Materials Science and Engineering A 419 (2006) 283–289

Study on the eutectic modification level of Al–7Si Alloy by computer

aided recognition of thermal analysis cooling curves
Xiang Chen, Huiyuan Geng, Yanxiang Li ∗
Department of Mechanical Engineering, Key Laboratory for Advanced Manufacturing by Materials Processing Technology,
Tsinghua University, 100084 Beijing, China
Received 19 September 2005; accepted 31 December 2005

Abstract
The effect of Sr content on the Al–7Si solidified microstructure was investigated. And the eutectic silicon modification level assessment of
Al–7Si alloys was studied combined with the computer aided cooling curve pattern recognition method. It has found that the eutectic silicon
modification level of Al–7Si alloy increases with the increase of Sr content. The eutectic structure is fully modified when the Sr content reaches
56 ppm. While the modifier addition is given, the modification level decreases with the increasing of holding time. When the modifier addition is
small, the modification level decreases with the increasing of holding time. But when the Sr addition is at a higher level, the modification level
sustains at the initial period of holding time, and then decreases with the holding time. The results of modification level assessment show that
the modification level difference converges to zero when the comprehensive parameter, which expresses the difference between cooling curves,
approaches to zero. The whole shape of the solidification segment of a thermal analysis cooling curve can token the eutectic silicon modification
level of the Al–7Si alloy melt. The modification level can be precisely assessed by comparison of the cooling curve of the melt to be evaluated
with those in a database to find the one most similar to it. Based on a database established from a large amount of experimental results, the on-line
prediction of eutectic modification level of Al–7Si alloy melt has been realized.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Aluminum–silicon alloy; Modification; Thermal analysis; Cooling curve recognition

1. Introduction Most contemporary evaluations of the modification level are

Due to their excellent castability and good mechanical prop-
erties, aluminum–silicon (Al–Si) alloys are the most impor-
tant and most widely used casting aluminum alloys. A further
increase in mechanical properties can be achieved by means of
a modification treatment with sodium or strontium. Modifica-
tion of eutectic silicon has become a basic practice for the near
eutectic alloys. Without this treatment, the unmodified eutec-
tic silicon crystallises into an acicular or lamellar morphology;
when the modifying elements are added, the eutectic silicon
phase becomes a very fine and fibrous silicon network resulting
in an additional improvement to the alloy mechanical properties,
especially in a remarkable increase in elongation [1–7]. So it is
very important to determine the modification condition reliably
prior to casting.
∗ Corresponding author. Tel.: +86 10 62773640; fax: +86 10 62770190.
E-mail address: yanxiang@tsinghua.edu.cn (Y. Li).
done according to the standard wall chart prepared by American
Foundry Society (AFS) that attempts to classify microstructure
of aluminum–silicon alloys with different modification condi-
tions by the method of metallographic investigation of a section
taking from the casting or a special sample. But this qualitative
analysis procedure is subjective to and quite dependent on expe-
riences of the operator and can introduce human-caused errors.
And this procedure is also expensive, time-consuming and can-
not be used to evaluate the modification level on-line.
The on-line prediction of grain refining and modification
level is very important for quality evaluation and control of
aluminum–silicon alloy castings. Generally, thermal analysis is
used to evaluate the melt quality. By this method, some char-
acteristic values are extracted from a cooling curve and/or its
derivative, and then a regression relationship is built up between
the characteristics and quality indexes as grain size, eutectic
structure, silicon morphology and so on. For silicon modifi-
cation assessment, the eutectic growth temperature difference
between modified and unmodified melts (
TE ) are used to indi-
cate the modification level [5,6]. The larger the magnitude of

0921-5093/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2005.12.036
284 X. Chen et al. / Materials Science and Engineering A 419 (2006) 283–289

