROAM BoTTOoM, 2¥ preck. A SN N2 g 7 A { 50 keV), and the resulting dimensional changes should have been less than 0.1%.2° These
dimensional changes should not have resulted in significant changes in the mechanical properties of the
graphite, so no tests were run on the samples. Numerous samples were used to study fission product
deposition and penetration into the graplnte, and the results of these studles have been summarized
elsewhere.?
INOR-8 specimens were removed from the surveillance facilities inside and outside the reactor vessel.
These specimens were examined visually and metallographically and were subjected to various mechanical
property tests. The details of these examinations are presented in other reports??2™25 and will only be
summarized here.
16-
16. W. H. Cook, MSR Program Semiannu. Progr. Rep. Aug. 31, 1966, ORNL-4037, pp. 97—-102.
17. W. H. Cook, MSR Program Semiannu. Progr. Rep. Aug. 31, 1967, ORNL4191, pp. 196-200.
18. W. H. Cook, MSR Program Semiannu. Progr. Rep. Aug. 31, 1968, ORNL-4344, pp. 211~-15.
19. W. H. Cook, MSR Program Semiannu. Progr. Rep. Aug. 31, 1969, ORNL-4449, pp. 165—-68.
20. C. R. Kennedy, MSR Program Semiannu. Progr. Rep. Aug. 31, 1968, ORNL-4344, pp. 233--35.
(1972). :
22. H. E. McCoy, An Evaluation of the Molten-Salt Reactor Experiment Hastelloy N Surveillance Specimens — First
Group, ORNL-TM-1997 (November 1967).
23. H. E. McCoy, An Evaluation of the Molten-Salt Reactor Expenment Hastelloy N Surveillance Specimens — Second
Group, ORNL-TM-2359 (February 1969).
24. H. E. McCoy, An Evaluation of the Molten-Salt Reactor Expenment Hastelloy N Surveillance Specimens — Third
Group, ORNL-TM-2647 (January 1970).
25. H. E. McCoy, An Evaluation of the Molten-Salt Reactor Experiment Hastelloy N Surveillance Specimens - Fourth
Group, ORNL-TM-3063 (March 1971). :
21. M. W. Rosenthal et al., The Development Status of Molten-Salt Breeder Reactors, ORNL-4812, pp. 116-35
4
X
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#)
15
Specimens outside the reactor vessel were above 500°C up to 17,483 hr and received a peak thermal
fluence of 2.6 X 10'° neutrons/cm?. They were oxidized, and metallographic examination revealed that
the oxide penetrated about 5 mils. The specimens from the core were exposed to fuel salt and were only
slightly discolored. They were above 500°C for periods up to 19,136 hr and received thermal fluences up to
1.5 X 10?! neutronsfcm?. Metallographic examination revealed only minor changes in microstructure. A
shallow layer of modified structure less than 1 mil thick was noted. This layer etched more rapidly and
contained some lamellar product. The amount of this modified layer did not vary systematically with time
or temperature of exposure. Experiments produced evidence that the effect was likely due to cold work
from machining, causing carbide to precipitate more rapidly near the surface during h1gh -temperature
service. This structural change is not of significant importance.
The postirradiation mechanical property tests on the INOR-8 samples showed that the high?t_emperature
fracture strain of the alloy was decreased by irradiation. This is attributed to the helium produced by the
10B(n,a)?Li transmutation. However, considerable progress has since been made in developing an alloy
with modified chemical compositiori that has improved resistance to helium-induced embrittlement.?®
Metallographic examination of the deformed surveillance samples revealed shallow intergranular
cracking, particularly in samples deformed at 25°C. This type of cracking indicates intergranular
embrittlement, and considerable evidence shows that the embrittlement is due to the inward diffusion of
the fission product telturium.?” Although the cracks were only a few mils deep in samples from the MSRE,
there is considerable concern over how cracks would propagate by this process in a power reactor over a
30-year operating period.
o EXAMINATION OF INOR-8 CONTROL ROD THIMBLE
Physical Description
The MSRE used three control rods fabricated of Gd,0; and Al,0; canned in Inconel 600.2® The
control rods 0peiated iriside' thimbles made of 2-in.-OD X 0.065-in.-wall INOR-8 tubing. The assembly
before insertion in the MSRE is shown in Fig. 10. Thimble 3 was examined in some detail.
The detailed shop drawings for the thimble are shown in Fig. 11. The thimble tubing was made from
INOR-8 heat Y-8487, and spacers were machined from INOR-8 heat 5060 (see Table 4 for compositions).
