CALPHAD

Vo1.6, No.3,
Printed in the USA.

QQ.

229-251,

H.T,.

Lukas,

0364-5916/82/030229-23$03,00/O
(c) 1982 Pergamon Press Ltd.

1082

,T. Veiss

Yax-Planck-Institut
Tnstitut
f;ir
Yeisenbergstrasse

and T.-h.

:Jnni,n

fjr letallforschung,
Uerkstoffwissenschaften,
5, n-7000
Stuttgsrt

50

ABSTRACT. Strategies
for the calculation
of phase diagrams
as well
as of their
using
the Newton Raphson method,
are described.
he
plane
sections,
the Gibbs free
ener,gy in
most
anR1.ytica.l
descriptions
of
useful
Different
equilibrium
multicomponent
solution
phases
are outlined.
used
compared.
Two sets
of
conditions
for
the
eal.culaition
are
programs
are cfescribed
in detail.

1.
-_

Introduction

to
be
a valuable
tool.
in
the
Thermodynamic
calculations
have
proved
equil.i.hria.
investigation
of
multicomponent
phase
In
the course
of these
a e v e 1.o r>t?,?
investigations
several
calculation
methods
and strategies
have been
this
paper
is to compare
the fnathematinal
and
programmed.
The
purpose
of
treatment
and strategy
0.f some of these
methods
with respect
to the analytical
representation
of the Gibbs free
energy
function,
the
equilibrium
cond i t ions
and the solution
strategy,
7. . 4nalytical
-_

Representation

Before
we
can
derive
and compare
define
the Gibbs
free
energy
1) as a function
of the temperature
and
2) in solution
phases
as a function
of
models
may be used.
Temperature

2.1.

of
the

the

Gibbs
-

Free

equil.ihrium

of the pressure
the
concentration,

Rnergv
-_-

conditions,
whereby

we have

to

several

dependence_

The
Gibbs
free
energy
of the one-component
system,
created
by the element
can be represented
by a series
of temperature
functions.
mirst
for
r:
the
series
suggested
by Kuhaschewski
!1/
is used,
which applies
for tempergtures
above the Debye temperature
and
for
elements
or
compounds,
in
which
no
magnetic
or chemical
ordering
effects
are present:
J,

cpj

mj7

+ mj4T

This
series
entropy
S are

+ mj5i

+ mj6

T2 + qjT P7 f

also
by
other
authors
/?-4/.
The enthalpy
used
is
derived
from this
series
by the well
known equations:
m
m
L

Hj

=
_-__

-Rkcelveh

Hj(TO)

1.1

Cpj

S-!ip?iYlIDZ--

d7

--229

9 and the

H.L. L&as et al.

230

added to the expressions

The integration constants R.('! )
integrals at the lower ljrnie T
two more coefficients m.
the series. Vow the Gibbs free en rgy G. = H. - T*S. as well as C 51
each can be representeii by a series containiaa the dame coePficie84;
different functions of T as factors of these coefficients:
V+2
Cpj(T)

\m.

Hj(rnJ

of

the

J1l

r
I+

N+2

Gj(T) =
(7)
mjlKl
"jlJl
c
l=l
l=l
In these functions the coefficients m. are specific material constants, while
F
I
.J and K are material inddbendent temperature functions, which may
f&knalf$ beLEreatedlas elements of vectors of the dimension V+?. All these
vectors-are given in table 1.
Sj(T)

TARLF 1
Descr iption of different thermodynamic functions vs. temperatl:re.
C

II

m,

m,-

+ mg/T2

m?J

+ m *I!
4

m *T
3

+ m4*T2/2 - m5/T
+ m4*T

+ m6*Y2

3
+ m,,*T

+ mg+T'/7 + m7*T4/4

- m5/2T2 + m6 *T2/2 + m7*T3/7

m2

+ m *In?
3

m2*T

+ m7*71*(1-1nT) - m4+T2/2 - m5/2T

- m6*m7/6 - m +T4/12
7

2.2. Pressure dependence

The .pressure dependence in our program is restricted to the entropy term
-R*ln(p/p ) in the gas phase. Ln high pressure thermodynamics of condensed
phases tR, constants
of table 1 may be expressed as linear or quadratic
mj More complicated expressions may be needed only for
functions of the pressure.
the gas phase under high pressure or for liquids in the vicinity of their
critical points.
2.3. Concentration dependence
Next the description of one component systems has to be extended into
binary and finally into multicomponent systems. In solution phases the Gibbs
free energy G of a phase depends not only on the temperature but also on the
composition. In solutions of the substitutional type it is most commonly
written:
x. g. + R
x. lnx
+ exg
(4)
zz
J
j
2
j=l
J J
The fire-t term in equ?=)4) corresponds to a mechanical mixture, the second to
an ideal solution and the third one is the so called excess term.
G

2.3.1. Binary solution phases

The excess term exg is a function of concentration. It depends on the model
used to describe the thermodynamic properties. ?he simplest description is by
a polynomial of the concentration
(Margules 151). Because the excess term
disappears at the pure components, the polynomial for a binary system has the

231

CALCULATION OF PHASE DIAGRAMS

remaining
factor
may be written
as a
i&ZgulZ~)
,*l~~F)theThZrgument
= 1-2x
(Qedlich
and
x1 -x3
as a homogeneous
polynomial
of the two arguments
x, and x3 (or
,_ I.
l-x and x) (Borelius
/7!),
or as a
series
of
Legendre
polynomib1.s
of. the
argument
x,-x?
= l-%x (Rale
and Pelton
/Sl).
The related
formulas
are given
in
table
3.
these
of polynomials
are equivalent
in the sense,
that each of
types
exactly
be transformed
into
each other
in
a binary
system,
where
Rut
they
have
different
behavior
with respect
to rounding
off
x&+x?
e ro s = in * numerical
calculations,
with respect
to the
transformation
of
the
coefficients,
if
the degree
of-the
polynomial
is changed
and with respect
o-f
same
the
usage
of
the
expression
as
part
of
the
excess
term
of
a
mult icomponent
?e
best
phase.
expression
in all
the three
respects
is the
minimized
Legendre
polynomial
series.
Rut the rounding
off
errors
here
are
if the T,egendre
polynomial
values
are calculated
by a recursion
formula
only,
and not by the polynomial
expressions
of the
Legendre
pol.ynomisls
/8/.
We
Redlich
Kister
form is not significantly
worse,
but it has the advantage,
that
it can more easily
be handled.
All

them

can

2.3.2.

Ternary

solution

phases.

In
a
ternarg
solution
phase the descriptions
of the
the
description
of
adjacent
binary
solution
phases
must appear.
nifferent
ways, how to
do
this,
are
proposed
by
Kohler
/9/,
Yuggianu
et al.
/IO/,
moop /11f
and Ronnier
and
Caboz /12/.
There are two principles:
1) All the three
components
shall
be treated
in the same way
2) If in a ternary
system
A-B-C
3 and
C become
equal,
the
binary
system
A-B = A-C shall
be reproduced
in the whole ternarTy system.
Sxcept
of only one polynomial
term in each hinarg
description,
the
the
case
two principles
contradict
each other.
Therefore
the descriptions
by Kohler
and
Nuggianu,
which both satisfy
the first
principle,
do not reproduce
the
binary
A-B,
if
system
Ye formulas
of moop and Sonnier
treat
B and C become equal.
the component
A differently
from the other
two. They are
if
the
preferable,
components
U and C are very similar
and different
from A.
In
higher
which components
have to be treated
order
systems
the question,
differently,
may be cumbersome.
Therefore
only the formulas
after
Kohler
and
Nugg
here.
The expressions
of table
2. auh.iect
to the
- i an II shall be considered
to the Yuggianu
formalism
in
Kohler
formalism
are given
in table
7 and subject
table
4.
For the description
of
with
the
common
factor
binary
systems,
where one
ex

%ern

*1**2**7

The total
excess
table
7 or 4 for
2.7.3.

