Macrosegregation During Solidification

Resulting From Density Differences

in the Liquid
N. STREAT AND F. WEINBERG

M a c r o s e g r e g a t i o n has b e e n o b s e r v e d in d i r e c t i o n a l l y solidified P b - 2 0 pct Sn alloys, over a

r a n g e of f r e e z i n g r a t e s and t e m p e r a t u r e g r a d i e n t s . The m a c r o s e g r e g a t i o n was shown to r e -
sult f r o m the upward flow of l e s s dense, tin rich, i n t e r d e n d r i t i c liquid d u r i n g s o l i d i f i c a t i o n ,
u s i n g r a d i o a c t i v e t r a c e r t e c h n i q u e s . F o r c o m p a r i s o n , it was shown that m a c r o s e g r e g a t i o n
o c c u r r e d in the opposite d i r e c t i o n in a Sn-4 pct Pb alloy, where the i n t e r d e n d r i t i c liquid
was lead r i c h , and c o n s e q u e n t l y m o r e dense. Shrinkage t r a i l s and pipes w e r e o b s e r v e d in
s o m e of the P b - 2 0 pct Sn ingots, s i m i l a r to " f r e c k l e s " o b s e r v e d in d i r e c t i o n a l l y c a s t
superalloys.
A m a t h e m a t i c a l model for m a c r o s e g r e g a t i o n in v e r t i c a l l y solidified ingots is p r e s e n t e d ,
the d r i v i n g f o r c e b e i n g the d e n s i t y d i f f e r e n c e s in the i n t e r d e n d r i t i c liquid d u r i n g s o l i d i f i -
cation. Liquid flow through the d e n d r i t i c a r r a y is e s t i m a t e d by c o n s i d e r i n g the p a r t i a l l y
solidified alloy as a porous m e d i u m of v a r i a b l e porosity. F o r s i m p l i c i t y , the m o d e l n e -
glects backflow due to v o l u m e s h r i n k a g e ( i n v e r s e s e g r e g a t i o n ) . The e x p e r i m e n t a l r e s u l t s
a r e c o m p a r e d to the model p r e d i c t i o n s .

M A C R O S E G R E G A T I O N caused by i n t e r d e n d r i t i c fluid convection. They c o n s i d e r the fluid d y n a m i c s through

flow has b e e n t r e a t e d a n a l y t i c a l l y in a n u m b e r of r e c e n t
p a p e r s . Most of t h e s e models a r e for i n v e r s e s e g r e g a -
tion, where an a n a l y t i c a l solution can be obtained by
c o n s i d e r i n g backflow through a v o l u m e e l e m e n t as the
solid and liquid c o n t r a c t d u r i n g s o l i d i f i c a t i o n . Chill
face s e g r e g a t i o n u n d e r t h e s e conditions was f i r s t p r e -
dicted b y Scheil ~ and his model was l a t e r extended by
K i r k a l d y and Youdelis to p r e d i c t the solute d i s t r i b u t i o n
along the whole c a s t i n g . 2'3
A m o r e g e n e r a l s o l u t i o n for m a c r o s e g r e g a t i o n con-
s i d e r i n g fluid flow in t h r e e d i m e n s i o n s for a b i n a r y a l -
loy with a c o n s t a n t p a r t i t i o n r a t i o was f i r s t published
b y F l e m i n g s and N e r e o 4 and used to p r e d i c t solute d i s -
t r i b u t i o n s for i n v e r s e s e g r e g a t i o n in A1-Cu alloys. The
model was b a s e d on the lafann equation, which gives
the c o m p o s i t i o n of solid at the s o l i d - l i q u i d i n t e r f a c e
( C s ) when t h e r e is c o m p l e t e m i x i n g in the adjoining
liquid:
C s = kCo(1 - fs)/~l
where
k = equilibrium partition ratio
fs = weight f r a c t i o n solid ( i . e . , c o m p o s i t i o n s a r e
in wt pet)
C O = i n i t i a l alloy c o m p o s i t i o n
The model has s u b s e q u e n t l y b e e n r e f i n e d and e x -
tended s'6 and has b e e n applied by M e h r a b i a n , Keane
and F l e m i n g s 7 to p r e d i c t m a c r o s e g r e g a t i o n c a u s e d by
a c o m b i n a t i o n of s o l i d i f i c a t i o n c o n t r a c t i o n and solute
N. STREAT, formerly Research Associate, Department of Metal-
lurgy, University of British Columbia, is now MetallurgicalResearch
Engineer, British Columbia Hydro and Power Authority, Vancouver,
Canada. F. WEINBERGis Professor, Department of Metallurgy, Uni-
versity of British Columbia, Vancouver, Canada.
Manuscript submitted October 22, 1973.
a v o l u m e e l e m e n t where the f o r c e s acting a r e solid
c o n t r a c t i o n , liquid c o n t r a c t i o n and g r a v i t y . The liquid
is of v a r i a b l e d e n s i t y , and the s o l i d - l i q u i d r e g i o n is
t r e a t e d as a porous m e d i u m of v a r i a b l e p o r o s i t y . E q u a -
t i o n s a r e d e r i v e d r e l a t i n g i n t e r d e n d r i t i c fluid p r e s s u r e ,
i n t e r d e n d r i t i c flow velocity, f r a c t i o n liquid and liquid
c o m p o s i t i o n which can, in t h e o r y , be solved to give
t h e s e v a r i a b l e s as a function of position. In p r a c t i c e ,
solutions for the g e n e r a l c a s e a r e difficult to obtain,
s i n c e this would involve the solution of s i m u l t a n e o u s
p a r t i a l d i f f e r e n t i a l equations. They have t h e r e f o r e
made the following s i m p l i f y i n g a s s u m p t i o n s :
1) F o r the p u r p o s e of c a l c u l a t i n g flow v e l o c i t i e s , it
is a s s u m e d that the f r a c t i o n liquid v a r i e s with p o s i t i o n
in the m u s h y zone only as a function of t e m p e r a t u r e ,
and is c a l c u l a t e d by a s s u m i n g s t e a d y - s t a t e , u n i d i r e c -
tional heat and fluid flow. A new d i s t r i b u t i o n of f r a c -
tion liquid in the m u s h y zone is s u b s e q u e n t l y p r e d i c t e d
when these flow v e l o c i t i e s a r e included in the m a c r o -
s e g r e g a t i o n equation d e r i v e d by Nereo and F l e m i n g s . 4
2) P l a n a r i s o t h e r m s a r e a s s u m e d , so that for a c o n -
s t a n t liquidus slope, the liquid c o m p o s i t i o n v a r i e s l i n -
e a r l y with position in one d i r e c t i o n .
3) The d e n s i t y of liquid v a r i e s l i n e a r l y with c o m p o -
sition.
4) The d e n s i t y of solid is c o n s t a n t .
The model has b e e n applied to the s p e c i a l case of
h o r i z o n t a l , u n i d i r e c t i o n a l heat flow and s t e a d y - s t a t e
solidification, where a v a l u e for the p a r a m e t e r c h a r -
a c t e r i z i n g the s t r u c t u r e and t h e r m a l conditions has
been assumed.
In addition, M e h r a b i a n e t a l have d i s c u s s e d the
m e c h a n i s m whereby, u n d e r c r i t i c a l conditions, u p -
ward flowing liquid b e c o m e s s u p e r h e a t e d and can d i s -
solve d e n d r i t e b r a n c h e s in its path to f o r m v i s i b l e
t r a i l s or " p i p e s " of high solute content. T h e s e have

