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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 inoculation on the eutectic arrest temperatures is discussed. The


hypoeutectic gray irons exhibit a dome-shaped bulk eutectic
U s e of C o o l i n g Curves arrest and the hypereutectic gray irons generally exhibit a more
or less flat eutectic arrest. Following a M g addition, the
in D u c t i l e Iron hypoeutectic alloys show a flat or a continuously declining
Process Control 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.
by M . D . Chaudhari, Metallurgist a n d Materials The effect of silicon post inoculation of a Mg-treated melt is to
bring the eutectic arrest temperatures close to the equilibrium
Engineer,
temperature for graphite eutectic.
Baker Manufacturing Co., Evansville, Wisconsin,
The features associated with desirable microstructure are
R. W . Heine a n d C. R. Loper, Jr., Professors,
discussed. It is concluded that a strong correlation exists
Dept. of Metallurgical Engineering, between the eutectometer cooling curves and the
University o f Wisconsin, M a d i s o n , Wisconsin microstructures in the corresponding eutectometer samples.
Introduction
ABSTRACT Cooling curves have been used for several years in cast iron
Solidification characteristics of hypo- and hypereutectic cast foundries to determine carbon equivalent (CE) from liquidus
irons were investigated by the cooling curve method. The arrest temperatures. N o extensive work1"* has been performed,
eutectometer cooling curves reported in this paper were however, on the possibility of predicting the as-cast
obtained for gray irons, nickel-magnesium treated irons and microstructure by a cooling curve control test before pouring
final irons melted in laboratory induction furnaces. the production molds. It was the object of the investigation to
Significant features of the cooling curves are defined. These examine the possibilities for following the course of
features are discussed with reference to corresponding solidification of ductile irons, the kind of microstructure that
microstructures in eutectometer samples in order to dissect the develops during solidification events detected by eutectometer
ductile iron solidification process. cooling curves and its potential for process control.
A n attempt is m a d e to resolve certain controversies regarding This paper deals with the portion ofthe work performed since
the occurrence of an anomalous arrest which has been observed the publication of a preliminary report4 by the authors, and it is
usually on gray iron curves. A calculation is shown to prove the presented in two parts. This part deals with the fundamental
existence of a primary graphite liquidus o n curves of aspects ol dissection of the solidification process in its
hypereutectic alloys. relationship to the cooling curve. The second part1" describes
It is shown that magnesium treatment of a hypoeutectic gray several ways of utilization of cooling curves in ductile iron
iron causes insignificant change in the austenite liquidus process control.
temperature and that a similar treatment of a hypereutectic gray Specifically, the cooling curve technique and sample known
iron causes suppression ofthe graphite liquidus temperature by as the eutectometer was employed to obtain results. This use of a
as much as 100 F (55.5 C). standardized mold resulted inconsistent heat dissipation during
AFS Transactions 74-96 431
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 cooling curves do not indicate the presence of melt \Mthin the
relationship between the shape of the cooling curves and protective refractory. Longitudinal sections were taken to
microstructures obtained. Variations in the as-cast conlirm this. It was observed that the melt enters the refractory
microstructures can only be caused by variations in the freezing tube due to dissolution ofthe bead coat and also due tocracking
process, and thus variations in the cooling curves. Analysis of ofthe tube itself. Failure ofthe refractory was further confirmed
the cooling curve enables an evaluation of the corresponding as- by yet another test, A sample was kept in a 1:3 mixture of
cast microstructure. bromine and methyl alcohol at about 50 C ( 140 F) for 24 hours
Nomenclature to dissolve the metallic matrix completely. Several cracks and
holes were observed in the refractorv.
To facilitate tabulation and analysis of the data a new
nomenclature was adopted to describe cooling curves. Listing Presence of hot metal in the cracked sheath results in a short-
the temperatures for each stage of cooling in data tables reveals circuit, thereby shifting the thermocouple hotjunction toa point
the approximate shape ofthe cooling curve without recourse to vertically below the thermal center where the thermocouple
the actual curve. O n several occasions, it is difficult to assign bead is supposed to be normally located. In effect, the portion of
specific values ofthe thermal arrest temperatures. In such cases the cooling curve subsequent to this represents cooling of a new
it is better to refer to the average cooling rate in that particular hot junction.
part ofthe cooling curve. Several schematic cooling curves are Since the anomalous arrests were observed more often on
