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A new concept in thermal analysis of castings

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A New Concept in Thermal
Analysis of Castings
E. Fras
W. Kapturkiewicz
University of Mines and Metallurgy
Cracow, POLAND
A. Burbielko
Dnepropetrovsk Metallurgical Institute
Dniepropetrovsk, UKRAINE
H.F. Lopez
University of Wisconsin-Milwaukee
Milwaukee, Wisconsin
ABSTRACT
In rhis work, a new method o f the rmol analysis called the Fourier
analysis is presented. The proposed method avoids the introduc­
tion o f any arbitrary assumptions on the relative shape o f the
baseline. The Fourier analysis is based on measurements o f the
temperature fields o f the liquid metal during solidification. Fur­
thermore. this method is compared with the Newtonian analysis,
which assumes a exponential shape fo r the baseline. It isfound that
the predictions o f these methods differ greatly in predicting cool­
ing rates and volume fractions o f solidified phases. Comparisons
of predictions o f the Fourier method in cast iron o f eutectic and
hypoeutectic composition are in good agreement with experimen­
tally determined cooling curves and heat generated curves.
Fig. 1. Cooling curves and cooling rate curves for cast iron.
AFS Transactions
INTRODUCTION
Thermal analysis is a very useful tool in investigating the thermal
events that take place when a given material is cooled (or heated). In
the case of liquid-solid transformations, the whole solidification
process can be analyzed and recorded from cooling curves. The
information thus generated can be used in a quantitative or qualita­
tive sense to discern the solidification phenomena.1 Among the
thermal analysis techniques currently used are:
• Cooling curves and derived cooling curves (cooling rate
curves)
• Differential Thermal Analysis (DTA)
• Differential Scanning Calorimetry (DSC)
• Newtonian Heat Analysis
The use of cooling curves is perhaps the oldest technique,2 and it
consists of plots of temperature versus time for a solidifying metal,
as shown in Fig. 1. Although the solidification history is contained
in the cooling curve, the most frequently measured changes are only
related to alloy composition and phase transition temperatures.2' 9 An
example of this is the existing relationship3 between the temperature
of the austenite liquidus arrest (TLA) and the carbon equivalent (CE).
Figure 1 also shows the first derivative of the cooling curve.
Notice that the derivative at each point along the cooling curve is
numerically equivalent to its slope and represents the rate of cooling
of the metal. Mathematically, the data on the cooling curves can be
differentiated by means of analogical or digital computers.10- 15As a
result, cooling rate curves are generated that, in conjunction with the
cooling curves, enable the determination of characteristic param­
eters. These parameters are then correlated with properties such as
the strength or hardness16 of the as-cast microstructure.17-22 A more
recent development has been the employment of two thermocouples
in the melt, one of which is located at the center of the casting whereas
the other is placed near the mold walls.23 This method enables the
determination of an otherwise undetected reaction by any of the
previous techniques (Fig. 2).
Alternatively, a understanding of the solidification processes has
been achieved by the use of differential thermal analysis (DTA)24 or
differential scanning calorimetry (DSC).23 By these means, the
magnitudes of the heats generated and, consequently, the volume
fractions of solidified phases can be established. In the case of DTA,
t i m e <s>
Fig. 2. Experimental determinations of temperature differences
(T^-Tc) with time between the wall and the temperature of the
center of a casting.22
93-131 505
the heat evolution or absorption during the phase transformations is
determined from the difference in thermal events that occur between
This experimental method has been used by various workers,1'3'
the sample and a reference. The DSC works under a similar principle,
'2-18~5-:9
but it also includes a source of heat that is used to balance the
coworkers.18-27 The method is based on the following:
temperatures of the sample and the reference. Consequently, the heat
generated during the solidification process can be determined.
Although the DTA and DSC techniques provide useful informa­
tion, they are of limited use in foundries due to limitations in
sampling and laboratory instrumentation. A different approach use­
ful in generating similar information to that produced by DSC or
DTA equipment has been proposed in various reports,'O-12-18'23-26-29
and it will be referred to as the Newtonian method in this work.
Newtonian Thermal Analysis Theory
The heat flow generated during solidification (q5) can be determined
from the heat balance equation for a casting-mold system.
qs = qac - q« = c vT - q su /M (1)
1i
T = dT/dt (2)
where qac is the rate of heat accumulated in the metal
q* is the heat transferred to the mold
Cv is the volumetric specific heat (J/cm-K)
