Structure and properties of cast AlSi based alloy with ZrVTi

additions and its evaluation of high temperature performance

Wojciech Kasprzak
a,
, Babak Shalchi Amirkhiz
a
, Marek Niewczas
b
a
CanmetMATERIALS, Natural Resources Canada, 183 Longwood South St., Hamilton, ON L8P 0A1, Canada
b
McMaster University, 1280 Main St. West, Hamilton, ON L8S 4L8, Canada
a r t i c l e i n f o
Article history:
Received 30 September 2013
Received in revised form 9 November 2013
Accepted 27 November 2013
Available online 7 December 2013
Keywords:
AlSiCuMg alloy
ZrVTi additions
Age hardening
Microstructure
High-temperature mechanical properties
Dilatometer analysis
a b s t r a c t
A hypoeutectic AlSi based alloy with Cu, Mg and additions of Zr, V and Ti, was evaluated to determine its
suitability for applications at higher temperatures. The as-cast alloy consists of a-Al matrix, AlSi eutectic
and Al
2
Cu, Al
5
Mg
9
Si
8
Cu
2
and Al
14
Mg
4
FeSi
6
/Al
5
FeSi, intermetallic phases, plus two distinct ZrVTi-based
phases. Solutionizing treatment leads to dissolution of Al
5
Mg
8
Si
6
Cu
2
and Al
2
Cu and the partial dissolution
of ZrVTi-based intermetallics. Integration of aging kinetics with mechanical properties data allowed to
establish different aging parameters leading to T6 peak-aging and T7 over-aging conditions correspond-
ing to hardness of 96 and 68 HRF respectively. T7 condition enabled higher hardness retention than T6
condition; the alloy softening was observed at 260 C versus 240 C after T6 treatment. TEM characteriza-
tion of the alloy in the T6 condition revealed GP zones, and rod-shaped trialuminide Al
3
(Zr, V, Ti) with
average size of 230 nm as well as S-phase (Al
2
CuMg) precipitates. After T6 treatment followed by isother-
mal annealing at 475 C, the alloy showed hardness retention improvement by approximately 30%. Sub-
sequent TEM analysis revealed a higher density of the Al
3
(Zr, V, Ti) rod-shaped precipitates along with
formation of new lath shaped Q
0
-phase AlSiCuMg precipitates. Two over-aging reactions between 250
350 C and 440460 C were associated with the stability of CuMg and Al-ZrVTi based nanoprecipi-
tates respectively. Temperature of 250 C was established as the transition temperature above which
degradation of mechanical properties was observed from UTS of approximately 311 MPa at room temper-
ature to 208 MPa at 250 C. The results indicate that additions of Zr, V and Ti improve yield strength and
cyclic yield strength at room temperature but lower ductility, while slightly improve elevated tempera-
ture hardness with almost no effect on tensile strength.
2014 Crown Copyright and Elsevier BV. All rights reserved.
1. Introduction
Growing concerns over vehicle emissions and the price of en-
ergy have stimulated the transportation industry to take renewed
interest in ways of improving fuel economy. One way of increasing
fuel efciency is to reduce the overall mass of the vehicle, by using
light weight alloys for structural and powertrain applications and
employing more efcient manufacturing technologies with short
heat treatment cycles. Such approaches can result in cast compo-
nents having higher strength allowing for consequent reduction
of the size of casting products.
The powertrain offers an area of the vehicle structure where
signicant improvements in energy utilization are achievable.
Modern engines require higher operating temperatures up to
250 C and pressures up to 180 bar to meet demands for a lower fuel
consumption and higher Greenhouse Gas emission standards. The
existing AlSi-Cu and AlSi-Mg alloy systems lose strength above
150 C and are not suitable in these applications but are still being
used due to the lack of standardized alternates capable
to substitute existing alloys. This in turn creates signicant
challenges in terms of the properties and performance of materials
used.
Analysis of various castings for powertrain engine applications
suggests strong benets of using 319 type alloy chemistry (Al
7%Si3%Cu0.1%Mg) with various non-standard modications of
these alloys carried out by individual producers [17]. Current
research is focused on the development of new alloys with
improved high temperature performance and the optimization of
existing alloys such as 319 and 356-based chemistries and corre-
sponding processing technologies [79]. Literature data indicates
that for automotive powertrain components operating at higher
temperatures, such as gasoline and diesel engine cylinder heads,
the following alloys have been used or are being considered for fu-
ture applications: (i) AlSiMg (A356, A357) characterized by good
ductility but lack of strength above 250 C, (ii) AlSiMgCu alloys
(319, A356 + 0.5%Cu) characterized by good ductility and strength
between 200 and 250 C, (iii) AlSiMgCu alloys with additions of
0925-8388/$ - see front matter 2014 Crown Copyright and Elsevier BV. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2013.11.209

Corresponding author. Tel.: +1 905 645 0697.

