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)
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VIAS T Ei
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it
ORNL-2760 |
Metallurgy and Ceramics
WELDING OF NICKEL-MOLYBDENUM ALLOYS
G. M. Slaughter
P. Patriarca |
R. E. Clausing |
|
OAK RIDGE NATIONAL LABORATORY
operated by
UNION CARBIDE CORPORATION
for the
U.S. ATOMIC ENERGY COMMISSION
LEGAL NOTICE
This report was prepared as an account of Government sponsored work. Neither the United States,
nor the Commission, noer any person octing on behalf of the Commission:
A. Makes any warranty or representation, expressed or implied, with respect to the ocecuracy,
completeness, or usefulness of the informotion contained in this report, or thot the use of
any informotion, apparatus, method, or process disclosed in this report may not infringe
privately owned rights; or
B. Assumes any liabilities with respect to the use of, or for domages resulting from the use of
any information, apparatus, method, or process disclosed in this repart.
As used in the obove, "person acting on behalf of the Commission® includes any employee or
contractor of the Commission, or employee of such controctor, to the extent that such employee
or contractor of the Commission, or employee of such controctor prepores, disseminotes, or
provides access to, any information pursuant to his employment or contract with the Commission,
or his employment with such controctor.
ORNL-2760
Contract No. W-7405-eng-26
METALLURGY DIVISION
WELDING OF NICKEL-MOLYBDENUM ALLOYS
G. M. Slaughter, P. Patriarca,
and
R. E. Clausing
DATE ISSUED
pdj(a 1_1_ngE3
OAK RIDGE NATIONAL LABORATORY
Oak Ridge, Tennessee
operated by
UNION CARBIDE CORPORATION
for the
U.5. ATOMIC ENERGY COMMISSION
WELDING OF NICKEI~-MOLYBDENUM ALLOYS
G. M. Slaughter, P. Patriarca,
and
R. E. Clausing
ABSTRACT
| The use of nickel-molybdenum alloys as structural materials for high-
temperature fused-salt reactor systems requires that they be readily
weldable., The welded Jjoints must also possess adequate mechanical properties
at room and elevated temperatures. This paper describes the welding studies
conducted on a commercial alloy, Hastelloy B, and a developmental alloy
(how commercial), INOR-8. Hastelloy B is age hardenable, while INOR-8 is
immune to this undesirable condition.
The influence of aging temperature and time upon the hardness of
Hastelloy B welded joints was determined. The tensile properties of all-
weld-metal samples of these alloys, both in the as-welded and welded and
aged conditions were also determined. Photomicrographs of welds in both
conditions are shown.
INTRODUCTION
The relatively extreme conditions of corrosion encountered in the petro-
leunm, petro—chemicsl, and chemical industries have necessitated the use of
structural materials possessing outstanding resistance to corrosion. In
order to handle the various corrosive liguids, the structural materials must
be capable of being readily fabricable into pressure vessels, heat exchangers,
tanks, and other related equipment. Nickel-base alloys contalning molybdenum
have been utilized extensively in a large number of these applications,
including service in hydrochloric acid, sulfuric acid, oxidizing salts,
1,2,3,4
alkaline solutions, and many other highly corrosive media.
lHastelloz High-Strength, Nlckel -Base, Corrosion-Resistant Alloys
Haynes Stellite Company, pp 6 — 13 (September 1, 1951).
C G. Chisholm, "Welding and Other Fabrication Methods for Hastelloy
Alloys," Welding J. 25, 1179 — 1183 (1946).
3R P. Culbertson, "Weldability of Wrought High-Alloy Materials,” Welding
J. 3k, 220 — 230 (1955).
- R. P. Culbertson and R, C. Perriton, "The Welding of High-Nickel Alloys
for Chemical Plant and Equipment,” 1958 Annual Assembly of Internatlonal
Institute of Welding at Vienna (June 1958).
The American Society of Mechanical Engineers' Pressure Vessel Code has
recognized the nickel-molybdenum alloys Hastelloy Alloy B and Hastelloy Alloy
C as being suitable materials for use in unfired pressure vessels.S’6 The
service-temperature limitations are 650 and 1000°F, respectively. In addition,
these alloys have been used extensively at higher temperatures for such appli-
cations as turbine blades, conveyor chains, and bolting and shafting com.ponents.7
Other nickel-molybdenum alloys have also been frequently utilized for various
industrial applications, but these have not yet been Code approved.
