69

Solidification of Metais and ł ł
Krzepniecie Metali i Stop6w, 16
PL ISSN 0208 - 9386
Model of the Peritectic Alloy Solidification
Edward ś Wojciech Kapturkiewicz
University oj Mining and Metallurgy, Krakow, Poland
ABSTRACT
Tanzilli, Heckel and Lanam's works [1,2] on the diffu-
sion problem in solid phase transformation, are used for cre-
ating a model of peritectic solidification. This model in-
cludes: a) heat transfer in the casting, with the boundary
condition of the casting cooling; b) nucleation and growth of
primary 8-phase grains as undercooling functions; c) caropo-
nent diffusion in the growing primary grains; d) peritectic
y growth on the primary 8-grains; e) caroponent diffusion be-
tween 8 and y, with 0/Y border moving and 8-phase dissolution
(peritectic transformation); f) 8-phase melting in case of
"negative undercooling" forthis phase (peritectic reaction).
The (a) and (b) problems described in the (3,4] are connected
with (c-f) points. ·
The computer program allows us to observe the course of
solidification process, and afterwards the kinetics of growth
of the peritectic phase with the simultaneous disappearance
(because of the diffusion process and remelting) of the pre-
peritectic phase. It was found that the latter part of non-
equilibrium phases strongly depends on diffusion coeffi-
cients of elements in solidified phases and on cooling con-
ditions for casting.
INTRODUCTION
Peritectic solidification is a one of the base liquid-
solid phase transformations that provides to formation of the
structure. Peritectic equilibrium occurs in the
large amount of the phase equilibrium diagr,ams, likewise in
the Fe-C system. The eutectic transformation is a basis of
the cast iron solidification as the peritectic transformation
is the ground element of steel casting one, and this problem
is a source of interest of theoretical and experimental stud-
ies (5-17].
Peritectic alloy solidification is a multistage process.
It includes the hypo-peritectic phase solidification (stage
70
I), peritectic reaction and transformation (stage II) and
growth of the peritectic phase (stage III) in the hyper-pe-
ritectic alloy. Hypo- (or pre-) peritectic phase a (or 8 for
Fe-C alloy) grows like as in hypo- eutectic alloy. The
phase (ar y for Fe-c alloy) begins to grow when the tempera-
ture of liquid reduces below a peritectic equilibrium tem-
perature. In this time the a-phase starts to decay. The
phase growth and a-phase decaying can to run when the a-
phase is in a contact with liquid. This is a peritectic reac-
tion [6). The case is named as a peritectic transformation
when covers grain of a-phase. The growth is
, connected with a caroponent diffusion from liquid to a-phase
through the increasing shell of In Fig. l [17) the
scheme of sequences of the peritectic alloy solidification is
showed with the scheme of concentration field (Fig. lh) for
a-a intersection (Fig. le).
Modeling of the peritectic solidification process ought
to include as the process of heat transfer and grain nuclea-
tion as the diffusion process in non-stationary and
boundary conditions. It is accepted generally that hypo-
peritectic phase is named a and hyper-peritectic as but in
Fe-C system they are named 8 and y, respectively. These names
we accept in the wark because Fe-C equilibrium diagram is
considered.
Mathematical model of solidification includes the equa-
tion for the f irst and second stages of the proces s. The
third stage is treated as a continuation of second one.
ASSUMPTIONS OF MODEL
The Tanzilli, Heckel and Lanam's works (3,4) on the dif-
fusion problem in solid phase transformation are used for
creating a mode l of peritectic solidification. Thi s model in-
cludes:
a) heat transfer in the casting, with a bounda ry condi-
tion of the casting cooling;
b) nucleation and growth of primary 8-phase grains as un-
dercooling functionsi
c) the caroponent diffusion in the growing primary grainsi
d) the peritectic y growth on the primary 8-grains (on
each grain) i
e) the caroponent diffusion between 8 and y, with 8;y bor-
der moving and 8-phase dissolution (peritectic transforma-
tion) i
f) 8-phase melting in case of "negative undercooling"
and in case o f direct eon ta et w i th a liquid i y-phase grows
in same time (peritectic reaction).
71
al
b) c) d)
e) f) J!..::.2... g)
m 1
--
----
----
---
: fT)
c, ---------
c
.• ---------
c
g
8 6
Distonce
Fig. l. Sequence of directional so-
lidification of peritectic alloy.
Scheme g - concentration field in
a-a cross (Fig. le).
1538 A
•c
.n • 1523 . 14 - 165. 52 . '
- 1394 - 1122. :u · te
· •C
Fig. 2. Fragment of Fe-c diagram
[ 18 l.
The a and b problems are described in the (3,4] and they
are connected with c-f elements.
It is assumed that liquid alloy with peritectic composi-
tion (binary alloy from BH space - Fig. 2) cools in the mold.