E-mail address: wkasprza@nrcan.gc.ca (W. Kasprzak).
Journal of Alloys and Compounds 595 (2014) 6779
Contents lists available at ScienceDirect
Journal of Alloys and Compounds
j our nal homepage: www. el sevi er . com/ l ocat e/ j al com
Mn, Zr, V, Ti and Cr (A319 + 0.15%Mn + 0.25%V + 0.15%Zr) charac-
terized by higher yield stress, lower ductility and improved creep
at 250 C [14]. Efforts are being made to substitute Ni by
combined addition of Zr and Co in AlSi-CuMg based alloy for im-
proved high temperature performance as well as cost reduction
[5]. Research is also being carried out on the AlZrTiFe alloy sys-
tem due to its potential for applications requiring age hardening
and precipitates stability up to 450 C [6]. Candidate alloys must
exhibit better mechanical strength and ductility, better fatigue
and creep as well as corrosion resistance properties particularly
if bio-fuels are to be used. If these properties can be delivered using
cost-effective measures, this would represent an attractive tech-
nology for the industry.
There is an interest in adding Zr, Ti as well as V into cast alloys
for the purpose of grain rening (Ti/Zr) as well as improvement of
high temperature performance via strengthening mechanism by
both primary and secondary phases. Some published data exists
but there is rather limited information on the detailed effect of
Zr, V and Ti on the AlSi cast alloy microstructure and mechanical
properties (room and elevated temperature) as well processing
parameters for casting and heat treatment processing routes
[2,3,10,11,1820,25,26].
A hypoeutectic AlSi alloy, with an increased Cu and Mg con-
centration of up to 1% and 0.5% respectively and additions of tran-
sition metals such as Zr, V and Ti has been studied from the
perspective of its potential usage in powertrain components that
require improved high temperature performance [4,8,10,11]. The
objective of this paper is to evaluate the microstructural and rele-
vant mechanical properties, as well as aging and softening charac-
teristics of cast AlSi-CuMg alloy with additions of Zr, V and Ti.
2. Experimental procedure
2.1. Alloy preparation and test bar casting
A hypoeutectic Al7%Si1%Cu0.5%Mg alloy containing additions of Zr, V and Ti
was used in the present studies [4,8,10,11]. For reference mechanical properties the
base alloy, without Zr and V and identical concentration of other alloying elements,
was used. The alloy was prepared in a 30 kg induction furnace by mixing commer-
cial master alloys, i.e., Al50%Cu, Al35%Si, Al6.1%Ti, Al85%V, Al10%Zr and Al
10%Sr and pure metals, Mg and Al. The alloy was melted at 760 C under a protec-
tive atmosphere. During addition of subsequent alloying elements the melt temper-
ature was increased to approximately 800850 C to ensure the proper dissolution
of alloying elements. Degassing was done using a graphite lance with a porous cake
lter for improved Ar gas dispersion in the melt. The alloy was cast from 740 C into
the ASTM B108 steel mold held at a temperature of 400 C and solidied with the
average cooling rate of approximately 20 C/s. Casting temperature was selected
at 740 C to prevent premature nucleation of Zr, V and Ti based primary phases
in the melt prior to the casting operation. The exact determination of liquids tem-
perature for this type of alloy creates difculties because thermal effect associated
with nucleation of Zr, V, Ti based primary phases is within the resolution limits of
thermal analysis equipment and cannot be accurately detected [13,19]. For the al-
loys casting temperature of 740 C the rst thermal event upon cooling was de-
tected at approximately 620 C. The 60 ppm addition of Sr was used for the AlSi
eutectic modication as well as dispersion of potential porosity that could develop
during test bars solidication process. The Secondary Dendrite Arm Spacing (SDAS)
in as-cast alloy was 27 3.6 lm and was measured using line intercept method
[12]. Table 1 gives the chemical composition of the modied alloy determined by
Optical Emission Spectroscopy (OES), together with concentrations of Zr and V ob-
tained using Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES)
methods. Base alloy without additions of Zr, V is included as well for the selective
comparative analysis. All alloy concentrations discussed throughout this work are
given in weight%.
2.2. Alloy heat treatment and process parameters
After casting, the AlSi-CuMg(Zr, V, Ti) alloy was subjected to various ther-
mal cycles to meet testing requirements including T4, T6 and T7 tempers. An air cir-
culating resistant furnace (Blue M, Park Thermal), with accuracy of 3 C on
isothermal heating cycles was used for alloy heat treatment. After solution treat-
ment the alloy was quenched to 65 C water with an average quenching rate of
approximately 30 C/s. The heat treatment parameters were optimized based on
the results from previous studies [12,22,27]. Specic details about alloy conditions,
processing parameters and testing are summarized in Table 2.
2.3. Microstructure analysis and phase identication
Metallographic observations of the modied alloy microstructure were carried
out using a light optical microscope under working magnication between 100
and 1000. Nova NanoSEM 650 (FETM) Scanning Electron Microscope (SEM) and
Tecnai OSIRIS Transmission Electron Microscope (TEM) equipped with ChemiSTEM
energy dispersive X-ray (EDX) spectroscopy were used to study the microstruc-
ture of the as-cast and heat treated samples (Table 2). Electron transparent
samples for TEM characterization were prepared by initially cutting 500 lm thick
slice of the sample using diamond wafering blade, followed by punching 3 mm
diameter disk with a Gatan puncher and followed by mechanical polishing of
the disk to the thickness of approximately 8090 lm. Dimpling was done using
46 lm CBN paste with a felt wheel and nished using alumina suspension down
to about 10 lm at samples center. The nal ion milling of the dimpled disk was
done using a Gatan 691 PIPS with liquid nitrogen cooling at 5, 3, and 1 keV and
gun angle of 4 for 130, 10 and 30 min average time at each step respectively,
until the perforation.
The EDX spot and elemental map analyses were performed at 15 kV and back-
ground corrections were applied to improve minor elements quantication accu-
racy. Quantication of each phase was based on analysis of at least four different
locations from which mean and standard deviation values were obtained.
2.4. Assessment of thermo-physical properties
The BHR DIL 805A/D quench dilatometer was used for aging kinetics analysis
during isochronal heating of a saturated solid solution from 25 to 500 C with a
heating rate of approximately 0.1 C/s. The continuous heating of a saturated solid
solution results in precipitation (increase of sample length) and dissolution (de-
crease of sample length) processes [8,1416]. Cylindrical test samples with a
dimension of OD = 5 mm and a gauge length of L = 10 mm were used in dilatometric
studies. The sample length change (dL, lm) and its derivatives curves (dL/dt, lm/s)
were calculated and plotted as a function of temperature. This represents an energy
Table 1
Chemical composition of the modied alloy obtained using Optical Emission Spectroscopy (OES) and Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES)
methods. Base alloy without additions of Zr and V was used for comparative analysis of the selected mechanical properties.
Analysis Alloying elements, (wt.%)
Al Si Cu Mg Fe Sr Ti Zr V
OES Base Alloy Balance 7.1 0.98 0.53 0.11 0.006 0.18
OES Modied alloy Balance 7.1 0.98 0.53 0.11 0.006 0.18 0.15 0.28
ICP-AES 0.118 0.119
Table 2
Summary of the investigated alloys processing conditions and testing.
Condition Processing parameters Testing applied
As-Cast Cast into STHAL B106 permanent mold HRB, MA
T4 ST at 500 C/1 h + 514 C/0.5 h + WQ DIL, HRB, ER, MA
T6 ST at 510 C/0.5 h + 525 C/4.5 h + WQ + AA
at 150 C/120 h
HRB, TT, DIL RAM,
ETT, MA
T7 ST at 510 C/0.5 h + 525 C/4.5 h + WQ + AA
at 250 C/16 h
HRB, TT, DIL RAM,
ETT, MA
T6 + IH T6 + Isothermal holding at 250, 400, 475 C
from 0.5 to 128 h
HRB, DIL, ETT, MA
DIL Dilatometer analysis, ER Electrical resistivity, HRB Hardness, TT Tensile
testing, RAM Ramping experiments, ETT Elevated temperature testing, MA
Microstructure analysis, ST Solution treatment, AA Articial aging, IH Iso-
thermal holding, WQ Water quench.
68 W. Kasprzak et al. / Journal of Alloys and Compounds 595 (2014) 6779
signature of aging transformation reactions occurring after various alloy testing
conditions. Three types of experiments were conducted for modied alloy: (i) Iso-
chronal heating experiments carried out on the solution treated and quenched test
samples to study phase transformation sequence upon re-heating. (ii) Isochronal
heating experiments carried out on the solution treated, quenched and articially
aged test samples at 250 C for time varying from 15 min to 128 h. (iii) Isochronal
heating experiments carried out on the test samples in the T6 and T7 conditions
as well as T6 conditions followed by annealing at 475 C for 128 h (Table 2). This
last testing was done to analyze the effect of aging parameters on the degree of
phase transformation.
To complement aging kinetics analysis performed using dilatometer technique,
studies of electrical resistivity (ER) were carried out on alloy samples with dimen-
sions of 2 2 60 mm. The electrical resistivity measurements were conducted
during continuous isochronal heating from 25 to 500 C for the test samples in
the as-cast as well as solution treated and quenched conditions (Table 2). A four-
point method of measuring a potential drop across the sample was used. The poten-
tial and the current leads were spot-welded to a sample and the measurements of
potential drops were performed continuously during heating by reversing the
known current owing through the circuit. The samples were heated with the rates
in the range 125 C/min in the Argon protective atmosphere. The temperature of a
sample was measured with an accuracy of 1 C by a K thermocouple attached to it.
The resistances of the samples were obtained from the measured potential drop and
known current. To avoid an experimental error in determination of absolute value
of resistivity arising from the shape factor, the ER data were normalized to the resis-
tance of the samples at room temperature. A detailed description of the technique is
given elsewhere [14].
2.5. Aging characteristics assessment
The modied alloys aging characteristics were evaluated by measuring hard-
ness of test samples in the solution-treated and quenched conditions. Experiments
were carried out for aging temperatures between 25 and 400 C and time periods
from 15 min to 128 h on disc-shape samples having OD = 20 mm and height of
20 mm, obtained from ASTM B108 mould feeder bars. The alloys over-aging tem-
perature during isochronal heating was established based on the Dilatometer and
Electrical Resistivity (ER) studies (Section 2.4) and was used to evaluate the alloys
suitability for high-temperature performance [4,8,14]. The over-aging temperature
can be linked to the casting critical-service temperature. When the latter is ex-
ceeded, the components mechanical properties rapidly deteriorate due to precipi-
tates coarsening, resulting in the loss of precipitate coherency with the metal
matrix. The alloys dimensional stability was evaluated by dilatometer analysis
using the samples relative length change as a function of temperature and by ana-
lyzing the energy signature of aging transformation remaining after various arti-
cial aging operations (Section 2.4).
2.6. Mechanical testing
Alloy hardness in the as-cast and T6/T7 heat-treated conditions was measured
using a Behler Rockwell Tester (B scale, 100 kg load and F scale, 60 kg load) (Ta-
ble 2), while Vickers (HV) hardness equivalents are included on selected charts if
applicable. For each test sample twenty measurements were done and the average
hardness and standard deviation were calculated and plotted. Hardness was se-
lected as an indicator of the heat treatments effectiveness and evaluation of the al-
loys high temperature performance. Additionally, the hardness measurements
were carried out for the test samples subjected to (i) the ramping test, i.e., incre-
mentally heated from 25 to 500 C with 50 C step and isothermally held at each
temperature for 15 min, (ii) isothermal holding at 250 C, 400 C, 475 C for a time
between 15 min and 128 h to evaluate alloy hardness degradation as a function of
long temperature exposure time.
Tensile testing for samples taken from base and modied alloys in the T6 heat
treated condition (Table 2) was carried out between 25 and 450 C using a special-
ized attachment in the BHR DIL 805A/D quench dilatometer. Test samples were
heated to a given testing temperature with 1 C/s heating rate and held isother-
mally for 15 min to stabilize the temperature, followed by tensile testing with a
constant strain rate of 1.3 10
3
s
1
. Experimental data for stress and strain were
acquired with a 5 Hz acquisition rate. The data for Ultimate Tensile Stress (UTS) and
corresponding strain at failure are presented as a function of testing temperature.
3. Results
3.1. Characterization of the as-cast microstructure
The modied alloys as-cast microstructure after rapid solidi-
cation in the steel mould had an average SDAS of 27 3.6 lm.
The microstructure consisted of a-Al dendrites, partially unmodi-
ed AlSi eutectic and at least six distinct intermetallic phases that
were located within interdendritic regions (Fig. 1a and b). More
detailed analysis of intermetallic constituents was obtained with
a scanning electron microscope combined with X-ray microanaly-
sis. These results are shown on Fig. 1c and d while the stoichiom-
etric compositions of specic intermetallic constituents and their
referenced equivalents obtained from published data are given in
the table in Fig. 1e. Additions of approximately 1%Cu and 0.5%Mg
to the alloy containing Si, Fe, Mn (Table 1) resulted in the forma-
tion of intermetallic phases with the following stoichiometric
compositions: Cu
15
Al
43
Si, Al
5
Mg
9
Si
8
Cu
2
and Al
14
FeMg
4
Si
6
.
The analysis of the microstructure reveals that Cu
15
Al
43
Si phase
(referred as Al
2
Cu phase in the literature) is typically present in
two different morphologies, i.e., blocky, and eutectic, as shown in
Fig. 1, phase #3. Relative proportion of each phase morphology
depends on several factors including cooling rate, level of modica-
tion and Cu and Mg content. Inspected under an optical micro-
scope, Cu
15
Al
43
Si phase appears in distinct pink colour, as shown
in Fig. 1a and b (phase #3).
The Mg
2
Si phase present in the alloy is typically seen as small
dark spots on the black-and-white metallographic image, while
Al
14
FeMg
4
Si
6
appears in characteristic Chinese script, visible in
Fig. 1b as phase #5a. In addition, Al
5
FeSi phase was found in the
as-cast microstructure appearing in plate-like morphology
[17,21,2833], as seen in Fig. 1b (phase #5b).
Additions of Zr, V and Ti up to 0.118%, 0.019% and 0.18% respec-
tively resulted in the formation of Al
3
Si
26
TiV
10
Fe and Al
13
Si
2
Ti
3
Zr
phases. These phases have distinct morphologies. Al
13
Si
2
Ti
3
Zr
forms in regular blocky shape in light dark grey color, up to
30 lm in length (Fig. 1b phase #6), whereas Al
3
Si
26
TiV
10
Fe phase
grows in regular, hexagonal shape in dark grey color, up to
20 lm length, clearly visible under optical microscope in Fig. 1b
(phase #7). These phases were often observed in the form of
agglomerates adjacent to each other (Fig. 1b, #6 and #7), indicat-
ing that they could nucleate simultaneously during solidication
process. The Zr content in the investigated alloy was below peritec-
tic concentration of 0.15% (Table 1), therefore the pre-peritectic
primary Al
3
M (M = Zr or V, Ti) phase was most likely not formed
as a stand-alone structure. Similar observations were reported by
Knipling and co-workers for AlZr and AlZrTi alloys containing
0.2%Ti and Zr additions of 0.1% and 0.2% respectively [34,35].
3.2. Characterization of heat-treated microstructure
Fig. 2 shows the metallographic data combined with the SEM/
EDX analysis of the modied alloy samples in the T6 condition.
The analysis conrmed the presence of the primary macro-size
intermetallic phases AlSiCuFe, Al
9
Mg
12
Si
6
Fe, Al
27
SiTiZr
9
and
AlSiTiVFe that resulted from addition of the transition metals (pre-
cipitates #3, #4, #5, #6 in Fig. 2) as well as a-Al dendrites and AlSi
eutectic (#1 and #2 phases in Fig. 2). Thermal modication of the
AlSi eutectic as a result of a two-step solution treatment was
clearly visible. Silicon morphology in eutectic structure was chan-
ged from unmodied (characteristic to as-cast condition) via its
transitional change to modied, achieved due to fragmentation,
spheroidization followed by subsequent coarsening of the Si
particles for longer solution treatment times and higher solution
temperatures [10,23]. Addition of the 60 ppm of Sr results in accel-
eration of eutectic Si thermal modication leading to a shorter
solutionizing time required to achieve specic morphological
changes [14]. Analysis of the microstructure in as-cast and heat-
treated alloy revealed that the two-step solution treatment
affected the average Aspect Ratio (AR) of the AlSi eutectic chang-
ing it from 1.85 0.01 in as-cast condition to 1.65 0.13 in heat-
treated alloy. It appears also that Cu
15
Al
43
Si and Al
5
Mg
9
Si
8
Cu
2
phases dissolve during solution treatment, while Fe-rich and
ZrVTi-rich phases remain in the microstructure after partial
dissolution (Fig. 2).
W. Kasprzak et al. / Journal of Alloys and Compounds 595 (2014) 6779 69
The TEM characterization combined with EDX and diffraction
analysis conrmed the presence of rod-shaped secondary precipi-
tates in the T6 heat condition as a major phase inuencing the al-
loy strength, along with the primary GP zone as shown in Fig. 3a.
Electron diffraction analysis and high resolution imaging revealed
secondary precipitates containing ZrVTi. They were identied
as Al
3
(ZrVTi) trialuminides with tetragonal D0
23
type structure.
It should be noted that these precipitates were also found in smal-
ler sizes (below 50 nm) which are assumed to be of L1
2
type struc-
ture. The EDX spot analysis showed varying amount of Zr, V and Ti.
Fig. 3b shows Selected Area Diffraction (SAD) pattern close to
[011] zone axis of the Al matrix. Fig. 3c shows High Resolution
TEM (HRTEM) observations with indexed FFT patterns taken from
a region inside the precipitate and a region in the base metal. It ap-
pears that the precipitates are oriented with their [114] towards
[111] of the Al matrix. HRTEM shows that these precipitates are
semi-coherent. It is speculated that presence of Si and Cu particu-
lates attached to these precipitates could help to retain the
coherency with the matrix. The average size of the rod-shaped pre-
cipitates was 230 nm with an aspect ratio over 10. The Z contrast
high angle annular dark eld image (HAADF) shown in Fig. 3d
along with corresponding elemental maps reveals two types of sec-
ondary precipitates in T6 condition. The ubiquitous phase was the
rod-shaped Al
3
(Zr, V, Ti). Also visible in these micrographs are
precipitates of a phase containing Mg and Cu, believed to be the
plate-like S-Al
2
CuMg ternary phase precipitation typically
observed in AlSiCuMg cast alloys [23,24]. The EDX mapping
at higher magnications throughout the structure in T6 condition
reveal V, Mg or Zr rich regions in the base metal close to the pre-
cipitates. Other intermetallic particles were also identied in insig-
nicant amounts but are not discussed here.
The EDX analysis of the microstructure of the sample in T6 con-
ditions followed by isothermal holding at 475 C for 128 h is shown
in Fig. 3e. The ubiquitous phase was the Al
3
(Zr, V, Ti) trialuminides
in the rod-shaped form as observed previously in T6 condition. The
average size of these precipitates were 250 nm with an aspect ratio
higher than 10. The second major type of precipitates was lath-
shaped Q
0
-phase with average size of 310 nm and an aspect ratio
below 5 with variable compositions (e.g. Al
5
Cu
2
Mg
8
Si
6
) as reported
in [24]. It is unclear if this phase has formed during prolonged
holding at 475 C or as a result of subsequent cooling after comple-
tion of heat treatment. The rod-shaped trialuminides formed under
two conditions can be best compared by inspecting the representa-
tive Ti maps in Fig. 3d and e respectively. Similarly, as observed in
the T6 condition other phases were also identied in T6 + isother-
mal holding at 475 C for 128 h condition but were in insignicant
amounts. It is interesting to note that subsequent alloy holding at
475 C for 128 h after T6 treatment did not cause any dissolution of
the ZrVTi containing precipitates but clearly resulted in their
higher density. The EDX quantication of the rod-shaped trialumi-
nides showed variable composition sometimes with presence of Si,
Cu, or Mg in their structure (e.g. (Al, Si)
3
(Zr, V, Ti)). These elements
Alloy Condition: As-Cast
No. Phases Present Dimensions, m Morphology Description
Reference from Published
Data
1 -Al matrix
-
- c i t i r d n e D
2
Al-Si eutectic
50
Plate like, unmodified Al-Si eutectic
3
Cu15Al43Si
20
Eutectic and blocky Al2Cu
4 Al5Mg9Si8Cu2
20
Blocky phase Q-Al5Mg8Si6Cu2
5a Al14FeMg4Si6
50
Chinese script -Al8FeMg3Si6
5b
Al5FeSi
25
Plate like Al5FeSi
6
Al13Si2Ti3Zr
30
- A N - y k c o l B
7
Al3Si26TiV10Fe
20
Hexagonal -NA-
(e)
(b)
#3
#4
#5a
#6
#5b
#7
#1
#2
(a)
#2
#3
(c) (d)
#3
#2
#3
#5a
#5b
#4
#3
#6
#7
#2
#1