Nuclear reactor systems utilizing molten fluoride salts as the fluid
fuels are very attractive as heat sources for modern steam power plants.8’9
One important requirement of these reactor systems is that the structural
materials possess exceptionally good corrosion resistance in the operating-
temperature range of 1200 — 1300°F. The nickel-molybdenum alloys adequately
meet this requirement, and in addition, their elevated-temperature strengths
are comparable to those‘of the conventional high-temperature alloys. The
1500°F stress-rupture properties of a commercially available nickel-molybdenum
alloy (Hastelloy Alloy B) are shown in Fig. 1 and are compared with those of
type 316 stainless steel and Inconel.
This commercially available alloy (Ni—27% Mo~5% Fe) was investigated in
detail by the Metallurgy Division of the Oak Ridge National Laboratory in
order to determine its general suitability for service in the 1200 — 1300°F
10,11
temperature range. Unfortunately, age hardening of this alloy in this
5R. M. Wilson, Jr., and W. F. Burchfield, "Nickel and High-Nickel Alloys
for Pressure Vessels," Welding J., 35, 32-s — 40-s (1956).
6Hastelloy Corrosion-Resistant Alloys, Haynes Stellite Company (1957).
7Haynes Alloys for High-Temperature Service, Haynes Stellite Company (1950).
8J. A. Lane, H. G. MacPherson, and F. Maslau, Fluid Fuel Reactors, Addison
Wesley Publishing Company, Inc., pp 567 — 697 (1958).
9W. D. Manly, et al., Metallurgical Problems in Molten Fluoride Systems,
Paper 1990 of Second United Nations Intérnational Conference on the Peaceful
Uses of Atomic Energy (September 1958).
lOR. E. Clausing, P. Patriarca, and W. D. Manly, Aging Characteristics of
Hastelloy B, ORNL-2314 (July 1957).
llC. R. Kennedy and D. A. Douglas, High-Temperature Mechanical Properties
of Hastelloy B and Hastelloy W, ORNL-2402 (November 1958),
UNCLASSIFIED
5 ORNL-LR-DWG 16917A
10
10
STRESS (psi}
10
10 2 5 102 2 5 10° 2 5 10%
TIME FOR FAILURE (br)
Fig. 1. Stress-Rupture Properties of Hastelloy Alloy B, Type 316
Stainless Steel, and Inconel at 1500°F.
o P P e R S SRR RO S ] T e AR AR IR g R St SR T s TR R R e e e
- It -
temperature range makes it subject to significant embrittlement, both at
room and at elevated temperatures. In addition, the oxidation resistance
is marginal and becomes poor at temperatures above 1500°F,
Consequently, an extensive program was carried out by the Metallurgy
Division to develop a non-age~hardenable,high;strength,nickel—molybdenum
alloy which possesses excellent corrosion resistance to the molten salts and
g00d oxidation resistance. An alloy, INOR-8 (Ni~17% Mo—7% Cr—hi% Fe), which
adequately satisfied these conditions »9 was developed and is now commercially
available. The favorable creep properties of INOR-8 as compared with those
of Hastelloy Alloy B and Inconel in molten salts at 1300°F are shown in Fig. 2.
Recognizing that a study of the weldability of these alloys was needed,
the properties of welds in Hastelloy Alloy B and INOR-8 at the temperatures of
interest were determined. A commercially available filler metal, Hastelloy
Alloy W (Ni—25% Mo—~5% Cr—5% Fe), which age hardens to a lesser extent than
Hastelloy Alloy B, was also investigated, since it was used extensively for
test-component fabrication during the time interval in which INOR-8 was i
under development.
MATERTAT,
The Hastelloy Alloy B and INOR-8 parent plate used for this study was
1/2 in. thick., Hastelloy Alloy B weld wire, 3/32 in. and 1/8 in. in diameter,
was used for the deposition of the test welds of this material. Hastelloy
Alloy W weld deposits on Hastelloy Alloy B plate were also made with filler
wire of these two sizes.
