CALPHADioZ.

2, No. 3, pp. 227-238.

D Pergamon Press Limited, 1978. Printed in Great Britain.

A MODEL FOR ALtOylNG

EFFECTS tN P~RR~NAGN~TlC METALS

Mats Hillert
and Magnus Jar1
Division
of Physical
Metallurgy
Royal institute
of Technology
S-100 44 STOCKHOLM 70
Sweden

Abstract
A mathematical
representation
of the magnetic
specific
heat,
recently
suggested by Inden,
was applied to iron in an evaluation
of the difference
in Gibbs energy between the fee and bee
states.
The resulting
equations
were then used for a treatment
of alloying
effects
in ferromagThe result
was approximated
in order
netic
metals due TV the change of the Curie temperature.
term was obtained.
to conform to the subregular
solution
model. A strong asymmetric

Introduction
It was pointed
out by Zener (1) long ago that the effect
of an alloying
element on the
base metal should result
in a strong thermodynamic effect,
magnetic
state
of a ferromagnetic
This effect
has recently
attracted
considerable
attention
(2-4)
but the results
t&ke complicated
analytical
forms. An attempt will
now be made to develop a treatment
in a simpler
form.
In particular,
an attempt
will
be made to put the result
into the regular
or subregular
type of representation.
The work will
be based upon a type of description
of the thermodynamics
of a ferromagnetic
metal,recentfy
developed by lnden (3) and it wiI1 be applied
to iron and iron base

at ioys.
The regular
and subregular
solutian
models are useful
tools for
of the thermodynamic
properties
of binary alloys.
They are particularly
cerned with the coupling
between thermodynamics
and phase equilibria
sive use in that field.
Description
Provided

that

use a polynomial
state5

of

a pure

the temperature
for the description
element,

AG = A + BT 4 CTlnJ

of

Gibbs

energy

is much higher
than
of the difference

for

approximate
descriptions
valuable
in work conand they have found exten-

iron

the Debye temperature,

it is possible
in Gibbs energy between two possible

+ DT2

to

flf

The ferromagnetic
metals constitute
an important
exception
and it has been customary to present
the result
of evaluations
of Gibbs energy for iron in Tables
(5-11).
Kaufman and Nesor (12) who
used an expression
like eq. 1 had to give different
parameter
values above and below the Curie
temperature.
lnden (3) has recently
shown that the following
types of expressions
can be used for a
rather
accurate
description
of the magnetic
contribution
to the specific
heat of a ferromagnetic
metal A
_1
ym! = KzRln -!.%?
cA

for

T <

for

T >

l-2

5
CrnB

= K;Rln

The quantity

7 -1
T is defined

as T/TC

where

TC is

the

Curie

temperature.

Ki and Kt are

two constants

228

M. Hillert and M. Jar1

for

the element A in its ferromagnetic

(9) and paramagnetic
(8) state.
By integration
of the specific
heat lnden derived
expressions
for the magnetic contribution to the Gibbs energy.
The final
expressions
are very complicated
and in part based upon a
power series
expansion.
in order to arrive
at a simpler
expression
it is possible
to expand the
expressions
given by eq. 2 and 3 in a power series
and to truncate
the series
before
integration.
The usefulness
of such a procedure will
be explored
in the present
report.
The following
approximations
of eqs. 2 and 3 will
be used.
2\

= 2KaR(~3+,g/3+~15/5)
A

m8 = 2K;R(T-5+~-5/3+~-25/5)
CA

for

T < 1

(4)

for

T > 1

(5)

They approximate
eqs. 2 and 3 very well except for a temperature
range very close to T . Eqs. 2
and 3 go to infinity
at T which is in agreement wit $ many theories
pheno &na.
of ordering
Eqs.
respectively,
and may thus be an attrac4 and 5 approach finite
vglues,
46/15RKa and 46/15RK
fi.
tive alternative
from this point of viea,
also.
The erght at T, can be adjusted
by keeping
wi 11 be Test if many tel;ms are retained.
more terms but some of the advantage with eqs. 4 and
finding
KFe=0.554
and
lnden evaluated
the numerical
values of Ka and Ki? for bee iron
KFe=0.714.
According
to his procedure
eqs. 4 affd 5 yifild
the following
result.
T
B;(=)

- G;(B)

= 6

m8

c CM
$dT

+ 7 $dT

= gR(K;

(6)

+ 0.6K;).