The spacers were joined to the thlmble by beads of weld metal that were deposxted on the tubmg through
clearance holes in the sleeves.
The exterior of the thlmble was exposed to fuel salt and the intefior to the cell enwronment of N, +
O,. The tubing was above 500°C for 30,807 hr and received a peak thermal fluence of 1.9 X 10?1
neutrons/cm?. The lower portion of the control rod thimble was severed by electnc arc cutting and moved
to the hot cells for examination. Flgure 12 shows the electric arc cu_t at the left (about at the midplane of
the core),-the spacer sleeves, and the end closure (located at the bottom of the core). The fuel salt appears
“to have wet the INOR-8 near the center of the core, where the tempereture and flux were highest (as shown
around the left and_;center;sp'acer 'sleeves), but not at the bottom (as shown on the _right sleeve). Some of
26, M. W. Rosenthal P. N. Haubenrelch H. E. McCoy, and L. E. McNeese, “Recent Progress in Molten-Salt Reactor
Development,” At. Energy Rev. 9(3), 60150 (September 1971).
27. H. E. McCoy and B. McNabb, Intergranular Cracking of INOR-8 in the MSRE, ORNL-4829 (November 1972).
28. G. M. Tolson and A. Taboada, MSRE Control Elements: Manufacture, Inspecnon Drawings, and Specifications,
ORNL-4123 (July 1967).
Fig. 10. Control rod thimble assembly before insertion in the MSRE,
Table 4. Heats of INOR-8 examined after exposure in MSRE
| PHOTO 74410 §
. Content (%)
Heat Location
Mo Cr Fe Mn C Si S P Cu Co Al v Ti w B
Y-8487 Control rod thimble 168 73 41 03 0.05 0.17 0.0075 0.004 0.03 0.1 0.16 0.25 0.007
5060 Rod thimble sleeve 164 7.05 39 045 0.06 0.52 0.006 0.001 001 0.07 001 0.28 0.01 0.005
5094 Freeze valve 105 163 7.1 3.8 0.52 0.07 0.76 0.007 0.001 0.01. 0.08 0.02¢ 0.39 0.05 0.004
5059 Sampler cage 169 6.6 39 035 007 0.59 0.003 0.001 0.07 0.01 0.21 0.01 0.04
5075 Sampler mist shield 164 6.6 40 046 0.07 0.58 0.006 0.003 0.01 006 0.02 0.26 0.02 = 0.09 0.001
5068 Heat exchanger shell 16.5 6.45 4.0 045 0.05 0.58 0.008 0.03 002 0.1 0.01 0.27 0.01 _ -
N2-5101 Heat exchanger tubes 164 6.9 39 045 0.06 0.60 0.009 0001 001 0.1 0.01 0.33 0.01 0.06 0.006
5097 Radiator tubes 16.2 7.0 42 047 0.06 0.62 0.01 0.001 0.01 0.18 0.02¢ 0.33 0.20 - 0.02
24717 Thermocouple wells 163 7.1 43 004 0.057 0015 0.003 0.008 0.10 0.14 0.055 - 0.10 047
Y-8699 Radiator header 169 638 32 030 0.06 0.13 0.003 0.03 0.20 0.002 0.24
" 8Al plus Ti.
‘e o« H « "
91
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17
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SCALL: FULL YERTICARl YLEN, GENERAL NOTES
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INSPRETION MET-WE- 259
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v _:: N OAK 0oL NATIONAL LABORATORY
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3 i senz Umion Cansipe NucLEAR ComPany
: ¥ g DIVISION OF UMION CARMIDE
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Fig. 11. Control rod bottom thimble assembly and details, drawing BB-B-56346E.
18
Fig. 12. Portion of control rod thimble examined after operation of MSRE was terminated. The thimble is made of
2-in.-OD X 0.065-in.-wall INOR-8 tubing (heat Y-8487). The electric arc cut on the left was near the center line of the
core. :
the variations in light and dark areas are due to uneven lighting for the several photographs that make up
Fig. 12. |
The first saw cut was made through the sleeve and thimble nearest the electric arc cut. The spacer sleeve
had been machined with ribs 0.100 in. high and 0.125 in. wide to position it relative to the graphite
moderator, and the sleeve had four drilled holes through which weld beads were deposited on the thimble
to hold the sleeve in place. According to the shop drawings, the minimum and maximum diametral
clearances between the thimble and the sleeve were 0.000 and 0.015 in, respectively. Thus salt would likely
enter this annular region and be in contact with most of the metal surfaces.
