Experimental investigation and thermodynamic calculation

of the AlSiTi system in Al-rich corner

Qun Luo, Qian Li, Jie-Yu Zhang, Shuang-Lin Chen, Kuo-Chih Chou

Shanghai Key Laboratory of Modern Metallurgy & Materials Processing, Shanghai University, Shanghai 200072, China
a r t i c l e i n f o
Article history:
Received 8 October 2013
Received in revised form 14 November 2013
Accepted 18 February 2014
Available online 26 February 2014
Keywords:
Intermetallics
Phase diagrams
Scanning electron microscopy
X-ray diffraction
Thermodynamic modeling
a b s t r a c t
The phase equilibria in Al-rich corner of the ternary AlSiTi system were investigated using X-ray
diffraction (XRD), scanning electron microscopy (SEM) and differential scanning calorimeter (DSC). The
ternary phase s
2
(Ti
33
Al
15
Si
52
, ZrSi
2
-type) existed stably and equilibrated with TiAl
3
, fcc(Al) and Si. The
DSC results from room temperature to 1000 C indicated that the endothermic peaks corresponded to
the quasi-peritectic reaction, liquid + TiAl
3
?s
2
+ fcc(Al), at 595 C and the eutectic reaction, liquid ?
s
2
+ fcc(Al) + Si, at 575 C. Based on the experimental results, a set of self-consistent thermodynamic
description of the AlSiTi system was obtained. The calculated isothermal section at 450, 500, 550
and 700 C and the invariant reactions agreed well with the experimental data.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Owing to its high wear resistance, low thermal-expansion
coefcient, good corrosion resistance and excellent mechanical
properties at a wide range of temperatures, the casting AlSi alloys
are widely used in military, automobile and general engineering
industry [13]. The application of grain rener and Ti containing
master alloys for increasing wear resistance and mechanical
properties [4,5] may result in the formation of TiAl based inter-
metallics [6]. However, limited work has been reported on phase
equilibria in the Al-rich corner of the AlSiTi system. The avail-
able data on the ternary compounds were contradictory [7,9,13],
which were summarized as follows.
Raman and Schubert [7] investigated the isothermal section of
the AlSiTi system at 700 C and discovered two ternary interme-
diate phases, Ti
7
Al
5
Si
12
and Ti
2
AlSi
3
. The crystal structure of
Ti
2
AlSi
3
is identical to that of Ti(Al
x
Si
1x
)
2
(s
2
, ZrSi
2
-type) given
by Brukl et al. [8]. Mondolfo [9] suggested that no ternary phase
formed in the Al corner of the AlSiTi system and the recorded
phases Ti
7
Al
5
Si
12
, Ti
2
AlSi
3
and TiAlSi
2
were the solid solution of
Al in TiSi
2
. Zakharov et al. [10,11] determined a ternary intermedi-
ate phase Ti
2
Al
3
Si
2
with a relatively narrow composition region
42.543.3 wt.% Ti, 22.124.8 wt.% Si, and remainder Daud and
Saheb [12] reported a ternary compound AlSi
2
Ti whose crystalline
structure was different from those of TiAl
3
(DO
22
-type) and TiSi
2
(C54-type) compounds and the existence of other ternary com-
pounds were not observed in their study. Liu et al. [13] reinvesti-
gated the phase equilibria of the AlSiTi system over the entire
composition range. The results showed that the ternary phase s
2
(ZrSi
2
-type orthorhombic) formed incongruently at 1338 C with
composition ranging from Ti
33
Al
21
Si
46
to Ti
33
Al
8
Si
59
at 1000 C
and the ternary phase s
1
(Zr
3
Al
4
Si
5
-type tetragonal) melts incon-
gruently between 953 and 1000 C with the composition of Ti
33.4-
Al
8
Si
58.6
. The phase equilibria in the TiAlSi system were
studied in the temperature range of 7001000 C using ternary
diffusion couples, in which two ternary intermetallic compounds
Ti
3
Al
2
Si
5
and Ti
3
AlSi
5
were observed [14]. Gao et al. [15] found that
the increase of Si addition in AlxSi2Ti alloys led to a phase evo-
lution fromTi(Al
1x
Si
x
)
3
to Ti
7
Al
5
Si
12
and the limited solubility of Si
in Ti(Al
1x
Si
x
)
3
lay between 12.5 and 18.75 at.%. The results of Sa-
heb et al. [4] showed that the addition of Ti led to the precipitation
of TiAl
3
phase which dissolved Si up to 13.12 at.%. From the exper-
iment results above, it can be seen that the composition of ternary
compounds and the phase equilibria in Al-rich corner of AlSiTi
system are still unconrmed. However, it is very signicant to
clarify this issue for designing the casting AlSi alloys.
With regard to thermodynamic calculation, the CALPHAD
assessment of the Ti-rich part of the diagram (<25 at.% Al and
<5 at.% Si) between 700 and 1200 C was carried out by Azevedo
and Flower [16,17]. Grbner et al. [18] provided a thermodynamic
description of AlSiTi system to understand the mechanism of
http://dx.doi.org/10.1016/j.jallcom.2014.02.107
0925-8388/ 2014 Elsevier B.V. All rights reserved.