shown in Fig. 1 to illustrate the nomenclature used in the text. base iron curves, it is strongly believed that the partial failure of
An appendix is included to clarify the notations used in some of thermocouple assembh is a result of an exogenous m o d e of
the references quoted in this paper. freezing of the corresponding irons. In such irons the melt
Experimental Procedure remains in contact with the thermocouple for a relatively long
duration because the solidification front travels from the surface
All cooling curves were obtained with standard eutectometer to the center of the casting.
samples. Sample dimensions are approximately 40 m m diam x
60 m m length and a sample weighs about 680 grams. The sources Occurrence of Graphite Liquidus
of the samples are eutectometer samples cast at the University of
Wisconsin laboratory.
It has been reported in the literature* that a primary arrest is
The base irons were treated with nodularizing agent using the not seen on hypereutectic iron cooling curves because the
sandwich method. The treatment temperatures ranged between associated latent heat evolution is very little. In the initial stages
2800 and 2900 F (1538 to 1593 C). Melts were held in the furnace of the present investigation it was felt that this applies to the
at about 2750 to 2800 F (1510 to 1538 C ) after treatment or entire range of hypereutectic compositions. However, the
following post-inoculation as the case m a y be. High pouring laboratory experiments indicate that this is true onlv in the case
temperatures were intentionally employed with a specific of mildly hypereutectic compositions. It has been repeatedly
purpose oi' obtaining the liquid representing portion of the observed that strongly hypereutectic irons do show prominent
cooling curve. Though this procedure impaired the possibility of primary arrests. The authors are ofthe opinion that these arrests
producing a fully nodular graphite structure, it helped to obtain represent graphite growth. A n example is given below to prove
a variety of microstructural constituents along with the cor- this.
responding cooling curves. Consider an iron containing about 4.06% C and 2.569c Si (see
Samples were drawn from the furnace using a small clay curve 1401, Fig. 2). The graphite liquidus occurred at about 2298
graphite ladle. The time elapsed following nodularizing F (1259 C ) in this sample. The following assumptions and data
treatment, before first samples were taken, varied between two are necessary to calculate the duration of the arrest:
and eight minutes. I) Assume that all the primary graphite grew at 2298 F (1532
Cooling curves were obtained using single and multi-point K). Subtracting an amount of about 0.69? C as combined
recorders. The chart speed was one inch per minute for all the carbon, the amount of free carbon would be about 3.46c?.
curves. The cooling curves included in the following discussion 2) Atomic weights: Fe = 55.85 grams; C = 12 grams. Casting
are tracings of the originals. The accuracy rating for the weight ~ 1.5 lbs. = 680 grams.
recorders is 0.5ff. for the span used. The recorders were 3) Latent heat1" of graphite precipitation: 4633 cal g.mole.
calibrated several times during the course of the investigation. Specific heat of casting alloy: (1.84+ 4.66 x 10"' x Tical.K
Several eutectometer castings representative of typical per g m mole.
cooling curves were sectioned transversely as close as possible to 4) Average cooling rate at 2298 F (1259 C ) = 300F/min.
the thermocouple tip and were carefully prepared for (I67C) = 3C sec. N o w . that latent heat evolved due to
metallographic examination. T o retain graphite particles graphite would be:
repeated etching and polishing technique was used and the time 4633_x_680_| 0-03*6 __ 8950 calories.
on wheel was kept as short as possible. Nodularity ratings were
obtained using the nodule count method" (200X) when
necessary. Assuming an average cooling rate of about 300F/min.
(167C per min). in one second the temperature would drop
Controversial Features on Cooling Curves by 5 F (that is, by 3C). A loss of 3 C corresponds toa heat
A n o m a l o u s Arrest D u e to 'Thermocouple Failure loss ( A H ) from the eutectometer casting given by the
Considerable controversy surrounds the occurrence ol an following equation:
anomalous arrest5 which has been observed in the last portion of A H = mass x sp. heat x temperature drop
some of the cooling curves. It was observed more often in the Hence
base iron curves and was thought to be associated with
formation of a carbide-austenite eutectic. Several attempts to 690 x 0.965 x (1.84 + 4.66 x 10~3 x 1423) x 3
reproduce this anomaly failed. Several examples of the AH
55.85
anomalous arrest m a y be seen in Fig. 2 (see curves 3201. 2201
and 2402 in the figure).
= 656 x 8.48 x 3 55.85
In order to determine the cause of the arrest m a n y eu-
= 300 calories
tectometer castings were studied. All samples which gave the
anomalous arrests exhibit penetration of the melt into the Thus, to dissipate 8950 calories from the casting approximately
thermocouple sheath. Those samples which show normal 30 seconds (8950; 300 * 29.80) would be required. This means a

