Scripta Materialia 55 (2006) 259–262

www.actamat-journals.com

The microstructure and precipitation kinetics of a

cast aluminium alloy
D. Ovono Ovono,a,* I. Guillotb and D. Massinonc
a
Laboratoire Roberval, University of Technology of Compiègne, 60205 Compiègne, France
b
Centre d’Etudes de Chimie Métallurgie, UPR2801 CNRS, 94407 Vitry-sur-Seine, France
c
Fonderie Montupet, 60181 Nogent-sur-Oise, France
Received 3 February 2006; revised 23 March 2006; accepted 31 March 2006
Available online 15 May 2006

The microstructure of a cast Al–Si–Cu alloy was studied quantitatively in detail by a combination of differential scanning
calorimetry, scanning electron microscopy, scanning tunnelling microscopy and transmission electron microscopy. The kinetics
of coarsening can be described by the classical ripening theory. The plot of the rate constant of coarsening and the temperature
follows an Arrhenius behaviour with an activation energy of about 140.4 kJ/mol1, which is approximately the activation energy
for diffusion of Cu and/or Si in Al, indicating diffusion-controlled precipitate growth.
Ó 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Cast aluminum alloys; TEM; Aging; Coarsening; Precipitation kinetics

Over the past decade, the automotive industry has
increasingly employed cast aluminium alloys as a
replacement for cast iron in the production of engine
components. Improvements in engine performance have
caused the temperatures in aluminium cylinder heads to
increase, especially in the inter valve zone, from 170 °C
in earlier engines to peak temperatures above 300 °C
in recent engines [1]. The A319 aluminium family is
commonly used in casting cylinder heads, due to its
low density, good thermal conductivity and good cast-
ing properties. This class of material exhibits mechanical
properties that depend strongly on microstructural fea-
tures such as secondary dendrite arm spacing (SDAS),
porosity, intermetallic compounds, hardening precipi-
tates [2–4]. The effects of porosity [5,6], intermetallics
[7,8], grain refinement [9,10], silicon concentration
[11,12] are well established and the performance of these
alloys has also been improved by modelling casting pro-
cesses and thermal treatments [9,13].
The use of structural hardening models, including the
effect of precipitate size distribution is still rare for alu-
minium casting alloys. One of the reasons is that a good
knowledge of precipitate coarsening law during aging is
needed in order to build a physically supported model of
* Corresponding author. Tel.: +33 3 44 23 44 23; fax: +33 3 44 23 44
15; e-mail: delavand.ovono-ovono@utc.fr
the mechanical behaviour. The stability of mechanical
properties at elevated temperature of cast aluminium al-
loys depends on the resistance to dissolution and coars-
ening offered by operative strengthening precipitates. In
Ostwald ripening, the evolution over time of precipitates
of one phase embedded in a matrix of another phase was
formulated by Lifshitz, Slyozov and Wagner, and is
widely referred to as the LSW theory [14,15]. The
LSW theory states that the cube of the average precipi-
tate radius grows proportionally with the ageing time if
the mass transport is governed by a diffusion mecha-
nism. A number of papers have been published regard-
ing coarsening of h 0 precipitates in the A319 alloy
[2–4]. These investigations, however, have not provided
information about the overlap of h precipitates with oth-
ers precipitates during over-ageing. Therefore, we want
to know if this strong overlap of precipitates can influ-
ence the activation energy of the process.
In the present study, we investigated the microstruc-
ture of an A319 aluminium alloy by scanning electron
microscopy–energy dispersive spectroscopy (SEM–
EDS), scanning tunnelling microscopy (STM), and
differential scanning calorimetry (DSC). Transmission
electron microscopy (TEM) was used to obtain informa-
tion on the mechanisms and kinetics of particle growth.
A cast Al–Si–Cu alloy was investigated in the pres-
ent work, the chemical composition of which is shown
in Table 1. The average SDAS, the distance between

1359-6462/$ - see front matter Ó 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2006.03.065
260 D. O. Ovono et al. / Scripta Materialia 55 (2006) 259–262

