Resistance of materials to attack by liquid metals

142 Pages·1950·7.281 MB·English

by  LeRoy R Kelman, Walter D Wilkinson, Frank L Yaggee, Argonne National Laboratory

ANL -44 17
Metallurgy and Ceramic s
- .- ARGONNE NATIONAL LABORATORY
*.:
i j_ P. 0. Box 5207
Chicago 80, Illinois
RESISTANCE OF MATERIALS TO ATTACK
BY LIQUID METALS
LeRoy R. Kelman, Walter D. VJilkinson, and
Frank L. Yaggee
. . Metallurgy Division
LEGAL NOTICE
July, 1950
Operated by the Uiiiiversity of Chic-
und e r
-
Contract W -3 1 109- eng- 38
,
.
DISCLAIMER

This report was prepared as an account of work sponsored by an
agency of the United States Government. Neither the United States
Government nor any agency Thereof, nor any of 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. Reference herein to any specific commercial product,
process, or service by trade name, trademark, manufacturer, or
otherwise does not necessarily constitute or imply its endorsement,
recommendation, or favoring by the United States Government or any
agency thereof. The views and opinions of authors expressed herein
do not necessarily state or reflect those of the United States
Government or any agency thereof.
DISCLAIMER

Portions of this document may be illegible in
electronic image products. Images are produced
from the best available original document.
2
No. of
Copies
Distribution
252
Argonne National Laboratory
Armed Forces Special Weapons Project 1
- 2
Atomic Energy Commission Washington
1
B a tt e 11e Me mo ria1 Institute d. 1
Brush Beryllium Company
Brookhaven National Laboratory 4
1
Bureau of Medicine and Surgery
Bureau of Ships 1
Carbide and Carbon Chemicals Division (K-25 Plant) 4
Carbide and Carbon Chemicals Division (Y-12 Plant) 4
1
Chicago Operations Office
1
Columbia University (J. R. Dunning)
1
Columbia University (G. Failla)
1
Dow Chemical Company
H. K. Ferguson Company 1
3
General Electric, Richland
1
Harshaw Chemical Corporation
1
Idaho Operations Office
2
Iowa State College
1
Kansas City Operations Branch
Kellex Corporation 2
4
Knolls Atomic Power Laboratory
3
Los Alamos Scientific Laboratory
1
Mallinckrodt Chemical Works
1
Massachusetts Institute of Technology (A. Gaudin)
1
Massachusetts Ins'titute of Technology (A. R. Kaufmann)
Mound Laboratory 3
1
National Advisory Committee for Aeronautics
National Bureau of Standards 3
2
Naval Radiological Defense Laboratory
1
New Brunswick Laboratory
3
New York Operations Office
1
North American Aviation, Inc.
8
Oak Ridge National Laboratory
1
Patent Branch (Washington)
1
RAND Corporation
1
Sandia Corporation
2
Santa Fe Operations Office
1
Sylvania Electric Products, Inc.
15
Technical Information Division (Oak Ridge)
1
USAF, Surgeon General (Col. A. P. Gagge)
1
USAF, Director of Armament (Captain C. I. Browne)
USAF, Director of Research and Development
2
(Col. R. J. Mason, Fr.ed W. Bruner)
3
No. of
Distribution Copies
USAF, Eglin Air Force Base (Major A. C. Field) 1
USAF, Kirtland Air Force Base (Col. Marcus F. Cooper) 1
USAF, Maxwell Air Force Base (Col. F. N. Moyers) 1
USAF, NEPA Office 2
USAF, Office of Atomic Energy (Col. H. C. Donelly,
A. A. Fickel) 2
USAF, Offutt Air Force Base (Col. H. R. Sullivan, Jr.) 1
USAF, Wright-Patterson Air Force Base
(Rodney Nudenber g) 1
U. S. Army, Atomic Energy Branch (Lt. Col. A. W. Betts) 1
U. S. Army, Army Field Forces (Captain James Kerr) 1
U. S. Army, Commanding General, Chemical Corps
Technical Command (Col. John A. MacLaughlin thru
Mrs. Georgia S. Benjamin) 1
U. S. Army, Chief of Ordnance (Lt. Col. A. R. Del Campo) 1
U. S. Army, Commanding Officer, Watertown Arsenal
(Col. Carroll H. Deitrick) 1
U. S. Army, Director of Operations Research
(Dr. Ellis Johnson) 1 --
U. S. Army, Office of Engineers (Allen O’Leary) 1 .
U. S. Army, Office of the Chief Signal Officer
(Curtis T. Clayton thru Maj. George C. Hunt) 1
U. S. Army, Office of the Surgeon General
(COI. W. S. Stone) 1
U. S. Geological Survey (T. B. Nolan) 2
USAF, Director of Plans and Operations (Col. R. L. Applegate) 1
U. S. Public Health Service 1
University of California at Los Angeles 1
University of California Radiation Laboratory 5
University of Rochester 2
University of Washington 1
Western Reserve University 2
Westinghouse Electric Company 4
Naval Medical Research Institute -1
Total 381
I
4
.
i
TABLE OF CONTENTS
.
Page No
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Distribution 2
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Foreword 5
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Introduction 7
.............................
Summarizing Chart 14
. . . . . . . . . . . . . . . . .
Sodium and Sodium-Potassium Alloys 15
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Lithium 48
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mercury 57
. . . . . . . . . .
Lead. Bismuth. and Alloys of Lead and Bismuth 69
