metals

Article
Effect of T6 Heat Treatment on the Microstructure
and Hardness of Secondary AlSi9Cu3(Fe) Alloys
Produced by Semi-Solid SEED Process
Alberto Fabrizi , Stefano Capuzzi, Alessandro De Mori and Giulio Timelli *
Department of Management and Engineering, University of Padova, Stradella S. Nicola, 3 I-36100 Vicenza, Italy;
fabrizi@gest.unipd.it (A.F.); capuzzi@gest.unipd.it (S.C.); alessandro.demori@phd.unipd.it (A.D.M.)
* Correspondence: timelli@gest.unipd.it; Tel.: +39-0444-998-769




Received: 3 September 2018; Accepted: 19 September 2018; Published: 23 September 2018


Abstract: The effect of the T6 heat treatment on the microstructure and hardness of a secondary
semi-solid AlSi9 Cu3 (Fe) alloy have been investigated by using optical, scanning and transmission
electron microscopy and hardness testing. The semi-solid alloy was produced using the swirled
enthalpy equilibration device (SEED). The solution heat treatments were performed at 450, 470 and
490 ◦ C for 1 to 6 h followed by water quenching and artificial ageing at 160, 180 and 220 ◦ C for holding
times ranging from 1 to 30 h. The microstructural investigations have revealed the spheroidization of
the eutectic Si and the dissolution of the majority of Cu-rich compounds after all the solution heat
treatments; moreover, the greater the solution temperature and time, the higher the hardness of the
alloy. Unacceptable surface blistering has been observed for severe solution condition, 490 ◦ C for
3 and 6 h. The artificial ageing at 160 ◦ C for 24 h has led to the highest alloy strengthening thanks to
the precipitation of β” and Q’ (or L) phases within the α-Al matrix. The hardening peaks at higher
temperatures have been early achieved due to faster hardening kinetic; however, the lower number
density of β” and Q’ (or L) phases and the presence of coarser θ’ precipitates result in a reduction of
hardness values for peak aged condition at 180 and 220 ◦ C, respectively.

Keywords: aluminium alloys; semi-solid; SEED; heat treatment; microstructure; mechanical

properties

1. Introduction
Aluminium-silicon casting alloys are widely used in the automotive industry due to their good
castability, good corrosion resistance, high strength stiffness to weight ratio as well as recycling
possibilities at low energy costs. Furthermore, mechanical properties of as-cast components can
significantly be improved by suitable heat treatments. However, the application of a post-casting
thermal treatment on high-pressure die-cast (HPDC) components is still a limited practice in industry.
Due to the extreme turbulent flow of molten metal during filling of the die cavity, internal or sub-surface
porosity, originated from entrapped gases, can usually occur in the diecastings [1]; consequently,
during typical thermal treatment at elevated temperature (470÷500 ◦ C [2]), gas expansion can produce
unacceptable surface blisters on the components [2,3].
Beside the use of vacuum-assisted HPDC to reduce the level of entrapped gas [4], semi-solid metal
(SSM) processes have been considered a valid alternative for producing sound Al-Si-based light-weight
parts with satisfactory response to heat treatments, especially for the automotive sector. Some examples
are fuel rails, control arms, steering knuckles, engine brackets, or even engine blocks [5–7].
Generally, SSM processing is divided into two main categories such as rheocasting and
thixocasting. The former involves the preparation of a SSM slurry directly from the molten metal,

Metals 2018, 8, 750; doi:10.3390/met8100750 www.mdpi.com/journal/metals

Metals 2018, 8, 750 2 of 18

which is cooled and stirred up to the desired solid fraction, followed by forming process. Nowadays,
this approach is more widely used than thixocasting where a specially prepared alloy (with globular
or rosette-like α-Al grains) is reheated to the desired semi-solid forming temperature prior to casting.
Contrary to the turbulent metal flow during die cavity filling in conventional HPDC, both the
SSM casting approaches experience a laminar flow of semi-solid metal having a higher viscosity than
the liquid state; consequently, the risk of gas entrapment is largely limited and blistering phenomena
are prevented during further heat treatments or welding operations [8].
The typical thermal treatment for automotive components made by Al foundry alloy is T6 temper,
which generally induces higher alloy strengthening. The T6 thermal cycle consists of a solution heat
treatment followed by a water quenching and then an age hardening (or precipitation hardening).
The solution heat treatment leads to the dissolution of intermetallic phases and the spheroidization
of eutectic Si with a resulting improvement of alloy ductility [9,10]. The time for solution treatment
is strongly dependent on the microstructural scale [10], ranging from few minutes up to several
hours [11–13]. In general, too short solution treatment does not guarantee that all alloying elements
are dissolved in the α-Al matrix and made available for further precipitation hardening; on the
contrary, too long solution treatment shows economic limitations because it uses more energy and
time than necessary.
Age hardening at room temperature (natural ageing) or elevated temperature (artificial ageing,
AA) increases the alloy strengthening because of the ultra-fine particles which precipitate from the
supersaturated solid solution and act as obstacles to the dislocation movement.
In the last years, an increasing attention from researchers has been paid on the heat treatment
sequence of primary semi-solid Al-Si cast alloys such as A356, A357 alloys [14–16] in order to increase
their mechanical properties. However, to date, only few studies have investigated the age hardening
response of a secondary (or recycled) Al-Si alloy produced via SSM route [17] although secondary Al
foundry alloys are the most used Al diecasting alloys in the automotive industry.
In this work, the microstructure evolution and the precipitation hardening response of a rheocast
secondary AlSi9 Cu3 (Fe) alloy used for automotive components were investigated as a function of
different T6 heat treating parameters.

2. Materials and Methods

In this study, automotive components (lower suspension arm) were manufactured with
a secondary AlSi9 Cu3 (Fe) alloy (EN AC-46000) by the Swirled Enthalpy Equilibration Device (SEED),
which operates by using a liquid-based method (rheocasting) for producing the Al slurry over a wide
range of Al-Si alloy compositions (up to 17 wt.% Si) [18,19].
According to this process, the slurry is prepared by means of three stages [18]. Firstly, the molten
metal of the desired composition and temperature is poured into a vessel whose thermal capacity is
able to cool the alloy in order to obtain the desired solid fraction in the range between 30 and 45%.
During this stage, the vessel is swirled to homogenize the temperature and the distribution of the
solid phase which is generated at the walls of the vessel. The duration of this stage depends upon
the dimensions of the container and the mass of the charge, even if an extremely close control of the
mixing time is not necessary. Furthermore, Doutre et al. [18] demonstrated how the mixing intensity
does not affect the process yield over the range of 150 to 300 rpm.
In the second stage of the process, a valve at the bottom of the vessel can be opened and some of
the remaining liquid phase is drained to produce a self-supporting semi-solid billet, which is depleted
in the eutectic forming elements (Si, Mg, Fe) and enriched in the peritectic forming element (Ti) [18].
In the third stage, the vessel is inverted, and the billet is de-moulded and transferred to the
forming unit.
Information about the SEED method and processing parameters are reported in the Ref. [18,20]
where the potential of the SEED process as a route of preparing high quality feedstock has been also
tested to produce an automotive front upper control arm weighing approximately 1 kg.
Metals 2018, 8, 750 3 of 18

In the present work, the ingots were supplied by Raffineria Metalli Capra Spa (Brescia, Italy) while
the demonstrators were produced at the CIE Automotive (Bilbao, Spain). The chemical composition of
the alloy, measured on separately poured samples, is shown in Table 1.

Table 1. Chemical composition of the experimental AlSi9 Cu3 (Fe) alloy (wt.%).

Si Fe Cu Mn Mg Ni Zn Cr Sn Ti Al
8.820 0.691 2.122 0.23 0.32 0.065 0.90 0.05 0.01 0.04 bal.

