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Computer-Aided Cooling Curve Analysis

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Computer-Aided Cooling
Curve Analysis Revisited
J.O. Barlow
D.M. Stefanescu
University of Alabama
Tuscaloosa, Alabama
ABSTRACT
Computer-aided cooling curve analysis (CA-CCA) of alloys is
used extensively for the evaluation of several processing and
material parameters. Primarily, cooling curve analysis is used
for process control in the metalcasting industry, usually to
predict alloy composition, alloy propensity for production of
sound castings and elements of the microstructure. However,
the use of CCA may be expanded to other areas of solidification,
but only if the calculated values are reasonably accurate. Cal-
culation accuracy depends heavily on the evaluation of the zero
curve. Most papers on the subject avoid an exact description of
zero curve calculation. Consequently, the calculated features
are questionable.
This paper provides a mathematical description of several
methods of zero curve calculation, and then an evaluation of the
performance of various approaches based upon calibration
using latent heat calculation. It was found that Fourier analysis
has the potential for the most accurate description of solidifica-
tion events based on CCA. Significant discrepancies were found
among predictions of evolution of fraction solid, dendrite coher-
ency, Fourier analysis and more established methods, such as
Newtonian analysis.
MATHEMATICS AND INTERPRETATION
Computer-aided cooling curve analysis of alloys can provide infor-
mation about the composition of the alloy, the latent heat of solidi-
fication, the evolution of the fraction solid, the amounts and types of
phases that solidify, and even dendrite coherency.14 There are also
many other uses for CCA, such as, determining dendrite arm spac-
ing,5,6 degree of modification and grain refining in aluminum al-
loys,710 graphite morphology and the degree of nodularity in cast
irons,1,11,12 and even determining the most effective heat treatment
cycle for the production of austempered ductile iron.13 The use of
cooling curves for process control in the foundry is very extensive.
There are remarkable differences from paper to paper, both in
terms of experimental devices used and in interpretation of results.
Traditional CCA uses a sand cup with one thermocouple. Newtonian
analysis is used to generate the zero curve required in subsequent
analysis of the cooling curve.1 More recent investigators have used
two thermocouples. The advantage of the two-thermocouple setup is
that it allows a more complete analysis, either in terms of analysis
output, e.g., dendrite coherency,2,3 or in terms of the mathematics
used to generate the zero curve, e.g., Fourier analysis.4
In the following paragraphs, we will discuss the mathematical
foundation of CA-CCA, and the way the information generated is
interpreted to yield answers of interest to the foundryman.
AFS Transactions
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Characteristic Features
A typical cooling curve and its time derivative for an Al-Si alloy are
presented in Fig. 1. The shape of the cooling curve is the result of the
heat lost to the surroundings by the cooling metal and the heat
evolved in the cup during phase transformation. The various events
that can be observed on the cooling curve may be associated with
various transformations occurring during cooling. However, be-
cause the thermocouple actually indicates only an average tempera-
ture over a certain volume, the timing of the event on the curve may
not necessarily be that of the actual transformation. Thus, care must
be exercised when using cooling curve events to pinpoint the occur-
rence and amplitude of a phase transformation.
In principle, TAL (temperature of liquidus arrest) is the point
where primary dendrites (-aluminum for Al-Si alloys) begin to
solidify from the liquid. The change in slope of the cooling curve at
TAL results from the heat of solidification of the phase. TEU
(temperature of eutectic undercooling) is the point where the signifi-
cant eutectic growth occurs. The change in slope arises from the
latent heat of solidification of the eutectic. TES (temperature of the
end of solidification) corresponds to an inflection on the cooling
curve (minimum on the first derivative) that is close to the end of
