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Computerized Prediction of the

Phase Diagram for the
Ternary System Be-Fe-AI

M. I.BMkM

Sandia Laboratories

*M0«7-73I

DISTff: .
wm JMUf.liTED
 SAND74-8664
Unlimited Release
Printed Febnu^y 1975

Computerized Prediction Of The Phase

Diagram For the Ternary System Be-Fe-Al

M. 1. Baskes
Theoretical Division 8341 •NOTICE
Tni* report was prepared a* an account oT work
Sandia Laboratories sponsored by the United Slate* Government. Neither
the United Slates not the United Slates Energy
Livermore, California Research and Development Administration, nor any of
ihelr employee*, nor any of their contractors
subcontractors, or their employees, maker any
warranty, «prew or implied, or anuroti any legal
liability or responsibility fur the accuracy, completeness
or uvfulncu of any information, apparatus product or
process disclosed, or represents thai Ms use would no I
infringe privately owned rights.

ABSTRACT
phase stability of the Be-Fe-Al ternary system has been calculated
over the entire composition range and for temperatures between 1000K and
1800K. Gibbs free energy functions have been calculated for seven phases
over this same range of composition and temperature. Experimental information
used in these calculations consists of the binary phase diagrams and thermo­
dynamic data. Interactive graphics computer codes have been developed to fit
the experimental data with the free energy model and also to calculate and
display isothermal sections.

3/4
 Computerized Prediction Of The Phase
Diagram For The Ternary System Be-Fe-Al

I. Introduction

I t has long been recognized that thermodynamic data may be used to pre­
d i c t phase s t a b i l i t y . Equilibrium diagrams for iron-based ternary systems
have been successfully calculated from binary phase diagrams and thermodynamic
properties. This paper is an extension of the iron-based alloy calculations
for the Be-Fe-Al ternary system. The method involves the calculation of
the Gibbs free energy for each of the candidate phases ( l i q u i d , f . c . c , b . c . c ,
h.c.p., and three compounds) using the experimental binary phase diagrams
for Be-Fe; Be-Al and Fe-Al» and the known thermodynamic data. Functional
forms are assumed for the free energy functions and the unknown parameters
are determined by a weighted least squares f i t to the known data. To aid in
the determination of the parameters, the f i t t i n g is done with an interactive
graphics computer code. Isothermal sections are calculated from the free
energy functions using another interactive graphics computer code to locate
the boundaries of the three phase regions.

II. Theory

Calculation Of The Free Energy

Two models are used for the free energy. The f i r s t model (subregular
Q
solution) i s used for the l i q u i d and solid solutions. The second model
(Bragg-Williams long-range order) is used for the compounds. These simple
models are chosen rather than more sophisticated ones because the parameters
must be determined by comparison with experiment. The sophisticated model
would thus lead to unnecessary complexity with l i t t l e difference in the
resultant free energy.

5
Solution Phases. Consider an alloy at atmospheric pressure with n atom
species of atom fraction X-, i=1»2»...,n. The Gibbs free energy per g-atcrn
of a particular phase a is given by:

a
G = L. X. G«. (T) - T E S i I D (X.)

+ ^ l .
5 > X X. Gjj (T.Xj)
i
(1)

where T is the absolute temperature* G-- (T) is the free energy per g-atom of
purs element i ; S (X.) is the ideal configurational entropy per g-atom of
Tn

th
of the * atom; and G.. {T,X.) is a function that represents the excess
free energy per g-atom. The ideal entropy is given by:

S ( = R X l n ( 2 )
ID V " i <V
where R is the gas constant.

Compound Phases. Consider a compound with a crystal structure that may be

decomposed into two sublattices with the r e l a t i v e number of sites N and
(1-N) respectively. In an ordered compound, consider the f i r s t m atom
species to reside randomly on the f i r s t sublattice and the remainder of the
atoms to reside randomly on the second sublattice. Let S be a long-range
order parameter. A random alloy has S=0; a completely ordered stoichiometric
alloy has S=l. The Gibbs free energy per g-atcm of a particular phase w is
given by:
T ( T
* • . * *i ^ j <> * *i W i V u -V
- T " , S Oyx)-T} ID s ID (x./O-x))
1=1 1«m

U 2
+ W" AE N ( l - N ) S - T S C D p (3)

energy
parameter
and the behavior of AE with distance, X * I
10
X and $
i c p [ ) is the entropy
of the compound given by:

