Proceedings of the 2013 International Symposium on Liquid Metal Processing & Casting

Edited by: Matthew J. M. Krane, Alain Jardy, Rodney L. Williamson, and Joseph J. Beaman
TMS (The Minerals, Metals & Materials Society), 2013

EFFECT OF SOLIDIFICATION FRONT ANGLE ON FRECKLE FORMATION IN ALLOY 625

Koji Kajikawa, Masaru Tanaka, Tomoki Sawada, and Shigeru Suzuki
The Japan Steel Works, Ltd.; 4 Chatsu-machi, Muroran, Hokkaido, 051-0006, JAPAN

Keywords: Freckle, Channel segregation, solidification, solidification front angle, Ni-base alloy

Abstract Weinberg’s group performed several vertical directional

experiments. Kaempffer and Weinberg6) used a Cu-8mass%Ag
Freckle formation depends on solidification front angle in ingots. alloy whose interdendritic liquid was denser than the bulk liquid.
Freckles can be divided into two types; one is a solute-enriched They found that there seems to be no segregation plume and only
liquid trail growing upward and the other is a solute enriched the displacement of interdendritic liquid occurred at the bottom of
liquid trail growing downward. The effect of solidification front the ingot. Also, Streat and Weinberg7) used Sn-Pn binary alloy
angle on upward type freckling alloy was reported by Sakurai et and, by changing its composition ratio, two types of segregation
al. However there are few studies on the effect on downward type tendencies were studied. In upward type segregation alloy Pb-
freckling alloys. In this study, the effect of solidification front 20mass%Sn, macro segregation plumes appeared. These
angle on freckle formation was investigated using downward type originated in the interior of the ingot as an interdendritic channel,
freckling Alloy 625. Although freckle becomes difficult with which subsequently widened and moved towards the mold wall.
decrease in the solidification front angle as expected, the effect on However, Sn-4mass%Pb, which was selected as an example of a
its solidification front angle was larger than that on upward type composition where the interdendritic liquid would be denseer than
alloy A286. It is suggested that the difference is due to the freckle the bulk liquid above, did not show any segregation plumes.
formation mechanism These results suggest that the freckle tendency of the downward
type alloy is different from that of the upward type alloy.
Introduction
Our previous study8) showed that freckling tendency can be
"A" segregation (inverted “V” segregation) is one form of marshaled by using liquid density difference and freckle
macrosegregation that appears in conventional cast ingots. This formation index proposed by Suzuki and Miyamoto 8). The study
form of segregation is often termed “channel type segregation” or indicated the importance of distinguishing upward type
“freckle” (the term “freckle” is commonly used in Ni-based segregation from downward type segregation. There are few
superalloy field). It is widely accepted that freckle (channel type studies on the effect of the solidification front angle on freckle
segregation) is induced by gravity-driven flow. Freckle appears in formation in downward segregation alloys. Also few articles
some specific solid fraction.1) discuss formation of the two freckle types.

Experimental literatures reported the effect of solidification front In this study, we investigated the effect of the solidification front
angle on freckle formation. Sakurai et al.2) studied the effect of angle on freckle formation in the case of the downward type
the solidification front angle on freckle formation in A286 alloy segregation alloy.
using a horizontal directional solidification furnace and assessed
the effect quantitatively. The result revealed that lowering Si and Experimental procedure
Ti contents and reducing the liquid pool angle, which
corresponded to shallow liquid pool in an actual ESR ingot, were Alloy 625 was selected for this experiment, because the value of
favorable for reducing "A" segregation (channel type the freckle formation index2) of the alloy is close to that of A286
segregation). that was reported by Sakurai et al. If the value is too small, it may
be impossible to form freckle in the tilted solidification front
Wan-hong Yang et al. 3) conducted similar experiments, however, condition. Also Alloy 625 is a typical downward type freckling
they did not distinguish between upward type and downward type alloy8).
segregation. Also, they did not show the macrostructure of their
tilted solidification experiment ingots and it is difficult to know The horizontal directional solidification furnace used for this
the details of the experimental results. Auburtin et al. 4) showed study is schematically illustrated in Figure 1. The furnace is a
the effect of the solidification front angle on freckle formation. rectangular-shaped resistant heat furnace using a Kanthal Super
However, their freckle is not channel type segregation but a heater. An Al2O3 crucible was used for the experiment. The inner
freckle in dendrite arms. size of the crucible was 55Wx190Lx230Hmm. The chiller was
cooled by compressed air. In order to simulate the titled
In terms of liquid density difference, researchers have identified solidification front condition, specially designed chillers were
two types of freckle based on the liquid density difference used for this experiment. The designs of the chillers are shown in
between bulk liquid and solute enriched liquid. Grugel and Figure 2.
Brush5) used Sn-Pn binary alloy and two alloy compositions, Pb-
45mass%Sn and Pb-75mass%Sn, were selected for investigation. The chillers are composed of silicate sand filled in stainless steel
The 45mass% tin alloy is a less-dense solute alloy. In contrast, the casing. In this series of experiments, the chiller angle of the
75mass% tin alloy is a dense solute alloy. Although the 45mass% original straight shape was 90 degrees. 60, 45, and 30 degree
tin alloy showed freckles in the ingots, there are few freckles in chillers were made in addition to 90 degrees. In order to work the
the 75mass% alloy ingots. slope portion as the major cooling interface, silicate sand on the
straight portion of the top side of the chiller was thicker than that