solidification. However, it is not necessarily the end of solidification.
TES is best determined from the first derivative.
The use of the first derivative of the cooling curve, which is the
cooling rate, improves the accuracy of the determination of the
characteristic features of the cooling curve. A zero value of the first
derivative curve indicates a minimum or maximum on the cooling
curve. Thus, the time-temperature coordinates of TEU can be pre-
cisely identified.
At the beginning of solidification of any phase, the derivative
increases in value (regions 1, 4, 6 on Fig. 1), and decreases at the end
of solidification (regions 2 and 5 on Fig. 1). For the case of dendritic
solidification, one must distinguish between free dendritic growth,
when the dendrites do not touch one another, and dendrite thicken-
ing, which occurs after dendrite coherency. Dendrite coherency is
defined as the fraction of solid at which dendrite tips come in contact,
resulting in a fixed dendritic skeleton. Regions 1 and 2 of the
derivative correspond to free dendritic growth, while region 3
corresponds to dendrite thickening. Region 6 corresponds to the
nucleation and growth of the Mg2Si phase in the 356 alloy, which was
used for this experiment. Note that this event is not visible on the
cooling curve.
TES is shown by the dip in the derivative curve at the end of
solidification (region 7). The inflection on the cooling curve that
corresponds to TES cannot be accurately determined without the
help of the first derivative.
Fig. 1. Cooling curve for an Al-6.5% Si alloy and its first-derivative
curve, with major points labeled.
97-04 349
Calculation of Zero Curve
The zero curve (ZC) is, in principle, the derivative of a cooling curve
of the metal-cup system, in which it is assumed that the metal does
not undergo any phase transformation. This is obviously an imagi-
nary curve. Its calculation is one of the most controversial issues in
CCA. Very few papers explain the procedure used to produce it.
However, any information based on the zero curve will be signifi-
cantly influenced by the method used. Accordingly, a detailed
analysis of available methodologies for zero curve calculation will
be presented in the following paragraphs.
The following approaches to zero-curve calculation will be
considered:
Newtonian analysis
empirical analysis, one heat transfer coefficient
empirical analysis, three heat transfer coefficients
Fourier analysis
The fundamentals of the mathematics of these approaches are
presented in the following text.
Newtonian Analysis
In this analysis, Newtonian cooling of the sample is assumed. This
means that the thermal gradient across the sample is considered to be
zero and that heat transfer between the casting and the mold occurs
by convection. The zero curve is the time evolution of the cooling rate
of the alloy, assuming that no phase changes take place. There is no
unique accepted method to obtain this curve.
Empirical Analysis, Three Heat Transfer Coefficients
In the preceding methods, the common assumption is that the heat
transfer coefficient, h, is a unique monotonous function of time or
temperature. However, a simple examination of the cooling curve
shows that a significant change occurs between the start and end of
solidification. Clearly, the heat transfer coefficient cannot obey the
same continuous function before and after solidification. It is directly
affected by the heat released during solidification. Thus, h is not a
simple function of time, temperature and casting geometry, but also
a function of solidification kinetics.
Simple solutions to this problem are not available. Nevertheless,
an approximation can be used to improve on the Newtonian analysis
of the cooling curve. Such an approximation is illustrated in Fig. 4.
The cooling curve is fitted both before and after solidification, and
zero curves for the liquid state (ZC-L) and for the solid state (ZC-S)
are obtained. Finally, a linear approximation is used in the solid/
liquid region (ZC-S/L).
Fourier Analysis
Fourier analysis assumes that heat transfer takes place by conduction
only. The following analysis closely follows the method suggested
by Fras et al.4 The Fourier equation with a heat source is:
T 1 Q
= 2 T + (2)
t c v t
where cv is the volumetric specific heat, and Q is the heat evolved
during solidification. Rearranging and substituting gives:

