The influence of magnesium treatment and silicon post
P r i n c i p l e s I n v o l v e d in t h e
U s e of C o o l i n g Curves
in D u c t i l e Iron
Process Control
by M . D . Chaudhari, Metallurgist a n d Materials
Engineer,
Baker Manufacturing Co., Evansville, Wisconsin,
R. W . Heine a n d C. R. Loper, Jr., Professors,
Dept. of Metallurgical Engineering,
University o f Wisconsin, M a d i s o n , Wisconsin
ABSTRACT
Solidification characteristics of hypo- and hypereutectic cast
irons were investigated by the cooling curve method. The
eutectometer cooling curves reported in this paper were
obtained for gray irons, nickel-magnesium treated irons and
final irons melted in laboratory induction furnaces.
Significant features of the cooling curves are defined. These
features are discussed with reference to corresponding
microstructures in eutectometer samples in order to dissect the
ductile iron solidification process.
A n attempt is m a d e to resolve certain controversies regarding
the occurrence of an anomalous arrest which has been observed
usually on gray iron curves. A calculation is shown to prove the
existence of a primary graphite liquidus o n curves of
hypereutectic alloys.
It is shown that magnesium treatment of a hypoeutectic gray
iron causes insignificant change in the austenite liquidus
temperature and that a similar treatment of a hypereutectic gray
iron causes suppression ofthe graphite liquidus temperature by
as much as 100 F (55.5 C).
AFS Transactions 74-96
inoculation on the eutectic arrest temperatures is discussed. The
hypoeutectic gray irons exhibit a dome-shaped bulk eutectic
arrest and the hypereutectic gray irons generally exhibit a more
or less flat eutectic arrest. Following a M g addition, the
hypoeutectic alloys show a flat or a continuously declining
eutectic arrest. O n the other hand, the Mg-treated hypereutectic
alloys feature a distinct eutectic initiation arrest followed by a
dome-shaped eutectic arrest.
The effect of silicon post inoculation of a Mg-treated melt is to
bring the eutectic arrest temperatures close to the equilibrium
temperature for graphite eutectic.
The features associated with desirable microstructure are
discussed. It is concluded that a strong correlation exists
between the eutectometer cooling curves and the
microstructures in the corresponding eutectometer samples.
Introduction
Cooling curves have been used for several years in cast iron
foundries to determine carbon equivalent (CE) from liquidus
arrest temperatures. N o extensive work1"* has been performed,
however, on the possibility of predicting the as-cast
microstructure by a cooling curve control test before pouring
the production molds. It was the object of the investigation to
examine the possibilities for following the course of
solidification of ductile irons, the kind of microstructure that
develops during solidification events detected by eutectometer
cooling curves and its potential for process control.
This paper deals with the portion ofthe work performed since
the publication of a preliminary report4 by the authors, and it is
presented in two parts. This part deals with the fundamental
aspects ol dissection of the solidification process in its
relationship to the cooling curve. The second part1" describes
several ways of utilization of cooling curves in ductile iron
process control.
Specifically, the cooling curve technique and sample known
as the eutectometer was employed to obtain results. This use of a
standardized mold resulted inconsistent heat dissipation during
431
 irPOEuTECnc IRONS EUTECTIC IRONS MILDLY HYPEREUTECTIC IRONS STRONGLY HYPEREUTECTIC
@ IRONS
PRIMARY LIOUIDUS
CORRESPONDS TO PRECIPI-
TATION OF AUSTENITE OR
GRAPHITE IS NOT IDENTI- GRAPHITE
FIABLE ON SUCH COOLING 'LIOUIDUS (TGL)
BEGINNING OF CURVES INITIAL TEI INITIAL NUCLEATION
BULK EUTECT NUCLEATION AND LIMITED GROWTH
TEU GROWTH i<_BFGINNING OFANO LIMITED GROWTH OF EUTECTIC
BULK EUTECTIC GROWTHOF EUTECTIC
TIME

KEY TO SYMBOLS USELp THUS

T - TEMPERATURE TAL DENOTES THE TEMPERATURE AT WHICH PR MARY AUSTENITE FORMS IN HYPOEUTECTIC IRON MELTS
AUSTEMTE TGL DENOTES THE TEMPERATURE AT WHICH PRIMARY GRAPHITE FORMS IN HYPERUTECTIC IRON MELTS
I LIOUIDUS TEN DENOTES THE TEMPERATURE AT WHICH INITIAL NUCLEATION AND LIMITED GROWTH OF EUTECTIC OCCURS (THIS ARREST IS ABSENT ON CURVES 8 @ ABOVE
E - EUTECTIC TEU DEMOTES THE LOWEST TEMPERATURE TOWH.CH IRON MELTS UNDERCOOL PRIOR TO BEGINNING OF BULK, EUTECTIC Gf!OWTH
N - NUCLEATION TER DENOTES THE MAXIMUM TEMPERATURE ON EUTECTIC ARREST, WHICH RESULTS FROM RECALESCENCE OUE TO LATENT HEAT OF SOLIOIFICATION
U- UNDER-COOLED OF EUTECTIC PHASES
fi - RECALESCENCE OFTEN TER TEU, AS SHOWN BY CURVE ABOVE
G - GRAPHITE TS DENOTES THE SOLIDUS TEMPERATURE FOR THE ALLOY (GENERALLY DIFFICULT TO IDENTIFY ON EUTECTOMETER COOLING CURVES)
S - SOLIDUS BY DEFINITION THE REFERENCES QUOTED IN THE TEXT. REFER APPENOI*
(TEN-TEU) ' EUTECTIC UNOERCOOLING
Fig. 1. Typical e u t e c t o m e t e r cooling c u r v e illustrating the n o m e n c l a t u r e u s e d in text.
I 'ER -TEU I EUTECTIC RECALESCENCE
-FOP ALTEPNATivE 'F = MiNCLOGY USED IN SOME OF