The primary 8-grains nucleate and grow when the metal tem-
perature decreases below the 8-liquidus temperature (TLsl . It
is the first stage of solidification.
Grains of the y-phase begin to nucleate and they begin to
grow when the liquid composition exceeds border value for
this phase (point B in Fig. 2) and temperature drops under
the y-liquidus temperature The second stage of solidi-
fication begins in this time. There are three different situ-
ations in this stage:
a) y-grains nucleate in liquid independently from exist-
ing 8-grains;
b) y-phase nucleates on existing 8-grains covering its
surface and cutting them from liquid;
c) y-phase covers a part of 8-phase grains surface.
In the first case (a) the remelting of 8-phase is pos-
sible when the temperature of liquid increases up the equi-
librium 8-liquidus temperature for current liquid composi-
tion. We can accept that there does not exist the diffusion
interchange between the solid 8 and y grains during the so-
lidification. This course can be treated as·a specific case
of (c) .
In the (b) case the phase y covers all
face and cuts of it from liquid. The
(peritectic reaction) is impossible. Only
the 8-grains sur-
8-phase melting
diffusion inter-
72
change of components in al
the 0-phase y-phase
liquid can take place.
This course also can be
treated as a specific case
of (c).
In the (c) case as 2::..!I.sy:..f-t<.,
well the melt i ng of S-
phase (peritectic reac-
tion) as a diffusion dis-
solution (peritectic
transformation) are possi-
ble. The scheme of this
process is in the Fig.
le-f or 3b.
Let assume that 8-
Fig. 3 . Scheme of growth of peritectic
grain: a - stage I, growth of phase &; b
- stage II, of phase y, remelting
(peritectic reaction) or dissolving
(peritectic transformation) of phase &.
2Xo - dimension of EDF.
phase grows as plates in the liquid volume element with X
1
=1
cm and Y
1
=1 cm dimension. They have thickness (Fig. 3).
The number of plate grains is a function of the nucleation
conditions. Plate form is assumed for the basie calculation,
but the model can wark with any shape of grain.
It is assumed that certain number of 8-grain can nucleate
in the casting volume element. This number is a function of
the undercooling. Diffusion skips before the fixing of grain
number i. e. before the determine o f maximum undercooling
The temperature field with the solidification heat source
from growing grains takes into account only. Elementary Dif-
fusion Field (EDF) sets up in the given casting element when
the undercooling crosses the maximum. It is the field (or
volume) assigned to one grain of 8 phase. Caroponent transport
between the diffusion fields is ignored. Specific size x
0
of
EDF may be counted from sirople grain volume v
0
= 1/Nv (where
Nv - volume grain density) for given grain form. This dimen-
sion for plate system (plate casting and plate grains) is x
0
= 1/(2Nx), where Nx is a linear grain density.
The specific size of EDF is constant in time during the
solidification in the each point of casting but its distribu-
tion in casting is a function of grain density distribution .
Coefficient of surface cover is equal a fraction of 8-
grain surface covered by growing y-phase. It can be con-
stant, e.g . , ar can enlarge during solidification
(from o to l).
In these terros and assumption of one-dimension
flow (straight to 8-plate axis) we can select the
diffusion fields:
caroponent
following
in the first stage (0-phase growth only) : 8-phase
liquid diffusion field;
- in the second stage: 8-phase - y-phase - liquid (in the
space); 8-phase- liquid (in the space.)
73
If the 0-grains have a contact with liquid (in the
space) then the melting of o-phase is possible in the II
stage. Diffusion peritectic transformation with moving of the
0/Y border occurs in space (Fig. 3b) where these phases are
in contact.
SET OF EQUATIONS
Field of concentration in solidified phases:
for o phase:
dCo = ( xmD dCo )
d't xm ax o ax l
for phase y:
(l)
dCr = (xmD dCr )
d't X m ax r dx ' ( 2 )
where m = o, l or 2 for planar, cylindrical and spherical
coordinate system,
C, 't, x - concentration of constituent, time and coor-
dinate, respectively; .
D - diffusion coefficient;
o, y - index of phase.
Mass balance for solidification front for the first stage
of process:
planar geometry;
( )
_ dCo l dCL (
CL - Co L Uli - Do -- + -- Xo
· dx d 't ·
-
( 3)
where Co.L - concentration of o phase at the solidification
front,
CL - concentration of liquid phase,
u
0
- linear rate of growth for o phase,
- coordinate of solidification front (dimension of
solidified phase o);
cylindrical geometry:
2 ( CL - Co .L) = 2 D s dCo l
ax
spherical geometry:
(3b)
4 ( 3 )'3) dCL
+-7t X --, --
3 o s d't
( 3c)
74
Mass balance at the solidification front:
planar geometry:
(cL- C
1
.L)u
1
11 + (cL- CS.L)u
5
(l -11) = 110
1
ddC: +
+(l- ll)D dCsl +dCL (x - 11- (l- 11))
s ax - d't o '1 '1

