Refracto~ Metals & Hard Materials 11 (1992) 303-307

Brazing of Single-CrystallineMolybdenumby Using

Pd-20% Ag Alloy
Yutaka Hiraoka
Graduate School of Science, Okayama University of Science, 1-1 Ridai-Cho, Okayama 700, Japan

(Received 30 July 1992; accepted 21 April 1993)

Abstract: Single-crystalline Mo was brazed by using one of the noble metal-

base alloys, Pd-20% Ag alloy. Microstructure, hardness and chemical composi-
tion in the brazed layer were examined, and room-temperature bend properties
of the brazed joint were evaluated.
The brazed layer of the as-brazed specimen consisted of three phases. The
region near the interface between the layer and the base metal, consisting of
Mo- and Ag-rich phases, deformed predominantly and the joint fractured,
indicating a certain amount of ductility.
The brazed layer of the specimen heated at higher temperatures basically
consisted of two phases. The region near the interface, consisting of a Mo-rich
phase, seemed to be the most brittle, and fracture occurred there first.

1 INTRODUCTION bend test at room temperature. Their deformation

In our previous studies, ~, 2 single-crystalline Mo
was brazed successfully by using M o - 4 0 % R u
alloy. The brazed joint exhibited a certain amount
of bend ductility at room temperature, though
substantial hardening occurred in the brazed
layer. Its embrittlement after annealing at higher
temperatures in vacuum was interpreted in terms
of microstructure changes in the brazed layer, that
is, the proceeding and coarsening of second-phase
precipitation and/or the formation of large voids.
The ductility of the joint was severely degraded
after annealing at 1800°C for a duration of 36 ks.
In this investigation a pair of single-crystalline
Mo parts was brazed by using Pd-20% Ag alloy.
Noble metal-base alloys including Pd-Ag alloy
generally possess a good fluidity and a superior
rolling ductility. In this respect Pd-20% Ag alloy is
considered to be a candidate for the brazing
material applicable to Mo. The strength and
ductility of the joints in the as-brazed and heated
specimens were evaluated by using a three-point
303
Refractory Metals &Hard Materials 0263-4368/93 S06.00 © 1993 Elsevier Science Publishers Ltd, England. Printed in Great Britain.
and fracture behaviour are discussed in terms of
microstructure and chemical composition of the
brazed layer.
2 EXPERIMENTAL PROCEDURES
Single-crystalline Mo produced by means of
secondary recrystallization 3 was used in this study.
Principal interstitial impurities were oxygen of
0.0006% mass, nitrogen of less than 0-0003% and
carbon of 0.0006%.
Sample blocks of 15 minx 15 m m x 10 mm
were cut from the single-crystalline sheet and sub-
jected to the brazing. The scheme of the brazing
process and specimen preparation has been
already given in our previous papers. ~,2 The
brazing material was a thin sheet of Pd-20% Ag
alloy. A pair of single-crystalline blocks with the
brazing material being inserted between them was
heated and brazed in a vacuum furnace. The
brazing temperature was 1500°C and the brazing
304
time was 120 s. A load of 0.00588 N / r a m 2 w a s
applied during the brazing. The sample was then
cooled in the furnace.
Specimens of 5 mm wide, 30 mm long and
1 mm thick were cut from the brazed sample with
the brazed layer being located at the centre of the