TE , the higher the level of modification. Then the regression

analysis and/or the artificial neural network method are used to
analyze the relationship between them. This method requires the
eutectic growth temperature of aluminum–silicon alloys unmod-
ified which is time-consuming and sometimes unrealizable if the
metal comes from the supplier already pre-modified with stron-
tium in production. On the other hand,
TE also could be largely
influenced by many other factors, i.e., the content of Si, Mg, Fe,
Cu and cooling rate of the melt and thus make the assessment
of modification level unbelievable [7].
Go beyond the
TE , many other characteristic parameters
determined from the cooling curves, such as eutectic recales-
cence temperature, eutectic recalescence time, eutectic growth
time, etc., are also correlated to the modification level of eutectic
silicon [8]. Based on the Newton heat transfer equilibrium equa-
tion, square root law and equilibrium diagram of Al–Si alloy,
Xiong et al. [9] calculated the mean solid growth acceleration Fig. 1. A schematic diagram of the cooling curve pattern recognition methods.
during eutectic solidification, and the results showed that the
mean solid growth acceleration can be used to quantify the mod-
as the fingerprint of the melt quality, not only any tiny differen-
ification level of Al–Si alloys. But under modification and over
tiation in the melt quality will give rise to changing of the shape
modification of Al–Si alloys cannot be identified by this method.
of the cooling curve, but also similar cooling curves should indi-
Mackay et al. [10] investigated solidification range and fraction
cate similar melt quality. So we can comprehensively evaluate
solid of eutectic solidification of A319 alloys. It was found that
the melt quality by measuring the shape of the thermal anal-
the solidification range and fraction solid of eutectic solidifica-
ysis cooling curve, and the quality of the measured melt can
tion has a distinct relationship to silicon modification level. But
be evaluated by another melt whose freezing zone of cooling
the fraction solid of eutectic solidification can also be influenced
curve is very similar to that of the measured one under a fixed
by grain refinement of the alloy.
solidification condition.
All those facts mentioned above have proved that the cor-
Fig. 1 shows a schematic diagram of the cooling curve pattern
relation of the characteristic parameters depends on the set up
recognition method. To recognize a cooling curve, a comprehen-
condition very much. So, by present, the assessment of modi-
sive method to compare cooling curves was developed. The total
fication level of Al–Si alloys with thermal analysis method has
difference between two cooling curves could be expressed with
not been widely used in practice.
the following parameter Ω:
The authors brought forward a new pattern recognition


method to evaluate the melt quality [11–16], that is the shape |
Ti |
of the freezing zone of a thermal analysis cooling curve can be Ω= +S (1)
n
served as the fingerprint of the melt quality. This method has

been used to comprehensively evaluate the grain refining effi- where

Ti = Ti − Ti  , S = [ (
Ti −
T)2 /(n − 1)]1/2 ,
ciency of aluminum–silicon alloys [13], nodularity of ductile
T =
Ti /n, and Ti and Ti  are the temperature values of two
irons [14], and graphite morphology of heavy section ductile compared cooling curves at the same time respectively, and n
irons [17] successfully. In this paper, this new method was used is the number
of comparison points of the two cooling curves.
to evaluate the modification level of Al–7Si alloys. In Eq. (1), |
Ti |/n calculates the average distance between
two cooling curves, and the parameter S indicates the fluctuation
2. General principle of computer aided recognition of degree of them. So, the two thermal curves must be similar when
thermal analysis cooling curves the value of Ω is small enough. In other words, when Ω is a
minimum, the two curves must be the nearest couple, and the
According to prior research of the authors [11–16], the shape quality of the two melts corresponding to the two curves must
of a thermal analysis cooling curve reflects the solidification be most similar too.
process of melt aluminum–silicon alloys under a given solidi-
fication condition. So it is clear that all factors influencing the 3. Experimental procedure
solidification process, i.e., normal chemical composition and
trace elements, grain refinement and eutectic silicon modifica- 3.1. Materials and experimental procedure
tion, etc., will influence the shape of the cooling curve. Actually,
only the freezing zone, which is the segment of a thermal analy- Al–7Si alloy melts were prepared using pure aluminum
sis cooling curve from liquidus temperature to the end of eutectic (99.99 wt.%) and pure silicon (99.999 wt.%). The chemical
solidification, is determined by solidification procedure and cor- compositions of the main impurities from inductively coupled
responding to the melt quality. In other words, the shape of the plasma-atomic mission spectroscopy (ICP-AES) analysis are
freezing zone of a thermal analysis cooling curve can be served listed in Table 1. A total of 1000 g of the Al–7Si alloy was
 X. Chen et al. / Materials Science and Engineering A 419 (2006) 283–289 285

Table 1 ter of a single silicon particle and/or plate and n is the number
Chemical composition of alloys prepared by pure aluminum and silicon of particles and/or plates in a single field.
Alloy Unmodified Due to the solidification process is non-equilibrium, there
Al Balance will be a fluctuation of the microstructure at different areas on
Si (wt.%) 6.73 the same specimen section. So the influence of the different
Cu (ppm) <15
Fe (ppm) <15
microstructure at different areas must be considered while using
Ti (ppm) <10 the digital image analysis, and abundant analysis fields must be
Mg (ppm) <5 captured to make the image analysis results representative. Our
Sr (ppm) <5 prior study [16] has shown that the mean area, mean perime-
P (ppm) <5 ter and shape factor will keep constant when the field number
observed is greater than 15. Thus a total of 16 fields were mea-
Table 2
sured on each specimen’s cross-section. The mean area, mean
Concentration of Sr in testing samples perimeter and mean shape factor values of a specimen was the
average value for the 16 fields.
No. Sr (ppm)

