Metal Powder Report  Volume 00, Number 00  May 2016 metal-powder.

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Powder metallurgy for thermoelectrics
Andrei Melnikov1,2
1
National University of Science and Technology MISIS, 4, Leninskiy Pr., 119049 Moscow, Russia
2
Crystal Ltd., 45B, Stantsionnaya Str., 141060 Korolev, Russia

Thermoelectric materials, which directly convert thermal energy into electricity, have become quite
popular recently due to the development and world spreading of alternative power energy sources.
Nowadays powder metallurgy methods are widely used for production of almost all types of
thermoelectric (TE) materials, from low-temperature bismuth-telluride-based materials to high-
temperature (operating above 1000 K) Cu2 xSe alloys. Historically, crystallization methods were widely
used in production [1], for example, Czochralski method, Bridgman method and zone melting method
are the most common. However, in case of crystallized materials, we face one disadvantage that is weak
mechanical properties. In TE devices working bodies in the devices are bulk TE materials with
dimensions about millimeters, so they can be exposed to different shifts or tensile stresses. Therefore,
powder metallurgy methods were used to improve mechanical strength, in particular, various sintering
methods. Later, it was found that sintering from powders allows to reduce one significant parameter
for thermoelectrics thermal conductivity, and in the 2000s the propagation of powder technologies
started over.

Traditionally there were two stages of powder method production:
first, synthesis and crystallization [1], and then, grounding and
sintering by hot vacuum pressing, which is the simplest and the
most cost-effective from all powder metallurgy technologies used.
Then, with the invention of powerful ball mills, mechanoactivation
was applied. It allows to eliminate the process of crystallization
synthesis, and yet, due to the complexity of TE materials, the
complete formation of solid solutions without any initial phases
was not always possible to achieve [2]. Extrusion is one of the
promising technologies. The samples prepared by this method
are very dense and solid. The quality factor of the material (which
will be described below) is very high too, but the structure seems
rather isotropic, which is typical of many powder technologies, so
the N-type conductivity material, which is sensitive to anisotropy,
turned out to be markedly worse than P-type. However, with the
usage of some improved technologies, for example, equal channel
E-mail address: q.melnikov@gmail.com.
angular extrusion, it is possible to achieve certain texturing and high
properties of n-type material [3]. The Spark Plasma Sintering and the
melt spinning as the two most promising powder technologies for
preparing thermoelectric materials will be described in detail below.
Melt spinning
In metallurgy, melt spinning (MS) is a process of obtaining ribbons
and powders of solid material based on fast cooling of a melt by
rotating cold wheel or plate. Since 1960s [4] this process has been
used to make different amorphous metal alloys, usually magnetic
Fe, Ni, Al and Mg alloys [58]. Then, in 1980s, it was adapted for
thermoelectric BiTe and BiSb alloys [911]. The principal scheme
of the process is shown in Fig. 1. The whole process is usually
conducted in the defensive Argon atmosphere. The material is
loaded into a quartz ampoule with a nozzle and heated to the
temperature a bit higher than the melting temperature, by the
induction heating. The surface tension does not allow melt to spill
out freely, but after applying more pressure a stream of melt drips

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SPECIAL FEATURE Metal Powder Report  Volume 00, Number 00  May 2016

Dimensions of such samples usually vary from microns to

several millimeters. Finished the MS process, materials could be
considered either as finished commercial product (such as ribbons)
and follow to further cutting and other treatment stages, or
compacted to a bulk material with macroscopic dimensions with
the usage of powder metallurgy technologies such as Spark Plasma
Sintering.