Fig. 1. Microstructural observations of the modied alloy in the as-cast condition: (a and b) Optical microscopy observations under various magnications. (c and d) SEM/BSE
images with EDS quantitative results included in the table (e). (e) Summary table for different phases in the modied alloy structure. Note: Reference stoichiometric
compositions are presented where applicable.
70 W. Kasprzak et al. / Journal of Alloys and Compounds 595 (2014) 6779
were visible in T6 conditions in the form of nanoparticulates or
concentrated regions in the base metal surrounding the nano-rods.
It is not clear if these elements occupy substitutional or interstitial
sites in the structure of the trialuminides.
3.3. Aging assessment by dilatometer analysis and hardness
measurements
Fig. 4a shows a derivative of the dilatometer curve calculated
for re-heating cycle to 500 C obtained for modied alloy. Dilatom-
eter analysis reveals the presence of two aging reactions. One reac-
tion, marked #1 in Fig. 4a, is observed between 250 and 350 C
with a maximum at 300 C. The second reaction, marked #2, occurs
between 440 and 460 C with maximum at 450 C. The peak over-
aging temperature interval was conrmed by ER measurements
during the continuous heating of saturated solid solution samples
(Fig. 4b) for identical temperature vs. time prole.
The aging transformation temperature range (250350 C),
determined based on the dilatometer analysis, corresponded well
with aging curves established based on hardness measurements
carried out for various aging temperatures between 100 and
400 C and aging times between 15 min and 128 h. Fig. 5 shows
aging characteristics where alloy hardness is plotted as a function
of aging temperature and time. It was observed that the peak hard-
ness values decreased from approximately 68 to 52 HRB once the
aging temperature approached 250 C and decreased below the
as-cast value of 36 HRB when the aging temperature reached
300 C (Fig. 5). It was observed that increasing the aging tempera-
ture resulted in a shorter aging time required to reach maximum
alloy hardness. This phenomenon was accompanied by lower alloy
hardness for higher aging temperatures. For example, alloy aging at
150 C resulted in a hardness of 68 HRB after 150 h, while aging at
250 C yielded a hardness of 53 HRB after 16 h.
3.4. Dimensional stability
Fig. 6a and b shows the aging transformations kinetics for the
modied alloy in the solution-treated and quenched condition fol-
lowed by aging at 250 C for a time duration between 15 min and
128 h. Fig. 6a shows length change vs. temperature curves whereas
Fig. 6b presents analysis of the derivatives of the length change vs.
temperature curves. All investigated samples after completion of
these heat-treatment cycles were re-heated to 500 C. The highest
peak on Fig. 6b corresponds to the sample which has been solu-
tion-treated, quenched and aged at 250 C for 15 min. It can be
seen that the peak height diminishes with increasing the aging
time at 250 C. A test sample that spent more than 8 h at 250 C
did not show any remaining aging transformation and in practice
it should experience minimum dimensional change if re-heated
after completion of the heat-treatment cycle.
3.5. Mechanical properties
Hardness measurements for the modied alloy in the T6 and T7
conditions annealed between 25 and 500 C are presented on
Fig. 7. The hardness remains unchanged up to approximately
Alloy Condition: T6
Spectrum No.
Phases Present
(EDS)
Phases
Dissolved
Dimensions,
m
Morphology
Description
Reference from
Published Data
#1 -Al matrix - - Dendritic -
#2 Al-Si eutectic No 20 Plate like, Modified Al-Si eutectic
#3 AlSiCuFe Partially 5 Fine eutectic Al2Cu
#4 Al9Mg12Si6Fe Partially 15 Fine blocky - Al8FeMg3Si6
#5 Al27SiTiZr9 Partially 15 Needle like -
#6 AlSiTiVFe Partially 5 Hexagonal -NA-
(a)
#4
#2
(b)
#3
#3
#5
#2
#5
(c)
(d)
#3,4
#1
#2
#4
#5
#6
#5
#5
#7
#3, 4
#3
#3
#6
#3
#5
(e)
#1