Undeformed Samples
Samples of the control rod thimble and the spacer sleeve were cut and examined to determine their
condition at the end of service. Typical photomicrographs of the inside of the thimble tube are shown in
Fig. 13. This surface was oxidized to a depth of about 2 mils by the cell environment of nitrogen containing
2 to 5% 0, . The oxidation process modified the microstructure to a depth of 4 mils, likely by the selective
removal of chromium. o ‘_ |
Photomicrographs of one of the weld beads are shown in Fig. 14. All of the surface shown was exposed
to flowing fuel salt. Some grains were dislodged near the surface, and grain boundaries are visible in the
as-polished condition to a depth of 1 to 1.5 mils. | |
Photomicrographs involving the interface between the thimble and sleeve are shown in Fig. 15. Figure
15(2) shows the annular region with a separation of about 7 mils and some salt present. Few surface
irregularities are visible at a magnification of 100x, indicating that they are considerably below 1 mil.
Figure 15(b) is a 500x view of the thimble and shows some surface cracks to a depth of 0.3 mil. The
outside of the sleeve is shown in Fig. 15(c); a few grain boundaries to a depth of about 1 mil are visible.
Additional photomicrographs of the sleeve are shown in Fig. 16. The sleeve material does not appear to
have received much work, since the carbide is very inhomogeneously distributed. Grain size is larger than
usual away from the stringers. The inner and outer surfaces both have modified structures. A higher
magnification view of the inner surface [Fig. 16(b)] shows that much of the modification is a high density
of primary carbide. The outer surface [Fig. 16(c)] has a shallow layer of small grains, likely due to a
working operation,
o
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(2}
19
R— 54244
D.038 INCHES
I
'
- Fig. 13. Inner surface of INOR-8 control thimble in as-removed condition. This surface was exposed to cell
environment of N, containing 2 to 5% O,. (@) As polished;_ (b) etched; (¢} etched, typical microstructure. Etchant: aqua
regia. Reduced 30.5%. ' ’ o S
|
20
R-54237) -
I~
e
0.007 INCHES
500
o
o
8
IS
0.007 INCHES
S00X
fem
Fig. 14. Outer surface of INOR-8 control rod thimble showing weld deposit made to hold spacér sleeve. The weld .
surface was exposed to flowing salt. (@) As polished; (b) etched with aqua regia. o _ .
i
i
-
-
«}
)
—_— e
10010 . - I
0.035 INCHES
100X
oo™
-
0.007 INCHES
300x%
Fig. 15. As-polished surfaces of INOR-8 control rod thimble and sleeve. (@) Annulus between thimble and sleeve;
thimble surface is in upper part of picture. (b) Outside surface of control rod thimble, showing presence of some salt and
shallow surface cracking. (¢) Outside surface of sleeve; surface exposed to flowing fuel salt.
22
100X
0.035 INCHES r—————————— ey
tog0 . 1
0.030 In.
123
0.007 INCHES
» kst
900X
o
I
1=
15
0.007 INCHES
!u
300X
I
Fig. 16. INOR-8 control rod sleeve. Etched with aqua regia. (@) General microstructure; inner surface is on left and
outer surface is on right. (b) Inner surface of sleeve. (c) Outer surface of sleeve. Reduced 30.5%.
oy
"
s
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)
23
A second cut was made away, from the sleeve, and typical photomicrographs are shown in Fig. 17. This
part of the thimble was exposed: to flowing salt. Some of the grain boundaries are v1s1b1e in the as-polished
condition. to a depth of about 4 mils, and there is some surface modxficatlon [Fig. 17(a)] Etching [Fig.
17(b)] delineates more of the grain structure and shows the shallow surface modification.
Microprobe scans were run on the thimble samples that were taken from under the sleeve and outside
the sleeve. In the first case the thimble wall was exposed to almost static fuel salt, and no gradients in iron
and chromium concentration could be detected within the 3-um region of uncertainty near the surface, The
sample outside the sleeve, which was exposed to flowing fuel salt, was depleted in chromium to a depth of
almost 20 um and in iron to a depth of 10 um (Fig. 18). Thus the amount of corrosion that occurred varied
considerably in the two regions. Measureménts were not actually made, but we would expect similar results
for the spacer sleeve. The inside surface was exposed to almost static salt and was likely not corroded
detectably. The outside surface was exposed to flowing salt and probably was depleted in iron and
chromium.