Quaternary

additional
polynomial
mhese terms disappear

ternarv
solution
phases
x,*x
*x
can be used.
of thg x7 becomes
zero.
n-i
L

fc ,

i=O

( Ai jXx$-~Xxy-i-.~

j=O

Gibbs free
energy
is the sum of one of the
all
three
binary
sys ferns and the expression
and higher

terms
in the

order

solution

expressions
of equation

after
(5).

phase::

In quaternary
and higher
order
solution
phases
the expressions
derived
from
are
to one of the equations
of table
3 or 4,
the
binary
identical
sgs terns
depending
on the choice
of formalism
(Yohlers
or Mugginnus)
and on the
type
4 generalization
of Yohl.ers
the binary
descriptions.
of
the
polynomial
of
formalism
to the extension
of the ternary
terms after
equ.
(5) into
the higher
order
systems
is given
by the formula:

H-L.

232

et al.

Idas

?ARLr;:2
Different types of' po~.~nomi~ls for binary excess terms.
n

ex

&

x,*x2*

"largul.es151

Ai*x;

i=O

Qefilich anil Yister f6/

n
ex

ex

x1 *x2*

x,*x2*

c
i=O

ci*x, (n-i) *
*G

lyPi(X,

Bale and Pelton fSl

- x,)

i=O
(x, - x,).
P.(x, - x,1 = Legendre polgnomial of degree i of the argument
L.
x, tdd x2 ma$ be replaced by (1 - x) and x respectively.
Sach of the coefficients Ai, Ri, Ci or Di ma.y he a function of temperature
after table 1.

TART,=!
7
Equations of table 2, subject to Rohler"s formali~:~.

ex

63 =

x,*x**

f?x
g = x,+xg

A.*:x,/(x,+x,))~
1.

Ri*t

(x,-x,)

/(X,fX2W

id

i=O
n
ex

g = x,*x2*

C.*x/"-i)*x:/(xl+x2)n
z: 1
i.4

sxg = x,*x2* -%
?+p ((x -x f/(x +x >t
ii.
13
1 2
t
id3

Equations of table 2, subject to Vuggiaril"s forlnslism.

n
ex

63 = x,+x2*

Ai*+

exg = *,*x2*

id
n

ex

63 =

x,*x**

z:

Ci*yi)*y;

exg = x,*x2*

i=O

with

v, = xl - (l-x,-x2)/2

n
1 Ri*(X,-X2) i
c
id-)

and

v* = x2 -.(I-X,-X;?

If2

ni*pi(x,-x2)
T
r=Ti

233

CALCULATION OF PHASE DIAGRAMS

ex

gtern =

(51
i=l

j=i+l

A generalisation of Mugginnu"s formalism is given by Hillert /15/:

ex
gtern

2
i=l

2
j=i+l

xi*xj*xk f.

k=j+l

l=O

Alm*v:*~;*v;-~-l

(7)

m=O

The v are generated from the x by subtracting the quantity (I-xi-xj-xk)/3,

which disappears in the ternary systems.
Additionally quaternarg excess
terms may be added:
ex
gqua

x1*x2+x7*x4

i=O

j=O

n~Aijk~x~*x~*x~*x~-i-j-k

(8)

k=O

The extension to solution phases with more.than 4 components is done by the

same principles,
either using the generalized Kohler formalism or the
generalized Muggianu formalism after Hillert.
Each of the coefficients A
R., . . A..
., 4..
in the formulas (5) to (8)
and of the tables 2 to 4 may 6: eapresseajks fun&d!on of the temperature after
equ. (7).
2.3.4. Qualitative comparision of Kohler's and Muggianu"s formalism
In order to get an idea of the physical meaning of Kohler's and
formalism, the following rough explanation may be helpful:

Muggianu's

In the regular solution model the energy F: of an A-B pair, compared to f/2
A-A and 112 B-B pairs, is assumed as:
(&)=
(9)
EAB - @AA + EBB)/2
If random mixing is assumed, the number of A-B pairs is proportional to the
product x,*x2*Z of the concentrations of A and R and the coordination number
Z, or:
H

x,*x2*~*Z*NL

(10)
If C: is set equal to H, this is identical to the formulas of table 2 with one
parameter A = W*Z*N
only. The additional parameters may be roughly explained
~~)~heT~~~umption, tkat various small effects change the value ofW after equ.
may be expressed as w being a function of the neighbourhood of the
A-B bond in question. By other words, the A-B bond with more A neighbours has
a different energy than an A-B bond with more R neighbours. The sums in the
formulas of table 2 express this difference by approximation polynomials of
the concentrations,
which are proportional to the probabilities of A- or
B-neighbours.
In a ternary solution with A-, B- and C-neighbours, Kohler's equation
treats the C-neighbours
like A, if many A- and few B-neighbours are present
formula always
and like B, if few A- and many B-neighbors exist. Muggianu's
like an equal mixture of A- and R-neighbours. Of course
treats C-neighbours
the different treatment of C, depending on the relative amount of A- and
B-neighbours,
is a disadvantage of Kohler's formalism. But the influence of
the CIneighbours may be different from that of an equal mixture of A an3 R by
the same amount as the influence of A is different from that of B. That means,
the values after Muggianu'a formula may differ from the experimental values by
the same magnitude as from the values after Kohler's formalism. If the values
adjusted
to
are
either after Mustaianu's or after Kohler's formulas
by ternary terms according to equ. (5), it is-exspected,
experimental values
--

H.L.

234

Lukas et al.

that they yield equally good expressions. 'Iherefore there is no severe

to prefer one of the both formalisms.

reason

2.7.5. Wore sophisticated analytical descriptions

2.7.5.1. The associate model
Especially in the gas phase, but also in some liquids, molecules or
associates are formed. These must be treated as additional species with
respect to the formulas of the mixing entropy. "hey do not have to be treated
phase rule, because these
as additional components with respect to Gibbs
species are in homogeneous equilibrium with each other and the pure elements
inside the homogeneous phase. If the number of molecules or associates is
greater than the number of components, their concentrations can not all be
additional
the
phase.
?he
derived from the bulk concentration
of
concentrations are parameters to describe the homogeneous equilibria in the
phase.
?he
occur.
associates
interaction
Between the molecules or
may
corresponding interaction energies can be described by approximation formulas
as described in chapters 2.7.1. to 2.7.7.. The arguments of the polynomials
are the concentrations of the molecules, referred to 1 mole of phase. The kind
of formula (binary, ternary etc.) depends on the number of species, not on the
number of components.
2.7.5.2. Sublattices
In solid solutions often the atoms (or ions or molecules) are restricted to
different sublattices. In this case, the configurational entropy is calculated
for each sublattice separately by equ. (4), referring the concentrations to
the total amount on the sublattice in question, not to the total amount of the
the
phase. The total configurational entropy is calculated by summing up
contributions of each sublattice, multiplied by the site fraction of this
sublattice. The site fraction is the number of moles of sites in one mole of
the phase. Rxcess terms of enthalpy, entropy and specific heat are introduced
by approximation polynomials of the kind of tables 3 and 4 and equ. (5) to
(8). Mainly the interaction of species within the same sublattice must be
considered, but interaction between species on different sublattices is also
possible and may be described by extra polynomial terms.
2.7.5.7. Combined formula
A formula for the total Gibbs free energy of one mole of a phase, combining
the associate model and the sublattice model with polynomials of the
generalized Muggianu type, is:
Gi =

xalxyk*(Gk
lk

where

+ RT lnyk)

~Aj*yp*yq*v~-l*v~-l
j

B jj*Yp*yq*yr*wpm-l *wn-l*wo-l
q
r

jj
i =
1 =
k =
j =
jj =

phase index
sublattice index
species index
polynomial index (binary terms)
polynomial index (ternary terms)

....

