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Effect of Cooling
Rate on Ordering
Behavior
in a CuPt Alloy
CuPt,
Ordering,
in crystal
Cooling
structure
of excess-vacancies
in the grain interior.
during cooling.
Hardening
is
size.
rate
INTRODUCTION
Copper-platinum
alloys
age-hardenable.1)
above
the
this
The
critical
of
The
Recently,
are
to
some
et
spots
suppress
CuPt
alloys
cooling
CuPt
Torfs
during
be
on
ordering
is
lattice
has
the
behavior
this
CuPt
factor
study
is
for
to
the
Wire
specimens
of
to
the
The
ments,
alloy
equiatomic
are
rate,
cooling
hardness
rate
used
alloy
was
modes
cooling
the
(1mm)
the
alloy
cooling
of
the
the
below
structure
which
Tc
results
the
alloys
have
alloys,
two
sharp
is
very
rate
on
effect
indicated
been
modes
According
show
it
cooling
on
planes.4)
interior.
that
of
reported
The
grain
above
suggests
effect
ordering
the
in
these
be
structure
(111)
CuPt
in
to
structure
of
to
ordering
the
that
super-
difficult
in
quenching
the
difference
process.
effects
of
various
cooling
rates
on
ordering
alloys.
composition
the
parallel
from
fact
alloys.9)
MATERIALS
close
and
already
clarify
in
known
cubic
ordered
of
quenched
have
an
ordering
boundary
This
well
rhombohedral
the
Therefore,
in
becomes
mechanisms
grain
are
face-centered
atoms
of
specimens
We
face-centered
patterns.
quenching.
CuPt
has
platinum
ordering
al.8),
important
of
morphology
at
et
which
8242,3)
and
the
the
investigated.
an
purpose
about
on
to
composition
CuPt
of
diffraction
must
rate
The
in
and
equiatomic
copper
ordering
electron
ordering
temperature
in
al.7)
in
of
studies
respect
namely,
Mitchell
lattice
sheets
With
recognized,
(Tc)
ordered
alternating
reported.5`8)
the
alloy
temperature
temperature.
consists
near
equiatomic
were
in
at
in
Table
on
ordering
in
tests,
X-ray
namely, gAh
METHODS
from
study
was
99.95%Pt
and
49.37at%Cu
99.99%Cu.
and
The
50.63at%Pt,
chemical
which
is
very
CuPt.
disordered
listed
prepared
this
of
AND
has
900
1.
the
CuPt
diffraction,
and
The
fastest
was
ordered
notation
cooling
studied
and
electron
by
of
by
the
cooling
at
mode
is
rate
and gIh
means
of
microscopic
various
in
the
electrical
descending
slowest.
resistivity
observations.
rates.
These
order
The
of
effect
measure-
K. HISATSUNE,
M. OHTA
Table
Electrical
with
resistivity
a constant
welded
at
For
The
tests
The
X-ray
to
speed,
of
10
made
used
in
specimens
vacuo
were
at
diffraction
40mm/min;
Thin
using
4-terminal
1mm~50mm
average
mesh
in
an
various
apparatus
length
powder
were
with
Ni
leads
indentor
least
five
with
was
prepared
from
silica
tube,
disordered
follows:
the
alloy
at
difractometer*
Cu
target;
speed,
by
an
by
filter;
1 or
filing.
900,
was
Ni
scanning
a 500-gram
indentations.
and
employed.
tube
voltage,
0.5/min;
chart
0.3mm.
were
at
at
X-ray
2 or 10s;
microscopy
examined
An
as
constant,
slit,
hardness
of
evacuated
rates.
used
receiving
were
pyramid
the
300
time
electron
foils
are
sealed
80mA;
for
a diamond
a minus
was
X-ray
Specimens
nique.
using
results
temperature
current,
or
were
The
made
diffraction,
room
tube
0.5A.
hardness
specimen
Conditions
45kV;
were
Vickers
powdered
cooled
of
modes
end.
Hardness
load.
Cooling
measurements
current
each
and M. YAMANE
prepared
1000kV
in
using
a JEM-1000
ion
beam
thinning
tech-
microscope.
