Bulletin of the Transilvania University of Braşov • Vol.

3 (52) - 2010
Series I: Engineering Sciences

ANALYSIS OF PHASE TRANSFORMATION

IN HIPOEUTECTIC Al-Si ALLOYS

I. LICHIOIU1 B. VARGA1 V. GEAMĂN1

Abstract: Measurement of temperature and transformation duration provides

information on structure generation. Improving the structure of hypoeutectic
Al-Si alloys can be achieved both by introducing small quantities of additives
and by applying high cooling rates. Dilatometric studies allowed
determination of activation energy for the decomposition of supersaturated α
solid solution. Increased cooling rates cause an increase of the activation
energy from a value of 152 kJ/mol for casting in refractory brick to a value of
201 kJ/mol for casting in steel mould in case of ATSi5Cu1 alloy.

Key words: silumin, cooling rate, dilatometry, activation energy.

1. Introduction of the eutectic silicon and crystalline

refinement. The eutectic silicon form is
Al-Si alloys, the most important aluminium modified by means of superficially active
based metal materials used in foundries are elements such as: Na, Sr, while the refinement
known for their very good castability and of the solid solution dendrites is achieved
adequate mechanical properties; further, by hard fusible elements such as Ti, B etc.
these alloys have a very good corrosion Modification of the form of silicon can
strength, are easily machined by cutting also be achieved by applying high cooling
processes and have a good weldability. rates. It has to be pointed out, that at high
Form and dimensions of eutectic silicon cooling rates, the proportion of Si in α
crystals generated during solidification solid solution increases over the 1.65%,
have an unfavourable effect on silumin value which is indicated in the thermal
properties, due to the growth effect as well equilibrium diagram. In this case α solid
as to the high fragility and hardness of this solution becomes oversaturated, the generated
non-metallic phase. structure being metastable [2].
In order to improve the structure and
consequently to improve the mechanical 2. Experimental Determination
and technological properties of hypo-
eutectic silumins, prior to casting these The analyses of the untreated ATSi5Cu1
alloys are subjected to certain treatments and ATSi8Cu3 hypo-eutectic alloys reported
aimed at improving their structure. Such in this paper were conducted by simple
treatments involve introducing of small thermal analysis, microscopic study and
quantities of additives for both globulization dilatometric analysis. The latter has allowed

1
Dept. of Technological Equipment and Materials Science, Transilvania University of Braşov.
190 Bulletin of the Transilvania University of Braşov • Vol. 3 (52) - 2010 • Series I

determining of the activation energy related moulds - Ø50x60 mm, the second ones
to the decomposition of the supersaturated cast in graphite moulds - Ø30x70 mm, and
α solid solution into Si. the third ones cast in steel moulds -
The ATSi5Cu1 and ATSi8Cu3 alloys 14x80x160 mm respectively. Melted charges
were melted in an electric furnace with of untreated alloys were followed by alloys
graphite crucible; subsequently ATSi8Cu3 treated with master alloys, namely Al-Sr10
was cast in graphite and refractory brick in the case of ATSi8Cu3 and Al-Ti5-B1 in
moulds and ATSi5Cu1 in steel and the case of ATSi5Cu, by means of added
refractory brick moulds, respectively. them in the melt. Table 1 displays the
Dimensions of the cast test pieces were: chemical composition of the main elements,
the first ones cast in refractory brick the weights of charges and additive materials.

Chemical composition, the weights of charges and additive materials Table 1

AlSi8Cu3 AlSi5Cu1 AlSr10 AlTi5B1 Chemical composition [%]
No. [g] [g] [g] [g] Al Si Cu Fe Sr Ti
1 1440 - - - 87.39 7.99 2.29 0.57 - -
2 900 - 4.85 - 87.24 8 2.32 0.59 0.05 -
3 - 886 - - 90.93 5.59 1.65 0.66 - -
4 - 890 - 35.60 92 4.75 1.37 0.59 - 0.2

alloys for three cooling conditions are present

in Figures 2 and 3.
The cooling conditions for each casting
mould type were considered by the cooling
rates in liquid state, computed with:

