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materials

Article
High-Pressure Spark Plasma Sintering (HP SPS):
A Promising and Reliable Method for Preparing
TiAlSi Alloys
Anna Knaislov 1, *, Pavel Novk 1 , Sawomir Cygan 2 , Lucyna Jaworska 2 and Marcello Cabibbo 3
1 Department of Metals and Corrosion Engineering, University of Chemistry and Technology Prague,
Technick 5, 16628 Prague, Czech Republic; panovak@vscht.cz
2 The Institute of Advanced Manufacturing Technology, Wroclawska 37A, 30-011 Krakow, Poland;
slawomir.cygan@ios.krakow.pl (S.C.); lucyna.jaworska@ios.krakow.pl (L.J.)
3 DIISM/Universit Politecnica delle Marche, Via Brecce Bianche, 60131 Ancona, Italy;
marcello.cabibbo@univpm.it
* Correspondence: knaisloa@vscht.cz; Tel.: +420-220-444-205

Academic Editor: Steven L Suib


Received: 23 March 2017; Accepted: 25 April 2017; Published: 27 April 2017

Abstract: TiAlSi alloys are prospective material for high-temperature applications. Due to low
density, good mechanical properties, and oxidation resistance, these intermetallic alloys can be used
in the aerospace and automobile industries. TiAlSi alloys were prepared by powder metallurgy
using reactive sintering, milling, and spark plasma sintering. One of the novel SPS techniques is
high-pressure spark plasma sintering (HP SPS), which was tested in this work and applied to a
Ti10Al20Si intermetallic alloy using a pressure of 6 GPa and temperatures ranging from 1318 K
(1045 C) to 1597 K (1324 C). The low-porosity consolidated samples consist of Ti5 Si3 silicides in an
aluminide (TiAl) matrix. The hardness varied between 720 and 892 HV 5.

Keywords: high-pressure spark plasma sintering (HP SPS); powder metallurgy (PM); intermetallics;
hardness

1. Introduction
The high-pressure spark plasma sintering (HP SPS) is an innovative variant of a well-established
spark plasma sintering method for the sintering of materials, especially superhard materials based
on polycrystalline diamond or cubic boron nitride, ceramic composites, nanopowders, or refractory
materials. Using this and other new SPS methods, it is also possible to synthetize materials with
metastable phases or intermetallic alloys [14]. The HP SPS method belongs to a new generation of
SPS processes, and it was already successfully employed for example for the sintering of ZrC-based
composites [5]. Among these processes, pulsed electric current SPS [1], hot pressing before SPS,
which involves high-temperature exposures and long-term durations [2], and self-propagating
high-temperature sintering prior to SPS [3] are now well-established modern and reliable SPS
techniques. The pulsed electric current SPS has the advantage of heating the compacting system from
outside and inside, which guarantees quite favorable powder densification [4]. The HP SPS is generally
carried out under ultra-high pressure (up to 8 GPa) for a short time. Pressure facilitates the new
arrangement of grains, reduces the diffusion during the sintering of the material, increases the material
density, and eliminates porosity, thus reducing the temperature and sintering duration. The short
sintering time (up to 3 min) decreases the major drawback potential induced by the high-temperature
process, which is the grain growth tendency with temperature and time in the sintered material [6,7].
Moreover, due to the high pressure of the process, it can be expected that the process can be applied