At the time of this investigation, INOR-8 filler wire was not available
for the deposition of welds on this material. Consequently, strips of approxi-
mately square cross section were sheared from 0.10-in.-thick sheet material.
The chemical analyses of these materials are shown in Table I.
EQUIPMENT
The inert-gas-shielded tungsten-arc process was used throughout the investi-
gation for the preparation of all weldments. The 0.252-in.-dia, reduced-section,
leHastelloy Corrosion-Resistant Alloys, Haynes Stellite Company, b 89 (1957).
e 5 A TR SN GRS PO RB SN o 7 b ke o b o A TR AG ih +
UNCLASSIFIED
ORNL-LR- DWG 35052
105
5 HASTE | oy ALLOY g
INOR-g
104 INCOng,
STRESS (psi)
3
10
10 20 50 100 200 500 1000
TIME TO 1% STRAIN AT 1300°F (hr)
Fig. 2. Comparison of Creep Properties of Hastelloy Alloy B,
INOR-8, and Inconel in Molten Salts at 1300°F.
TABLE T
CHEMICAL COMPOSITION OF WROUGHT PLATE AND WELD FILLER WIRE
Chemical Composition (Weight Per Cent)
Material Ni Mo Fe Cr Mn o1 C P S Vv Co
Hastelloy Alloy Bal 26.55 5.05 0.62 0.68 0.61 0.03 0.006 0.013 0.37 0.9k
B Plate
Hastelloy Alloy Bal 27.10 5.05 0.38 0.85 0.35 0.02 0.001L 0.012 0.28 0.35
B.Filler-Wire:
Hastelloy Alloy Bal 24.36 5.20 5.94 0.40 0.29 0.05 0.004 0.012 0.28 O.7h4
W Filler Wire
INOR-8 plate and Bal 16.65 4.83 7.43 0.48 0.04 0.06 0.010 0.015 0.10 0.51
Filler Wire
-7 -
all-weld-metal tensile specimens shown in Fig. 3 were machined in accordance
with the recommendations of the American Welding Society.l3 Testing was
performed on a 12,000-1b-maximum hydraulic tensile-testing machine at a
strain rate of 0,05 in./min.
Aging of hardness, tensile, and metallographic specimens at elevated
temperatures was performed in evacuated quartz capsules to eliminate the
effect of the atmosphere. The encapsulated specimens were heated in box-type
electric~-resistance furnaces.
The etchant used in the metallographic examination was chrome regisa
(1 part l% chromic acid solution, 3 parts hydrochloric acid, and 10 parts
water), Etching was performed at room temperature for times varying from
3 to 5 sec.
Hardness measurements were made with a Vickers diamond pyramid indenter
with a 10-kg load,
EXPERIMENTAL PROCEDURE
The preparation of the numerous all-weld-metal tensile, hardness, and
metallographic specimens used in this investigation required the manual
deposition of extensive quantities of weld metal in the grooves of weld test
plates. A Jjoint design was selected which would provide a relatively large
weld-metal cross section, Parent plates, 1/2 in. thick and 20 in. long, were
machined and assembled to permit a square-groove weld with a 5/8-in. width.
All-weld-metal 0.252-in.-dila reduced-section tensile specimens were machined
from these weld test plates, and hardness and metallographic specimens of
adequate size were readily obtalned from the remaining portions of the plate.
A sketch showling the welding sequence used in the fabrication of a
typical weld-test plate is shown in Fig. 4. A photograph of a typical setup
after completion of welding is shown in Fig. 5. The utilization of the large
hold-down plates provided restraint and prevented appreciable distortion of
the base plate during welding. The welding operators were qualified in accord-
ance with approved practices for high-quality a:a.p_pl.ica.tions.llF The data for each
13Welding Handbook, American Welding Society, pp 1125 — 1126 (1942).
1lFOzatl«: Ridge National Laboratory Reactor Materisl Specifications, TID-7017,
pp 141 — 1b6l, (October 29, 1953).
UNCLASSIFIED
ORNL—LR-DWG 35053
21/2 in.