specimen and perpendicular to the tensile axis.
The surface orientation of the specimen was 15 °
from the < 100 > -direction, and its axial orienta-
tion was 20 ° from the < 001 > -direction. The sur-
faces of the specimens were mechanically
polished and then heated in a vacuum at 900,
1100 and 1300°C for 3.6 ks prior to the tests. In
this paper the specimen heated at 900°C for 3.6 ks
is referred to as an 'as-brazed' specimen.
The microstructure of the brazed layer was
observed by using an optical microscope and a
scanning electron microscope. The changes in
hardness and chemical composition across the
layer were then measured. The hardness was
determined by using a knoop hardness tester (the
load is 0"98 N and the holding time is 20 s). The
chemical composition was determined by using an
EDAX analyser. The strength and ductility of the
brazed layer were evaluated by an ordinary three-
point bend test. The test was performed at room
temperature and with a cross-head speed of
0.017 mm/s. All the fracture surfaces were
examined by using a scanning electron micro-
scope.
3 RESULTS AND DISCUSSION
A typical microstructure of the as-brazed speci-
men is shown in Fig. 1. The width of the brazed
layer was about 0.065 mm, which is much
narrower than that in the brazement with
Mo-40% Ru alloy. 2 Neither cracks nor large voids
were observed at the surfaces of the layer. Even
Fig. 1. Typical microstructure of the as-brazed specimen.
Yutaka Hiraoka
after chemical etching, most of the layer (desig-
nated by 'region ~ ) was relatively featureless
except for the dark region (designated by 'region
B"). The latter region is like 'island', as indicated
by an arrow. The region B had a different compo-
sition from the region A, as shown later. Heating
at higher temperatures of 1100 or 1300°C
induced almost no apparent changes in the micro-
structure of the layer. The width of the layer was
almost unchanged, and the region B was still
distinguished.
Changes in hardness in the layer of the as-
brazed and heated specimens are shown in Fig. 2.
In the as-brazed specimen the hardness of the
layer was roughly as low as that of the base metal,
although the hardness near the interface tended to
be higher. After heating at 1300°C for 3.6 ks the
hardness in the layer increased by 60 to 110 in
knoop hardness number. However, the degree of
hardening was much less in the case of
Pd-20% Ag alloy than that of Mo-40% Ru alloy. 2
Changes in chemical composition in the layer of
the as-brazed and heated specimens are shown in
Fig. 3. In the as-brazed specimen, most of the
layer (region A) consisted of a Pd-Mo phase,
although there existed a slight composition
gradient. The Pd content was the highest and Mo
content the lowest in the centre of the layer. In
addition an abrupt change in composition existed
at the interface between the layer and the base
metal. The latter result might correspond to the
phase diagram of a Mo-Pd system.4
The solid solubility of Pd and Mo is much less
than that of Mo in Pd over the temperature ranges
400
--o-- As brazed
--L~-Heated at 13OO*(2
3OO
I
e-J
E
I= i
i
§ zoo -- t --
0
0 Ii
Y I00
Brazed Base metal
layer
O
Distance l O.t mm
Fig. 2. Changes in hardness of the brazed layer in the as-
brazed and heated at 1300°C specimens.
 Brazing of single-crystalline molybdenum 305