In principle, the zero curve may be obtained by equating the rate

of heat loss to the surroundings with the rate of heat evolved from the
metal specimen (assuming no transformation):

hA(T T 0 ) = VC p
dT
(1)
dt
where h is the overall heat transfer coefficient, A is surface area over
which heat is lost, T is the instantaneous temperature of the specimen,
To is the ambient temperature, V is the volume of the specimen, is
its density, Cp is its specific heat, and dT/dt is the cooling rate.
Solving for dT/dt, the zero curve is found. The main issue here is the
value of the heat transfer coefficient.
Assuming that the heat transfer coefficient, as well as the other
thermophysical parameters, are constants, this equation can be Fig. 2. Calculation of ZC by fitting to FDC before and after
integrated to obtain the cooling curve without transformation, which solidification.
is an exponential function. It was shown that the zero curve can also
be expressed as an exponential.1,14 Then, a zero curve can be found
by fitting two points on the first derivative.

Empirical Analysis, One Heat Transfer Coefficient

With the advent of simple spreadsheet software, such as Excel 5.0,
Newtonian analysis can be simplified by fitting a logarithmic or
polynomial curve to selected data on the first derivative curve (FDC).
In one approach, a number of points are selected on the first part
(before solidification) and last part (after solidification) of the FDC,
as shown in Fig. 2. The selection of the number of points to be fitted
is, unfortunately, rather arbitrary, and subsequent analysis will be
influenced by this selection.
In another approach,15 the cooling curve before the beginning of
solidification is fitted. The ZC can be calculated as the derivative of Fig. 3. Calculation of ZC by fitting to cooling curve before solidi-
this curve (Fig. 3). fication.

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 Q T where, fS is the fraction of solid, and the subscripts s and e stand for
= = cv Z F with Z F = 2 T (3)
t t the start and end of solidification, determined from differential
thermal analysis. At each iteration, the thermophysical properties are
where, ZF is the Fourier zero curve. To calculate this curve, the calculated with:
temperature field must be known. For a cylindrical mold, it can be
demonstrated that: (t) = s [1 f S (t)] + e f S (t) (7)

4(T 2 T1 ) c v (t) = c v [1 f S (t)] + c v f S (t) (8)

2T = (4)
R 22 R12
The latent heat and the fraction of solid are calculated as:
where, T2 and T1 are temperatures at radii R2 and R1, respectively. R1
and R2 need to be as close as possible to each other. t Q
L = e (t)dt (9)
t s t
The difference between Newtonian and Fourier CCA lies in the
fact that the thermophysical parameters are considered to be variable
1 t Q
L ts t it
(time/temperature dependent) in Fourier analysis. This is accom- f S (t) = (t)dt (10)
plished through an iterative method. First, the thermal diffusivity
before and after solidification is determined from experimental data
through the use of the following equation: Equation 3 and Equations 710 are used iteratively to calculate
the Fourier zero curve. Typical results are shown in Fig. 5. The time
T / t close to the end of solidification, when FDC and the Fourier zero
= (5)
2T curve start coinciding, can be considered the end of solidification.
This occurs earlier than the minimum at the end of the FDC (position
Then, in order to start the iteration, the fraction of solid curve is 7 on Fig. 1).
assumed to be linear:

T Ts t ts Interpretation
fS = = (6)
T e Ts t e t s
As discussed previously in this paper, there are many different uses
for the cooling curve. The following discussion will be restricted to
the use of CCA for quantitative solidification interpretation. Accord-
ingly, we will analyze the application of CCA to the evaluation of
latent heat, to the study of fraction of solid evolution and to the
assessment of the onset of dendrite coherency.

Latent Heat Calculation

The latent heat released by the solidifying alloy at any time, t, can be
calculated as:

n dT dt t dT dt
C pi tS
t
Lt =
dt CC tS dt
i =1 ZC
(11)
[ C pi ( A CC |t A ZC |t )]
n
=
i =1
Fig. 4. Calculation of ZC by fitting to cooling curve before and after
solidification, and using three different heat transfer coefficients. where n is the number of phases evolved during solidification, (dT/
dt)CC is the FDC of the cooling curve, ACC is the area under the FDC
and AZC is the area under the zero curve. Integration is performed
between the start of solidification, tS, and the current time, t, to find
the latent heat evolved at the current time, or between tS and the time
of end of solidification, tE, to find the total latent heat evolved. This
equation can then be numerically solved by using a spreadsheet.

Fraction of Solid Calculation

The fraction solid can also be found by using the zero curve and the
FDC. It can be calculated on the spreadsheet as:
Lt
fS = n
(12)
(L i f Si )
i =1

where, Li is the tabulated latent heat of phase i, and fSi is the total
Fig. 5. Calculation of ZC by Fourier analysis. fraction of phase i.