The ingots were firstly melted at 670 ◦ C in a tower furnace of 800-kg capacity and then the molten
metal was tapped into an electric resistance furnace where it was N-degassed with a rotary degasser
(MTS Rotor Ø190, at 600 rpm, Foseco Española S.A., Izurtza, Spain) for 8 min. The metal was manually
skimmed and held at 640 ◦ C. No grain refinement or chemical eutectic modification were performed.
The melt was transferred by means of a ladle and poured into a steel vessel preheated at about
130 ◦ C to avoid thermal shock and to better control the amount of solid fraction. At this stage, in order
to improve the distribution of the primary solid phase, the vessel was swirled for 115 s at a rate of
150 rpm with an eccentricity of the swirl motion. To achieve homogenisation of the temperature and
structure, a delay time of 10 s was maintained before transferring the slurry to the shoot sleeve of
a cold camber die casting machine. Then, the slurry was injected into the die cavity and the plunger
velocity of the HPDC machine (Petransa, Alió, Tarragona, Spain) was lower than 1 ms−1 for the filling
phase; once the die-cavity was filled, a pressure of ~115 MPa was applied to guarantee high-integrity
castings. Detailed investigations and results regarding the final rheocasting quality are described in
Ref. [21].
A calorimetry analysis of the as-rheocast alloy was preliminary performed with a Labsys Evo
differential scanning calorimeter (DSC) (SETARAM Instrumentation, Caluire, France) to identify
the solidification reaction sequence of the alloy. The samples in the form of 4 mm discs weighting
approximately 30 mg were drawn from the castings. Samples were weighted before and after DSC scan
and no significant mass increase was observed. The DSC test was carried out with an empty reference
pan, as cooling (solidification) scan in a protective gas atmosphere of pure Argon. The sample was
heated up to 800 ◦ C at 2 ◦ C/min and maintained at this temperature for 15 min before cooling to room
temperature at 2 ◦ C/min.
Specimens of about 30 × 10 × 15 mm3 size were drawn from the as-rheocast components
and they were heat treated according to the following conditions: solution treatment inside an
electric-resistance heated-air-circulating furnace, water quenching at room temperature and then
artificial ageing. The solution treatments were performed at 450, 470 and 490 ◦ C for 1, 3 and 6 h,
respectively. These process parameters were selected in order to minimize blistering and residual
stresses in the castings after water quenching and to reduce the risk of localised incipient melting of
Cu-rich compounds. Moreover, the experimental solution treatments were also chosen in accordance
with the conventional solution cycles normally applied in the automotive industry, where shortening
the total time is a key issue to increase the productivity and to reduce the manufacturing cost [11–13].
As mentioned before, after the solution heat treatment, the specimens were water quenched at
room temperature. To avoid natural ageing prior to the artificial ageing, the specimens were stored at
4 ◦ C for 1 day; subsequently, the artificial ageing was carried out respectively at 160, 180 and 220 ◦ C
for different ageing times ranging between 1 and 30 h. The temperature control during solution and
ageing treatments was ±1 ◦ C.
The heat-treated specimens were mechanically prepared by grinding with abrasive SiC papers and
polishing with 6- and 3-µm diamond pastes and colloidal silica suspension. Optical microscope and
quantitative metallographic analysis were used to determine the main characteristics of eutectic
Si particles (size and aspect ratio) and the amount of undissolved Cu-rich phases. Before the
quantification, the polished samples were chemically etched by using a water solution of HNO3
at 70 ◦ C to improve the contrast of Cu-rich phases. A FEI Quanta™ 250 scanning electron microscope
Metals 2018, 8, x FOR PEER REVIEW 4 of 18

Metals 2018, 8, 750 4 of 18

quantification, the polished samples were chemically etched by using a water solution of HNO3 at 70
°C to improve the contrast of Cu-rich phases. A FEI Quanta™ 250 scanning electron microscope
(SEM) (Thermo Fisher Scientific, Hillsboro, OR, USA) operating at 20 kV and coupled with an an energy
energy
dispersive
dispersive spectrometer
spectrometer (EDS)(EDS) (EDAX™,
(EDAX™, AMETEK
AMETEK BV, BV, Tilburg, The Netherlands)
Netherlands) and and an electron
back-scattered
back-scattered diffraction
diffraction (EBSD)
(EBSD) (EDAX™,
(EDAX™, AMETEKAMETEK BV, BV, Tilburg, The Netherlands) detector was
used to study the nature and the distribution of the intermetallic phases.
In order
order totobetter
betterunderstand
understandthe theeffects
effects
of of
thethe ageing
ageing treatment
treatment on alloy
on the the alloy microstructure,
microstructure, peak
peak
ageingageing conditions
conditions at 160,
at 160, 180 and 220 ◦
180 Candwere220 °C were
selected selected
for an extended formicrostructural
an extended microstructural
characterization
characterization
by using a JEM™by2000 using
EXaIIJEM™ 2000 EXelectron
transmission II transmission
microscope electron
(TEM)microscope
(JEOL Ltd,(TEM)
Akishima,(JEOL Ltd,
Japan)
Akishima, Japan) operating at 200 kV. In particular, TEM observations supported
operating at 200 kV. In particular, TEM observations supported by selected area electron diffraction by selected area
electron diffraction
(SAED) analyses were (SAED)
carried analyses were the
out to study carried
phaseout to study the
precipitation in phase
the α-Alprecipitation
phase. TEMinspecimens
the α-Al
phase. TEM specimens
were mechanically were mechanically
prepared prepared practice.
according to standard accordingFinally,
to standard
the TEMpractice.
discs Finally, the TEM
(3 mm diameter,
discsµm
~25 (3thickness)
mm diameter, ~25 μm by
were processed thickness) were
ion milling up processed by ion
to the electron milling up
transparency to precision
using the electronion
transparency
polishing systemusing precision
(PIPS, Modelion polishing
691, system (PIPS,
Gatan, Pleasanton, CA,Model
USA).691, Gatan, Pleasanton, CA, USA).
In order
order to evaluate
evaluate thethe strengthening
strengthening response of the alloy as function
function of thethe solution
solution and
and ageing
ageing
treatments,
treatments, Vickers
Vickers hardness
hardness measurements
measurements were were performed
performed on on each
each sample
sample by by applying
applying aa load
load of
60 kgf, in accordance
accordance to to the
the standard
standard ASTMASTM E92-17,
E92-17, and
and the
the average
averagehardness
hardnessvalues
valueswere
werereported.
reported.
The hardness evolution of the alloy alloy allowed
allowed to toeasily
easilyindividuate
individuatethe thepeak
peakageing
ageing(temperature,
(temperature,time),
time),
that is the greatest material hardening obtained during ageing treatment.

Results and
3. Results and Discussion
Discussion

3.1. As-Rheocast
3.1. As-Rheocast Condition
Condition
The microstructure
The microstructureofofthetheas-rheocast
as-rheocastAlSiAlSi9Cu3(Fe)
9 Cu3 (Fe) alloyalloy
exhibits the typical
exhibits structure
the typical of rheocast
structure of
Al-Si alloy, characterized by globular or rosette-like primary α-Al crystals surrounded
rheocast Al-Si alloy, characterized by globular or rosette-like primary α-Al crystals surrounded by by the Al-Si
eutectic
the Al-Sinetwork (Figure 1).
eutectic network The shape
(Figure 1). Theofshape
the α-Al
of thecrystals is due is
α-Al crystals todue
the to
fragmentation
the fragmentationof theofα-Al
the
dendrites
α-Al due todue
dendrites thetoswirl motion
the swirl during
motion the SEED
during process.
the SEED As reported
process. in Ref.in
As reported [21],
Ref.the average
[21], size of
the average
the primary
size α-Al crystals,
of the primary estimated
α-Al crystals, by quantitative
estimated image analysis,
by quantitative results results
image analysis, in ~70 µm with
in ~70 μmanwithaspect
an
ratio of 1.6. Moreover, the volume fraction of the primary α-Al phase is
aspect ratio of 1.6. Moreover, the volume fraction of the primary α-Al phase is 55 ± 6%. 55 ± 6%.
The eutectic
The eutectic Si
Si particles
particles generally
generally show
show fibrous
fibrous morphology,
morphology, as as illustrated
illustrated in in Figure
Figure 2. It is
2. It is worth
worth
noticing that a larger amount of Al-Si eutectic is observed near to the casting surface
noticing that a larger amount of Al-Si eutectic is observed near to the casting surface (Figure 3): this (Figure 3): this
microstructural inhomogeneity is due to liquid segregation phenomena occurring
microstructural inhomogeneity is due to liquid segregation phenomena occurring during the SSM during the SSM
processing, as
processing, as described
described inin Ref.
Ref. [22,23].
[22,23].

Figure
Figure1.
1. Microstructure
Microstructureof
ofas-rheocast
as-rheocast AlSi9Cu3(Fe)
AlSi9 Cu3 (Fe) alloy.

Figure 4,4,the
In Figure theDSC
DSCcooling
coolingcurve
curve
ofof AlSi9 Cu3 (Fe)
AlSi9Cu3(Fe) alloy
alloy is plotted.
is plotted. TheThe thermogram
thermogram reveals
reveals the
the liquidus and solidus temperatures approximately at 610 and 485 ◦ C, respectively, and according
liquidus and solidus temperatures approximately at 610 and 485 °C, respectively, and according to
to Ref.
Ref. [24],
[24], thethe sequence
sequence of of phaseprecipitation
phase precipitationduring
duringthe
thesolidification
solidificationpath
pathcan
canbebe identified
identified as
as
following: primary Fe-rich phase (~612 ◦ C), α-Al crystals (~578 ◦ C), eutectic Si and Fe-containing
following: primary Fe-rich phase (~612 °C), α-Al crystals (~578 °C), eutectic Si
phases (~567 ◦ C), Al2 Cu phase (~503 ◦ C) and formation of eutectic structures containing Al2 Cu and
Al5 Mg8 Si2 Cu2 (~498 ◦ C).
Metals 2018, 8, x FOR PEER REVIEW 5 of 18

phases (~567
Metals 2018, °C), Al22Cu phase (~503 °C) and formation of eutectic structures containing Al 22Cu5 and
8, 750 of 18
Al55Mg88Si2i2Cu22 (~498 °C).