Materials 2017, 10, 465; doi:10.3390/ma10050465 www.mdpi.com/journal/materials


Materials 2017, 10, 465 2 of 8

for intermetallics similarly as for the minerals [8]. Initially, brittle materials after the process will be
Materials 2017, 10, 465 2 of 8
characterized by improved mechanical properties, due to the extended plastic deformation range.
The HPprocess
SPScan be applied for
apparatus intermetallics
(Figure similarly
1) consists of as
a for
high the tonnage
minerals [8]. Initially, brittle
hydraulic press materials
equipped with
after the process will be characterized by improved mechanical properties, due to the extended
Bridgman type anvil and a generator of direct-pulsed current. The entire process of sintering is
plastic deformation range.
managed by a The computer
HP SPS control
apparatussystem.
(Figure The Bridgman
1) consists type
of a high anvil hydraulic
tonnage has a toroidal shape, which
press equipped with helps to
achieve the quasi-isostatic
Bridgman type anvilcompression
and a generatoron ofthe material current.
direct-pulsed due to Thethe entire
plastic deformation
process of sintering ofisthe gasket
managed
with sintered by a computer
material. control system.
The heating The Bridgman
is carried out by type
a 1 anvil
kHzhas a toroidal
pulsed shape, that
current whichpasses
helps directly
to achieve the quasi-isostatic compression on the material due to the plastic deformation of the
through the graphite heater in the gasket and through conductive sintered material as well. This
gasket with sintered material. The heating is carried out by a 1 kHz pulsed current that passes
method ofdirectly
heating, compared
through to conventional
the graphite sintering
heater in the gasket methods,
and through has the
conductive main
sintered advantage
material as well.of a lower
sintering temperature.
This method of heating, compared to conventional sintering methods, has the main advantage of a from the
Another advantage given by direct-pulsed current heating is derived
applicationlower sintering
of very high temperature.
heating and Another advantage
cooling ratesgiven
andby thedirect-pulsed current heating
surface activation is derived by in situ
of powders
from the application of very high heating and cooling rates and the surface activation of powders by
plasma cleaning, which can lead to the synthetizing of new phases [9].
in situ plasma cleaning, which can lead to the synthetizing of new phases [9].

Figure 1. High-pressure spark plasma sintering (HP SPS) apparatus in the Institute of Advanced
High-pressure
Figure 1. Manufacturing spark plasma
Technology, Krakow. sintering (HP SPS) apparatus in the Institute of Advanced
Manufacturing Technology, Krakow.
The techniques of sintering and preparation of intermetallic compounds is quite a challenging
task. For this reason, conventional melting metallurgy has been the most common preparation
The techniques of sintering
method of intermetallic and preparation
compounds yet. Nowadays, of intermetallic compounds
due to the high melting points ofisintermediary
quite a challenging
task. For this reason,
phases conventional
and the exothermic melting metallurgy
reaction during has been new
their formation, the most common
methods preparation
of preparation are method
currently
of intermetallic under investigation
compounds and promising
yet. Nowadays, dueresults
to thestarted
highto melting
appear in points
international journals. In
of intermediary phases
this sense, powder metallurgy may be one of them. It is the rapidly growing technology dealing with
and the exothermic reaction during their formation, new methods of preparation are currently under
the production of powders and then their consolidation. Intermetallic compounds can be produced
investigation and promising
by reactive results
sintering, but started
the high to of
porosity appear in international
the resulting journals.
samples complicates theirInuse
this sense, powder
in many
metallurgybranches
may beofone of them.
industry. It isofthe
The step rapidly
spark plasmagrowing
sintering technology dealing
(SPS) after reactive withcan
sintering thebeproduction
the of
appropriate way to achieve compacted materials virtually without porosity (or
powders and then their consolidation. Intermetallic compounds can be produced by reactive sintering, bearing a minimal
and almost insignificant porosity level) and with good mechanical properties. The HP SPS has been
but the high porosity of the resulting samples complicates their use in many branches of industry.
shown to successfully produce intermetallic compounds [10]. A further issue consists of the porosity
The step oflevel
spark plasma
of the sintering
produced (SPS)
material, whichafter
canreactive sintering
be minimized can be high
by applying the appropriate
pressure during way
theto achieve
compactedsintering
materials virtually
process [1113].without porosity (or bearing a minimal and almost insignificant porosity
level) and with good mechanical properties. The HP SPS has been shown to successfully produce
intermetallic compounds [10]. A further issue consists of the porosity level of the produced material,
which can be minimized by applying high pressure during the sintering process [1113].
TiAlSi alloys could be a substitute of conventional iron- and nickel-based heat resistant alloys
for high-temperature environments, which contain also chromium and other critical raw materials
(CRM) [14,15]. One of the key mechanical properties of the TiAlSi system is the particularly high
wear resistance shown. Therefore, it can be beneficial to consider this alloy as a CRM-free (or low-CRM)
Materials 2017, 10, 465 3 of 8
Materials 2017, 10, 465 3 of 8