11/4 in.
/4 in. /4 in.
’-1-in. GAGE LENGTH
-
{
\ —0.252 *+ 0.005 in.
AMERICAN STANDARD COARSE
THREAD —CLASS 2 FIT
Fig. 3. All-Weld-Metal Tensile Specimen.
UNCLASSIFIED
ORNL—LR~DWG 34798
-
1oNJ2 i
BASE PLATE 74 5”8 BASE PLATE
1 ;
BACKING STRIP
---, '/ain.
— Yin—
WELDING CONDITIONS:
PASS NUMBER WELDING ‘ FILLER WIRE ' CURRENT
(STRINGER TYPE)| PROCESS DIA (in.) (DCSP)
{ INERT-ARC 3'/32 140 o
2 INERT-ARC %o 140 a
3-12 INERT-ARC A 170 q
WELDING SPEED:
2% in. per min (APPROX.)
Fig. L. Welding Sequence for Test Plates.
N RO e sl B TNTL S A TR M T T R S R T A B R el S S TN A MR S TS ST e
- 11 -
weld was recorded, evaluated for possible trends or discrepancies, and
filed for reference.
The welded Jjoints were then dye-penetrant inspected and radiographed
to determine the presence of porosity, cracking, or other defects. All the
alloys discussed in this report were found to be readily weldable, and no
difficulties were encountered. The all-weld-metal tensile, hardness, and
metallogrephic specimens were machined from the 20-in.-long weld deposits.
All-weld-metal tensile specimens were tested at room temperature and
at 1200°F in the as-welded and welded-and-asged conditions. Hardness trav-
erses across welded Jjoints were made in order to determine the extent of age
hardening occurring in both weld metal and parent plate at various temperatures
and time intervals.
RESULTS
Since the aging behavior of Hastelloy Alloy B and Hastelloy Alloy W
welds appeared to be the result of the precipitation of a phase or phases,
the effects of aging time and aging temperature on the room-temperature
hardness were studied and correlated with the observed microstructures.
The mechanical properties of weld metal, before and after aging at 1200°F,
were also determined. Welds of the non-age-hardenable alloy, INOR-8, were
included in this study for comparative purposes.
The nickel—molybdenum binary-phase diagram shown in Fig.-6(15) was used
extensively as a guide in this investigation, as was other available information
16,17 This information was particularly useful in interpreting
on this system,
the mechanical property, hardness, and microstructural changes occurring as &a
result of aging, although the presence of chromium and other elements have been
shown to have some influence upon the phase boundaries.l
Metals Handbook, American Society for Metals, p 1230 (1948).
l6F. H. Ellinger, "The Nickel-Molybdenum System,” Trans. Amer. Soc. for
Metals, 30; 607 (1942).
lTD. W. Stoffel and E. E. Stansbury, A Metallographic and X-Ray Study of
Nickel Alloys of 20 — 30 Per Cent Molybdenum, University of Tennessee Thesis
(M.S.), (1955).
l8T S. Lundy and E. E, Stansbury, A Metallographic and X-Ray Study of
Nickel-Bage Alloys of 20 — 25 Per Cent Molybdermum and 3 — 15 Per Cent Chromlum,
University of Tennessee Thesis (M.S.), (1957).
TEMPERATURE (*F}
- 12 -
UNCLASSIFIED
ORNL-LR-DWG 16923
2498°F. ny
2600 L ae5 | /50 /|62
2400 = Tl
2408°F
2200
2000 045
1800 aty
163 4°F
1600 1544 °F
1400
1200
1000 T4
800
Ni 10 20 30 40 50 60 70
MOLYBDENUM (wt. %)
Fig. 6. WNickel-Molybdenum Equilibrium Phase Diagram.
- 13 -
A, Hardness Studies
Hastelloy Alloy B - The effect of aging for 200 hr at 1100, 1200, 1300,
and 1500°F upon the room-temperature hardness of Hastelloy Alloy B welded
Joints is shown in Fig. 7. These hardness traverses across the welded Jjoint
indicate that hardening of both the weld metal and parent plate occurs during
exposure in the temperature range 1100 — 1500°F, This condition is the most
pronounced upon aging at 1300°F, but significant hardening at 1100, 1200, and
1500°F is also evident. Aging at 1300°F appears to cause the area immediately
adjacent to the weld fusion line to be particularly susceptible to hardening.