Figure
Figure 2.
2. Eutectic
Eutectic Si
Si particles
particles in
in as-rheocast
as-rheocast condition.
condition.

Figure
Figure 3.
3. Distribution
Distribution of
of Al-Si
Al-Si eutectic
eutectic from
from the
the outer
outer surface
surface to
to the
the centre
centre of the casting.
of the casting.

Figure
Figure 4. 4. Differential
Differential scanning
scanning calorimetry
calorimetry curve
curve of
of experimental
experimental AlSi9Cu3(Fe)
AlSi9 Cu3 (Fe) alloy
alloy recorded
recorded during
during
cooling
cooling at 2 C/min; peak 1 = primary Fe-rich phase; peak 2 = α-Al crystals; peaks 3 and 44 == eutectic
at 2 °C/min;
◦ peak 1 = primary Fe-rich phase; peak 2 = α-Al crystals; peaks 3 and eutectic Si
Si
and Fe-containing phases;
and Fe-containing peak 55 == Al
phases; peak Al222Cu
Cu phase; peak 66 =
phase; peak = eutectic
eutectic structures
structures containing
containing Al
Al222Cu
Cu and
and
Al
Al555Mg
Mg888Si
Si222Cu
Cu22.2 .

Deeper SEM investigations

investigations revealed
revealed the intermetallic
intermetallic phases
phases distributed
distributed solely
solely in
in the eutectic
Al-Si
Al-Si network
network (Figure
(Figure 5);
5); inin addition,
addition, the
the EDS
EDS elemental
elemental maps
maps seemseem
to to confirm
confirm the the presence
presence of θ-Alof2 Cu,
θ-
Al 22Cu, polygonal
polygonal α-Al(Fe,Mn,Cr)Si
α-Al(Fe,Mn,Cr)Si (α-Fe),β-Al(Fe,Mn)Si
(α-Fe), acicular acicular β-Al(Fe,Mn)Si (β-Fe) and Q-AlMgSiCu
(β-Fe) and Q-AlMgSiCu intermetallic
intermetallic
phases (Figurephases
6). (Figure 6).
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Figure
Figure 5. 5.Scanning
Scanningelectron
electron microscopy
microscopy micrograph
micrograph of as-rheocast alloy.
Figure 5.5.
Figure Scanningelectron
Scanning electronmicroscopy of
micrographof
microscopy micrograph as-rheocast
ofas-rheocast alloy.
as-rheocastalloy.

Figure 6. Composition mapsby

Composition by energydispersive
dispersive spectroscopy related totothe micrograph in Figure 5
Figure 6. 6.
Figure Compositionmaps
maps byenergy spectroscopyrelated
energy dispersive spectroscopy relatedto themicrograph
the micrographin in Figure
Figure 5 5
and
Figure
and showing the
6. Composition
showing the distributions of
maps byofof
distributions Mg,
energy
Mg, Si, Cu, Fe,
dispersive Mn and Cr elements.
spectroscopy related to the micrograph in Figure 5
and showing the distributions Mg,Si,
Si,Cu,
Cu, Fe,
Fe, Mn
Mn and Cr elements.
and Cr elements.
and showing the distributions of Mg, Si, Cu, Fe, Mn and Cr elements.
ForFor
a more
a moreaccurate
accurateidentification
identification ofofthe
theintermetallic
intermetallic phases,
phases, EBSD
EBSD analyses
analyses werewere performed
performed on
For a more accurate identification of the intermetallic phases, EBSD analyses were performed on
the
onthe
theθ-Al
For 2Cu,
θ-Al
a more α-Al(Fe,Mn,Cr)Si
2 Cu, α-Al(Fe,Mn,Cr)Si
accurate and β-Al(Fe,Mn)Si,
identification and
of the and the and
β-Al(Fe,Mn)Si,
intermetallic associated
the EBSD patterns
associated EBSDwell match the
patterns well
θ-Al 2Cu, α-Al(Fe,Mn,Cr)Si and β-Al(Fe,Mn)Si, and thephases, EBSD
associated analyses
EBSD were
patterns performed
well match theon
nominal
match the
thenominal crystallography
nominal
θ-Al2Cu,crystallography
α-Al(Fe,Mn,Cr)Si structures,
crystallography i.e.,
structures,
and β-Al(Fe,Mn)Si,tetragonal,
i.e., cubic
tetragonal,
and the and
cubic
associated monoclinic
and crystal
monoclinic
EBSD patterns systems,
crystal systems,
well systems,
match the
structures, i.e., tetragonal, cubic and monoclinic crystal
respectively
respectively [25],
[25], as
asas reported
reported inFigure
inin Figure 7.
nominal crystallography
respectively [25], reported Figure7.7.
structures, i.e., tetragonal, cubic and monoclinic crystal systems,
respectively [25], as reported in Figure 7.

Figure 7. Experimental patterns by electron back-scattered diffraction acquired from (a) Al2Cu, (b) α-
Figure
Figure 7. 7. Experimental
Experimental patternsbybyelectron
patterns electronback-scattered
back-scattereddiffraction
diffractionacquired
acquiredfrom
from(a)
(a)Al
Al2Cu,
Cu, (b)
(b) α-
α-Fe
Fe and (c) β-Fe phases with superimposed tetragonal (space group, s.p. I4/mcm), cubic (s.p. 2 Pm-3)
andFe and
(c) (c)
β-Fe β-Fe
phasesphases
with with superimposed
superimposed tetragonal
tetragonal (space
(space group,
group, s.p. s.p. I4/mcm),
I4/mcm), cubic
cubic (s.p.
(s.p. Pm-3)
Pm-3) and
and monoclinic
Figure (s.p. 2/m)
7. Experimental pattern
patterns simulations,
by simulations, respectively.
electron back-scattered
and monoclinic
monoclinic (s.p. 2/m)
(s.p. 2/m) pattern
pattern simulations, respectively.diffraction acquired from (a) Al2Cu, (b) α-
respectively.
Fe and (c) β-Fe phases with superimposed tetragonal (space group, s.p. I4/mcm), cubic (s.p. Pm-3)
and monoclinic (s.p. 2/m) pattern simulations, respectively.
Metals 2018, 8, x
750
FOR PEER REVIEW 77of
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3.2. As-Quenched Condition

3.2. As-Quenched Condition
The specimens, which were solution heat treated at 450, 470 and 490 °C, showed essentially
Themicrostructural
specimens, which wereThesolution heat treated at 450, 470 and 490 ◦
similar features. microstructure of the AlSi9Cu3(Fe) alloyC,solutioned
showed essentially
at 470 °C
similar microstructural features. The microstructure of the AlSi
for 6 h is shown as an example in Figure 8. As expected, the 9solution Cu 3 (Fe) 470 ◦ C for
treatment has noatcoarsening
alloy solutioned
6 h is shown
effects on theasprimary
an example
α-Alincells,
Figure 8. Asshow
which expected, the solution
a similar treatment
size to the has no
as-rheocast coarsening
condition (~70effects
μm);
on the primary α-Al cells, which show a similar size to the as-rheocast condition
while the eutectic Si is considerably modified in size and morphology. The eutectic Si particles (~70 µm); while
the eutectic
fragment andSiacquire
is considerably modified in(Figure
a more round-shape size and
8b)morphology. The eutectic
due to the reduction of theSi particles
total fragment
Al/Si interfacial
and acquire
energy a more
during theround-shape (Figure 8b)
solution treatment; due to thesmaller
moreover, reduction of the total
eutectic Al/Si interfacial
Si particles energy
in as-rheocast
during the solution treatment; moreover, smaller eutectic Si particles in as-rheocast
microstructure dissolve and favour the coarsening of coarser ones according to Ostwald ripening microstructure
dissolve and[26].
mechanism favour the coarsening of coarser ones according to Ostwald ripening mechanism [26].

Figure 8. Micrographs
Figure 8. Micrographs at
at (a)
(a) low
low and
and (b)
(b) higher
higher magnifications
magnifications of
of AlSi9Cu3(Fe) alloy solutioned
AlSi9 Cu3 (Fe) alloy solutioned at
at
470 °C
◦ for 6 h.
470 C for 6 h.

The size and morphological

morphological variations
variations of of the eutectic
eutectic Si particles as a function of solution
treatments
treatments are summarized
summarized in in Table 2. The
The eutectic
eutectic Si
Si particles
particles fragment
fragment and
and spheroidize,
spheroidize, mainly,
mainly,
during the
the early
earlystage
stageofofthe
thesolution
solution treatment;
treatment; then,
then, theythey
tendtend to coarsen
to coarsen during
during the subsequent
the subsequent stage
stage of treatment, maintaining essentially the
of treatment, maintaining essentially the same shape. same shape.

Table 2. Size and morphology of the eutectic Si particles, and area fraction of Cu-rich compounds as
Table 2.
a function of the solution heat treatments.