Table 1. Chemical composition (wt.%) of the A319 aluminum alloy after aging for various values of temperature were ob-
Elements tained with populations of about 100 particles.
Si Cu Mg Fe Mn Zn Al
The SEM micrograph of alloy is shown in Figure 1.
The microstructure of the alloy consisted of primary
Alloy 7 3 0.3 0.1 0.1 0.05 Rest aluminum dendrite, eutectic silicon, iron and copper
intermetallic. It shows that fine and well-distributed eu-
tectic silicon has been obtained. The samples were ana-
centers of adjacent dendrite arms of the a-Al dendrites, lysed by means of SEM–EDS. Figure 1 shows the phases
in the microstructure was 20 lm. The alloy was given a which exist in these alloys. It seems that bright phases in
T5 heat treatment (peak aged) consisting of a solution Figure 1 are a mixture of the Al2Cu phase and iron
treatment at 490 °C in an air furnace, a room tempera- intermetallics, since peaks for each element were de-
ture water quench, and an artificial age of 5 h at tected by EDS analysis. Also, in Figure 1, dark gray
210 °C. The microstructure of T5 material consists of phases show eutectic silicon. The EDS analysis revealed
dendrites of the aluminum a-phase containing Cu and that the compounds formed in the alloy during solidifi-
an aluminum–silicon eutectic with intermetallic com- cation are ‘‘Chinese script’’ a intermetallic phases
pounds between dendritic arms. The eutectic Si particles (Fig. 2), plate shaped b-Al5FeSi particles and Al2Cu
were modified by using Sr and Na and a commercial Ti– phase. Figure 3a shows a dark-field TEM image of the
B grain refiner was also added. The modified eutectic precipitates (T5) viewed edge-on in the [0 0 1]Al zone
structure enhances the mechanical properties of the cast- axis. From the analysis of diffraction patterns and
ing. Other T5 specimens were subsequently aged at 100,
200, 250, 280 and 320 °C for different times.
DSC runs were carried out on 10–25 mg sample
discs obtained from the T5 heated specimens using a dif-
ferential scanning calorimeter (DSC Q100). The instru-
ment was calibrated at the temperature corresponding
to the indium melting point and to a heating rate
20 °C/min. The sample disc was placed in the sample
pan and a super purity aluminum of equal mass in the
reference pan of the cell. The cell was equilibrated at
100 °C and then heated to 600 °C at 20 °C/min in an ar-
gon atmosphere. The heat effects associated with trans-
formation reactions were then obtained by subtracting
a super purity Al baseline run from a given heat flow
Figure 1. Microstructure of A319 alloy in the T5 condition.
curve. The peak precipitation temperature and the disso-
lution temperatures of other phases were determined
with an accuracy of ±1 °C using the microprocessor of
the thermal analyzer. Samples were metallographically
prepared by mechanical polishing, following by etching
in 0.5% HF solution. These samples were investigated
with a Philips XL30 ESEM–FEG scanning electron
microscope equipped with EDS. Thin foils for TEM
studies were prepared by jet electropolishing using the
conditions of 12 V in an electrolyte consisting of
33 vol.% HNO3 in methanol solution cooled at
30 °C. The electropolished foils were examined in a
JEOL JEM 100CXII operated at 100 kV. EDS and
STM analyses were performed on a Tecnai F20 field
emission gun instrument operating at 200 kV. The aver- Figure 2. SEM micrograph of A319 alloy showing a-Al15(Fe,Mn)3Si2
age precipite sizes of h 0 , h and Si from the A319 alloy intermetallic and EDS spectrum of this compound.