I) As brazed 2) Heated at 1300°C I000 I J

Brazed layer
I00 o Pd-20%Ag
13_
I~ --~-- Mo-40%Ru
(3 ~ , , --RegionB /

E
2 5OO
gc) 50

Region A ---~
b_

0 I I
Distance L O.Imm
(a)
500
I) As brazed 2) Heated at 1300qC O ~ ,~. •
Brazed layer
10o
F-/'//~/A U//////A "o

>.-
Region A
E o I I
I000 1500 2000
As brazed
§ 50-
Heating t e m p e r a t u r e /qC

Fig. 4. Plots of yield and fracture stresses of the brazed

joints against the heating temperature.

0 ,:b--

Distance I Qlmm f the levels of Pd and Mo contents were almost

(b) unchanged. In the region B, in contrast, the
I) As brazed 2) Heated at 13~90°C
composition changed drastically. The Pd content
Brazed layer increased and the Mo content decreased, and the
IOO compositions in the regions A and B became
l//~//d r'///////,~
apparently comparative with each other. The
v
increase of hardness in the layer after heating at
E higher temperatures seems to be due to the
E 50- uniform and higher content of Pd.
g
Bend properties of the joints of as-brazed and
g Region B
heated specimens are shown in Figs 4 and 5. The
- A\"~ • •
data obtained for the single crystals brazed with
o Mo-40%Ru alloy2 are also plotted in the figures.
Distance L O. I rnrn j It is obvious that the strengths and ductility of the
(c) joints brazed with Pd-20% Ag alloy are almost as
Fig. 3. Changes of (a) Mo, (b) Pd and (c) Ag contents in the good as those of the joints brazed with
brazed layer of the as-brazed and heated at 1300°C speci- Mo-40%Ru alloy. However, heating at higher
mens. temperatures after brazing reduced the fracture
stress and consequently the bend ductility, whilst
almost no change occurred in yield stress. The
of interest. Thereby only Mo atoms can diffuse degree of degradation in ductility was much more
into the molten Pd-Ag alloy during the brazing. substantial in the case of Pd-20%Ag alloy than
The dark region (region B), in contrast, consisted that of the M o - 4 0 % R u alloy. Typical fracture
of a Mo-rich phase. From the data of EDAX surfaces of the as-brazed and heated specimens
analysis it is concluded that the brazed layer in the are shown in Fig. 6. In both specimens the frac-
as-brazed specimen consisted of two phases, ture sites were near the interface between the
mostly Pd-Mo and the much less Mo-rich phases. layer and the base metal. The fracture surface of
After heating at 1300°C for 3"6 ks the chemical the as-brazed specimen was distinctive. A rela-
compositions in the regions A changed slightly. tively flat region that looked brittle and a well
The composition gradient disapppeared, though deformed region that looked much less brittle
306 Yutaka Hiraoka

were distinguished. EDAX analysis indicated that Mo-rich phases (typically, Mo 86-90%, Pd 4-9%
the flat region consisted of a Mo-rich phase and Ag 5%).
(typically, Mo 96%, Pd 2% and Ag 2%). The Based on the data of optical microscope obser-
deformed region, on the other hand, consisted of vation, hardness measurement, EDAX analysis
a Ag-rich phase (typically, Ag 78%, Pd 20% and and fractography, the microstructures and chemi-
Mo 2%). In the heated specimen the fractography cal compositions in the layer of the as-brazed and
was apparently similar to that in the as-brazed heated specimens are schematically drawn in Fig.
specimen, though the fracture surface of the 7. In the as-brazed specimen the brazed layer,
heated specimen was generally more fiat. EDAX strictly speaking, consisted of three phases. Most
analysis indicated that both regions consisted of of the layer consisted of a Pd-Mo phase. The Mo-
rich phase was dispersed in the layer just like an
'island'. Besides, the Ag-rich phase existed only at
5OO the interface between the layer and the base metal.
I I I
The degree of hardening was much less in the case
~ + Pd-20%Ag ---z~-M0-40%Ru of Pd-20%Ag alloy than that of Mo-40%Ru
alloy. General hardening in the layer in the former
20" case might be due to the dispersion of the Mo-rich
c phase since the hardness of the Pd-Mo phase
o
"o seems to be as low as the base metal by comparing
g Figs. 2 and 3. The hardening near the interface
O3
seems to be due to the existence of a Mo-rich
phase of higher Mo content.
Judging from the fractography in Fig. 6(a) it is
deduced that the Mo-rich phase seems to be the
oo most brittle, and the Ag-rich phase is much less
'~ I000 1500 2000
As brazed brittle. Hence, the deformation and fracture
Heotincj temperature /°C behaviour of the joint is described as follows. In
Fig. 5. Plots of bend angle of the brazed joints against the the early stage of deformation, all regions of the
heating temperature. layer deform together, but in the later stage the

(o) (b)

--I

I i
50/.zm
Fig. 6. Typical fractographs of the (a) as-brazed and the (b)heated at 1300°C specimens.