1 5 4. Results and discussion

2 14
3 38
4 56
5 70
6 120
melted in a 5 kW electric resistance furnace and kept at 720 ◦ C.
Degassing was done with 0.6 wt.% of hexachloroethane after
holding the melt for about 1 h at 720 ◦ C. The melt was modified
through the addition of master alloy Al–10 wt.% Sr. The melt
was then stirred for 30 s with an Al2 O3 rod. An incubation time
of 15 min was allowed after strontium addition. The contents of
strontium in testing samples were analyzed by ICP-AES and are
listed in Table 2.
3.2. Thermal analysis
After holding, the melt was poured at regular intervals into a
cylindrical sand cup (30 mm in diameter, 40 mm high and 6 mm
thick). A thermocouple, sheathed in quartz, was placed into the
cup to measure the temperature of the melt as it cooled. The
data for thermal analysis were collected using the Melt Quality
Evaluation System [12] developed by our research group.
3.3. Image analysis
Quantitative metallographic analysis specimens were cut
from the test samples close to the thermocouples tips. After
polishing, the specimens were etched with 5% HF.
An image analysis system based on a Neophot 32 micro-
scope was used to capture the images of the etched specimens
and assess their silicon modification level. A parameter so called
mean shape factor of eutectic silicon phase, was selected for the
quantitative metallographic analysis of eutectic silicon modifi-
cation level. Mean shape factor is calculated as follows:
√ growth temperature was calculated from the cooling curves of

n 2 πAi
i=1 Ai Pi
S=
n (2)
i=1 Ai
where S is the mean area weighted shape factor of silicon phase;
Ai the area of a single silicon particle and/or plate; Pi the perime-
4.1. Influence of Sr content on the silicon modification level
of Al–7Si alloy
Fig. 2 shows the morphology of eutectic silicon phase versus
Sr content. A coarse lamellar silicon structure is observed in the
unmodified alloys (Fig. 2a). With the increasing of Sr content
up to 56 ppm, the eutectic silicon changes from to a fully mod-
ified fibrous shape, and the modification level reaches grade 6
according to AFS Standard Charts. There is little shape change
with a Sr content over 56 ppm.
Fig. 3 shows the relation of modification level calculated by
the quantitative metallographic analysis method of mean shape
factor of eutectic silicon mentioned above versus the Sr content.
It is evident that the modification level increases rapidly at a low
Sr addition level, and then reaches a maximum modification
level of 6 when the Sr content is 70 ppm. And than with the
further increasing of Sr content, the modification level of eutectic
silicon sustains at the maximum modification level of 6.
The fading of modification was greatly related to the Sr
content in the melt. The influence of holding time on the modi-
fication level is shown in Fig. 4 for Sr modifier content varying
from 14 to 120 ppm, respectively. It is a common phenomenon
that, when the master alloy addition is given, the modification
level decreases with the holding time increasing. And when the
master alloy addition is small, the modification level decreases
with the holding time increasing. But when the Sr addition is at
a higher level, the modification level sustains at the initial period
of holding time, and then decreases with the holding time.
4.2. Quantifying silicon modification level using
TE
For comparison with the new thermal analysis method pre-
sented in this work, the relationship of
TE and the modifica-
tion level of eutectic silicon were studied. The Al–Si eutectic
the unmodified melt. And the modification level of eutectic sil-
icon was given by the method of quantitative metallographic
analysis mentioned above.
Fig. 5 shows the response of
TE with the modification
level when Sr contents are elevated from 5 to 120 ppm. It
286 X. Chen et al. / Materials Science and Engineering A 419 (2006) 283–289

Fig. 2. Eutectic microstructure of Al–7Si alloy: (a) unmodified, (b) 14 ppm Sr, (c) 38 ppm Sr, (d) 56 ppm Sr, (e) 70 ppm Sr, and (f) 120 ppm Sr.

