Intermetallics 14 (2006) 236–240

www.elsevier.com/locate/intermet

Thermal expansion of the Ti5Si3 and Ti6Si2B phases

investigated by high-temperature X-ray diffraction
Geovani Rodrigues*, Carlos Angelo Nunes, Paulo Atsushi Suzuki, Gilberto Carvalho Coelho
Faculdade de Engenharia Quı́mica de Lorena (FAENQUIL), Departamento de Engenharia de Materiais (DEMAR),
Polo Urbo-Industrial, Gleba AI-6, Caixa Postal 116, 12600-970 Lorena, SP, Brazil
Received 20 October 2004; accepted 18 May 2005
Available online 9 August 2005

Abstract
The thermal expansion coefficients (CTE) of the Ti5Si3 and Ti6Si2B phases were determined using high-temperature X-ray diffraction
from 298 to 873 K. Alloys with nominal compositions Ti66Si34, Ti62.5Si37.5, Ti59Si41 and Ti66.7Si22.2B11.1 (at%) were prepared through arc-
melting followed by heat-treatment at 1473 K during 60 h under argon atmosphere. The Ti5Si3 phase has a hexagonal structure, space group
P63/mcm (No. 193) with room temperature lattice parameters aZ7.4561 Å and cZ5.1485 Å. This binary compound presents high thermal
expansion anisotropy (ac/aay2.7), as a consequence of the large difference between the thermal expansion coefficients along the a (5.98!
10K6 KK1) and c (16.64!10K6 KK1) axes. The Ti6Si2B phase crystallizes with a hexagonal unit cell, space group P62m (No. 189) with
room temperature lattice parameters aZ6.8026 Å and cZ3.3374 Å. This phase exhibits a low thermal expansion anisotropy (ac/aay1), with
the thermal expansion coefficients along the a and c axes equal to 9.7!10K6 KK1 and 9.6!10K6 KK1, respectively.
q 2005 Elsevier Ltd. All rights reserved.

Keywords: A. Silicides, various; A. Ternary alloy system; B. Anisotropy; B. Thermal properties; F. Diffraction