COOLING curves for hypo and hypereutectic gray iron M E L T S

mold: l sn mk-it (plain) eutectometer
F
SI2-I H2500

S12-L ^.71 L.04 3.26

SL5-1 3.U2 1.40 3.49 2400
UCU 2.80 2.04 3.75
12UJ J.lb 2.o4 4.04
3201 3.53 2.20 4.26
1301 3.74 2.46 <..56
2201 3.H4 2.63 4.72
1401 4.06 2.56 4.91
24.; j 4.11 2.54 4.96

TIME (MINUTES)
Fig. 2. Note the following:
Hypoeutectic Irons
(Curves S12-1, S15-1, 1101, 1203 & 3201)
1) Austenite liquidus drops from 2319 F (12~70.5 C) on curves S12-1 to 2142 F (1172.2 C ) on curve 3201.
2) All eutectic arrests are recalescent type.
Hypereutectic Irons
(Curves 1301, 2201, 1401 & 2402)
1) Graphite liquidus absent in curve 1301.
2) Graphite liquidus rises from 2200 F (1204.4 C) on curve 2201 to 2335 F (1279.4 C) on curve 2402.
3) Little or no recalescence on strongly hypereutectic iron curves.
Dashed portion on three of the above curves indicates abnormal pattern as a result of thermocouple failure.
432 A T S Transactions
the solidification process, and thereby enables one to study the
relationship between the shape of the cooling curves and
microstructures obtained. Variations in the as-cast
microstructures can only be caused by variations in the freezing
process, and thus variations in the cooling curves. Analysis of
the cooling curve enables an evaluation of the corresponding as-
cast microstructure.
Nomenclature
To facilitate tabulation and analysis of the data a new
nomenclature was adopted to describe cooling curves. Listing
the temperatures for each stage of cooling in data tables reveals
the approximate shape ofthe cooling curve without recourse to
the actual curve. O n several occasions, it is difficult to assign
specific values ofthe thermal arrest temperatures. In such cases
it is better to refer to the average cooling rate in that particular
part ofthe cooling curve. Several schematic cooling curves are
shown in Fig. 1 to illustrate the nomenclature used in the text.
An appendix is included to clarify the notations used in some of
the references quoted in this paper.
Experimental Procedure
All cooling curves were obtained with standard eutectometer
samples. Sample dimensions are approximately 40 m m diam x
60 m m length and a sample weighs about 680 grams. The sources
of the samples are eutectometer samples cast at the University of
Wisconsin laboratory.
The base irons were treated with nodularizing agent using the
sandwich method. The treatment temperatures ranged between
2800 and 2900 F (1538 to 1593 C). Melts were held in the furnace
at about 2750 to 2800 F (1510 to 1538 C ) after treatment or
following post-inoculation as the case m a y be. High pouring
temperatures were intentionally employed with a specific
purpose oi' obtaining the liquid representing portion of the
cooling curve. Though this procedure impaired the possibility of
producing a fully nodular graphite structure, it helped to obtain
a variety of microstructural constituents along with the cor-
responding cooling curves.
Samples were drawn from the furnace using a small clay
graphite ladle. The time elapsed following nodularizing
treatment, before first samples were taken, varied between two
and eight minutes.
Cooling curves were obtained using single and multi-point
recorders. The chart speed was one inch per minute for all the
curves. The cooling curves included in the following discussion
are tracings of the originals. The accuracy rating for the
recorders is 0.5ff. for the span used. The recorders were
calibrated several times during the course of the investigation.
Several eutectometer castings representative of typical
cooling curves were sectioned transversely as close as possible to
the thermocouple tip and were carefully prepared for
metallographic examination. T o retain graphite particles
repeated etching and polishing technique was used and the time
on wheel was kept as short as possible. Nodularity ratings were
obtained using the nodule count method" (200X) when
necessary.
Controversial Features on Cooling Curves
A n o m a l o u s Arrest D u e to 'Thermocouple Failure
Considerable controversy surrounds the occurrence ol an
anomalous arrest5 which has been observed in the last portion of
some of the cooling curves. It was observed more often in the
base iron curves and was thought to be associated with
formation of a carbide-austenite eutectic. Several attempts to
reproduce this anomaly failed. Several examples of the
anomalous arrest m a y be seen in Fig. 2 (see curves 3201. 2201
and 2402 in the figure).
In order to determine the cause of the arrest m a n y eu-
tectometer castings were studied. All samples which gave the
anomalous arrests exhibit penetration of the melt into the
thermocouple sheath. Those samples which show normal
A F S Transactions
cooling curves do not indicate the presence of melt \Mthin the
protective refractory. Longitudinal sections were taken to
conlirm this. It was observed that the melt enters the refractory
tube due to dissolution ofthe bead coat and also due tocracking
ofthe tube itself. Failure ofthe refractory was further confirmed
by yet another test, A sample was kept in a 1:3 mixture of
bromine and methyl alcohol at about 50 C ( 140 F) for 24 hours
to dissolve the metallic matrix completely. Several cracks and
holes were observed in the refractorv.
Presence of hot metal in the cracked sheath results in a short-
circuit, thereby shifting the thermocouple hotjunction toa point
vertically below the thermal center where the thermocouple
bead is supposed to be normally located. In effect, the portion of
the cooling curve subsequent to this represents cooling of a new
hot junction.
Since the anomalous arrests were observed more often on
base iron curves, it is strongly believed that the partial failure of
thermocouple assembh is a result of an exogenous m o d e of
freezing of the corresponding irons. In such irons the melt
remains in contact with the thermocouple for a relatively long
duration because the solidification front travels from the surface
to the center of the casting.
Occurrence of Graphite Liquidus
It has been reported in the literature* that a primary arrest is
not seen on hypereutectic iron cooling curves because the
associated latent heat evolution is very little. In the initial stages
of the present investigation it was felt that this applies to the
entire range of hypereutectic compositions. However, the
laboratory experiments indicate that this is true onlv in the case
of mildly hypereutectic compositions. It has been repeatedly
observed that strongly hypereutectic irons do show prominent
primary arrests. The authors are ofthe opinion that these arrests
represent graphite growth. A n example is given below to prove
this.
Consider an iron containing about 4.06% C and 2.569c Si (see
curve 1401, Fig. 2). The graphite liquidus occurred at about 2298
F (1259 C ) in this sample. The following assumptions and data
are necessary to calculate the duration of the arrest:
I) Assume that all the primary graphite grew at 2298 F (1532
K). Subtracting an amount of about 0.69? C as combined
carbon, the amount of free carbon would be about 3.46c?.
2) Atomic weights: Fe = 55.85 grams; C = 12 grams. Casting
weight ~ 1.5 lbs. = 680 grams.
3) Latent heat1" of graphite precipitation: 4633 cal g.mole.
Specific heat of casting alloy: (1.84+ 4.66 x 10"' x Tical.K
per g m mole.
4) Average cooling rate at 2298 F (1259 C ) = 300F/min.
(I67C) = 3C sec. N o w . that latent heat evolved due to
graphite would be:
4633_x_680_| 0-03*6 __ 8950 calories.
Assuming an average cooling rate of about 300F/min.
(167C per min). in one second the temperature would drop
by 5 F (that is, by 3C). A loss of 3 C corresponds toa heat
loss ( A H ) from the eutectometer casting given by the
following equation:
A H = mass x sp. heat x temperature drop
Hence
690 x 0.965 x (1.84 + 4.66 x 10~3 x 1423) x 3
AH
55.85
= 656 x 8.48 x 3 55.85
= 300 calories
Thus, to dissipate 8950 calories from the casting approximately
30 seconds (8950; 300 * 29.80) would be required. This means a
433
 F
S5-2 2.54 1.63 3.08 0.023 25 .__ COOLING CURVES FOR NI MG TREATED HYPO S HYPEREUTECTIC CAST 2500
S3-2 2.81 1.74 3.39 0.059 50
S2-2 3.06 1.81 J.bb 0.098 39 IRON MELTS
1211 3.13 2.53 3.97 0.067 3d 57 V = M 2450
j 203 3.46 2.17 4.18 0.062 18 72 MOLD: STD. L8N MK-n(PLAIN) EUTECTOMETER
1309 3.74 2.43 4.55 0.058 29 85
2203 3.76 2.72 4.67 0.056 33 81
2303 3.91 2.60 4.78 0.055 70 92 2400
1409 4.02 2.56 4.87 0.060 120 100
2407 4.07 2.61 4.94 0.042 io; 96 none S5-2