T is the rate of metal cooling (K/s)
M is the casting modulus (cm)
qsu is the heal flow from the surface of the casting to the
surroundings (W/cm).
Equation 1 can be rewritten as:
q* = cv( T -Z n) (3)
where Z n can be considered as the Newtonian zero curve or baseline
and it is given by:
Z n = qsu / cvM (4)
In order to find out Zn. the heat released to the surroundings has
to be determined. This can be accomplished in various ways depend­
ing on the shape of the casting. In the case of relatively thick plate
shapes and sand molds, qsu can be estimated from:
(Ts Tn cm Ym (5)
where the subscript m refers to the mold
Ts is the temperature of the inner mold surface
Tm is the initial temperature
cm is the specific heat
Xn, is the thermal conductivity
Yn, is the mold density.
The Newtonian zero curve can be determined by combining
Equations 4 and 5, and. hence, the kinetics of the solidification
process can be established from:
(6 )
where fs is the fraction of solid phase
L is the volumetric latent heat (J/cm3)
tb is the time at the onset of solidification.
506
Extrapolation Methods of Experimental Data
js described in some detail by Stefanescu and
• Obtaining a cooling curve as well as its first and second time
derivatives.
• Identifying the onset and the end of solidification from the
second derivative. The time, lb, is given by the inflection point
at which this derivative changes sign. The end of solidification
is characterized by a sharp minimum in the cooling rate curve
(Fig. 3a).
• Fitting, by extrapolation, a carve of the type T = -A exp(-B l)
between the onset and the end of the cooling rate curve (Fig.
3a). This defines the Newtonian zero curve, and it represents
the cooling curve after excluding solidification effects. The A
and B constants are determined from data on the cooling rate
curve at the beginning and end of solidification.
• Calculating the areas between the cooling rate curve and the
zero curve for the tb - t* time interval. This area, times the
specific heat, yields the latent heat of solidification and can be
used for the determination of the volume fraction of solidified
phases.
The major drawbacks of the Newtonian method are:
• It does not take into account the temperature gradients exist­
ing in the casting. In general, this gradient gives rise to in­
homogeneous volume fractions of solidified phases at differ­
ent locations within the casting, as shown in Fig. 4.
• Experimentally, it is arbitrarily assumed that the zero curve
obeys an exponential expression that can be determined by
extrapolation of the cooling rate curve. Nevertheless, this
assumption can give rise to a large source of error in interpret­
ing the solidification kinetics.
In the next section, a new thermal method that avoids the
shortcomings of the Newtonian method will be presented. The bases
for this method have already beer, described elsewhere,30 and it will
be called Fourier thermal analysis.
Fourier Thermal Analysis
Assuming that heal transfer by heat conduction is dominant in metal-
mold systems, the temperature of the metal after mold pouring can be
determined from the Fourier equation, which includes a heat source.
This equation can be written as:
0 2T / dt2) = aV 2T + (q5/ c») (7)
This equation can be described in terms of the heat generated
during solidification qs:
q* = cvT - a c v V 'T (8)
where a is the thermal diffusivity (cm2/sec). Equation 8 can be
rewritten as:
qs = c v( T - Z f ) (9)
where Zf is the Fourier zero curve or baseline, and it is given by:
ZF = aV :T ( 10)
According to the above expressions, when the thermal diffusivity
and the temperature field T(x,t) are known inside the metal, the
magnitudes of the various heat rate contributions can be established.
AFS Transactions
Experimentally, a minimum data of three temperature points is Constant Thermophysical Parameters
necessary for the determination of the laplacian V2T. Nevertheless, When there is no heat generated during the solidification of a given
in symmetric temperature fields (with respect to the vertical axis of cast metal (i.e., during melt cooling from the pouring temperature to
the system), these data points are reduced to only two (see Fig. 5). the liquidus temperature, or alter solidification), q, = 0 and the
Thus, by introducing two thermocouples in the casting, it is possible thermal diffusivity can be determined from Equation 7 as:
to find V2T.
Consider a cylindrical casting in which the laplacian can be (15)
written in cylindrical coordinates as:
V2T = 0 2T / d r 2) + ( l / r ) (3T/ dr) ( 11 ) Thus, when T and are experimentally known before and
alter solidification, the thermal diffusivities of the liquid and solid
The components of Equation 11 can be tscribed by:
can be found. If both thermal diffusivities have similar values, the
kinetics of the solidification process can be established by:
a^r jq ^ -° = 2 (T2 -T ,) • determining the zero curve Zp from Equation 10;
( 12)
Sr2 R1 + ^ R f-R f • determining the rate of heat generation during solidification
(Eq. 9);
and • determining the solidification kinetics by means of Equations
6 and 9.