(R*T*lnp)

Gi = molar Gibbs free energy of phase i

a 1 = site fraction of sublattice 1 in phase i
= concentration of species k, referred to sublattice sites
'k
Gk = Gibbs free energy of formation of species k

!ll)

CALCULATION OF PHASE DIAGRAMS

vP

= Yp-(l-Yp-Yqm
= yp-(l-Yp-Yq-Yr)/7

v9

235

= Yq-(l-Yp-sp2

wq = yq-(l-yp-Yq-Q/3

wr = .vr-(l-Tp-Tq-YrV~
wP
The G and the coefficients A. and 3.. are functions of the temperature
ES:&':;eq&. (3). The exponents m, Jn and a3as well as the indices p, q qnd r are
individually to each j or jj. Thus in the data base only the polynomial
term8 which do not vanish are necessary, and not all, which belong to the
chosen degree8 of the polynomials. Condensed phases are assumed to be
independent of the pressure p. The term R*T*lnp is used in the gas phase only.
The interaction terms in equ. (11) are not applicable to the gas phase,
since
there
the
partial
pressures should be taken instead of the
concentration8 y. That means, the
expressions containing
nroducts
of
concentration variable8 must be multiplied by a power of the pressure of the
same degree a8 the sum of degrees of the powers of the concentrations. 'Ising
equ. (11) therefore only an ideal gas can be treated. This is not a serious
restriction, if equilibria only at high temperatures and pressures near or
below atmospheric pressure shall he calculated.
In phases containing
ions, the G cannot be determined for al.1 the ions
individually, since only neutral comb14 ations of cations and anions have
measurable G-values. That means, the Gk value of one ion must be arbitrarilg
taken, then the G -value
of the ion with opposite charge can he adjusted to
the G-value of th& pure salt. Also the A.-values of the binary combtnations of
one cat ion and one anion each, can se used to express G of the pure salt,
since the binary combination exists only at one definite composition, that of
the neutral salt. However attention must be paid using these terms, since in
quasibinary salt solutions AX-RX, the value expressed by equ. (11) is
different,
if the G-values of the pure salts are given by the G or by the A.
terms (with the exponents m=l and n=l). Therefore it is preferablfe to describa
the G-values of the pure salts by the G
only. JJnfortunately that is not
possible for salt solution8 with more th%n one cation and more than one anion.
Here the G of the 1st anion X may be chosen arbitrarily. ?hen the G of all
the cations k, B, C . .. are adjusted to fit the G-values of the pure s&lts AX,
BX, CX .** - Then the Gk-value of the 2nd anion Y is chosen to fit the G-value
of pure AY for example.
The G-values of the remaining pure salts RY, GY ,..
can only be adjusted by A -terms in equ. (111, preferably with m=l and n=f. If
adjusted td BY instead of AY, the differences of the G1-values,
%lczfatid ty equ. (11)
can be compensated by an A.-term for the pair of
cations A and B. BuE in a four-ion mixture the Jroblem arises again. Here
different choice8 of Gk of Y may be compensated by a R.. term in equ. (11).
This is similarly true for higher order ionic solutiond? Thus in equ. (11) the
must not be fixed each for itself. Only the data set as
values G
a whole i$'atieatdo ild e a thermodynamic description, which may be compared
with experimental values or with other thermod.ynamic descriptions.
In equ. (11) one mole is defined as Avogadro"s number of species, where
each molecule or associate is counted as one species. Also vacancies are
counted as one species each. This definition facilitates the calculation. Tf
G-values shall be output after calculating the equilibrium content of
molecules, associate8 and vacancies, they easily may be transformed to a
reference amount of one mole of atoms.
3. Calculation of a Single equilibrium
3.1. Equilibrium Condition8 after Gibbs
Thermodynamic equilibrium at given constant values of temperature T,
pressure p and amounts of the components N. is determined by the minimum of
the Gibbs free energy. J.W. Gibbs derived fro4 this condition the well known
equilibrium conditions:

H.L.

236

.
m

G;

. . . .

Lukaa

et al.

(121

G(r)

for heterogeneous equilibrium between r phases consisting of m components. In

these conditions the amounts of the components V. are eliminated. That means,
these formulas can be used without referringJto an overall composition for
which the equilibrium shall be expressed.
These equations may be used in numerical calculations of the equilibria,
for example by the Newton Raphson technique. ?he Gj are derived from the
analytical expressions of the integral Gibbs free energy, discussed in chapter
2, by the formula:
m
G; =

Gi

c
k=l

x;*(aGi/3

xk)

(13)

aGi/a xj

The xj are the unknowns, which shall be calculated.

The usage of equ. (12) in this numerical
calculation
three
has
disadvantages:
1) In stoichiometric or partially stoichibmetrc phases (line compounds) the G.
cannot be defined individuallv. but onlv combinations of them
ara
meaningful.. Tn a ternary line co;hpound AB-AC-for example, these are the two
combinations
the equations out of (12),
but added to
of the same phase. The
be transformed, t;o
eliminate
equations to solve this

2) The system of equ. (12) contains (r-l)*m independent equations,

but

there

may be formulated r*(r-l)*m/2 different equations of the form:

Gii)

= c(i)
J

7)

(14?

If r>2,
the total number of different equations is greater than the
number of independent equations. The question, which equations are the best
ones, is not easy to answer in a general way. Rut in the case of small
solubilities, some of these equations may be severely subject to rounding
off errors. In this case it is necessary, to select the best ones and a
general criterion therefore must be found.
In more sophisticated analytical descriptions, the G-value of a phase may
3epend on more variables, than there are concentrations. That means, there
are reactions possible in the homogeneous phase without changing the
composition (for example associate formation). In heterogeneous equilibrium
the phase also must be in homogeneous equilibrium with respect to each of
the independent ones of these reactions. The corresponding parameter values
have to be calculated first. All the derivatives of the G-value used in t'le
Vewton Raphson iteration have to be calculated under the condition of
remaining homogeneous equilibrium.

The first two points are overcome by an idea of Yillert /l5/. Ye introduced
the equilibrium chemical potentials /uj as additional unknowns. Then the set
of equations (12) is replaced by:

for all phases i and all components j. The advantages of (15) compared*to (12)
are: Each equation contains data of one phase only and the number of possible

CALCULATION OF PHASE DIAGRAMS

237

equations
is equal
to the number of independent
equations.
Therefore
no choice
equations
is
between
linearly
dependent
necessary.
TF a
phase
is
stoichiometric
with respect
to one or more elements,
the
equations
belonging
replaced.
For the ternary
line
compound A,B, - AmCn for
to
this
phase
are
example
their
three
equations
are replaced
by:
G

xB*(i)Ci/J(xr

i
G

xC*(aGi/&xB

m/(m

x,))

(m,uA

+ n,uB)/(m+n)

I)

XC))

(m,uA

+ n,uC)/(m+n)

+ n)

(16)

The derivatives
of G with respect
to the difference
(x
- xB) are well
defined
in this
partially
stoichiometric
phase,
whereas
the de F ivatives
with
respect
are not defined
and therefore
the partial
Gibbs free
energies
cannot
he
to
x
calcu 4xted after
equ.
(17).
Based on equ.
(15)
and (16)
we
wrote
programs
calculating
binary,
for
ternary
and
quaternary
phase diagrams.
The Gibbs
free
energies
of the phases
(4) to (8) and tables
2 to 4 only.
must be expressed
by terms of equ.
7.2.

Equilibrium

Conditions

after

M.rTillert

In recent
papers
/16,17/
Hillert
gave
a formulation
of
the
equilibrium
also
the third
disadvantage
mentioned
above in the
conditions,
which
avoid
numerical
calculations.
The derivation
may be summarized
by two principles:
1) The unknowns are all
the variables,
by which the total
Gibbs free
energy
of
a system
of n phases
is described
by the
analgt ical
expressions.
In
the
case
of
descriptions
after
equ.
(II),
the unknowns are the concentr~I;;.ons
of the species,
including
the associates,
referred
to the sum of species
in
the same sublattice
and the molar amounts of the n phases.
2) All the side
conditions
between
the unknowns
multiplied
by
Lagrange
are
multipliers
added
to
the expression
of the total
Gibbs free
energy.
and
Applied
to equ.
(11)
the resulting
function
is:
L

&

ni*Gi

/Uj

[z

ni

al

1=1

+ g

&h[gy:l

rbjk*y;

- Uj]

k=l

Q[galgYytl]

(17)