( 4a)
where 11 - surface fraction of y phase on the surface of O
phase,
- dimension of in 11 area ,
- dimension of in (1-11) area,
uy- linear rate of ' growth of phase y,
Cy. L - . concentration of constituent in y phase at the
solidification front;
cylindrical geometry:
21t/;'1 (cL- C
1
.L)u
1
11 + 21t/;l - '1 (cL- CO.L)u
5
(l- 0)
(
2 2 2 ) dCL
+1t Xo - - '1 (l - 11)
( 4b)
spherical geometry:
(cL- C
1
.L)u
1
11 + (cL- C
5
_r:)u
5
(l- 11)
( 4c)
At a border of 0/Y phase (the second stage of the proc-
ess) the mass balance is:
( )
* acs l acr l
Có /r - Cr/ó uó/r = -Do dX - + Dr dX +
ó ó
(5)
where Co;y , Cy;o - concentration of O and of y phase at the
surface contact of these phases (Fig. 4);
a)
b)
Fig. 4. Scheme of
concentration
field for stage I
(a) and stage II
(b) of peritectic
solidification
ójPWSE r yuo
. .l.!1d
FL r

. x.
Fig. S. Scheme of
differential grid
Ct.
75
u\/r- rate of move of phase O/Y border.
Initial and boundary condition for dif-
fusion field:
stage I of process:
c =
Co i
o < X < Xoi
't o;
OCIOX = o; X = o; 't o;
C= CoiL(T);
X

According to equilibrium diagram( Fig. 2)
COIL =
(1538-T}I477.78 ();
stage II of process:
CL > ca, T
< TL.y i
C = Co/"((T) i
c Cyf'&CT);
C CyiL(T) i
X
X
X
i