S = R [ N H ( X + ( 1 N ) S )
CPD ~ "

+ (l-N)H (1-X) + NS ] . (4)

Here, H(X) * X In (X) + (1-X) In (1-X). For example, consider a binary

alloy with a and b atoms and a compound crystal structure of AB type. A 3

stoichmetric alloy would have X-| » X * N = ,25, X- = .75, m = 1 , and AE" =

E E w n e r e s t n e
^ ah ' aa " ^hb* ^-H ^ interaction energy (at first neighbor
distance) of an i and j atom. If only first nearest neighbors are considered
W
W = 1/3 and G, * AE . In general, W* ^ 1 and G*f. ^ AE"* where 1 <. i <.m and
2

m + 1 <. j <. n.

The long-range order parameter is determined by minimization of the

free energy i . e . .

3G* (5)

Calculation Of The Two Phase Boundaries

The partial molar free energy of a k-atorn in the a phase is given by
a „„a
a . 3G" . v 3G
(6)

In a two phase region, the partial molar free energy of a k-atom in the a
phase is equal to that in the P phase; i . e . ,

G£ - G£ k • 1 , 2 , . . . , n (7)
 III. Discussion

To determine the unknown parameters: a number of additional assumptions

have been made. The free energy function of the pure elements G.. (T) has
been taken from experiment when possible. Otherwise it has been assumed to
be linear in T. Tne excess free energy function G*. (T,X.) for the solution
IJ J
phases has also been assumed to be linear in T and X,. This assumption is
valid provided the free energy is not used near T = 0. The compound para­
W 10
meters G?. {T,X-)» AE and W are assumed to be independent of temperature.
The phases to be considered are denoted by a (b.c.c), Y (f.c.c), e (h.c.p.),
L (liquid), 1 (Be^Fe), 2 (Be Fe), and 3 (Be„Fe). The first four phases are
g

solution phases while the last three are compound phases.

The parameters are determined by fitting the calculated two phase
Q-ll
boundaries to those determined experimentally. In addition, the
calculated thermodynamic functions (excess free energy, enthalpy, and
12
entropy) are fit to experiment when data is available. The procedure
for calculating the two phase boundaries is outlined below.
For each temperature and a given set of parameters it is possible to
calculate the boundaries of the two phase region in a binary system. Since
N*2 Eq. (7) yields two equations. There are four unknowns x?, xF, x?, x?
of which tvo are determined by normalization. The two equations are thus
determinate and are solved by the Newton-Raphson technique. If either (or
both) of the phases of Interest is a compound, the long-range order para-
meter is determined from Eq. (5) using ZEROIN, a zero finding code. There
•ay not be a two phase region at this temperature; i.e., Eq. (7) may have no
solution 0 i X?, X? <. 1. In this case the parameters must be changed to
insure a solution. Once a solution exists at all data points, the choice of
parameters is assisted by TJHAR1, a nonlinear least squares minimization
code. This code minimizes the sum of squares of the difference between the
calculated and experimental phase boundaries.
Because Eq. (7) may have no valid solution, it is v^ry useful to super­
vise the choice of parameters by TJHAR1 through an interactive graphics code
BEFE (CDC-250). This interactive code allows the user to (1) view the current
predicted and experimental phase boundaries; (2) change the parameters by hand;
(3) allow TJHRR1 to change any number of the parameters by fitting any portion