Corresponding author. Tel.: +86 21 56333853.

E-mail address: kcc126@126.com (K.-C. Chou).
Journal of Alloys and Compounds 602 (2014) 5865
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
grain rening in this ternary alloys. Based on the experimental data
from Al10 wt.% Si/Ti diffusion couple, Li et al. [19] reassessed the
Al-rich corner of AlSiTi system. In this study, the phase equilibria
in the Al-rich corner were investigated experimentally, and a
consistent thermodynamic description of AlSiTi system was as-
sessed. We hope to obtain the fundamental knowledge on the
phase relationship in this system for designing the target material
with desired properties.
2. Experimental procedures
Three AlSiTi alloys were prepared in a medium frequency induction furnace
under high purity argon atmosphere (99.999%). Owing to the insulation and high
melting point of Si, the Al30 wt.% Si alloy (99.99%) was used as raw material.
The weighted Al30 wt.% Si blocks, Al blocks (99.99%) and Ti blocks (99.995%) were
melted in the furnace. The ingots were all re-melted for ve times to ensure their
homogeneity. Small strips of 4 mm 4 mm 20 mm were wire electro-discharge
machined from the ingots and sealed respectively in evacuated quartz capsules
with atmospheric pressure at 10
2
10
1
Pa. Then the samples were annealed at
450, 500, 550 and 700 C for 3103360 h (hrs), and nally quenched in water.
The actual composition of each alloy was measured by inductively coupled
plasma atomic emission spectrometry (ICP). XRD analysis was performed on the
sample using a D/MAX 2500 diffractometer with Cu Ka radiation. The microstruc-
ture and composition of phases in the samples were examined by JSM-6700F SEM
equipped with energy dispersive X-ray spectrometer (EDS, semi-quantitative
analysis in this work). The samples annealed at 550 C for 1128 h were studied
by NETZSCH 404C DSC under argon atmosphere at the owing rate of 50 mL/min
and the heating rate of 10 C/min.
3. Results and discussions
Fig. 1 shows the backscattered electron (BSE) images of the
samples #1#3 annealed at 550 and 700 C. Fig. 2 shows the
XRD patterns of the three samples, from which it can be seen that
a three-phase equilibrium of fcc(Al) + TiAl
3
+ s
2
exists in sample #1
in the temperature range of 450550 C, and a two-phase equilib-
rium TiAl
3
+ fcc(Al) is observed at 700 C. Small amount of s
2
phase
in sample #1 presents at the edge of TiAl
3
. At 700 C, the liquid
phase presents in all samples and the diffusion of components be-
come faster. It is clear that the microstructures of samples become
obviously coarser at 700 C than that at 550 C, as shown in Fig. 1.
No amorphous phase found in the XRD patterns, which indicates
that the liquid phase is not preserved after quenching. The content
of Si in fcc(Al) phase of sample #2 greatly exceeds its saturated so-
lid solution. Therefore, the liquid should transform to the supersat-
urated fcc(Al) phase during cooling process.
The stable phases observed in sample #2 are s