material forTiAlSi alloys could beapplications


high-temperature a substitute of and
conventional iron- and
in principle as anickel-based heat resistant
tool material. alloys
High brittleness at
for high-temperature environments, which contain also chromium and other critical raw materials
room temperature is the main drawback of the TiAlSi alloy system, which is likely to be solved by
(CRM) [14,15]. One of the key mechanical properties of the TiAlSi system is the particularly high
modifying the resulting structure through an appropriate and dedicated, processing technology [16,17].
wear resistance shown. Therefore, it can be beneficial to consider this alloy as a CRM-free
(or low-CRM) material for high-temperature applications and in principle as a tool material. High
2. Materials andatMethods
brittleness room temperature is the main drawback of the TiAlSi alloy system, which is likely to
be solved byalloy
Ti10Al20Si modifying the resulting
was prepared by structure through an appropriate
powder metallurgy and dedicated, high-temperature
using self-propagating processing
technology [16,17].
synthesis (SHS), milling, and consolidation by high-temperature, high-pressure spark plasma sintering
in IZTW 2. Krakow. TheMethods
Materials and main problem of the material produced by SHS method itself is a porous and
often very heterogeneous structure. For these reasons, we included milling in a vibratory mill after
Ti10Al20Si alloy was prepared by powder metallurgy using self-propagating high-temperature
SHS and HP SPS
synthesis for subsequent
(SHS), consolidation
milling, and consolidation of the milled powder.
by high-temperature, It wasspark
high-pressure aimed at asintering
plasma formation of a
more homogeneous structure with lower porosity.
in IZTW Krakow. The main problem of the material produced by SHS method itself is a porous and
SHS of pre-pressed
often very heterogeneouspowders Ti10Al20Si
structure. alloy was
For these reasons, conducted
we included for in
milling 30amin in electric
vibratory resistance
mill after
SHS and HP SPS for subsequent consolidation of the
milled powder.
furnace preheated to a temperature of 1173 K (900 C). After the SHS process, the ampoules It was aimed at a formation of a with
samplesmorewerehomogeneous structure with lower porosity.
air-cooled to laboratory temperature. Prepared samples were then milled in vibrating
SHS of pre-pressed powders Ti10Al20Si alloy was conducted for 30 min in electric resistance
laboratory mill VM4 (Brio Hranice, Czech Republic) for 7 min.
furnace preheated to a temperature of 1173 K (900 C). After the SHS process, the ampoules with
In samples
IZTW Krakow, powders
were air-cooled were pre-pressed
to laboratory temperature. at Prepared
100 MPasamples
into discs
were15then
mmmilled
in diameter and 5 mm
in vibrating
high. These greenmill
laboratory bodies wereHranice,
VM4 (Brio then put in the
Czech graphite
Republic) for 7heater,
min. which was subsequently inserted into
In IZTW elements
remaining ceramic Krakow, powders were pre-pressed
of the high-pressure at 100
spark MPa into
plasma discs 15gasket
sintering mm in assembly.
diameter and Sintering
5 mmout
was carried high.at These green bodies
the pressure of 6 were
GPa.then Theput in the graphite
temperatures heater,
were which
chosen was1318
from subsequently
K (1045 C) to
inserted into remaining ceramic elements of the high-pressure spark plasma sintering gasket
1597 K (1324 C). These temperatures were adjusted by calibration for the 40 ms impulse length and
assembly. Sintering was carried out at the pressure of 6 GPa. The temperatures were chosen from
the 20 ms1318impulse
K (1045 C)interval,
to 1597 where temperature
K (1324 C). changedwere
These temperatures with the change
adjusted of the for
by calibration impulse
the 40 msdegree of
filling. The degree of filling is a programmable parameter of the HP SPS device,
impulse length and the 20 ms impulse interval, where temperature changed with the change of the which describes the
percentage of filling
impulse degree of filling.
the programmed
The degree of 40 msisimpulse
filling of 1 kHz
a programmable direct pulsed
parameter of the HP current with initial
SPS device,
whichTemperature
1 ms pulses. describes the percentage
calibration of is
filling of the due
required programmed 40 ms
to the lack impulse of 1 to
of possibility kHz direct pulsed
measure temperature
directlycurrent
duringwith initial 1 ms pulses. Temperature calibration is required due to the lack of possibility to
sintering processes. The duration of the sintering was from 30 to 150 s depending on
measure temperature directly during sintering processes. The duration of the sintering was from
the sintering temperature. Figure 2 shows the prepressed tablet in the form. In Table 1, the conditions
30 to 150 s depending on the sintering temperature. Figure 2 shows the prepressed tablet in the form.
of HP SPS are summarized.
In Table 1, the conditions of HP SPS are summarized.