Alloy condition Solutionheat

Solution Heattreatment
Treatment Eutectic
EutecticSi
SiParticles
particles Cu-Rich Compounds
Cu-rich compounds
Alloy Condition
Temperature (◦ C)
Temperature(°C) Time(h)
Time (h) Area (µm22)
Area (μm ) Aspect Ratio
Aspect ratio Area
AreaFraction (%)(%)
fraction
As-rheocast -- -- 2.4 ± 1.5 2.4 ± 1.3 2.1 ± 0.5
As-rheocast 2.4 ± 1.5 2.4 ± 1.3 2.1 ± 0.5
1 1.1 ± 0.7 1.8 ± 0.5 1.0 ± 0.1
As-quenched 450 13 1.1±± 0.8
1.9 0.7 ± 0.5
2.01.8 ± 0.5 ± 0.1
0.31.0 ± 0.1
As-quenched 450 36 1.9±± 0.6
1.9 0.8 ± 0.6
2.02.0 ± 0.5 ± 0.1
0.30.3 ± 0.1
1 1.8 ± 0.6 2.1 ± 0.5 0.5 ± 0.2
6 1.9 ± 0.6 2.0 ± 0.6 0.3 ± 0.1
As-quenched 470 3 1.9 ± 0.7 1.9 ± 0.4 0.3 ± 0.1
16 1.8±± 0.8
1.9 0.6 ± 0.4
1.72.1 ± 0.5 ± 0.2
0.20.5 ± 0.2
As-quenched 470 31 1.9±
1.6 0.7
± 0.7 ± 0.4
1.81.9 ± 0.4 ± 0.1
0.20.3 ± 0.1
As-quenched 490 3 2.2 ± 0.9 1.7 ± 0.5 0.1 ± 0.1
66 1.9±± 0.8
2.2 0.8 1.7 ± 0.4
1.7 ± 0.4 0.2 ± 0.2
0.1 ± 0.1
1 1.6 ± 0.7 1.8 ± 0.4 0.2 ± 0.1
As-quenched 490 3 2.2 ± 0.9 1.7 ± 0.5 0.1 ± 0.1
Moreover, fine polygonal and rod/platelet-shape particles appear within the α-Al matrix after
6 2.2 ± 0.8 1.7 ± 0.4 0.1 ± 0.1
solution treatments, as shown in Figure 8b. The EDS profile across the α-Al crystals suggests that
the particles are Si-rich phase (Figure 9, red line). The bright field TEM micrograph correlated to
SAED Moreover, fine polygonal
investigations confirmed and rod/platelet-shape
that most of the particlesparticles appear
are Si crystals within
with the α-Al matrixshape
irregular-polygonal after
solution treatments,
(Figure 10). as shown in Figure 8b. The EDS profile across the α-Al crystals suggests that the
particles
In theareas-rheocast
Si-rich phase (Figure the
condition, 9, red line). The
Si content inbright
the α-Alfield TEM micrograph
matrix, correlated
over its solubility leveltoatSAED
room
investigations confirmed that most of the particles are Si crystals with irregular-polygonal
temperature, is almost homogeneously distributed; this is indicated by the Si profile across the width shape
(Figure 10).
Metals
Metals2018,
2018,8,
8, xxFOR
FOR PEER
PEERREVIEW
REVIEW 88 of
of 18
18

In
In the
the as-rheocast
as-rheocast condition,
condition, the the Si
Si content
content in in the
the α-Al
α-Al matrix,
matrix, over
over its
its solubility
solubility level
level at at room
room
Metals 2018, 8, 750 8 of 18
temperature,
temperature, is is almost
almost homogeneously
homogeneously distributed;
distributed; this
this is
is indicated
indicated by by the
the Si
Si profile
profile across
across the the width
width
of
of an
an α-Al
α-Al crystal
crystal which
which appears
appears almost
almost constant
constant (Figure
(Figure 9, 9, black
black line).
line). When
When the the alloy
alloy isis solution
solution
of
heatantreated,
heat α-Al crystal
treated, the which Si
the excess
excess appears
atomsalmost
Si atoms move,constant
move, clustering
clustering(Figure
and
and the9, black
the line).
clusters
clusters When
begin
begin the alloy isTherefore,
coarsening.
coarsening. solution heat
Therefore, the
the
treated,
final Si the excess
particles, Si atoms
crossed by move,
the EDS clustering
scan and
line, the
cause clusters
a begin
corresponding coarsening.
final Si particles, crossed by the EDS scan line, cause a corresponding rise of the Si level showing aa
rise of the Therefore,
Si level the
showing final
Si particles,
final
final “spiky”crossed
“spiky” by the
distribution
distribution EDS scan
profile.
profile. line, cause
Moreover,
Moreover, by a corresponding
bycomparing
comparing the rise ofprofiles
the elemental
elemental the Si level
profiles in showing
inFigure
Figure 9, aisfinal
9, ititis thus
thus
“spiky”
clear
clear thatdistribution
that the profile. of
the precipitation
precipitation Moreover,
of Si by comparing
Si particles
particles in
in the
the α-Al
α-Al the elemental
phase
phase after profiles
after the in Figure
the solution
solution 9, it is leads
treatment
treatment thus clear
leads to
to aa
that the
subsequent precipitation
subsequent reduction
reduction ofof Si particles
of the
the siliconin the α-Al
silicon content
content in phase
in the after the
the surrounding solution
surrounding Al-matrix treatment
Al-matrix with leads to
with respect a subsequent
respect to to the
the as- as-
reduction
rheocast of the silicon content in the surrounding Al-matrix with respect to the as-rheocast condition.
rheocast condition.
condition.

Figure
Figure 9. 9. The
The distribution
distribution of
distribution of Si
of Si across
across the
the width
width of
of an α-Al
an α-Al crystal in
α-Al crystal in as-rheocast condition and
as-rheocast condition and after
after
66 hh of
of solution
solution treatment
treatment at 470◦°C.
at 470 °C.
C.

Figure
Figure 10.
Figure 10. Transmission
10. electron
Transmission electron
Transmission microscopy
microscopy micrograph
electron microscopy (TEM)
micrograph (TEM)
micrograph micrograph
(TEM) micrograph showing
micrograph showing
showing Si Si dispersoids
Si dispersoids
dispersoids
the
withinthe
within α-Al
theα-Al matrix
α-Almatrix in
matrixin the
inthe rheocast
therheocast
rheocast AlSi9Cu3(Fe)
AlSi9Cu3(Fe)
AlSi alloy
alloy after
after solution
solution treatment
treatment at ◦
at 470
470 °C
°C forh.66Inh.
6for In
h.the
In
9 Cu3 (Fe) alloy after solution treatment at 470 C for
the
the inset,
inset,inset, the
the selected
selected
the selected area
area electron
area electron electron diffraction
(SAED)(SAED)
diffraction
diffraction pattern pattern
(SAED) pattern acquired
acquired from a Sifrom
acquired from aa Si
dispersoidSi dispersoid
is reported.is
dispersoid is
reported.
reported.
Similar Si-containing dispersions were also found to form in an Al-7Si-Mg alloy during solution
Similar
treatments Si-containing
Similar[27]. Moreover,
Si-containing dispersions
Lasagni etwere
dispersions also
al. [28]
were found
found to
alsoshowed form
tothe in
in an
presence
form an Al-7Si-Mg alloy
alloy during
of nanometrical
Al-7Si-Mg solution
globular
during and
solution
treatments
treatments [27].
platelet-like [27]. Moreover,
Moreover, Lasagni
Si precipitates Lasagni
in et
et al.
an Al-1.7Sial. [28]
[28] showed
alloy showed the
the presence
after solution presence of
of nanometrical
treatment nanometrical globular
with a controlledglobular and
and
cooling
platelet-like
rate (20 K/min)
platelet-like Si
Si precipitates
and how the
precipitates in
in an
an Al-1.7Si
size alloy
alloy after
of Si particles
Al-1.7Si solution
increases
after solutionby treatment
reducing
treatment with
theaacooling
with controlled
ratecooling
controlled (3 K/min)
cooling rate
rate
(20
at K/min)
(20the
K/min) and
andof
expense how
how the
their size
size of
thedensity.of Si
Si particles
Theparticles increases
increases
precipitation of by reducing
by particles
Si reducingin the
the cooling
cooling
the rate
rate (3
α-Al matrix K/min)
(3 after
K/min) at
at the
solutionthe
expense
expense of
treatment their
ofcould density.
theirthus
density. The
The precipitation
be ascribed precipitation
to the excess of Si
ofSi particles
Siatoms
particles in
in thein the
the α-Al
α-Al matrix after
after solution
matrixmatrix
supersaturated achievedtreatment
solution treatment
after the
could
could thus be
be ascribed
ascribed to
thus process.
rheocasting to the
the excess
excess SiSi atoms
atoms in in the
the supersaturated
supersaturated matrixmatrix achieved
achieved after
after the
the
rheocasting
rheocasting process.
process. of Cu-rich compounds was also investigated, as it is generally considered
The dissolution
a key-factor for the strengthening enhancement. The fraction of undissolved Cu-rich phases in
the as-quenched specimens is reported in Table 2. In the as-rheocast condition, the fraction of Cu-rich
Metals 2018, 8, x FOR PEER REVIEW 9 of 18