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

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 4.26 4.5 4.60 5.0
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 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 ofthe order of about 15F(8C). Retarded cooling towards
T E R events shift to lower and lower temperatures as the the tail end is generally associated with intercellular carbides.
silicon content increases. This phenomenon m a y be The amount of carbides in the structure decreases with
explained as follows: increase in C E .
The graphite eutectic nucleation and its limited growth 6) The duration of the eutectic arrest ( T E N thru 2000 F =
almost always appears to precede nucleation of cementite. 1193.3 C ) increases with increase in C E a n d a m a x i m u m is
Once nucleated, the cementite-austenite eutectic grows obtained for near eutectic composition. This is not un-
rapidly. While silicon tends to promote growth of graphite expected on account of the fact that the amount of austenite
eutectic, magnesium creates conditions suitable for initiation dendrites in the microstructure decreases continuously with
and growth of cementite eutectic. Thus the two elements increase in C E .
compete with each other. If silicon content of a melt is low In case of the hypereutectic alloys the duration of the
(e.g. S5-2) magnesium effect is strong enough to give a eutectic arrest decreases with increase in carbon equivalent.
completely carbidic structure around 2050 F(112l.l C). O n This decrease is generally too small and sometimes it maybe
the other hand, if the silicon content is high (e.g. curve I2l I), difficult to detect because of the eutectic undercooling
nucleation of cementite is delayed (and because of interval and an overlap between the T G L and T E N events.
magnesium, growth of graphite eutectic is retarded). Hence, Physically, this phenomenon m a y be associated with the
the eutectic plateau shifts to temperatures around 2020 F increasing amount of the primary phase (which can be either
(M04.4C). graphite or cementite) with increase in carbon equivalent. In
5) In case of Ni Mg-treated hypereutectic melts, the curves the irons studied, however, the primary phase in
invariably exhibit eutectic undercooling ( T E N - T E U ) of the hypereutectic irons was predominantly graphite.
order of 40 F (22 C ) and eutectic recalescence ( T E R - T E U ) 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
F
Mg-Treated Iron 2350
Post Inoculation of Nl-Mg Treated Hypereutectic Melt 3403
' C Si CE Mg n :' CARB / Post inoculated uon 2300
3403 4.03 2.34 4.81 0.060 yes / 3405
3405 4.00 2.80 4.93 0.048 171 98 no 2250

2200
or
LU
a.
2150 5
2100 UJ

2050

2000
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 2) The first major arrest (2136 F = 1169 C ) is m u c h more
alloys shows generally spheroidal graphite. The morphology prolonged (approx. 1 2 minute) compared to the one shown
of the carbide eutectic is generally platey. The ledeburitic by curve 3203. This arrest is interpreted to be an eutectic
type of carbon eutectic (if any) is present in small amounts. initiation arrest and not an austenite liquidus arrest.
Effect of Silicon Post Inoculation on Cooling Curves 3) With a limited growth at the initiating arrest, the melt
undercooled to temperature T E U which equals 2088 F
Hypoeutectic Compositions (I 142.2 C). The cooling curve also indicates that the bulk of
The effect of si licon post inoculation of a Ni-Mgtreated melt can the graphite eutectic formed much above the 2050 L (1121.1
be illustrated with the help of the cooling curves in Fig. 5. Prior C) level. Thus, the result of FeSi addition was to raise the
to the addition of Si in the form of a FeSi alloy, the coolingcurve eutectic plateau from 2040 F (1115.6 C ) to about 2092 F
(3203) exhibits a proeutectic austenite liquidus arrest at 2159 F (1144.4 C ) , that is by as m u c h as 52* F(29C). The increase in
(1181.7 C). This is followed by undercooling ofthe melt to about the silicon content is 0.4707. According to the following
2040 F(ll 15.6 C ) before appreciable amount of eutectic formed. formula' for equilibrium eutectic temperature (TE) can be
The microscopic examination indicates this eutectic to be calculated:
carbidic (Fig. 6). A s a consequence of post inoculation, the T E = (2110 + 11.7 Si) F.
cooling curve changed to curve 3208 in Fig. 5. The following For sample 3203, the calculated value of T E is about 2135 F
observations are evident: (1168.3 C). Hence, the T23 event at about 2040 F (1115.6 C)
1) The cooling of the melt prior to 2136 F (1169 C) appears to represents undercooling of the eutectic reaction b\ about
have been retarded. This m a y be attributed to the nucleation 95 F (52 C). The value of T E for sample 3208 is about 2141
and limited growth of graphite particles. 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