2000
TIME (MINUTES)
Fig. 3. Note the following:
Hypoeutectic Irons
(Curves S5-2, S3-2, S2-2, 1211 & 3203)
1) Austenite liquidus drops from 2358 F (1292.2 C) on curve S502 to 2139 F (1170.6 C) on curve 3203.
2) N o recalescence on eutectic arrests. These arrests are either flat or continuously declining.
Hypereutectic Irons
(Curves 1309, 2203, 2303, 1409 & 2407)
1) Graphite liquidus absent on curve 1309.
2) Graphite liquidus appears at 2101 F (1149.4 C) on curve 2203 and rises to 2212 F (1211.1 C) on curve 2407.
3) All curves exhibit a eutectic initiation event, (e.g. At 2088 F (1142 C) on curve 2203).
4) All curves show recalescent bulk eutectic arrest.

primary graphite liquidus arrest can be certainly expected on a
eutectometer cooling curve because the rate of evolution of
latent heat within the casting is considerably greater than the
rate at which heat is lost to the surroundings.
Very often, the wiggles corresponding to graphite formation
are so small that they may be considered a result of recorder
malfunction or of "thermal lag". However, a discrepancy due to
recorder malfunction can be easily resolved by a careful
observation of the curve. As regards the thermal lag
phenomena, it has been reported in the thermal analysis
literature that an error due to thermal lag is only a few tenths of a
second duration which is too short to be recorded by the
equipment used for the present investigation.
Cooling Curves of Base Irons
Figure 2 illustrates several salient features of base iron cooling
curves. These curves arc arranged in order to ascending values of
CE. The following observations are made:
I) All the hypoeutectic iron(CE<4.26%)curves(S12-1, S15-L
IIOL 1203 and 320I) show a prolonged primary liquidus
arrest (TAL) which corresponds to formation of austenite
dendrites in the melt. This arrest occurs at 2319 F(I270.5 C )
on curve S12-1 for 3.26% C E and gradually declines, as
shown by arrows, with increasing C E , with a value of 2142 F
(1172.2 C ) on curve 3201 for 4.26% CE. Usually, these arrests
are not recalescent type and their duration is ofthe order of
30 seconds.
2) For C E values in the range 4.26 lo 4.60%, no primary
liquidus arrest is visible. Curve 1301 is a representative curve
for such an alloy. This curve shows a fairly uniform cooling
to 208I F (1138.3 C) ( T E U ) where bulk eutectic growth
begins, and it is followed by recalescence to 2100 F (1148.8 C )
( T E R ) as a consequence ol a rapid heat evolution due to bulk
growth of the graphite eutectic.
434
3) With increase in C E beyond 4.60%. the primary liquidus
arrest ( T G L ) corresponding to precipitation of proeutectic
graphite (kish graphite) becomes increasingly prominent.
These arrests are generally associated with considerable
recalescence (up to 10 F = 5.5C)and their duration is only
about 15 seconds which is m u c h shorter than that of T A L
arrests. This is clearly seen on curves 2201, 1401 and 2402.
Also, note the rise in the graphite liquidus temperature
( T G L ) from about 2200F (1204.4 C ) on curve 2201 to about
2335 F (1279.5 C) on curve 2402. This rising trend is yet
another indication that a graphite liquidus can occur on a
cooling curve. This fact, surprisingly, has not been reported
in the literature.
4) It may be noted that none of the hypereutectic gray iron
curves shows an arrest ( T E N ) which corresponds to in-
itiation and partial growth of the eutectic.
5) For C E values up to about 4.60%, the eutectic plateau shows
considerable recalescence from T E U to T E R . This
recalescent interval is about 2 F(lC) (2049 F to 2051 F =
1120.6 to 1121.7 C ) on curve SI2-1 and as much as 19F
(I0.5C)(2081 to 2100 F = 1138.3 to 1149 C ) on curve 1301.
O n the contrary, for C E greater than 4.60%, recalescence
Irom T E U to T E R is little or zero and the eutectic arrest
appears to run parallel to the time axis.
6) The temperatures T E U and T E R of eutectic plateau move
upward with increase in C E . The silicon content ofthe irons
appears to be a determining factor. The low values of T E U
on curves SI2-1 and SI5-1 (2049 F a n d 2062 F (1120.6 and
1127.8 C ) respectively) arc believed to be a result of low
silicon contents (1.64% and 1.40% respectively). Comparison
a m o n g the curves 1301, 2201, 1401 and 2402 shows that the
iron (2201) containing 2.63% Si exhibits T E U = 2119 F
(1159.5 C ) and the iron (1301) containing 2.46% Si shows a
lower T E U at 2080 F (I 137.8 C).
Al-S | ransactions
7) The duration of the eutectic plateau decreases on either side
of the eutectic composition ( C E = 4.26%). This decrease is
proportional lo the a m o u n t of the eutectic present in the
microstructure and, hence, conforms to what is expected
from the phase diagram.
8) All hypoeutectic alloys represented by the curves in Fig. 2
exhibit carbides. While alloy SI2-1 shows a completely white
iron microstructure, alloy 3201 shows small areas of
intercellular carbides.
For all hypereutectic alloys (corresponding to curves 1301,
2201, 1401 and 2402) the eutectic arrests ( T E U , T E R ) lie above