∆T
vrl = , (1)
∆τ

Fig. 1. Principle diagram of a thermal where: ∆T - the temperature variations; ∆τ -

analysis the time variations.
The temperatures highlighted on the cooling
The experimental arrangement from Figure curves of Figures 2 and 3 correspond to the
1 was used for plotting the cooling curves. separation of α solid solution crystals, the
Temperature was recorded by means of eutectic and other intermetallic compounds
an EBI-2T-1202-TYPK logger, using coaxial (e.g. CuAl2 for ATSi8Cu3). The occurrence
thermocouples type K-TPN-101 with a of undercooling phenomenon interfering
diameter of 0.6 mm. The experimental data before the primary crystallization can be
were processed by the EBI-WINLOG observed on the curves corresponding to
2000-S software and OriginPro. Dilatometric slow cooling rates.
studies were conducted by means of a Undercooling disappears in the case of
LINSEIS L75/230 dilatometer. ATSi5Cu1 treated with hard fusible elements
(Ti + B) for structure finishing (Figure 2b -
3. Experimental Results curve 1), what is in agreement with the
general theory on the structure finishing
The cooling curves obtained for ATSi5Cu1 mechanism with hard fusible elements by
and ATSi8Cu3 untreated respectively treated means of heterogeneous germination.
Lichioiu, I., et al.: Analysis of Phase Transformation in Hipoeutectic Al-Si Alloys 191

a) b)
Fig. 2. Cooling curves for AlSi5Cu1 alloy cast in steel and refractory brick moulds:
untreated alloy (a), treated alloy with Al-Ti5-B1 master alloy (b)

a) b)
Fig. 3. Cooling curves for AlSi8Cu3 alloy cast in graphite and refractory brick moulds:
untreated alloy (a), treated (modified) alloy with Al-Sr10 master alloy (b)

The addition of Sr causes changes of the

cooling curve (Figure 3b) by extending the
time required for the eutectic reaction. At
the structure level Sr has a strong impact
on the shape of the silicon crystals [3].
Figures 4 and 5 present the microstructures
of the AlSi8Cu3 alloy modified with 0.05%
Sr, after the adequate metallographic
preparation of the samples.
In the case of the casting into moulds
which ensuring slow cooling rates, the effect
of Sr modification on parts properties is
diminished by the presence of coarse Fig. 4. Microstructure of AlSi8Cu3
intermetallic compounds. The presented alloy alloy modified with 0.05% Sr cast in
structures reveal that only the cumulated refractory brick mould
192 Bulletin of the Transilvania University of Braşov • Vol. 3 (52) - 2010 • Series I

 v
d  ln 
 T  = − Ea , (3)
1 R
d 
 
T

Fig. 5. Microstructure of AlSi8Cu3 alloy

modified with 0.05% Sr cast in graphite
mould
Fig. 6. Dilatation curves and dilatation
effects of Sr modification and graphite coefficient for ATSi8Cu3 unmodified (0)
mould casting (high cooling rate) ensure an and modified alloy (M)
adequate modification of the eutectic Si
and a fine distribution of the intermetallic
compounds.
The results of the dilatometric analysis are
presented in Figures 6 and 7 for ATSi8Cu3,
and Figures 8-11 for ATSi5Cu1, respectively.
The dilatation curves reveal that the heating
process of the alloy with cast structures causes
the separation of Si from the supersaturated
α solid solution and its deposition on the Si
separations existing in the eutectic.
The separation of the Si from the Fig. 7. Dilatation and contraction curves,
supersaturated s.s. α can be represented as and dilatation and contraction coefficients,
follows: respectively for ATSi8Cu3 modified alloy
s.s.α Si >1,65% → s.s.α Si =1,65% + Si . (2)

This transformation occurs accompanied

by an increase in volume, clearly highlighted
by the first derivative of the dilatation curve.
The curves of Figure 6 reveal that in the
presence of strontium, the decomposition
of the supersaturated solid solution takes
place as in the unmodified alloy. Structural
transformations cease to occur at cooling
rates of 5 ºC/min of the modified alloy Fig. 8. Dilatation curves and dilatation
(Figure 7). coefficient for ATSi5Cu1 untreated (0) and
The activation energy (Ea) is determined the treated alloy (M) cast in refractory
by the Kissinger equation [1], written as: brick mould
Lichioiu, I., et al.: Analysis of Phase Transformation in Hipoeutectic Al-Si Alloys 193