TC
- H~~TC) = 7

$(=)

mB
cAdT = ~~CK~

(7)

TC
- H;(D)
H,m(T,)

= ILcrmdT = GRTCK;
0 A
Let f be the fraction
of the total
magnetic
ture.
Eqs. 7 and 8 then yield,

(8)
enthalpy

which

is absorbed

above

the

Curie

tempera-

(9)
When analyzing
the specific
heat data for bee iron,
inden found f=O.4.
For fee metals he found
f=O.28.
He suggested
that the f value depends upon the structure
and proposed that 0.4 could
be used for all
bee metals and 0.28 for all
fee metals.
The total
magnetic entropy
is often expressed
by the following
expression
where 8,
is the
mean atomic moment expressed
in Bohr magnetons (9),

q-4

- St(O)

Combination

with

= Rln(BA
eq.

+ 1)

(0)

6 yields

(11

K; + 0,6KB - 675 ln(OBA + If

By combining

Kfi
=
A
K; =

this

5ii8

with

eq.

9 and using

the value

f=O.4

we obtain

for

bee metals,

n(OBA + 1)
= 0.64t71n(BA

(12)

+ 1)

518.
1125

o.g80~(~A

For bee i ron the value

f=O.28 would yield

+ 1)
of 0BA=2.22

(3)
yields

KE=1.073

and Ki=O.7504.

For

fee metals

the

value

Ki = 0.426Bn(BA

+ 1)

(14)

K; = .o46gn(BA

+ 1)

(15)

zero

When evaluating
the magnetic contribution
at Td.
For temperatures
above the Curie

IF
A

= *K;RTC[/10r4

By continuing
tic
to) state.

om
GA

the

+ [35T

integration

8
= -KART&79/140

to Gibbs enorgy we shall

temperature
the following

define
this quantity
as
expression
is obtained

(17)

+ /YOT241
TC one abtains

below

- 58~/125J

-K;BTC[.4/6

the

folIowing

expression

for

the

ferromagne-

~~D/l~~~r6/600+71./120-51~~/675]

(19)
in

Gibbs energy batweeh foe and bee iron wilt

now be described
by aubtr~ting
tke magnetic
contribution
for bee Iron,
according
to erg* 7 or 3, from eq. , whfch cxmtains
four adjustabfe
parameters.
They can be determined
from experimentaT
~nfor~tj~
on the eq~ilfbrium between the two phases.
From Qrr and Chipman (31) we can choose the ~~~~~~ng
vaguer for
the equi Jibrium
temperatures,
eorrectsd
to the fPTS 68 t~m~~rat~re
scale,
85 and 667K.
From
Braun and Koohthaatt (131 we can choose sin enthalpy
of transformation
of 9iD Jlmol at 1185K and
-850 J/ma\ at 166TK, Inserted
in our equations
these data yield
the following
parameter
values,
A=-5188.3,
Bs45.79,
C*-6.3
and D=D,DD24, expressed
in J/ma and K. Above the Curie temperature
we thus obtain

The difference

the

Below

Curie

OGY
- G$
Fe

temperature
*

3883.4

we obtain
+ 36.07

- 6,3TnT

+ D.0D24T2

+$309[T4f6T~+TD/35~~+T16/600T~6)

J&no

(21

rkese exprassions
a value of TC=lOQK
must be used,
The function
given by eqs. 2D and 23 was evasrated n~~~~~~~~
and in Figs,
t and 2 it is
compared with the evaluations
present&
by Orr and ChIpman f]
and by Kaufman and Besot (2).
Above the trans~~~rn~t~on
point at il85K the new evaluatian
agrees wet1 w3th Grr and Chipman
and below the transformation
it agrees well with Kaufman and Nesor. This is partcuiary
satisfactory
because they based their
evaluation
on the previous
evaluation
by Kaufman, Clougherty
and Weiss (14) who used a realistic
astIrnate
of the Debye temperature
for fee iron.
Eqs. 20 and
21 thus seem to give an adequate
representation
of the Gibbs; energy for iron,
Wwever,
they
shauld not be usc?d much below the Debyo temperature.

fn

ho&

Previous

treatments

of

the magnetic

aloying

effect

Long ago ile-ner ftf pointed

out that an important
effect
of alloying
additions
to iran is
caused by the change of the magnetit: state,
He suggested
that this effect
couid be described
approximately
by a paratfef
disptacement
along the temperature
axis of the magnetic part of
the Gibbs energy for Iron,
a displacement
corresponding
to the change of the Curie temperature.
This suggestion
WM followed
by Hilert,
Wada and Wada (HWW) who derived
the following
expression
for low alloy
content,
x, (151,
Gze = x

QS;edTC/dx

(221

M. Hillert and M. Jar1

230

--

Orr and Chipmon

-.-

Koutman

awl

--

0~

-.-

Kc&non

and

Now

Fig.