The dissolution of Cu-rich compounds was also investigated, as it is generally considered a key-
factor for 8,
Metals 2018, the
750strengthening enhancement. The fraction of undissolved Cu-rich phases in the as-
9 of 18
quenched specimens is reported in Table 2. In the as-rheocast condition, the fraction of Cu-rich
compounds is about 2% and it drastically decreases in the earlier stages of solution treatment, more
compounds
rapidly as theissolution
about 2% and it drastically
temperature decreases
increases. in the by
In addition, earlier stages the
extending of solution
solutiontreatment,
time up tomore6 h,
rapidly as the solution temperature increases. In addition, by extending
the Cu-rich compounds are almost completely dissolved; very few blocky θ-Al2Cu particles the solution time up to 6 h,
remain,
the Cu-rich
being compounds
more complex are almost
to dissolve completely
if compared to dissolved;
θ-phase invery few
binary blockyAl
eutectic θ-Al 2 Cu
+ Al 2Cuparticles remain,
structures and
being more complex to dissolve if compared to θ-phase in binary eutectic Al + Al
Q-Al5Mg8Si2Cu2 phase, as also resulted from the precipitation sequence in Figure 4.2As a consequence Cu structures and
Q-Al Mg
of θ-phase
5 Si Cu phase,
8 dissolution,
2 2 as also resulted from the precipitation sequence in Figure 4. As
the Cu level in the α-Al solid solution increases as it clearly appears by a consequence
of θ-phase dissolution,
comparing the EDS profiles the Cu level
across theinα-Al
the α-Al solid
crystals in solution increases
the as-rheocast as it clearly
condition appears
and after 6 h byof
comparing the EDS profiles across the α-Al crystals in the as-rheocast
solution treatment at 470 °C (Figure 11a). Similar behaviour was also found for the Mg and condition and after 6 hZn of
solution treatment atby
470 ◦
elements, as reported theCEDS
(Figure 11a). profiles
elemental Similarinbehaviour
Figure 11b,c,wasrespectively.
also found for the Mg and Zn
elements, as reported by the EDS elemental profiles in Figure 11b,c, respectively.
Finally, the different solution treatments do not affect the α-Fe and β-Fe intermetallics because
Finally,
of their high the different
thermal solution
stability, as ittreatments
results from dothe
notDSC
affectthermograph
the α-Fe andinβ-Fe intermetallics
Figure 4. because of
their high thermal stability, as it results from the DSC thermograph in Figure 4.

Figure 11. The distributions of (a) Cu, (b) Mg and (c) Zn across the width of α-Al crystals in as-rheocast
Figure 11. The distributions of (a) Cu, (b) Mg and (c) Zn across the width of α-Al crystals in as-rheocast
condition and after 6 h of solution treatment at 470 ◦ C.
condition and after 6 h of solution treatment at 470 °C.
The Vickers hardness of the as-quenched AlSi9 Cu3 (Fe) alloy as a function of the solution treatment
The Vickers hardness of the as-quenched AlSi9Cu3(Fe) alloy as a function of the solution
conditions is illustrated in Figure 12; the hardness value of as-rheocast alloy has also been reported in
treatment conditions is illustrated in Figure 12; the hardness value of as-rheocast alloy has also been
the graph.
reported in the graph.
For the solution conditions considered in this work, it results that the hardness of the alloy
increases by increasing the solution temperature and time; therefore, the optimal strengthening
response of the alloy is achieved after thermal treatment at the most severe condition.
It is worth noting that the solution treatments carried out at 450 ◦ C led to lower hardness values
with respect to as-rheocast condition. In particular, the material softening is larger in the earlier stage
Metals 2018, 8, x FOR PEER REVIEW 10 of 18

For the solution conditions considered in this work, it results that the hardness of the alloy
increases by increasing the solution temperature and time; therefore, the optimal strengthening
response
Metals 2018,of the alloy is achieved after thermal treatment at the most severe condition.
8, 750 10 of 18
It is worth noting that the solution treatments carried out at 450 °C led to lower hardness values
with respect to as-rheocast condition. In particular, the material softening is larger in the earlier stage
of the treatment, then the hardness slightly improves by prolonging the holding time and finally
maintains at a steady value after 3 h. Similar behaviour was found for a thixocast 319 alloy solutioned
at 500 ◦°CC [29]. The
The initial
initial softening
softening of
of the
the alloy
alloy may
may be
be due
due to the eutectic Si particles coarsening,
coarsening,
which is characterized by the increase of the inter-particle distance of the eutectic Si [30]; on the other
side, the subsequent strengthening can be associated with the increasing content of Cu, Mg and Si in
solid solution. TheThe hardness
hardness evolution
evolution approaches
approaches the
the as-rheocast
as-rheocast value,
value, and
and itit stabilizes
stabilizes after
after 44 h,
h,
indicating how the α-Alα-Al matrix is saturated.

Figure
Figure 12.
12. Hardness
Hardness of
of rheocast
rheocast AlSi9Cu3(Fe) time.
AlSi9 Cu3 (Fe) alloy as function of solution temperature and time.

As mentioned, the alloy solutioned

solutioned atat the most severe conditions
conditions (i.e.,
(i.e., 490 ◦ C for 3 and 6
490 °C for 3 and 6 h)
exhibits higher hardness values; however, blistering phenomena were occasionally observed on the
specimens’
specimens’ surface
surfaceafter thethe
after aforementioned heat treatment
aforementioned conditions.
heat treatment Blisters are
conditions. generally
Blisters are associated
generally
to the expansion
associated of gas porosity,
to the expansion of gaswhich includes
porosity, whichgas from physical
includes gas fromentrapment, gas from lubricant
physical entrapment, gas from
decomposition, and gas initially dissolved in the molten metal (e.g., hydrogen). The
lubricant decomposition, and gas initially dissolved in the molten metal (e.g., hydrogen). The discrimination of
each contribution
discrimination to the
of each total porosity
contribution duetotal
to the to gas entrapment
porosity due toisgas
notentrapment
possible in isthis
notwork. However,
possible in this
the gas porosity due to dissolved hydrogen is not common in pressure casting
work. However, the gas porosity due to dissolved hydrogen is not common in pressure casting processes, where the
formation of gas pores is mainly attributed to the decomposition of coolant and die lubrication
processes, where the formation of gas pores is mainly attributed to the decomposition of coolant and [31].
In the present
die lubrication [31].study, the subsequent ageing treatments were applied to the alloy solutioned at
470 ◦In
C for 6 h which achieved
the present study, high hardness
the subsequent values
ageing and, concurrently,
treatments showed
were applied to thea free-defects surface.
alloy solutioned at
470 °C for 6 h which achieved high hardness values and, concurrently, showed a free-defects surface.
3.3. Ageing Condition
3.3. Ageing Condition
3.3.1. Hardness Testing
3.3.1.The Testing behaviour at 160, 180 and 220 ◦ C is shown in Figure 13. The results indicate
age hardening
Hardness
that the maximum hardness value is achieved at 160 ◦ C for 24 h. By temperature increasing, the peak
The age hardening behaviour at 160, 180 and 220 °C is shown in Figure 13. The results indicate
hardness is reached for shorter times because of faster precipitation kinetics, i.e., 5 h at 180 ◦ C and
that the maximum hardness value is achieved at 160 °C for 24 h. By temperature increasing, the peak
2 h at 220 ◦ C. It is well known that the precipitation rate during heat treatment is related to the
hardness is reached for shorter times because of faster precipitation kinetics, i.e., 5 h at 180 °C and 2
diffusion of the solute elements in the α-Al matrix and this strictly depends on the temperature [32].
h at 220 °C. It is well known that the precipitation rate during heat treatment is related to the diffusion
As described in the literature [15], the experimental peak value progressively decreases as the ageing
of the solute elements in the α-Al matrix and this strictly depends on the temperature [32]. As
temperature increases: 117 ± 3 HV at 160 ◦ C, 103 ± 3 HV at 180 ◦ C and 95 ± 2 HV at 220 ◦ C. It is
described in the literature [15], the experimental peak value progressively decreases as the ageing
worth noting that the hardness in the earlier stages of ageing is slightly lower when compared to the
temperature increases: 117 ± 3 HV at 160 °C, 103 ± 3 HV at 180 °C and 95 ± 2 HV at 220 °C. It is worth
as-quenched condition after the solution treatment at 470 ◦ C for 6 h; for these relative short times,
the mechanical response appreciably decreases by decreasing the ageing temperature. As reported
by Maksimovic et al. [33], this trend can be ascribed to the dissolution of GP zones formed during
previous solution heat treatment.
noting that the hardness in the earlier stages of ageing is slightly lower when compared to the as-
quenched condition after the solution treatment at 470 °C for 6 h; for these relative short times, the
mechanical response appreciably decreases by decreasing the ageing temperature. As reported by
Maksimovic
Metals et al. [33], this trend can be ascribed to the dissolution of GP zones formed during
2018, 8, 750 11 of 18
previous solution heat treatment.