: 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 43"
TYPICAL UNDESIRABLE COOLING CURVES BI6 - 2350
0 C SI CE Mg Bi CARB
C26 3.91 2.45 4.73 0.034 2300

2250

2200 cr
|
2150
2
uJ
2100

2050

2000
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 A low value of T E U and T E R (2040 F = 1115.6 C ) for sample
is believed that the elevation of the eutectic arrest is as a result 3203 is associated with carbide eutectic. O n the other hand, the
of an increase in the carbon equivalent as well as an increased higher values of T E U and T E R (2088 and 2096 F = 1142.2 and
number of nucleation sites, where graphite-eutectic growth is 1146.7 C respectively) are associated with the graphite eutectic.
favored. A relatively slow cooling rate at the tail end of curve 3208
4) The microstructure ofthe final iron (3208) is shown in Fig. 6. indicates retarded heat liberation due to austenite-graphite
Nodular and vermicular graphite forms are present in equal eutectic growth. O n the contrary, the steep tail end of curve 3203
proportion. Ferrite rings are present on all graphite particles. indicates that the austenite-cemenite eutectic solidification was
The matrix is largely pearlitic and carbides are not visible. almost completed at about 2040 F(ll 15.6 C ) . It m a y be pointed
The cause of vermicular graphite in 3208 is probably a lower out here, that once nucleated the cementite eutectic grows
actual magnesium residual than one obtained by chemical rapidly as compared to the graphite eutectic.
analysis.
5) It is interesting to note the steepness of the tail ends ofthe Hypereutectic Compositions
two cooling curves. The cooling rate at any instant is Commercial ductile irons represent either near-eutectic or
determined by the heat liberated due to phase transfor- hypereutectic compositions. It m a y be noted that the irons are
mations within the casting and the heat lost to the ambient designated hypo-or hypereutectic assuming the eutectic com-
atmosphere. In the absence of any phase transformation, the position to be 4.26f f calculated on the basis ofthe formula: C E
temperature gradient would be determined by ability ofthe = C + Si/3.
mold to extract heat. Hence, the steepness ofthe tail end m a y I n Fig. 7 are presented typical eutectometer cooling curves to
be used as a measure of the amount of solid formed. illustrate the effect of Si inoculation of the melts. It has been
However, the bulk arrest temperature determines the type of observed that the proeutectic graphite arrest and the eutectic
eutectic that m a y have formed.

'- .-'''- *': !

Fig. 10. Microstructures associated with undesirable cooling curves, Nital etch, 50X.