8
of the data; (4) change the starting values for the iterative solution of
Eq. (7); (5) change the control constants of TJHAR1; i.e.* number of itera­
tions, step size, etc.; (6) view the free energy curves; and (7) obtain
printouts or plots of any of the above information. Figure 1 shows a typical
CRT display of the predicted and experimental phase boundaries vs. data point
number for the Be-Ke binary system. The f i t to the data is well within
experimental error. Also shown are the parameters B, the current sum of
squares PHI, and the previous sum of squares PHIL, The underlined parameters
are those held fixed by TJHAR1. Figure 2 shows a typical free energy vs.
composition CRT display for the Be-Fe system. The free energy shown is t h *
minimum of the candidate phases. The free energy curves to the l e f t and the
right of the vertical line have undergone different transformations so that
the detail may be observed. The boundaries of the two phase regions may be
seen by the "common tangent method", which is the geometric equivalent to
Eq. (7). Tangents may not be drawn between regions. The points a, b„ c, d ,
e, f , g, and h represent boundaries of the L, 2, 2, 3, 3, L, L, and a phases
respectively. The regions between a and b, c and d , e and f , and g and h
are two phase regions.
The preceding procedure is eKtended to include the experimental thermo­
dynamic data by including this data as constraint residuals 1n TJMAR1. The
u,
resultant free energy functions (cal/g-aton:) are shown in Table 1 . The AF t
are taken as equal to the G ^ ^ ' s and the V's are taken as .182, .217, and
.393 for compound 1 , 2, and 3 respectively. After the parameters for the
three binary systems Be-Fe, Be-Al, and Fe-AI have been determined, a fev
additional assumptions are necessary before the ternary s t a b i l i t y may be
predicted. All ternary interactions ere assumed to be small and are thus
taken as zero. I t is assumed that Al substitutes freely for Be in the
compound phases, i . e . , Be and Al reside on the same sublattice in the ordered
compound so that the two sublattice treatment of the compounds used above is
valid. Finally, i t is assumed that the Be-Al interaction in the compounds 1s
the sare as the Be-Al interaction in the other solid phases.
The procedure for calculating two phase boundaries for ternary isothermal
sections is similar to that used i n calculating the boundaries of the two
phase region In the binary systems. Since N*3» Eq. (7) yields three equations
There are six unknowns X- , X- , X^» X- , X , and X«« of which two are
p

determined by normalization. Therefore, one composition may be chosen and

the other three determined by Eq. (7). TJMAR1 is used to solve the nonlinear
systems of three equations and three unknowns. As above, this system may not
have a valid solution, so i t is useful to control the calculation through
another interactive graphics code TTER. TTER allows the user to (1) chose a tem­
perature of interest; (2) choose the two phases to be considered; (3) choose
starting values for the boundaries; (4) choose the composition to be f i x e d ;
(5) f i n d the phase boundary (using TJJttRl); (6) expand the CRT display to
view more d e t a i l ; (7) save or recall any phase boundary previously created;
and (8) plot the isothermal section including t i e l i n e s . The interactive
program is extremely useful in locating the three phase regions which occur
at the intersection of two two phase boundaries. Figure 3 shows a p a r t i a l l y
complete isothermal section with intersecting two phase regions. The points
a, b, and c are the corners of the three phase triangle. The same section
with the t i e lines and three phase region included is shown in Figure 4.
The extent of the two phase regions is limited by the three phase region.
The completed isothermal sections are shown in Figures 5a and 5b. At
1600K (Figure 5a) both Be and A1 are l i q u i d . Iron 1s f . c . c . and shows a
closed "Y loop". Aluminum has a s o l u b i l i t y of 5-10% in the two compounds
Be Fe and Be Fe. At 1300K (Figure 5b) Al is l i q u i d , but the liquid region
5 g

has shrunk considerably. The compound Be^Fe si;ows a m i s c i b i l i t y gap with

an Al rich and a Be rich phase occurring. Aluminum has a very low s o l u b i l i t y
in the Be^Fe phase. The s o l u b i l i t y of Al in the Be Fe phase ranges to
g

almost 40%. The Be r i c h corner of the phase diagram is shown in Figures 6a

--•rsd 6b. I t may be seen that the s o l u b i l i t y of both Fe and Al in Be f i r s t
increase and then decrease with decreasing temperature. The maximum
s o l u b i l i t y is obtained at about 140OK.

10
 References

1. L. Kaufman, Progress in Materials Science, 14, 55 (1969).

2. L. Kaufman and H. Bernstein, Computer Calculations of Phase Diagrams,

Academic Press, New York, NY (1970).

3. A. M. Alper, (Ed.) Phase Diagrams, Academic Press, New York, NY (7970)

4. M. M. Rao, R. J . Russell, and P. G. Wichell, Trans. AfflE, 239, 634,

(1967).

5. H, I . Aaronsen, H, A. Domain, and G. M. Pound, Trans. AIME, 236,

753, (1966).

6. M. I . Baskes, Materials Science and Engineering, 15, p. 195-202 (1974).

7. L. S. Darken and R. W. Gurry, Physical Chemistry of Metals, McGraw-Hill

Book Co., New York, NY (1953).