The equilibrium
conditions
are now: All the derivatives
of
the
resulting
function
with
respect
to
the
unknowns
or
with
respect
to the Lagrange
multipliers
are zero.
The derivatives
with respect
to the Lagrange
multipliers
are the side
conditions
themselves.
(11)
subect
to these
derivations,
yields
the
The analytical
description
equ.
and (49)
of reference
/16/
or
(45)
(44)
(46j
(48)
~~~li:I;$,e?~~~iP~Be~~~~in
(Ii);
(5j),
(1j)and
(56)ofreference
/17/):
8
il

2
k=l

f:
i=l

yk

ni

2
l=l

al

r
k=l

bjk*yil

- Vj

i = l....r
1 = l....s

(18)

(19)

= l....c

H.L. L&as et al.

238

.l f

1=1

Gi -

kfy;l

i = l....r

(20)

i = l....r

(21)

k=l'

/uj 2

j=l

al p

ykl) -

k=l

1=1

n i*(aGi/>

bjk*ylf' =

,uj*al*bjk +

ni

Ai' +

hie*a'*uk

(22)

=: 0

i=l
i

where

r
c
8
sp

=
=
=
=

number
number
number
number

of
of
OP
of

l....r,

1 = l....e,

k = l....~>

phases
components
sublattices in phase i
species in sublattice 1 of phase i

y;l = concentration
b.

of species k in sublattice 1 of phase

= number of atoms of component j in species k

a:k = site fraction of sublattice 1 in phase i

n1

= number of moles of phase i in total system

Nj
pk

amount of component j in total system

=
= electric charge of species k

/p,

/Uj,

hie =

Lagrange multipliers corresponding to side conditions

equ. (18) to (20)

The Gi are the molar Gibbs free energies after

definition of one mole given in chapter 2.7.5.3..

equ.

(11)

with

the

The Lagrange multipliers

to be identical to the equilibrium
partial Gibbs free energies of
In a numerical calculation the
unknowns:
i
il
/uj, Ai1
and ye
n9
yk'
can be calculated, using simultaneousely the equations (18) to (22) in a
Newton Raphson technique. Hillert 116,171 proposes a calculation in two steps
Par each calculation. This may be an advantage at small computers, where the
storage capacity is limited. But the number of quantities, which have to be
calculated is the same for a one step as well as for a two step calculation.
3.3. Modification of Hillert's equilibrium conditions
In the strategy outlined below in chapter 4., the property of the Gibbs
equilibrium conditions, that there is no overall composition referenced, is
very helpful. Therefore we transformed Hillert's equations to a form with the
same property. Connected with the overall composition are the amounts of
phases in equilibrium. They must be eliminated too. For the calculation of
invariant equilibria this elimination is necessary, since their phase amounts
cannot be defined without additional assumptions. To do this elimination, the
equations of the type (22) are divided by the coffespondf$g phase amount nl.
For that purpose the Lagrange multipliers h
are replaced by new
and h
unknowns:
U

il

,lil/ni,

CALCULATION OF PHASE DIAGRAMS

In the case of disappesrence

95 has
been shown for some
of reference
/16/).
%quations

aGi/3yi'-

,uj*a*bjk

of ni
speci:l
(2)

239

the limits
of these
Tao
quotients
cases
by Yillert
(equations
(75)
transform
now to:

*>
an??~~~

i = l....?
1 = I....3

+ vi1

k=l

j=l

(23)

. . ..s..

The equations
of the type (19)
may be omitted,
if r, the number of
phases,
equal
to c, the number of components.
If phase amounts
shall.
be calculated
is
be
used
for a given
overall
composition,
eql.l. (lo)
ma.
seoarate1.g
after
calculating
the
equilibrium.
If r > c equ.
(lo Y are not independent
and must
to
balance
the
number
of
unknowns
and
necessarily
be omitted.
In
order
if
r-c=l,
the temperature
or pressure
or,
if r - c = 2, both,
equations,
This
is
no
contradiction
to
the
have to he introduced
as
new unknowns.
evaluation
of
the equilibrium
conditions,
where the temperature
and pressure
The question
may be formulated
in this
way: Rich are
have to be kept constant.
conditions
the constant
values
of T and p, for which the equil.ibrium
can
be
satisfied.
If r C c according
to Gibbs
phase rul.e,
there
are c - r degrees
of freedom
left,
if temperature
and pressure
are fixed.
The equations
of type
(l(3) may be
which selects
specific
conditions
for the
replaced
by
any
set of equations,
remaining
degrees.
of freedom.
We
(, 9).
use for that
purpose
equations,
which
are
formally
very similar
to equ.
1)

4n extremum of a phase field

with respect
to T or p is characterized
by the
independent,
or
the
fact,
that
the concentrations
of the phases
are
not
concentration
of
the
last
phase can be expressed
as a linear
function
of
the concentrations
of the other
phases:

2
i=l

ni f:

a1 f

bjk*yil-

k=l

l=l

2
I=1

a1

bjk*yE

= 1 . . . .J

(24)

k=l

Any phase may be chosen

as phase No. r, but attention
must be paid,
if
the
The
phases,
which
do
extreaum
is
degenerated.
not
take place
in the
invariant
reaction
corresponding
to the extremum,
or take place
with a ver.
must not be taken as phase Vo. r. The n
in
equ.
!24y
small
amount onlg,
phase amounts and may have negative
values.
Sut formally
they may
are
not
be interpreted
as phase amounts,
which are necessary
to produce
one mol
of
by the invariant
reaction.
phase r out of the other
phases
2)

If the boundary
of the r-phase
is wanted for
phase
No.
r,
equations
are applicable:

2
i=l

ni f:
l=l

ai

bjk*yi

field
with
a T-c-section

?Tj - XXV;

the
(or

r-l -phase
p-c-section),

field,
the

missing
following

= l....s

(25)

k=l

The R, are the cpncentration

coordinates
of
the
starting
point
of
sectidn,
the
NY the elements
of the vector
from the starzing
point
to
Y is an unknown and represents
the
abscissa
end point
of theJsection,
the calculated
boundary
in the section
at given
temperature
and pressure.

the
the
of

The
summation
over the interval
I....?-1
means,
phase Yo. r takes
place
defining
the
above
mentioned
in the equilibrium
with the amount 0, thus
(25) may also be used with X fixed
and
of the r-phase
field.
Vqu.
boundary
T-c-section
T (or p) taken as an unknown.
That means,
the abscissa
of
the
p-c-section)
is chosen
and the ordinate
is calculated.
This version
.iH
(or
Plat ,
the
section
is
image
of
the
boundary
in
preferable,
if
the
if it has a minimum or maximum.
especially,

H.L.

240

Lukas

et al.

Also for plane sections

through,isotherms
equ. (251 can be used. In this
in the plane, which is changed
case
N
represents
a point and V. R vector
stepwisd
for consecutive
calculati&s.
The concentration
of the boundary is
after
represented
by the right hand side of equ. (251 and can be determined
calculating
X.
The ni here mean phase amounts at the overall
composition
shown in
Vegative
values of these amounts indicate,
that the equilih~ium
section.
outside
the section
at the prescribed
? or X.

the
is

potentials
(equilibrium
Gibbs
free
energies)
3) One or more of the chemical
are fixed,
or more general
are referred
to the G-value of a reference
phase
at the same temperature
and pressure
by a fixed
value v:
Gief
v
=
0
(26)
j = chosen components
Pj
This
equation
may be used with either
of the equ. (19),
(24) or (25).
lath
equation
of the type (26) reduces the degree of
freedom
by
1, since
an
equation
only and no unknown is added. Therefore
the number of components c
(19),
(24) or (25) must be diminished
by 1 for each equation
of the
;;pZq:;6j.
Baaed on these
equations
we wrote
a program,
which, contrary to the
programs mentioned in chapter 3.1.,
is able to calculate binary, ternary
and
up to 7 - component systems by the same program. The Gibbs free ener y must be
expressed
by equ. f 11) , which includes
all descriptions
using equ. ts41 to (qj
and tables
2 to 4 as special
cases.
3.4.

Extrema

or Sections

together

with

Gibbs

Equilibrium

Conditions

In the programs mentioned in chapter 7.1.

instead
of
equ.
(34)
and
(25)
equations
without
the
variable
n
are preferable.
Since in these programs
sublattices
and molecular species or associates
are
not
allowed,
only
the
concentrations
of the phases must appear in the corresponding
equations.
Instead
of
equ. (24) the condition
is used, that the concentration
matrix
has a nonmaximum rank 1181. (The concentration matrix is a matrix
containing