Deformed Samples
The next step was to deform some of the thimble and the sleeve to determine whether surface cracks
were formed similar to those noted in the surveillance samples. Since the product was tubular, we used a
relatively quick and cheap ring test. The fixture shown in Fig. 19 was made by (1) cutting % in. through a
1-in.-thick carbon steel plate with a 2.in.-diam hole saw, (2) cutting out the partially cut region with ample
clearance around the hole, (3) cutting the plate in two along the diameter and removing 1% in. of material
on each side of the cut, and (4) tapping a % -in.-diam thread into the two pleces Then rings % in. wide
were cut from the thimble and the sleeve. They fit into the groove and were pulled to failure, with the
resultant geometry shown in Fig. 19. The initial loadmg curves include strain associated with the ring
conforming to the geometly of the grip, so we cannot tell precisely how much the sample is deforming.
Thus the yield strength and the elongation are only relative numbers, but the ultimate tensile strength and
reduction in area obtained from these tests are true values. Obviously, this type of test is deficient in giving
good mechanical property data, but is sufficient for deforming the matenal and observing the mcxdence of
surface cracking. : "
The tensile properties of the rings are shown in Table 5. The test results show the following important
facts: - '
1. All the unannealed specimens of heat Y-8487 tested at 25°C have a “yield stress” of 52,000 to
61,000 psi, with these values appearing to be random in the variables examined.
2. At 25°C the crosshead displacement was about 1.2 in. for the unirradiated tubing and O 4 to 0.5 in.
-for the irradiated tubing. Again the variations from 0.4 to 0.5 in. appeared random.
*3. The yield stresses at 650°C were about equwalent for irradiated and unirradiated tubing. However
the crosshead displacement before fracture decreased from about 0.4 in. to 0.1 in, after irradiation. This
was due to embrittlement from helium formed from the ' *B(r, @)’Li transmutation.
.4. No material of heat 5060 (sleeve matenal) is available for unirradiated tests, but the vendor’s
cé;tification sheet showed a yield stress of 46,300 psi, an ultimate tensile stress of 117,000 psi, and a
fracture strain of 52%. The values that we obtained show higher strengths and lower ductility.
Several of the specimens that had been strained were examined metallographically to determine the
extent of cracking during straining. Photomicrographs of the control rod thimble, which was exposed to
flowing salt, are shown in Fig. 20. The inside surface was oxidized, and the oxide cracked as the specimen
was strained. The oxide should be brittle, but it is important that these cracks did not penetrate the metal.
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1o f FUEL PROCEJHNG_QEL._L._ ' .
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‘m‘fmcouFuj (Fes) smdee ”5: v _ ’ REFERENCE DRAWINGS NO.
. ATTACHED N dccomEAnce WirH : . RIDGE NATIONAL LABORATORY
I MSR-G3-940; ENTITLED Onx o':*mm o
; ‘PEOCEDURE FOR WeELDNG THERMO COUpLES o UNioN CARBIDE NUCLEAR COMPANY
_ . ! O MSRE FPrrinG f COMponenTS" : S _ DIVISION OF UNION CARBIDE CORPORATION
i TAreD Mo /132, 1963 OAK RIOGE, TENNESSEE
| ;
{ B | maufb see Den 30 AT ' LTS ON DIMENSIONS UNLESS BLDG.
_ _ o , GENERAL SPECIFICATIONS _ | MSRE NO. 72, -
Ald 7 See Dow 2737 Foar? 'Y r/ : ! , onmt*mvu - 72, -
?LT : FRACTIONS & ——— | 1. BREAK ALL SHARP EDGES 1/64 MAX. " ,
NO. REVISIONS DATE [APPO| APPD - ‘ . |é MSRE FREEZE VALVE
DRAWN T DATE ?ar e DECMALS AR . : o
CHURTE Inerraa](y 11916 —_— 3. ROUGHNESS HEIGHT OF MACHINED, 5 | : _ BREACIQ 17RO
APPAOAD _ ANGLES * SURFACES BHALL NOT EXCEED \/ D
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= X it Fig. 26. Fabrication drawings for freeze valve 105, drawing D-GG-C-55509. _— ARE IN ACCORDANCE WATH ASA ) —0 =5C | . [
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|_GENERAL SPECIFICATIONS | TOLEWCES UMLESS et P i - P
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Fig. 27. Modifications for freeze valve 105, drawing R-GG-C-56395.
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Fig. 28. Diagram showing possible cause of freeze-valve failure after modification.
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Fig. 30. Bottom portion of freeze valve 105.
e e ——————
Fig. 31. Closeup of the bottom of freeze valve 105 showing INOR-8 gas inlet and outlet line of type 304 stainless steel
that was commoded completely. The crusty substance is the salt. Note that there is no salt in the air annulus.