AFS Transactions 351

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Determination of Dendrite Coherency
The two-thermocouple method allows one to follow the formation
and progression of solidifying phases as heat waves, because the
phases will nucleate at the wall and then move toward the center. The
temperature difference between the wall and the center thermo-
couple, T, can be used to evaluate dendrite coherency, as shown in
Fig. 6. The minimum of the curve is dendrite coherency because the
forward growth of the dendrites stops in the center, and then the T
curve begins to return to the steady-state value of approximately 0C
as the dendrites thicken throughout the casting.2,3
However, rather than returning to the steady-state value after
region 3, the temperature difference curve indicates another event at
region 3a. This is the precipitation of the iron-bearing phases in alloy
356. This reaction cannot be seen on the FDC shown in Fig. 1. The
ability to see the formation of additional phases and to determine
dendrite coherency shows the advantage of using the two-thermo-
couple method.
Fig. 6. Plot of temperature difference between wall and center of
the cup for an Al-7.8% Si alloy.
EXPERIMENTAL PROCEDURE
The purpose of the experimental work was to compare the various
methods of CCA discussed in this paper. The comparison included
latent heat, solid fraction evolution and dendrite coherency calcula-
tions.
The cup used for the CCA in this work is shown in Fig. 7. It was
instrumented with three type K thermocouples. This cup allows for
CCA by all the methods previously discussed. However, for any
method, a maximum of two thermocouples are needed. The cup was
made of 1.0-mm steel sheet and was coated with graphite spray.
A 20-lb melt of alloy 356 was prepared in a silicon carbide
crucible, using a 100-kW high-frequency induction furnace. The
composition of the melt, as determined by mass spectrometry on a
chilled sample, was as follows: 6.55% Si, 0.42% Fe, 0.30% Mn and
0.30% Mg. Then, the composition was altered by raising the silicon
content to 7.81% by additions of an Al-50%Si alloy. Finally, the
silicon content was raised to 8.36%. Thus, three melts of different
compositions were obtained.
Each melt was superheated to approximately 750C, after which
a cooling curve was collected on a data acquisition system at a rate
of 1 Hz. To obtain a cooling curve, the cup was immersed into the
melt for approximately 20 sec to fill up and allow the temperature in
the cup to equilibrate with the temperature of the melt. The cup was
then immediately placed onto a cast iron plate and the thermocouples
were quickly inserted into the molten sample at the appropriate
positions.
After solidification, the samples were removed from the cup, and
the positions of the thermocouples were measured using a caliper.
The collected cooling curve data was then processed in various ways
using a spreadsheet. The processing included different smoothing
and curve fitting techniques.
Five-point central smoothing of the temperature was used for all
of the plots generated. More smoothing eliminated the initial cooling
portion of the curve, and less smoothing introduced electrical noise
into the FDC. Using the average at every third point for smoothing
proved to be almost identical to three-point central smoothing. Both
still exhibited significant noise in the FDC.
After evaluation of results for all thermocouples, final calcula-
tions were performed for the center and mid-radius thermocouples
because they exhibited less noise than the wall thermocouple.

RESULTS AND DISCUSSION

Latent Heat Evaluation

Fig. 7. Thermocouple cup used for several CCA methods. The sole purpose of latent heat evaluation from CCA in this work was
to calibrate the method used for cooling curve interpretation. Specifi-
cally, it was assumed that, if the latent heat predicted was close to that
Table 1. tabulated for the respective alloy, the method employed to obtain this
Latent Heat Values (kJ/kg). latent heat was correct.
One heat One heat Three heat The calculated latent heat and the literature values for the three
transf. coef. transf. coef. transf. coef.
%Si Fit of FDC Fit of initial CC Fourier Literature16 alloys used in this work are shown in Table 1. Four different methods
6.55 220 195 246 419 389 of interpreting the cooling curve were used. It can be seen that the
closest value was obtained with the Fourier analysis.
7.81 240 201 247 418

8.36 245 254 288 440 It is also seen that the evaluation of the latent heat, through the
Calculated values obtained using Cp = 963 J/(kgC) and = 2685 kg/m3 (from Ref. 16).
Newtonian analysis, is strongly dependent upon the fitting method
used. This implies that this is not a very reliable method to determine