METALLURGICALTRANSACTIONS VOLUME 5, DECEMBER 1974-2539

b e e n o b s e r v e d in e x p e r i m e n t s on A1-Cu a l l o y s , e and
t h e y p r o p o s e that the c r i t i c a l c o n d i t i o n for the f o r m a -
tion of c h a n n e l - t y p e d e f e c t s i s when the d i r e c t i o n of the
i n t e r d e n d r i t i c fluid flow v e c t o r goes f r o m the c o l d e r
to the h o t t e r r e g i o n s of the c a s t i n g . Upward flowing
c h a n n e l s have b e e n o b s e r v e d b y o t h e r a u t h o r s in t r a n s -
p a r e n t a m m o n i u m c h l o r i d e - w a t e r m o d e l s and t h i s
m e c h a n i s m is thought to be r e s p o n s i b l e for the f o r -
m a t i o n of f r e c k l e s in n i c k e l - b a s e s u p e r a l l o y s , 9' lo and
A s e g r e g a t e s in s t e e l , n
The p u r p o s e of the p r e s e n t i n v e s t i g a t i o n is to e x -
p e r i m e n t a l l y d e t e r m i n e the e x t e n t of m a c r o s e g r e g a -
tion and f r e c k l e f o r m a t i o n in v e r t i c a l l y s o l i d i f i e d l e a d -
tin a l l o y s a s a function of the s o l i d i f i c a t i o n v a r i a b l e s .
Since it would b e difficult to a p p l y the m o d e l d e v e l o p e d
b y M e h r a b i a n et al to the type of ingot and a l l o y s y s -
t e m u s e d in t h i s i n v e s t i g a t i o n , a s i m p l e m a t h e m a t i c a l
m o d e l was d e v e l o p e d which would t a k e into a c c o u n t
the effect of growth r a t e , t e m p e r a t u r e g r a d i e n t and
s t r u c t u r e . Some of the a s s u m p t i o n s f o r t h i s m o d e l
d i f f e r f r o m t h o s e u s e d b y M e h r a b i a n et al, the m a j o r
differences being:
1) The p a r t i t i o n r a t i o v a r i e s a s a function of t e m -
perature.
2) The d e n s i t y of the liquid is a function of t e m p e r -
a t u r e and c o m p o s i t i o n , o b t a i n e d f r o m e x p e r i m e n t a l
data.
3) The s t r u c t u r e of the m u s h y zone is c h a r a c t e r i z e d
b y a p a r a m e t e r which is a l s o o b t a i n e d f r o m e x p e r i m e n -
tal data.
4) Since the m o d e l i s a p p l i e d to the s o l i d i f i c a t i o n of
P b - S n a l l o y s , backflow due to v o l u m e s h r i n k a g e is n e -
glected.
EXPERIMENTAL PROCEDURE
Cylindrical ingots 14 c m long and 1.27 c m in diana
were solidified in graphite molds by lowering the
molds through a two zone furnace. By adjusting the
temperature of the furnace zones, the gradient and
growth rate could be varied independently. During
solidification, the alloy was quenched when desired
by surrounding the mold by water. Quenching occurred
in less than 20 seconds.
For each set of solidification conditions, four ingots
were made. The temperature gradient and freezing
rate were established in one ingot using three thermo-
couples positioned along the axis. The cast structure
was determined from longitudinal and transverse sec-
tions of two of the ingots which were polished and etched
after sectioning. The fourth ingot was used for m e a -
surements of macrosegregation. Radioactive tracer
was well mixed into the liquid prior to solidification,
and after solidificationthe ingot was placed in a lathe
and cuttings were taken in a plane perpendicular to the
ingot axis. Starting at one end, the cuttings were col-
lected at 0.37 c m i n t e r v a l s and the a c t i v i t y of e a c h
group of c u t t i n g s was m e a s u r e d in a s c i n t i l l a t i o n
counter.
The i s o t o p e s u s e d w e r e e i t h e r Sn n3 (half life 112
d a y s , p r i m a r i l y a low e n e r g y ~ e m i t t e r ) o r T1 a~ (half
l i f e 4.1 y e a r s , p r i m a r i l y a # e m i t t e r , but a l s o s o m e
low e n e r g y ~). The Sn u3 was u s e d in the l e a d r i c h a l -
l o y s , and T1 a~ in the tin r i c h a l l o y s . F r o m the m e a -
s u r e d a c t i v i t y and the weight of e a c h s a m p l e , the s o l -
2540-VOLUME 5, DECEMBER 1974
ute content was d e t e r m i n e d a s a function of d i s t a n c e
f r o m the b o t t o m of the ingot.
C o m p o s i t i o n p r o f i l e s f o r ingots quenched d i r e c t l y
f r o m the l i q u i d w e r e c o m p a r e d to the d i r e c t i o n a l l y
s o l i d i f i e d ingots, to c o n f i r m that the e f f e c t s o b s e r v e d
f o r the l a t t e r w e r e due to the s o l i d i f i c a t i o n c o n d i t i o n s ,
and not due to p o o r m i x i n g of the o r i g i n a l a l l o y c h a r g e ,
or other extraneous factors.
To o b s e r v e c o n v e c t i o n through the bulk liquid and
s o l i d - l i q u i d r e g i o n s , 0.1 g p e l l e t s of the c a s t i n g alloy,
containing Sn ns, w e r e p l a c e d in the liquid at the top of
the m o l d d u r i n g s o l i d i f i c a t i o n . S o l i d i f i c a t i o n was c o n -
t i n u e d f o r one h o u r ; following which the ingots w e r e
quenched in the f u r n a c e , then s e c t i o n e d and p o l i s h e d .
A u t o r a d i o g r a p h s of t r a n s v e r s e and l o n g i t u d i n a l s e c -
tions showed the e x t e n t of t r a c e r m o v e m e n t . A s i m i -
l a r e x p e r i m e n t was p e r f o r m e d on an ingot of the s a m e
c o m p o s i t i o n h e l d c o m p l e t e l y liquid u n d e r the s a m e
t e m p e r a t u r e g r a d i e n t for one hour. In t h i s c a s e ,
s p r e a d i n g of the t r a c e r could b e a t t r i b u t e d to the c u -
m u l a t i v e e f f e c t s of d i s t u r b a n c e s a s s o c i a t e d with a d d -
ing the p e l l e t and quenching. The fluid flow r e s u l t i n g
f r o m the s o l i d i f i c a t i o n p r o c e s s could b e e v a l u a t e d b y
c o m p a r i n g the r e s u l t s of t h e s e t e s t s .
A s m a l l s a m p l e (150 g) of the m o l t e n a l l o y was
p l a c e d in a g r a p h i t e c r u c i b l e and o b s e r v e d d u r i n g
s o l i d i f i c a t i o n u n d e r v a c u u m . No b u b b l e s w e r e s e e n .
T h i s e v i d e n c e , t o g e t h e r with i n f o r m a t i o n in the l i t e r -
a t u r e that only oxygen is v e r y s l i g h t l y s o l u b l e in m o l -
t e n F o - S n a l l o y s , la c o n f i r m e d that g a s evolution could
b e i g n o r e d a s a p o s s i b l e f r e c k l i n g m e c h a n i s m in t h i s
system.
RESULTS
i. Composition Profiles
The composition profiles of the ingots, determined
b y the a c t i v i t y m e a s u r e m e n t a n a l y s i s , a r e shown in
F i g s . 1 and 2. The s o l i d l i n e s a r e t h e o r e t i c a l c u r v e s
c a l c u l a t e d f r o m the m a t h e m a t i c a l m o d e l . The s o l i d i -
f i c a t i o n v a r i a b l e s and the m e a s u r e d v a l u e s of m a c r o -
s e g r e g a t i o n , t o g e t h e r with the r e s u l t s f o r quenched
ingots, a r e given in T a b l e I. Cooling c u r v e s showed
that e s s e n t i a l l y c o n s t a n t growth r a t e s and t e m p e r a -
t u r e g r a d i e n t s w e r e m a i n t a i n e d under the slow f r e e z -
ing c o n d i t i o n s i m p o s e d in t h e s e e x p e r i m e n t s .
M a c r o s e g r e g a t i o n (AC), in t h i s c a s e , h a s b e e n d e -
fined a s the d i f f e r e n c e in a v e r a g e c o m p o s i t i o n b e -
t w e e n the u p p e r and l o w e r h a l v e s of the ingot. It is
c o n s i d e r e d p o s i t i v e when the s o l u t e c o n c e n t r a t i o n i n -
c r e a s e s in the d i r e c t i o n of s o l i d i f i c a t i o n , and n e g a t i v e
f o r the r e v e r s e .
C o m p a r i n g the m a c r o s e g r e g a t i o n f o r d i r e c t i o n a l l y
s o l i d i f i e d and quenched c a s t i n g s , l i s t e d in T a b l e I, it
can b e s e e n that the s o l u t e d i s t r i b u t i o n is a function
of the s o l i d i f i c a t i o n c o n d i t i o n s . In g e n e r a l , the amount
of m a c r o s e g r e g a t i o n for i ~ - 2 0 p c t Sn a l l o y s d e c r e a s e d
a s the p r i m a r y d e n d r i t e s p a c i n g d e c r e a s e d . F i g s . l(a)
and (b) show that m a c r o s e g r e g a t i o n i n c r e a s e s for the
s l o w e r growth r a t e at the s a m e t e m p e r a t u r e g r a d i e n t ,
and F i g s . l(b) and (c) show the s a m e effect for the
s h a l l o w e r g r a d i e n t when the growth r a t e s a r e a l m o s t
the s a m e . F o r the Sn-4 pet Pb a l l o y (Fig. 2), t h e r e
was m o r e s o l u t e at the b o t t o m of the c a s t i n g and l e s s
at the top, r e s u l t i n g in s o m e n e g a t i v e m a c r o s e g r e g a -
tion.
METALLURGICAL TRANSACTIONS
 The reproducibility of the analysis technique was
AVERAGE TEMPERATURE GRADIENT 1.5*C/cm tested by counting a single sample of turnings several
AVERAGE GROWTHRATE 0-0047 crn/sec
times, emptying and refilling the container in which it
was held, to vary the geometry of packing. The error
bars shown in Figs. 1 and 2 are • 2s limits based on
these tests, and for castings with a m e a n composition
of Fo-20 pct Sn, they represent a scatter of ~0.38 pct
Sn (percentage error = 1.9 pct). This was considered
acceptable, since the composition difference between
the ends of the castings was, in general, significantly
larger than the scatter.
For the Sn-4 pct Pb castings, the error bars repre-
--0 0 2:O 4~0 670 ' S~O ' IO:O ' 12~0 ' 14"0 sent a scatter of +0.22 pct Pb, which is a larger per-
DISTANCE FROM BOTTOM OF CASTING (cat)
centage error (4.3 pct), probably due to greater ab-
(a) sorption of the low energy emission from Tl 2~