+
Coly (T - 1394.0) l 1122.22;
ey
10
(T- 1394.o) 1 594.12;
CyiL (1523.14 -T) l 165.52.
The time rate of change of concentration
at an interna! whose location is
always a constant percentage of instantane-
ous phase thickness, may be represented by
the Murray-Landis variable-grid, space trans-
formation as follows (1):
de . ac . dx· ac .
__ l. = __ l. (--l.)+ __ l..
d't axi d't o't
(6)
The rate of travel of an interna! point is functionally
related to the solidification front velocity by:
dxi = xi
d't d't.
(7)
Combining Eqs. (3) and (4) one arrives the relationship
for the time rate of change of the phase concentration at the
interna! nade, i ( 1,2]
de . x. ac. ac.
__ l. = ____!_ __ l. - + __ l. l
d 't ox i d 't o't
(8)
for i=l, 2, 3 ... n-1 (Fig. 5),
where oCio't according to eq. (l) or (2).
Equation (8) gives a possibility of assuming of differen-
tial grid with constant number of grid elements and with
variable dimension of these elements.
COMPUTATION
As follows from the description, model connects a set of
equations:
76
a) diffusion equations in o and y phases;
b) heat transfer equation;
c) nucleation equation;
d) equation of the grain growth kinetics.
The equations are merged to the set. After transformation
into the differential form, the set of equations is solved by
means of iteration method of secants. Iteration number is no
larger then 5 in assumption of precision 0.01 K.
The time step is defined by Fourier criterion for heat
process and analogous criterion·for diffusion process:
D · Ó't
D · Ó't
r 2 ~ o. 5 i
5
< o 5.
( )
2 - • l
óxó
( ÓX
1
)
(9)
The variable time step is assumed because of changing
dimension of grid size.
RESULTS AND DISCUSSION
The purpose of calculations is a checking a possibility
of function of mathematical model in a form of computer pro-
gram. Fig. 6 shows the temperature against the time for the
2-cm plate casting cooling in a sand mold (Fe-C alloy, 0.17
%C.) There is the equilibrium line of temperature of liquidus
for O and y phase. Point A shows the dividing between the
first and the second stage of solidification process. Begin-
ning of the point B the temperature T is higher then liquidus
temperature of phase O and there is condition for the melting
of this phase.
The concentration line in the grain during solidification
is shown in Fig. 7. The dashed line gives the field of con-
centration at the beginning of peritectic transformation. A
dimension of phase o is ~ O . l and the concentration of liquid
is cL.l· Beginning from this time,the phase Y starts to grow
and i t is connected with two processes: remelting and dis-
1550
~
..
~ 1500
~
E
.. ,_
1450
o 100 200 300 400 500 600
Time . s
Fig. 6. Temperature against the
time for 2-cm plate casting. Fe-C,
0.17 %C. TL.
5
and TL.r - equilibrium
liquidus temperature for 5 and r
phase , respectively.
~

.2
f!
~
u
c
o
u
0.6
0.5
Q4
03
0.2
0.1
o
o Q2 0.4 0.6
r---- Cu
l
l
0.8 10
Undimensioned Dislance from the Gran Center
Fig. 7. Computed distribution
of concentration in the grain.
0.20
§

o
0.15
c3

3
l
0.10
o

0.05
.12

o
o
Fig.
and
Y
1.00
0.75
..
"'

o
0.50
?:
"i
o
Q25
a
o
77
o 200 400 600
Time , s
8. Kinetics o f dimension o f ó
phase during solidification.
-----. / Vr
--../ ___ _
--- _____ ... ___ _
o 0.005 001 0015 002
lntonsity ot Coolin<;J . W/cm
1.0
"
l.o.-1 X ł /s
"
"
3
"
"
"
o. e

"
,.
'5
,.
l;'
..".,."' r ,.
,.
l:
,.
o
0.5
"
:l

o
l
"
"'
0.3
----7------... "" v,
.,.-'"' - -- .....

' ,- .... _
o -- --
10"
7
w
() ..
()"' () ..
Diffusion Coeflicient of T Phase
Fig. 9. Influence of interdiffusion
coefficient of element in ó and y
phase after solidification. Vs.tr'
Vs.mlt volume of transformed
(dissolved) and remelted phase,
respectively.
solving of 8 phase. Amount of
8 phase decreases and at the
end of the solidification
reaches a value The line
in the range shows the
concentration of constituent
(carbon) in the y phase.
The kinetics of growing of
Fig. 10. Influence of intensity of
co.oling for quantity of ó and y
phase. vo.tr' vy.tr - as in fig. 9.
8 and y phase is shown in
Fig. 8. We can see the disappearing of 8 ph_ase after start of
growing y phase. Fig. 9 and lO show the considerable in-
fluence of interdiffusion coefficient in y phase and in-
tensity of cooling on the final amount of each phase and on
the amount of remelting and dissolving of 8 phase.
CONCLUSIONS
Mathematical model transformed to computer program allows
us to observe the course of solidification process, and af-
terwards the kinetics of growth of the peritectic phase with
the simultaneous disappearance (because of the diffusion
process and remelting) of the pre-peritectic phase.
It was found that the latter part of nonequilibrium
phases strongly depends on diffusion coefficients of elements
in solidified phases and on cooling conditions for casting.
78
APPENDIX
The base differential transformations
Planar geometry
For ie(l, n-1) (Fig. 5) the differential form of eq. (8)
is:
cJ:t+l.- eJ:<
l. l. =