1. Introduction different crystallographic directions, resulting in high

Alloys of the Me–Si–B (MeZTi, Zr, V, Nb, Ta, Cr, Mo)
systems have been recently investigated under several
aspects motivated by characteristics, which make them
promising materials for high-temperature structural appli-
cations [1–8]. The existence of phases (T2; D88) containing
significant Si and B amount, with high melting point [9–11]
and good creep and oxidation resistance [12–14] has
particularly inspired the studies in the Mo–Si–B and
Nb–Si–B systems. The evaluation of the thermal expansion
anisotropy is important to control the degree of microcrack-
ing during processing and high-temperature applications of
a given alloy. Phases with non-cubic crystal structures can
exhibit high degree of thermal expansion anisotropy owing
to the differences in thermal expansion coefficients (CTE) in
* Corresponding author. Tel.: C55 12 3159 9912; fax: C55 12 3153
3006.
E-mail address: geovani@ppgem.faenquil.br (G. Rodrigues).
0966-9795/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.intermet.2005.05.007
degree of strain or microcracking.
Rawn et al. [15] have shown that the thermal expansion
anisotropy (ac/aa) of the tetragonal Mo5SiB2 (T2) phase is
significantly smaller than that of the tetragonal Mo5Si3 (T1)
phase (0.8–1.1 for T2-phase and 2.2 for Mo5Si3). In addition,
Fu and Schneibel [16] have shown that the ac/aa ratio of
Mo5Si3 (T1) can be significantly reduced through ternary
alloying additions (Nb, V). It was shown that a partial
substitution of Mo by either Nb or V leads to a decrease of the
ac/aa ratio from 2.0 (Mo5Si3) to 1.5 and 1.0 for the MoNb4Si3
and Mo4VSi3 stoichiometries, respectively. In a previous
work [17], we assessed the effect of boron content on the CTE
anisotropy of the T2-phase of Nb–Si–B system. The results
indicated that an increase of the boron content results in a
significant decrease of ac, while aa is almost unchanged,
diminishing the ac/aa ratio from approximately 1.2 (Nb5Si3
stoichiometry) to approximately 0.7 (T2 in an alloy with
stoichiometry Nb64Si14.4B21.6). The Ti5Si3 phase crystallizes
in a Mn5Si3-type cell (D88: strukturbericht designation),
hexagonal structure, lattice parameters aZ7.460 Å and
cZ5.152 Å, space group P63/mcm, Wyckoff positions:
Ti1Z4d (1/3, 2/3, 0); Ti2Z6 g (XTi, 0, 1/4) where
XTiz0.25; SiZ6 g (XSi, 0, 1/4) where XSiz0.61. This phase
 G. Rodrigues et al. / Intermetallics 14 (2006) 236–240
displays a high melting point, low density and with certain
interstitial additions, good oxidation resistance. Williams
et al. [18] has shown that the ac/aa ratio of Ti5Si3 is
approximately 2.9 for non-doped Ti5Si3 and approximately 2
for this phase doped with small additions of C, B or N atoms.
In another work, Schneibel et al. shown that the thermal
expansion anisotropy of Ti5Si3 phase can be reduced from 2.7
to 2.5 with 2 at% of Cr addition [19]. However, some
discrepancies in the ac/aa ratio of this phase have been
reported by different authors: 2.8 [20]; 2.4 [21]; 1.7 [22] and
4.4 [23]. The Ti6Si2B phase, recently identified by Ramos et
al. [24], is isotypic with Ni6Si2B (Fe2P-type structure;
Zr6CoGa2 ternary variant), hexagonal structure, lattice
parameters aZ6.8015 Å and cZ3.3377 Å, space group
P62m, Wyckoff positions: Ti1Z3 g (XTi1, 0, 1/2), where
XTi1Z0.2418; Ti2Z3f (XTi2, 0, 0) where XTi2Z0.5996;
BZ1a (0, 0, 0) and SiZ2d (1/3, 2/3, 1/2) [24]. No data was
found in the literature with respect to the thermal expansion
properties of this phase. In the present work, we have
measured the thermal expansion of the Ti5Si3 and Ti6Si2B
phases by means of high-temperature X-ray diffraction
(HTXRD).
2. Experimental procedures
An important aspect to be considered in the measurement
of thermal expansion coefficients through high-temperature
X-ray diffraction is the production of a single-phase alloy or
an alloy with large volume fraction of the phase of
interest. The Ti5Si3 phase was obtained from alloys with
nominal compositions Ti66Si34, Ti62.5Si37.5 and Ti59Si41
(at%) and the Ti6Si2B phase from an alloy with composition
Ti66.7Si22.2B11.1 (at%). The alloys (5 g) were initially
prepared from high purity materials, titanium (min.
99.7 wt%), boron (min. 99.5 wt%) and silicon (min.
99.998 wt%) through arc-melting on a water-cooled copper
crucible under pure argon (min. 99.995%). In order to
produce homogeneous ingots, multiple melting steps were
carried out for each alloy. Before each melting step, a
titanium getter was melted to remove residual O2 and N2
gases from the furnace atmosphere. The mass losses due to
the melting process were lower than 1%. After arc-melting,
the alloys were sealed in thick walled quartz tubes under
argon and heat-treated at 1473 K for 60 h.
The alloys in the as-cast and heat-treated conditions were
characterized through powder X-ray diffraction (XRD) at
room temperature (RT) and Scanning Electron Microsco-
pe/Back-Scattered Electron images (SEM/BSE). For the
XRD experiments the powder was sieved to below 20 mm.
The experiments were carried out in a Seifert ISO-
DEBYEFLEX 1001 diffractometer, using Ni filtered
Cu Ka radiation, angular interval (2q) from 20 to 908;
angular step of 0.058 and 3 s counting time. For the
SEM/BSE analyses, the alloys were hot mounted, ground
using silicon carbide paper (Nos 180–2400) and polished
237
with colloidal silica suspension. The SEM/BSE images
were acquired in a LEO ZEISS 1450 VP equipment.
The HTXRD experiments were carried out from RT up to
873 K under high-vacuum (10K5 mbar) in a Johanna Otto
HDK 2.4 chamber attached to the previously specified
diffractometer. For these experiments, powder samples
(!20 mm) of the heat-treated alloys were mixed with
aAl2O3 and placed on the surface of a tantalum strip heater.
The aAl2O3 was used as internal standard to determine the
actual temperature of the sample in each experiment based
on the well-known variation of its lattice parameters with
temperature [25]. The lattice parameters of the Ti5Si3 and
Ti6Si2B phases and aAl2O3 internal standard at each
temperature were determined using the DBWS-9807a
software [26]. The dependence of the lattice parameters as
function of the temperature was established through linear
and polynomial regression analyses. The thermal expansion
coefficients were calculated through the expression:
 