R-54212
Fig. 32. Weld at one end of cooling shroud. The crack begins at the round salt stain and ’proceed's for about 1 in, along
the pipe. The arrow points to the salt stain with the crack at 90° to the arrow. ' - '
. R-b5164
i
37
Fig. 33. INOR-8 tube wall of freeze valve 105 where the failure occured. As polished, S0X. Bottom surface was
exposed to fuel salt and the upper surface to air, with some salt after the leak occurred. Reduced 15%.
38
PHOTO 4185-71
"y
Fig. 34. INOR-8 tube wall of freeze valve 105 where the faflure occurred. The weld supports the end of the cooling
shroud; the failure occurred outside the cooling shroud. Etchant: aqua regia. 50X. Reduced 15%.
a“
,
39
A comparison of the etched and Unetched views shows that somié attack occurred along the crack and the
-outer surface of one tubing and that etchmg completely removed material from the attacked region. The
attack was likely due to the simultaneous exposure of the INOR-8 to salt and moist air, and probably
involved the selective removal of chromium and iron, leaving metal that was heavily attacked by the
etchant. No such attack occurred on the inside, where only salt was present.
The failure that released salt was due to thermal fatigue. The cooling shroud was 1mt1ally 0.020 in.
thick, but the added cooling tubes increased the thickness to 0.083 in. on the bottom. This made the
shroud relatively rigid on the bottom. During freezing and thawing, the outer part of the shroud changed
temperature more rapidly than the wall of the salt-containing tube. Whereas the outer part of the shroud
was- originally thin enough to deflect to accommodate the differences in length of the two members, the
field modifications made the bottom portion quite rigid. The result was that differences in temperature
imposed on the cooling shroud a stress that was tranéférred by the rigid (%-in.) end plate to the tube wall.
A crack was nucleated at the surface and propagated through the pipe wall during the numerous cycles. .
Parts of three tubes are visible in Figs. 30 and 31. The large tube in .reldtively good condition is the type
304 stainless steel air inlet tube, the center tube is the original INOR-8 air outlet tube with two
‘thermocouples visible, and the hole is the remains of the type 304 stainless steel outlet tube. The original
'INOR-8 air inlet line was capped off and is hidden by the salt. Attack of the type 304 stainless steel by salt
when air was present is as expected. The relative nobility of INOR-8 in this environment is a strong
argument for the use of INOR-8 where salt may be present.
Mechanijcal Properfy Tests
Three rings % ¢ in. wide were cut from the pipe away from the flattened section and were pulled in
tension in the same manner as previously described for the control rod thimble rings. One rectangular piece
was cut and bend-tested with the inside surface of the pipe in tension. Table 6 lists the observed mechanical
. properties. The yield stress was essentially unchanged, and the ultimate stress was reduced about 15% from
the vendor’s certified properties. The elongation was reduced considerably but was still greater than 25%. A
gage section is difficult to define in a ring test, so crosshead travel and reduction in area are reported for the
rings from freeze valve 105 rather than percent elongation. The bend test was discontinued because of
strain limitations of the bend fixture after 0.41 in. crosshead travel, which corresponds to 33% strain in the
outer fibers of the specimen and to a 90° bend angle. The yield stress calculated from the forces on the
bend specimen is too high because elastic formulas were used in the calculation and the specimen deformed
plastically, but this calculated quantity is useful for comparison with other bend tests that will be reported
later for the mist shield. '
Table 6. Results of mechanical property tests on specimens from freeze
valve 105 (heat 5094) at 25°C and a deformation rate of 0.05 in./min
Yield Ultimate Crosshead Reduction
Type of test stress tensile stress travel in area
(psi) (psi) (in.) (%)
~ Vendot’s, tensile - 45,800 106,800 52.6
Ring, tensile 45,800 89,700 0.72 25
Ring, tensile " 48,900 - 90,100 0.59 29
Ring, tensile 41,900 90,300. 0.73 37
Wall segment, bend 71,300 0.41 334
2Maximum strain in outer fibers.
40
*
Fig. 35. INOR-8 surfaces exposed to salt in freeze valve 105 after deformation at 25°C. (z) Fracture of ring specimen
pulled in tension. Note surface cracks near fracture. 4X. (b) Surface of bend specimen. Note some cracks on surface and
edge cracks. 7X. Reduced 18.5%.