Fig. 2. Microstructural observations of the modied alloy in the T6 heat treated condition: (a and b) Optical microscopy observations under various magnications. (c and d)
SEM/BSE images under various magnications with EDS analysis of different phases depicted by the arrows. (e) Summary table for different phases in the modied alloy
structure. Note: Reference stoichiometric compositions are presented where applicable.
W. Kasprzak et al. / Journal of Alloys and Compounds 595 (2014) 6779 71
250 C followed by a transitional drop beyond 250 C from approx-
imately 94 to 55 HRF for T6 treatment and approximately from 70
to 55 HRF for T7 condition (Fig. 7). Above 450 C the hardness in-
creased from approximately 55 to 65 HRF for T6 and T7 samples.
The dilatometer isochronal aging curves (dL/dt vs. T) are superim-
posed to show their correlation with the alloys softening (anneal-
ing) characteristics. It is seen that for the T6 conditions, the over
aging peak at 300 C on dL/dt curve corresponds to the rapid
hardness decrease. On the other hand, the hardness decrease ob-
served at about 250 C for T7 samples is associated with no signif-
icant effect from phase transformation, apart from the gradual
increase of dL/dt curve arising from the thermal expansion.
Fig. 8 shows the effect of temperature on the evolution of Ulti-
mate Tensile Stress (Fig. 8a) and corresponding strain at break
(Fig. 8b) for the modied alloy in the T6 heat treated condition.
The UTS decreased from approximately 311 MPa at room temper-
ature to approximately 205 MPa at 250 C followed by a further
decrease to 30 MPa at 450 C.
The dilatometer isochronal aging curve (dL/dt vs. T) and total
strain at a break curve are superimposed to show their correlation
with the alloys strength. It was found that a signicant drop in
strength occurs when the testing temperature reaches the 250
300 C interval, accompanied by an increase in strain at break
above 250 C, as shown in Fig. 8b. The range of the temperatures
Fig. 3. TEM observations of the secondary precipitates in T6 condition (modied alloy). (a) Bright eld TEM image and selected area diffraction pattern (SAD) taken from
[111] zone axis (inset). The GP Zones oriented parallel to the beam appear as dots while the ones oriented towards [020] appear as streaks. (b) Bright eld image of an Al
3
(Zr,
V, Ti) precipitate and the corresponding SAD pattern (inset), the direction of the precipitate is parallel to [111] of the Al matrix. (c) High resolution image of a precipitate in
[011] zone axis orientation of the Al matrix, along with an FFT pattern taken from a highlighted area in the Al
3
(Zr, V, Ti) precipitate. (d) Z-contrast high angle annular dark
eld image (HAADF) of the secondary precipitate structure in T6 condition along with elemental maps showing the two types of Al
2
CuMg (S-phase) secondary precipitates
and nano-rods of Al
3
(Zr, V, Ti), covered by Si and Cu nano-particles. TEM micrographs showing secondary precipitates in T6 + holding at 475 C for 128 h condition. (e) HAADF
image of the precipitate structure in T6 + holding at 475 C for 128 h condition showing along with EDX elemental maps two types of precipitates: lath shaped AlSiCuMg (Q
0
-
phase) and nano-rods of Al
3
(Zr, V, Ti).
72 W. Kasprzak et al. / Journal of Alloys and Compounds 595 (2014) 6779
between 250 and 300 C corresponds to the over-aging peak (start-
ing at 250 C and reaching its maximum at 300 C) associated with
the precipitate coarsening and their subsequent dissolution.
Isothermal annealing experiments of the modied alloy in the
T6 condition, carried out at 250 C, 400 C and 475 C for different
annealing times between 15 min and 128 h are shown in Fig. 9. The
results reveal that the largest hardness drop, from approximately
95 to 55 HRF, exhibits sample isothermally held at 250 C for about
0
20
40
60
80
100
120
0.035
0.04
0.045
0.05
0.055
Length change, dL
Derivative, dL/dt
Temperature, T /
o
C
(a)
L
e
n
g
t
h

c
h
a
n
g
e

r
a
t
e
,

d
L
/
d
t

/

m
/
s
L
e
n
g
t
h

c
h
a
n
g
e
,

d
L

/

m

(b)
R
e
s
i
s
t
a
n
c
e
,

Temperature, T /
o
C
R
e
s
i
s
t
i
v
i
t
y

c
h
a
n
g
e

r
a
t
e
,

d
R
/
d
T

1
0
-
6
,

/

o
C
#1
#2
0.0008
0.0010
0.0012
0.0014
0.0016
0.0018
100 150 200 250 300 350 400 450 500
100 150 200 250 300 350 400 450 500
1
1.24
1.48
1.72
1.96
2.2
2.44
2.68
Resistance, R
Derivative, dR/dT
#1
#2
Fig. 4. Dilatometer (a) and Electrical Resistivity measurements (b) carried out
during continuous heating (isochronal) of the modied alloy in the saturated
condition, used in aging kinetic analysis. (a) Length change rate (dL/dt) during re-
heating cycle to 500 C. (b) Resistivity change rate (dR/dT) during re-heating cycle
to 500 C. Note the over-aging peak interval between 250 and 350 C (#1) as well as
440 to 460 C (#2) conrmed by dilatometer (a) and electrical resistivity (b)
measurements.
Log Time, hrs
R
o
c
k
e
w
l
l