1 vlT
al Z (1)
l298 K vT p
where:
al linear thermal expansion coefficient
lT lattice parameter value at temperature T
l298 K lattice parameter value at room temperature (298 K)
T temperature
3. Results and discussion
Fig. 1 presents the X-ray diffractograms (RT) of the heat-
treated Ti66Si34, Ti62.5Si37.5 and Ti59Si41 alloys. The
diffractogram of the Ti66Si34 indicates the presence of Tiss
(minor) and Ti5Si3 phases, showing that this composition is
located in the TissCTi5Si3 two-phase field of the Ti–Si
phase diagram [27]. The alloy with Ti62.5Si37.5 composition
is Ti5Si3 single-phase. The Ti59Si41 alloy presented Ti5Si4
(minor) in addition to Ti5Si3, indicating that this compo-
sition is located in the Ti5Si3CTi5Si4 two phase-field of the
Ti–Si phase diagram [27]. These results were confirmed by
the analysis of the SEM/BSE micrographs taken from
these alloys.
Fig. 2 shows the X-ray diffractogram (RT) of the heat-
treated Ti66.7Si22.2B11.1 alloy. The Ti6Si2B, Ti5Si3 and Tiss
phases are identified. However, the intensity of the
reflections indicates that Ti6Si2B constitutes the major
phase, Ti5Si3 and Tiss being present in small amount. This
result shows that the Ti66.7Si22.2B11.1 alloy is located in
TissCTi6Si2BCTi5Si3 three-phase-field of the Ti–Si–B
system at 1200 8C [28]. The existence of this three-phase
microstructure in this alloy was confirmed by SEM/BSE
analysis.
The RT lattice parameters of the Ti5Si3 and Ti6Si2B
phases are shown in Table 1. The values for both phases are
238 G. Rodrigues et al. / Intermetallics 14 (2006) 236–240

Table 1
Lattice parameters of Ti6Si2B and Ti5Si3 phases at RT

Phase Compositions (at%) a (Å) c (Å)

Ti5Si3 Ti66Si34 7.455 (3) 5.145 (3)
Ti 66Si34 Ti5Si3 Ti62.5Si37.5 7.458 (3) 5.149 (3)
Ti5Si3 Ti59Si41 7.456 (3) 5.152 (3)
Ti6Si2B Ti66.7Si22.2B11.1 6.803 (2) 3.337 (2)

Literature values: Ti5Si3 phase: aZ7.4591 Å and cZ5.1515 Å [18],

aZ7.4538 Å and cZ5.1453 Å [19], aZ7.4514 Å and cZ5.1464 Å [21],
Intensity (a. u.)

aZ7.466 Å and cZ5.151 Å [23]; Ti6Si2B phase: aZ6.8015 Å and

20 30 40 50
2θ (deg)
Fig. 1. XRD pattern of the Ti66Si34, Ti62.5Si37.5 and Ti59Si41 alloys after heat-
treatment at 1473 K/60 h, measured at RT (B: Ti5Si3, 6: Ti, C: Ti5Si4).
close to those reported in the literature. Comparing the
lattice parameters of the Ti5Si3 phase in the three binary
alloys, it can be observed that the values of the a and c
parameters remain almost unchanged.
Figs. 3 and 4 show the a and c lattice parameters of the
Ti5Si3 and Ti6Si2B phases as a function of temperature.
Both lattice parameters increase with temperature with no
abrupt variation.
The thermal expansion coefficients of the Ti5Si3 phase in
the three different alloys, calculated using linear
cZ3.3377 Å [24].
Ti 62.5Si 37.5
regression analysis were: aaZ5.88!10K6 KK1, acZ
16.55!10K6 KK1 (Ti66Si34 composition); aaZ5.98!
10K6 KK1, acZ16.64!10K6 KK1 (Ti62.5Si37.5 compo-
sition) and aaZ6.44!10K6 KK1, acZ17.12!10K6 KK1
(Ti59Si41 composition). These results lead to ac/aa ratio
close to 2.7 (2.66–2.81) which compares well with some
Ti59Si41 reported values in the literature (2.9 [18], 2.7 [19] and 2.8
[20]) and confirms the high degree of thermal expansion
anisotropy of the Ti5Si3 phase. Fig. 5 shows the CTE values
of the Ti5Si3 phase calculated from the second order
60 70
polynomials, indicating that the ac/aa ratio of this phase
does not vary significantly with the temperature.
Through linear regression analysis, the CTE values of the
Ti6Si2B phase were aaZ9.7!10K6 KK1 and acZ9.6!
10K6 KK1, leading to ac/aa close to 1 which indicates an
isotropic phase. Fig. 6 shows the CTE values of the Ti6Si2B
phase as a function of temperature calculated from the
second-order polynomial fit. The results indicate that the
anisotropy ratio (ac/aa) does not change significantly in this
temperature range, varying from 1.1 (at RT) to 0.96 at
873 K. This behavior was confirmed through the evaluation
of several other Ti6Si2B-rich samples.
Fu et al. have calculated the thermal expansion
coefficients of 5-3 type transition metal silicides (e.g.
Mo5Si3, Ti5Si3, Mo5SiB2) from first-principles [29].

