Int.

Journal of Refractory Metals & Hard Materials 28 (2010) 550–557

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Int. Journal of Refractory Metals & Hard Materials

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Densification behaviour of pure molybdenum powder by spark plasma sintering

R. Ohser-Wiedemann *, U. Martin, H.J. Seifert, A. Müller
Institute of Materials Science, TU Bergakademie Freiberg, Gustav-Zeuner-Str. 5, 09599 Freiberg, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Pure molybdenum was sintered with SPS under various temperatures, external pressures and heating
Received 18 December 2009 rates. The microstructure of the specimens representing the different sintering conditions was investi-
Accepted 15 March 2010 gated by classical metallographic methods. The relative density, the microhardness and the chord length
distribution were measured. Linear shrinkage, depending on time or temperature, was calculated from
piston travel, which was recorded during sintering process. These results show that the main part of con-
Keywords: solidation takes place during fast heating up. The densification behaviour is controlled mainly by sinter-
Molybdenum
ing temperatures and applied pressure. The molybdenum powder was successfully consolidated by SPS in
Spark plasma sintering
Densification
very short times. A relative density of 95% was reached by sintering temperatures of 1600 °C and external
Microstructure pressure of 67 MPa.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction This allows the sintering of nanosized or metastable powders

Pure molybdenum (Mo) is an important refractory metal used
for a wide scale of engineering applications, due to advantageous
properties. Some examples are ribbons and wires for lighting tech-
nology, semiconductor base plates for power electronics, elec-
trodes for glass melting, parts for high-temperature furnaces,
spraying wires for automotive industry and sputter targets or
evaporation sources for coating technology. Components from
pure molybdenum or its alloys are produced either by powder
metallurgy or by melting processes. Generally, powder metallurgi-
cal route is preferred since a fine-grained microstructure is ob-
tained, which improve the mechanical properties of final
products considerably. Additionally, the powder route is the exclu-
sive possibility for production of molybdenum–copper–alloys or
for doping molybdenum with high-temperature resistant oxides
[1].
Spark plasma sintering (SPS) is a new technology for compac-
tion of metallic or ceramic powders. It is a short-time sintering
process, where powder particles are compacted by uniaxial press-
ing and heating simultaneously. The heating results from a pulsed
electric field and a high heating rate of more than 100 K/min can be
achieved.
Compared to conventional sintering methods applying external
pressure like Hot Pressing (HP) or Hot-Isostatic-Pressing (HIP),
densification by SPS is extremely fast. Thus, the sintering temper-
atures can be lower which limits the grain growth.
* Corresponding author. Tel.: +49 3731 39 2647; fax: +49 3731 39 3657.
E-mail address: ohser@ww.tu-freiberg.de (R. Ohser-Wiedemann).
close to the theoretical density with slight grain growth or reten-
tion of metastability as well as cleaned grain boundaries. Further
advantages are sintering of powders without any additives, no
need of cold compaction and less sensitivity to initial powders
characteristics. SPS is therefore an economical alternative to con-
ventional sintering [1–9]. However, the densification mechanism
during SPS process is unclear as yet [8]. It is assumed that small
spark discharges appear between individual powder particles caus-
ing locally high temperatures in few minutes. These high temper-
atures induce vaporization or melting of the powder surface,
destruction of oxide layers and raising sinter activity. Necks be-
tween the powder particles are formed. This and the high compres-
sive force lead to the sintering of the particles [2,3,5,10]. However,
the existence of spark plasma in SPS process is not clearly demon-
strated, in particular when non-conductive powders are used.
However, the fundamental effect of electric current on mass trans-
port has been clearly shown, elucidated in [8]. The electrical cur-
rent affects also the diffusion kinetics of reaction between
different phases, for example between Mo and Si, see [6]. Early
densification stages of nanocrystalline ceramics by SPS were dis-
cussed by Chaim [7], where the author identified two atomistic
mechanisms. Nanocrystalline ceramics with low yield stress were
mainly compacted by plastic deformation. Ceramics with high
yield stress consolidate dominantly by collective grain rotation
and sliding. This is a hint on the important role of applied pressure
during spark plasma sintering.
First studies on short-time sintering of molybdenum powders
by Plasma Pressure Compaction (P2C) are reported in [9,11,12].
Similar to the SPS process, the powders were filled in a graphite
die. The heating by P2C was carried out at first with pulsed electric