B

h
a
r
d
n
e
s
s
,

H
R
B

/

k
g
f

V
i
c
k
e
r
s

h
a
r
d
n
e
s
s
,

H
V

/

k
g
f

Fig. 5. The effect of articial aging temperature between 100 and 400 C and time
between 15 min and 128 h on modied alloy hardness. Prior to aging treatment the
alloy was solution-treated and water-quenched. The T6 (peak aging) and T7 (over-
aging) conditions are dened as AA at 150 C for 100 h and AA at 250 C for 16 h
respectively. Note that as-cast (AC) and as quenched (AQ) hardness were 35 and 25
HRB respectively.
Temperature, T /
o
C
L
e
n
g
t
h

c
h
a
n
g
e
,

d
L

/

m

L
e
n
g
t
h

c
h
a
n
g
e
,

d
L

/

m

(a)
Temperature, T/
o
C
(b)
0.03
0.034
0.038
0.042
0.046
0.05
0.054
0.058
As-quenched
15 mins
2 hours
8 hours
16 hours
128 hours
6.5 30 108 81 54 135
0
20
40
60
80
100
120
140
50 100 150 200 250 300 350 400 450 500
50 100 150 200 250 300 350 400 450 500
As-quenched
15 mins
2 hours
8 hours
16 hours
128 hours
Fig. 6. The kinetics of the modied alloy aging transformation during isochronal
heating from 50 to 500 C in the following conditions: solution-treated, quenched
and aged at 250 C within times that varied between 15 min and 128 h. (a)
Temperature vs. length change curve. (b) Temperature vs. length change derivative
curve. Note that the highest peak in (b) corresponds to the alloy in the solution
treated and quenched condition as well as after aging at 250 C for 15 min. Its
height diminishes with increasing aging time to 16 h, where no further transfor-
mation occurs.
40
50
60
70
80
90
100
0 50 100 150 200 250 300 350 400 450 500 550
0.03
0.034
0.038
0.042
0.046
0.05
0.054
0.058
T6 (HRF)
T7 (HRF)
T6 (dL/dt)
T7 (dL/dt)
Temperature, T /
o
C
R
o
c
k
w
e
l
l

F

h
a
r
d
n
e
s
s
,

H
R
F

/

k
g
f
L
e
n
g
t
h

c
h
a
n
g
e

r
a
t
e
,

d
L
/
d
t

/

m
/
s
Fig. 7. Determination of the softening characteristics between a temperature range
of 25500 C for the modied alloy in the T6 and T7 conditions. The dilatometer
isochronal aging curve (dL/dt) is superimposed to show its correlation with the
alloys hardness characteristics. The beginning of the over-aging peak at 230 C
corresponds to the rapid hardness decrease for T6 condition, while T7 shows
softening starting at 250 C with no visible transformation as detected on the
dilatometer curve.
W. Kasprzak et al. / Journal of Alloys and Compounds 595 (2014) 6779 73
100 h. Samples annealed at 400 C and 475 C showed initial drop
in hardness from approximately 95 HRF to 65 and 80 HRF respec-
tively, followed by their steady state hardness value during subse-
quent annealing. Sample annealing at 475 C caused approximately
30% hardness increase, indicating that some precipitation process
takes place in the microstructure.
Isochronal heating curves between 25 and 500 C of the modi-
ed T6 test samples subjected to the isothermal annealing at 250
and 475 C are presented in Fig. 10. Dilatometer curves of the sam-
ple in T6 condition annealed for 128 h show a visible transforma-
tion occurring during the analyzed temperature interval. The
shape of the curve is similar to the modied alloys curve in the
T7 over-aged condition (Fig. 7). The T6 modied sample subjected
to the isothermal annealing at 475 C for 128 h showed a distinct
transformation between 300 and 425 C with peak at 350 C. The
peak maximum is shifted up by approximately 100 C with respect
to the test sample in the T6 condition. For comparison, the isochro-
nal aging curve for the modied alloy in the T6 condition showing
peak centered at 300 C is included in Fig. 10.
4. Discussion
4.1. Characterization of the as-cast microstructure
The published data on cast AlSi alloys with the addition of
transition metals is rather limited and relates predominantly to
wrought aluminum alloys with the addition of Zr, Ti, and Sc. Con-
sequently, it cannot be used as a direct reference for the present
work. The A319 foundry alloy has been analyzed by Mahmudi
and co-workers [25,26] where the inuence of 0.15 wt.% Zr addi-
tions on the aging behaviour and mechanical properties of the alloy
such as hardness, tensile strength and wear resistance was re-
ported, but no specic information on microstructural develop-
ment was provided. Similar is true in the case of studies
conducted by Garat and Laslaz [3] on the AlSi-CuMg alloy con-
taining additions of Zr and V, where the focus was on mechanical
properties and strengthening processes without corresponding
microstructural analysis.
Present results reveal that AlSi-CuMg modied alloy contain-
ing Zr, V and Ti exhibit a complex microstructure in the as-cast
conditions, as depicted on Fig. 1. Except intermetallic phases con-
taining Zr, V and Ti, the alloy has a similar microstructure as ob-
served in reference AlSiCuMg based alloys. The stoichiometric
compositions derived here for Cu, Mg, Fe based intermetallic
phases agree with data reported for similar alloy type, C355.2 alloy,
without addition of transition metals by Backerd [21] and other
authors [17,22,23,2833]. The results suggest that the phase iden-
tied as Cu
15
Al
43
Si (Fig. 1) is most likely related to Al
2
Cu phase re-
ported in the literature, Al
5
Mg
9
Si
8
Cu
2
to Q-Al
5
Mg
8
Si
6
Cu
2
phase,
whereas Al
14
FeMg
4
Si
6
phase is most likely derived from one of
the Fe-rich, possibly p-Al
8
FeMg
3
Si
6
phase that are typically formed
in similar AlSiMg cast alloys systems containing 13.5%Cu
[612]. Due to the limitations in SEM/EDX quantitative analysis,
the presented stoichiometric compositions are considered as
approximate, particularly when carried out on phases smaller than
10 lm in size. Other techniques like XRD analysis combined
with extraction techniques should be used for more in-depth
assessment.
Literature data suggest that trialuminides, typically referred to
as Al
3
M in Al-alloys with additions of Sc, Ti, V and Zr, can be formed
in two different stable structures, as Al
3
M/(D0
23
) phases rich with
Zr, and as AlM/(L1
2
) phase containing Ti and V. The ZrVTi-rich
intermetallic phases found in the as-cast microstructure, rst the
Al
3
Si
26
TiV
10
Fe phase rich with Ti, V and Fe and the second the Al
13-
Si
2
Ti
3
Zr phase containing Ti and Zr shown in Fig. 1, are compatible
with above classication of Al
3
M trialuminides. The Zr content in
the investigated alloy was below peritectic concentration of
0.15% (Table 1), therefore the pre-peritectic primary Al
3
M (M = Zr
or V, Ti) phase was not formed as a stand-alone structure. Similar
observations were reported by Knipling and co-workers for AlZr
and AlZrTi alloys containing 0.2%Ti and Zr additions of 0.1%
and 0.2% respectively [34,35].
T
e
n
s
i
l
e

s
t
r
e
s
s
,

/

M
P
a
Temperature, T /
o
C
(a)
(b)
0
50
100
150
200
250
300
350
Temperature, T /
o
C
L
e
n
g
t
h

c
h
a
n
g
e

r
a
t
e
,

d
L
/
d
t

/

m
/
s
T
o
t
a
l

s
t
r
a
i
n

a
t

b
r
e
a
k
,

/

m
m
/
m
m

0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0 50 100 150 200 250 300 350 400 450 500
0 50 100 150 200 250 300 350 400 450 500 550
0.03
0.034
0.038
0.042
0.046
0.05
0.054
0.058
Strain
DIL (dL/dt)
Fig. 8. Modied alloy strength development between 25 and 450 C. (a) The effect
of testing temperature on UTS for the modied alloy in the T6 condition. (b) The
dilatometer isochronal aging curve (dL/dt) is superimposed onto total strain at the
break to show its correlation with the alloys high-temperature performance. The
beginning of the over-aging peak at approximately 250 C corresponds to the rapid
increase in strain and drop in alloys tensile strength.
R
o
c
k
w
e
l
l

