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ORNL-2373.txt
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‘ IR A sy
3 445L 00LODOOS2 5 ._
AEG RESEARCH AND DEVELOPMENT REPORT < oi™veccron- .. 5 4
Special Features of Aircraft lgaactors
EFFECT OF RADIATION ON CORROSION
OF STRUCTURAL MATERIALS BY
MOLTEN FLUORIDES
4 G. W. Keilholtz
J. G. Morgan
W. E. Browning
E
| o IS SR
o A-JL-&.‘L
B (LT e T
il o a0
Y /
B
OAK RIDGE NATIONAL LABORATORY
OPERATED BY
UNION CARBIDE NUCLEAR COMPANY
A Division of Union Carbide and Carbon Corporation
POST OFFICE BOX X * OAK RIDGE, TENNESSEE
LEGAL NOTICE
This report was prepared os an occount of Government sponsored work. Neithsr the United States,
nor the Commission, nor any parson acting on behalf of the Commission:
A. Mokss any warranty or representation, express or Implied, with respect to the accurocy,
completeness, or usefulness of the informotion contained in this report, or thot the use of
any informotion, apporatus, methed, or process disclosed in thiz report may not infringe
privately owned rights; or
B. Assumes cny liabilities with respect to the use of, or for damages resulting from the use of
any information, opparatus; mathod, or process disclosed in this report.
As used in the above, "'person acting on bahall of the Commission" Includes any employes or
comtroctor of the Commission to the extent thot such employese or contractor prepares, handles
or distributes, or provides occess fo, any information pursuant to his employment or contract
with the Commission.
— ORNL—EfiS R
This document consists of 2
ages. Copy /1P of 246 copi
Contract No. W-Th05-eng-26 gefies A.py P
SOLID STATE DIVISION
EFFECT OF RADIATION ON CORROSION OF STRUCTURAL MATERIALS BY
MOLTEN FLUORIDES
G. W. Kellholtz
J. G. Morgan
W. E. Browning
DATE ISSUED
AUG 131957
OAK RIDGE NATIONAL LABORATORY
Operated by
UNION CARBIDE NUCLEAR COMPANY
A Division of Union Carbide and Carbon Corporation
Post Office Box X
Oak Ridge, Tennessee
‘l Hiflflm’m MA|R1|E‘T|'I"|\’ ENERGY SYSTEMS LIBRARIES —
J 4456 00LOOSE 5
'
WO O3\ Fwhn -
10.
12.
13.
1k,
15.
16.
17.
18.
19.
20.
21,
22,
23.
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25,
26,
27,
28.
29,
30.
31.
32,
33.
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35.
36.
37.
39.
Lo.
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Lo,
43.
Ly,
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L6,
* J.
° FI
. R. Grimes
» G.
G. Affel
J. Barton
Bender
S. Billington
. F. Blankenship
P. Blizard
Borkowski
Boudreau
Boyd
Bredig
Breeding
Browvning
E.
A.
Je.
E.
. R. Bruce
. Do
Callihan
W. Cardwell
Center (K-25)
A. Charpie
Clark
E. Clifford
H. Coobs
. B. Cottrell
Cromer
Crouse
L. Culler
. R. Cuneo
DeVan
M. Doney
. A. Douglas
Dytko
Eister
Emlet (K-25)
Ferguson
Fraas
H. Frye, Jr.
Furgerson
Gray
Gresky
Grindell
Guth
S. Harrill
S. Householder
gT. Howe
=11~
INTERNAL DISTRIBUTION
ORNL-2373
¢-84 - Reactors-Specifl
Features of Aircraft Reactors
7. W. H. Jdbrdan
418. G. W. geilholtz
k9, C. P ffeim
50. F. / eller
51. M. P¥Kelley
52. F. J¥rtesz
53. J. 5. Keyes
5k, JFA. Lane
55. B B. Lindauer
56. F. S. Livingston
57.#R. N. Lyon
5Gf H. G. MacPherson
. R. E. MacPherson
FO0. F. C. Maienscheéin
61, W. D. Manly
62. E. R. Mann
63. L. A. Mann
64. W. B. McDonald
65. R. MeNally
66. R. McQuilkin
67. R. V. Meghreblian
68. R. P. Milford
69. J. Miller
T0. E. Moore
. G. Morgan
. Z. Morgan
obmudmbpz>9U>mwhwmzqmmm?mqufl
»
® P'
L.