AVERAGE TEMPERATURE GRADIENT 1'5*C/era

2. Convection in the Liquid
AVERAGE GROWTHRATE O-OIScm/sec
The results demonstrating convection in the liquid
during solidification are given in Fig. 3(a). The auto-
radiographs shown are of sections parallel to the
freezing direction of a 1~-20 pet Sn alloy under the
conditions listed in Table II. In Fig. 3(a), the regions
which are uniformly dark (sections i-iv) indicate that
the ltqutdus isotherm passed through this region after
tracer had become mixed through the bulk liquid. In
section (v), only the interdendritie regions are dark,
Indicating tracer penetration into the solid-liquid zone.
-OO 2:0 ' 4?0 " 6?0 ' e~o ' ~o'o 12'0 14'0 Fig. 3(b) shows autoradtographs for an ingot quenched
D~STANCE FROM BOTTOMOF CASTING (cm)
from the liquid. Tracer has moved down less than 3 cm,
as compared to 6.5 cm for Fig. 3(a). The difference in

~] AVERAGETEMPERATURE GRADIENT 2.3"C/cm

. AVERAGE GROWTHRATE OOII cm/sec AVENGE TEMPERATURE GRAOIENT 1.9*C/cm
AVERAGE GROWTH RATE 0OO33cm/sec

. /

--OO 2:O 4:O 6:O 8~O ' IO~C) ' 12'O ' 14'O
DISTANCE FROM BOTTOM OF CASTING (cml
2"0 4YO 670 SYO I0'0 12'0 E4'O
(c) DISTANCE FROM BOTTOM OF CASTING (cm)

Fig. l--Solute profiles for direetionally solidified Pb-20 pet F i g . 2 - - S o l u t e profile for directionally solidified Sn-4 pct
Sn alloys under the conditions shown. The solid lines are Pb. No raaerosegregation i s predicted by the model for this
theoretical curves calculated using the data in Table ITI. a l l o y , shown by the solid l i n e .

Table I . Solidification Variablesand M a a r o ~ o n

Calculated
Average Average Distance Between Primary
Alloy Temperature Growth Liquidus and Dendrite Macro-
Fig. Composition Gradient Rate Solidus Isotherms Spacing segregation
No. (wt pet) (~ (cm/sec) (cm) (microns) Structure (txC pet)

l(a) Pb-20 Sn 1.5 • 0.05 0.0047 62.0 206 columnar 1.07

l(b) Pb-20 Sn 1.5 • 0.2 0.013 62.0 172 half columnar 0.73
half equiaxed
l(c) Pb-20 Sn 2.3 • 0.3 0.011 40.4 119 equiaxed 0.13
- Pb-20 Sn - quenched - - equiaxed -0.04
2 Sn-4 Pb 1.9 0.0033 24.7 - half columnar -0.35
half equiaxed
Sn-4 Pb quenched equiaxed 0.11

METALLURGICAL TRANSACTIONS V O L U M E 5, D E C E M B E R 1 9 7 4 - 2 5 4 1

(a)
p e n e t r a t i o n is a t t r i b u t e d to solute convection a s s o c i -
ated with the s o l i d i f i c a t i o n p r o c e s s . T h e r e is no i n d i -
cation, however, of the flow p a t t e r n which c a u s e d m i x -
ing.
3. F r e c k l e s
E v i d e n c e of s t r u c t u r e s r e s e m b l i n g f r e c k l e s was s e e n
in ingots solidified at the s l o w e s t growth r a t e s . In one
case (Fig. 4(a)), the o u t e r s u r f a c e showed a s h r i n k a g e
t r a i l a p p r o x i m a t e l y 7 cm long n e a r the top. A s h r i n k -
age defect of this type i n d i c a t e s that a long c h a n n e l of
eutectic liquid was p r e s e n t j u s t b e f o r e the c a s t i n g b e -
c a m e c o m p l e t e l y solid. This b e a r s a close r e s e m -
b l a n c e to p r e v i o u s l y p u b l i s h e d photographs of f r e c k l e s
in n i c k e l - b a s e s u p e r a l l o y s . 9
Fig. 4(b) shows l o n g i t u d i n a l s e c t i o n s through a n o t h e r
ingot which c o n t a i n e d an i n t e r n a l t r a i l that could be
c l a s s e d as a f r e c k l e . An e n l a r g e d view of a t r a n s v e r s e
s e c t i o n (Fig. 5(a)) shows that the t r a i l had a fine d e n -
2542-VOLUME 5, DECEMBER 1974
Fig. 3-Autoradiographs
showing the extent of
tracer movement one hour
after tracer was added (a)
directionally solidified (b)
quenched from liquid.
Solidification conditions
given in Table II. Magnifi-
cation 2 times.
(b)
d r i t i c s t r u c t u r e . Fig. 5(b) is an e n l a r g e d view of the
lowest p o r t i o n of the t r a i l , showing that it o r i g i n a t e d
in the i n t e r i o r of the ingot as an i n t e r d e n d r i t i c c h a n -
nel, which s u b s e q u e n t l y widened and moved t o w a r d s
the mold wall, in the s a m e d i r e c t i o n as the p r i m a r y
d e n d r i t e s t a l k s . The s o l i d i f i c a t i o n conditions for the
ingots in F i g s . 4 and 5 a r e given in T a b l e II.
DISCUSSION O F R E S U L T S
The curves in Fig. 1 showing positive macrosegre-
gation resemble curves for normal segregation with
diffusion controlled mixing ahead of a planar solid-
liquid interface. There is, however, considerable ex-
perimental e v i d e n c e in the l i t e r a t u r e 13'x4 to show that
only a n e g l i g i b l e amount of solute is r e j e c t e d ahead
of d e n d r i t e tips when growth is not p l a n a r . N o r m a l
s e g r e g a t i o n t a k e s place over a d i s t a n c e of the o r d e r
of m i c r o n s in the liquid b e t w e e n d e n d r i t e b r a n c h e s ,
l e a d i n g to m i c r o s e g r e g a t i o n . However, one would not
METALLURGICAL TRANSACTIONS
 Table II. Cooling Conditions