F

h
a
r
d
n
e
s
s
,

H
R
F

/

k
g
f
Time, t / hrs
40
50
60
70
80
90
100
0.1 1 10 100 1000
T6+250C holding
T6+400C holding
T6+475C holding
Fig. 9. The effect of annealing time at 250, 400 and 475 C on hardness develop-
ment for the modied alloy in the T6 condition. Note that isothermal annealing at
475 C resulted in improved hardness retention compared to annealing at 250 C
and 400 C, indicating possible alloy age hardening capacity at this temperature.
74 W. Kasprzak et al. / Journal of Alloys and Compounds 595 (2014) 6779
Microstructural analysis of cast AlSi-CuMg alloys with Zr, V
and Ti have not been reported in the literature making difcult
any comparisons with the present results [2,3,20,25,26,34,35].
4.2. Characterization of heat-treated microstructure
Microstructural observations identied two distinct Fe-rich
phases containing Cu or Mg i.e., Al
9
Mg
12
Si
6
Fe and AlSiCuFe phases.
The former phase due to its relatively small size (5 lm) was dif-
cult to evaluate by quantitative EDX analysis and the exact stoi-
chiometric formulas of the phase are not provided. Both phases
had similar morphology, but Cu-rich phases showed enhanced
contrast on SEM/BSE image (Fig. 2, #3 and #4). Both types of Zr
VTi intermetallic phases, needle shape Al
27
SiTiZr
9
phase (Fig. 2,
#5) and hexagonal shape AlSiTiVFe phase (Fig. 2, #6) remain in
the microstructure after heat treatment. It was noticed that the
volume fraction of these phases in the heat-treated alloy decreased
by approximately 50% accompanied by their size reduction as com-
pared to the as-cast alloy. Partial dissolution of these intermetallics
indicates that some concentrations of Zr, V were available for sec-
ondary precipitation process. In general, the presence of Al
27
SiTiZr
9
and AlSiTiVFe precipitates indicates that for the permanent mold
casting process, as used in the present study, the combined addi-
tion of Zr, V, Ti results in primary precipitation of the pro-peritectic
trialuminides. Consequently, the formation of these precipitates
could decrease the amount of solute retained in the solid solution
and its subsequent concentration in metal matrix would depend on
solutionizing parameters. In addition, the presence of trialuminide
phases could negatively affect the alloys ductility since they only
partially dissolve during solution treatment.
X-ray microanalysis of metal matrix in the as-cast modied
alloy and in the alloy after T6 solution treatment is presented on
Table 3. The data reveal that after T6 conditions the concentrations
of Mg and Cu increased from 0.73 to 1.04 and 0.16 to 0.47, concen-
trations of Zr and Ti decreased from 0.05 to 0.03 and 0.17 to 0.14,
whereas the concentration of V was on the similar level 0.13% after
the heat treatment process. This indicates that indeed the dissolu-
tion of CuMg based phases occurs during T6 treatment and the
X-ray microanalysis is in good agreement with metallographic
observations showing evidence for dissolution of CuMg based
phases in T6 samples. A similar trend is true in case of Al
3
Si
26
TiV
10-
Fe phases. The phases were less frequently observed in the T6 con-
dition, in contrast to needle-like Al
13
Si
2
Ti
3
Zr phases, which were
commonly observed in the samples after T6 condition. It is worth
to note that theoretical solid solubility limit of Zr, V and Ti in Al al-
loys at RT is less than 0.01 at% for all three elements. This might
possibly explain the lower content of Zr in the metal matrix since
this alloying element was used during the formation of Al
13
Si
2
Ti
3
Zr
based primary phases.
TEM observations suggest that the rod shaped secondary pre-
cipitates containing Zr, V and Ti identied in T6 condition contrib-
ute to the strength retention at elevated temperatures. These
phases are more thermally stable than Cu and Mg-based precipi-
tates [24]. The Cu and Mg additions are typically used in existing
alloys to induce alloy strengthening via precipitation of the Al
2
Cu
or Mg
2
Si nanosize phases in the aluminum matrix. The application
of these elements in heat resistant alloys is limited up to a temper-
ature range 150200 C because of the particles coarsening and
dissolution, taking place above 150 C [24,3638]. Introduction of
alloying elements forming more thermally stable precipitates, such
as Zr, V and Ti with low diffusivity and solubility in Al is driven by
requirements for improved strength retention at temperatures up
to 350 C [34,35]. These transition elements precipitate in the form
of Al
3
M (M = Zr or Zr, Ti, V) trialuminide phases of cubic L1
2
(coher-
ent phase), structurally and chemically analogous to Ni
3
Al (c
0
)
phase in Ni-based super alloys. By substituting V and/or Ti for Zr
one promotes nucleation of Al
3
(Zr,Ti,V)/(L1
2
) precipitates which
exhibit reduced coarsening compared to the binary Al
3
Zr phase,
as well as a smaller lattice parameter mismatch between Al
3
Zr
and a-Al matrix. This in return, results in improved precipitates
stability and consequently better ability to retain their coherency
with the metal matrix at elevated temperatures [34,35]. However,
due to their limited number of slip systems, higher stacking fault
energies and lower cleavage strength, these precipitates are brittle
in nature [39,40]. They also tend to stabilize into more brittle
tetragonal, semi-coherent to incoherent phase structures D0
22
/
D0
23
[4143]. The present results reveal that majority of Al
3
M pre-
cipitates have D0
23
structure with small amount of L1
2
precipitates
observed only in T6 conditions. Consequently, the strengthening
effect by trialuminides precipitation could come at the expense
of ductility, which in turn would limit the practical applications
of the alloys. Some of these effects were observed in the previous
studies where it was demonstrated that additions of Zr, V and Ti
(Table 4) decreased ductility and hardening capacity, while they
had positive impact on YS and LCF properties [11]. Therefore the
heat treatment must be designed to promote fast precipitation of
thermally stable phases that lead to improved ductility without
the potentially negative effect of trialuminides precipitates on
mechanical properties [8].
Results presented in Sections 3.3 and 3.5 indicate that second-
ary ZrVTi-rich particles could precipitate during the solutioniz-
ing process in the T6 temper and after subsequent prolong
isothermal holding at 475 C that is evident from the increased
density of Al
3
(Zr, V, Ti) precipitates in the microstructure. For
wrought alloys cast using the direct chill casting process (DC), Zr
based precipitates are typically formed upon aging of non-equilib-
rium solidied DC castings.
4.3. Aging assessment
Dilatometer analysis supported by electrical resistivity mea-
surements indicates that the precipitation process is associated
with the formation of nanoscale precipitates and the depletion of
the solid solution with the precipitating solute. In the case of ER
measurements, precipitation leads to a decrease in the resistivity
of the alloy due to a lesser contribution of the solute to electron
scattering. The process is pronounced by a decrease in the rate of
0.03
0.034
0.038
0.042
0.046
0.05
0.054
0.058
0 50 100 150 200 250 300 350 400 450 500 550
T6
T6 + 250C for 128 hrs
T6 + 475C for 128 hrs
L
e
n
g
t
h