2
, fcc(Al) and Si at
450550 C, and since fcc(Al) phase would melt at 700 C, the ob-
served phases should be s
2
, liquid and Si. The s
2
and TiAl
3
phase
separate completely in sample #3 after annealing at 700 C for
310 h because of the fast diffusion rate in liquid. The XRD result
of sample #3 indicates the three-phase equilibrium of fcc(Al) +
TiAl
3
+ s
2
. The phase compositions determined by XRD are consis-
tent with that of EDS. The comparison of phase compositions
identied by XRD and EDS for different alloys at different
Fig. 1. The BSE images of the samples #1#3 annealed at 550 C for 3168 h and 700 C for 310 h.
Q. Luo et al. / Journal of Alloys and Compounds 602 (2014) 5865 59
temperatures is summarized in Table 1. It should be noticed that
there is merely one ternary phase, s
2
, appearing at the Al-rich re-
gion, which located at 3335 at.% Ti, 818 at.% Al, 4759 at.% Si.
In other words, no other ternary phase is observed in those sam-
ples. The XRD results indicate that the crystal structure of s
2
is
orthorhombic and of ZrSi
2
-type, which is different from TiAl
3
(DO
22
-type) and TiSi
2
(C54-type).
The phase transition temperature was determined by DSC from
room temperature to 1000 C. Fig. 3(a) is the graph of DSC heating
curves of samples. The endothermic peaks shown in curves of sam-
ples #2 and #3 indicate that there are two phase transitions at
575 C and 595 C, respectively. Fig. 3(b) is the enlarged graph of
DSC curve of sample #1, which shows that two small endothermic
peaks present at 595 C and 608 C. In order to reveal the types of
phase transition and solidication procedure, the microstructure of
cast samples needs to be determined. Fig. 4 shows the BSE images
of the cast samples #1#3. With regard to sample #1, the TiAl
3
phase is the primary phase and the surrounded fcc(Al) phase forms
subsequently. The bright lamellate s
2
in cast sample #2 randomly
occur and traverse the Si particles, so the s
2
should be the primary
phase. Then the Si particles form and nally the remainder liquid
transforms into fcc(Al) + Si eutectic microstructure through a
eutectic reaction. The presence of irregular Ti
5
Si
4
phases in cast
sample #3 was veried by XRD results. It is easy to know that
the Ti
5
Si
4
phase rstly crystallizes from liquid, and then the s
2
and TiAl
3
phases form simultaneously through a quasi-peritectic
reaction, liquid + Ti
5
Si
4
?s
2
+ TiAl
3
. Therefore, the Ti
5
Si
4
phase is
enveloped in the s
2
and TiAl
3
phases (showed in the enlarged
image of sample #3). Finally, the residual liquid transforms into
fcc(Al). The composition of each phase listed in Table 1 is averaged
for at least three measurements.
4. Thermodynamic modeling
4.1. Thermodynamic models
For the binary subsystems AlSi [20], AlTi [21] and SiTi [22]
the thermodynamic data sets were accepted as published. In the
following, the analytical expressions for the Gibbs energies of the
phases in AlSiTi system are presented.
The Gibbs energy function