Calculated
Average Average DistanceBetween
Alloy Temperature Growth Liquidus and
Fig. Composition Gradient Rale Solidus Isotherms
No. (wt pct) (~ (cm/sec) (cm)
3(a) Pb-20 Sn 1.9 0.0033 48.9
3(b) Pb-20 Sn - quenched -
4(a) Pb-20 Sn 1.5 0.0047 62.0
4(b),5 Pb-20 Sn 1.9 0.0033 48.9

(a)

~'~-"%* :~ ~ ~' 7--. .----~

r" ~,i ~i.... i ..~

? ?- : ..(/

If ,r

I~--;.~7:7~- "r i,

(a) (b) (b)

Fig. 4--(a) Shrinkage trail, approximately 7 cm long, along
the outside of an ingot solidified under conditions given in
Table II. Magnification 2 times. (b) Longitudinal sections
showing a freckle trail on right side. Horizontal white areas
are spaces between sections caused by t r a n s v e r s e sawcuts.
Magnification 5 times.
Fig. 5--(a) T r a n s v e r s e section of freckle trail in Fig. 4(b)
showing the fine dendritic structure within the trail. (b) Lon-
gitudinal section showing that the trail originates from widen-
ing interdendritic channels in the interior of the ingot. Mag-
nification 25 times.

e x p e c t a n e t m o v e m e n t of s o l u t e in the d i r e c t i o n of
g r o w t h u n l e s s t h e r e w a s l i q u i d m i x i n g on a m a c r o -
scopic scale. This mixing could take place either
w i t h i n the s o l i d - l i q u i d z o n e , o r b e t w e e n t h i s z o n e and
the b u l k l i q u i d a h e a d of the d e n d r i t e t i p s .
An e s t i m a t e of t h e s i g n i f i c a n c e of t h e m a c r o s e g r e -
g a t i o n v a l u e s in T a b l e T c a n be o b t a i n e d b y u s i n g e l e -
mentary statistics. The composition measurements
f o r e a c h s a m p l e a r e s u b j e c t to m i c r o s e g r e g a t i o n and
g e o m e t r i c a l s c a t t e r , h o w e v e r , it is r e a s o n a b l e to a s -
s u m e t h a t t h e m e a n of s a m p l e s o v e r h a l f the ingot
l e n g t h w i l l o n l y b e s u b j e c t to g e o m e t r i c a l s c a t t e r ,
since microsegregation only extends over relatively
s h o r t d i s t a n c e s . K n o w i n g t h e m e a n s and s t a n d a r d d e -
v i a t i o n s f o r t h e top and b o t t o m h a l v e s of the ingot, the
" t - t e s t " m a y b e u s e d to c h e c k w h e t h e r t h e c o m p o s i -
tion differences are significant.
F o r a s i g n i f i c a n c e l e v e l of 0.01, one m a y c o n c l u d e
t h a t t h e r e is no s i g n i f i c a n t m a c r o s e g r e g a t i o n w h e n
AC < 0.19 p c t Sn f o r P b - 2 0 p c t Sn i n g o t s , o r AC < 0.11
p c t lab f o r S n - 4 p c t Pb i n g o t s . T h u s t h e m e a s u r e d v a l -
u e s of AC in T a b l e I f o r both q u e n c h e d i n g o t s s h o w no

METALLURGICAL TRANSACTIONS VOLUME 5, DECEMBER 1974-2543

 s i g n i f i c a n t m a c r o s e g r e g a t i o n , n o r c a n the v a l u e of 0.13
o71
p e t Sn for the ingot in Fig. l ( c ) b e r e g a r d e d a s a s i g -
n i f i c a n t d i f f e r e n c e . The r e m a i n i n g ingots, h o w e v e r , # O6

show a s i g n i f i c a n t amount of m a c r o s e g r e g a t i o n c o m - 0.5

p a r e d to the quenched ingots, and s i g n i f i c a n t d i f f e r -
e n c e s when c o m p a r e d to one a n o t h e r . ~ 0.4

g,
The e x p e r i m e n t w h e r e t r a c e r was added to the liquid ~ 03
$
at the top of the c a s t i n g ( F i g . 3) c o n f i r m s that s o l u t e
c o n v e c t i o n took p l a c e , which is a t t r i b u t e d to the f o r m a -
0.1
tion of l o w e r d e n s i t y liquid in the s o l i d - l i q u i d r e g i o n .
In the c a s e of P o - 2 0 pct Sn, the i n t e r d e n d r i t i c liquid ~0 20 30 40 50 60 70 80 90 I00
b e c o m e s e n r i c h e d in tin, up to the e u t e c t i c c o m p o s i - We~t Percent Tm