the
concentrations
of
all
components
in all
phases).
This condition
is
formulated
differently
depending on the number of phases r and the
number of
If
r is equal to c, the concentrtition
matrix is quadratic
md
components
c.
the-appropriate
condition
is, that the determinant
of the concentration
matrix
is zero,
lf r = 2. there are fc - 1) conditions.
that the (c - 1)
indeoendent
concentrations
of
both
phases are equal.
These conditio&
areformulated
in
table 5 for binary to quaternary
systems.
Tn the case of an extremum
of
a
three-phase-field
in
a quaternary
system
fr=3,
c=4),
the 4 different
3*3
determinants
of the 4*3 elements of the concentration
matrix must be zero. But
only two of these conditions
are independent.
An arbitrary
selection
of two of
these conditions
is given in table 5. The lines
containing
only ones
are
due
to the fact,
that adding other lines
to one line of the matrix does not change
the rank and the sum of the concentrations
of all components is one.
The condition
similar
to equ. (25),
that the boundary between the r - phase
equilibrium
and the
equilibrium
containing
the first(r
- 1) phases is-on a
section,
may be formulated
bv similar
conditions
given in table 6. In case
1
the matrix- composed
of the concentrations
of the (r - 1) first
phases and a
polnt of the section
(index
01 is
of
nonmaximum rank.
That means,
the
concentration
coordinate
in the section
is given and the temperature
is asked
for (it is an additional
unknown).
In case
2 the
matrix
containing
the
concentrations
of the (r - If first
phases and two points
(indices
A and R) is
of
nonmaximum rank. This condition
yields
one equation
less than that of case
1. In accordance
with that,
the temperature
is fixed in the calculation. A and
3 may be two points defining a T - c - section,
or
A is
a fixed
and R a
scanned point in a plane section
through an isothermal,
isobaric
quaternary
system.

241

CALCULATION OF PHASE DIAGRAMS

CABLE 5
Conditions

for
be

an extremum of a r - phase field

user1 tog~1;hr-t~ with equ.
(15)
and

to

X'

in a c eventually

X"

system,

X5

-x';

x;

x;

xix;

xi

x; x;

x;

x5

component
(16).

=O

xy x;

*
- x;
x2
.
x7 - x;

x;

x;

xi

x5

x;

x;

x;

- xi

Conditions
for the boundary
r - 1 first
phases
to be
c

point

0,

T calculated

xs-x;
3

x5 -

between
a r - phase field
at a fixed
cc.ncerikr%tion

points

and the field

or on a line
4 and R,

x1

x; =

A R
xS x2 x2

of
4 -

the
9

v fixed

xA
xB
1
1
=r)

4 B
x4 x3 x7

x; -

x; =

xi

x;

I)

a x4 xB
x1
1
1

xj

x;

x1* x;

x;

* X;
x;!

0
x2

=O

x;

x;

x;

x;

xi

xx

x;

= 0

11
=o

x;

x7

T3

x3

= r)

A R
*2 x2
x1

x;

xfxp

x;

A 3
x2 x2

(-)

H.L. Edas et al.

242

4.

Calculation

of

Whole Phase Diagrams

and Plane

Sections

of
-

Phase Diagrams

In chapter 3 equations
to calculate
a single
equilibrium
are
fieacribed,
which
may be solved
by the Newton Raphaon technique
or by other methofls. A
whole phase diagram or even a section
through a phase diagram is a combination
of many single
equilibria
(tie-lines).
(15,
or
The results
of the calculation
of a single
equilibrium
after
equ.
after
chapter 3.2. and 3.3. contain
the values of all the intensive
parameters
equilibrium
T,
in
p and U. either
aa values given before
calculation
or as
molar
enthalpiea
and
calculated
values.
The cone k ntrationa
x of the phaaea,
easily
be calculated
from the equilibrium
concentrations
y OP
entropies
can
well
Therefore
these equations
are
the species
in the different
sublattices.
suited
for
each
of
the
different
types of phase diagrams distinguished
by
Schmalzried
and Pelton /IS/ and Pelton and Thompson 1201. The distinction
is
after
the coordinates
of the diagram, which may be either
intensive
parameters
enthalpy,
of
extensive
parameters
(concentrations,
molar
(T,
P or endudiy E; r;~~~~.
the
intensive
parameters
are
In phase diagrams,
where one
or
more of
restricted
to
constant
values,
the terms invariant,
univariant
etc.
shall be
applied
to the remaining
degrees
of
freedom.
For
example
in
an isobaric
isothermal
n-component
system the invariant
equilibrium
contains
n phases and
the univariant
equilibrium
n-l phaaes, since two of
the
degrees
of
freedom
after
Gibbs
phase
rule
f = n + 2 - r are
used to separate
the system in
question
from the polythermal
polybaric
n-component
system.
4.1 . Strategies
There are mainly two different
strategies
to construct
a phase
diagram
by
of single
equilibria.
au Isequent calculations
between specified
phases are calculated,
regardless,
if they
1) The equilibria
of
freedom
are
are stable
or metastable.
The conditions
for the
degrees
incremented
for
consecutive
calculations.
Afterwards
the
different
equilibria
are compared, which are the moat stable
ones.
of
coordinates
for
the
external
parameters
(for
example
2) A pattern
temperature,
pressure
and overall
composition!
is selected.
To each set of
these coordinates
the equilibrium
between
different
sets
of
phases
is
calculated
and the moat stable
one is selected.
A strategy
in between,
suggested
by Rillert
/17/,
calculates
equilibria
between specified
phasss like atrateRs
1.
but
asks
at
each
step.
if
the
of
another
phase
G-value
is beloWthe
tangent hyperplane
of the-calculated
equilibrium.
Strategy
1 is uaed by Kaufman 1211, whereas
examples for strategy
programs of Erikaaon /4/ and of Lin
et
al.
1221.
Strategy
1 is
flexible
one, but it is leas easy to be fully
automated.

2 are the
the
more

To eetabliah
a whole phase diagram by strategy
1, it ia suitable
to start
with the invariant
and univariant
equilibria.
In type 2 phase diagrams (in the
nomenclature
of Schmalzried
and Pelton
/19/J,
like
the
usual
temperature
composition
diagrams,
these
equilibria
can be
clearly
arranged
on a
twodimenaional
paper by a reaction
scheme after
Scheil
1231.
The Newton Raphson iteration
needs for starting
a set of approximate
values
of all the unknowns to be calculated.
Therefore
the begin of
the
calculation
is preferably
done, where these approximate
values may be eaaily
eatimated.
If
all
the
aubaystems
with
one component leas are already
calculated,
one may
atart
with
the
univariant
equilibria,
which
arise
from
the
invariant
equilibria
of
the
subsystems.
These
equilibria
are calculated
at atepwiae
increased
or decreased
temperatures.
Where two of them intersect,
which
each
have
the
aame phaaea
except one, an invariant
equilibrium
muat be present.
This can be calculated
in the next step, uaing the
calculated
concentrations
of
the
univariant
equilibria
as
starting
values
of
the
Newton Raphaon
iteration.
In the type 2 phase diagrama,
where one coordinate
is an intenaive

CALCULATION OF PHASE DIAGRAMS

243

parameter, each invariant equilibrium can be characterized by a reaction

equation. After the equilibrium concentrations are calculated, the amounts of
the phases taking place in this reaction can be determined. They are
orooortional to the determinants of the concentration matrix /IA/. The sum of
theAdeterminants must be zero. Dividing all the determinants by the sum of the
positive determinants,
the amounts are normalized to 1 g-atom. Tegative
amounts belong to the left hand side, positive amounts to the right hand side
of the reaction equation. If the intensive parameter is the temperature, the
direction of the reaction is that occuring on cooling or, where the enthalpy
The enthalpy of reaction can be calculated as the sum of the
is decreasing.
enthalpies of the phases times their amount. Tf it is positive, the signs of
all amounts must be changed, to get the direction of the reaction occuring on
cooling.
prom an invariant r-phase equilibrium there start r (r-l)-phase equilibria.
Which ones 09 them go to higher and which ones go to lower temperatures can be
seen from the reaction equation. These univariant fr-l)-phase fields can now
be calculated at stepwise increased respectively decreased temperatures.
The intersection of two univariant equilibria in ternary systems usurtlly ia
well detected in a projection like a liquidus surface. In higher order systems