. J.
B.
G.
Murray (Y-12)
Nelson
Nessle
Oliver
Overholser
Patriarca
. K.
. MI
Penny
Perry
Phillips
C.
E.
T.
W.
. W.
D
L.
D.
Scott
Pigg
Richt
Robinson
Savage
Savolainen
Schulthelss
Scott
Shipley
. Simon
Sisman
r
93. J.
9L, M.
95. A.
96. C.
97. J.
98. E.
99. R.
100. D.
101. D.
102. G.
103. A.
120.
121-.122.
123,
12k,
125,
126-128.
129,
130-131.
132,
133.
134,
135.
136.
137-139.
1L0.
141,
142,
143,
1k,
145-150.
151,
152,
153-154,
155.
156.
157.
158.
159.
160.
161,
162,
163.
164-167.
168.
169.
170.
171-172.
-iii-
Sites 10k. G. D. Whitman
J. Skinner 105. EP. Wigner (consultant)
H. Snell 106. J#FC. Wilson
D. Susano 107. X E. Winters
A. Swartout 108 M. Zobel
H. Taylor 109-11147 ORNL - Y-12 Technical Library
E. Thoma ## Document Reference Section
B. Trauger 112-36. Laboratory Records Department
K. Trubey #17. Laboratory Records Department
M. Watson y ORNL R.C.
M. Weinberg Po-119. Central Research Library
EXTERNAT, DiSTRIBUTION
Aerojet-General CRrporation #F
AFPR, Boeing, Seale y
AFPR, Boeing, WichRta
AFPR, Curtiss-Wrighk, Clifffon
A¥PR, Douglas, Long¥eac
AFPR, Douglas, SantafMo
AFPR, Lockheed, Burbahk
AFPR, Lockheed, Marielt
AFPR, North American,
AFPR, North American,
Air Materiel Command
Air Research and De
Air Technical Inteljigefge Center
ANP Project OfficeConviir, Fort Worth
Albuguerque Operaiifons OXfice
Argonne National Msboratofey
Armed Forces Spegllal Weaplhs Project, Sandia”
Armed Forces Spglfial Weapols Project, Washington
Assistant Secreffiry of theWir Force, R&D
Atomic Energy @mmission, Whshington
Atomics Interpgtional ‘
Battelle Memogal Institute
Bettis Plant JWAPD)
Bureau of Aeffonautics
Bureau of Agffonautics GeneralYRepresentative
BAR, Glenn f. Martin, Baltimo
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y- 2
bnoga Park
Rovney
L ofgnent Commend (RDGN)
Curtiss-Wiight Corporation
Engineer Research and DevelopmenW Laboratories
General Mectric Company (ANPD)
General Buclear Engineering Corpoftion
Glenn L.MMartin Company
Hartford@Area Office
Heddquajers, Air Force Special Wedons Center
173.
17k,
175.
176.
177,
178.
179.
180.
181.
182,
183.
184,
185.
186.
187.
188.
189,
160-193.
194,
195,
196,
197.
1498,
'199.
200.
201.
202.
203-220,
221-2k45,
2L6.
o,
Idaho Opegations Office
Knolls AtoNie Power Laborato
Lockland Args Office
Los Alamos Sgientific Laborgtory
Marquardt Aingraft Companyy
National Advidory Committelf for Aeronautics, Cleveland
National Advis@ry Commitige for Aeronautics, Washington
Naval Air Develépment Ceper
Raval Air Materi-x Cent-
Naval Air Tufbine est
Naval Research Labig ato
New York Operations Al
Nuclear Development‘ %
Office of Naval Res#
Office of the Chief;
Patent Branch, Washj
Patterson-Moos 4”’
Pratt and Whitney §
San Francisco 0pe¢' f_l- Office
Sandia Corporatiqpg N
School of AviatiqlllMedd ine
Sylvania-Corningf cle-gsCorporation
Technical Reseajfy Groujiy
USAF Headguarte Y
USAF Project fff “x
U, 8. Naval R'@;slogical ) fense Leboratory
University of} l” ifornia Hg iation Laboratory, Livermore
Wright Air Dgfflopment Centdr . (WCOSI=3)
Technical I fy mation Serv-Q' Extension, Oak Ridge
Division ofJ search and Dey fflopment AEC, ORO
fn
ation
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h
KNaval Operations (OP-361)
aton
NJ
A ft Division
A
]
Abstract
A survey of the experimental methods used in testing the radiation
stability of molten salts and their corrosion properties is presented.