1 Difference
in Gibbs energy
between FCC and BCC iron in the
temperature
range 1000-1800
K
according
to different
works.

Fig.

2 Difference
in Gibbs energy
between FCC and BCC iron in the
temperature
range 300-1lOD
K
according
to different
works.

Chipman
and

Nuor

500

lOOa

A MODEL FOR ALLOYING EFFECTS IN FERROMAGNETIC METALS

231

Grn is the magnetic

contribution
to the Gibbs energy of an iron-base
alloy
in the bee state
the magnetic entropy
in pure bee iron.
Z&ers
suggestion
was somewhat arbitrary
and cannot be strictly
justified
on thermodynamic grounds.
A formally
more satisfactory
treatment
could be based on any mathematicl
model of
Such treatments
were recently
discussed
by Miodownik (4).
HOWthe magnetic
properties
of iron.
ever,
apart
frcnn the work of HWWno treatment
has yet been put in analytical
form.
The change in the magnetic
contribution
to the Gibbs energy due to the addition
of an
alloying
element can be written
in the following
general
form

a& OSrnis

AG; = G; - xAoG; -

xBG;

(23)

The superscript
m is here used to denote magnetic contributions
whereas the subscript
m denotes
lnden (16) has suggested
that one should use the same type of demolar integral
quantities.
inserting
the
acription
for the magnetic contribution
in an alloy,
Gm, as in a pure elementoby
8,. An al ternamean value of the atomic moments for the mixture
of elements
in the alloy
as
It is based upon a separation
of the effects
from
tive will
be examined in the present
paper.
different
elements.
For a binary
alloy
we shall
write

AG; = xA(G; - "c;c,+ xg(G; - G;)

(24)

Zeners
original
suggestion
one should
This equation
can be used in different
ways. Following
neglect
the direct
effect
of the alloying
element and describe
the magnetic contribution
from
the base metal by displacing
the Gibbs energy function
for the pure base metal along the temperature
axis by the same aa-ount AT as the Curie temperature
has been changed.

AG; = xAtoG;(T-AT)

- G;(T)

(25)

HW approximated
this expression
by the first
term in a series
expansion
and assumed that the
This method actually
yields
the
Curie temperature
varies
linearly
with the alloying
content.
following
expression
which has sometimes been used (17)
AGE = -ATxAdoG;/dxB

= xAxBoS;(T)dTCA/dxB

(26)

The magnetic
alloying
effect
thus takes the form of the regular
solution
model although
the
temperature
dependence is quite
unique.
Nishizawa
et al.
(18) have emphasized that it may be essential
to retain
another
term.
This is particularly
evident
if one wants to calculate
a miscibility
gap. They derived
an equation for the spinodal
in the following
way by putting
the second derivative
of the Gibbs energy
equal to zero.
From eq. 25 one obtains
the following
expression
for the case where the Curie
temperature
varies
linearly
with the alloying
content,

d2AGm

dT

dx;
The following
d2Gm
-=
dx2,

d2'Gm(T-AT)

dG;(T-AT),,,

-=2* m

equation

dXg + B
is

thus

obtained

A
dT2

for

(ddT)2
dxB
the

(27)

spinodal.
dS;(T-AT)

-2L

+ RT/xAxB

- 2'S;(T-AT)$$ - xA
B

dT

(daT)2=G
dx

(28)

where L is a regular
solgtion
parameter
whic,hmdescribes
the nonmagnetic
deviation
from ideal
solution.
The quantity
d S /dT is equal to c IT and it is thus evident
that the last term in
eq. 28 has a very strong e e feet
in the neigh 6 orhood of the Curie line where the specific
heat
goes to large values.
In fact,
Nishizawa
et al. were able to predict
that a miscibility
gap,
which is primarily
due to a chemcial
effect
expressable
by a regular
solution
parameter
L, may
develop a horn along the Curie line
if intersected
by such a line.
New approach
tive