181
on the slope portion. This thicker sand portion acted as a type of
insulation. 1400
1380 CH1
CH2
Cooling air Thermocouple Chiller side 1360 CH3
Solidified CH4
alloy 1 2 3 4 5 6 1340 CH5

Temperature（℃）
Chiller
1320
Heater
Growth 1300
direction
1280
Growth 1260
direction
Crucible 1240
Height :200mm
Width : 55mm 1220
Length: 70mm
1200
Furnace
0 20 40 60 80 100
Time from teeming start(min)
Figure 1. Schematic of the horizontal directional solidification Figure 3. Thermal history of 60 degree chiller ingot
furnace
1400
1380 CH1
Thermo couple CH2
chiller
1360 CH3
1340 CH4

Temperature（℃）
metal
CH5
1320
1300
1280
1260
1240
30° 45° 60° 90° 1220
Chiller angle 1200
0 20 40 60 80 100
Figure 2. The chillers used for the experiment Time from teeming start(min)

The alloy was melted in an induction furnace and poured into the Figure 4. Thermal history of 30 degree chiller ingot
crucible using a small ladle. Just after pouring, cooling air was
blown into the chiller. The cooling rates were controlled by the In each photograph, left hand side arrays are the chiller side. The
flow rate of the compressed air. Thermocouples were inserted into directional solidified structure was obtained in each condition
the crucible in order to acquire the temperature profile during although the primary crystal structures were not perpendicular to
solidification. The ingots were cut perpendicular to the cooling the chiller face. Yellow dotted lines in both figures indicate
interface. The cut plane was polished and macro etched to confirm freckles observed in the ingots
the existence or non-existence of freckles in the ingots. If freckles
were found in the ingot, the ingot was cut on the vertical cross Chiller face angle, chemical composition, liquid density
section of the freckle spot that is close to the chiller face. The difference, and freckle formation index in each experiment are
cooling rate (K/min) and growth rate R(mm/min) are obtained shown in Table 1. Liquid density data10-13) and Thermo-calc14)
from the thermal history of the ingot. By using those two values, with Ni-data15) were used for the liquid density calculation. There
are some deviations in the chemical composition.
freckle formation index = ･ R1.1 was calculated. Chemical
analysis of the alloy was conducted by an X-ray fluorescence Accordingly, liquid densities vary slightly. However, the
method. deviation is not too large to analyze the condition of freckle
formation. The relationship between freckle formation indexes
Results and chiller angles is shown in Figure 7. In this figure, the freckle
formation criterion proposed by Suzuki and Miyamoto8) was used
Examples of the thermal histories of the ingots are shown in for the vertical axis. The criterion is an empirical value come from
Figures 3 and 4. In the 30 degree chiller experiment, the sequence their experimental results. The equation of the criterion is
of 4CH and 5CH was reversed, i.e., 5CH was solidified faster than expressed as follows:
4CH. This may be because the location of 5CH is close to the face
and the liquid mass was small. However the freckle initiation
α = ε R1.1 (1)
point was far from 5CH; therefore, data was considered usable for
freckle formation condition analysis. where α is a critical freckle formation index, ε is the cooling rate,
and R is the growth rate. This α means that if the actual
The vertical cross section of each ingot is shown in Figures 5-6.
solidification condition exceeds the value, freckle forms. There
Hereafter, the straight chiller is described as a 90 degree chiller.
seems to be a relationship between the chiller face angle and

182
freckle formation index, i.e., if the chiller angle is smaller, the
freckle formation index becomes smaller. This tendency is almost 8.0
the same as the result of upward segregation alloy A286 2). Alloy625

ε･R1.1(K/min･(mm/min)1.1)
Freckle formation index
However, it is noteworthy that the result of 45 and 30 degree A286※
chiller. In this angle, freckling tendency is steeply decreases 6.0 ※Sakurai et al.：
compared to that of A286. This figure suggests that the effect of

Freckle prone
Tetsu-to-Hagane,
the solidification front angle on freckle formation in downward 74 (1988), p. 2286

type segregation alloy is larger than that of the upward type 4.0
segregation alloy.