1 3T 1 ( T2 - T , >| 2(T2 - T , )
(13) Variable Thermophysical Parameters
7 * r=r> = R ) + ! l i M r2 -R J Rt - R ? When the thermal diffusivities of liquid and solid are different (Fig.
6), it can be assumed that the thermal diffusivity is a function of the
Thus, substituting Equations 12 and 13 into equation 11 yields: volume fraction of solid phase. The same argument can be applied to
the specific heat. Hence, when the cooling curves and the cooling
4(T2 - T |) rates are known from beginning to end of solidification, the follow­
V2T = (14)
R |- R 2 ing expression can be assumed as a first order approximation:
f = f sJ(l) = (t-tb) / ( t e- t b) (16)
Determination of the heat rates generated are also influenced by
a and cv. In gray cast irons, it is found that the thermal diffusivities
and specific heats vary from 0.0397 to 0.0701 cm2/s, and 5.278 to
5.859 J/(cm3s), respectively. In the following sections, two cases are
considered.

Fig. 4. Influence of carbon on the volume fraction of solidified

cementite eutectic in a 30-mm dia rod of Fe-C alloy. Continuous
lines correspond to experimental data, dashed lines are calculated
volume fractions from the phase diagram.
(3a)

(3b)

Fig. 3. Newtonian zero curves: (a) predicted from dT/dt = A exp

(Bt) for A and B values o f-2.253 C/s, and -0.003, respectively; (b) Fig. 5. Schematic representation of the temperature field used for
Newtonian zero curve predicted by Backerud and Krol.29 the determination of V?T.

AFS Transactions 507

 This is a lineal function that can give rise to significant error when COMPARISON OF FOURIER AND
the differences in a or e» values between liquid and solid are NEWTONIAN METHODS
relatively large. To avoid this problem, an iterative procedure, in
which Equation 16 is only the first iteration, can be employed: An illustration of the previously described method is now presented.
For this purpose, experimentally determined cooling curves for-a
a „ (t) = a b [l- f ,.,,( t) ] + o q fs,„(t) (17) gray iron are used. Also, a comparison is made with cooling curves
produced by computer simulations31 based on the data of Table 1.
C v .ii( t) = C v .|[ l - - f i . i i ( t ) + C v ,s f s . i t ( t ) ] (I8)
ZF.„(t) = a ,t( t) V 2T (19)
Eutectic Alloys
q s .ii (t) = cViil(t)(T (t)-Z F.il(t)] (20)
Figure 7 shows the cooling curves and the first and second deriva­
tives predicted at 1.6 and 8 mm away from the center of the casting.
U = f \.i« ( U d t (21) The corresponding Fourier and Newtonian zero curves are given in
\ Fig. 8. According to this figure, there is a remarkable difference in
these curves. In particular, the Newtonian zero curves are described
l f
fs .i,( t) = — (22) by a rather artificial exponential expression. In contrast, the Fourier
H i \ analysis is based on the natural temperature gradient curve.
Consequently, the predictions of the generated heat rates exhibit
Here cv.i and cv,5 are the specific heats of liquid and solid, different trends (Fig. 9). The Fourier method predicts a curve qStF,
respectively, cq, and cq are the initial and final values of thermal which exhibits a maximum at the end of solidification, in contrast
diffusivity. The thermal diffusivity values are determined from plots with the Newtonian analysis, which predicts a maximum qs_Nnear the
of Equation 15, and it is shown in Fig. 6 for cast iron of eutectic onset of solidification. Consequently, at a given solidification time,
composition. these methods predict completely different eutectic solidification
Since, in addition to the thermal diffusivities. T and V-T can be rates and fractions of solidified eutectic (Fig. 10). Also, the predicted
experimentally determined, then the Fourier zero curve, and the heat curves on solidified fraction arc concave in the Fourier analysis
flow components qac and qu can be established. Finally, from these whereas they exhibit a convex shape in the Newtonian method.
data, the rate of heat generated and, consequently, the volume Experimentally, it has been found31 that the Fourier analysis is able
fractions of solid phase can be estimated. to replicate, very closely, cooling curves in eutectic cast iron.

Table 1.
Thermophysical and Initial Parameters

N am e and U nits Value

Thermal conductivity, W/(cmK):

• liquid cast iron 0.18
• solid cast iron 0.37
■ sand mold 0.065+(T-625)2xlO '‘
Specific heat, J/(g K):
• liquid cast iron 0.837
• solid cast iron 0.754
• sand mold 1.6
Latent heat, J/cm 3:
Fig. 6. Evolution of T/ V2T with time and calculated thermal • austenite 1905
diffusivities using the iteration method. • graphite eutectic 1833
Linear growth coefficient, cm/(K s2):
1350 • austenite 7 .0x10s
• graphite eutectic 2.0x10*
1300
Nucleation coefficient, l/(cm 3KI):

1250 • austenite 0.5X103

<U • graphite eutectic 3.5
1 1200 Initial temperature, °C:
• cast iron 1340
I 1150
• mold 20
1100 Composition of cast iron, % mas.:
• C (eutectic/hypoeuteciic) 3.70/3.51
1050 1.92
• Si
0 50 100 150 200 250 300
• P 0.106
Time, s
• Mn 0.36
Fig. 7. Cooling curve and first and second derivatives predicted by Distribution coefficient: C Si P
computer simulations for eutectic cast iron. The cast part is • austenite-liquid
assumed to be cylindrical of 32-mm dia and r is the distance from
• carbide-liquid 0.05 0.09
the center of the casting.