..................................
Lead 75
................................
Bismuth 84
. . . . . . . . . . . . . . . . . .
Bismuth-Lead Eutectic Alloy 88
. . . . . . . . . . . . . . .
B ism uth-Lead-Tin Lutectic Alloy 96
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Magnesium 102
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Cadmium 105
.....................................
Thallium 107
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Indium 108
.....................................
Gallium 109
....................................
Aluminum 117
........................................
Tin 119
........................................
Zinc 122
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Antimony 124
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
List of References 127
5
RESISTANCE OF h4ATERLALS TO ATTACK BY LIQUID METALS
by
LeRoy R. Kelman, Walter D. Wilkinson, and Frank L. Yaggee
FOREWORD
Existing information on the resistance of materials to attack by
liquid metals is, for the most part, very meager; and much of the informa-
tion that does exist is buried in progress reports and in personal files.
Therefore, designers of engineering systems using liquid metal coolants
often have little concrete evidence on which to base their selection of
materials.
The Committee on the Basic Properties of Liquid Metals has recog-
nized the need for assembling this information as well as information on the
properties, techniques in handling, and uses of liquid metals. With the inten-
tion of publishing this material in a Liquid Metals Handbook, the Committee
requested various member organizations to prepare specific chapters for
the Handbook, As their contribution, the Metallurgy Division of Argonne
National Laboratory was asked to assemble all available unclassified and
declassifiable data on the resistance of materials to attack by liquid metals.
The resulting collation of data is contained in this report.
Since the editors of the proposed Handbook indicated a desire for a
concise summary of available data, the authors have eschewed detailed de-
scriptions of test setups and have limited theoretical considerations. How-
ever, in order to prevent misinterpretation, they have found it necessary to
delimit and explain many of the results in considerable detail. Also, data
obtained from classified reports and private communications are described
in some detail because this information is not readily available to the general
public. As a consequence, this report is longer than was first intended and
will probably be condensed for use in the Liquid Metals Handbook. However,
it is felt that publication of this survey in its present form is desirable in
that it gives a truer evaluation of available information than would be possible
in a condensed version.
- *
Although a substantial amount of the experimental data herein pre-
sented is the result of work done at the Argonne National Laboratory, the
major portion of it is the result of the efforts of investigators at other lab-
oratories, as is indicated by the numerous references in the bibliography.
6
Principal sources of information which are gratefully acknowledged
by the authors are reports and private communications from:
Aerojet Engineering Corporation
Aluminum Company of America
American Smelting and Refining Company
Babcock and Wilcox Company
Dow Chemical Company
General Electric Research Laboratory
Knolls Atomic Power Laboratory
Mine Safety Appliances Company
Stanford University
University of California
Special thanks are due L. F. Epstein (KAPL) who supplied most of
the data on mercury as well as the KAPL data on sodium. The authors also
wish to thank Miss Muriel Morris and others who helped in preparing this
survey for publication.
... .. .... .
.
7
INTRODUCTION TO
RESISTANCE OF MATERIALS TO ATTACK BY LIQUID METALS
The practical value of a liquid metal as an engineering heat-transfer
fluid is very much limited if ordinary materials of construction cannot be
used to contain it. For example, the unusually low melting and high boiling
points of gallium, together with its acceptable heat-transfer properties,
have aroused interest in its use as a high-temperature coolant. However,
the use .of gallium as a coolant is very much restricted because of the
extreme aggressiveness with which it attacks common engineering metals
110).
(see Page
Until recently, the only large-scale application of a liquid metal as
an engineering coolant was that of mercury in the mercury-vapor turbine
process. In this connection the General Electric Company made an exten-
sive study of the behavior of several ferrous metals in mercury (see
P a g e x ) . Recent interest in sodium, sodium-potassium alloys, lithium,
lead, lead-bismuth alloys, and gallium has resulted in organized labora-