G
/
i
T G
/
i
T H
SER
i
for element i
(i = Al, Si and Ti) in all the phases detected (liquid, Al (FCC), Ti
(HCP & BCC), and Si (Diamond)) is described as:

G
/
i
T a bT cT ln T dT
2
eT
3
fT
1
gT
7
hT
9
1
where H
SER
i
is the molar enthalpy of the component i in its stable
state at 298.15 K and 1 atm, and T is the absolute temperature.
The Gibbs energies for Al, Si and Ti are taken from the SGTE compi-
lation by Dinsdale [23].
The Gibbs energy function of the ternary system containing the
phases of liquid, fcc(Al), hcp(Ti), bcc(Ti) and diamond(Si) are de-
scribed using substitutional-solution model:
G
/

X
3
i1
x
i

G
/
i
RT
X
3
i1
x
i
ln x
i
G
ex;/
2
where x
i
is the mole fractions of Al, Si or Ti. G
ex,/
is the excess Gibbs
energy of the phase, which dened as following equation in this
work.
G
ex;/
x
Al
x
Si
X
m
k0
k
L
/
Al;Si
x
Al
x
Si

k
x
Al
x
Ti
X
m
k0
k
L
/
Al;Ti
x
Al
x
Ti

k
x
Ti
x
Si
X
m
k0
k
L
/
Ti;Si
x
Ti
x
Si

k
x
Al
x
Si
x
Ti
x
Al

0
L
Al;Si;Ti
x
Si

1
L
Al;Si;Ti
x
Ti

2
L
Al;Si;Ti
3
where
k
L
/
Al;Si
;
k
L
/
Al;Ti
and
k
L
/
Ti;Si
are the binary interaction parame-
ters, the
0
L
Al;Si;Ti
,
1
L
Al;Si;Ti
and
2
L
Al;Si;Ti
are the ternary interaction
parameters.
The binary intermetallic phases are modeled based on its binary
thermodynamic data sets. The solution of the third element in
Ti
2
Al
5
, TiAl
2
and Ti
3
Si were small and can be negligible. Therefore,
Fig. 2. The XRD patterns of cast and annealed samples.
60 Q. Luo et al. / Journal of Alloys and Compounds 602 (2014) 5865
their binary Gibbs energy descriptions were used in the ternary cal-
culation. The Ti
2
Al
5
, TiAl
2
and Ti
3
Si, are modeled as stoichiometric
compounds. For the other binary intermetallic phases, TiAl, Ti
3
Al,
TiAl
3
, Ti
5
Si
3
, Ti
5
Si
4
, TiSi and TiSi
2
are treated as compound energy
formalism accounting for their defect structure and Si- or Al-solu-
bility in those phases. The Gibbs energy function for an intermetal-
lic phase with compound energy formalism is described as:
G
/

ref
G
/

id
G
/

ex
G
/
4
where
ref
G
/
is expressed in terms of compound energies and their
associated sublattice species (Al, Si and Ti) concentrations y
i
,
id
G
/
is the ideal mixing term which is assumed to be the random mixing
of species in each sublattice. Taking TiAl
3
as an example, the Si-
solubility in TiAl
3
is modeled as (Ti, Al)
0.25
(Ti, Al, Si)
0.75
by extend-
ing the binary model (Ti, Al)
0.25
(Ti, Al)
0.75
in order to reect the
experimental observation that Si mainly substituted Al on the
second sublattice. The Gibbs energy per mole formula for TiAl
3
is
expressed as:
G
TiAl
3
y
0
Al
y
00
Ti
G
TiAl
3
Al:Ti
y
0
Al
y
00
Al
G
TiAl
3
Al:Al
y
0
Al
y
00
Si
G
TiAl
3
Al:Si
y
0
Ti
y
00
Ti
G
TiAl
3
Ti:Ti
y
0
Ti
y
00
Al
G
TiAl
3
Ti:Al
y
0
Ti
y
00
Si
G
TiAl
3
Ti:Si
0:25RT y
0
Al
ln y
0
Al
y
0
Ti
ln y
0
Ti

0:75RT y
00
Al
ln y
00
Al
y
00
Ti
ln y
00
Ti
y
00
Si
ln y
00
Si

y
0
Ti
y
0
Al
y
00
Al
0
L
TiAl
3
Ti;Al:Al
y
0
Ti
y
0
Al
y
00
Ti
0
L
TiAl
3
Ti;Al:Ti
y
0
Al
y
00
Al
y
00
Ti
0
L
TiAl
3
Al:Al;Ti
y
0
Ti
y
00
Al
y
00
Ti
0
L
TiAl
3
Ti:Al;Ti
y
0
Ti
y
00
Al
y
00
Si
0
L
TiAl
3
Ti:Al;Si

1
L
TiAl
3
Ti:Al;Si
y
00
Al
y
00
Si

h i
5
in which y
0
Al
and y
0
Ti
are the site fractions of Al and Ti on the rst sub-
lattice, and y
00
Ti
, y
00
Si
and y
00
Al
are the site fractions of Al, Si and Ti on the
second sublattice. The terms
0
L
TiAl
3
Ti;Al:Al
,
0
L
TiAl
3
Ti;Al:Ti
,
0
L
TiAl
3
Al:Al;Ti
,
0
L
TiAl
3
Ti:Al;Ti
,
0
L
TiAl
3
Ti:Al;Si
and
1
L
TiAl
3
Ti:Al;Si
represent the interaction parameters that are functions
of temperature.
The ternary phase s
2
is modeled as a stoichiometric compound:
(Ti)
0.333333
(Al)
0.15
(Si)
0.516667
. The Gibbs energy per mole formula for
s
2
is expressed as:
G
s
2
0:333333