The effects of irradiation on the corrosion on Inconel exposed to fluoride
fuel mixtures and on the physical and chemical stablility of the fuel
mixtures have been investicated by irradiating in the MIR capsules
filled with static fuel and by operating in-pile forced-circulation loops
in the LITR and in the MTR. In the many capsule tests and in the three
in-pile loop tests made to date, no major changes have occurred in the
fuel mixtures that can be attributed to irradiation, other than normal
burn-up of uraniumf Metalluregical examinations of the Inconel capsules
and tubine have likewise shown no chanees in corrosion that can be the
result of radiation damaese. The low corrosion results obtained for the
in-pile loops have been confirmed by chemical analyses for corrosion
products in the fuel mixtures.
-D-
The use of molten fluorides as reactor fuels (1) requires that they be
stable both thermally and in intense radiation fields. The fission process in
the salt causes resions of hish ionization density to exist, as well as very
hich heat fluxes. However, since molten salts are eenerally ionic liquids,
there is no crystalline lattice to disrupt, nor are there.covalent bonds to
sever. Thus, fast neutrons, fission fraemsnts, and ecamma radiation cannot
cause severe damage of the type found in crystalline materials. However, the
interface between the molten salt and its container offers a site where
radiation effects mieht meake themselves evident in an acceleration of the
corrosion process. With this possibility, it has been necessary to test the
compatibility of various salts with structural metals in the hichest neutron
fluxes available.
The principal methods used in in~pile testing of molten salts are listed
in Table I. Capsule tests were performed first because of their simplicity
and their ability to produce information susceptible to statistical analysis.
The successive techniques listed in the table are of increasine desrees of
complexity and approach closer and closer to the desien conditions of a
practical nuclear power plant. Each step, however, introduces new variables
and requires far ecreater expenditure of effort and time than the previous
step does, rapidly decreasine the number of tests which can be performed.
Although consideration was eiven to their use, rockineg capsule tests and
thermal convection loops have not formed a part of the work described hers.
Capsule tests have been made with nickel, types 316 and 347 stainless
steel, and Inconel. The salts employed and their compositions are listed
in Table II. The first salt irradiations were conducted by Van De Graaf (2)
and cyclotron (3) bombardments. Proton bombardments {3b)were employed to
TABIE T
METHODS OF STUDYIN~ RADIATION EFFECTS ON CORROSION BY MOLTEN FLUORIDE FUELS
1,
2.
3.
Lo
5.
In-Pile Capsule Tests
Rocking Capsule Tests
Thermal Convection Loops
Forced-Flow loops
Experimental Reactors
i
TABIE II
MOLTEN SALTS TESTED IN RADIATION EFFECTS PRONRAM
System
KOH
NaF-KF--UF4
NaF—Ber-UF
NaF-BeFZ-
NaF-BeF ~UF
NaF-ZrF ,=UF
I~
NaF=ZrF, -UF
,F\
&7 e
o~
NaF=2rF, -
NgF~ZrF -
=~
w o
Compogition (molgi)
100
46,5-26.0-27.5
25,0-60,0-15.0
47.0-51,0-2,0
50.0-46.0-4.0
63.0-25,0-12.0
53.5=-40.0-12.0
50.0-48.0-2,0
50,0-48.0-2.0
-5~ | S
supplement parallel experiments in the ORNL fraphite Reactor because of the high
gspecific power attainable in this way. These irradiations were continued for 1
to 92 hours, usineg 20 to 22 Mev. protons in the ORNL 86-in. cyclotron. Specific
power generation ranged from 500 to 4700 watts em™>. With the starting of the
MTR, a sufficiently hish-flux reactor became available for these experiments.