2080 F (1137.8 C). Intercellular carbides are undetectable in
these alloys. Generally, study of several samples indicates that in
order to obtain a true gray iron microstructure, free of
intercellular carbides, both the T E U and T E R temperatures
should lie above about 2080 F (1137.8 C ) .
Cooling Curves of N i M g Treated Irons
The inoculation of a gray iron melt, essentially a Fe-C-Si
ternary system, with a magnesium alloy introduces a fourth
component to the system. The effect of magnesium is to alter the
mode of solidification to one which results into a spheroidal
graphite morphology. A s a consequence of this change the shape
of the cooling curve varies.
Magnesium is a carbide stabilizer and silicon is a ferrite
stabilizer. The presence of silicon decreases the chilling tendency
of cast irons. Thus, the use of a M g F e S i alloy as a treatment
agent would impair the possibility of separating the individual
effects of the two elements on the cooling curves. Therefore, to
aid in the dissection of the solidification process in its
relationship to the cooling curve, several heats were prepared
using a nickel-magnesium alloy as the treatment agent. It is
known that nickel mildly promotes graphitization in cast iron.
W h e n used alone, nickel is somewhat effective in reducing the
amount of silicon which must be present to develop a gray iron.
and thus m a y cause refinement of the graphite and pearlitic
structure. M o r e highly alloyed irons produce an austenitic or
martensitic structure. In the present work, the a m o u n t of nickel
added in the form of a N i - M g alloy ranged between 0.40 and
1.70%. However, the most c o m m o n addition was about 0.85%.
In the following analysis, the graphitizing or austenite
stabilizing effect of nickel has been assumed to be negligible.
Figure 3 shows typical eutectometer cooling curves to
illustrate the changes as a result of magnesium treatment with a
N i M g alloy. These curves are also arranged in order of
LABORATORY IRONS
A BASE
O NIMG TREATED
2400
-a^S
' ^
tr. **>,
$ 2300
>-
VC
c<r. 2200
O 2140 IN THIS REGION
% 2100 THE GRAPHITE
LIQUIDUS AND EUTECTIC
2055 INITIATION EVENT
TEND TO MERGE.
3.0 3.5 4.0
CARBON EQUIVALENT ( CE = C + Si/3 ) . P E R C E N T
Fig. 4. Graph showing elevation of austenite liquidus arrest and depression of graphite
liquidus arrest as a result of M g treatment.
A F S Transactions
ascending values of C E and m a y be compared with those for
base irons in Fig. 2.
In Fig. 4, the primary liquidus temperatures for base as well as
treated iron melts are plotted versus carbon equivalent. This
graph illustrates that the variation in the austenite liquidus
temperature ( T A L ) as a result of magnesium treatment is very
small. O n the contrary, the suppression of graphite liquidus
( T G L ) is substantial in the presence of magnesium in the alloys.
Note the following remarks with reference to Figs. 3 and 4.
1) In case of hypoeutectic alloys the austenite liquidus
temperature ( T A L ) decreases from 2358 F (I292.2C) at
3.08%, C E to 2159 1(1181.7 C ) at 4.19% C E . The duration of
the flat portion ofthe austenite liquidus ( T A L ) is ofthe order
of about 15 seconds. This duration ofthe primary austenite
arrest is considerably shorter than that on the base iron curve
(Figs. 2,3). The magnitude of the T A L temperature is greater
by a few degrees as compared to the corresponding base iron
curves (see Fig. 2). A s the eutectic composition is approached
the T A L temperature continues to drop and T E N gradually
rises. This makes it increasingly difficult to distinguish T A L
and T E N from each other.
2) O n the hypereutectic side, the graphite arrest ( T G L ) appers
to merge with the T E N event (for example, see curve 1309 in
Fig. 3). This is true for the C E range of 4.26-4.60%.
approximately. For C E > 4.60%.., the graphite liquidus rises
from 2101 F('l 149.4 C ) at 4.67% C E to about 2212 F( 1211.1
C ) at 4.94%, C E . The T G L arrests are flat or recalescent type
and their duration is almost equal to that ofthe T A L arrests
(= 15 seconds). Comparison with T G L for base irons (Fig. 4)
indicates that magnesium suppresses graphite growth by as
m u c h as about 100F(55C).
3) Similar to the hypoeutectic base iron curves, there appears to
be a smooth transition from the end of the austenite dendrite
growth to the beginning of the formation of graphite-eutectic
on hypoeutectic treated iron curves. Hence, it is difficult to
determine the T E N temperature at which appreciable
amount of eutectic m a y have formed. However, as indicated
by the arrows, the T E N temperature appears to rise with
increase in C E (see Fig. 3). This trend continues in a similar
manner in the hypereutectic iron curves. The T E N event in
hypereutectic alloys is very distinct in contrast with that in
the hypoeutectic alloys.
4) The T E R temperature is generally equal to or lower than the
T E U temperature in the hypoeutectic irons which were
treated with a magnesium alloy. The eutectic plateau appears
at a temperature level which is determined by the silicon and
4.26 4.5 4.60 5.0
435
 F