this intersection must be observed in a higher dimensional space. Here the
projections vf a chemical potential temperature diagram may be useful. The
diagrams is 'recommended by Hillert 1241. In these
these
usage Of
4
*
diagrams the univa iant equilibria are onedimensional curves, which can easily
be projected onto all the subdiagrams containing two of the coordinates of
this multidimensional diagram. If one coordinate, for example the temperature,
is the same in all the projections, the images of the univariant equilibria
must intersect in all projections at the same value of this coordinate.
Projections of the in- and univariant equilibria of ternary systems onto
the p-T-plane were already used by Schreinemakers /25/. These diagrams may be
considered as twodimensional analoga to the reaction schemes after Scheil,
which use only one axis, the temperature. Contrary to Scheil's scheme there is
not an unique reaction connected with an invariant equilibrium, but there are
two independent reactions possible and all the linear combinations of them.
Instead of the two directions up and down, which are distinguished in Scheil's
u - T - or u - p - T - diagrams the exact direction of the
scheme, in the
line representing Ln univarian 4 equilibrium is given by a generalized Clausius
Clapeyron equation /19,20,25,26/.
The projections of the u - T - or /u - p - ? - diagrams must not be mixed
up with the type 1 ph L se diagrams after Schmalzried, Pelton and coworkers
/19,20/. The first ones are projections of multidimensional
phase diagrams
onto the plane of two intensive variables, whereas the latter ones are phase
diagrams in two intensive variables, which are made twodimensional by keeping
the necessary number of intensive variables constant.
Cie- t,y,e"";'
4" - p - T - diagrams therefore are the more general case ZZ
iagrams after Schmalzried and Pelton are the special cases of twodimensional
diagrams.
If the dimension of a diagram is reduced by one by keeping one intensive
variable constant, the univariant equilibria of the initial diagram become
invariant equilibria of the reduced diagram. They can all be found, If the
is already calculated. The univariant equilibria of the
initial diagram
reduced diagram can now be calculated. This case happens for example, if a
four component system was calculated in fourdimensional coordinates (?, x,,
isotherms of this system shall be
x71 x or-/u instead of x) and now
calcu s ated,. To this ouroose a diagram similar to Scheil's reaction scheme may
in boxes connected by lines
be helpful. It shows the-invariant-equilibria
representing the univariant equilibria. Part of the univariant equilibria is
connected with the boundary of the system. Contrary to Scheil's scheme no
reactions between the phases of an invariant equilibrium can be defined and
the relations above and below have no meaning with respect to two invariant
equilibria. The content of this diagram is the topological connexion of the

H.L.

244

in-

and univariant

Lukaa

et al.

equilihria.

reduced
to
two
not
by
keeping
If the dimension
of a. phase diagram
is
variables
constant,
there
results
R
ratio
of
extensive
intensive
but
the
equil.ibrium
diagram,
because
the
which is not itself
a
complete
section,
of the phase3
of a multiphase
field
are generally
outside
the section.
images
equil.ihria
in the section
are
found
by
The images of the in- and univariant
calculating
the intersection
points
of the plane
of section
with the straight
equilibria
in
the
geometrical
structures
representing
these
lines
of
multidimensional
coordinates.
can now be calculated
between
the
The
divariant
equilibria
in
section3
boundaries
given
by the univariant
equilibria
and fixing
one degree
of freedom
after
tab17
6. These equilibria
leave
the plane
of section,
where one
of
the
There trivariant
equilibria
(one
(25)
becomes
negative.
amounts
n
in
equ.
hase 1e::n)
etart.
They may be calculated
in the next step
using
again
f3p.
of
freedom.
The same is clone with the
which
now
fixes
two
degrees
P25)
until
the boundaries
of the two phase fields
multivariant
equilibria,
against
the one phtisc: ields
are calculated.
4.2.

Derivatives

of

the

boundaries

in

a- phase

diagra?

The
TJewton Raphson
method
for
starting
needs approximation3
of all
the
values
to be calculated.
The better
the
approximation,
the
faster
is
the
iteration.
Also the possibility
to jump to another
(metastable)
branch
of the
same equilibrium
is diminished
by a better
approximation.
Tf
an
univariant
equilibrium
is
calculated
in
steps,
the
best
approximation
to start
the
iteration
of the next step can be found
using
the
derivatives
of
all
the
unknowns
with
calculated
respect
to the scanned
variahles.
The same is true
for a multivariant
equilibrium,
which is made univariant
by fixing
conditions
for
the
remaining
degrees
of
freedom
(e.
g. calculating
of the image of a
boundary
in a plane
section.
The most well
known derivative
of this
kind
is
defined
by
the
Clausius
Clapeyron
equation.
This
was
generalized
to
multicomponent
systems
by
Tchreinemakers
/25/.
General
formulas
of the derivatives
of the boundaries
in
binary
x-T-diagrams,
which
show
especially
the
ilependence
on measurable
thermodynamic
quantities,
are
given
by
Wagner
!27/.
Scheil
!?8/
used
derivatives
of
the
edges
of a three
phase eyuilihrium
in a ternary
system.
Sillert
/26/
gave general
formulas
of derivatives
in multicomponent
systems.
A
general
method to get numerical
values
of the derivative
of any boundary
in
a
multicomponent
with respect
to any external
variable
was given
by the
present
authors
??Fzonference
report
1291.
?his
method
shall
he
briefly
outlined
again
here.
4.2.1.

Numerical

values

of

The s stems of equations

sets
(19 3; or (24)
to (26)
the general
problem:
F,(X,X2

,...

Yn,t,,t2

derivatives
or

,...

(18),
the
tm)

~2(x,x2.xnt,t2,...tm)

Fn(X,,X2

,...

where
the
F.
t
the set o?
d&able,
equ.

xn,t,,t2

,...

tm)

of

(20),
system
=

implicitelg

defined

functions

(21)
and (23)
to ether
with one of the
of equations
(12 7 or (15)
are case3
of

(27)

are functions
of the variables
x i and ti.
With fixed
values
of
equations
defines
values
of the
x..
I?
the
t.
are
assumed
(27)
define
implicitelg
the xi as Functions
of the ti:

245

CALCULATIONOF PHASE DIAGRAMS

xl
x2

f,(t,'t2'".'tm)

f2(t,,t2,...'tm)

.......................
X

fn(t,,ty..,tJ

Values of these functions for given t. are calculated by the Newton Raphson
method, using the set of
equations (27). To get the derivatives of the
functions
(28) with respect to t
(27) with respect to ti,
assuming the x. beeing functions
the other t. beeing
OfJ t.. Since along the whole cour&k of the functions (24) the F.
are z&ro, also these derivatives with respect to ti must b&
zero:

b2 dx,
aF2 fix2
--t---_...+--

ax,

ati

b, ax,

--+--+..,+-3x1

at i

ax2

ati

3Fnax2
ax 2 lit i

+ a2
=

JF2n
ax, dti

aPn

dxn

ax

at

ihi.

Jn
at

r)
,

(29)

If
the
values
F./ t.
are taken to the right hand side, equ. (29) are A
system of n linear equhtiohs defining the n unknown values of the derivatives
dx./dt. of the implicitely defined functions (25) at the point (t t2,...,t ).
Tha right hand side are the partial derivatives of the F with r&Lpect
to 0
The matrix of coefficients of the left hand sidle is identical to that use? 4;
the Newton Raphson
iteration to find the corrections of the xi for the next
step.
In our
roblem equ. (15),
(20))
(21) and (23) together
with
one
of
sets
to
(26)
are
inserted
as F in equ. (29).
Uow values of the
(19)
or P24)
derivatives
of all the variables,
which are called
unknowns
in chapter
3.,
of the prescribed
variables,
which may be stepped
with
respect
to
any one
during calculation
of an univariant
equilibrium,
can he calculated.
In equ. (IS) to (26) the unknowns are
the
yk,nitlu
,Qil
and flie.
mhey
giving
the overall
correspond
to
the x of equ. (27) to (29).
The values f
(27)
to
corn osition,
are pres&ribed
variables
and correspond
to t!