As already
emphasized,
would be to inserteqs.

to the maqnetic

alloying

effect

Zeners
suggestion
was somewhat arbitrary
and an attrative
alterna17 and 19 in eq. 24 which could be done by using the individual

M. Hillert and M. Jar1

232

values of B for each element

in the evaluation
of the K values from eqs. 12 and 13 but using
the Curie temperature
for the alloy
in eqs. 17 and 19 and assuming that f in eq. 9 is a constant.
Admittedly,
the theoretical
basis for such a procedure
co$d
be qtieestioned but at least
it does not violate
the rules of thermodynamics.
The quantities
GA and G in the alloy
would
dspend ypon the concentration
due to the koncentrafign
dripendence of f3 a!!d TC.21n2partlfular,
d G,/dxB will
again contain
a term with c since a GA/aT
Is equal to
1: *a GA/aT .
this model may also pre 8.tct the deveio frment of a horn along a Curie line
As a consequence,
Indens original
model which gives infinite
spewhich intersects
a miscibility
gap. In fact,
cific
heat values at T would predict
that at least a very thin miscibility
gap should always
develop along the who1 ti Curie line.
it is necessary
to know the indiIn order to apply the new treatment
to a specific
case,
vidual
values of @A and 8, whereas magnetic measurements only yield
the average B for the alloy

B = XABA+ XBB8
When other kinds of infor~tion
is lacking
an arbitrary
assumption must be made. According
to
Bates (19) it is often
reason?bie
to put G,=O for nonmagnetic
alloying
elements
in iron and to
They were now used for a comparitreat
GA as a constant.
These were also Zeners
assumptions.
son between the HW version
of Zeners
model and the neir model at low alloy
contents.
As a
basis for the comparison
the magnetic
Gibbs energy was defined
as zero at Tm. The results
are
presented
in Fig. 3. They are quite
similar
but the new model predicts
a slightly
smaller
effect.
Miodownik (4) discussed
the short-comings
of the Zener treatment
and pointed out that it
might be important
to include
the effect
of changes in the saturation
magnetisation.
For the
alloys
Fe-It% Cr and Fe-lo% Co he made a quantitative
comparison with values obtained
from his
own treatment.
In order to compare the treatment
developed
in the present
report with Miodowniks
treatment
the new treatment
was applied
to the same two alloys.
The comparison
is made
in Figs. 4 and 5. For the Fe-11% Cr alloy
the new treatment
was applied
in two different
ways.
In Model 1 is was assumed that the G value of the Fe atoms is independent
of the composition
a fair
representation
of the
and that the B value for the Cr atoms is always zero. This yields
satusation
magnetisation
of the Fe-Cr sy5tem. A more accurate
description
is obtained
with
-0.8x
which makes the b value for Fe atoms decrease
from 2.2 for pure Fe to 1.4 at a
!!$
t!Eh diifltion
in Cr. This value was used in Mode1 2. Both models were used with a value
of dT /dx
=-700 K/moi which is a very rough approximation
and does not take into.account
the
initr .E 1 I?i crease of T when Cr is added to Fe. The curve given, for the HWW treatment
in Fig. 4
For the Fe-lo% Co alloy
Model 1 may not be very realistic
was also calculated
w$th this value.
It was found that the saturation
magnesince the G value for the Co atoms is not negligible.
tisation
curve for the Fe-Co system could be represented
rather
accurately
with B =OB + 1.9X,
The curve denoted by Model 3 in Fig.
5 was obtar *i 8d wfeh
and a constant
value of B =1.7.
of 1200K for pure bee Co and with dT Idx
=1050 K/m01
these values,
with a Curl &temperature
for Fe rich alloys.
The latter
value was also used in the calculation
of th 5 cu F
ves from Hw
treatment
and from Model 1. Ail the curves are very simi iar and it may thus be concluded that
all
the models are rather
equivalent.
Figs. 4 and 5 indicate
that the change in the saturation
magnetisation
has not a drastic
effect
but in the case of Fe-lo% Co the effect
is appreciable
at low temperatures.
Sub-regular