Figure 35 shows the tension side of the bend specimen. Some very fine shallow cracks are visible on the
surface in tension, and cracking is visible at the edges in the burrs remaining from the remote cutting
operation. . _ | _
One of the three tensile-tested rings was examined metallographically. Figure 36 is a composite of
photomicrographs of a section through the specimen showing the inside surface, which was exposed to fuel
salt (top), and the outside, which was exposed to the cell environment of 2 to 5% O, in nitrogen. The
reason for the unevenness of the oxide on the outside is not known. Possibly it was due to corrosion after
the leak, although the rings were cut approximately 4 in. away from the nearest visible residue from the salt
leak. Figure 37 shows at 500x the oxide in one of the worst areas. The crack ends tend to be blunted and
did not penetrate the metal beyond the oxidized surface. Figure 38 shows at 500x the inside of the pipe
exposed to fuel salt. About 1 crack per grain or 240 cracks per inch show, but the cracks are shallow and
blunt, having an average depth of 0.75 mil and a maximum depth of 1.5 mils. Figure 39 shows that a large
amount of strain occurred before fracture.
-—— O —
Fig. 36. Composite of photomicrographs of INOR-8 ring from freeze valve 105 that was pulled in tension. Upper
surface was exposed to salt and the lower surface to thg‘ cell environment of Ny plus 2 to 5% O;. Top portion is the
tension side, and the lower part is the compression side.
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Fig. 39. Fracture of an INOR-8 ring specimen from freeze valve 105 that was deformed at 25°C. {a) As pollshed )
etched with lactlc acid, HNO3, HCL. 40X . Reduced 29.5 %.
Summary of Observations
The failure in freeze valve 105 was due to thermal fatigue as a result of the cooling shroud being too
rigid. The mechanical properties of the INOR-8 in the freeze valve were not degraded seriously by the long
exposure to fuel salt containing some fission products. Numerous intergranular cracks were formed on the
surfaces exposed to the salt during postoperation deformation. These cracks were similar to those on the
surfaces from the primary circuit but were shallower.
EXAMINATION OF THE SAMPLER ASSEMBLY
Physical Description
A schematic view of the MSRE fuel pump is shown in Fig. 40; more details are reported elsewhere.??
The components examined were the mist shield and the sampler cage. The fabrication drawings for these
parts are shown in Fig. 41, Salt-sample capsules or additions of uranium or beryllium were lowered by a
windlass arrangement into the sampler cage. The mist shield was provided to minimize the amount of salt
spray that would reach the sampler. The vertical sampler cage rods were Y, in. in diameter and were made
of INOR-8 heat 5059, and the mist shield was made of Y;-in. sheet of INOR-8 heat 5075 (see Table 4 for
29. R. C. Robertson, MSRE Design and Operatiohs Report, Part I, Description of Reactor Design, ORNL-TM-728
(January 1965).
45 3
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A ] " i
- LUBE oL ouT SHIELD COOLANT PASSAGES %
7 SEAL OIL LEAKAGE {In Parallel With Lube Oil) |
. S : ' DRAIN SHIELD PLUG |
" LEAK DETECTOR- GAS PURGE OUT (See Inset) |
| © SAMPLER ENRICHER GAS FILLED EXPANSION
- L , (Out of Section) SPACE
(See Inset)
BUBBLE TYPE
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OPERATING
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Fig. 40. Section of MSRE fuel 'pump with details of several areas. The mist shield and the sampler cage examined are
shown in the lower left insert.
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Kig. 82. Asreceived INOR-8 tubing used in the MSRE radiator. Etched electrolytically in aqueous solution of 5%
sodium citrate, 5% sodium acetate, 1% citric acid, 1% potassium thiocyanate. 600 mV, 1.5 mA for 15 sec plus 700 mV, 2.5
mA for 10 sec. (@) 250X ; (b) 1000X.
87
an. 83. Tubing from the inlet end of the MSRE INOR-8 radlator. Etched electrolytxcally in an agueous solution of 5%
sodium citrate, §% sodium acetate, 1% citric acid, 1% potassmm thiocyanate. 700 mV for 10 sec, started at 8 mA and
dropped to 4 mA. (a) 250X ; (p) 1000X.
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Fig. 84. INOR-8 thermocouple well removed from the inlet line to the radiator of the MSRE. Much of the
discoloration and the fragments of metal resulted from cutting the part out with a coated welding electrode.
g
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Fig. 85. Cross section of INOR-8 thermocouple well from the inlet line to the MSRE radiator. From left to right the
components are the 5-in. coolant line, the weld, and the thermocouple well. The side having the most weld metal was
exposed to air, and the other side was exposed to coolant salt.
o
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-89
Table 10. Chemical analyses of sections Qf as-received
: i INOR-8 radiator tubing -
o
U S . Silicon (%) ; -+ Carbon (%)
" Inner 5 mils of wall 0.53 0.095
~ Center 62 mils of wall 0.79 0.073
Outer § mils of wall - 079 0.036
Bulk composition 0.62°% 0.067
4Vendor analysis; others made at ORNL.