2.0

0.0
0 30 60 90
chiller

Chiller angle (deg.)

Figure 7. The relationship between freckle formation indexes and
chiller angles
chiller

Solidification front angles are slightly different from the chiller

60°
angles. The solidification front angles were estimated from
primary dendrites morphology in the ingots. The angles in A286
ingots were estimated from the photographs of each macro etched
structure. The relationship between freckle formation indexes and
50mm 50mm
solidification front angles is shown in Figure 8. Although the
tendency of the curvature is the same as the diagram using the
Figure 5. Vertical cross section of 90 and 60 degree chiller ingots chiller angle, the convex shape shifts toward the lower angle side.
This figure suggests that the effect of the solidification front angle
on freckle formation may be marshaled factor that utilize the
angle.

8.0
※Sakurai et al.：
Alloy625
ε･R1.1(K/min･(mm/min)1.1)

Tetsu-to-Hagane,
Freckle formation index

A286※ 74 (1988), p. 2286

6.0
Freckle prone

4.0

chiller 2.0
45°
chiller
30°

50mm 0.0
50mm
0 30 60 90
Figure 6. Vertical cross section of 45 and 30 degree chiller ingot
Solidification front angle (deg.)
Figure 8. The relationship between freckle formation indexes and
solidification front angles
Table 1: Chemical composition of test alloys (mass %)
Angle Chemical composition ⊿ρ
deg C Ni Cr Mo Al Ti Nb Fe g/cm3 Discussion
90 0.055 64.06 20.35 9.00 0.12 0.23 3.56 2.34 0.0115
60 0.046 63.30 21.18 8.86 0.24 0.19 3.60 2.28 0.0134 As described above, the chiller face angle is not equal to the
45 0.049 63.04 21.23 8.96 0.21 0.19 3.59 2.62 0.0118
30 0.025 63.10 21.36 8.93 0.16 0.17 3.57 2.57 0.0132 solidification front angle. The solidification front angle in the
horizontal directional solidification experiment is around 70 – 80
degrees in the case of the straight shape chiller that gives a 90
degree angle. The freckle formation index proposed by Suzuki
and Miyamoto9) is considered to be the index for the solidification
front angle of 70 – 80 degrees. The freckle formation index
indicates good prediction for freckling location in conventional
ingots 16,17), because the solidification front angle in the side mold

183
is in the same range as the solidification front angle in the
horizontal directional solidified ingot. In the previous study8), the
90 degree chiller and the freckle formation index were used to R
evaluate the freckling tendency of commercial alloys. Our unified
evaluation was successful using the same experimental condition
and the same index for each alloy. The freckle formation index
g・cosθ g・sinθ
worked well for the evaluation.

g
θ
Figure 9. A vector diagram of gravity induced force at the tilted
solidification front

Here, in order to simplify the problem, other effects such as bulk

liquid convection are ignored. In this figure, the component of
gravity force parallel to the solidification front is extracted using
sin. The driving force of the flow direction is expressed using
liquid density difference, gravity and the angle.

Wan-hong Yang et al. 3) reviewed all freckling criteria, including

Fleming’s solute redistribution equation19), several Rayleigh
criteria20-26), and so forth. There should be interdendritic flow
owing to solidification shrinkage and bulk liquid convection.
They ultimately proposed that freckle formation criterion G･R
Figure 9. Vertical cross section of 90 and 60 degree chiller A286 divided by sin is the freckle formation index for the tilted
ingot solidification front angle. They proposed the following equation
for freckling criterion.
G  R 2.1
 (2)
sin 
where G is temperature gradient, R is growth rate and  is the
angle of solidification front from the horizontal line. G ･ R2.1
equals ･R1.1 in the steady state solidification.

Freckle formation is affected by fluid flow 18). In order to discuss

the effect of fluid flow on the freckle formation, numerical
simulation was performed. The model did not consider
solidification for simplification and only the effect of the tilted
solidification front on fluid flow is discussed. The convection
driven by the intentionally given driving force was considered to
be affected by the solidification front angle. The driving force in
the system is solutal convection only. The governing equations in
the model are as follows:

u p  c  
 u  u    2u  1  L g (3)
Figure10. Vertical cross section of 45 and 30 degree chiller A286 t    0 cL 
ingot
cL
The macro structure of A286 alloy horizontal directional  u  cL  D 2cL (4)
t
solidified ingots using tilted chillers is shown in Figures 9, 10. All
freckle streaks shown here grow upward and the directions are where u is flow rate, D is Diffusion coefficient, p is pressure, is
almost the same regardless of those solidification front angles. dynamic viscosity, g is gravity force, is liquid density, and CL is
Meanwhile, in contrast to conventional cast ingots, solidification chemical composition of the liquid. In the calculation, the order of
proceeds with a more angled solidification front in the secondary the ratio of dynamic viscosity and diffusion coefficient (Pr
melt process such as ESR and VAR. The experiment aimed to number in solute) was accorded with liquid metal and viscosity
simulate the tilted solidification front. The effect of the was increased to prevent turbulent flow.
solidification front angle is considered using a vector diagram. A
vector diagram of gravity induced force at the tilted solidification Maximum flow rates were compared at the steady state using the
front is shown in Figure 9. model. It may be necessary to consider the solute distribution in
the liquid. The flow rate equation by solutal effect is expressed as
the following formula:

184
 D 1  Thermosolutal convection in the mushy zone affects freckle
U2  g cL L (5) formation in an ingot, which may account for the deviation.
  cL Although there is some deviation in freckle formation indexes
Where g’ is the component of gravity force and L is characteristic derived from the horizontal directional solidification experiment,
length. The value g’ along with the solidification front is g･sin this method showed the tendency of freckling. Simple criterion
Accordingly, the flow rate would relate to the solidification front such as ･R1.1or G･R2.1 is desirable from an industrial perspective.
angle . Figure 10 shows the fluid flow simulation result. Criterion using , R, G may need further modification to make
more precise estimation for freckle formation at tilted
4.00 104 solidification front.

The effect of the solidification front angle on freckle formation

varies depending on the type of freckle, such as upward type and
2.00 104 downward type. There are two types of freckle suppression
mechanism. Figure 12 is a schematic of freckle formation in the
tilted solidification front for upward type and downward type
segregation.
0.00   60 deg   30 deg
Liquid
U max  4.00 104 U max  1.76 104 Gravity
Liquid
induced
driving
Figure 10. Fluid flow simulation result in tilted side wall force
Growth Growth
direction direction
The result indicates that the flow rate at the tilted wall depends on
the angle. If the gradient becomes shelved, the flow rate is small. Freckle Freckle
It is important to note that the flow rate is not exactly proportional
to sin. CL in equation (5) also depends on the side wall angle
because solute distribution in the vertical direction varies in the Gravity
calculation. The result shows that if the solidification front angle solid induced solid
decreases, flow rate at the solidification front decreases. driving force
Upward type Downward type
There should be other effects on the freckle formation in the tilted
solidification front. Modification of freckle formation criterion Figure 12. The effect of tilted solidification front for freckle
may be required. Figure 11 shows the value derived from formation
multiplying the freckle formation index at the 90 degree chiller by
sin One is in the case of upward type segregation formation alloy.
Freckle streak formed in solidification grow upward owing to its
density difference from bulk liquid. If the solidification front is
8.0 tilted, the direction of freckle floating up is close to the
solidification direction. The formed freckle streak proceeds
ε･R1.1(K/min･(mm/min) 1.1)

toward low solid fraction direction. Morikawa et.al. made a series

Freckle formation index

6.0 of experiment that cast ingots were inclined in some solidification

period. Carbon steels that are typical upward type segregation
alloy were used for their study. Figure 13 is schematic drawing of
freckle observation in the inclined ingot 9) based on the result of
4.0
90° Morikawa et.al. experiment27).
60°
2.0 45°
30°
sinθ
0.0
0 30 60 90
Solidification front angle (deg)
Figure 11. The effect of sin for the freckle formation indexes

The values of the indexes at 60 degrees and 45 degrees are larger

than that of multiplying the index at 90 degrees by sin. Since the
deviation of 60 degree and 45 degree values is large, simple Figure 13. Schematic model of inclined ingot26)
modification using sin may not be able to evaluate the effect of
the solidification front angle on freckle formation. They reported that if a carbon steel ingot is inclined during
solidification, the diameter of the freckle streak becomes large and
it disperses toward the upper direction. The result suggests that a

185
solute-enriched liquid would be easy to diffuse at the tilted 3. Simple modification using sin may not be able to evaluate
solidification front in upward type segregation alloys. This may be the effect of the solidification front angle on freckle
the effect of freckle suppression by the tilted solidification front formation.
for upward type segregation. 4. The effect of the solidification front angle on freckle
formation varies depending on the type of freckle, such as
In contrast, solute-enriched liquid is dense in downward type upward type and downward type.
freckling alloys. In the case of downward type segregation, 5. There are two types of freckle suppression mechanism. The
gravity driven force owing to liquid density difference is in the suppression mechanism in downward type segregation is
direction of the reverse of upward type segregation. Therefore, different from that in upward type segregation.
solute-enriched liquid tends to move toward the bottom of the
ingot. If the solidification front is tilted much (freckle growth References
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186