Figure 2. View of the high-pressure gasket assembly (a); cross-section diagram of the sintering process
Figure 2. View of the high-pressure gasket assembly (a); cross-section diagram of the sintering
(b): 1ceramic gasket (outer part); 2ceramic gasket (inner part); 3ceramic disc; 4sample;
process 5graphite
(b): 1ceramic gasket (outer
disc; 6graphite tube;part); 2ceramic
7sintered carbidegasket
dies. (inner part); 3ceramic disc; 4sample;
5graphite disc; 6graphite tube; 7sintered carbide dies.

Table 1. Conditions of sintering in HP SPS.

Sample Pressure (GPa) Time (s) Degree of Filling (%) Temperature (K)
Ti10Al20Si #1 6 0.2 150 55 1320 50
Ti10Al20Si #2 6 0.2 130 57 1420 50
Ti10Al20Si #3 6 0.2 30 60 1600 50
Materials 2017, 10, 465 4 of 8

This entire experimental work was aimed at a formation of a more homogeneous structure with
lower porosity. For this reason, the appropriate time of heating given by experiences of HP SPS
operators in Krakow was used. At higher temperatures, compared to lower temperatures, it was
not possible to use the same time because there was a higher risk of explosions and damage to the
equipment. This is due to the fact that these materials required a lower pressure range (6 GPa instead
of the maximum 8 GPa) to be obtained with gasket assembly in order to limit the presence of cracks.
When employing a lower range of pressure for this gasket assembly, the applicable temperature and/or
the process time also decrease (the higher the temperature, the shorter the possible sintering duration).
The reference material was prepared from the same powder by conventional spark plasma
sintering at the temperature of 1373 K (1100 C) for 5 min using the heating rate of 100 K/min and
the pressure of 48 MPa in UCT Prague using the FCT HP D10 SPS device (FCT Systeme GmbH,
Rauenstein, Germany).
The microstructure of the TiAlSi alloys was observed by the metallographic optical microscope
Olympus PME3 and was documented using the digital camera Carl Zeiss AxioCam ICc3 (Carl Zeiss,
Jena, Germany) and AxioVision software (version 4.8.2, Carl Zeiss, Jena, Germany). Porosity and pore
size were evaluated by using image analyzer Lucia 4.8. (Laboratory Imaging, Czech Republic) The
electron microscope TESCAN VEGA 3 LMU equipped with an EDS analyzer (SEM-EDS) (SEM: Tescan,
Brno, Czech Republic, EDS: Oxford Instruments, High Wycombe, Great Britain) was used for a more
detailed view of the structure and an identification of present phases. Vickers hardness with a load of
5 kg (HV 5) was measured from 10 indentions into the polished compacted sample.