(a) (b) •
; Brazed Base
layer ql~ metal
/ P d - Mo
: ~ / , ~, uA_ r ,~c~, ~
Mo-rich
Fig. 7. Schematic presentations of the microstructures and
chemical compositions in the (a) as-brazed and the (b) heated
at 1300°C specimens.
region near the interface deforms predominantly
and fractures. This result might be due to the
existence of the less brittle Ag-rich phase. The
reason why the Ag atoms are enriched at the
interface is interpreted as follows. Silver is rela-
tively volatile at the brazing temperature of
1500°C. However, the region near the interface is
rapidly quenched after brazing and the Ag can
remain successfully. The appearance of the multi-
phase structure, that is, Pd-Mo, Mo-rich and Ag-
rich phases, is due to the nonequilibrium
condition in the brazed layer of the as-brazed
specimen. Anyway, such a nonequilibrium condi-
tion in the as-brazed specimen resulted in the
favourable ductility, apparently as good as the
Mo-40% Ru alloy.
The effects of heating at higher temperatures
on the bend properties of the joints are inter-
preted as follows. During the heating at high
temperatures, diffusion of Mo in Pd and in Ag
proceeds. Molybdenum atoms in the Mo-rich
phase, dispersing in the layer, diffuse into the
Pd-Mo phase and consequently this homogenizes
the composition in the regions A and B. At the
interface, on the other hand, diffusion of Mo
atoms into the Ag-rich phase proceeds and conse-
quently a Mo-rich layer of higher Mo content is
formed. In the early stage of deformation all
regions of the layer deform and the fracture
occurs at the interface containing the brittle Mo-
rich phase. The degradation in the ductility after
heating in the case of Mo-40% Ru alloy was due
to the proceeding and coarsening of second-phase
precipitation and the formation of large voids as
well. However, the degradation in the ductility in
Brazing of single-crystalline molybdenum 307
the case of Pd-20% Ag alloy is due to the homog-
enization of the composition particularly near the
interface between the layer and the base metal.
i.~ . . : : :-d.
~ / Mo-rich
4 CONCLUSIONS
\\ 1. In the as-brazed specimen the brazed layer
P d - Mo
consisted of three phases, that is, Pd-Mo,
Mo-rich and Ag-rich phases. The region
near the interface between the layer and the
base metal deformed predominantly and
fractured.
2. In the specimen heated at higher tempera-
tures changes in chemical composition of
the layer occurred. The layer basically con-
sisted of two phases, that is, a Pd-Mo phase
in the layer and a Mo-rich phase near the
interface. Fracture occurred near the inter-
face and the brazed joint was embrittled.
ACKNOWLEDGEMENTS
The author would like to thank the Okayama
Ceramics Research Foundation for EDAX and
SEM experiments. The author is also indebted to
the National Research Institute for Metals in
Tsukuba for the bend testing and heating experi-
ments.
REFERENCES
1. Hiraoka, Y. & Fujii, T., Welding and joining of single
crystals of BCC refractory metals. In Proc. 12th Int.
Plansee Seminar, ed. H. Bildstein & H. M. Ortner. Plansee
Metall AG, Reutte, Tirol, Austria, 1989, pp. 265-79.
2. Hiraoka, Y., High-temperature annealing embrittlement
of single-crystalline molybdenum joined by using
Mo-40% Ru alloy. Int. J. Refractory Met. & Hard Mater.,
(1993) 11 (1992)89.
3. Fujii, T., Watanabe, R., Hiraoka, Y., Okada, M. &
Okamoto, K., Preparation of a large-scale and optional
shape molybdenum single crystals by means of secondary
recrystallization. In Proc. l lth Int. Plansee Seminar, ed. H.
Bildstein & H. M. Ortner. Plansee Metall AG, Reutte,
Tirol, Austria, 1985, pp. 27-43.
4. Constitution of Binary Alloys, ed. M. Hansen. McGraw-
Hill, New York, 1958, pp. 970-1.