2350
Post-Inoculated
II C SI CE MB n N 2300
3203 3.46 2.17 4.18 0.062 18 72 Mg-Treated Iron^ Iron-.
3208 3.42 2.62 4.29 0.048 67 59 3203- ^ 3208'
2250

2200

2150 2
UJ
2096 2100

2050
2040 ~*i one min. y ~
2000
TIME (MINUTES)
Fig. 5. Effect of silicon post inoculation. Note the austenite liquidus at 2159 F (1126 C) on
curve 3203. The liquidus at 2136 F (1168.8 C) on the curve 3208 for the post inoculated
iron is interpreted as a eutectic initiation arrest. Also, note the rise of the eutectic
plateau from 2040 F (1115.6 C) to 2096 F (1146.7 C).

carbon contents. At a given carbon content the T E U and
T E R events shift to lower and lower temperatures as the
silicon content increases. This phenomenon m a y be
explained as follows:
The graphite eutectic nucleation and its limited growth
almost always appears to precede nucleation of cementite.
Once nucleated, the cementite-austenite eutectic grows
rapidly. While silicon tends to promote growth of graphite
eutectic, magnesium creates conditions suitable for initiation
and growth of cementite eutectic. Thus the two elements
compete with each other. If silicon content of a melt is low
(e.g. S5-2) magnesium effect is strong enough to give a
completely carbidic structure around 2050 F(112l.l C). O n
the other hand, if the silicon content is high (e.g. curve I2l I),
nucleation of cementite is delayed (and because of
magnesium, growth of graphite eutectic is retarded). Hence,
the eutectic plateau shifts to temperatures around 2020 F
(M04.4C).
5) In case of Ni Mg-treated hypereutectic melts, the curves
invariably exhibit eutectic undercooling ( T E N - T E U ) of the
order of 40 F (22 C ) and eutectic recalescence ( T E R - T E U )
ofthe order of about 15F(8C). Retarded cooling towards
the tail end is generally associated with intercellular carbides.
The amount of carbides in the structure decreases with
increase in C E .
6) The duration of the eutectic arrest ( T E N thru 2000 F =
1193.3 C ) increases with increase in C E a n d a m a x i m u m is
obtained for near eutectic composition. This is not un-
expected on account of the fact that the amount of austenite
dendrites in the microstructure decreases continuously with
increase in C E .
In case of the hypereutectic alloys the duration of the
eutectic arrest decreases with increase in carbon equivalent.
This decrease is generally too small and sometimes it maybe
difficult to detect because of the eutectic undercooling
interval and an overlap between the T G L and T E N events.
Physically, this phenomenon m a y be associated with the
increasing amount of the primary phase (which can be either
graphite or cementite) with increase in carbon equivalent. In
the irons studied, however, the primary phase in
hypereutectic irons was predominantly graphite.
7) While the hypoeutectic alloys exhibit compact and

./: y y

Fig. 6. Left, sample 3203, nickel-magnesium treated hypoeutectic iron. Right, sample 3208, melt 3203 following silicon
post inoculation, note disappearance of carbides and increased amount of graphitic carbon. (Nital etch. 50X)