352 AFS Transactions

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Copyright 2002 American Foundry Society.
the latent heat of an alloy. The Fourier analysis provides a better fit. Table 2.
This method requires that the values of the thermal diffusivity Dendrite Coherency as Predicted by Selected Fits of Zero Curve
directly before and after solidification be used. This was not entirely
Silicon Newtonian Fourier
obvious in the method described in Reference 4.
% Analysis Analysis Ref. 2,3

6.55% 0.43 0.14 0.23

Fraction of Solid Evolution
The fraction of solid vs. time curves for all three compositions are
shown in Fig. 8 for Newtonian and Fourier analysis. There are visible
differences in the two fraction of solid curves calculated. The Fourier
zero curve more closely resembles modeled data using heat trans-
fer-solidification kinetics models. The main reason is believed to be
the fact that the Fourier analysis uses variable thermophysical
properties.
Dendrite Coherency
To evaluate dendrite coherency, the two-thermocouple method was
used, as described earlier in this paper and as illustrated in Fig. 6. The
fraction of solid corresponding to dendrite coherency was calculated
from the Newtonian and Fourier analysis of the respective samples.
The results obtained by these methods, as well as literature results,
are shown in Table 2. It is seen that relatively large differences exist
between the prediction resulting from the Fourier and Newtonian
analysis. Our calculations are also different from that of Backerud
et al.2,3
While Backerud does not report the method of generation of the
zero curve, from the shape of these curves it can be concluded that
they are most probably produced through fitting by empirical analy-
sis for one heat transfer coefficient. In view of the previous discus-
sion, it is believed that the results obtained through Fourier analysis
are conducive to the most accurate data from all the methods
presented in this paper.
7.81% 0.35 0.13
8.36% 0.30 0.11
Figure 9 illustrates the dependency of dendrite coherency on the
Si content and on the cooling rate (taken at the minimum between
primary and eutectic solidification). Increasing the silicon content
decreases the point of dendrite coherency. This is probably because,
as the silicon content increases, the dendrites have less time to
develop secondary and higher-order arms, and thus are thinner, and
occupy less volume.
Also, as the magnitude of the cooling rate increases, the solid
fraction of dendrite coherency increases. This is to be expected
because the sample with the greater cooling rate will also have
larger gradients in it, which will allow the dendrites to thicken more
and, therefore, dendrite coherency will occur at higher fraction
solid.
CONCLUSIONS
A limited number of experiments involving Al-Si alloys with three
levels of silicon (6.55, 7.81 and 8.36%), and CCA cups using three
thermocouples were run. An in-depth analysis of the methods
presently used for CA-CCA was presented and performed on these
alloys.

Fig. 8. Calculated evolution of fraction of solid at center of samples.

Fig. 9. Variation of dendrite coherency with: (l) %Si and (r) cooling rate.

AFS Transactions 353

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Copyright 2002 American Foundry Society.
 To evaluate the accuracy of the methods used, literature and
computed latent heat values were compared. In general, using the
best fit of the Newtonian zero curve, unsatisfactory results were
obtained. A better approximation was achieved when using the three-
heat transfer coefficient method developed in this paper.
The Fourier analysis provides a more accurate means of deter-
mining the zero curve. The iterative technique is, however, very
dependent upon the points chosen for the beginning and end of
solidification. The beginning and ending values are determined by
the thermal diffusivity values chosen for the fit. The correct values
to choose can be determined by differential thermal analysis. Also,
the method requires two thermocouples.
The evolution of the fraction of solid, in time, is significantly
affected by the choice of zero curve. A Newtonian zero curve results
in a nearly linear fraction of solid evolution. The fraction of solid
evolution calculated through the Fourier method is more accurate
because variable thermophysical properties are used. Thus, a more
realistic picture of solidification can be provided. The Fourier
analysis-based fraction of solid curves also more closely resembles
the fraction of solid curves generated by heat transfer-solidification
kinetics models.
Dendrite coherency was determined from both Newtonian and
Fourier analyses, and compared with literature data. The values for
dendrite coherency obtained from Fourier analysis were in the range
of 0.110.14, which is considerably smaller than data obtained
through Newtonian analysis, or the 0.23 value found in the litera-
ture,2,3 probably also obtained through some Newtonian-type calcu-
lation. Dendrite coherency decreases with increasing Si content and
decreasing cooling rates.
354
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AFS Transactions