can be seen from the figure that the
TE increases with the
increasing of modification level from 1 to 4 (the associated
microstructure showed Sr levels increases from trace level up
to 38 ppm), but when the modification level is greater than 4
(the associated microstructure showed Sr contents varying from
38 to 120 ppm),
TE becomes relatively invariant. So it can
be drawn a conclusion that
TE can be used as a characteris-
tic parameter to qualitatively evaluate the modification effect
of Al–7Si alloys, but
TE cannot serve as the parameter to
quantitatively predict the modification level of Al–7Si alloys,
especially when the Si modification level is in a high level range
of 4–6.
4.3. On-line prediction of silicon modification level of
hypoeutectic aluminum–silicon alloys by computer aided
recognition of cooling curves
Different from traditional thermal analysis method based on
the cooling curves’ characteristic parameters, the authors intro-
duce a new pattern recognition method based on the fact that
the similar cooling curves possess similar structure under fixed
solidification conditions. Before using this method, a database
must be built up. The database contains some valid segments of
cooling curves and their corresponding modification levels and
microstructures. The valid segment of a cooling curve is defined
 X. Chen et al. / Materials Science and Engineering A 419 (2006) 283–289
Fig. 3. Modification level versus content of Sr for Al–7Si alloy.
Fig. 4. Modification level versus holding time for Al–7Si alloy.
as the freezing zone that is from liquidus to the end of eutectic
solidification. The modification levels by mean area weighted
shape factor were analyzed using quantitative metallographic
method.
Fig. 5.
TE vs. modification level.
287
Fig. 6. Modification level difference vs. Ω.
The assessment process was performed in the following way.
Firstly, the valid segment of the measured cooling curve of
the aluminum–silicon alloy melt poured into a sand cup was
extracted. Then the valid segment of the measured cooling curve
was compared with the valid segments of the cooling curves
stored in the database respectively; if only the valid segment of
the measured cooling curve was similar enough to that of a cool-
ing curve in the database, the alloy of measured cooling curve
would have the same microstructure and the same modification
level as the alloy of the compared cooling curve in the database.
The total difference between the two curves is expressed with a
comprehensive parameter Ω.
Cooling curve difference Ω versus modification level differ-
ence of aluminum–silicon alloys after modifying is shown in
Fig. 6. It is clear that modification level difference converges to
zero when the comprehensive parameter Ω, which expresses the
difference between the two cooling curves, approaches to zero.
When Ω is less than 1.5 ◦ C, the modification level difference
between the two nearest cooling curves is less than level 0.5.
The following are some examples supporting the conclusion
drawn above. Fig. 7 shows two cooling curves with very small
Fig. 7. Two cooling curves with small difference (Ω = 1.1 ◦ C) and the solidifi-
cation segments of the cooling curves for comparing.
288 X. Chen et al. / Materials Science and Engineering A 419 (2006) 283–289

Fig. 8. Microstructure corresponding to the cooling curves shown in Fig. 7: (a) microstructure associated with the cooling curve A shown in Fig. 7 and (b)
microstructure associated with the cooling curve B shown in Fig. 7.

difference, the eutectic growth temperatures are both 569.8 ◦ C

(the curves on the right top of the figure are the segments of the
freezing zone of cooling curves). The comprehensive cooling
curve difference parameter Ω between them is 1.1 ◦ C. Fig. 8
shows their microstructure, and the modification level of samples
A and B is 5.8 and 6, respectively.
Fig. 9 shows two samples at a lower Si modification level,
the two cooling curves also have very small difference, and the
eutectic growth temperatures are both 573.2 ◦ C (also the curves
on the right top of the figure are the segments of the freezing
zone of cooling curves). The comprehensive cooling curve dif-
ference parameter Ω between them is 0.75 ◦ C. Fig. 10 shows
their microstructure with coarse lamellar silicon structure, and
the modification level of samples C and D is 1.9 and 1.8, respec-
tively.
Those results support the conclusion that the modification
level of the measuring melt can be identified by another melt, Fig. 9. Two cooling curves with small difference (Ω = 0.75 ◦ C) and the solidifi-
whose freezing zone is very close to that of the measured one (as cation segments of the cooling curves for comparing.
long as the value of Ω is small enough) under the same solidi-
fication condition. If different databases were established under

Fig. 10. Microstructure corresponding to the cooling curves shown in Fig. 9: (a) microstructure associated with the cooling curve C shown in Fig. 9 and (b)
microstructure associated with the cooling curve D shown in Fig. 9.
 X. Chen et al. / Materials Science and Engineering A 419 (2006) 283–289 289

different plant conditions and the number of cooling curves in 4. When the comprehensive cooling curve difference param-
the databases was cumulated to a certain degree, the modifi- eter Ω approaches zero, the modification level difference
cation level of the measured cooling curve can be evaluated converges to zero. The modification level can be precisely
by the most similar cooling curve saved in the database. The assessed by comparison of the cooling curve of the melt to
more cooling curves in the database, the more accuracy the be evaluated with those in a database to find the one most
assessment. similar to it.
Comparing with traditional thermal analysis method of tak-
ing some critical values such as
TE from cooling curve as References
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