RESULTS
(1)
Cooling
curves
Figure
drastic
that
the
(2)
of
the
obtained
ordering
cooling
Hardness
obtained
* RU-100PL
(A)
variations
resistivity
rate,
disorder-to-order
Figure
was
of
degree
the
quenching
was
shows
decrease
slower
the
at
at
the
of
the
room
further
the
by
ordering
air-cooling
of
resistivity
Tc
temperature
the
transformation
electrical
vicinity
reaction
is
ordering
was
at
be
different
to
at
At
completed.
suppressed.
various
due
proceeds.
mostly
was
may
state
cooling
rates.
ordering.
It
various
rates
On
A
the
cooling
of
the
less
other
clear
rates.
than
The
25/min,
hand,
intermediate
The
is
by
water-
between
them
(E).
tests
2 shows
the
by
air-cooling
, Rigaku
effect
of
(E).
the
cooling
rate
With
rates
Japan
on
both
hardness.
faster
The
and
slower
highest
rates
value
than
of
that
hardness
of
air-
ORDERING
BEHAVIOR
IN
Figure
CuPt
Variations
in microvickers
Electrical
cooling
resistivity
changes
at various
Figure
during
rates
Variations
in X-ray
line
profiles
with
cooling
rate
rate
hardness
K.
cooling,
by
lower
an
X-ray
diffraction
3 shows
of
namely
the
CuPt,
It
X-ray
line
superlattice
respectively.
indicating
the
superlattice
that
ordering
the
X-ray
Figure
line
of
and
M.
that
the
appeared
YAMANE
the
peak
The
(753)
profile.
value
for
(E)
at
hardness
well
to
(B)
higher
at
is attained
diffraction
explain
the
the
and
the
broad
angle
slower
variations
of
to
split,
reflection,
profiles,
It
rate,
the
disordered
(420)D
line
side.
cooling
By
began
ordered
only
very
rates.
ones
the
showed
gave
The
various
fundamental
refer
mode
air-cooling.
results
cooled
the
D
specimen
air-cooling
during
These
also
and
appeared
occurred
specimen
and
iced-brine-quenched
state.
CuPt
profiles
lines
reflection
of
clear
Subscripts O
The
disordered
is
OHTA
rate.
(420)D(840)O+(840)O.
phases,
M.
obtained.
cooling
Figure
ordering
(4)
were
intermediate
(3)
is
values
HISATSUNE,
and
is
obvious
the
sharper
hardness
shown
in
2.
Microstructure
Figure
was
taken
field
image
area
shows
from
the
and
diffraction
dark-field
Figure
(b)
is the
pattern
image
transmission
specimen
the
dark-field
of
indicated
Bright-field
image
CuPt
air-cooled
alloy
electron
having
one
[110]
the
(a),
zone.
existence
dark-field
from
900.
micrographs
of
hardness
value
peak
by
using
Sharp
of
image
a (111)O
the
superlattice
superlattice
very
(b)
Incidental
finely
and
the
beam
(E).
spots
ordered
selected
[110]
air-cooled
(a)
specimen,
represents
spot.
were
(c)
which
the
is the
recognized
brightselected
and
the
domains.
area
diffraction
pattern
(c)
of
the
ORDERING
BEHAVIOR
IN
CuPt
in
cooling
DISCUSSION
(1)
Ordering
behavior
From
the
Figures
order
at
resistivity
room
and
their
was
to
decrease
at
about
be
divided
into
two
of
0.1/min
until
in
temperature
portional
to
Figure
5(b).
have
already
quenched-in
On
endothermic
I)
was
the
the
and
state
two
vacancies
present.
the
its
We
Figure
two
already
900
their
at
annealing
various
This
behavior
that
curves
(a)
of
(b)
rate
started
decrease
at
more
considered
to
the
due
can
the
clearly
to
are
be
the
pro-
found
disordering.
to
rate
in
We
migration
of
respectively.11)
only
The
stage
much
of
electrical
heating
curve
peaks
latter
were
showed
curve.
is
endothermic
the
large
is
d/dT
degree
of
resistivity
cooling
vacancies,
(D)
rates.
electrical
300.
reactions
derivatives
rates
one
and
the
curves
previous
If
and
ordering
equilibrium
temperature
various
the
This
ordering
reported
the
5(b)).
derivatives
Anisothermal
and
the
specimen
temperature
have
of
air-cooled
around
attained.
exothermic,
exothermic
at
(B)
met
(Figure
to
and
at
curve
was
curve
correspond
that
on
steeply
changes
heating
cooling
specimen
this
rate
anisothermal
after
dropped
heat,10)
former
shows
quenched
derivative
specific
difference
5
Thereafter,
disordered
hand,
the
derivatives
In
200
reported
one
that
Figure
stages.