436 A F S Transactions

Post Inoculation of Nl-Mg Treated Hypereutectic Melt 3403
' C Si CE Mg n :' CARB / Post inoculated uon
3403 4.03 2.34 4.81 0.060
3405 4.00 2.80 4.93 0.048 171 98 no
TIME (MINUTES)
Fig. 7. Effect of silicon post inoculation in raising the eutectic arrest temperatures TEN,
TEU, and TER. (Hypereutectic melts).
spheroidal graphite in the as-cast structure, the hypereutectic
alloys shows generally spheroidal graphite. The morphology
of the carbide eutectic is generally platey. The ledeburitic
type of carbon eutectic (if any) is present in small amounts.
Effect of Silicon Post Inoculation on Cooling Curves
Hypoeutectic Compositions
The effect of si licon post inoculation of a Ni-Mgtreated melt can
be illustrated with the help of the cooling curves in Fig. 5. Prior
to the addition of Si in the form of a FeSi alloy, the coolingcurve
(3203) exhibits a proeutectic austenite liquidus arrest at 2159 F
(1181.7 C). This is followed by undercooling ofthe melt to about
2040 F(ll 15.6 C ) before appreciable amount of eutectic formed.
The microscopic examination indicates this eutectic to be
carbidic (Fig. 6). A s a consequence of post inoculation, the
cooling curve changed to curve 3208 in Fig. 5. The following
observations are evident:
1) The cooling of the melt prior to 2136 F (1169 C) appears to
have been retarded. This m a y be attributed to the nucleation
and limited growth of graphite particles.
: P*i
Fig. 8. Left, sample 3403, nickel-magnesium alloy treated hypereutectic iron. Right, sample 3405, iron 3403 following
silicon post inoculation, note the increased nodule count and small nodule size. (Nital etch, 50X)
AFS Transactions
F
Mg-Treated Iron 2350
2300
yes / 3405
2250
2200
or
LU
a.
2150 5
2100 UJ
2050
2000
2) The first major arrest (2136 F = 1169 C ) is m u c h more
prolonged (approx. 1 2 minute) compared to the one shown
by curve 3203. This arrest is interpreted to be an eutectic
initiation arrest and not an austenite liquidus arrest.
3) With a limited growth at the initiating arrest, the melt
undercooled to temperature T E U which equals 2088 F
(I 142.2 C). The cooling curve also indicates that the bulk of
the graphite eutectic formed much above the 2050 L (1121.1
C) level. Thus, the result of FeSi addition was to raise the
eutectic plateau from 2040 F (1115.6 C ) to about 2092 F
(1144.4 C ) , that is by as m u c h as 52* F(29C). The increase in
the silicon content is 0.4707. According to the following
formula' for equilibrium eutectic temperature (TE) can be
calculated:
T E = (2110 + 11.7 Si) F.
For sample 3203, the calculated value of T E is about 2135 F
(1168.3 C). Hence, the T23 event at about 2040 F (1115.6 C)
represents undercooling of the eutectic reaction b\ about
95 F (52 C). The value of T E for sample 3208 is about 2141
F (1171.8 C ) and the difference ( T E - T E U ) is only about 53 F
(29-C). Hence, the effect of increased silicon level was to
43"
 TYPICAL UNDESIRABLE COOLING CURVES
0 C SI CE Mg Bi CARB
C26 3.91 2.45 4.73 0.034
TIME (MINUTES)
Fig. 9. Undesirable cooling curves. Such curves indicate that the iron should be either
reprocessed or dumped.
raise the bulk eutectic growth temperature by about 42 F.lt
is believed that the elevation of the eutectic arrest is as a result
of an increase in the carbon equivalent as well as an increased
number of nucleation sites, where graphite-eutectic growth is
favored.
4) The microstructure ofthe final iron (3208) is shown in Fig. 6.
Nodular and vermicular graphite forms are present in equal
proportion. Ferrite rings are present on all graphite particles.
The matrix is largely pearlitic and carbides are not visible.
The cause of vermicular graphite in 3208 is probably a lower
actual magnesium residual than one obtained by chemical
analysis.
5) It is interesting to note the steepness of the tail ends ofthe
two cooling curves. The cooling rate at any instant is
determined by the heat liberated due to phase transfor-
mations within the casting and the heat lost to the ambient
atmosphere. In the absence of any phase transformation, the
temperature gradient would be determined by ability ofthe
mold to extract heat. Hence, the steepness ofthe tail end m a y
be used as a measure of the amount of solid formed.
However, the bulk arrest temperature determines the type of
eutectic that m a y have formed.
'- .-'''- *': !
Fig. 10. Microstructures associated with undesirable cooling curves, Nital etch, 50X.
138
BI6 - 2350
2300
2250
2200 cr
|
2150
2
uJ
2100
2050
2000
A low value of T E U and T E R (2040 F = 1115.6 C ) for sample
3203 is associated with carbide eutectic. O n the other hand, the
higher values of T E U and T E R (2088 and 2096 F = 1142.2 and
1146.7 C respectively) are associated with the graphite eutectic.
A relatively slow cooling rate at the tail end of curve 3208
indicates retarded heat liberation due to austenite-graphite
eutectic growth. O n the contrary, the steep tail end of curve 3203
indicates that the austenite-cemenite eutectic solidification was
almost completed at about 2040 F(ll 15.6 C ) . It m a y be pointed
out here, that once nucleated the cementite eutectic grows
rapidly as compared to the graphite eutectic.
Hypereutectic Compositions
Commercial ductile irons represent either near-eutectic or
hypereutectic compositions. It m a y be noted that the irons are
designated hypo-or hypereutectic assuming the eutectic com-
position to be 4.26f f calculated on the basis ofthe formula: C E