7.49

7.48
a axis
Lattice parameters (Å)

7.47
Intensity (a. u.)

7.46

7.45
5.20
c axis
5.18

5.16

5.14

300 400 500 600 700 800 900

20 30 40 50 60 70 80 90 Temperature (K)
2θ (deg)
Fig. 3. Lattice parameters of the Ti5Si3 phase in the heat-treated Ti66Si34,
Fig. 2. XRD pattern of Ti66.7Si22.2B11.1 alloy after heat-treatment at Ti62.5Si37.5 and Ti59Si41 alloys as a function of temperature (&: Ti66Si34,
1473 K/60 h, measured at RT (!: Ti6Si2B, B: Ti5Si3, 6: Ti). C: Ti62.5Si37.5, :: Ti59Si41).
 G. Rodrigues et al. / Intermetallics 14 (2006) 236–240 239

6.85 13
6.84
a axis
6.83 12
a axis
Lattice parameters (Å)

6.82
11

αl (10–6K–1)
6.81
6.80 c axis
10
3.355
c axis
3.350 9

3.345
8
3.340
3.335
300 400 500 600 700 800 900 7
300 400 500 600 700 800 900
Temperature (K)
Temperature (K)
Fig. 4. Lattice parameters of the Ti6Si2B phase as a function of temperature.
Fig. 6. Thermal expansion coefficients of the Ti6Si2B phase as a function of
temperature.
The values are in excellent agreement with the reported
experimental data [19,30]. According to their interpretation, (dZ2.848 Å) than that found for Ti1–Ti1 distance in Ti5Si3
the high anisotropy found in Ti5Si3 could be explained by (dZ2.573 Å). Then, the lattice anharmonicity should be
two different mechanisms: in the basal planes, strong lower than that in the Ti5Si3 and consequently, the lower
covalent bonds between Ti–Si atoms seems to play a thermal expansion is exhibited.
dominant role in the aa. On the other hand, closely spaced Ti
atoms along the c-axis increase the lattice anharmonicity,
which should be responsible for the higher thermal
expansion in this direction. In Ti6Si2B, the CTE in the 4. Summary
basal plane (aaZ9.7!10K6 KK1) was found to be higher
In this work we have measured the thermal expansion
than that in Ti5Si3 (aaZ6.0!10K6 KK1). It could be an
coefficients of the Ti5Si3 and Ti6Si2B phases. Confirming
evidence that the bonds in the basal planes Ti6Si2B should
previous investigations, the Ti5Si3-phase exhibited a high
be weaker than that in the Ti5Si3 structure. On the other
thermal expansion anisotropy ac/aaz2.7, value which does
hand, the thermal expansion of Ti6Si2B in c crystallographic
not vary significantly with temperature (298–873 K). In
direction (acZ9.6!10K6 KK1) is smaller than that in
opposition, the Ti 6Si 2B was found to be isotropic
Ti5Si3 (acZ16.6!10K6 KK1). In Ti6Si2B, it could be
(ac/aaz1), which is a beneficial factor for the development
detected Ti atoms forming chains, as in Ti5Si 3. of structural materials containing this phase.
Nevertheless, the Ti1–Ti1 distance in Ti6Si2B is larger

19
Acknowledgements
18
17 The authors gratefully acknowledge the financial support
16 c axis of CNPq and FAPESP through grant Nos. 141884/2001-0
15 and 01/09529-7, respectively.
αl (10–6K–1)

14

7.0
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