where k, k+l - time step index;
L\ 't - t i me step;
L\xs = -l);
n - number of grid elements;
xi.s = (i - 1) ••
After transformations we obtain:
X · · L

t·U
et + l = et + l.. S s ( cl.t - cl.t ) +
. l. + l 1.-l
D s L\ 't
where oo.s = .
(L\xs )2
For i e (n
1
+ l, n
2
- 1) (Fig. 5) equation ( 8) . becemes:
X· · d't · U ( )
cl:t+ l = cl:t + l..y r cl:t - cl:t +
l. l. ): . A . 1. - l 1. - l
2..,1 Lll..y
(Al)
(A2)
+D
0

1
(ct
1
-2ct+ct
1
). (A3)
Equation (3) of mass balance at the solidification front
becomes:
k k k k+ l k
k C
0
_
2
- 4C
0
_ l + 3C
0
CL - CL ( J: )
CL {l - ko. s ) U s = D s + X
0
- '>s 1 (A4)
L:
where k
0

0
= c
0
. LICL ( carbon distribution coefficient for 8
phase),
and we obtain:
k+ l k ( k ( ) ) L\ 't
CL = CL + CL l- k
0
.s us - qs l' 1 (AS)
Xo -'>s
Ds ( k k k)
where qs = -- C
0
_
2
- 4C
0
+ 3C
0

2L\xs
For the second stage of process eq. (4) transforros to
where qr
79
+l = + ( ( 1 - 11) (l - k
0
.s ) u
5
- qJ +
k
0
.T )uT :t,
L
(A6)
k
0
.T = CT.L/CL (carbon distribution coefficient for Y
phase).
Parameters q
5
and qT mean fluxes of element from liquid
to solidified phase.
For n, n
1
and n
2
of differential grid (Fig. 5) concentra-
tion of element results from boundary condition:
for stage I of process: ck+ l
n =
(1538- Tk+
1
)/477. 78
for stage II of process: ck+ l
( Tk+
1
- 1394. O )/1122. 22,
n
ck+ l
=
(Tk+l- 1394.o)js94.12,
n l

1
= (1523. 14 - Tk+
1
)/1165. 52.
From the equation (5) we obtain the velocity of inter-
face boundary O/Y in second stage of process:
u;/r = (or o p
1
- D
5
o

(A7)
where
p
1
=

+

P2 =

+

).
ACKNOWLEDGMENTS
This work was supported and carried out within the Polish
KBN project No 3 0139 91 Ol.
REFERENCES
l. R.A. Tanzili, R.W. Heckel: Trans. Met. Soc. AIME, v. 242, 1968, p.
2313.
2. Lanam R.D., Heckel R.W.: Met. Trans., v. 2, 1971, p. 2255.
3. Kapturkiewicz W.: Zeszyty naukowe AGH, Metalurgia i Odlewnictwo, z.
119, Krakow 1988.
80
4. Fras E., Kapturkiewicz w. (in:) Metallurgy of cast Iron"
IV, Mat.Res.Soc., Pittsburgh, Pennsylvania, 1990, p.469. ·
S. Barker N., Hellawel A.: Met. Sci., 1974, v. 8, p. 353.
6. Kerr H., Cisse J., Belling G.: Acta Met., 1974, v. 22, p. 677.
Titchener A., Spittle J.: Acta Met. i 1975, v. 23, p. 497.
8. Chuang Y., Reinisch D., Scherdtfeger K.: Metal. Trans., 1975, v. 6A,
p. 235.
9. Maxwell J. Hellawel A.: Acta Met., 1975, v. 23, p . 901 .
10. Ostrowski A., Langer E. (in:) Solidification and Casting of Metals,
The Metala Society, London, 1979, p. 139 .
11. Brody H., David s. (in:) Solidification and Casting of Metals. The
Metala Society, London, 1979, p. 144.
12. Hillert M. (in:) Solidification and Casting of Metals. The Metals
Society, London, 1979, p. al.
13. Fredriksson H. (in:) Solidification and Casting of Metals . The Metals
Society, London, 1979, p. 131.
14. Fredriksson H., Stjerndhal J. Metals Science, 1982, v . 16, p. 575.
15. Fredriksson H. , Nylen T. Metals Science, 1982, v. 16, p. 238.
16. Fras E. Journal of erystal Growth, 1985, v. 73, p. 460.
17. Fras E. Krystalizacja metali i stopow. PWN, 1992, p. 214.
18. Sinary Alloy Phase Diagrams, AMS, Metals Park, Ohio 1986, v. l,
p. 561.