3. Results and Discussion


In Figure 3, the microstructure of the Ti10Al20Si alloy sintered at various temperatures and
pressures is shown. The samples were etched by Krolls reagent (10 mL of HF + 5 mL of HNO3 + 50 mL
of H2 O). The four prepared compacts showed a very heterogeneous microstructure characterized by
fine sharp-edged Ti5 Si3 silicides embedded in a TiAl matrix. The detected phase composition was
independent from the sintering temperature and applied pressure. In particular, the microstructure of
Figure 2bd clearly showed cracks through the structure. This is likely to be generated by the high
pressure of sintering. On these samples, it is possible to see many microcracks in the silicides, which
are believed to have been initiated and propagated by the thermal expansion of the sharp-edged Ti5 Si3
silicides (essentially because of their morphology).
Phase composition is shown in Figure 4. The phase composition of milled powder and after
compaction is equal. The TiAl10Si20 alloy is characterized by Ti5 Si3 silicides and the TiAl matrix.
The formation of silicide Ti5 Si3 is given by the high mutual affinity of titanium and silicon and its high
thermodynamic stability.
The porosity and pore size of Ti10Al20Si alloys is reported by the histogram in Figure 5.
It shows that the high pressure induced a significant overall alloy porosity reduction and higher
densification. Thus, the Ti10Al20Si alloy sintered at 1597 K (1324 C) showed the lowest porosity
level accounting for less thanq 1%, corresponding to the lowest mean pore size of 11 m (in equivalent
4
diameter calculated as d = A where A is the measured pore area). It is interesting to note that
the mean pore size did not change significantly with increasing sintering temperature in the range of
13731422 K (11001149 C), while, in this temperature range, the porosity volume fraction varied in
the range from 1.2 to 2.2%. These results show that a proper alloy densification can be obtained for
temperatures not below ~1597 K (~1324 C) at 6 GPa.
Materials
Materials 2017,
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465465 5 of5 8of 8

Materials 2017, 10, 465 5 of 8

Figure 3. Microstructure of Ti10Al20Si (a) prepared by SPS at 48 MPa and 1373 K (1100 C);
Figure (b) Microstructure
3. prepared by HP SPSofat Ti10Al20Si (a)(1045
6 GPa and 1318 K prepared by SPS
C); (c) 1422 at C);
K (1149 48 MPa and
(d) 1597 K (1100 C);
1373C).
K (1324
Figure 3. Microstructure of Ti10Al20Si (a)
prepared by SPS at 48
MPa
(b) prepared by HP SPS at 6 GPa and 1318 K (1045 C); (c) 1422 K (1149 C); (d) 1597 K (1324and 1373 K C).
(1100 C);
(b) prepared by HP SPS at 6 GPa and 1318 K (1045 C); (c) 1422 K (1149 C); (d) 1597 K (1324 C).
1: Ti5Si3
2: TiAl
1: Ti5Si3
2: TiAl

Figure 4. XRD patterns of powders after milling and compacted alloys prepared by SPS. 1: Ti5Si3; 2: TiAl.

The porosity and pore size of Ti10Al20Si alloys is reported by the histogram in Figure 5.
It shows that the high pressure induced a significant overall alloy porosity reduction and higher

Figure
Figure 4. 4.XRD
XRDpatterns
patterns of
ofpowders
powdersafter milling
after and and
milling compacted alloys alloys
compacted prepared by SPS. 1:by
prepared TiSPS.
5Si3; 2: TiAl.
1: Ti5 Si3 ;
2: TiAl.
The porosity and pore size of Ti10Al20Si alloys is reported by the histogram in Figure 5.
It shows that the high pressure induced a significant overall alloy porosity reduction and higher
level accounting for less than 1%, corresponding to the lowest mean pore size of 11 m (in
equivalent diameter calculated as = where A is the measured pore area). It is interesting to
note that the mean pore size did not change significantly with increasing sintering temperature in
the range of 13731422 K (11001149 C), while, in this temperature range, the porosity volume
fraction varied in the range from 1.2 to 2.2%. These results show that a proper alloy densification can
Materials 2017, 10, 465 6 of 8
be obtained for temperatures not below ~1597 K (~1324 C) at 6 GPa.

Porosity
Figure 5. Figure and and
5. Porosity pore
poresize ofthe
size of the Ti10Al20Si
Ti10Al20Si alloy prepared
alloy prepared by SPS
by SPS and HP SPSat different
and HP SPS at
temperatures.
different temperatures.