G
HCP
Ti
0:15

G
FCC
Al
0:516667

G
Diamond
Si
a bT
6
The models and parameters in the thermodynamic descriptions
of AlSiTi system are listed in Table 2.
Table 1
The comparison of phase compositions identied by XRD and EDS for different alloys at different temperatures.
Samples #1 #2 #3
Actual composition at.% 78.2Al, 9.2Si, 14.3Ti 68.1Al, 28.0Si, 3.9Ti 57.7Al, 23.8Si, 18.5Ti
As cast XRD TiAl
3
fcc(Al) Si s
2
fcc(Al) Si Ti
5
Si
4
fcc(Al) s
2
EDS Al 65.6 Al 100.0 Al 14.0 Al 100.0 Si 100.0 Al 1.3 Al 100.0 Al 18.1
at.% Si 7.4 Si 50.8 Si 41.7 Si 46.5
Ti 27.0 Ti 35.2 Ti 57.0 Ti 35.4
450 C, XRD TiAl
3
fcc(Al) s
2
s
2
fcc(Al) Si TiAl
3
fcc(Al) s
2
3360 h EDS Al 64.7 Al 98.8 Al 9.7 Al 7.7 Al 99.9 Al 0.6 Al 58.8 Al 98.0 Al 11.5
at.% Si 8.9 Si 0.8 Si 57.3 Si 58.6 Ti 0.1 Si 99.4 Si 14.7 Si 1.3 Si 55.0
Ti 26.4 Ti 0.4 Ti 33.0 Ti 33.7 Ti 26.5 Ti 0.7 Ti 33.5
500 C, XRD TiAl
3
fcc(Al) s
2
s
2
fcc(Al) Si TiAl
3
fcc(Al) s
2
3168 h EDS Al 66.7 Al 98.4 Al 14.8 Al 10.9 Al 99.0 Al 1.0 Al 59.9 Al 100.0 Al 10.7
at.% Si 6.2 Si 1.2 Si 50.5 Si 53.2 Si 1.0 Si 99.0 Si 12.7 Si 52.9
Ti 27.1 Ti 0.4 Ti 34.7 Ti 35.9 Ti 27.4 Ti 36.4
550 C, XRD TiAl
3
fcc(Al) s
2
s
2
fcc(Al) Si TiAl
3
fcc(Al) s
2
3168 h EDS Al 67.4 Al 99.0 Al 14.2 Al 10.9 Al 98.9 Si 100.0 Al 60.8 Al 99.1 Al 14.0
at.% Si 6.2 Si 0.9 Si 51.9 Si 53.7 Si 1.1 Si 12.5 Si 0.9 Si 50.8
Ti 26.4 Ti 0.1 Ti 33.9 Ti 35.4 Ti 26.7 Ti 35.2
700 C, XRD TiAl
3
fcc(Al) s
2
fcc(Al) Si TiAl
3
fcc(Al) s
2
310 h EDS Al 63.7 Al 98.9 Al 8.3 Al 88.6 Si 100.0 Al 60.6 Al 96.9 Al 12.6
at.% Si 9.3 Si 1.1 Si 55.3 Si 11.4 Si 12.5 Si 3.1 Si 51.6
Ti 27.0 Ti 36.4 Ti 26.9 Ti 35.8
Fig. 3. (a) The DSC heating curves of alloys annealed at 550 C for 1128 h and (b)
the enlarged image of DSC curve of sample #1.
Q. Luo et al. / Journal of Alloys and Compounds 602 (2014) 5865 61
Fig. 4. The BSE images of the cast samples #1#3.
Table 2
The thermodynamic data sets of the AlSiTi system.
Parameters a b Refs.
Liquid, substitutional-solution, (Al, Si, Ti)
1
0
L
Liquid
Al;Si
11,655.93 0.92934 [20]
1
L
Liquid
Al;Si
2873.45 0.2945 [20]
2
L
Liquid
Al;Si
2520.0 0 [20]
0
L
Liquid
Ti;Al
112,570 41.11378 [21]
1
L
Liquid
Ti;Al
7950.8 0 [21]
0
L
Liquid
Ti;Si
255,852 21.8741 [22]
1
L
Liquid
Ti;Si
25,025.3 2.00203 [22]
2
L
Liquid
Ti;Si
83,940.6 6.71526 [22]
bcc(Ti), substitutional-solution, (Al, Si, Ti)
1
0
L
bccTi
Ti;Al
129,396.7 40.0631 [21]
0
L
bccTi
Ti;Si
275,629 42.5094 [22]
1
L
bccTi
Ti;Si
25,025.3 2.00203 [22]
2
L
bccTi
Ti;Si
83,940.6 6.71526 [22]
Diamond(Si), substitutional-solution, (Al, Si, Ti)
1
0
L
DiamondSi
Al;Si
111,417.70 46.1392 [20]
0
L
DiamondSi
Si;Ti
0 80 [22]
fcc(Al), substitutional-solution, (Al, Si, Ti)
1
0
L
fccAl
Al;Si
3423.91 0.09584 [20]
0
L
fccAl
Ti;Al
124,270 43.8967 [21]
0
L
fccAl
Ti;Si
10,000 0 [22]
hcp(Ti), substitutional-solution, (Al, Si, Ti)
1
0
L
hcpTi
Ti;Al
123,789 33.209 [21]
1
L
hcpTi
Ti;Al
16,034.9 12.1827 [21]
0
L
hcpTi
Ti;Si
302,731 69.0847 [22]
1
L
hcpTi
Ti;Si
25,025.3 2.00203 [22]
2
L
hcpTi
Ti;Si
83,940.6 6.71526 [22]
62 Q. Luo et al. / Journal of Alloys and Compounds 602 (2014) 5865
Table 2 (continued)
Parameters a b Refs.
TiAl, compound energy formalism, (Ti, Al, Si)
0.5
(Ti, Al, Si)
0.5
0
G
TiAl
Al:Al