Related Interests

t·U
et + l = et + l.. S s ( cl.t - cl.t ) +
. l. + l 1.-l
D s L\ 't
where oo.s = .
(L\xs )2
For i e (n
1
+ l, n
2
- 1) (Fig. 5) equation ( 8) . becemes:
X· · d't · U ( )
cl:t+ l = cl:t + l..y r cl:t - cl:t +
l. l. ): . A . 1. - l 1. - l
2..,1 Lll..y
(Al)
(A2)
+D
0

1
(ct
1
-2ct+ct
1
). (A3)
Equation (3) of mass balance at the solidification front
becomes:
k k k k+ l k
k C
0
_
2
- 4C
0
_ l + 3C
0
CL - CL ( J: )
CL {l - ko. s ) U s = D s + X
0
- '>s 1 (A4)
L:
where k
0

0
= c
0
. LICL ( carbon distribution coefficient for 8
phase),
and we obtain:
k+ l k ( k ( ) ) L\ 't
CL = CL + CL l- k
0
.s us - qs l' 1 (AS)
Xo -'>s
Ds ( k k k)
where qs = -- C
0
_
2
- 4C
0
+ 3C
0

2L\xs
For the second stage of process eq. (4) transforros to
where qr
79
+l = + ( ( 1 - 11) (l - k
0
.s ) u
5
- qJ +
k
0
.T )uT :t,
L
(A6)
k
0
.T = CT.L/CL (carbon distribution coefficient for Y
phase).
Parameters q
5
and qT mean fluxes of element from liquid
to solidified phase.
For n, n
1
and n
2
of differential grid (Fig. 5) concentra-
tion of element results from boundary condition:
for stage I of process: ck+ l
n =
(1538- Tk+
1
)/477. 78
for stage II of process: ck+ l
( Tk+
1
- 1394. O )/1122. 22,
n
ck+ l
=
(Tk+l- 1394.o)js94.12,
n l

1
= (1523. 14 - Tk+
1
)/1165. 52.
From the equation (5) we obtain the velocity of inter-
face boundary O/Y in second stage of process:
u;/r = (or o p
1
- D
5
o

(A7)
where
p
1
=

+

P2 =

+

).
ACKNOWLEDGMENTS
This work was supported and carried out within the Polish
KBN project No 3 0139 91 Ol.
REFERENCES
l. R.A. Tanzili, R.W. Heckel: Trans. Met. Soc. AIME, v. 242, 1968, p.
2313.
2. Lanam R.D., Heckel R.W.: Met. Trans., v. 2, 1971, p. 2255.
3. Kapturkiewicz W.: Zeszyty naukowe AGH, Metalurgia i Odlewnictwo, z.
119, Krakow 1988.
80
4. Fras E., Kapturkiewicz w. (in:) Metallurgy of cast Iron"
IV, Mat.Res.Soc., Pittsburgh, Pennsylvania, 1990, p.469. ·
S. Barker N., Hellawel A.: Met. Sci., 1974, v. 8, p. 353.
6. Kerr H., Cisse J., Belling G.: Acta Met., 1974, v. 22, p. 677.
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