Fig. 9. Dilatation curves and dilatation Fig. 11. Dilatation curves and dilatation
coefficient for ATSi5Cu1 untreated (0) and coefficient for ATSi5Cu1 treated alloy cast
the treated alloy (M) cast in steel mould in refractory brick mould, heated at
different rates

Fig. 10. Dilatation curves and dilatation Fig. 12. Determination of the activation
coefficient for ATSi5Cu1 treated alloy cast energy by graphic representation for
in steel mould, heated at different rates ATSi5Cu1 alloy

where: T - the temperature corresponding to The temperatures corresponding to the

the peaks on the derivatives of the dilatation peaks on the derivatives of the ATSi5Cu1
curves [ºC]; ν - cooling rate [ºC/s]; Ea - dilatation curves were used for determining
activation energy [J/mol]; R - gas constant: the activation energy. Tables 2 and 3 feature
8.3144 [J/K·mol]. the experimental and computed values required
 v  1
for plotting the ln 2  = f   diagrams.
T  T 

4. Conclusions

Treating liquid alloys with hard fusible

elements eliminates the undercooling phe-
nomenon.
Dilatometric analysis reveals the impor-
tance of heat treatments for dimensions
stabilizing applied to unmodified and
Fig. 13. Activation energies for ATSi5Cu1 modified silumins in order to avoid
alloy processed under different conditions dimensional modifications caused by the
194 Bulletin of the Transilvania University of Braşov • Vol. 3 (52) - 2010 • Series I

Experimental results and computed quantities for ATSi5Cu1-M Table 2

Casting condition
Parameters
Steel mould Refractory brick mould
ν [ºC/min] 2.5 5 10 2.5 5 10
ν [ºC/s] 0.041 0.083 0.16 0.041 0.083 0.16
t [ºC] 241.4 247.7 254.4 211 219.5 228
T [K] 514.4 520.7 527.4 484 492.5 501
1 -1
⋅ 10 3 [K ] 1.94 1.92 1.89 2.07 2.03 2
T
T 2 ⋅ 10−5 [K2] 2.64 2.71 2.78 2.34 2.42 2.51
v -1
⋅ 107 [s K] 1.54 3.06 5.75 1.75 3.43 6.37
T2
 v 
ln 2  −15.68 −14.99 −14.36 −15.55 −14.88 −14.26
T 
Ea [kJ/mol] 215 152

Experimental results and computed quantities for ATSi5Cu1-0 Table 3

Casting condition
Parameters
Steel mould Refractory brick mould
ν [ºC/min] 2.5 5 10 2.5 5 10
ν [ºC/s] 0.041 0.083 0.16 0.041 0.083 0.16
t [ºC] 231.8 231 241.5 226 235.7 245.1
T [K] 504.8 504 514.5 499 508.7 518.1
1 -1
⋅ 10 3 [K ] 1.98 1.98 1.94 2 1.96 1.93
T
T 2 ⋅ 10−5 [K2] 2.54 2.54 2.64 2.49 2.58 2.68
v
⋅ 107 [s-1 K] 1.6 3.26 6.04 1.64 3.2 5.96
T2
 v 
ln 2  −15.64 −14.93 −14.31 −15.62 −14.95 −14.33
T 
Ea [kJ/mol] 202 152

transformation of the metastable structure References

of the deployed material. The phenomenon
is of major importance for parts of high 1. Kissinger, H.E.: Reaction Kinetics in
dimensional accuracy. Differential Thermal Analysis. In:
Increased cooling rates cause an increase Analytical Chemistry 29 (1957) No. 11,
of the activation energy for decomposition p. 1702-1706.
of supersaturated α solid solution in Si. 2. Lasagni, F., Falahati, A., et al.: Precipi-
tation of Si Revealed by Dilatometry in
Acknowledgements Al-Si-Cu/Mg Alloys. In: Kovove
Materially 46 (2008) No. 1, p. 1-6.
This paper is supported by the Sectoral 3. Tenekedjiev, N., Closset, B., et al.:
Operational Programme Human Resources Microstructures and Thermal Analysis
Development (SOP HRD), ID59321 of Strontium-Treated Aluminum-Silicon
financed from the European Social Fund Alloys. Ed. by Thomas S., American
and by the Romanian Government. Foundrymen’s Society, USA, 1995.