c
h
a
n
g
e

r
a
t
e
,

d
L
/
d
t

/

m
/
s
Temperature, T /
o
C
Fig. 10. The dilatometer isochronal curves (dL/dt) obtained during heating cycles
between 25 and 500 C from modied alloy samples subjected to the following heat
treatment conditions. T6 heat treated. T6 heat treated and annealed at 250 C for
128 h. T6 heat treated and annealed at 475 C for 128 h. Note visible over-aging
transformation for T6 condition, and two distinct peaks for T6 + 475 C, while
T6 + 250 C shows lack of distinct transformations. Corresponding hardness data is
on Fig. 9 and indicates improved hardness retention for modied alloy treated at
475 C.
W. Kasprzak et al. / Journal of Alloys and Compounds 595 (2014) 6779 75
the resistivity increase with the temperature during continuous
heating i.e., the decrease of the rst derivative of resistivity versus
the temperature curve (dR/dT = f(T) in Fig. 4b) at the onset of pre-
cipitation. On the other hand, during the dissolution process, the
solid solution is enriched with the solute from the dissolving pre-
cipitates and this leads to an increase in the alloys specic resistiv-
ity and an increase in the rst derivative of resistivity versus
temperature curve (dR/dT = f(T)), at the onset of dissolution. The
two stages of precipitation and dissolution reactions are clearly
visible in Fig. 4b and correspond well to the stages of increase fol-
lowed by decrease of dL/dt characteristic as observed in Fig. 4a.
Two transformation peaks, #1 and #2 visible in Fig. 4a and b are
associated with the precipitation and dissolution of S-phase (Al
2-
CuMg) between 250 and 350 C and precipitation of Al
3
(Zr, V, Ti)
and possibly the precipitation and subsequent dissolution of Q-
phase (AlSiCuMg) between 440 C and 460 C. It is worth mention-
ing that in nanoscale, the Si and Cu nanoparticles covering Al
3
(Zr,
V, Ti) nano-rods (Fig. 3d) along with S-phase (Al
2
CuMg) may get
dissolved into the matrix and new Q
0
-phase precipitates. The pre-
cipitation process of Al
3
(Zr, V, Ti) trialuminides which seemed
incomplete after in T6 condition, completes once subjected to iso-
chronal heating to 500 C.
Studies performed by Knipling and co-workers [34,35] on Al
0.1%Zr and Al0.1%Zr0.1%Ti alloys aged isochronally in the range
of 300600 C showed that precipitation of Al
3
Zr intermetallics
commences between 350 and 375 C in the binary alloy, followed
by rapid over-aging beyond 475 C. The Al
3
Zr phase forms in binary
AlZr alloys as either a semi-coherent tetragonal phase or a coher-
ent cubic phase (usually observed in wrought alloys), both of
which have low interfacial energy with the a-Al matrix and are
responsible for providing hardness at elevated temperatures. Pres-
ent results indicate that SiZrV-rich precipitates could be respon-
sible for the second high temperature peak. Isothermal annealing
of the investigated alloy at 475 C shows a hardness increase indi-
cating the precipitation process of some precipitates (Fig. 9). TEM
analysis of the test samples re-heated up to 500 C during dilatom-
eter experiments conrmed the precipitation of dominant phase
nano-sized Al
3
(Zr, V, Ti) precipitates and nano-sized lath shaped
Q
0
-AlSiCuMg precipitates along with other less frequent complex
precipitates. However, one has to keep in mind that the present
alloy is more complex in terms of the alloying content than alloys
investigated by other researchers [34,35]. Therefore, a more
detailed analysis is required to substantiate this conclusion, which
is beyond the scope of this work.
Alloy aging characteristics shown on Fig. 5, are in good agree-
ment with data published for AlSiMg and AlSi-Cu alloy systems
[31,34,35] indicating that peak hardness decreases when the aging
temperature is increased. The rationale behind this phenomenon
relates to the fact that increasing the aging temperature leads to
a decrease in the supersaturation of the metal matrix and as in
any precipitation reaction, reduces the chemical driving force for
nucleation.
Based on the hardness characteristics shown on Fig. 5, it was
determined that the T6 (peak-hardness) condition corresponds to
articial aging at 150 C for 100 h while the T7 (over-aging) condi-
tion corresponds to articial aging at 250 C for 16 h. These explicit
aging parameters for the over-aging conditions were established
based on methodology presented in Section 2.5. Various precipi-
tates in different combinations have been reported for AlSi-Cu
Mg alloys in peak-aged conditions, e.g., Mg
2
Si, h
0
(Al
2
Cu) and Q(Al
5-
Mg
8
Si
6
Cu
2
) precipitates [33]. The Mg
2
Si type precipitates were
very likely formed in the investigated alloy, as discussed before.
Since the alloy contains also Zr, V, and Ti additions, ZrVTi-rich
precipitates should contribute to the overall alloy response to the
aging process. An excessive articial aging duration, more than
100 h at 150 C (Fig. 5), makes it impractical for an industrial appli-
cation but this treatment is discussed here to show that the alloy
can achieve the maximum hardness approaching 70 HRB at a suit-
ably designed chemical composition and processing parameters
[8]. The investigated alloy showed approximately 100% increase
in hardness at peak-aged condition as compared with as-cast hard-
ness. This indicates the alloys good age hardening ability,
measured as a difference between as-cast and peak aged hardness
[33].
4.4. Dimensional stability
Cast components from Al-based age-hardenable alloys are heat-
treated to ensure satisfactory strength and dimensional stability
during in-service operations. Therefore, it is required to determine
heat-treatment parameters, particularly the articial aging treat-
ment, that will ensure the alloys minimal dimensional change dur-
ing its in-service operation. From a physical metallurgy point of
view, aging transformation must be completed and no further
Table 3
Concentration of alloying elements in the metal matrix of the modied alloy in the as-cast and in the T6 conditions obtained using SEM/EDS analysis.
Condition Alloying elements in the matrix, (wt.%)
Mg Al Si Zr Ti V Cu
As-cast 0.73 97.92 0.83 0.05 0.17 0.13 0.16
0.06 0.1 0.05 0.02 0.07 0.05 0.04
T6 1.04 97.40 0.78 0.03 0.14 0.13 0.47
0.28 0.37 0.14 0.02 0.04 0.02 0.04
Table 4
Tensile properties and low cycle fatigue parameters of base and modied alloys. Available typical tensile properties of 356-T6 and 319-T6 alloys are included for comparison [11].
Alloy properties Base alloy (PM) Modied alloy (PM) 319-T6 (SC) 319-T6 (PM) 356-T6 (PM)
YS (MPa) 297 5 309 3 165 185 185
UTS (MPa) 340 4 335 12 250 275 260
Elongation (%) 2.8 0.4 2 0.2 2 3 5
Hardening capacity 0.14 0.08 0.52 0.49 0.41
Cyclic yield strength, r
0
y
(MPa) 330 347
Cyclic strain hardening exponent (g
0
) 0.24 0.28
Cyclic strength coefcient, K
0
(MPa) 1758 2393
Base alloy: Al7%Si1%Cu0.5%MgTi; Modied alloy: Al7%Si1%Cu0.5%Mg(ZrVTi); SC: Sand Casting; PM: Permanent Mold Casting.
76 W. Kasprzak et al. / Journal of Alloys and Compounds 595 (2014) 6779
precipitation can occur during subsequent heating and cooling cy-
cles within the working temperature range. Quantitative data on
the kinetics of aging transformation shown in Fig. 6, are summa-
rized on Table 5. It is evident that articial aging beyond 8 h at
250 C yields the optimal dimensional stability of the alloys
microstructure.
The results discussed in Section 3.4 are in good agreement with
the modied alloy aging characteristics described in Section 3.3
and presented on Fig. 5. The hardness aging curve at 250 C clearly
shows the increase when holding from 0.01 to 0.5 h reaching a
maximum of approximately 51 HRB, followed by a gradual de-
crease up to 25 HRB after approximately 8 h and followed by a
steady hardness value of approximately 20 HRB when aging from
8 to 144 h. A steady hardness value of 25 HRB conrms that no
further transformation takes place in the microstructure during
articial aging beyond 8 h at 250 C.
The absolute length change of the sample during heating from
100 to 500 C was in the range of 6.5135 lm (Fig. 6a), which cor-
responds to less than a 1% change in the sample length. The results
clearly demonstrate the applicability of this kind of dilatometer
analysis approach for proper selection of articial aging
parameters.
4.5. Mechanical properties
Hardness characteristics between 25 and 500 C provide valu-
able insight on the effect of heat treatment on the modied alloys
mechanical properties and the retention of hardness after various
treatment conditions. It was observed that modied alloy softening
in the T7 condition took place at approximately 270 C, about 20 C
higher than the softening of the alloy in the T6 condition observed
at approximately 250 C. These results are in agreement with dila-
tometer isochronal aging curves, where the beginning of the over-
aging transformation peak is observed at approximately 250 C for
T6 condition, most likely due to precipitate growth that could re-
sult in loss of precipitate coherency with metal matrix. At the same
time, the T7 curve shows no visible transformation peak, except a
gradual increase of the length change rate due to an increase in al-
loy thermal expansion (Fig. 7). For both testing conditions it was
evident that above 450 C the hardness increased by approxi-
mately 20% when the temperature was ramped to 500 C. For the
alloy in T7 condition, the hardness almost reached the initial T7 va-
lue as measured prior to the ramping test.
Hardness measurements and the microstructure analysis of the
modied alloy subjected to annealing at 250, 400 and 475 C
shows satisfactory agreements with dilatometer and ER data. Both
techniques showed transformation reaction occurring between
440 and 460 C, whereas the microstructural analysis of the test
samples reveals distinct rod shaped Al
3
(Zr, V, Ti) trialuminides
along with S-phase Al
2
CuMg precipitates. Thus, the present data
suggest that these precipitates are responsible for enhanced hard-
ness between 440 and 460 C however, further study is required to
understand the structure and the effect of these precipitates on the
alloys properties.
The existing reference data indicates that the high tempera-
ture aging behaviour of direct chill cast Al alloy is associated with
the precipitation process occurring between 350 C and 375 C in
the binary AlZr alloy, followed by beginning of the over-aging
beyond 475 C of Al
3
Zr precipitates [34,35]. Since the investigated
alloy has a much more complex chemistry than direct chill cast
Al alloys, more detailed analysis is required to correlate the
microstructure and peak transformation characteristics. The
observed high-temperature hardening response, as shown in
Fig. 9, is critical for understanding the alloys performance at
elevated temperatures and demonstrates its potential for high
temperature applications. Casting and heat treatment processing
parameters need further optimization to take full advantage of
the effectiveness of Mg and Cu-based secondary precipitation at
temperatures up to 250 C as well as ZrVTi based precipitates
up to 475 C.
4.6. Comparison of mechanical properties for alloys without and with
Zr and V additions
Previous studies of the effect of transition elements on the
mechanical properties at roomtemperature has revealed that addi-
tion of small quantities of Zr, V and Ti increases Yield Stress (YS) of
the modied alloy in the T6 condition from 297 5 MPa to
309 3 MPa at a similar value of Ultimate Tensile Strength (UTS)
335 MPa, while the elongation is reduced from 2.8 0.4% to
2 0.2%. A similar trend has been observed for Low Cycle Fatigue
(LCF), where the addition of Zr, V and Ti improves fatigue proper-
ties of the modied alloy by increasing Cyclic Yield Strength a
0
y