G
FCC
Al
0 0 [21]
0
G
TiAl
Ti:Al
0:5

G
FCC
Ti
0:5

G
FCC
Al
37,445.1 16.7938 [21]
0
G
TiAl
Al;Ti
0:5

G
FCC
Ti
0:5

G
FCC
Al
37,445.1 16.7938 [21]
0
G
TiAl
Ti:Ti


G
FCC
Ti
0 0 [21]
0
G
TiAl
Si:Si
50,000 0 This work
0
G
TiAl
Al:Si
50,000 0 This work
0
G
TiAl
Si:Al
50,000 0 This work
0
L
TiAl
Al;Ti:Al
=
0
L
TiAl
Al;Ti:Ti
63,490.1 7.7928 [21]
1
L
TiAl
Al;Ti:Al
=
1
L
TiAl
Al;Ti:Ti
39,488.4 0 [21]
1
L
TiAl
Al:Al;Ti
=
0
L
TiAl
Ti:Al;Ti
28,311.6 10.8517 [21]
Ti
2
Al
5
, stoichiometric, (Ti)
0.285714
(Al)
0.714286
0
G
Ti2Al5
Ti:Al
0:285714

G
FCC
Ti
0:714286

G
FCC
Al
40,495.4 9.52964 [21]
Ti
3
Al, compound energy formalism, (Ti, Al)
0.75
(Ti, Al)
0.25
0
G
Ti3Al
Al:Al


G
HCP
Al
0 0 [21]
0
G
Ti3Al
Ti:Al
0:75

G
HCP
Ti
0:25

G
HCP
Al
29,633.6 6.70801 [21]
0
G
Ti3Al
Al:Ti
0:75

G
HCP
Al
0:25

G
HCP
Ti
29,633.6 6.70801 [21]
0
G
Ti3Al
Ti:Ti


G
HCP
Ti
0 0 [21]
0
L
Ti3Al
Al;Ti:Al
=
0
L
Ti3Al
Al;Ti:Ti
71,277.9 25.47 [21]
TiAl
2
, stoichiometric, (Ti)
0.333333
(Al)
0.666667
0
G
TiAl2
Ti:Al
0:333333