Figure 13. Age

13. Age hardening
hardening curves
curves of rheocast
of rheocast AlSi9 Cu3 (Fe)
AlSi9Cu3(Fe) alloyalloy solutioned
solutioned at 470at for 6◦ Ch. for
°C470 The6as-
h.
The as-quenched
quenched condition
condition after
after the the solution
solution treatment
treatment is also indicated.
is also indicated.

3.3.2. Precipitation Microstructure

3.3.2. Precipitation Microstructure
The artificial ageing treatments induce no visible effects at microscale in the alloy. Therefore, high
The artificial ageing treatments induce no visible effects at microscale in the alloy. Therefore,
magnification bright field TEM observations were carried out for the peak ageing conditions at 160,
high magnification bright field TEM observations were carried out for the peak ageing conditions at
◦ C, in order to investigate the nature of strengthening phases responsible for the greatest
180 and 220
160, 180 and 220 °C, in order to investigate the nature of strengthening phases responsible for the
material hardening. Where not differently specified in the text, TEM micrographs and SAED patterns
greatest material hardening. Where not differently specified in the text, TEM micrographs and SAED
have beenhave
patterns acquiredbeenclose the <100>
acquired zone<100>
closeAl the axis Alto zone
have aaxis higher contrast
to have between
a higher the precipitates
contrast between and the
the matrix.
precipitates and the matrix.
In
In an
an Al-Si-Cu-Mg
Al-Si-Cu-Mg system, system, thethe precipitation
precipitation sequence
sequence is is normally
normally considered
considered quite
quite complex
complex
because of the occurrence of a great variety of structures that can
because of the occurrence of a great variety of structures that can range from binary to complex range from binary to complex
quaternary
quaternary phases.
phases. Therefore,
Therefore,aalargelargediscrepancy
discrepancyabout about thethe
strengthening
strengthening mechanism
mechanism of Al-Si-Cu-Mg
of Al-Si-Cu-
alloys after solution and artificial ageing treatments emerges from
Mg alloys after solution and artificial ageing treatments emerges from the literature; consequently,the literature; consequently,
more
more experimental investigations are
experimental investigations are requested
requested to to consolidate
consolidate the the understanding
understanding of of the
the age
age
hardening mechanism.
hardening mechanism.
In
In order
order to to support
support the the TEM
TEM findings,
findings, several
several works
works were were examined
examined concerning
concerning thethe ageing
ageing
response of hypoeutectic cast Al-Si-Cu(-Mg) alloys and wrought Al-Mg-Si(-Cu)
response of hypoeutectic cast Al-Si-Cu(-Mg) alloys and wrought Al-Mg-Si(-Cu) and Al-Cu-Mg(-Si) and Al-Cu-Mg(-Si)
alloys. Although the
alloys. Although the experimental
experimental alloy alloy in
in this
this work
work is is aa foundry
foundry Al-Si-based
Al-Si-based alloy,
alloy, the α-Al matrix
the α-Al matrix
results to be Mg- and Cu-enriched due to the dissolution of the Mg- and
results to be Mg- and Cu-enriched due to the dissolution of the Mg- and Cu-rich intermetallic phases Cu-rich intermetallic phases
after
after the
the solution
solution heat heat treatment,
treatment, as as illustrated
illustrated in in Figure
Figure 11. Moreover, the
11. Moreover, the Si
Si content
content inin the
the solid
solid
solution
solution α-Al matrix is further reduced due the precipitation of Si particles, as previously reported
α-Al matrix is further reduced due the precipitation of Si particles, as previously reported
(Figures
(Figures 99 and 10). Therefore,
and 10). Therefore, the
the age
age hardening
hardening mechanism
mechanism in in wrought
wrought Al-Mg-Si
Al-Mg-Si or or Al-Cu-Mg
Al-Cu-Mg based
based
alloys has to be also considered in order to better understand the precipitation
alloys has to be also considered in order to better understand the precipitation mechanism in the mechanism in the
rheocast AlSi 9 Cu
rheocast AlSi9Cu3(Fe) 3 (Fe) alloy.
alloy.
The ◦ C for 24 h (Figure 14a) reveals a large
The TEM investigation of
TEM investigation of the
the peak
peak ageing
ageing condition
condition at at 160
160 °C for 24 h (Figure 14a) reveals a large
amount
amount ofoffine black
fine dotsdots
black with awith
square-like shape and
a square-like an average
shape and an sideaverage
length ofside
~4 nm, homogeneously
length of ~4 nm,
distributed in the α-Al matrix. Several authors [34–36] have reported
homogeneously distributed in the α-Al matrix. Several authors [34–36] have reported the presence the presence of very similar
of
precipitates
very similarin precipitates
Al-Mg-Si-(Cu) inalloys after ageingalloys
Al-Mg-Si-(Cu) treatments
after and they treatments
ageing have been identified
and theyas have
metastable
been
coherent
identifiedβ” as phase
metastableprecipitation
coherent through
β’’ phasethe analysis ofthrough
precipitation SAED patterns and of
the analysis high-resolution
SAED patternsTEM and
micrographs. The appearance of nanometric dots with similar size and
high-resolution TEM micrographs. The appearance of nanometric dots with similar size and shape shape were also observed in an
aged AlSi7Cu3Mg alloy by Li et al. [35], who stated that the square-shaped particles correspond to
the cross sections of needle-like β” precipitates. Some needle-like precipitates that lie along the <100>
directions of the α-Al matrix are visible in Figure 14a, confirming the typical orientation relationships
Metals 2018, 8, x FOR PEER REVIEW 12 of 18

were also observed in an aged AlSi7Cu3Mg alloy by Li et al. [35], who stated that the square-shaped
Metals 2018, 8, 750 12 of 18
particles correspond to the cross sections of needle-like β’’ precipitates. Some needle-like precipitates
that lie along the <100> directions of the α-Al matrix are visible in Figure 14a, confirming the typical
orientation
between β” relationships
and α-Al phases between
[37]. The β’’ mean
and α-Al
length phases [37]. Theβ”mean
of needle-like length along
precipitates of needle-like
the <100>β’’ Al
precipitates
directions was along the <100>
measured Al directions
about 30 nm. was measured about 30 nm.
Beside
Beside the black dot
the black dot particles,
particles, some some precipitates
precipitates appear
appear withwith aa rectangular
rectangular cross-section
cross-section withwith
mean
mean sizesize of
of22××5757
nm nm2 . By
2 tilting
. By the the
tilting sample
samplecloseclose
to <110> Al direction,
to <110> these precipitates show a lath-
Al direction, these precipitates show
shaped morphology
a lath-shaped (Figure(Figure
morphology 14b) with 14b)awith
dimension of ~7 nm.
a dimension of ~7Linm.
et al.
Li [35]
et al.observed that the
[35] observed thatlath-
the
shaped precipitates in an aged AlSi7Cu3Mg alloy are quaternary Al-Mg-Si-Cu
lath-shaped precipitates in an aged AlSi7Cu3Mg alloy are quaternary Al-Mg-Si-Cu phase and their phase and their
chemical
chemical composition
composition and and crystal
crystal structure
structure fit the Q’
fit the Q’ phase.
phase. The
The presence
presence of of Q’
Q’ phase
phase was was also
also
observed in an aged AlSi9Cu3.5Mg alloy and the corresponding SAED pattern
observed in an aged AlSi9 Cu3 .5Mg alloy and the corresponding SAED pattern seems to be close to the seems to be close to
the experimental one obtained in the present work (see
experimental one obtained in the present work (see inset in Figure 14a). inset in Figure 14a).
It is worth
It is worthmentioning
mentioning that,
that, beside
beside Q’ phase,
Q’ phase, lath-like
lath-like L precipitates
L precipitates with rectangular
with rectangular cross
cross section
section and longer dimension lying along the <100> direction, can also
and longer dimension lying along the <100>Al direction, can also precipitate in aged Al-Mg-Si-Cu as
Al precipitate in aged Al-Mg-
Si-Cu[38,39].
well as wellMoreover,
[38,39]. Moreover,
contrary contrary to the Lthe
to the L phase, phase, the section
Q’-laths Q’-lathshas
section has the
the long sidelong
at anside at an
angle of
angle
about of ~11 ◦ with
about ~11° with to
respect respect
the <100>to theAl<100> Al directions
directions or, equivalently,
or, equivalently, Q’ precipitates
Q’ precipitates have {510}haveAl{510}
habitAl

habit planes with the Al matrix [36,40–42]. In an aged Al-Mg-Si alloy with
planes with the Al matrix [36,40–42]. In an aged Al-Mg-Si alloy with Cu excess, it is found that theCu excess, it is found that
the decomposition
decomposition of the
of the supersaturated
supersaturated solid
solid solution
solution (SSSS)takes
(SSSS) takesplace
placeby byaa complex
complex precipitation
precipitation
sequence [43]:
sequence [43]:
→atomic
α(SSSS)→
α(SSSS) atomicclusters →GP
clusters→ zones→→β”,L
GPzones β”,L→→β’,Q’
β’,Q’→→
QQ (1)
(1)
where
where the
the L
L phase
phase is
is believed
believed to
to be
be aa Q’
Q’ precursor.
precursor.