Because of the pronounced hardening of the Hastelloy Alloy B welded
Joints occurring at 1300°F, this temperature was used to determine the effect
of time at the aging temperature. From the hardness profiles shown in Fig. 8,
it can be seen that significant weld-metal hardening occurs in times as short
as 24 hr. The hardness of the base metal and weld metal increases appreciably
with increasing time at temperature until a VHN of 525 is obitained near the
fusion line after 500 hr. A VHN of 275 was observed in this area in the
as-welded condition.
It will be noted that the hardness traverses of the aged specimens in
Figs. 7 and 8 reveal a gradual increase in parent-metal hardness as the weld
fusion line is approached. This hardness gradient in the specimens aged at
1300°F for 200 and 500 hr occurs over a distance of 0.7 in. or greater, which
1s considerably wider than the conventional heat-affected zone of the weld.
This condition is a result of accelerated precipitation as shown in Fig. 9.
A similar panorama of the material in the as-welded condition is shown in
Fig, 10,
| The precipitation gradient is thought to be attributable to the presence
of plastic strain in the weldment created by the repeated heating and cooling
of the base metal during the welding operation. The restraint provided by the
thick hold-down plates was sufficient to inhibit free movement of the base
metal, and a readily visible reduction in cross sectional area resulted. Un-
published work at ORNL has indicated that wrought Hastelloy Alloy B containing
a slight degree of cold work hardens very rapidly at these temperatures, with
the amount of hardening occurring during a given time interval varying signifi-
cantly with the amount of cold work.
- 14 -
UNCLASSIFIED
ORNL-LR—-DWG 35055
500 l [
A@ (AGED 200 hl AT 13,02‘,F
e %
400 \\& 5
= NAN
; 4 . AGED 200 hr AT 110\:& \\'
150 LN RS I
450
FUSION
LINE
VICKERS HARDNESS NUMBER (10 kg LOAD)
TONI =] ‘ RN LI 1 t 1 X _
sl e N AGED 200 hr AT 1200°F B
AGED 200 hr AT 1500°F N
300 g el at
AS WELDED — - o 0
2 3 —_— e -
50 d - o
7 ’ x/'.,, ‘/fi, //‘// K . ",- 3
=—— WELD METAL ——=1{= PARENT METAL
200 - : f ! f T
0 0.1 0.2 0.3 04 0.5 0.6 0.7 0.8 0.9 1.0
DISTANCE FROM WELD CENTERLINE (in.)
Fig. 7. Effect of Aging Temperature on Room-Temperature Hardness
of Hastelloy Alloy B Welds.
- 15 -
UNCLASSIFIED
ORNL—-LR—DWG 35056
550
500
l l ‘
- AGED 500 hr AT 1300°F ]
450
400 P
350
FUSION LINE
|
AGED 24 hr AT 1300
VICKERS HARDNESS NUMBER (10 kg LLOAD}
250 L4 weLpep |
|
% /;é%;lww/. >
——— WELD METAL
| PARENT METAL | ]
200
0 01 0.2 0.3
04
0.5 0.6 0.7 0.8 0.9 1.0
DISTANCE FROM WELD CENTERLINE (in.)
Fig. 8. Effect of Aging Time on Room-Temperature Hardness of
Hastelloy Alloy B Welds.
Weld 0.150-in. 0.300-in. 0.450-in. 0.600-in.
Fusion-Line From Fusion-Line From Fusion-Line From Fusion-Line From Fusion-Line
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Y-27832 Y-27833 Y-27834 Y-27835 Y-27836
VHN 450-485 VHN 430-460 VHN 400-430 VHN 360-395 VHN 320-350
Fig. 9. Composite Showing Increasing Amount of Precipitate in Hastelloy Alloy B
Parent Plate as Weld Fusion Line is Approached. Aging treatment — 200 hr at 1300°F.
Weld
Fusion-Line
0.150-in.
From Fusion-line
e
-