Irradiation with fieutrons, gamma rays, and fission fragments obtained in this
way are far more realistic than those using elementary charced particles. The
emphasis was therefore shifted to reactor irradiations.
A typical capsule used in the MIR irradiation prooram is shown in Fie. 1.
It is 0.100 in. i.d. with & 0.050 in. wall. The length of the salt column is
1 in. In salts with hich o35 contents, the diameter of the fuel column is
reduced to 0.055 in. This avoids excessive temperatures at the center Sf the
salt colums when working with fuels penerating as hish as 8000 watts em™ (4)
Fie, 2 illustrates the arranrement of control instrumentation on the north
balcony of the MIR, Electrical and cooling-air lines extend from the instrument *
panels to the top of the reactor. The capsule is loaded through the reactor
inlet water line. It is inserted down an aluminum tube into a beryllium
piece located in the reflector recion. Fig. 3 shows the MIR irradiation
facility. The temperature of the fuel is controlled by a variable flow of
air, the outer surface temperature of the capsule being monitored with
thermocouples. The weicht of salt is chosen so that about 250 watts of
fission heat are cenerated in the capsule. This requires about 3 c¢fm of
cooling air. Usine 45 psig air, the velocity throuesh the capsule restriction
is about 700 ft.sec.™t,
It was necessary to develop special thermocouple junctions for use in
such hich=-velocity cooline air streams. The air produces a large thermal
-6
gradient in the capsule wall and in the thermocouple heads. In poorly censtructed
thermocouples, errors as pgreat as 30000 have been observed., The thermocouple shown
in Fiec. 4 wes made by a resisténce spot-weldine technique. The bead 1is desigmed to
have & laroe area of contact with the capsule and to be very thin, thus ensuring
that the part which measures temperature is at the same temperature as the surface
of the capsule.
After irradiation, capsules are returned to ORNL where detailed examinastions
are made in the Solid Btate Division hot cells, Fir. 5 shows a cell equipped
for chemical analyses. Right-to-left are a vertical lathe for opening capsules,
a master-slave manipulator, a drill press for removine salt samples, and a
chemical hood. Operations involvine radioactive powders are enclosed in lucite
cases which are exhausted through a filter system. Fie. 6 shows a tool for
slittine capsules longitudinally (5), to obtain specimens sometimes desired for
metalloeraphic studies. Fig. 7 shows the hot cell in which metalloesraphic
specimens are prepared (6). Some salt samples have been examined using the *
shielded petroeraphic microscope (7) shown in Fie. 8,
The principal variables studied in the static corrosion program have been
flux, fission power, time, and temperature. In a fixed neutron flux, the fisaion
power is varied by adjusting the U235 content of the fuel mixture. Thermal
neutron fluxes have raneed from 1011 to 1014 neutrons em 2 sec.™t and fission
power-densities from 80 to 8000 watts em™, Capsules have generally been
irrediated for 300 hours at 1500°F (815°C), although in recent tests the
experiments have been extended to 600 to 800 hours. The techniques used for
examinine capsules after irradiation are listed in Table III.
1,
2o
TABLIE III
TECHNIQUES FOR EXAMINING IRRADIATED MOLTEN FLUCRIDES
Pressure Tests (In-Pile)
Melting Point Determinations
Petrooraphic Analyses
Chemical Analyses
Mass Spectroscopic Assays
nemma-Ray Spectroscopic Studies
Metallopraphic Exemination of Containers
_8-
In the many capsule tests to date (over 100), no major chanees have been
observed which can be attributed to irradiation, except the normal burn-up of
U235. Metallooraphic examinationa (8) of Incbnel capsules tested in NaF-ZrFL-UFA
and in NaF-ZrFA-UF3 at 1500°F for 300 hours have shown corrosion comparable to
that foupd in unirradiated control tests; 1.e., penetrations to depths of less
than 4 mils, In capsules which experienced accidental excursions to 2000°F and
atove, there was penetration to depths of more than 12 mils, accompanied by
srain erowth. These results stimulated extensive development work on control
instrumentation and thermocouple construction. Chemical determinations of
chromium in irradiated salts have been shown (3) to bte seriously affected by
the intense beta radiatlon of the accompanyine fission products. Work is
currently in proeress on the circumvention of this problem.