G
FCC
Ti
0:666667

G
FCC
Al
43,858.4 11.0208 [21]
TiAl
3
, compound energy formalism, (Ti, Al)
0.25
(Ti, Si, Al)
0.75
0
G
TiAl3
Al:Al


G
FCC
Al
0 0 [21]
0
G
TiAl3
Ti:Al
0:25

G
FCC
Ti
0:75

G
FCC
Al
40,349.6 10.3653 [21]
0
G
TiAl3
Al:Ti
0:25

G
FCC
Al
0:75

G
FCC
Ti
40,349.6 10.3653 [21]
0
G
TiAl3
Ti:Ti


G
FCC
Ti
0 0 [21]
0
G
TiAl3
Ti:Si
0:25

G
FCC
Ti
0:75

G
Diamond
Si
40,000 10 This work
0
G
TiAl3
Al:Si
0:25

G
FCC
Al
0:75

G
Diamond
Si
40,000 10 This work
0
L
TiAl3
Al;Ti:Al
=
0
L
TiAl3
Al;Ti:Ti
12,500 0 [21]
0
L
TiAl3
Al:Al;Ti
=
0
L
TiAl3
Ti:Al;Ti
61,849.5 36.5337 [21]
0
L
TiAl3
Ti:Al;Si
9000 0 This work
1
L
TiAl3
Ti:Al;Si
143,000 0 This work
Ti
3
Si, stoichiometric, (Ti)
0.75
(Si)
0.25
0
G
Ti3Si
Ti:Si
0:75

G
HCP
Ti
0:25

G
Diamond
Si
50,000 0.79981 [22]
Ti
5
Si
3
, compound energy formalism, (Ti, Si)
2
(Ti, Si)
3
(Ti)
0.25
0
G
Ti5Si3
Ti:Si:Ti
5

G
HCP
Ti
3

G
Diamond
Si
583,564 2.68514 [22]
0
G
Ti5Si3
Ti:Ti:Ti
8

G
HCP
Ti
40,000 20 [22]
0
G
Ti5Si3
Si:Si:Ti
5

G
Diamond
Si
3

G
HCP
Ti
206,191 16.4953 [22]
0
G
Ti5Si3
Si:Ti:Ti
2

G
Diamond
Si
6

G
HCP
Ti
417,373 33.8102 [22]
0
L
Ti5Si3
Ti;Si:Ti:Ti
=
0
L
Ti5Si3
Ti;Si:Si:Ti
500,000 40 [22]
0
L
Ti5Si3
Ti:Si;Ti:Ti
=
0
L
Ti5Si3
Si:Si;Ti:Ti
43,024.3 3.44194 [22]
Ti
5
Si
4
, compound energy formalism, (Ti, Al)
0.555556
(Si, Al)
0.444444
0
G
Ti5Si4
Ti:Si
0:555556

G
HCP
Ti
0:444444

G
Diamond
Si
79,000 2.48595 [22]
0
G
Ti5Si4
Ti:Al
0:555556

G
HCP
Ti
0:444444

G
FCC
Al
50,000 0 This work
0
G
Ti5Si4
Al:Si
0:555556

G
FCC
Al
0:444444

G
Diamond
Si
10,000 0 This work
0
G
Ti5Si4
Al:Al


G
FCC
Al
10,000 0 This work
TiSi, compound energy formalism, (Ti, Al)
0.5
(Si, Al)
0.5
0
G
TiSi
Ti:Si
0:5

G
HCP
Ti
0:5

G
Diamond
Si
77,530.9 3.81725 [22]
0
G
TiSi
Ti:Al
0:5

G
HCP
Ti
0:5

G
FCC
Al
27,445.1 16.7938 [22]
0
G
TiSi
Al:Si
0:5

G
Diamond
Si
0:5

G
FCC
Al
10,000 0 This work
0
G
TiSi
Al:Al


G
FCC
Al
10,000 0 This work
TiSi
2
, compound energy formalism, (Ti)
0.333333
(Si, Al)
0.666667
0
G
TiSi2
Ti:Si
0:333333

