Dental Materials Journal 1(1): 1-7, 1982

Effect of Cooling

Rate on Ordering

Behavior

in a CuPt Alloy

Kunihiro HISATSUNE*, Michio OHTA and Masaji YAMANE

Departmentof Dental MaterialsEngineering,Schoolof Dentistry,KyushuUniversity,Fukuoka812,Japan
*Present address: Departmentof Dental MaterialsScience,Nagasaki UniversitySchool of Dentistry,
Nagasaki852,Japan
Receivedon September13, 1982

Some amount of transformation

was achieved by the consumption
Homogeneous
ordering resulted from the formation
of microdomains
due to the strain
Key Words:

caused by the difference

CuPt,

Ordering,

in crystal

Cooling

structure

of excess-vacancies
in the grain interior.

and by the fine domain

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

Denki Co. Ltd., Tokyo,

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

values with cooling

Figure

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)

Nowack,

2)

Geiken,

3)

Hisatsune,

L.:

Scripta

Ohta,

11:

C.H. und

lreihen

Au-Cu,

Rept.
M.

Met.,

Johansson,

Edelmetall-Legierungen,

USAEC

K.,

CuPt,
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Irani,

R.S.

and

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in

(in

in

equiatomic

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in

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(a).

temperature

in
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8-14,

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annealing

in

91

Cupt

, ,

CuPt
(900)

:

,-25/min

(fcc) ,

(fccfcr)

,X