Table 11. Tensile properties at 25°C of INOR-8
tubing from the outlet end of the MSRE
heat exchanger and as-received material
Yield Ultimate Fracture Reduction
stress tensile strain, in
(psi) stress(psi) %in2in. area (%)
As received 63,500 123,100 52.0 44.1
Heat exchanger 64,600 123,800 38.8 29.5
Metallographic examination of the mounted cross section shown in Fig. 85 revealed that the weld had
cracked on the salt side of the pipe. The cracks on both of the polished surfaces in Fig. 85 are shown in Fig.
86. In the worst case the cracks penetrated to a depth of about 3 mils. The remaining half of the well was
cleaned by acid etching to remove the metal left from the cutting operation, and the weld was checked with
dye penetrant. A photograph of the weld with dye still present is shown in Fig. 87. Note that the crack, as
indicated by the dark color, extends almost completely around the weld. There is also an area where
penetration of the root. pass was incomplete. We propose that the cracks formed as the weld was made,
because of the poor fit-ip of the parts to be welded. The welds were not stress relieved, and the fact that
the cracks did not penetrate further attests to the lack of stress and crevice COI‘l’OSlOIl by lithium-beryllium
fluoride salts. _ ' ;
We did not section the outlet well but we did clean the weld and examine it with dye penetrant. No
cracks were observed.
The outside surface of the S-in. ‘pipe was exposed to air and was ox1dlzed Figure 88 shows the spotty
nature of the oxide and its maximum thickness of about 3 mils.
A cross section from the bottom of the well was examined. A macroscoplc view of this section is shown
m Fxg 89 The inside of the well was prepared by drlllmg, and the pointed shape of the drill is still apparent
at the bottom The weld metal deposit on the bottom was made to ensure that salt did not leak along the
carbide stringers. The amount of oxidation was greater at the bottom of the well than further up. The
transition to the thinner oxide about % in. from the bottom is apparent in Fig. 89. Figure 90(a) shows the
oxide layer of about 5 mils at the bottom of the well, and Fig. 90(b) shows the abrupt transition about %4
in. from the bottom. Since lubricant would have been used during drilling, we suggest that this difference
may have been due to the bottom of the well not being as clean as the sides. '
A further significant observation was that the surfaces of the well exposed to the salt looked qu1te
similar to those of survelllance samples removed from the MSRE (Fig. 91) We have previously attributed
this modified surface structure to cold workmg from machining and have shown that it can be produced in
the absence of salt. The structure likely results from carbide formmg on the slip bands produced by
machmmg Thus there is no ev1dence of corrosion of this part.
20
Y-101 78
in 100X
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Fig. 86. Cracks in the root pass of the inlet weld. The cracks occurred at the fusion line and likely resulted from the
poor fit-up of the parts. As polished.
M v-101474
Fig. 87. Underside (salt side) of half of the INOR-8 thermocouple well from the inlet line to the MSRE radiator. The
part was acid etched and coated with dye penetrant. Note the indication of a crack around most of the weld and an
incomplete root pass region.
.
91
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Fig. 89. Cross section of the infet INOR-8 thermocouple well. The outside was exposed to coolant salt, and the inside
contained the thermocouple in air. 8X; as polished.
Summary of Observations
The surfaces of the radiator (tubes and thermocouple wells) that were exposed to air formed a shallow
adherent oxide, while the surfaces exposed to salt were clean and showed no evidence of corrosion, Two
slight modifications of microstructure were noted. A shallow layer on the inside surface of the tubing
etched more readily, and we attribute this to contamination of the tubing by fabrication lubricants. A
structural modification near the surface of the machined thermocouple well was similar to that noted on
surveillance specimens and is attributed to the effects of cold working on carbide precipitation. '
The cracked weld where the inlet thermocouple well was attached to the 5-in. pipe header likely
resulted from poor fit of the parts during welding. The crack probably formed when the weld was being
made, and it is encouraging that it did not propagate further during service.
SUMMARY
The Molten-Salt Reactor Experiment operated above 500°C for 30,807 hr and was filled with fuel salt
for 21,040 hr. Operation of the system was never detained by materials problems, but the examination of
INOR-8 and graphite surveillance samples during operation and several cornponents after operation resulted
in several important observations.
1. Graphite exhibited excellent compatibility with the fuel salt. Machining marks and numbers were
clearly visible, with no evidence of chemical interaction with the fuel salt.