from 330 to 347 MPa, Cyclic Strain Hardening Exponent (g
0
) from
0.24 to 0.28 and extending fatigue life [11]. These properties have
been achieved for short cycle tempers where an application of a
two-step solution treatment allowed for up to a 50% solutionizing
time reduction for s given aging treatment parameters [1012].
Detailed mechanical properties data for alloys with and without
additions of Z and V is summarized in Table 4 together with data
for standard foundry alloys such as 356 and 319 cast using perma-
nent and sand casting processes [11].
Hardness characteristics between 25 and 500 C carried out for
base alloy without Zr and V showed similar values of hardness at
room temperature (95 HRF) and slightly but statistically signi-
cant higher hardness retention between 150 to 250 C and 350 to
450 Cobservedfor modiedalloywithadditionof transitionmetals
(Fig. 11). Both alloys experienced signicant hardness drop from
approximately 88 to 58 HRF between 250 and 330 C and gradual
hardness increase from 350 to 500 C. Modied alloy with Zr, V
and Ti retained more hardness by approximately 515% between
350 and 450 C. Higher values of hardness between 350 and 450 C
coincides well with temperature range for precipitation of
secondary Al
3
(Zr, V, Ti) nanophases and could support the hypothe-
sis that their nucleation occurs between approximately 450 to
475 C (Figs. 4 and 11). These nanosize precipitates have been iden-
tied in both T6 and T6 + holding at 475 C conditions as outlined in
the Section 4.2.
Table 5
Summary of articial aging conditions for modied alloy yielding dimensionally stable or unstable conditions obtained from dilatometer analysis.
W. Kasprzak et al. / Journal of Alloys and Compounds 595 (2014) 6779 77
Elevated temperature tensile testing carried out from 25 to
400 C revealed similar values of tensile stress (r) up to 150 C
for both alloys (approximately 320290 MPa) while between 200
and 400 C the strength was marginally higher for modied alloy
with additions of Zr, V and Ti (for example 260 vs. 247 MPa at
200 C) (Fig. 12).
The present results thus suggest that the additions of transi-
tion elements of Zr, V and Ti to the base Al7%Si1%Cu0.5%Mg
alloy in combination with the processing scheme used here, exert
positive but rather minor effect on mechanical properties. Further
research is required to develop the processing scheme to maxi-
mize the effect of transition metals on alloys mechanical proper-
ties. This should include optimization of the heat treatment
processing to ensure adequate microstructure renement and
the activation of secondary precipitation to establish processing
conditions yielding optimum mechanical properties for a given
alloy chemistry.
5. Conclusions
Based on the analysis of the correlation between microstructure
and properties of the hypoeutectic Al7%Si1%Cu0.5%Mg alloy
without and with Zr, V and Ti additions the following conclusions
can be drawn:
(a) The as-cast alloy microstructure consists of the following
phases: Cu
15
Al
43
Si, Al
5
Mg
9
Si
8
Cu
2
and Al
14
FeMg
4
Si
6
in addi-
tion to Al
3
Si
26
TiV
10
Fe as well as Al
13
Si
2
Ti
3
Zr intermetallic
phases. Solutionizing treatment during T6 treatment results
in dissolution of Cu
15
Al
43
Si and Al
5
Mg
9
Si
8
Cu
2
, while Fe con-
taining phases, AlSiCuFe and Al
9
Mg
12
Si
6
Fe remain undi-
solved. The Al
27
SiTiZr
9
and AlSiTiVFe intermetallic phases
remain in the microstructure in minor quantities.
(b) The TEM/EDX/diffraction analysis of modied T6 treated
samples reveals a primary GP-Zones, S-phase (Al
2
CuMg) pre-
cipitates, Al
3
(Zr, V, Ti) L1
2
nanoprecipitates with average size
below 50 nm, Al
3
(Zr, V, Ti) D0
23
rod shape precipitates with
average size of 230 nm covered with Si-rich nanoparticles
and to less extent with Cu-rich particles. The Al
3
(Zr, V, Ti)
secondary precipitates have varied concentration ratio of Z,
V and Ti.
(c) Dilatometer and electrical resistivity analysis of the modi-
ed alloy in the solution-treated and quenched condition
reveal two over-aging reactions occurring between 250
and 350 C most likely associated with the precipitation
and dissolution of S-phase (Al
2
CuMg) and 440460 C asso-
ciated with precipitation of Al
3
(Zr, V, Ti) and possibly the
precipitation and subsequent dissolution of Q
0
-phase
(AlSiCuMg).
(d) The modied alloy in the T6 heat treated condition (peak
aged) exhibits UTS of 311 MPa and strain at break of 0.02
at room temperature and 208 MPa and 0.08 at 250 C. The
maximum T6 hardness of 100 HRF was achieved after arti-
cial aging at 150 C for 100 h. Full dimensional stability for
the alloy aged at 250 C was achieved for aging time longer
than 8 h, where no further aging transformation was
observed. The T7 over-aged at 250 C for 16 h conditions
yield hardness of approximately 69 HRF and have been
selected as the conditions for the most dimensionally stable
alloy.
(e) High-temperature tensile testing shows a signicant drop in
strength of the modied alloy above the over-aging temper-
ature interval of 250300 C accompanied by a transitional
increase in strain at the break. Similar results were obtained
in hardness measurements, indicating that 250 C is a criti-
cal aging temperature for the given alloys chemistry and
heat treatment conditions and relates to stability of CuMg
based precipitates.
(f) As far as the hardness retention at elevated temperature is
concerned, the T7 temper enables retaining modied alloy
hardness up to 260 C, as compared to 240 C for T6 temper.
(g) Long temperature exposure at 475 C for 128 h for the mod-
ied alloy in T6 condition, results in improved hardness
retention and most likely is associated with further precipi-
tation of Al
3
(Zr, V, Ti) nanorods, their structural and compo-
sitional modication due to diffusion of Si, Mg, and Cu into
their structure and precipitation of lath shaped Q
0
type
precipitates.
(h) In comparison to the base Al7%Si1%Cu0.5%Mg alloy, the
modied alloy containing Zr, V and Ti show improved yield
strength and cyclic yield strength r
0
y
but lower ductility.
The modied alloy exhibits also slightly higher hardness
between 150 to 250 C and 350 to 450 C, but no signicant
improvement of tensile strength has been observed.
(i) Further studies are required to optimize the concentration of
Zr, V and Ti together with liquid metal processing and heat
treatment in order to maximize their effect on mechanical
properties at elevated temperatures.
Temperature, T /
o
C
R
o
c
k
w
e
l
l

F

h
a
r
d
n
e
s
s
,

H
R
F

/

k
g
f
Fig. 11. Softening characteristics for the base and modied alloys in the T6
condition. Note that both alloys show similar hardness at room temperature,
whereas modied alloy containing Zr, V and Ti shows slightly higher hardness in
the range of temperatures from 150 to 250 C and from 350 to 450 C.
T
e
n
s
i
l
e

s
t
r
e
s
s
,

/

M
P
a
Temperature, T /
o
C
Fig. 12. Comparison of strength for the base and modied alloys in the T6
condition. Above 150 C the modied alloy reveals marginally higher tensile
strength.
78 W. Kasprzak et al. / Journal of Alloys and Compounds 595 (2014) 6779
Acknowledgments
Financial support of the Advanced Materials for Transformation
(AMT) Program of Natural Resources Canada is gratefully acknowl-
edged. The authors thank also Drs. D. Emadi, M. Sahoo and F.
Fasoyinu for help in alloy development and Dr. J. Li as well as R.
Zavadil and C. Bibby for the microstructure analysis and M. Aniolek
and B. Voyzelle for dilatometer and thermal analysis measure-
ments. We thank Ibrahim Sadiq and Mubashir Mir from the
University of Waterloo for help with literature survey during Co-op
programs at CanmetMATERIALS.
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