0263-4368/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijrmhm.2010.03.003
 R. Ohser-Wiedemann et al. / Int. Journal of Refractory Metals & Hard Materials 28 (2010) 550–557
current up to 1100 °C, followed by heating with constant current
up to the final sintering temperature. Microsized powders (average
size 47 lm) were consolidated at 1650 °C, 48 MPa, for 1–2 min, up
to a relative density of 98%. ‘‘Nanosized” powders (average size
0.1 lm) were sintered at lower temperatures (1400 °C, 48 MPa,
3 min) up to a relative density of 97%. The smaller grain size of
nanocrystalline samples leads to a higher microhardness (2.95
GPa) in comparison to the microcrystalline samples (2.16 GPa).
Clean grain boundaries coupled with uniform grain structure were
taken as evidence for the occurrence of surface cleaning during
plasma activation stage.
Furthermore, Mo–Si–B multiphase alloys were successfully con-
solidated by SPS at 1200 °C and an applied pressure of 40 MPa [13].
Unfortunately, the relative densities after sintering are not
specified.
The motivation of the present work was to estimate the best SPS
conditions for consolidation of pure molybdenum powder and to
achieve information about the densification behaviour of molybde-
num during this process, compared with short-time sintering by
P2C and isothermal sintering.
2. Experimental
Pure molybdenum powders (99.95 wt%) with particle size of 3–
5 lm (produced by Plansee Metall GmbH Austria) were consoli-
dated by SPS. Before consolidation, the powder contains an oxygen
impurity of 400 ppm, as indicated by the producer of the material.
The powder particles (Fig. 1) are of spherical shape, some of them
include small pores. The particles agglomerates and tend to form
chains. The powders contain a fraction of fine particles with sizes
<1 lm.
The powders were filled without any additives in cylindrical
graphite dies either of 20 or 40 mm in diameter. The sintering runs
in a FCT-HP D 25 spark plasma sinter equipment, manufactured by
FCT Systeme GmbH (Germany). The compaction of all batches
starts with raising the external pressure up to 29, 57 and 67 MPa,
respectively, followed by heating up to temperatures between
850 and 2000 °C under vacuum. The heating rate was diversified
between 130 and 360 K/min, and the holding time at maximum
temperature was 3 min for all batches. The pulse pattern of the
electric current was adjusted on 2:1 (10 ms pulse time, 5 ms pause
time). The compaction pressure decreased during cooling step.
Fig. 2 gives an example of two typical SPS runs. Table 1 contains
sintering parameters of all batches.
The densities of all consolidated bulk molybdenum specimens
were measured by the Archimedes technique [14,15]. The relative
Fig. 1. Molybdenum powder before consolidation.
551
Fig. 2. Typical SPS runs with different heating rates.
densities were calculated based on the theoretical density of
10.28 g cm 3, listed in [1].
The microstructure was studied by optical microscopy as well
as by scanning electron microscopy at cross sections (sections par-
allel to the acting force). The preparation steps were grinding,
mechanical polishing up to 3 lm diamond abrasive, followed by
short electrolytic polishing and chemical etching using Murakami’s
reagent (a solution mixture of 2.5 g potassium hydroxide, 2.5 g
potassium ferricyanide and 50 ml of distilled water).
For the batches 3.1–3.7, the grain size was estimated by con-
ventional metallographic methods. In our setting, the grain size
distribution is defined as the chord length distribution, which
was measured at least as five measuring fields per cross sections
using the software ‘‘a4i Analysis” of aquinto AG.
The hardness of bulk molybdenum specimens was measured at
cross sections either by nanohardness tester (CSM Instruments) or
by microhardness tester (LECO Instrumente GmbH). The nanoin-
dentations were generated using a BERKOVICH-indenter, which
was loaded with a maximum load of 30 mN. The indentations
(20 in samples with high density, 40 in samples with low density)
were individually located inside of grains, away from grain bound-
aries and pores. Basing on the recorded load-displacement-curve,
the indentation hardness and the indentation modulus were calcu-
lated as described in [16]. The microhardness HV0.1 was measured
with a VICKERS indenter.
The X-ray diffraction (XRD) spectra of the carburized outer zone
were recorded with URD65 (Seifert FPM) powder diffractometer
using Cu–Ka radiation and a graphite monochromator in the dif-
fracted beam. The PDF data base [17] was used for qualitative
phase analysis. Quantitative pole figures were obtained by measur-
ing with the XRD system D8-Discover from Bruker AXS using Co–
Ka radiation.
3. Experimental results
3.1. Density
The measured densities and the calculated relative densities of
all sintered samples are listed in Table 1. Fig. 3 shows the relative
densities depending on sintering temperatures and pressures. The
correlation between relative density and temperature follows the
well-known sigmoid course of heating up during isothermal sinter-
ing. A relative density of 95% and higher can be reached if the sin-
tering temperature excites 1600 °C and the external pressure
amounts 57 MPa or more. In the experiments with low external
pressure of 29 MPa, the relative density does not exceed 95% even
at high temperatures. This indicates the applied pressure as an
important factor for the densification during the SPS process. The
heating rates, studied in the present article, do not influence the
552 R. Ohser-Wiedemann et al. / Int. Journal of Refractory Metals & Hard Materials 28 (2010) 550–557

Table 1
Sintering parameters and results of density and nanohardness measurements.