The hardness measurements, performed on three different HP SPS Ti10Al20Si intermetallic


The hardness
alloy samples, measurements,
varied from 720performed on three
to 892 HV 5 (Figure different
6). For HP SPS Ti10Al20Si
a sake of comparison, intermetallic
the hardness value
of the same
alloy samples, varied alloy prepared
from 720under
to 892a pressure
HV 5 of(Figure
48 MPa and
6). using
For aaconventional SPS at UCT Prague
sake of comparison, the hardness
is also reported by the histograms in Figure 5. All three alloys prepared by HP SPS had a greater
value of the same alloy prepared under a pressure of 48 MPa and using a conventional SPS at UCT
hardness than the conventional SPS Ti10Al20Si alloy. In particular, the hardness reached a
Prague is also
maximum reported by temperature
at HP SPS the histogramsof 1597in Figure
K (1324 C),5.
so All three
the most alloyscompacted
properly prepared by HP SPS had a
intermetallic
greater hardness than the
alloy exhibited the conventional SPSThese
hardness of 892 HV. Ti10Al20Si
results show alloy. In particular,
an improvement whenthe hardness
compared withreached a
previously published data on similar binary
intermetallic alloys (TiAl)
maximum at HP SPS temperature of 1597 K (1324 C), so the most properly compacted intermetallic produced by conventional
SPS at various temperatures up to 1373 K (1100 C) [18].
alloy exhibited the hardness of 892 HV. These results show an improvement when compared with
previously published
Materials data on similar binary intermetallic alloys (TiAl) produced by conventional
2017, 10, 465 7 of 8 SPS
at various temperatures up to 1373 K (1100 C) [18].

Figure 6. Hardness
Figure of the
6. Hardness of Ti10Al20Si alloy
the Ti10Al20Si alloyprepared bySPS
prepared by SPS and
and HPHP
SPSSPS at various
at various temperatures.
temperatures.

4. Conclusions
The TiAlSi alloys were successfully prepared by the HP SPS method in the Institute of
Advanced Manufacturing Technology in Krakow. This method has shown favorable potentials in
the case of preparation of intermetallic alloys of the TiAlSi system (namely, a Ti10Al20Si alloy
was produced). The resulting structure of the alloys exhibits low porosity (up to 1.5 vol %) with a
relatively small size of pores, but we can often see cracks through the structure and in the silicides,
which can be caused by a high pressure of sintering and/or relatively quick cooling after SPS. In
Materials 2017, 10, 465 7 of 8

4. Conclusions
The TiAlSi alloys were successfully prepared by the HP SPS method in the Institute of Advanced
Manufacturing Technology in Krakow. This method has shown favorable potentials in the case of
preparation of intermetallic alloys of the TiAlSi system (namely, a Ti10Al20Si alloy was produced).
The resulting structure of the alloys exhibits low porosity (up to 1.5 vol %) with a relatively small size
of pores, but we can often see cracks through the structure and in the silicides, which can be caused
by a high pressure of sintering and/or relatively quick cooling after SPS. In particular, the maximum
temperature of 1597 K (1324 C) at 6 GPa of the HP SPS process was able to show an alloy porosity
lower than 1 vol % with a mean pore size of ~10 m and a quite high hardness HV5 of approximately
900. Therefore, for all those applications, where high hardness is necessary, the high-pressure SPS
sintering seems to be a promising and reliable new SPS technique.

Acknowledgments: This research was supported by COST Action CA15102 and Czech Science Foundation,
project No. P108/12/G043.
Author Contributions: Anna Knaislov coordinated the work, compiled the paper, and prepared the initial
powders. Pavel Novk worked as a scientific supervisor and ensured an evaluation of results. Sawomir Cygan
realized HP SPS sintering. Lucyna Jaworska designed the HP SPS experiment. Marcello Cabibbo did a literature
review and helped with the discussion of the results.
Conflicts of Interest: The authors declare no conflict of interest.

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