in
equ.
T and the pressure
p may either
cbrrespond
to an xi or
(29p.
The temperature
to a ti, depending
on the cases distinguished
in chapter 7.7..
If several
of
the
prescribed
values
are
linear
functions
of
a step
parameter,
the derivatives
of the unknowns with respect
to the step parameter
from
the
derivatives with respect to the prescribed
can be calculated
variables. This is for example the case, if the overall composition is scanned
along a straight line.
4.2.1.1. Values of derivatives at the boundary systems
If the concentration of the element p is zero and the derivatives with
respect to this concentration are wanted, equ. (19) or (24) to (26) cannot be
becomes infinite. This
inserted into the system of equations (29), since
i8rium is started at the
situation takes place, if the calculation of an equi 4"
boundary system. In a recent paper 1291 the solution of this problem was given

H.L.

246

L&as

et al.

is replaced
by the
for
the
system
of equations
(15) inserted
into (29).
G is
R*T*ln(XP)
in
the &pression
of
expreeaion
R*T*ln(AP)
and the term
The two logarithmic
terms are brought to the left
hand side of the
extracted.
to
the
right
which contains
only finite
terms,
equation
and the remainder,
hand sida.
Ry exponentiation
a new equation
is formed, which contains
the
finite
activity
a as unknown instead
of the infinite
u . A similar
treatment
the following
sequence of tran8f~r~~t~on~~
with equ. (23) giglds

sl*R*T*ln(yi))

(aGi/dy;l-

not
-E

- a*b

*R*?*ln(a
pk

p
,uj*a*bjk

+ m

il

+C

ie,al*

)
P

Yk

f-30)

j=l ,c
=

if<' bpk) lap)

R*T*ln( yk

not
+

+ a*R*T*ln(y:)

/a1

+ R+T*ln( y:l)

j=r
c

c/jbjk

vll/al

+ r

id

yk

Ibpk)

+ R*T*ln{y~)

a *exp
P
not p
+

j=,
c

c/j*bjk

il

al

(32)

,
This transformation
is done only for the element p, which disa pears at the
boundary system, because equ. (72) ia more complicated
than equ. P.27\. tn equ.
the
corresponding
term
(21) it is not necessary
tpleliminate
fu , because
of logarithmic
degree
vanishes
with vanishing
yk , since /up b&comes infinite
only.
Therefore
replacing
equ. (23)
by
(72$al;;i
Aiserting
in
(29)
gives
R
the
derivatives
of
any
numerical
calculate
possibility
t0
entering
the
variable
equilibrium
parameter with respect
to a concentration
system in question
from the boundary system missing element p.
is

not unity,
the derivative
of equ. (72)
Seoause
the
product
containing
this
must be finite,
the other factor,
the derivative
of
from
the
with respect
to a concentration
variable
entering
the
system
therefore
must be zero. Of course this is true only in the bounrlrzrg
mean of
the
derivative
in
EI small
finite
aystem i)tself
and not for the
The 2nd or a higher
(the nth, if b
interval1
adjacent
to the boundary.
pk = n)
derivative
gets a positive
value.
This behaviour
is well known in
the
case
of
an equilibrium
between
a
monoatomic solute
(R, N or 0) in a metal snfi a rfiatomic gas. ?he concentration
of
the
solute
is proportional
to the square root of the partial
pressure
of
the gas. Vice versa the partial
pressure
of the diatomic
gas
ie
proportional
to
the aquare of the concentrntlon
of the monoatomic solute
anrf therefore
its
with
respect
to
the
solute
concentration
is
zero
at
zero
derivative
concentration.
These
derivatives
may be taken
starting
values for the next iteration
In this
case
the
boundary
system.

to
estimate
finite
increments
to get
if the calculation
ia etarted
*t
step,
not the value 09 the derivative
at the

247

CALCULATION OF PHASE DIAGRAMS

concentration
zero, but the mean of the derivative
in a finite
interval
urith
am.11
positive
concentration
is needed.
In the case of b
Chigk ~;~;;ert;ha;e*n;;~
higher derivatives
should
be taken
into
account.
cz;E;i;;t;PI
To get e~,~~~Ri~1ti9,~~~i~~
e;;.
i;z(f;pg
i;u;;;;;i.i;
f;;m ;;z
and the
of 0.1. This yields
a finite
value for the derivative,
which
f b k-l )th power
ma? be far from the correct
mean in the interval
in
question,
hut
in most
cases
it
is sufficient
to find starting
values,
which get the next iteration
step working.
5.

Details

of

Programming

In the present
stage of development
of the program each multiphase field is
selected
individually
by a set of input data. Uut most of these
data,
except
for
the invariant
equilibria,
are prepared by the computer during calculation
of the equilibria
with one additional
phase. The following
considerations
are
formulated
for the program based on equ. (19) to (261, but they are similarly
valid for the programs based on equ.
(16)
together
with
tables
(15)
and
5 and 6.

Beg1
n
L_

Read coeff,crants

Constrvct tentative
reoctlon

Calculate
wlthln

scheme

n-phase

range

of

fields

stoblllty
I

CoIculots

Coiculote
(n-I)-phase
for

each

fields

(n-I)-phase
f.

lsotherme

fields

each T-c-sect.

Calculate
h-2) -phase F lelds
for each dmpm

*
Colculote
2-phase
for

fleids

each dlogram

FIG. 1
Sequence of Calculation

PIG.

Flow Diagram of the Main Program

H.L. T.&as et al.

248

5.t.

Sequence

of

Calculations

fig.
as outlined
in chapter 4.1.,
is shown in
The sequence of calculation,
concentration
diagram.
If p is taken as an
1 for
an isobaric
temperature
of
a concentration
as
taken
instead
additional
variable,
or, if a u is
scheme
is valid,
where onlg the number of
variable,
a simllar
independent
phases of invariant,
univariant
etc.
equilibria
is different.
5.2.

Main Program

First
the
The flow diagram of the
main program
is
given
in
fig.
2.
from a data set with filecode
01. This
thermodynamic
coefficients
are
read
data set covers all the data of
a n - component
system
with
n up to
7.
Subsystems with less than n components may be calculated
using the same set.
the numbers of
contains
first
the
numbers
of
phases,
This
data
set
used
in headings
of
output
names of the components,
which are
components,
which
are
used in temperature
maximum number of
terms,
tables
and the
functions
after
table
1. For each phase there are given a name, the number of
and the
number of
polynomial
terms after
equ. (ll),
using the
sublattices
different
sublattices.
For
sublattice
concentrations
of species
from
each
the number of species
and the number of
there
are
given
the
site fraction,
of
this
sublattice
polynomial
terms, using concentrations
of species
only.
Each
is
characterized
by a name,
the
stoichiometric
numbers
species
corresponding
to the n components
and to
electric
charge
and a line
of
coefficients,
which
describe
the
value
G
of
equ. (11) as a function
of
o ynomial term there are given the
temperature
after
table
1. Finally
to each
integers
p, q, r, m, n and o after
equ. (11 P r.
and a line of coefficients,
which
describe
A3 or Bjj as a function
of temperature
after
table I.
A second iltita set with file
code 04 contains
the parameters
of
the
actual
calculation.
St
starts
with
the
number of diagrams,
the number and serial
numbers OS: the coinponents used. To each diagram a type is assigned
(Cartesian
coordinates,
Gibbs
triangular
coordinates,
?-c-sections
or plane sections
through isobaric
isothermal
systems).
Tach T-c-section
is characterized
by the
concentrations
of two points
and each
isobaric
isothermal
section
by the
concentrations
of three points
and the values of II and p.
After
that
to each equilibrium
there is assigned
a type, according
to the
different
possibilities
discussed
in chapter 7.3.,
the number r of phases,
the
number of steps,
for which the equil.ibrium
shall be calculated
and the
number
of diagrams,
in which it shall
appear. By type
the end of calculation
may be
defined.
After that the phases are specified
by their
serial
numbers referred
to data set 01. For the concentrations
of the species
approximate
values
are
given.
For
temperature,
pressure
and,
if
necessary,
overall
composition
starting
values and steps or final
values are
provided.
Finally
the
serial
numbers
of
the
diagrams
are
given,
into
which this equilibrium
shall be
plotted.
If a diagram is not a section,
the values are chosen,
which are taken
as abscissa
or ordinate.
:;I

f~~k~~~~sst~~c~~~