tion (62 pct Sn). The d e n s i t y of the b u l k liquid at the

i n t e r f a c e would be 9.7 g / c m 3, and the e u t e c t i c would
b e 8.2 g/cm3, TM thus t h e r e would be a d e n s i t y i n v e r s i o n
t h r o u g h the s o l i d - l i q u i d r e g i o n which c a u s e s the l e s s
d e n s e liquid to r i s e .
One can t h e r e f o r e c o n c l u d e that the s o l u t e p r o f i l e s
in F i g . 1 a r e a function of the growth r a t e , t e m p e r a -
t u r e g r a d i e n t and d e n d r i t e s p a c i n g . H o w e v e r , it is not
p o s s i b l e to d r a w f i r m c o n c l u s i o n s r e g a r d i n g the effect
of v a r y i n g any one of t h e s e p a r a m e t e r s alone, b e c a u s e
only one of the t h r e e v a r i a b l e s could b e h e l d c o n s t a n t
f o r a n y two i n g o t s . F o r t h i s r e a s o n , a s i m p l e m a t h e -
m a t i c a l m o d e l was d e r i v e d , b a s e d on the c o n c e p t of
m a s s t r a n s f e r t h r o u g h the s o l i d - l i q u i d r e g i o n c a u s e d
b y d e n s i t y d i f f e r e n c e s in the liquid.
The Sn-4 p c t l~b a l l o y was c h o s e n a s an e x a m p l e of
a c o m p o s i t i o n w h e r e the i n t e r d e n d r i t i c liquid would b e
m o r e d e n s e than the b u l k liquid above. The c o m p a r a b l e
d e n s i t i e s would b e 7.1 g / c m 3 in the b u l k liquid, and 8.2
g / c m 3 in the e u t e c t i c . ~s T h i s d e n s i t y c o n f i g u r a t i o n
would be s t a b l e , and one would not e x p e c t any c o n v e c -
tion. The r e s u l t i n g c o m p o s i t i o n p r o f i l e (Fig. 2) shows
a s m a l l i n c r e a s e in l e a d content c l o s e to the b o t t o m
of the ingot, which is p o s s i b l y due to the effect of i n -
verse segregation.
Consequently, the f r e c k l e t r a i l s o b s e r v e d in ingots
s o l i d i f i e d at the s l o w e s t f r e e z i n g r a t e s a r e a t t r i b u t e d
to the effect of s o l u t e convection. As the l e s s d e n s e
liquid t o w a r d s the b o t t o m of the m u s h y zone b e g i n s to
r i s e , it b e c o m e s s u p e r h e a t e d and can d i s s o l v e d e n d r i t e
b r a n c h e s in i t s path. If s u f f i c i e n t i n t e r d e n d r i t i c c h a n -
n e l s widen in t h i s f a s h i o n , t h e y can c o n v e r g e and r e -
s u l t in the f o r m a t i o n of a l a r g e v e r t i c a l pipe. D i r e c t
e v i d e n c e of t h i s m e c h a n i s m is shown in F i g . 5(b). The
e x p e r i m e n t a l e v i d e n c e s u g g e s t s that f r e c k l e s do not
a l w a y s f o r m when s o l u t e c o n v e c t i o n t a k e s p l a c e , but
t h e y a p p e a r when the v e l o c i t y of the r i s i n g i n t e r d e n -
d r i t i c liquid r e a c h e s a c r i t i c a l v a l u e .
To e x a m i n e the m a g n i t u d e of i n v e r s e s e g r e g a t i o n in
the lab-Sn s y s t e m , the Scheil m o d e l ~ was u s e d to c a l -
c u l a t e the m a x i m u m c h i l l f a c e s e g r e g a t i o n for a l a r g e
n u m b e r of a l l o y c o m p o s i t i o n s . Both t h e p a r t i t i o n r a t i o
and the s o l i d i f i c a t i o n s h r i n k a g e w e r e c o n s i d e r e d a s
functions of t e m p e r a t u r e and c o m p o s i t i o n , r e s p e c t i v e l y .
The r e s u l t s of t h i s c a l c u l a t i o n a r e given in Fig. 6. F o r
Sn-4 p c t Pb, i n v e r s e s e g r e g a t i o n would c a u s e the c o m -
p o s i t i o n at the c h i l l f a c e to r i s e b y 0.2 p c t l~b, which
c o r r e s p o n d s to the e x p e r i m e n t a l r e s u l t in Fig. 2. F o r
P b - 2 0 p c t Sn, i n v e r s e s e g r e g a t i o n would c a u s e an i n -
c r e a s e of 0.55 p c t Sn at the c h i l l f a c e . T h i s e f f e c t
would o p p o s e the p o s i t i v e m a c r o s e g r e g a t i o n c a u s e d
b y s o l u t e c o n v e c t i o n in the liquid. In view of the o b -
Fig. 6--Maximum chill face segregation for Pb-Sn alloys,
calculated using the Scheil model, t
from - 1.8 to - 1.0 pct Sn), the effect of inverse seg-
regation is considered to be small for this alloy sys-
tem.
MODEL OF THE SOLIDIFICATION
PROCESS
The mathematical model assumes that solidification
is described using the Pfann equation in exactly the
s a m e manner as previously presented by Kirkaldy and
Youdelis. 2 The partition ratio (k) can be considered a
variable during solidification if one assumes that it re-
.~malns constant over a small temperature interval.
Liquid composition, average solid composition and the
weight fractions of solid and liquid can be defined at
any temperature between the liquidus and solidus by
using data from the phase diagram.
In addition, if density data are available as a func-
tion of temperature and composition, volume fractions
and densities are also defined at any temperature.
INTERDENDRITIC FLUID F L O W MODEL
The m o d e l of the s o l i d i f i c a t i o n p r o c e s s d e s c r i b e s
how s o l u t e is r e d i s t r i b u t e d p e r p e n d i c u l a r to the d e n -
d r i t e s t a l k s . If no i n t e r d e n d r i t i c fluid flow o c c u r s , the
ingot would show m i c r o s e g r e g a t i o n on a s c a l e e q u i v a -
lent to the d e n d r i t e s p a c i n g , but t h e r e would b e no net
m o v e m e n t of s o l u t e o v e r g r e a t e r d i s t a n c e s . The a s -
s u m p t i o n is now m a d e that s o l u t e c a n b e m o v e d o v e r
much g r e a t e r d i s t a n c e s b y i n t e r d e n d r t t i c fluid flow
c a u s e d b y d e n s i t y d i f f e r e n c e s in the liquid. T h e r e is
e x p e r i m e n t a l e v i d e n c e t h a t D a r c y ' s Law c a n b e a p -
p l i e d to i n t e r d e n d r i t i c fluid flow, *a'*7 t h e r e f o r e , the
flow v e l o c i t y (v) is p r o p o r t i o n a l to the p r e s s u r e d r o p
a c r o s s the m u s h y zone (&P):
-K
v=-~&P
where
K = p e r m e a b i l i t y (in units of a r e a )
/1 = v i s c o s i t y of the liquid
h = length of the m u s h y zone
F u r t h e r m o r e , the p e r m e a b i l i t y of the d e n d r i t i c n e t -
w o r k c a n b e e x p r e s s e d in t e r m s of flow t h r o u g h a b u n -
d l e of c a p i l l a r y t u b e s : ~ ' ~ '
K = - -

s e r v e d c h i l l f a c e s e g r e g a t i o n in Fig. 1 (which r a n g e s 247rm-s