G
HCP
Ti
0:666667

G
Diamond
Si
58,346.15 1.516 [22]
0
G
TiSi2
Ti:Al
0:333333

G
HCP
Ti
0:666667

G
FCC
Al
33,858.4 11.0208 This work
s
2
, stoichiometric, (Ti)
0.333333
(Al)
0.15
(Si)
0.516667
0
G
s2
Ti:Al:Si
0:333333

G
HCP
Ti
0:15

G
FCC
Al
0:516667

G
Diamond
Si
73,150 4.54545 This work
Q. Luo et al. / Journal of Alloys and Compounds 602 (2014) 5865 63
4.2. Thermodynamic calculations of the AlSiTi system
Fig. 5 shows the comparison between experimental points and
the calculated isothermal sections at 450, 500, 550 and 700 C,
respectively. It can be seen that the calculated results agree well
with the experimental data. The experimental results of annealed
samples #1 and #3 indicate the three-phase equilibrium
TiAl
3
+ fcc(Al) + s
2
stabilizing at 450550 C and the two-phase
equilibrium TiAl
3
+ liquid at 700 C. It signies that at least one
phase transition happened between 550 and 700 C. The DSC
curves show the phase transition temperatures are 595 C and
608 C for sample #1 and 595 C for sample #3. The isopleths of
AlSiTi system with 14.0 at.% Ti (sample #1) and 18.5 at.% Ti
(sample #3) are calculated through Pandat software and showing
in Fig. 6(a) and (c), respectively. A quasi-peritectic reaction,
liquid + TiAl
3
?s
2
+ fcc(Al) is presented at 604 C, of which
temperature is close to that of endothermic peaks at 595 C. With
regard to sample #1, the line calculation result indicates that two
phase transitions, fcc(Al) + s
2
+ TiAl
3
?fcc(Al) + TiAl
3
(595 C) and
fcc(Al) + TiAl
3
?TiAl
3
+ liquid (605 C), happened near the temper-
atures shown in the DSC curves (595 and 608 C). The phases of
annealed sample #2 are fcc(Al) + s
2
+ Si at 450550 C and
Fig. 5. The isothermal sections of the Al-rich corner of AlSiTi system at 450, 500, 550 and 700 C.
Fig. 6. The isopleths of AlSiTi system with (a) 14.0 at.% Ti, (b) 3.9 at.% Ti and (c) 18.5 at.% Ti.
64 Q. Luo et al. / Journal of Alloys and Compounds 602 (2014) 5865
liquid + s
2
+ Si at 700 C, respectively. The calculated isopleth at
3.9 at.% Ti in Fig. 6(b) shows that a eutectic reaction liquid ?s
2
+
fcc(Al) + Si presents at 577 C, which agrees well with the temper-
ature of 575 C determined by DSC.
5. Conclusions
The Al-rich corner of AlSiTi system has been investigated
experimentally and thermodynamically. The phase equilibria in
the Al-rich corner of AlSiTi system were determined using equil-
ibrated alloys with methods of SEM, EDS and XRD. There is only one
ternary phase, s
2
, existing. Two three-phase equilibria (TiAl
3
+
fcc(Al) + s
2
and fcc(Al) + s
2
+ Si) present at 450550 C and become
TiAl
3
+ liquid + s
2
and liquid + s
2
+ Si at 700 C, respectively. The
DSC curves of samples indicate that two endothermic peaks oc-
curred at 595 C and 575 C corresponding to the quasi-peritectic
reaction of liquid + TiAl
3
?s
2
+ fcc(Al) and eutectic reaction of
liquid ?s
2
+ fcc(Al) + Si, respectively. A set of self-consistent ther-
modynamic description of the AlSiTi system is obtained by
accessing the phase equilibrium data and phase transition temper-
atures from DSC. What is more, the calculations are compared with
the experimental results and a good agreement is reached.
Acknowledgements
The authors thank Instrumental Analysis and Research Center
of Shanghai University for their support of materials testing and
research. This work was nancially supported by the National
Natural Science Foundation of China (51074103 and 51222402).
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