solution

representation

The new model predicts

a very complicated
concentration
dependence of the Gibbs energy
It is sometimes useful to have a power
through the concentration
dependence of GA, S, and T
series
expansion
and for many applications
the subre
formalism
is sufficient.
It
attempt will
now be made to
describes
the excess Gibbs energy with a term x x (L
regions above and below the
A Bfo
approximate
the new model in accordance with this
Curie line will
be treated
separately
but an attempt will
be made to decrease as much as POSsible
the creation
of artificial
discontinuities
on the Curie line where $the two regions meet.
The approximation
will
be developed
for the A rich side of an A-B system.
The variable
TC can be separated
from f3 or S, in view of the form of eqs. 12, 13, 17 and
lg. The following
type of relation
can be in e reduced
(30)
function
go(T,)
is obtained
where gG(T ) is obtained
by inserting
eq. 12 in eq. 17. A similar
from eqs. $2, 13 and 19.
The treatment
will
be limited
to cases where the Curie temperature
and the atomic moments

A MDEL

FOR ALLOYING EFFECTS IN F~~O~G~T~C

-101

0

500

Subrrgutaf

--

~il~rt,~da,Wada

3 Comparison
contents

between
according

233

This model

--

1000
Temperature

Fig.

METALS

1500

apprax

2000

(K f

the magnetic alloying

effect
at tow alloy
Wada and Wada and this work.
to Hillert,

EE
x

T~m~mture

Fig.

-lrnmW

4K 1

4 Comparison of predictions
of the magnetic
alloying
effect
in an Fe-11% Cr
alloy
according
to various models.

Temperature ( K)

Fig.

5 Comparison of predictions
of
alloying
effect
in an Fe-lo%
according
to various
models.

the magnetic
Co alloy

234

vary

M. Hillert and

linearly
TC = TCA

with

Jar1

composition,

(l+kxB)

(31)

+ ax

(32)

GA = OGA
GB = OGB

+ bx

(33)

are
where OB and G
factor
ii? eq. 30*gives
ln(BA+l)

M.

the values at
the following

= In(ORA+axB+l)

x 50. For pure 6 we thus

lower series
expansion,

z ln(OGA+l)

and a similar
approximation
is obtained
by inserting
eqs. 30 and 34 in eq.
AG; = xAln(BA+l)

+ xBg(fC)

(g(TC)

- g(TCA))

~n(*~~+l)

have

the

.2x2
axB
B
+ 2(oGA+l)2
OBA+l

value

GR+b.

The second

(34)

for ln(B,+l).
24 one oltaine
+ xAg(TC)

- x~g(TCB)ln(~~+b+l)

a2x2
B
2(Of3,+1)2 >

+ xag(TC)r

bXB
Be+

her powers are excluded

since they do not enter
into the subregular
solution
or g should be inserted
as g in eq. 35 depending upon whether T falls
above or
below the Curie temperature
of each term (T , T
or T ). The first
two terms in eq. 35 come
m-Gm) and should thus go to zero 5s t&8 aliobBapproaches
pure A. This property
is refrom
tained.xA(Gfl
1 e l&t
three terms come from x (G- Gm) and should thus go to zero as the alloy
expansion
is made in the
approaches
pure B. This property
is not pet!!ine 8 because the series
vicinity
of pure A instead
of B. This is not a serious
drawback since eq. 35 is intended
to be
On the other hand, the property
may easily
be restored
used in the vicinity
of pure A, only.
by multiplying
the last three terms by xA. This procedure
will
be used in the foliowing,
mainly
because it will
help making the expressions
conform to the subregular
solution
formalism.
When introducing
the concentration
dependence of TC is eqs. 17 aig 19, all
the higher
powers in TC will
first
be neglected
and only terms in
TC, TC and TC will
remain.

cm8
=-KBRT5,10T4
A C
A
GF
When the

(36)
- KoR[T4/6T3+T
/2-2T/3]
A
c c

-K;R[TC/2-2T/51
K values

are

derived

for

this

approximation

(37)
one finds

by the

method used before,

In(OBA+l)
= -#n(bA+l)

K; =

= 0.71431n(BA+1)

(38)

{+?j($l)
Ko = ZKG = 1 07141n(B
A

2A

+l)

(39)

For bee iron the value of OG =2.22 yields

Ko=l.2529
and KG=G.8353.
The expressions
given bf eqs. 36 and 39 p reserve
theAimportant
properties
that Gmo and GmB,
as well as their
derivatives,
have the same value on the Curie line where the two regl\ons meet,
i.e.
at T=T . When approximating
the various TC terms in eqs. 36 and 37 by truncated
power
series
expafisions
in x
it wouid be desirable
not to destroy
these properties.
If possible,
a
method of approximatioRshould
thus be used which is exact at T=T
The truncated
power series
expansions
take
the following
for Cs depending
upon what powers
one likes
to retain,

A MODEL FOR ALLOYIEJGEFFECTS IN F~~O~G~T~~

1 + 5kx B * 10(kxg?