2544-VOLUME 5, DECEMBER 1974 METALLURGICAL TRANSACTIONS

w h e r e gL is the v o l u m e f r a c t i o n liquid, n is the n u m -
b e r of c h a n n e l s , and ~ is a t o r t u o s i t y factor, which
takes into a c c o u n t the fact that the i n t e r d e n d r i t i c c h a n -
n e l s a r e n e i t h e r s t r a i g h t nor s y m m e t r i c a l .
P r e v i o u s e x p e r i m e n t a l work TM has shown that K is
p r o p o r t i o n a l to g ~ , when gL is l e s s than 0.3. In the
a b s e n c e of a b e t t e r model, it is a s s u m e d that the above
equation holds for all v a l u e s of gL" Thus, the i n t e r d e n -
d r i t i c fluid flow model is e s s e n t i a l l y the s a m e as that
used b y M e h r a b i a n et al ~ with the following d i f f e r e n c e s :
1) the n u m b e r of c h a n n e l s (n) is c a l c u l a t e d f r o m the
p r i m a r y d e n d r i t e s p a c i n g (;~), and is taken to be equal
to 1/X 2.
2) the t o r t u o s i t y factor is taken f r o m e x p e r i m e n t a l
work done in this l a b o r a t o r y , ~v and is equal to 4.6.
UNIDIRECTIONAL SOLIDIFICATION OF
A VERTICAL CASTING
As an e x a m p l e of the a p p l i c a t i o n of the model, c o n -
s i d e r the v e r t i c a l s o l i d i f i c a t i o n of an ingot of c o n s t a n t
c r o s s s e c t i o n , of the type e x a m i n e d in Fig. 1. To s i m -
plify the c a l c u l a t i o n s , c o n s t a n t growth r a t e (R) and
t e m p e r a t u r e g r a d i e n t (G) a r e a s s u m e d . In addition,
s i n c e the m o d e l will be applied to P b - S n alloys, where
the v o l u m e change on f r e e z i n g is s m a l l (of the o r d e r of
2 pct), backflow due to v o l u m e s h r i n k a g e is a s s u m e d to
be negligible. This a s s u m p t i o n is j u s t i f i e d in view of
the m a x i m u m c h i l l face c o m p o s i t i o n s shown in Fig. 6.
The ingot is divided into a n u m b e r of h o r i z o n t a l l a y -
e r s , and s o l i d i f i c a t i o n is c o n s i d e r e d to b e g i n when the
t e m p e r a t u r e of the bottom l a y e r is equal to the liquidus
t e m p e r a t u r e TL. F r e e z i n g p r o g r e s s e s in d i s c r e t e t i m e
s t e p s (At) and within each step, s o l i d i f i c a t i o n and fluid
flow a r e t r e a t e d s e p a r a t e l y . C o n s e r v a t i o n of solute
within each l a y e r applies d u r i n g each s o l i d i f i c a t i o n
step, and c o n s e r v a t i o n of solute through the whole i n -
got applies in each fluid flow step. Fluid flow through
any l a y e r stops when its t e m p e r a t u r e f a l l s below the
eutectic t e m p e r a t u r e TE, and the f i n a l c o m p o s i t i o n of
the ingot is obtained when the top l a y e r r e a c h e s T E.
Fig. 7 gives a s c h e m a t i c r e p r e s e n t a t i o n of the ingot
at an i n t e r m e d i a t e t i m e , and shows the t e m p e r a t u r e ,
c o m p o s i t i o n and d e n s i t y p r o f i l e s in the liquid, obtained
u s i n g the s o l i d i f i c a t i o n model (i.e., the Pfann equation)
for an alloy w h e r e i n c r e a s e d a m o u n t s of solute c a u s e
the liquid to b e c o m e l e s s dense.
The d r i v i n g f o r c e for flow through the m u s h y zone
is given b y the d e n s i t y d i f f e r e n c e b e t w e e n T L and TE,
and is equal to ApLgh, where ApL is the d e n s i t y dif-
f e r e n c e in the liquid, and g is gravity. Since the liquid
f
.... o-- --TL-- _ ~
r - - i -d ---1
CE
T TEMPERATURE LIQUID LIQU~O
COMPOSITION DENSITY
Fig. 7--Unidirectional ingot divided into layers. Tempera-
ture, composition and density profiles given by the solidifi-
cation model.
METALLURGICALTRANSACTIONS
o
L : 37
01 L=I
~
o
length of costlnq (H) : 1 4 c m
~i 28 femperalure gradient (G) = 1 5 ~
growJh rate (R) = 0 005 c m / s e c
14 n u m b e r of c h a n n e l s (NC) = 3 5 x tCr~
viscosity of the liquid = 0 03poise
%'0 ' Z'O ' 4'0 ' 6:0 ' 8'0 ' I0:0 ' /2~0
DISTANCE FROM BOTTOM OF CASTING (cm)
Fig. 8--Solute distribution as a function of the number of
layers.
is a c o n t i n u u m , the d r i v i n g f o r c e is c o n s i d e r e d to be
c o n s t a n t through the s o l i d - l i q u i d r e g i o n , d u r i n g the
t i m e i n t e r v a l At.
The r e d i s t r i b u t i o n of solute is then c a l c u l a t e d b y a s -
s u m i n g a flow p a t t e r n within the solid liquid r e g i o n .
T a k i n g into account the d r i v i n g f o r c e a c r o s s each l a y e r ,
and the r e s i s t a n c e to flow of the d e n d r i t i c network, s o l -
ute m a s s b a l a n c e s can be w r i t t e n for each l a y e r of the
ingot. This is d e s c r i b e d in m o r e detail in Appendix A.
The w o r k i n g of the model can be s u m m a r i z e d b r i e f l y
as follows: when the Pfann equation is applied to each
l a y e r of the ingot as it s o l i d i f i e s , the a v e r a g e c o m p o -
s i t i o n of both solid and liquid in the l a y e r r e m a i n s
equal to the m e a n alloy c o m p o s i t i o n C O. The additional
effect of i n t e r d e n d r i t i c fluid flow is to c a u s e liquid with
a high tin content, close to the b o t t o m of the m u s h y
zone, to flow upwards, and be r e p l a c e d b y liquid of a
lower t i n content. Consequently, the a v e r a g e c o m p o s i -
tion of l a y e r s t o w a r d s the top of the ingot will r i s e
above Co, and those t o w a r d s the bottom will fall below
C o.
RESULTS OF CALCULATIONS FOR
THE SOLIDIFICATION OF A P b - S n ALLOY
The model was used to c a l c u l a t e the f i n a l solute d i s -
t r i b u t i o n in a P b - 2 0 pct Sn alloy as a function of the
s o l i d i f i c a t i o n conditions. Data for the p a r t i t i o n r a t i o k
and the e q u i l i b r i u m liquidus line were obtained f r o m
the phase d i a g r a m , and the d e n s i t i e s of liquid P b - S n
alloys as a function of t e m p e r a t u r e and c o m p o s i t i o n
w e r e a v a i l a b l e in the f o r m of a table. 15
Fig. 8 shows the solute d i s t r i b u t i o n for d i f f e r e n t
n u m b e r s of l a y e r s , when the length of the ingot H, G,
R, ~, and the " e f f e c t i v e n u m b e r of c h a n n e l s , " NC,
have the v a l u e s shown. The c u r v e s show that, except
for the ends of the ingot, as the n u m b e r of l a y e r s i n -
c r e a s e s the solute d i s t r i b u t i o n c o n v e r g e s to a s i n g l e
solution. As the n u m b e r of l a y e r s i n c r e a s e s (i.e., the
size of l a y e r s d e c r e a s e s ) , the a s s u m p t i o n that the flow
r a t e b e t w e e n l a y e r s (q) is s m a l l (see Appendix A) c o m -
p a r e d to the a m o u n t of liquid in each l a y e r , no l o n g e r
holds. This b r e a k d o w n would appear f i r s t at the e x -
t r e m e ends of the ingot, t h e r e f o r e the end c o m p o s i -
tions shown in Figs. 8 through 12 a r e not c o n s i d e r e d
m e a n i n g f u l when they differ by m o r e than about 20 pct
of the m e a n value. However, within this l i m i t a t i o n , the
shape of the c u r v e s and the i n t e g r a t e d amount of solute
VOLUME 5, DECEMBER 1974-2545
 0

at NC = 1'7 x 10e ~ R 025 rn/,eo

NC = 3"5 x I0~ /i R=OIO "
// ~R=O05 "

o length of costing (H) = 14crn

temperature gradient (G) : I 5=C/cm o J .. ,e.g,, of cost,.Q oH): ,4cm
growth rote (R} = 0 0 0 5 cm/sec temperature qrodient (G) = I 5~
~ ~ ~ N C = 6"0 X I0" visr of the liquid = O 03 poise cm/sec number at channels (NC)=06x IC5
number of layers (L) = 28 ,~ t viscosity ~ the liquid = 0"03 poise
number of layers (L) = 28

DO ' 2r0 ' 470 ' 6tO ~ 8TO IOTO 1270 14'0 O J -w
~0 O ~]0 4~0 6FO ' 8:0 ' tOlO 1 ~2'0 ' t41C
DISTANCE FROM BOTTOM OF CASTING (cm)
OISTANCE FROM BOTTOM OF CASTING (cm)
Fig. 9--Solute distribution as a function of the structure (ef-
fective number of channels). Fig. ll--Solute distribution as a function of growth rate.