Figure 14. TEM

TEM micrographs
micrographs of of rheocast
rheocast AlSi9Cu3(Fe)
AlSi9 Cu3 (Fe) alloy
alloy after peak ageing
ageing treatment
treatment at
at 160 ◦ C,
160 °C,
acquired (a) close to
to <100>
<100>AlAl direction
direction and
and the
the corresponding
corresponding SAED
SAED pattern
pattern (inset),
(inset), and
and (b) after
specimen tilting to <110>
<110>AlAldirection.
direction.

peak aged
aged condition
condition atat 180
180 °C ◦ C for 5 h is shown in Figure 15.
The microstructure for the peak for 5 h is shown in Figure 15.
Parallelogram-like dots
Parallelogram-like dots and
and fine needles, associated
associated toto Q’ and β’’β” phases, are still the predominant
precipitates in the alloy.
alloy. While the dimensions of the precipitates seem comparable to those observed
after ageing at 160 ◦°C C for 24 h,
h, the
the precipitate
precipitate volume
volume fraction
fraction appears
appears lower.
lower. The SAED pattern
(Figure 15) shows some different reflections compared to those observed in the diffraction pattern of
condition at 160 ◦°C:
the peak-aged condition C: due to the
the complexity
complexity of thethe chemical
chemical composition
composition of the examined
alloy, the
alloy, the precipitation
precipitation of of an
an extra
extra phase
phase cannot
cannot bebe excluded.
excluded.
TEM micrograph of peak aged alloy at 220 ◦°C C for 2 h is reported in Figure
Figure 16. If compared to
previous peak aged conditions, fine parallelogram-like precipitates are not revealed. The significant
of β’’ fractiondue
duetotothe
the temperature increase from ◦ C seems in agreement
reduction of β”fraction temperature increase from 180180 to 220
to 220 °C seems in agreement with
with
YangYang
et al. et al.who
[44] [44] found
who found that
that β’’ β” precipitates
precipitates do notdo not easily
easily transform
transform intostable
into more more phases
stable phases
(semi-
(semi-coherent ◦
coherent β’ and β’ Q’and Q’ phases)
phases) at 175 °C at for
175prolonged
C for prolonged
time, whiletime,
thewhile the transformation
transformation process
process becomes
becomes more rapid at higher temperature (200 ◦ C). In the microstructure, fine precipitates with
Metals 2018,
Metals 2018, 8,
8, xx FOR PEER
750
FOR PEER REVIEW
REVIEW 13
13 of
13of 18
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more rapid
more rapid at
at higher
higher temperature
temperature (200
(200 °C).
°C). In
In the
the microstructure,
microstructure, fine
fine precipitates
precipitates with
with narrow
narrow
narrow rectangular
rectangular morphology morphology
morphology andand {100}and
{100}Al {100} habit plane are also present and identified as Q’
Al habit plane are also present and identified as Q’ phase. The
Al phase.
rectangular habit plane are also present and identified as Q’ phase. The ◦C
The dimensions
dimensions of of these
of these precipitates
these precipitates
precipitates seemseem comparable
seem comparable
comparable to to those
to those observed
those observed after
observed after ageing
after ageing
ageing atat 160
at 160 and
160 and 180
and 180
180 °C
°C
dimensions
for 24
for 24 and
and 55 h,
h, respectively.
respectively.
for 24 and 5 h, respectively.

Figure 15.
Figure 15. Microstructure
Microstructure of rheocast
Microstructure of rheocast AlSi9Cu3(Fe)
rheocast AlSi9Cu3(Fe) treatment at 180 ◦°C;
AlSi9 Cu3 (Fe) alloy after peak ageing treatment °C; SAED
C; SAED
pattern in the inset.
pattern in the inset.

Long needle-like precipitates

Long needle-like precipitates with
with aaa length
length up
length up to
up to ~150
to ~150 nm
~150 nm and
nm and oriented
and orientedalong
oriented along<100>
along <100>Al
<100> Al direction
Al direction
are also observed after ageing at 220 ◦ C for 2 h. By tilting the TEM specimen close to <110> direction,
are also observed after ageing ageing at
at 220
220 °C°C for
for 2 h. By tilting the TEM specimen specimen close
close to
to <110>
<110>AlAl direction,
Aldirection,
the longer needles transform into platelet-shape precipitates (Figure 16b) with an averageofsize
the longer
longer needles
needles transform
transform into
intoplatelet-shape
platelet-shape precipitates
precipitates(Figure
(Figure16b) with
16b) an
withaverage
an size
average about
size of
of
4.5 × 10 3 nm23. These can be identified as θ’ phase that forms fine platelets (thickness ~1 nm) lying
about 4.5 × 10 nm 2. These can be identified as θ’ phase that forms fine
about 4.5 × 10 nm . These can be identified as θ’ phase that forms fine platelets (thickness ~1 nm)
3 2 platelets (thickness ~1 nm)
on {100}
lying
lying planes,
onAl{100}
on {100} as largely
Al planes, as documented
largely documented in literature for Al-Si-Cu-Mg
in literature alloys [35,45,46].
for Al-Si-Cu-Mg
Al planes, as largely documented in literature for Al-Si-Cu-Mg alloys [35,45,46].
alloys Moreover,
[35,45,46].
the SAED
Moreover, pattern
the SAED(Figure 16a)
pattern shows
(Figure reflections
16a) shows at {110} positions
reflections at {110}
Moreover, the SAED pattern (Figure 16a) shows reflections at {110}Al positions and sharp streaks
Al and sharp
Al positionsstreaks
and parallel
sharp to the
streaks
<001>
parallel
parallel direction:
to the <001> by
Al comparing
direction: by it with
comparing the SAED
it with pattern
the analyses
SAED patternof
Al to the <001>Al direction: by comparing it with the SAED pattern analyses of thermal treated thermal
analyses treated
of Al-Cu
thermal and
treated
Al-Si-Cu–based
Al-Cu and
Al-Cu alloys reported
and Al-Si-Cu–based
Al-Si-Cu–based alloys
alloys inreported
literaturein
reported in[47,48],
literature
literature it can be stated
[47,48],
[47,48], canthat
it can
it the experimental
be stated
be stated that the
that diffraction
the experimental
experimental
pattern supports
diffraction pattern that the
supportsplatelets
that theare consistent
platelets are with θ’ phase.
consistent
diffraction pattern supports that the platelets are consistent with θ’ phase. with θ’ phase.

Figure 16.
Figure 16. TEM
TEM micrographs
TEM micrographs
micrographs of of rheocast
of rheocast AlSi9Cu3(Fe)
rheocast AlSi9Cu3(Fe) alloy
AlSi9 Cu3 (Fe) alloy after
alloy after peak
after peak ageing
peak ageing treatment
ageing treatment at
treatment at 220
at 220 °C,
◦ C,
220 °C,
acquired
acquired (a) close to <100>
acquired (a) close to <100>
<100>AlAl direction and the corresponding SAED pattern (inset) and (b) after
Al direction
direction and
and the
the corresponding
corresponding SAED
SAED pattern
pattern (inset)
(inset) and
and (b)
(b) after
specimen tilting
specimen tilting to
to <110>
<110> Al direction.
<110>Al direction.
direction.
Al

The evolution
The evolution of
of the
the volume
volume fraction
fraction of
of precipitates
precipitates during
during ageing
ageing treatment
treatment can
can be
be generally
generally
estimated according to the Johnson-Mehl-Avrami-Kolmogorov (JMAK) relationship
estimated according to the Johnson-Mehl-Avrami-Kolmogorov (JMAK) relationship [49]: [49]:
Metals 2018, 8, 750 14 of 18

The evolution of the volume fraction of precipitates during ageing treatment can be generally
estimated according to the Johnson-Mehl-Avrami-Kolmogorov (JMAK) relationship [49]:

fV = fm (1 − exp(−ktn ) (2)

where fV is the precipitated volume fraction at a given aging time, t, fm is the maximum volume fraction,
k is the overall rate constant that depends on the nucleation and growth rates of the precipitates, and n
is a constant usually known as Avrami’s exponent.
The volume fraction of the different phases precipitated at the peak aged conditions and observed
during TEM investigations was estimated by isothermal phase transformation calculation using
JMatPro® commercial software (Version 7.0, Sente Software Ltd., Guildford, UK) [50], where no phase
competition was considered. The values of the precipitation kinetics used in the JMAK equation at the
ageing temperatures of 160, 180 and 220 ◦ C are listed in Table 3. The volume fractions of the β”, Q’
and θ’ phases at the different peak ageing conditions are shown in Figure 17a.