138 A Is Transactions
initiation arrest tend to merge together for C E values in the Curve B16 shows recalescence of about 35F (19.4C), the
range between 4.26 and 4.60. Hence, intentionally, to bring out important difference is a low T E U of only 2040 F (1115.6 C).
the salient features of hypereutectic melt cooling curves, a high
value of C E was chosen. The cooling curve features are Figure 10 presentes micrographs corresponding to the curves
interpreted as follows: (Fig. 7) C36. C26 and B16. Whereas samples C26 and C36 do not exhibit
significant amounts of intercellular carbides, sample BI6 shows
1) Prior to the Si inoculation the curve (3403) exhibits a break almost 5 0 % of the carbide eutectic. This is not unexpected
at about 2198 F( 1203.3 C ) , signifying precipitation of carbon looking at the cooling curves. The eutectic growth plateau is in
from the melt. This was followed by retarded cooling d o w n the 2095-2110 F (1146.1 -1154.4 C ) range on curves C26 and C36.
to about 2108 F (1153.3 C ) . Subsequently, the eutectic O n the contrary, the bulk of the solidification occurred below
solidification took place (see Fig. 7). The slow decline in 2075 Fin B16. though, the T E U event occurred at about 2040 F
temperature towards the tail end of the curve indicates that a (1115.6 C) in C36, the amount of carbides in the structure is
small quantity of carbide eutectic m a y have formed. This is in negligible. This is attributed to the high Si (2.89%) level in that
fact true. The microstructure does show intercellular car- melt.
bides which may have formed during the last stages of A careful examination of Figures 9 and 10 would indicate that
freezing. the recalescent eutectic arrests are a sure indication of the
2) The second cooling curve (3405) was obtained after addition presence of vermicular and Hake graphite in the microstructure.
of post inoculant. The initial portion of this curve does not A study of several cooling curves indicates that eutectic
show a distinct graphite liquidus. It is believed that the recalescence in excess over about I5C (8.3C) is generally
increased number of nuclei were able to control the accompanied by degenerate graphite structure.
precipitation of carbon from the melt. Thus, the effect of Si
Conclusions
addition was to offset the influence of the residual
magnesium content. Carbon precipitation m a y have started The preceding discussion indicates a strong correlation betwee
at higher temperature and it continued at a uniform rate the significant features on eutectometer cooling curves and the
down to the eutectic initiation. as-cast microstructure in the corresponding eutectometer
3) As a proof of a very effective post inoculation treatment it samples. The following conclusions arc made:
may be noted that the melt did not undercool below 2114 C Magnesium treatment of a hypoeutectic gray iron causes
(1156.7 C) which is only 11F (6.1C) below the less insignificant change in the austenite liquidus temperature
prominent initiation arrest at 2125 F(l 162.8 C). The nodule (TAL).
count in the sample is 171 n/ m m " and the nodularity is close A graphite liquidus does exist for hypereutectic compositions
to one hundred percent (Fig. 8). N o intercellular carbides are beyond about 4.60% C E .
visible. This can be predicted from the tail end ofthe curve.
The average cooling rates between 2050 and 2000 F( 1121.1 Magnesium addition by the processes used to a hypereutectic
and 1093.3 C ) for the samples 3403 and 3405 are 7.8 F/min. gray iron suppresses the graphite liquidus ( T G L ) by as much as
and 21.7F/min. respectively. 100 F (55.6C).
4) As pointed out before for the case of hypoeutectic irons Cooling curves of hypo- as well as hypereutectic gray irons do
(curves 3203 and 3208), it m a y be noted that as a result of not exhibit a distinct eutectic initiation arrest (TEN). Whereas
post inoculation treatment the silicon of the original iron the hypoeutectic gray irons exhibit a d o m e shaped bulk eutectic
increased by about 0.46% and the C E by 0.12%. The T E N arrest ( T E U T E R T S ) the hypereutectic gray irons exhibit
temperature was raised by about 17F (9.4C). These a more or less flat eutectic arrest, ( T E U = T E R ) .
substantial increments cannot be only due to increase in C E . Presence of magnesium suppresses the bulk arrests
Thus, in hypereutectic melts the nucleating effect of post significantly. The hypoeutectic compositions show a flat
inoculation is very significant. In addition to nucleation sites, ( T E U T E R ) or a continuously declining ( T E R > T E R > T S )
the silicon provides pockets of high graphitizing potential. bulk eutectic arrest. O n the other hand, the hypereutectic