~ M
H=Scm
= ~ _ _ = ; H : [4 r ~
~. H=lOcm

~ " _

E p
/ number of channels (NC) =O-6x IOs numberof layers (L) =28
oj viscosity of the liquid 9 O-O~peise
number Of layers ( L ) - 2 B
~
9 DO 0 2:0 4'0 6:0 8'0 I0:0 12'0 14'O
| o:, dz o:3 o~, o:5 o~ dr o'.a o:9 ,.'o DISTANCE FROM BOTTOM OF CASTING (cm}
DISTANCE F ~ BOTTOM OF CASTING(X/H)
Fig. 12--S01ute distribution as a function of temperature
Fig. 10--Solute distribution as a function of ingot height. gradient.

which h a s m o v e d f r o m the b o t t o m of the ingot to the top

a r e a m e a s u r e of the r e l a t i v e amount of m a c r o s e g r e g a - Table III. Solidification Variables Used for Theoretical Plots
lion.
The s t r u c t u r e of the s o l i d liquid r e g i o n is e x p r e s s e d Fig. No. 1(a) 1(b) 1(c)
in t e r m s of the " e f f e c t i v e n u m b e r of c h a n n e l s " (NC) Temperature Gradient (G) ~ 1.5 1.5 2.3
w h e r e N C = nT3A (A = c r o s s s e c t i o n a l a r e a of the ingot) Growth Rate (R) cm/sec 0.0047 0.013 0.011
and the s o l u t e p r o f i l e s f o r d i f f e r e n t v a l u e s of N C a r e Length of Casting (//) cm 14 14 14
shown in F i g . 9. It can be s e e n that the amount of m a c - Number of Channels (NC) = n~-3A 2.96 X l 0 s 4.24 • l 0 s 8.86 X lOs
Viscosity of the Liquid (p) poise 0.03 0.03 0.03
r o s e g r e g a t i o n , c o n s i d e r e d in t e r m s of the amount of
Number of layers 28 28 28
s o l u t e which m o v e s f r o m the b o t t o m half of the c a s t i n g AC (theoretical) 1.95 0.39 0.31
to the top, i n c r e a s e s a s N C d e c r e a s e s . Since N C is r e - ~C (experimental) 1.07 0.73 O. 13
l a t e d to the d e n d r i t e s p a c i n g , t h i s m e a n s that for l a r g e r
s p a c i n g s the r e s i s t a n c e to flow t h r o u g h the s o l i d - l i q u i d
r e g i o n d e c r e a s e s . T h e r e f o r e , f o r the s a m e p r e s s u r e quently m o r e flow, when a l l o t h e r v a r i a b l e s a r e h e l d
d r o p t h e r e is m o r e flow. c o n s t a n t . The r e a s o n why t h i s a p p e a r s to c o n t r a d i c t
Fig. 10 shows the s o l u t e d i s t r i b u t i o n as a function of e x p e r i e n c e is that high t e m p e r a t u r e g r a d i e n t s a r e u s u -
ingot height. As the h e i g h t i n c r e a s e s , so the fluid head a l l y a s s o c i a t e d with high growth r a t e s , and it is not
will i n c r e a s e , c a u s i n g m o r e flow t h r o u g h the m u s h y n o r m a l l y f e a s i b l e to v a r y t h e s e two p a r a m e t e r s i n d e -
zone. H o w e v e r , t h i s o n l y a p p l i e s when the length of pendently.
the m u s h y zone can he equal to the ingot height. The
t h e o r e t i c a l length of the m u s h y zone i s ( T L - T E ) / G ,
COMPARISON WITH E X P E R I M E N T
which f o r the c o n d i t i o n s u s e d in F i g . 10 is 62 c m .
Fig. 11 shows that the amount of m a c r o s e g r e g a t i o n The d a t a used to g e n e r a t e the t h e o r e t i c a l c u r v e s in
i n c r e a s e s a s the growth r a t e d e c r e a s e s . This would F i g . 1, t o g e t h e r with t h e o r e t i c a l and e x p e r i m e n t a l v a l -
b e e x p e c t e d , s i n c e the amount of t i m e a v a i l a b l e for the ues of m a c r o s e g r e g a t i o n a c c o r d i n g to the p r e s e n t d e f t -
flow i n c r e a s e s , as R d e c r e a s e s . F i g . 12 shows that the nition, a r e given in T a b l e HI. In g e n e r a l , the m o d e l
amount of m a c r o s e g r e g a t i o n i n c r e a s e s a s the t e m p e r - p r e d i c t s p r o f i l e s of the s a m e shape a s the e x p e r i m e n -
a t u r e g r a d i e n t i n c r e a s e s , c o n t r a r y to the s e m i - q u a n t i - t a l p l o t s , but the c o m p o s i t i o n s at the ends of the ingot
t a t i v e t h e o r y p r o p o s e d b y Copley, G i a m e i , e t al. z~ This do not a l w a y s a g r e e well with t h o s e p r e d i c t e d . This is
is due to s t e e p e r c o m p o s i t i o n g r a d i e n t s through the due to the a s s u m p t i o n s used in d e r i v i n g the m o d e l . In
m u s h y zone at h i g h e r t e m p e r a t u r e g r a d i e n t s , which addition to those already discussed, the Pfann equation
would l e a d to a h i g h e r d e n s i t y d i f f e r e n c e and c o n s e - does not take into account that the liquid composition