Spark Plasma Sintering

Spark Plasma Sintering (SPS) is a newly developed process of
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FIGURE 1
Principal scheme of melt spinning.
FIGURE 2
Melt spinning on Youtube.
onto the wheel, cools and solidifies in the shape of a ribbon or its
pieces. This process may be very fast and spectacular (Fig. 2). Due
to high crystallization rate up to 104107 K/S [12], atoms do not
have time to take places in the crystal lattice, forming an amor-
phous structure in metals, which can be very useful in various
fields of industry. The shape of the finished product depends on its
composition, the conditions of its preparation and the purposes of
the manufacturer (Fig. 3), but almost always its shape and structure
are both curious and interesting.
material sintering, but it has its origins in the 30s when electric
current flow sintering was developed [13]. Further, in the 60s pulse
current was applied [14], but the method became widely used only
in 2000s due to the high-amperage pulsed DC generators and wide
fields of their applications.
SPS represents modified uniaxial hot pressing. Pressure is ap-
plied to materials as usual, by the two punches in a pressing die,
but the heating is due to the direct pulsed current flow through the
material, punches and graphite dies. The scheme of the process is
shown in Fig. 4. It is considered that pulsed DC current promotes
strong electrical discharge in the gaps between particles of the
material which causes an electric spark and local hot plasma with
temperature up to thousands K momentarily [13]. This causes
evaporation and melting on the surface of particles in the SPS
process, thereby activating mass transfer and sintering process.
Such direct heating of the material leads to ultra-intense heating
rate up to 300 K/min [15] and, consequently very short sintering
time (about several tens of minutes) which is the greatest
advantage of SPS technology, compared to others. The process
takes place in vacuum chamber with a defensive atmosphere.
Punches serve as electrodes and usually are water-cooled.
During the process, a pressing die and punches could be red-hot
heated (Fig. 5). After the process is finished, the material is pressed
to very solid and dense cylindrical samples (Fig. 6). Unfortunately,
the dimensions of the pressed samples are limited to about tens of
millimeters, which restricts mass production, but due to wide
spreading of the technology it is hoped that this drawback will
be overcome in the future.
Thermoelectricity underlying
The SPS can be used for thermoelectrics to sinter grounded
crystallized, mechanically activated and melt spun materials. A

FIGURE 3
Melt spun product: (a) Mg alloy ribbon by Franhoufer IFAM, (b)
AzoMaterials aluminum ribbon and (c) Molycorp Magnequench MQP FIGURE 4
powders. Spark Plasma Sintering scheme.

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Metal Powder Report  Volume 00, Number 00  May 2016 SPECIAL FEATURE

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FIGURE 7
Two thermoelectric effects.

noted that usually melt spinning combined with rapid sintering is

FIGURE 5
Inside of SPS camera Fraunhofer IFAM, Dresden.
FIGURE 6
Sample compacted by SPS.
combination of the two technologies (MS-SPS) is popular in ther-
moelectrics and is used in production of very different materials
[1621], but the greatest amount of works is dedicated to produc-
ing low temperature BiSbTeSe-based materials [2229]. It can be
aimed to develop multiscale nanostructures and, due to that, to
improve the TE performance.
Thermoelectricity is related with two mutually opposite ther-
moelectric effects: the Seebeck effect and the Peltier effect (Fig. 7).
The phenomenon consists in electric power or heat flow genera-
tion when applying heat load or direct electric current correspond-
ingly in a circuit of opposite charge carrier semiconductors
connected in series. A number of such semiconductor legs con-
nected this way provide TE devices Peltier modules (Fig. 8), which
serve as an assembly unit for more complex systems and can be
used for both effects applications.
TE performance of the devices mainly depends on the quality of
materials. The quality factor for a TE material is the dimensionless
figure-of-merit ZT, which is determined as ZT = a2sT/k, where a is
the Seebeck coefficient, V K 1; s is the electrical conductivity,
Ohm 1 m 1; T is a temperature, K; and k is the thermal conduc-
tivity, W m 1 K 1. Enhancing of ZT parameter with optimization
of intrinsic properties is the main aim of the thermoelectricity.
Now ZT of commercial materials is about 1, and these materials are
used in very specific fields such as stabilization of the telecommu-
nication cabinets temperature or power generation in distant
space flights (second sounds cool, right?). But if ZT would be
tripled, thermoelectricity could be used more widely as an alter-
native power source along with solar cells and wind turbines.
Powder metallurgy technologies are generally used to reduce
thermal conductivity and increase mechanical strength of TE

FIGURE 8
Peltier modules.