8. W. L. Bragg and E. J . Williams, Proc. Roy Soc., A145, 699 (1934);

A151, 540 (1935); E. 0- Hi111ams7TrocTRovToc.7Tr52, 231 (1935).

9. M. Hansen, Constitution of Binary Alloys, McGraw-Hill Book Co., New

York, NY (1555T

10. R. P. E l l i o t t , Constitution of Binary Alloys, First Supplement,

McGraw-Hill Book Co., New York, NY

11. F. A, Shunk, Constitution of Binary Alloys. Second Supplement,

McGraw-Hill Book Co., New York, NY (

12. R. Hultgren, R. L. Orr, P. D. Andersen, and Y, K. Kelley, Selected

Values of Thermodynamic Properties of Metals and Alloys. John Wiley
and Sons, New York "iff (1963), plus supplements.

13. I . F. Shanpine and H. A. Watts, Sandia Laboratories Report, SC-TM-70-631

(1970).

14. T. H. Jefferson, Sandia Laboratories Report, SLL-73-0305 (1973).

11/12
 Table I
Free Energy Functions G- for the Be-Fe-Al System i

1 Be Fe Al
*

J phase
a C
Y 2993
E -611 +Q.4T
Be L 2919 -1.875T
1 2237 -0.937T
2 -642 +0.556T
3 1610 -0.80T

ot -26880 +7.042T 0
+ioooox Fe

y -6681 +9.046T a
-15000X Fe

£ -23466 +5.353T -437 +1.12T - G ^ . e F e

Fe +ioooox Fe

L -37391 +10.08T 3300 -1.826T

+1548SX Fe

1 -88370 27320 +21.01T

2 -1H500 -50000 80190 +6.076T
X X
Be A1
3 -66880 17650 +15.58T

a 10000 -22062 +3.376T -7448X A1 0

Y 10000 -23477 +7.126T+13195X A1 1574 -3.14T

£
** y II~
II
^ F ^ P ^ V ^^^ -23000 +6.0T -lOOOOX., 4811
L 20771 -10.359T -15602 +3.5T +7200X., 4124 -5.873T
Al -9U0X A1 -6.1X T A1

+3.482X A1

4* A | h | | 4 f h ^ & ^^k ^ L ^^k ^ & ^^k ^ k ^^^^^^

1 ^vjjj^^^^^^m -88370 2237 -0-937T

2 ^ ^ ^ ^ ^ ^ ^ ^ | -114500 -SOOOOX^j -642 +0.556T
3 I w!f -56880 1610 -0.80T

13
 Table 1 (Cont'd)

i Be Fe Al
3 2 b 3
a 1202 -2.63 x 1 0 ' T + 1.54 x I 0 " T T « 850
3 2 6
16.7 + 0.226 (UOO-T) + 4.74 x 10"* (1100-T) - 7.81 x 10 850 < T < 1100
3
(1100-T)
3 2
6.85 - 0.990T + 0.341 x 10" T T > 1100
 3285 .4277 .3377 .4256 .3217
3353 7552T .8293 .7356 .5567
B
f
^^*** 4> * s *

t + Experiment

i
I
+ 4
4 4
I

I
4
I 1
4
\ •*

4
f 44 *
• 4 *
4
*

4 4 4 *
*
4
I * V ' ' , i f i i i J J *
! 1 1 •

10 15 20 25 30 35 40 45 50 55
.2376 .4837
PHI PHIL
Figure 1: CRT display of Be-Fe phase boundaries and parameters.
 i i._.-i _i i J. J —

.1 .2 .3 .4 .5
Atomic Fraction Fe i
ure 2: Free energy vs. composition at
two phase boundaries.
 M

A / \
TEMP - 1550 K

Be 'Fa

Figure 3: Partial isothermal section showing the formation of a three

phase region at the intersection of three two phase region .
Figure 4: Partial Isothermal section showing the formation of a three
phase region. Tie lines are shown in the two phase regions.
 1600K

0*
Figure 5a: Isothermal section for the Be-Fe-Al system at
1600K.

VD
Figure 5b Isothermal section for the Be-Fe-Al system at
1300K.
Figure 6a: Be rich corner of the Be-Fe-Al Isothermal section
for T = 1500K and 1600K.
 .002 A1

1300K

1200K

1100K
10MK

Be .01 Fe

Figure 6b: Be rich corner of the Be-Fe-Al isothermal section for

T * 1300K, 1200K, HOOK, and 1000K.