Three typesof forced-circulation in-pile loops have been.studied. A larece
loop was operated in a horizontal beam-hole of the LITR (1Q). The pump for
¢irculating the fuel in this loop was placed cutside the reactor shield. A
smaller loop was operated in a vertical position in the lattice of the LITR
(11), its pump mounted just above the lattice. A third loop was operated
completely within a beam-hole of the MIR (12). The operating conditions for
these loops are presented in Table IV. The dilution factor for a reactor may
be defined as the ratio of the total volume of fuel in the system to that in
the reactor core. A more useful definition for in-pils loop use is the ratio
of the maximum specific power to the averace specific power. 1In th;a two LITR
loops, metalloeraphic examinations showed less than 1 mil penetration of the
Inconel fuel tubes. Fipgs. 9 and 10 show drawings of these two loop models,
The MIR horigontal loop is shown in Fig. 11, Examination of etched and unetched
metallo~raphic sections of Inconel tubing from this loop showed no attack to a
depth ereater than 3 mils. A slicht amount of intersranular corrosion was noted,
e BB e w
..9_
but this was neither dense nor deep. Measurements of wall thickness showed no
variations attributable to corrosion. The loop was examined carefully for effects
of temperature variations between inside and outside walls of the tubine at the
bends, but no effects of overheatine were observed. The low corrosion is
attributatle to careful temperature control of the salt-metal interface and to the
maximum wall temperature beine below 1500°F at all times. The larger corrosion
value in the MTR loop results from the ereater fuel-temperature differential
(155°F) which was obtained during operation. Ioops operated in the absence of
radiation show similar effects, Studies of the behavior of fission product |
elements in these loops are discussed elsewhere (13).
The experiments described above show that, within the limits of tests to
date, there is no acceleration by radiation of the cofrosion of Inconel by
molten fluoride reactor fuels. Experiments are planned to extend the prosram to
cover new salt compositions and new alloys and to oberate in-pile loops for much
longer times with hicher flow-rates and orester fuel-temperature differentials,
-10-
TABIE IV
OPERATINA CONDITIONS FCR INCONEL FCRCED-CIRCULATION IN-PIIE LOOPS
Fuel Composition (mole%)
Max. Fission Power,
watt cm=3
Total Power
Dilution Factor
Mex, Fuel Temp.,°F.
Fuel Temperature
Differential, °OF.,
Fuel Reynoldas'! Number
Operatine Time, Hours
Time at Full Power
Depth of Corrosion
Attack, mils
LITR "LITR
Horlzontal Vertical
Ioop l1oo
NaF~ZrF -UF, “aF-irF,-
(62.5~12. 5-25) (63-25=12
400 500
208 5.0
180 10
1500 1500
30 71
6000 3000
645 130
475 30
<1 <1
MIR
Horizontal
oo
NaF—ZrFA-U
(53.5-40-6.5
800
20
5
1500
155
5000
467
271
{3
1
-1~
ACKNOWLEDCEMENTS
The work reported here has been obtained over the past six years with the
assistance of many members of the staffs of ORNL and of the Phillips Petroieum
Company, Idaho Falls, Idaho. We wish to acknowledes particularly the assistance
of the followines:
In-Pile Experimental Proorams: H. E. Robertson, P. R. Klein, M. ¥, Gsborne,
D. E, russ, H. L. Hemphill, H. V. Klaus, D. D. Davies, D. F. Weekes, W. R. Willis,
J. F. Mardock, C. D. Cac~le, J. T. Delorenzo, W. H. Tabor.
Post-Irradiation Studies: C. C. Webster, A. E. Richt, E. J. Manthos,.
Petroeraphic Studies: T. N. MeVay, 7. D. White.
Analytical Chemistry: J. H. Edeerton, L. C. Henley, J. E. lee
Mass Spectroscopy: C. F. Baldock, J. R. Sites, L. G. ~ilpatrick.
2.
3.
6o
9.
10.
11,
12.
13,
-12-
REFERBNOES
A. M, Weinberg, American Nuclear Society Meetins, Pittsbure, Pa., June
10-12, 1957,
W. E, Brownine, TID-5021, p. 44, March 6, 1951 (Secret); V. P. Calkins,