508 AFS Transactions

Hypoeutectic Alloys
Figure 11 a shows the experimental, as well as the predicted, cooling
curves found at 1.6 and 8 mm away from the center of a casting of
cylindrical shape the diameter of which is 32 mm. The corresponding
cooling rate curves are given in Fig. 11b. Again, the experimental and
predicted zero curves using the Fourier and the Newtonian methods
are completely different.
Fig. 8. Evolution of the first derivative T (cooling rate curve) and
zero curves predicted by the Fourier method (ZF) and various
Newtonian methods. ZNs, corresponds to the extrapolation method
by Stefanescu, ZNm is for the transfer of heat from the surface to
the surroundings, and ZNs,m is a computer simulated curve.
0 50 100 150 200 250 300
Time, s
Fig. 9. Heat generation curves predicted by Fourier and Newtonian
methods during the solidification of eutectic cast iron based on the
Fourier (qs, F) and Newtonian (qs, N) analyses. Notice the negative
peak disappearance as the distance Rz-R , used in V^T evaluations
is reduced.
Time, s
Fig. 10. Comparisons of solidified volume fractions predicted by
the Fourier, fs F and the Newtonian fs N methods for eutectic cast
iron.
AFS Transactions
Consequently, these methods predict rates of heat generation
(Fig. 12c) and solidified fractions (Fig. 13) that are in conflict with
each other. Since the Fourier analysis is based on the actual tempera­
ture field of the metal, it is expected to be more reliable in its
predictions when compared with the Newtonian method. Thiscan be
further confirmed by the comparisons of Figs. 11 and 12, which show
very close resemblance between the shape of the experimental
cooling curves and heats generated with those predicted by the
Fourier analysis.
Finally, the Fourier method can be applied in relatively fast
determinations of volume fractions of primary phases, such as
dendrites, which cannot be determined by other means—in particu­
lar. for gray iron and Al-Si alloys where the primary austenite or a
phase cannot be clearly distinguished from the eutectic constituents.
As a result, there is only a limited amount of information on the
influence of various factors on the volume fractions of solidified
phases.
Volume fraction determinations from phase diagrams are not
accurate because solidification occurs under non-equilibrium condi­
tions (Fig. 4). In addition, it is experimentally found that the solidi­
fied volume fractions are a function of the distance from the center
of the casting (see. for example, the case of white cast iron in Fig. 4).
The Fourier analysis enables the prediction of solidification rales and
solidifying fractions at different locations within the metal and can
be used for comparisons with experimental determinations. These
type of predictions are not possible by the Newtonian method.
CONCLUSIONS
A new method of thermal analysis called Fourier Analysis is pre­
sented in this work. The method is based on temperature measure­
ments during solidification at two points that are displaced a small
distance.
Fig. 11. Comparisons of (a) expehmentally and simulated cooling
curves and (b) experimental cooling rate curves and zero curves in
hypoeutectic cast iron versus simulated curves using the Fourier
and the Newtonian methods.
509
 This method enables the determination of the baseline without
introducing by arbitrary assumptions on its relative shape, unlike the
Heal Generation Role. W/ccm
Newtonian analysis.
Comparisons between the Fourier and the Newtonian thermal
analysis give rise to strikingly different observations on the solidifi­
cation kinetics. Since the Fourier analysis is based on the actual
temperature field of the metal, it is considered to be most reliable in
its predictions.
The Fourier method can be employed for determinations of
solidification rates and volume fractions of solidified phases as a
function of location within the metal. Furthermore, these results can
be correlated with parameters, such as chemistry, inoculation, time
Heal Generation Rale. W/ccm

and temperature of the melt. Finally, it can be used for verifications

between theoretical models and experimental measurements.

ACKNOWLEDGMENT
This work was partly supported under the Polish KBN Project, Grant
No. 301399101.

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Fig. 12. Predicted rates using the Fourier method for heat
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0 50 100 150 200
Time, s
Fig. 13. Comparisons of experimentally determined solidified
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methods and the predictions of the Fourier analysis for hypo­
eutectic cast iron.
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