This results in considerable reduction in eutectic under- compositions feature a distinct eutectic initiation arrest ( T E N )
cooling ( T E N - T E U ) and eutectic recalescence ( T E R - T E U ) . and a d o m e shaped bulk eutectic arrest ( T E U T E R T S )
Effect of Holding o n Cooling Curves following the T E U event.
Figure 9 presents three cooling curves which are certainly ofthe The eutectic initiation arrest for CE between 4.26 and 4.60%
undesirable type. The carbon and silicon contents of these melts should not be mistaken for an austenite liquidus ( T A L ) of a
are in the range for ductile irons. However, the magnesium levels hypoeutectic iron. A n austenite liquidus is relatively m u c h
are on the lower side (0.021 and 0.034%). Moreover, these melts shorter than a eutectic initiation arrest.
were held in the furnace for varying lengths of time. This was
The effect of ferrosilicon post inoculation of a Mg treated
done intentionally to produce curves for inferior quality irons.
melt is to bring the eutectic arrest temperatures (TEN. T E U and
With reference to Fig. 9 it m a y be noted that only one curve
T E R ) closer to the equilibrium temperature for graphite
(C26) exhibits a distinct graphite arrest at about 2135 F (1168.3
eutectic.
C). This arrest shows considerable recalescence. The most
probable reason for this behavior is a delayed, but rapid growth The rate of recalescence between TEU and TER is greater in
ofthe proeutectic graphite. Thecurves C36and B16do not show post inoculated irons than that in M g treated irons.
any primary arrest. This does not mean that the primary phase The tail end of a curve lor the final iron is more precipitous
did not grow in the high temperature range. Probable reason is than that for the corresponding treated iron prior to silicon post
that the precipitation of carbon occurred gradually over a wide inoculation.
temperature interval. The as-cast microstructure in irons is graphitic if the TEU and
All the three curves in Fig. 9 show distinguishable eutectic T E R events occur above about 2080 F (1137.8 C). A completely
initiation arrests. While C26 shows T E N equal to about 2092 F carbidic structure is associated with the T E U and T E R events
(1144.4C), BI6 exhibits a low value of about 2040 F(l I I5.6C). occurring well below about 2050 F (1121.1 C).
A low value of T E N on the curve BI6 shows the strong
suppressing effect of M g and Bi. Considerable undercooling of the eutectic events TEN and
Another important feature of an undesirable cooling curve is T E U followed by recalescence greater than I5F (8.3,:,C) is
a highly recalescent bulk eutectic arrest. Curve C26 shows associated with degenerate graphite microstructure.
recalescence from about 2077 F (1136.1 C ) to about 2104 F References
(1151.1 C). Curve C36 exhibits a eutectic recalescence interval of
about 60 F (eutectic recalescence = T E R T E U ) . Though the 1. S. Studlik and M. .lagos. "Assessment of Strength of Gray Ir
439
AFS Transactions
the Bums ol Cooling Curves,' roundiv trade Journal, p. 458-464 Ductile Iron." Trans. A F S . Vol. 75, p. 541 (1967).
(Mai 1969). 8 R. Jelle> and I. G. Humphreys. " H o w to Estimate Cupola Metal
2. R. P Dunphy and W S Pellini. "Solidification of Nodular Iron in Composition by Means of Cooling Curves." B C I R A Journal, Vol.
Sand Molds," I lans. A IS. Vol. 60. p. 775 (1952). 9. p 662-631 (1961).
3. W F. Shaw and T. Watmough. "Influence of Minor Elements on 9. R. \V, Heine. M. D. Chaudhari and C. R. Loper, Jr., "Characteriza-
the Properties of Ductile Iron," Trans. A F S . Vol. 79 (1971). tion and Interpretation of Ductile Iron Cooling Curves," Trans.
4. I. C. Humphreys. "Effect ol Composition on the Liquidus and A F S . Vol. 79. p. 399-410(1971).
Eutectic temperature, and on the Eutectic Point ol Cast Irons." 10. M. D. Chaudhari. R. VV. Heine and C. R. Loper. Jr., "Potential
BCIRA Journal, Vol. 9. p. 609-621 (1961). Applications of Cooling Curves in Ductile Iron Process Control,"
5. L. E. Menawati. R. \\ Heine and C. R. Loper, Jr.. "Relationshipof Trans. A F S . Vol. 82 (1974).
Cji.iv Iron Microstructure to Cooling Curves." Trans. A F S , Vol. 78, I I. M. D. Chaudhari. "A I hermoanalytical Study ofthe Solidification
p. 363-373 (1970) of Magnesium-1 reated Irons," Ph.D. Thesis, University of Wiscon-
r> R. 1. Garden, "Basic Principles ol Carbon Equivalent Determina- sin (1972).
tion and Dip Temperature Measurement of Cast Iron." Instrument 12. II. D. Merchant. "Recent Research on Cast Iron," Proceedings of a
Engineer, Vol. 2. p. 26-28 (1964). Seminar sponsored by A S M , Detroit, Michigan; Gordon and
7. C. R. Loper, Jr., R VV. Heine and A. Shah, "Thermal Analysis of Breach Science Publishers New York. p. 101-108 (June 1964).
APPENDIX

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