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FIGURE 9
Fine structure of melt spun BiSbTe alloy.
materials. When bulk material is compressed and sintered from
smaller particles, a large number of grain boundaries are generated,
on which phonon scattering occurs, reducing the lattice thermal
conductivity and, consequently, increasing the ZT parameter. A
negative feature coming from these technologies is crystal struc-
ture disorder which reduces electrical conductivity. Therefore,
scientists are forced to find the balance between these two. In
the next paragraph I describe my work with it, which, of course,
you can scroll with relief as boring science stuff. To make the long
story short, everything is complex.
Study of structural, dimensional and thermoelectric
properties of MS-SPS materials
A remarkably fine structure can be found in BiSbTe-based TE
materials obtained by MS technique (Fig. 9) [28]. The particles
FIGURE 10
SEM images of cross section of SPSed samples at different time and
temperature of sintering.
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Metal Powder Report  Volume 00, Number 00  May 2016
have the shape of flat plates whose dimensions are about hundreds
of microns and whose thickness is about 30 mm. The flat sides of
the particles are parallel to the cooled plane of the rotating wheel.
Particles consist of many submicron crystals connected together
with the gaps between them forming a columnar-like structure.
This unique structure seems to provide an advantage in TE prop-
erties, therefore, the main aim of the work was to sinter the
material in bulk shape and prevent the structure from degrading
under the thermal influence. It is assumed that due to very short
sintering time (about several minutes) and high heating rate Spark
Plasma Sintering preserves the structure. An experiment was con-
ducted in [29] to study the thermal influence on the structure, its
orientation and the TE properties of the material. Samples were
sintered by SPS at different time and temperatures and optimal
condition was aimed to be found.
It was established that even at rather short sintering time (5
10 min) active recrystallization processes take place, which signif-
icantly change the structure (Fig. 10). Sintering time did not
strongly affect the final structure of the material, while the influ-
ence of temperature was substantial. It seems that the original
structure was completely reorganized. The smallest fracture was
FIGURE 11
Improvement of ZT-value during years by [3038].
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Metal Powder Report  Volume 00, Number 00  May 2016
FIGURE 12
Number of articles on the topic published every year by Google Scholar.
preserved at 4108C only, and was absorbed by a larger fraction with
increasing sintering temperature alongside with pore formation.
According to XRD-patterns taken from the two mutually perpen-
dicular faces of samples, we investigated the orientation of the
structure. It was shown that due to the polycrystalline nature of
the material and sintering particularities, there were no strong
texture in all sintered samples, but there was slight predominant
orientation for (0 0 1) planes which disappear with increasing
sintering time.
Also, TE properties were measured and it was found that the best
observed properties are in a direction of a current parallel to the
pressure axis. The greatest amount of power factor, which is
calculated as PF = a2s was observed for the sample sintered at
4108C, one with finest structure preserved. But, it demonstrated
not so great mechanical properties, due to its small bulk density.
Thus, by results of the work, it can be concluded that the optimal
MS-SPS conditions of thermoelectrics will be those, which provide
minimal temperature influence on the material (such as reduced
sintering temperature or time) and ensure sufficient sintering for
satisfactory mechanical properties.
A few words about current situation
You already know that the main quality factor of thermoelectrics
affecting the development of all the field is the ZT parameter.
Figure 11 shows a dramatic increase of ZT values, which can be
found in science works, collected by Heremans et al. [30] and
complemented with data [3138]. We see that ZT is doubled since
1990, a jump in 2000s is due to the nano-revolution, of course.
But, to be honest, I drew a subjective my-own-understanding trend
for commercial mass production low-temperature materials, as, if
High-ZT materials were cost-effective, they certainly would have
been used in mass production of the final devices, and it would not
go unnoticed. But anyway, this is a normal and correct forward
movement of science, I think, and, of course, some time later, a
jump will take place for commercial materials too.
From Fig. 12 we can see a number of scientific works connected
with MS, SPS and MS-SPS. It is clearly seen that every year an
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SPECIAL FEATURE
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amount of articles published for all key-phrases increases. In 2011
a number of papers on Spark Plasma Sintering exceeded that for
melt spinning, which confirms a high degree of technology
interest. The number of articles dedicated to the application of
these technologies in thermoelectrics has also increased and with
the same or even higher increasing rate. So, as one can see, a work
is in full swing.
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