Table 3. Values of n, k and fm used to calculate the volume fraction of the precipitates by means of
Equation (2).

Ageing Temperature (◦ C) Phase n k fm (%)

β” 1.10 3.4 × 10−5 0.56
160
Q0 1.16 6.5 × 10−6 0.72
β” 1.09 8.1 × 10−5 0.55
180
Q0 1.12 1.7 × 10−5 0.79
θ0 1.79 9.8 × 10−7 1.93
220
Q0 1.09 8.1 × 10−5 0.79

Using Equation (2) and the mean dimensions of the particles measured on the TEM micrographs,
the average number density, NV , of the different types of precipitate per unit volume can be calculated
at the peak ageing conditions as follows

NV = fV /(w × l × t) (3)

where w, l and t are the average width, length and thickness of β”, Q’ and θ’ precipitates previously
described as needle-, lath- and plate-like particles. The calculated number density of precipitates is
shown in Figure 17b.
Figure 17 evidences how the greatest volume fraction as well as the highest number density of β”
and Q’ phases is obtained by ageing at 160 ◦ C for 24 h. On the other side, the highest volume fraction
of θ’ phase is attained after 2 h ageing at 220 ◦ C. However, increasing ageing temperature up to 220 ◦ C
leads to the coarsening phenomenon of precipitates as defined by Ostwald ripening theory in which
fine precipitates are incorporated into larger ones to reduce the surface energy per volume of system.
This can explain the reduced number density of θ’ phase at 220 ◦ C for 2 h (Figure 17b).
Increasing the number density of precipitates per unit volume leads to shortening the distance
between fine precipitates. Thus, the hardness of the material is increased accordingly as a function of
the different peak ageing condition, i.e., from 95 ± 2 HV (220 ◦ C for 2 h) up to 117 ± 3 HV (160 ◦ C
for 24 h). According to the Orowan mechanism, the increased strength of Al matrix can be estimated
through the following equation [51]

∆σOrowan = 0.84MGb/λ (4)

where M is the Taylor factor, G is the shear modulus, b is the Burgers vector and λ is the inter-particle
spacing. Then, the Orowan strength is inversely proportional to the inter-particle distance.
 Metals 2018, 8, 750 15 of 18

According to the Friedel mechanism, the mechanical properties can be also attributed to the ability
of the strengthening precipitates to withstand shearing by gliding dislocations [52].
In general, the precipitation hardening progressively increases with the coarsening of the
precipitates until they are shared by dislocations. With further increase of the size of precipitates,
the dislocations bypass the precipitates via the Orowan mechanism, i.e., by bowing. When the fraction
of precipitates
Metals 2018, 8, x FORpassed by shearing and bowing mechanisms is equal, the alloy reaches the
PEER REVIEW peak
15 of 18
hardness. Some works reported how β” precipitates are generally sheared by dislocations [53], while
theθ’θ’phase
the phaseisisconsidered
consideredaashear-resistant
shear-resistantphase,
phase,i.e.,
i.e.,by-pass
by-passbybydislocations
dislocations[54].
[54].OnOnthe
theother
otherside,
side,
the Q’ precipitates
the precipitatescan caninteract
interactwithwith
dislocation both by
dislocation shearing
both and bowing
by shearing and mechanisms, depending
bowing mechanisms,
on the particle
depending on thesize [53]. size [53].
particle
ItIt isis very
very difficult
difficult here
here to to reliably
reliably ascertain
ascertain thethe exact
exact interaction
interaction mechanism
mechanism between
betweenthe the
dislocationsand
dislocations andthe
theprecipitates
precipitatesatatthethedifferent
differentpeak
peakageing
ageingconditions.
conditions.AAtransition
transitionfromfromdislocation
dislocation
shearing to
shearing to dislocation
dislocation looping
loopingcouldcouldoccur
occurforfor
thethe
different phases
different (β”, Q’
phases and
(β’’, Q’θ’)
andandθ’)
forand
the different
for the
size andsize
different morphology of precipitates.
and morphology of precipitates.
However, the
However, the interaction
interaction between
between precipitates
precipitates and and dislocations,
dislocations, that
that isis the
the precipitation
precipitation
strengtheningofofthe
strengthening thealloy,
alloy,isisdetermined
determinedby byseveral
severalfactors
factorsincluding
includingbutbutnot
notlimited
limitedtotosize,
size,volume
volume
fraction,and
fraction, andnumber
numberdensity
densityofofprecipitates.
precipitates.The Thecrystal
crystalstructure
structureofofthe
theprecipitates,
precipitates,asaswellwellasasthe
the
coherency in the α-Al matrix, can significantly affect the dislocation/particle
coherency in the α-Al matrix, can significantly affect the dislocation/particle interaction mechanisms. interaction mechanisms.
ItItisisreported
reportedhow howβ’’ andθ’θ’phases
β”and phasesshowshowaacoherent
coherentinterface
interfacewith
withα-Al [55],while
α-Al[55], whileQ’ Q’phase
phasecan
canform
form
aacoherent
coherentor orsemi-coherent
semi-coherentinterface
interface[56].
[56].

(a) (b)
Figure
Figure17.
17.(a)
(a)Calculated
Calculatedvolume
volumefraction
fractionand
and(b)
(b)number
numberdensity
densityper
perunit
unitvolume
volumeofofthe
thephases
phases
observed
observedbybyTEM
TEMinvestigation
investigationatatthe
thedifferent
differentpeak
peakageing
ageingconditions.
conditions.

4.4.Conclusions
Conclusions

InInthis
thiswork,
work, the
the effects
effects of
of different
differentsolution
solutionand
andageing
ageingheat
heattreatments onon
treatments thethe
microstructure and
microstructure
hardness of secondary rheocast
and hardness of secondary rheocast AlSi Cu (Fe) alloy
9 AlSi9Cu3(Fe)
3 have been investigated. The following conclusions
alloy have been investigated. The following
can be drawn.
conclusions can be drawn.
•• Solution
Solutiontreatment
treatmentatat470 ◦ Cfor
470°C for66hhresults
resultsininbeing
beingaagood
goodcompromise
compromiseininterms
termsofofhardening
hardening
level
leveland
andsurface
surfacequality
qualityas
asnonoblisters
blistersappear
appearononthe
thecasting
castingsurface.
surface.
•• The
Thesolution
solutionheat
heattreatment
treatmentininthe
thetemperature
temperaturerange
rangebetween
between450450and
and490
490°C◦ Cleads
leadstotothe
the
fragmentation
fragmentationand andspheroidization
spheroidization of of
eutectic Si particles
eutectic andand
Si particles the dissolution of coarse
the dissolution Mg and
of coarse Mg
Cu-rich phases,
and Cu-rich which
phases, contributes
which to enhance
contributes the the
to enhance solute content
solute in in
content thethe
α-Al
α-Alsolid
solidsolution.
solution.
Moreover, fine polygonal and rod/platelet-shape Si particles appear within the α-Al matrix after
solution treatment.
• The best strengthening degree is achieved after artificial ageing at 160 °C for 24 h; however, by
increasing the ageing temperature, the age hardening peaks result for shorter times. On the other
hand, the hardness values progressively decrease.
• The co-existing of highest volume fraction and number density of fine needle-shaped β’’ and Q’
Metals 2018, 8, 750 16 of 18

Moreover, fine polygonal and rod/platelet-shape Si particles appear within the α-Al matrix after
solution treatment.
• The best strengthening degree is achieved after artificial ageing at 160 ◦ C for 24 h; however,
by increasing the ageing temperature, the age hardening peaks result for shorter times. On the
other hand, the hardness values progressively decrease.
• The co-existing of highest volume fraction and number density of fine needle-shaped β” and
Q’ (or L) precipitates is responsible for the maximum strengthening level of the rheocast and
heat treated AlSi9 Cu3 (Fe) alloy. Upon increasing the ageing temperature, fine precipitates
are incorporated into larger ones leading to a lower number density of strengthening phases;
this results in a reduction of the hardness.
• At higher ageing temperature, such as 220 ◦ C, the formation of large θ’ platelets explains the
incremental softening of the alloy with a decrease of about 19% respect to the artificial ageing at
160 ◦ C for 24 h.

Author Contributions: All the authors actively participated to the research: A.F. and S.C. worked on the
microstructural and mechanical characterization; G.T. followed the casting trials; A.D.M. carried out the DSC
investigation; A.F. and G.T. discussed the results; A.F. wrote the draft and G.T. revised and improved it.
Funding: This research was funded by Raffineria Metalli Capra Spa (Brescia, Italy).
Acknowledgments: The authors would like to acknowledge the skilful contribution of CIE Automotive S.A.
(Bilbao, Spain) for rheocasting experiments.
Conflicts of Interest: The authors declare no conflict of interest.

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