2. The INOR-8 surveillance specimens clearly demonstrated a progressive decrease in the creep ductility
with increasing fluence. The MSRE vessel did not become brittle enough to cause termination of operation,
but an alloy with better resistance to embrittlement by neutron irradiation will be necessary for power
reactors with a 30-year design lifetime. Considerable progress has been made in developing a modlficatlon
of INOR-8 that contains 2% Ti and has improved resistance to embrittlement. 3s
_35. M. W. Rosenthal et al., “Recent Progress in Molten-Salt Reactor Development,” Atomic Energy Review 9(3),
601-50 (September 1971).
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Flg. 90. Oxide inside the inlet INOR-8 thermocouple well As pohshed (@) At the bottom; (b) transition in depth
about /3 in. from bottom of well.
94
Y-101573
Fig. 91. The outside of the inlet INOR-8 thermocouple well that was exposed to coolant salt. Note the modified layer
near the outer surface. Etchant: glyceria regia.
3. The INOR-8 surveillance samples and components removed from the fuel salt were slightly
discolored, but no evidence of corrosion could be detected by standard metallographic examination. The
selective removal of chromium and iron from metal from the core was detectable by the electron
microprobe. No composition gradients were detectable in metal from the coolant circuit. (The coolant salt
did not contain uranium.) Thus the corrosion rate was very low in the fuel circuit, and this observation
agrees well with the chemical changes observed in the fuel salt.®®
4. Some of the INOR-8 surfaces showed shallow microstructural modlficatlons One type involved
increased carbide precipitation in a lamellar pattern and was likely due to cold working from machining.
The second type was noted only on tubing and was likely due to carbon contamination from fabrication.
Neither modification is thought to be of practical significance.
5. Grain-boundary embrittlement was noted on all INOR-8 surfaces exposed to fuel salt. The shallow
intergranular cracks were often visible in polished sections of INOR-8 as removed from the MSRE. In most
instances the material had to be strained to make the cracks visible. Cracking similar to that noted in the
MSRE was produced in laboratory experiments by exposure of INOR-8 to the fission product tellurium.®?
This experimental work has shown that the extent of cracking is very dependent on the alloy composition.
6. Freeze valve 105 failed from thermal fatigue due to nnproper construction and not from a basic
materials problem. '
36. R. E. Thoma, Chemical Aspects of MSRE Operation, ORNL-4658 (December 1971).
37. H. E. McCoy and B. McNabb, Intergranular Cracking of INOR-8 in the MSRE, ORNL-4829 (November 1972).
95
7. A crack was noted in the weld that attached the thermocouple well to the radiator coolant salt
header. This crack was restricted to the root pass and was likely a result of poor fit-up of the parts. The
crack probably formed when the weld was made and did not propagate during service.
8. Oxide films were formed on all the INOR-8 surfaces éprsed to air or the cell environment of
nitrogen containing 2 to 5% Q,. The oxide generally consisted of a uniform surface layer about 1 mil thick
and a selective oxidation front extending to a depth of 4 or § mils. This depth and type of oxidation are
what would be expected for an alloy that contains only 7% Cr, such as INOR-8.
9. A copper sample capsule that had been in the fuel salt pump bowl for several thousand hours was
very brittle. Chemical analysis showed that constituents of the fuel salt and INOR-8 had penetrated the
copper, but the element responsible for the embrittlement was not identified.
" ACKNOWLEDGMENT
The observations in this report cover several years and include contributions from many individuals.
W.H. Cook and A. Taboada designed the surveillance fixture, and W. H. Cook was responsible for its
assembly and disassembly. The MSRE operations staff, headed by P. N. Haubenreich, exercised extreme
care in handling the surveillance fixture and in removing the various components for examination. The
Hot-Cell Operation Staff, headed by E. M. King, developed several special tools and techniques for various
examinations and tests of materials from the MSRE. The metallography was performed by H. R. Tinch,
E.H. Lee, N. M. Atchley, and E. R. Boyd. The microprobe scans were made by T. J. Henson and R. S.
Crouse. The mechanical property tests were performed by B. C. Williams, H. W. Kline, J. W. Chumley, L. G.
Rardon, and J. C. Feltner. The chemical analyses were performed under the supervision of W. R. Laing,
E.I. Wyatt, and J. Carter. Assistance was received from several members of the Reactor Chemistry Division
in several phases of this work. J. W. Koger, J. R. DiStefano, P. N. Haubenreich, and J. R. Weir reviewed the
manuscript of this report and made many helpful suggestions. Kathy Gardner made the original drafts of
this report, and the drawings were prepared by the Graphic Arts Department.
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