Figure 3. (a) TEM micrograph of A319 alloy in T5 condition showing the presence of needle-like h 0 precipitates; (b) STM micrograph and EDS–
STM spectrum of the same precipitates (the arrow corresponds to the path followed by analysis points to obtain this spectrum).
 D. O. Ovono et al. / Scripta Materialia 55 (2006) 259–262
EDS–STM analysis (Fig. 3b), it was found that the disc
shaped precipitates were all h 0 . The metastable h 0 is
semicoherent and exhibits an orientation relationship
with the matrix such that (0 0 1)h 0 k{1 1 1}Al. Below
200 °C, the only microstructural change is the coarsen-
ing of the h 0 phase. The size of precipitates as a function
of ageing time are plotted in Figure 4. During ageing the
h 0 precipitate sizes increases from values around 18.2 nm
to about 30.9 nm. This increase is caused by the precip-
itation of Cu atoms from the Al-rich phase. As the age-
ing progresses, the gradual disappearance of the h 0 phase
and the sudden appearance of Si, h and Q phases occur
simultaneously (Fig. 5). Small dark flecks appearing in
the background have been identified (Fig. 5) as equi-
axed, lath-shaped precipitates of Q phase (a quaternary
Al–Cu–Si–Mg compound with a stoichiometry some-
times given as Al5Cu2Mg8Si6). The Q laths appear sim-
ilar in the [0 0 1]Al orientation, the measurements of the
Si and h precipitates may inadvertently include some
Q phase. The equilibrium h phase and Si phase are inco-
herent with the matrix lattice. At the final stage of age-
ing, the measured sizes of h and Si phases are greater
than 107 nm. The altered precipitation kinetics in the
Al–Si–Cu alloy as compared to those in the respective
binary alloys might be due to the presence of misfitting
silicon particles which influence the kinetics of precipita-
Figure 4. TEM micrographs of A319 alloy aging at 320 °C for 100 h
after T5 treatment and STM spectra showing Q-Al5Cu2Mg8Si6 and Si
precipitates.
Figure 5. DSC curve obtained at a heating rate of 20 °C/min for A319
alloy in the T5 condition.
261
tion from the matrix. The subsequent growth of the non-
coherent h and Si precipitates takes place at higher
temperatures. The precipitation sequence in A319 alloy
as the aging temperature increases is essentially : h 0 ! h
(Al2Cu) + Si + Q.
Figure 6 shows the typical DSC trace of the A319
alloy, in the T5 condition, scanned at a rate of 20 °C/
min between 100 and 600 °C. As seen in Figure 6, the
DSC scan exhibits six characteristic reactions, one exo-
thermic peak (A) at 243 °C, and five endothermic peaks
at 507 °C (effect B), 519 °C (C), 537 °C (D), 548 °C (E),
573 °C (F). As can be seen, it is evident that the last
effect (F) at 573 °C corresponds to the Si-eutectic disso-
lution, in accordance with the Al–Si phase diagram [16].
For effect E, its measured temperature 548 °C agrees
well with the reported b-Al5FeSi dissolution tempera-
ture [17]. The measured temperatures of effects B and
C are consistent with the values reported by Wang
et al. [17] and de la Sablonière et al. [18], respectively,
and correspond to the dissolution of the Q-Al5Cu2Mg8-
Si6 phase (effect B) and Al2Cu phase (effect C). The
endothermic effect, D, is attributed to the dissolution
of the a-Al15(Fe,Mn)3Si2 intermetallic particles. While
the effect A is due to the evolution of a state with h 0
phase to a state with h, Si and Q phases. TEM analysis
in conjunction with STM confirmed that in the T5 con-
dition all precipitates were h 0 phase. On the other hand,
a sample aged at 320 °C for 100 h does not show any h 0
but does show h, Si and Q phases.
The TEM observations show after T5 treatment, the
existence of h 0 phase, and during heat treatment these
observations indicate that the precipitation of Si, Q
and h phases strongly overlap. This finding corresponds
to DSC experiments performed on the same alloy, which
show that the precipitation of Q, Si and h phase gives
rise to a single heat evolution effect. Figure 4 shows
the change in precipitate sizes of h 0 , Si and h phases mea-
sured by TEM at different aging temperatures. The
precipitate size increases monotonically with increasing
aging temperature. Due to the strong overlap between
the h, Q and Si precipitation processes, it is not possible
to obtain the extent of the three precipitation processes
separately. It is considered that the two processes, h and
Si, are governed by one effective activation energy be-
cause of their spherically shapes. The activation energy
was obtained using the LSW method. From Figure 7,
it is clear that there exists an excellent linear correlation
between the logarithm of the precipitates’ growth time,
Figure 6. Aging temperature dependence of the size of h 0 , h and Si in
A319 alloy.
262 D. O. Ovono et al. / Scripta Materialia 55 (2006) 259–262
Figure 7. Effect of aging time on h 0 , h and Si precipitate size.
log (t), and the logarithm of the precipitate sizes of h 0 , h
and Si, log (r), with a slope of 1/3. The slope of 1/3 indi-
cates that the precipitate growth occurs in three dimen-
sions [19,20]. The excellent linear relationship between
log (r) versus log (t), with the slope of 1/3, corresponds
very well with the classical theory of Oswald ripening
[14,15].
According to the precipitate growth behaviour shown
in Figure 7, a growth law [14,15] can be described as
r3  r30 ¼ Kt
where r0 is the precipitate diameter at t = 0, r is the
precipitate size at t, and the rate constant K depends
on temperature in the Arrhenius relation. This constant
can be written as
j Eng. 299A (2001) 275–286.
K¼ expðQ=RT Þ ð2Þ
RT
where j/RT is a constant, R is the gas constant, Q is the
activation energy for precipitate growth and T is the
aging temperature.
Therefore, the activation energy for precipitate
growth can be calculated from the slope of the plot of
ln ½KðT Þ  T  ¼ f ðT1 Þ. Figure 8 shows the Arrhenius plot
of ln [K(T)ÆT] versus 1/T for h 0 , h and Si growth in
A319 alloy, where a straight line is obtained with a slope
of Q/R. Thus the activation energy for precipitate
growth can be calculated to be 140.4 kJ/mol. From this
value, it is possible to postulate a precipitation mecha-
nism. The activation energy of the growth of precipitates
in A319 alloy obtained in the present work is compara-
Figure 8. Arrhenius plot of ln [k(T)ÆT] versus 1/T describing the
precipitate growth in A319 alloy.
ble to the activation energy reported by some authors
[21–23], which was related to the diffusion of Cu and/
or Si in Al.
In this study we presented an experimental investi-
gation on the microstructure and precipitation of a cast
Al–Si–Cu A319 alloy. Our main results can be summa-
rized as follows: (1) The nature and dissolution temper-
ature of compounds and phases are identified by
SEM–EDS, STM analysis and DSC. Based on the re-
sults of DSC measurements and TEM observations we
suggest that the precipitation sequence in the heated
condition is follows: h 0 ! Q + h + Si. (2) Further ageing
leads to precipitates’ growth by coarsening according to
the LSW theory, and the plot of coarsening rate con-
stant and temperature follows a thermal activation
behaviour. (3) The activation energy of the A319 alloy
was calculated to be 140.4 kJ/mol, which indicates a dif-
fusion-controlled coarsening process in this alloy.
The authors would like to thank the Région Picardie
and Montupet SA for financial support. They are grate-
ful to F. Nadaud for useful technical assistance.
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