~~~i~~~r~~

ia calculated.
The resulting
values
of
all
, are stored
in a matrix.
After the last step
the content
oh this matrix is tabulated
and for each diagram
the
coordinates
of
the
image
are
calculated
and stored
onto a file
(file
code 08). If an
equilibrium
enters a section
between two steps,
the coordinates
of
the
point
Of entering
are
interpolated.
At these
interpolated
points
there start
(r-l)
- phase equilibria.
Most of
the
values
of
data
set
04 of
these
(r-1)
- phase
equilibria
are
derived
from
the
interpolated
values of the
unknowns. lhey are stored
in proper format onto a file
{file
code
091 for
subsequent
calculation.

This
file
09 is
completed
by hand input by the number of steps and the
final
values of the scanned variables
or the values of their
ateDs. These data
are used as data set 04 in the next run after
fig.
1. If a (r-l)-phase field
is between two r - phase fields,
it8 data appear twice in set 09. In this case

249

CALCULATION OF PHASE DIAGRAMS

the
starting
values
of
are a.lded as final
values
appearance
are omitted.
5.3.

Subroutine-_

for

the
to

Single

scanned
the 1st

variables
according
appearance
and

to
the

the 2nd appearanc?

data
of
the
2ncl

Equilibrium -_

of the suhroutine
RQCALC is shown, hv whI,:!t
In
fig
3
the
flow
diagram
ringle
equilibria
are calculated.
Since
the number or unknowns is different.
in
different
equilibria,
before
the first
iteration
step
these
unknowns
must
he
In subsequent
steps
this
numbering
remains
constant
with
counted
and numbered.
if the equilibrium
is started
at a boundary
one
exception
in the second
step,
tem..Refore
the first
step also
approximate
values
of
the
unknowns
must
be
computer
generated.
par the following
stepsyi;
t,
(rr
and
n
starting
values
of all
unknowns
are
calculated
from
the
results
of
the
previous
step,
using
the derivatives
described
in chapter
4.2..

1
Count
andnu&.r

PIG.
Flow Diagram
Calculating

of the
single

Subroutine
Equilibria

the
matrix
of the
The
elements
Of
the
mewton
Raphson
iteration
are
115),
(2nl,
1211,
derivatives
of
equ.
123)
and
one
of
th;,,;;:!
(;:I
(24)
- (25)
with
t:::
unknowns.
Te iteration
is assumed to be
remain
finished,
if
all
corrections
helow
a
limit,
which is chosen
1 .R-05
1 .R-04,
0.1
for
concentrations
above
the
concentration
for
times
concentrations
between
1 .X-4
and 1 .5-lQ),
~:~~ricentration
for
lower
0.3 times
the
concentrations,
0.1 Y for temperatures,
0.001
times
the
pressure
iQLnd $9
pressure,
10. .J!mol for ,u.,(rr
and 1 .R-04
for the phase aaounts.
If
all
corrections
were below
these
limits
in the previous
iteration
step,
the matrix
is not taken for a new Newton
but it is inverted
to be
Raphson
step,
derivatives
used for cal.culation
I)? the
of
the equilibrium
parameters
according
The calculation
returns
to chapter
4.2..
to the main program.
If the inversion
of
code
is
the matrix
Sailed,
an
error
If the previous
corrections
transmitted.
yet all
below the limits,
new
were
not
corrections
are calcul.ated
and added
to
values
of the unknowns.
If
the
current
more
adding
one
or
during
this
concentrations
leave
the
range O...l,
pressilre
if
temperature
or
get
or,
the
last
corrections
values,
negative
subracted
and
all
are ~Pivida 1 b:v
two
That
means
unknowns.
the
from
only half
of the values
of
effectively,
added
to
the
are
corrections
the
If
this
unknowns of the previous
step.
without
repeated
2
is
division
hg
are
corrections
until
all. the
success,
which are by a factor
of
below
limits,
mentioned
above
than
the
10
smaller
it is assumed,
that there
is
no
limits,
of
the
problem
within
the
solution
allowed
range and control
returns
to the
transmitting
error
code 3.
main program

H-L. L&as et al.

250

If the iteration
is not finished
after
exists
no solution
of
the
equilibrium
parameter8 and the calculation
returns
to
code 1.

100 steps,
?t
is
assumed,
there
conditions
with the given external
the main program tran8mittinR
error

Error
codes
1 and 7 in
the
main program stop the calculation
of the
current
equilibrium
and switch over to the tabulating
of results
after
Pig. 2.
In the case of an univariant
equilibrium
vs. temperature
or vs.
pressure
and
error oode 1, there is sought an extremum of this equilibrium
using equ. (24\.
If
the
extremum
is found, the calculation
is continued
with the temperature
and pressure
of the step before
the extremum and changing the sign of the step
of temperature
or pressure.
?he starting
concentrations
are taken as a mirror
image
with
respect
to
the
concentrations
of
the
extremum
from
the
concentrations
of the previous
step. With error code 2 the calculation
of
the
current
equilibrium
is continued,
but without using derivatives.
he starting
values of the next step in this case are the results
of the current
step.

-Acknowledgement
-.__

for

The author8 want to express

their thanks to
his interest
in and support of this work.

Financial
support
gratefully
acknowledged.

the

by

Deutsche

Prof.

T)r. Dr. h.

c.

Porschungsgemeinschaft

G.

Pet zow

(lSi??)

is

Qeferences
-1.

0. Kubaschewski,
X.Ll.
Evans and C.V.
chemistry,
Pergamon Press,
Oxford 1967

2. R.R.V.

Wiederkehr,

J.

Chem. Phys.

37,

r\lcock,

1192

Barin
and
0. Knacke,
Thermochemical
Substances,
Springer
Berlin/
Verlag,
supplement 1977

5. M.

vol.

Margules,
Sitzungsber.
104, 1243 (1895)

6. 0. Qedlich

and A.T.

7. G. Borelius,
8. C.W. Bale

10. Y.-M.

(1975)

Il. G.W. Toop,

E. Bonnier

13. M. Hillert,
14. E. Rudy,

Kister,

Trans.

100-103

Ind.
Series

Pelton,

Monatsh.

Muggianu,

8,

Akad. Wiss.

Ann. Physik,
and A.D.

9. P. Kohler,

12.

Chemica Bcripta

Met.

Chemie 2,

and R. Caboz,
CALPHAD4,

Chem. 40,

5, 20,

57 (1974)

7,. Yetallkde.

54,

of
Inorganic
New York,
1972,

5,

nlaturwisa.
345

Yl.,

1 la,

(194R)

2727 (1974)

778 (1960)
%-08,

.T.

Chimie

550 (1965)

C. Q. Acad.
l-12

vathem.

qngng.

M. Gambino and .1.-p.

AIMR, 277,

Properties
Heidelberg/

(1975)

Wien,

Trans.

?hermo-

(1962)

3. I.

4. G. qriksson,

Yetallurgical

Sci.

(1980)
112-122

(1963)

250,

527 (1960)

Physique,

2,

57

CALCDLATION OF PHASE DIAGRAMS

251

15. M. Hillert, Project Meeting CALPHAD VI, April 1%21,

16. M. Hillert, Materials Center, Royal Institute

Stockholm, TRITA-MAC-0161, September 1979

Yarwell, U.K. 1977

of

Technology,

S-10044

17. M. Hillert, Phyaica 103 R, 71-40 (1981)

18. L.S. Palatnik and A.I. Landau, "Phase Equilibria

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