= (l+kx b ) 5 =

(T,/T,,~~

(TC/TC~) 4 = (l+kxg15

(TC/TC,.jW3

= f l+kxg)-3

= 1 -

(TCJTC&-~

= (l+kx,)-3

= f + Na

=r+kx

f3

(40a)

+ LB(kxL@

(4fJb)

I + fjkxg + MRkxg

(T,IT,,)-~= (l+kxg)-3

TC/TCB

235

METALS

I - 3kxg + 6(kx,12

(40dl

La(kxB)*

(40e)

3kxN * MkxN

f40fI

cf-

=1+0

(4Og)

1, M, N and 0 are correction

parameters
which could make the relations
exact if they were
can easily
be calculated
allowed
to be funtions
of the composition,
x . Those exact functions
from the relations.
However, since the param!ters
are not allowed
to be functions
of x
in the
subregular
solution
formalism,
one could instead
give them constant
values,
e.g.
the v 8 lue zero.
On the other hand, any such value would introduce
an error
on the Curie line except for one
It may be a better
alternative
to let the parameters
vary along the Curie line according
point.
to their
exact functions
but to accomplish
this by treating
them as functions
of T instead
of
xB- This can be done by inserting
the approximate
value,
kxg = i

where

t = TIT

f4Tf

CA

in view of eq. 3&and r;bl the paramein the exact funcrions.

This relation
is exact at T = T
ters wi 11 thus get their
correct
values on the Curie 1 IEe. The property
GA = G
will
thus be
preserved.
However, their
derivatives
with respect
to temperature
wi 11 not be &al
since an
artificial
temperature
dependence has been introduced.
Unfortunately,
there seems to be no
method by which bath properties
can be preserved.
The following
expressions
were obtained
with
this method,

It
at

is interesting
to note that all
T=T
.
T64 five terms in eq. 35 will
noted by the superscript
B because
the first
term we obtain
fromeq.
AG; = x~o~~~(T~~-T~~~~~T4

The superscript

these

correction

parameters

take

the

value

zero

at

?=l,

now be evaluated.
The values at high temperature
wilt
they wilt
depend upon the properties
of the B state.
36 by applying
the approximation
given by eq. 40a,

= -~~xgkRTGAOL~Ikl10+C3~kxgli10+4

o indicate3
that the K value shoutd be calculated
characteristic
of pure A,
8,. The value of the first
term in eq.
luated from eqs. 37 and 40d,

i.e.

be deFor

$431
from eq, 38 with the
35 at low temperature

3 value
is eva-

M. Hillert and M. Jar1

236

AGa = x KBR(T CA-TC)/2

1
A A

- T4/T3 c + 3(T CATC)

+ xAK$T4/T;A

= -xAxBkRTCAIoK;/2

116
(44)

+ oK~[3-3_r4+(6cLa)kxB?4]/6~

These two expressions

have a sfirious
drawback.
Eq. 43 is intended
for use at high temperatures
and the correction
parameter
L then goes to very high values according
to eq. 42a. Eq. 44 is
intended
for use at low temperatures
and the correction
parameter
I. then goes to very high
values according
to eq. 42d. However, the corrections
were introduced
simply in order to avoid
a discontinuity
at the Curie temperature.
It is thus possible
to transfer
the correction
from
one of the equations
to the other with a change of sign,
Suppose, for instance,
that the Curie
temperature
is lowered by the alloying
addition,
i.e.
k is negative.
It is then convenienr
to
include
the L term from eq. 44 in eq. 43
AC! = -xAxBkRT~AtoK~~5+(10+L~)kxB]/,o~