the
The
peak
not
noted
employed.
excess
the
cooling
is
temperature
1/min
the
it
temperature.
of
seen
during
1-3,
one
first
exothermic
exothermic
I corresponds
electrical
after
to
resistivity
cooling
from
and
peak
the
ordering
one
(stage
by
K. HISATSUNE,
M. OHTA
and M. YAMANE
Figure
Figure
Variations
, with
the
annihilation
some
(I).
of
the
Both
(2)
changes
rate
softened
gives
softened
Figure
with
due
to
It is
is
can
on
rate
various
rapid
of
be
the
supposed
excess
obtained
d/dT
rates
that
vacancies.
by
curve
indicate
cooling
produced
state
the
with
(A)
slow
in
ordering
that
cooling
this
an
produced
a perfectly
of
that
produce
expected.
In
the
case.
intermediate
a disordered
ordered
is
fine
and
state,
responsible
(800)O
to
the
This
to
the
fine
matrix,
from
and
but
for
it
the
was
order-
reflection
broadening
domain
face-centered
the
X-ray
changes
is
(Figure
a considerable
that
of
hardness
thought
4).
cubic
lattice
be
When
of
into
during
in
to
amount
hardening
dif-
seen
the
strain
face-
cooling
was
size.
the
degree
of
was
of
twins
order
reflection
hardness
growth
many
of
similar
evident
superlattice
maximum
the
very
broadening.
is
domain
in
breadth
is
disordered
It
the
fact,
It
ordering
in
variations
between
will
integral
transformation
by
the
the
maximum
formed
the
and
noted
completely
in
cooling.
lattice.1,4)
7 shows
mode
at
most
intermediate
of
is
intensity
(400)O.
(I)
variations
of
ordering
integrated
The
cooling
accompanied
because
by
consumption
ordering
disappeared
cooled
value.
modes
rhombohedral
Figure
CuPt
the
structure
introduced
caused
specimen
E indicated
strain
CuPt
centered
than
shows
Mode
the
ordered
the
The
various
2.
completely
the
is
cooling
slowest
too.
by
sufficient
it
of
cooling
rate.
the ordering,
CuPt.
6
fraction
Figure
The
state,
in
of
Accordingly,
air-cooling
that
had
a maximum
state.
hardening
was
peaks
during
vacancies.11)
during
it is proposed
exothermic
in the degree
order with
B suppressed
i.e., S=0
excess
develops
hand,
Variations
breadth,
quenched-in
ordering
other
Hardness
is
rate
Order-hardening
cooling
integral
of
amount
On
in
cooling
obtained
ordered
were
S calculated
(331)O
at
domains,
observed
in
S=0.85
the
the
from
and
the
(E).
release
slow-cooled
the
ratio
of
fundamental
As
of
cooling
strain
slower
in
specimen
ordered
(I),
which
ordered.
CONCLUSION
Ordering
by
means
The
(1)
By
behavior
of
electrical
main
results
air-cooling
in
the
resistivity
obtained
from
above
equiatomic
alloy
measurements,
were
the
as
CuPt
at various
hardness
cooling
rates
and
X-ray
tests,
was
investigated
diffraction.
follows:
critical
temperature,
a degree
of
ordering
was
the
one
achieved
ORDERING
by
the
was
consumption
also
(2)
of
attained
The
by
the
fine
vacancies
some
in
is
the
difference
grain
in
domain
during
cooling
transformation
microdomains
by
excess
BEHAVIOR
cooling.
CuPt
considerable
amount
of
hardening
rates.
the
homogeneous
interior.
the
IN
ordering
The
crystal
hardening
structure
resulting
is
between
thought
from
to
ordered
and
be
the
due
to
disordered
formation
the
strain
states
of
caused
and
by
the
size.
ACKNOWLEDGEMENT
The
authors
wish
to
thank
Prof.
K.
Yasuda
for
stimulating
discussions.
REFERENCES
1)
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2)
Geiken,
3)
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L.:
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11:
C.H. und
lreihen
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M.
Met.,
Johansson,
Edelmetall-Legierungen,
USAEC
K.,
CuPt,
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Irani,
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annealing
in
91
Cupt
, ,
CuPt
(900)
:
,-25/min
(fcc) ,
(fccfcr)
,X