2 5 4 6 - V O L U M E 5, D E C E M B E R 1974 METALLURGICAL TRANSACTIONS


I r-'-~ ( - ~ l TL 6 ,
R4 ,q4
4 d e n d r i t i c c h a n n e l s have b e e n p r o d u c e d in the Pb-Sn
R3 ,q 3
(a) (b)
Fig. 13--(a) Assumed flow pattern showing two main flow
cells. (b) Resistances RI_~, and flowrates qt_~ for flow be-
tween six layers.
cannot r i s e above the e u t e c t i c c o m p o s i t i o n .
F o r F i g s . l(a) and (b) which w e r e s o l i d i f i e d under
the s a m e t e m p e r a t u r e g r a d i e n t , b u t with d i f f e r e n t
growth r a t e s and d e n d r i t e s p a c i n g s , both the t h e o r e t i -
c a l and e x p e r i m e n t a l r e s u l t s show m o r e m a c r o s e g r e -
gation at the l o w e r growth r a t e . F o r F i g s . l(b) and (c)
which w e r e s o l i d i f i e d at a p p r o x i m a t e l y the s a m e growth
r a t e , b u t with d i f f e r e n t t e m p e r a t u r e g r a d i e n t s and d e n -
d r i t e s p a c i n g s , the t h e o r y p r e d i c t s s l i g h t l y m o r e m a c -
r o s e g r e g a t i o n at the l o w e r t e m p e r a t u r e g r a d i e n t . This
i s q u a l i t a t i v e l y in a g r e e m e n t with e x p e r i m e n t . It should
b e noted t h a t although F i g . 12 p r e d i c t s l e s s m a c r o s e g -
r e g a t i o n at l o w e r t e m p e r a t u r e g r a d i e n t s (when a l l o t h e r
v a r i a b l e s a r e h e l d c o n s t a n t ) , t h i s effect has b e e n o u t -
weighed b y the d i f f e r e n c e in d e n d r i t e s p a c i n g . This
also corresponds with a p r e v i o u s i n v e s t i g a t i o n of
f r e c k l i n g , ~9 w h e r e it was r e p o r t e d that a r e d u c t i o n in
d e n d r i t e s p a c i n g e l i m i n a t e d f r e c k l e s in c o n s u m a b l e
a r c m e l t e d ingots.
Using the m o d e l p r e d i c t i o n s , it is p o s s i b l e to r e c -
o m m e n d a n u m b e r of c h a n g e s in c a s t i n g p r a c t i c e that
would r e d u c e g r a v i t y s e g r e g a t i o n e f f e c t s in v e r t i c a l
directional castings:
1) R e f i n e m e n t of the d e n d r i t i c s t r u c t u r e will in-
c r e a s e the r e s i s t a n c e to flow t h r o u g h t h e m u s h y zone.
2) R e d u c t i o n of ingot height for a l l o y s with a wide
f r e e z i n g r a n g e w i l l r e d u c e the d r i v i n g f o r c e for flow.
3) I n c r e a s i n g the growth r a t e will r e d u c e the t i m e
a v a i l a b l e for flow.
4) D e c r e a s i n g the t e m p e r a t u r e g r a d i e n t will r e d u c e
the d r i v i n g f o r c e f o r flow. H o w e v e r , t h i s r e c o m m e n -
dation should b e a p p l i e d with c a r e . Although the m o d e l
p r e d i c t s a d e c r e a s e in m a c r o s e g r e g a t i o n , t h i s would
only be the c a s e if a l l o t h e r s o l i d i f i c a t i o n v a r i a b l e s
remain constant.
COLIC LUSIONS
M a c r o s e g r e g a t i o n can o c c u r d u r i n g u n i d i r e c t i o n a l
s o l i d i f i c a t i o n of l e a d - t i n a l l o y s due to c o n v e c t i v e flow
c a u s e d b y the f o r m a t i o n of a l e s s d e n s e liquid in the
i n t e r d e n d r i t i c r e g i o n s . Under t h e s e c o n d i t i o n s , t h e r e
is a net flow of s o l u t e along the c a s t i n g which can p r o -
duce a c o m p o s i t i o n p r o f i l e s i m i l a r to n o r m a l s e g r e -
gation for a p l a n a r s o l i d - l i q u i d i n t e r f a c e . E x p e r i m e n t s
showed that t h i s p r o f i l e i s a function of the growth r a t e ,
t e m p e r a t u r e g r a d i e n t , d e n d r i t e s p a c i n g , and a l l o y c o m -
position.
A n u m e r i c a l m o d e l has b e e n p r o p o s e d which p r e -
d i c t s the c o m p o s i t i o n p r o f i l e s a s a function of the s o l -
i d i f i c a t i o n v a r i a b l e s . The d r i v i n g f o r c e f o r m a c r o s e g -
r e g a t i o n is the d e n s i t y d i f f e r e n c e in the i n t e r d e n d r i t i c
METALLURGICAL TRANSACTIONS
liquid, and the d e n d r i t i c s t r u c t u r e is c o n s i d e r e d to b e
a p o r o u s m e d i u m of v a r i a b l e p o r o s i t y . S h r i n k a g e t r a i l s
and p i p e s which o r i g i n a t e f r o m the w i d e n i n g of i n t e r -
s y s t e m when a d e n s i t y i n v e r s i o n e x i s t s d u r i n g s o l i d i -
f i c a t i o n and the growth r a t e s a r e v e r y low. T h e s e f i n d -
ings s u p p o r t the m e c h a n i s m for f r e c k l e f o r m a t i o n p r e -
viously proposed.
APPENDIX A
REDISTRIBUTION OF SOLUTE BY
FNTERDENDRITIC FLUID FLOW
The assumed flow pattern through the solid-liquid
r e g i o n c o n s i d e r s that flow can take p l a c e v e r t i c a l l y
f r o m one l a y e r to the next, and h o r i z o n t a l l y through
the l a y e r . F o r v e r t i c a l flow, half the c r o s s s e c t i o n a l
a r e a c o n t r i b u t e s to downward flow, and half to u p w a r d
flow. Fig. 13(a) shows the a s s u m e d flow p a t t e r n with
two m a i n flow c e l l s . H o w e v e r , p r o v i d e d downward and
u p w a r d flow e a c h o c c u p y half the c r o s s s e c t i o n a l a r e a ,
the a c t u a l n u m b e r of flow c e l l s is u n i m p o r t a n t . The
m o d e l d i f f e r s f r o m the p h y s i c a l s i t u a t i o n o b s e r v e d in
Fig. 3 in that it d o e s not c o n s i d e r fluid flow b e t w e e n
the m u s h y zone and the l i q u i d zone.
The r e s i s t a n c e of the d e n d r i t i c n e t w o r k to fluid flow
i s r e p r e s e n t e d s c h e m a t i c a l l y in Fig. 13(b). The r e s i s -
t a n c e s y m b o l s r e p r e s e n t p o r o u s m e d i a of a r e a equal
to half t h e c r o s s s e c t i o n a l a r e a of the c a s t i n g , and
length equal to the length of the l a y e r s . We a s s u m e
t h e r e is no r e s i s t a n c e to h o r i z o n t a l flow t h r o u g h the
l a y e r s , s i n c e the d i s t a n c e s w i l l b e s h o r t , e s p e c i a l l y
for a l a r g e n u m b e r of flow c e l l s .
P o r o u s l a y e r s s t a c k e d in t h i s m a n n e r o b e y the laws
of s e r i e s r e s i s t a n c e s , t h e r e f o r e , s i n c e the m a g n i t u d e
of the r e s i s t a n c e can be c a l c u l a t e d in t e r m s of the
liquid f r a c t i o n and s t r u c t u r e , and the p r e s s u r e d r o p
i s known, the v e l o c i t y of the i n t e r d e n d r i t i c l i q u i d
(v/gL) can b e c a l c u l a t e d u s i n g D a r c y ' s Law. The flow
r a t e of i n t e r d e n d r i t i c liquid (q) is then equal to 2 v / A g L,
w h e r e A is the c r o s s s e c t i o n a l a r e a of the ingot. F o r
b r i e f t i m e i n t e r v a l s At, t h e quantity of l i q u i d which
flows b e t w e e n l a y e r s w i l l be s m a l l , t h e r e f o r e the d r i v -
ing f o r c e for flow is a s s u m e d to r e m a i n c o n s t a n t .
In F i g . 13(b), s i x l a y e r s a r e shown, the r e s i s t a n c e s
b e t w e e n the l a y e r s a r e n u m b e r e d RI_ ~, and the flow
r a t e s a r e q~-s. The liquid c o m p o s i t i o n s of e a c h l a y e r ,
e x p r e s s e d a s weight p e r unit v o l u m e , a r e equal to
(pLCL)I_6. The v o l u m e s of the l a y e r s , VI_6, r e m a i n
constant.
E a c h l a y e r e x c h a n g e s l i q u i d with the a d j o i n i n g l a y -
e r s , and following t h i s notation, the v o l u m e flow r a t e
a c r o s s the top and b o t t o m s u r f a c e s of the i - t h l a y e r
a r e qi and qi-1, r e s p e c t i v e l y . A s o l u t e m a s s b a l a n c e
c a n , t h e r e f o r e , b e w r i t t e n f o r the i - t h l a y e r :
d
Vi ~ (pLCL)i = qi.l(PLCL)i_l + qi(PLCL)i.l
-- (qi + qi-1) (PLCL)i
This m a s s b a l a n c e can b e w r i t t e n for e a c h l a y e r ,
giving a s e r i e s of s i m u l t a n e o u s o r d i n a r y d i f f e r e n t i a l
equations which c a n be s o l v e d for the c o m p o s i t i o n of
e a c h l a y e r a f t e r a t i m e i n t e r v a l Z~t u s i n g s t a n d a r d nu-
merical methods.
VOLUME 5, DECEMBER 1974-2547
 ACKNOWLEDGMENT
Financial support provided by the National Research
Council and the Killam Foundation is gratefully ack-
nowledged.
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METALLURGICAL TRANSACTIONS