(451

4 - oK~LakxB~4/6}

The two L terms can now be included

in the calculation
above the Curie temperature
TC of the
is increased
to
alloy
using the L values given by eqs. 42a and d. However, as the temperature
both the L parameters
go to zero and the correction
terms
the Curie temperature
of pure A, T
The instruction
fpr ;he
can thus be omitted
above T
the creation
of a discontinuity.
and L -L 10
use of eq. 45 can thus be t&it
and La are taken from eqs. 42a and d for T < T
A&her
correcforT>T
. These corrections
will
thus be included
only between T and T
state
tion mustCilso
be made in this region because the alloy
is in a B s Fate bu FA;he reference
of pure A is a. The frst
part
f eq. 35 should then contain
GmB(T ) - Gnrr(T ) whereas eq. 43
mB
m13
LA to eq. 45 at the
G (T )
One should thus add theAfol~~ingAter
:,~:~~a,~d,Br~dGen~~~
;ak&
i~~o*acco~t,
AG*
1

=. x (Gm8 - OGy)
A
A

= xARTCA~oK~t5-4~-l/~4]/10

(46)

+ K;[3-4r+r4],6}

Formally,
this correction
affects
the standard
state
for pure A rather
than the regular
or
regular.solution
parameters.
On the other hand, all
the correction
terms should be included
in eq. 44 if the Curie
paerature
is increased
by the alloying
addition,
i.e.
k is positive.
AG; = -xAxBkRT~A{oK~[5-L~kxB/~4~/~0
In

this

+ oK~[3-3~4+(6~La)k~B~4]/6~

the correction
should be used below the Curie temperature
of the alloy,
TC,
by putting
Curie temperature
of pure A, TCA. Below TCA they can be omitted
~~LB~xp@=G
for T < T
Forthe
second terhAin
eq. 35 we obtain
the following
expressions
at high temperature
arranging
the correction
terms as just discussed,
AxBaRTCA

{$[+

(~A~~)ln~o~A+l)

+ kxB(y

+ $,(:;;:~4)]

(48)
where

MB=Ha=Oa=NB=Na=O at

AG; - -

T < TCA,

AxBaRTCA

{$[

For

low temperature

s-T+kxB(s

- $

we obtain,

$h~;;;;~)]

(OBA+l) ln(OBA+l)

A
4 _ 3-4~+30~+

(No+1 ) r4

(49)

2 (OBA+t 1 k/a
MB= Ma=Oa=NB=No=O at T < f
For the third
term in eq. 3SAwe obtain
arranging
the correction
terms as before,

where

at

high

temperature

by multiplying

tem-

(47)

- Ai+&

case,

AG; = -

sub-

with

xA and

and

by

A MODEL FOR ALLOYING EFFECTS IN FERRO~G~TIC

4-oKykxBT4/6]

AC; = -xAxBRTCAtoK~[1+(5+MB)kxg]/10-r
where

h=Mo=O

T > T CA. At

for

temperatures

low

237

METALS

(50)

we obtain

AG; = - xAx~RTCA{oK~[5-4~+kx~(5-~)/~4]/,0

+ K;[3-4r+r4+kxB(3+(Mo-3)T4)

(51)

l/6]

oB
KR and OKi are evaluated
from eqs.
where MR=Mo=O for T C T
, The quantities
the R value at x =O, i%.
BBOB *
at high temperature
by multiplying
For the four Bh term in eq. 55 we obtain

12 and 13 with
with

xA,

xAx~oK~RT~Bln(o~B+b+l)
(52)

A&;" =
~OT41(08B+~)
Below

the

AGaB
4

Curie

point

of pure

B, TCR, we find

x x RT In(bB+b+l)
AB
CR

{K;t5-4T/TCBI/10

+ oK~[T4/T~s+3-4T/TCB]/6)

In(BB+l)

An alternative
method to treat
this
term is to include
it in the term x OG which appears in
The result
wi?l Ee x (G - G 1 and
the complete expression
for the Gibbs energy of thealloy.
is equivalent
to choosing non-magnetic
B as the state of reference
for B, In f!ct,Bthi!
is how
Kirchner
et al.
treated
Mn in the Fe-W system (20).
For the fifth
term in eq. 35 we obtain
at high temperature
by multiplying
with xA and
arranging
the correction
terms as before,

where

N~=O~=~a=O for

AG; = -

T > T CA.