tory investigations of the container problem for these liquid metals so
that crude but more or less quantitative information is now available.
However, this information must be used with discretion in view of the lim-
ited experience in large-scale handling. For those liquid metals that have not
been considered for engineering heat-transfer applications, only meager
information exists to guide in the selection of containing materials.
I
I Mechanism of Attack
The mechanism whereby solid metals are attacked by liquid metals
is chiefly one of alloying where solubility and intermetallic compound
formation are important. The formation of chemical compounds,, such as
oxides, may also be involved as well as such phenomena as intergranular
penetration, and selective depletion of a constituent (i.e., decarburization
of steels). The term corrosion--defined as "destruction of a metal by
chemical or electrochemical reaction with its environment" (l 56) is not
strictly applicable to all of these processes and will not be used in this
survey.
Equilibrium relationships indicate the direction in which alloying
reactions tend to go although they give no information about the time
involved in any process. In general, the greater the difference in the
melting points of two metals, the less effect they will have on each other.
The ideal relationship is one of mutual insolubility between the containing
metal and the liquid. Very slight solubility may be tolerated up to tem-
peratures in excess of those under which the heat-transfer medium will
be used, although experience with liquid mercury in steel containers
8
suggests that caution be exercised in designing and using such systems (see
-
Page 59 ). The formation of intermetallic compounds is not desirable. How-
ever, such systems should not be entirely abandoned especially where there
is negligible solubility of the compound in the liquid metal and in the con-
tainer metal and where rates of diffusion are low. Compound layers may even
inhibit attack in otherwise unsatisfactory systems by acting as diffusion bar-
-
riers (see Page 112). The degree of protection in such systems depends upon
the relative permeability of the compound to the reactants which in turn de-
pends upon the relative volume of the compound to the volume of the metal
consumed. Also, differences in the thermal coefficients of expansion of the
compound and the underlying metal might decrease the protective value of a
compound by making it sensitive to thermal shock, particularly if the com-
pound is brittle.
The solution mechanism of attack and the influence of conditions
found in dynamic systems has been examined by Epstein who used iron in
sodium and in mercury as examples (see Pages 19, 59 ).(35) Conditions
of equilibrium solubility are upset where there is a temperature coefficient
of solubility and where temperature gradients occur. Even where equilibrium
solubility is very low, solution of metal in hot zones and deposition in cooler
zones can accelerate the rate of attack on the container walls in the hot region
and can cause plugging of small openings in the lower temperature regions
(see P a g e x ) . Under these conditions the rate of transfer of container metal
from one zone to another is observed to be greater for some systems (i.e.,
Fe in Hg) than for others (i.e., Fe in Na) even though the reverse of this
would be expected from consideration of equilibrium solubilities alone. Pos-
sible explanations of this anomoly have been offered. One explanation con-
siders a greater tendency for precipitated particles in certain systems than
in others to remain in suspension in the cold zone and to be carried into the
hot zone where they are redissolved (see P a g e a ) Another explanation that
appears applicable in some cases involves a consideration of the rate of dif-
fusion across the solid-liquid interface (solution) and the rate of diffusion
from a saturated solution into the bulk phase of the liquid (see P a g e x ) .
Mass transfer in multimetallic systems may be encountered even
though there are no temperature gradients. Instead of solution of one metal
stopping by virtue of saturation of the liquid, the equilibrium can be upset by
the presence of a second metal that, through an affinity for the first, reacts
with it to form solid solutinns or compounds. The first metal will therefore
dissolve and diffuse through the liquid and then alloy with the second metal.
The newly formed alloy layer will act as a diffusion barrier causing 'mass
transfer rate to decrease with time. Such a phenomena is important where
copper and nickel are exposed to sodium-potassium alloy in the same system
(see Page=). Data (such as changes in weight and dimensions of specimens)
obtained from such systems are often difficult to interpret.