= C + Si/3.
I n Fig. 7 are presented typical eutectometer cooling curves to
illustrate the effect of Si inoculation of the melts. It has been
observed that the proeutectic graphite arrest and the eutectic
A Is Transactions
initiation arrest tend to merge together for C E values in the
range between 4.26 and 4.60. Hence, intentionally, to bring out
the salient features of hypereutectic melt cooling curves, a high
value of C E was chosen. The cooling curve features are
interpreted as follows: (Fig. 7)
1) Prior to the Si inoculation the curve (3403) exhibits a break
at about 2198 F( 1203.3 C ) , signifying precipitation of carbon
from the melt. This was followed by retarded cooling d o w n
to about 2108 F (1153.3 C ) . Subsequently, the eutectic
solidification took place (see Fig. 7). The slow decline in
temperature towards the tail end of the curve indicates that a
small quantity of carbide eutectic m a y have formed. This is in
fact true. The microstructure does show intercellular car-
bides which may have formed during the last stages of
freezing.
2) The second cooling curve (3405) was obtained after addition
of post inoculant. The initial portion of this curve does not
show a distinct graphite liquidus. It is believed that the
increased number of nuclei were able to control the
precipitation of carbon from the melt. Thus, the effect of Si
addition was to offset the influence of the residual
magnesium content. Carbon precipitation m a y have started
at higher temperature and it continued at a uniform rate
down to the eutectic initiation.
3) As a proof of a very effective post inoculation treatment it
may be noted that the melt did not undercool below 2114 C
(1156.7 C) which is only 11F (6.1C) below the less
prominent initiation arrest at 2125 F(l 162.8 C). The nodule
count in the sample is 171 n/ m m " and the nodularity is close
to one hundred percent (Fig. 8). N o intercellular carbides are
visible. This can be predicted from the tail end ofthe curve.
The average cooling rates between 2050 and 2000 F( 1121.1
and 1093.3 C ) for the samples 3403 and 3405 are 7.8 F/min.
and 21.7F/min. respectively.
4) As pointed out before for the case of hypoeutectic irons
(curves 3203 and 3208), it m a y be noted that as a result of
post inoculation treatment the silicon of the original iron
increased by about 0.46% and the C E by 0.12%. The T E N
temperature was raised by about 17F (9.4C). These
substantial increments cannot be only due to increase in C E .
Thus, in hypereutectic melts the nucleating effect of post
inoculation is very significant. In addition to nucleation sites,
the silicon provides pockets of high graphitizing potential.
This results in considerable reduction in eutectic under-
cooling ( T E N - T E U ) and eutectic recalescence ( T E R - T E U ) .
Effect of Holding o n Cooling Curves
Figure 9 presents three cooling curves which are certainly ofthe
undesirable type. The carbon and silicon contents of these melts
are in the range for ductile irons. However, the magnesium levels
are on the lower side (0.021 and 0.034%). Moreover, these melts
were held in the furnace for varying lengths of time. This was
done intentionally to produce curves for inferior quality irons.
With reference to Fig. 9 it m a y be noted that only one curve
(C26) exhibits a distinct graphite arrest at about 2135 F (1168.3
C). This arrest shows considerable recalescence. The most
probable reason for this behavior is a delayed, but rapid growth
ofthe proeutectic graphite. Thecurves C36and B16do not show
any primary arrest. This does not mean that the primary phase
did not grow in the high temperature range. Probable reason is
that the precipitation of carbon occurred gradually over a wide
temperature interval.
All the three curves in Fig. 9 show distinguishable eutectic
initiation arrests. While C26 shows T E N equal to about 2092 F
(1144.4C), BI6 exhibits a low value of about 2040 F(l I I5.6C).
A low value of T E N on the curve BI6 shows the strong
suppressing effect of M g and Bi.
Another important feature of an undesirable cooling curve is
a highly recalescent bulk eutectic arrest. Curve C26 shows
recalescence from about 2077 F (1136.1 C ) to about 2104 F
(1151.1 C). Curve C36 exhibits a eutectic recalescence interval of
about 60 F (eutectic recalescence = T E R T E U ) . Though the
AFS Transactions
Curve B16 shows recalescence of about 35F (19.4C), the
important difference is a low T E U of only 2040 F (1115.6 C).
Figure 10 presentes micrographs corresponding to the curves
C36. C26 and B16. Whereas samples C26 and C36 do not exhibit
significant amounts of intercellular carbides, sample BI6 shows
almost 5 0 % of the carbide eutectic. This is not unexpected
looking at the cooling curves. The eutectic growth plateau is in
the 2095-2110 F (1146.1 -1154.4 C ) range on curves C26 and C36.
O n the contrary, the bulk of the solidification occurred below
2075 Fin B16. though, the T E U event occurred at about 2040 F
(1115.6 C) in C36, the amount of carbides in the structure is
negligible. This is attributed to the high Si (2.89%) level in that
melt.
A careful examination of Figures 9 and 10 would indicate that
the recalescent eutectic arrests are a sure indication of the
presence of vermicular and Hake graphite in the microstructure.
A study of several cooling curves indicates that eutectic
recalescence in excess over about I5C (8.3C) is generally
accompanied by degenerate graphite structure.