2
AxsbRTCA

At

tow

temperatures

we find

{K;[5+50a-4r-NB/T4]/10

+ oK;[3+30a-4T+(1+No)~4]/61

(551

("BB+l)ln(oBB+l)
Nb=Ob=N=O for T < T
.
mentioned
% may often be a good approximation
to put @=O and bB=O. The subresolution
representation
then reduces to the two terms AGa and AG
gc&
&
between TCQ and .TC. In addition
to the curves
discussed
efore,
AG1
curve for the su regular
sotution
approximation,
calculated
with
these
@ values
at low attoying
contents.
Lt is similar
to the other curves.
When compared
to the HWW treatment,
it should
be

where

As already

noticed
that
both versions
of the new treatment
predict
asymmetric
properties,
i.e.
non-regular solution
behavior.
This
fact
becomes
important
at larger
alloying
contents,
in particular
when one wants
to calculate
a phase equilibrium.
The new treatment
might
give
more realistic
predictions
for
such cases.
Of course,
the exact
form,
which
is obtained
by inserting
eqs.
17

and 19 into eq. 24, should

to handle thismathematical
miscibility
duced
into

gap because
the subregular

be preferred
expression.

a discontinuity
approximation.

to

the subregular

This

is

particularly

in

the

derivative

approximation
true

of

the

when

whenever
one

wants

Gibbs energy

it
to

has

is possible

calculate
been intro-

Conclusions

Indens
description
of the magnetic
specific
heat can be conveniently
using a series
expansion.
Analytical
expressions
can thus be derived
for
Gibbs energy between the fee and bee states
of iron, which yield
results
tabulation
sor.

published

by Orr

and

Chipman

and

analytical

expressions

applied
to
the difference

iron,
in

very
close
to the
presented
by Kaufman and

Ne-

M. Hillert and M. Jar1

238

The new analytical

expressions
provide
a useful
tool
for the description
of
fects
when the alloying
element
changes the Curie temperature
of the ferromagnetic
By means of some approximations,
this
treatment
can be conformed
to the subregular
del.
It indicates
that
this
magnetic
alloying
effect
is strongly
asymmetric.

This

Valuable
comments from
work has been financially

1.

C. Zener,

Trans
2.

Drs.

Peter Miodownik
supported
by the

alloying
efbase metal.
solution
mo-

and Gerhard
lnden are gratefully acknowledged.
Swedish Board for Technical
Development.

References
AIME,

1955,

vol.

203,

p.

619.

1975, vol. 66, p. 577.

2.

G.

3.

G. Inden,
Project
Meeting
CALPHAD V, 21-25 June 1976, Max-Planck-inst.
G.m.b.H.
D~sseldorf/W-Ge~any,
1976, p. 111. 4-l.

4.

A.P;

Miodownik,

CALPHAD, 1977, vol. 1, p. 133.

5.

C.H.

Johansson,

Arch.

EisenhDttenwes.,

AIME,

1946, vol. 167, p.

Inden,

6.

C. Zener,

7.

J.C.

Trans

Fisher,

Trans

8.

L.S.

Darken

9.

R.J.

Weiss

10,

R. Kohlhaas

11.

R.L.

12.

L.

Orr

Metallkunde,

and R.P.
and K.J.

and J.

13.

M. Braun
L.

Kaufman,

15.

M.

Hillert,

16.

G.

Inden,

1949,

Smith,

Chipman,

Z.

and R. Kohlhaas,

17.

H. Harvig,

18.

T.

19.

L.F.

20.

G. Kirchner,

E.V.

Nishizawa
Bates:

AIME,

stat.

and R.J.

Metallkunde,

G. Kirchner

1977,

and M. Hillert,

and M. Hasebe
Modern
T.

4th

ed.,

43,

p.

1815.

1963, vol. 34, p. 391.

1973, vol. 64, p. 249.

sol.,
Weiss,

1965, vol. 12, p. 429.

Acta

Met.,

1963, vol. 11, p. 323.

1967, vol. 205, p. 539.

68, p. 529.
Met.

Trans.,

Cambridge

and B. Uhrenius,

1972,

vol.

3,

p.

329.

Communications.

and M. Ko (Private

Magnetism,

Nishizawa

JISI,
vol.

VO!.

1951,

1967, vol. 239, p. 630.

Metallkunde,

Phys.

Clougherty

Chem.,

1956, vol. 102, p. 1490.

Review,

Eisenh~ttenwes.,

T. Wada and H. Wada,

Z.

Eng.ng.

Physical
Arch.

513.

185, p. 688.

vol.

Trans.

and H. Nesor,

1937, vol. 11, p. 241.

Industr.

Tauer,

and M. Braun,

Kaufman

14.

AlME,

Eisenforschung,

Met.

1963, p.
Trans.,

301.

1973, vol. 4, p. 167.