Conclusions
The preceding discussion indicates a strong correlation betwee
the significant features on eutectometer cooling curves and the
as-cast microstructure in the corresponding eutectometer
samples. The following conclusions arc made:
Magnesium treatment of a hypoeutectic gray iron causes
insignificant change in the austenite liquidus temperature
(TAL).
A graphite liquidus does exist for hypereutectic compositions
beyond about 4.60% C E .
Magnesium addition by the processes used to a hypereutectic
gray iron suppresses the graphite liquidus ( T G L ) by as much as
100 F (55.6C).
Cooling curves of hypo- as well as hypereutectic gray irons do
not exhibit a distinct eutectic initiation arrest (TEN). Whereas
the hypoeutectic gray irons exhibit a d o m e shaped bulk eutectic
arrest ( T E U T E R T S ) the hypereutectic gray irons exhibit
a more or less flat eutectic arrest, ( T E U = T E R ) .
Presence of magnesium suppresses the bulk arrests
significantly. The hypoeutectic compositions show a flat
( T E U T E R ) or a continuously declining ( T E R > T E R > T S )
bulk eutectic arrest. O n the other hand, the hypereutectic
compositions feature a distinct eutectic initiation arrest ( T E N )
and a d o m e shaped bulk eutectic arrest ( T E U T E R T S )
following the T E U event.
The eutectic initiation arrest for CE between 4.26 and 4.60%
should not be mistaken for an austenite liquidus ( T A L ) of a
hypoeutectic iron. A n austenite liquidus is relatively m u c h
shorter than a eutectic initiation arrest.
The effect of ferrosilicon post inoculation of a Mg treated
melt is to bring the eutectic arrest temperatures (TEN. T E U and
T E R ) closer to the equilibrium temperature for graphite
eutectic.
The rate of recalescence between TEU and TER is greater in
post inoculated irons than that in M g treated irons.
The tail end of a curve lor the final iron is more precipitous
than that for the corresponding treated iron prior to silicon post
inoculation.
The as-cast microstructure in irons is graphitic if the TEU and
T E R events occur above about 2080 F (1137.8 C). A completely
carbidic structure is associated with the T E U and T E R events
occurring well below about 2050 F (1121.1 C).
Considerable undercooling of the eutectic events TEN and
T E U followed by recalescence greater than I5F (8.3,:,C) is
associated with degenerate graphite microstructure.
References
1. S. Studlik and M. .lagos. "Assessment of Strength of Gray Ir
439
 the Bums ol Cooling Curves,' roundiv trade Journal, p. 458-464
(Mai 1969).
2. R. P Dunphy and W S Pellini. "Solidification of Nodular Iron in
Sand Molds," I lans. A IS. Vol. 60. p. 775 (1952).
3. W F. Shaw and T. Watmough. "Influence of Minor Elements on
the Properties of Ductile Iron," Trans. A F S . Vol. 79 (1971).
4. I. C. Humphreys. "Effect ol Composition on the Liquidus and
Eutectic temperature, and on the Eutectic Point ol Cast Irons."
BCIRA Journal, Vol. 9. p. 609-621 (1961).
5. L. E. Menawati. R. \\ Heine and C. R. Loper, Jr.. "Relationshipof
Cji.iv Iron Microstructure to Cooling Curves." Trans. A F S , Vol. 78,
p. 363-373 (1970)
r> R. 1. Garden, "Basic Principles ol Carbon Equivalent Determina-
tion and Dip Temperature Measurement of Cast Iron." Instrument
Engineer, Vol. 2. p. 26-28 (1964).
7. C. R. Loper, Jr., R VV. Heine and A. Shah, "Thermal Analysis of
APPENDIX
Ductile Iron." Trans. A F S . Vol. 75, p. 541 (1967).
8 R. Jelle> and I. G. Humphreys. " H o w to Estimate Cupola Metal
Composition by Means of Cooling Curves." B C I R A Journal, Vol.
9. p 662-631 (1961).
9. R. \V, Heine. M. D. Chaudhari and C. R. Loper, Jr., "Characteriza-
tion and Interpretation of Ductile Iron Cooling Curves," Trans.
A F S . Vol. 79. p. 399-410(1971).
10. M. D. Chaudhari. R. VV. Heine and C. R. Loper. Jr., "Potential
Applications of Cooling Curves in Ductile Iron Process Control,"
Trans. A F S . Vol. 82 (1974).
I I. M. D. Chaudhari. "A I hermoanalytical Study ofthe Solidification
of Magnesium-1 reated Irons," Ph.D. Thesis, University of Wiscon-
sin (1972).
12. II. D. Merchant. "Recent Research on Cast Iron," Proceedings of a
Seminar sponsored by A S M , Detroit, Michigan; Gordon and
Breach Science Publishers New York. p. 101-108 (June 1964).

Notation used in
Notation some of the
used References Quoted
in Text Solidification Event
in Text
TAL Til, T12, etc. Precipitation of austenite from the melt in hypoeutectic irons.
TGL Til, T12, etc. Precipitation of graphite from the melt in hypereutectic irons.
If a curve shows more than one short step corresponding to primary phase forma-
tion, these may be labeled Til, T12, T13, etc. If a curve shows one prolonged
arrest, the beginning and end of such an arrest are denoted by Til and T12 re-
spectively. In the discussion, only major arrests are referred to. Since Til
is generally approximately equal to T12, only Til is mentioned.

T21, T22 These denote the beginning and end of an initial nucleation and growth of
eutectic.

TEN TEN As T21 and T22 are difficult to determine accurately from the curve, TEN, which
is easy to locate, is chosen for multiple regression analysis.

TEU T23 Denotes beginning of bulk growth of eutectic and it is assumed equal to eutectic
initiation temperature, when T21 and T22 are absent.

TER T31 Denotes the peak of the eutectic plateau.

TS T40 Denotes solidus for the alloy. This temperature cannot be reliably determined
from cooling curves.

44(1 A F S Transactions