Batch Heating rate (K/ Final sintering Pressure Final density (g/ Final relative Indentation hardness Indentation modulus
min) temperature (°C) (MPa) cm3) density (%) (MPa) (GPa)
1.1 130 1600 29 9.19 89.4 1766 ± 194 214 ± 22
1.2 130 1800 29 9.47 92.1 1646 ± 185 280 ± 43
1.3 130 1900 29 9.50 92.4 1810 ± 138 227 ± 21
2.1 200 1400 57 9.30 90.5 1765 ± 194 214 ± 22
2.2 130 1600 57 9.70 94.4 2009 ± 169 246 ± 16
2.3 360 1800 57 9.80 95.3 1934 ± 88 281 ± 30
2.4 360 1900 57 9.80 95.3 2025 ± 143 288 ± 26
3.1 200 850 67 5.96 58.0 – –
3.2 325 1100 67 7.18 69.0 1504 ± 279 123 ± 13
3.3 200 1400 67 9.24 89.9 1665 ± 220 233 ± 28
3.4 280 1600 67 9.77 95.0 2085 ± 99 260 ± 21
3.5 340 1800 67 9.84 95.7 2152 ± 96 289 ± 29
3.6 360 1900 67 9.85 95.8 2151 ± 84 291 ± 31
3.7 200 2000 67 9.88 96.1 1751 ± 91 288 ± 31

Fig. 3. Relative density of spark plasma sintered molybdenum vs. sintering

temperature, compared with other published data.
Fig. 4. Results of nanohardness measurements depending on sintering temperature
and relative density.

density of molybdenum samples, significantly. This is in accor-

dance with the densification behaviour of copper powders with
and indentation modulus (Fig. 4, Table 1). Sintered bodies with
SPS [10]. Finally, it is observed that the density of spark plasma sin-
low density apparently exhibit lower hardness and modulus.
tered bulk molybdenum is primarily controlled by external pres-
If pores occur beneath grains, the indentation process is over-
sure and temperature.
lapped by elastic recovery, plastic deformation or crack propaga-
Our results are in good agreement with the P2C results in
tion. In order to exclude the influence of porosity, measured
[9,11,12], where a relative density of 98% was measured at
hardness values of each sample were divided by their relative den-
1650 °C and at 48 MPa external pressure. Additionally, we compare
sity. In this case, the indentation hardness’s of all investigated sam-
the densities obtained by SPS with those of isothermal sintering.
ples are in the same range, independent on sintering conditions.
The isothermal powder metallurgical route starts with hydraulic
The average indentation hardness is 2057 ± 152 MPa, which corre-
or isostatic pressing of the molybdenum powder into rods and
sponds to results of hardness measurement of P2C sintered molyb-
plates of various geometries and dimensions. The sintering process
denum powders in [12]. Furthermore, the indentation modulus
is carried out in furnaces at high temperatures (typically in the
depends on the porosity. At relative densities up to 95%, an average
range of 1800–2200 °C) and in hydrogen atmosphere over long
value of 297 ± 12 GPa can be calculated which shows an excellent
times (2–3 h) to get densities about 90% of the theoretical density
agreement with Youngs modulus of 305 ± 2 GPa, measured with an
[1,18–24]. For higher densities, hot rolling, extrusion or forging at
ultrasonic scanner at different sintered molybdenum samples, and
temperatures in the range 1200–1500 °C are subsequently used
with values from literature for example in [1,24]. The sintering
[1]. Fig. 3 contains relative densities published in [19], which were
temperature of 2000 °C leads to a softening of the material caused
estimated after 1 h isothermal sintering. For temperatures higher
by the large grain size, but keeping the indentation modulus
than 1400 °C, the comparison shows that the relative densities of
constant.
SPS are comparable or higher than relative densities generated
by isothermal sintering, although the sintering time is very short
at SPS. At lower temperatures isothermal sintered molybdenum 3.3. Microstructure
bodies becomes denser caused by the higher green density due
to higher compaction pressure. Fig. 5 gives an impression of microstructure development
depending on raising sintering temperature at constant external
3.2. Nanohardness pressure of 67 MPa. The cross sections exhibit relatively large
pores and the observed porosity does not agree with that measured
In spite of marginal loading during nanoindentation, porosity by Archimedes technique. The difference is a consequence of prep-
has also strong influence on the values of indentation hardness aration by electrolytic polishing. Caused by the low hardness of
 R. Ohser-Wiedemann et al. / Int. Journal of Refractory Metals & Hard Materials 28 (2010) 550–557
Fig. 5. Scanning electron micrographs of the microstructure of molybdenum at different sintering temperatures, SPS at 67 MPa pressure.
molybdenum (see above), a deformation layer is generated by
mechanical grinding and polishing on the cross sections surface.
This deformation layer covers the real microstructure. Addition-
ally, pores can be filled during grinding and mechanical polishing.
To remove the deformation layer, electrolytic polishing is nec-
essary. The polishing conditions have to be chosen in such a way
that the deformation layer is removed completely. However, it is
unavoidable then to enlarge existing pores strongly during this
preparation, whereas the etching extends the pores in minor
way. The single preparation steps are demonstrated in Fig. 6. After
mechanical grinding and polishing the surface appears without
contrast, it exhibits small pores and several scratches. At higher
magnification the deformation layer is detectable clearly. After
electrolytic polishing the surface is clean, the scratches are re-
moved, grain boundaries become apparent, but the pores are
strongly enlarged. In contrast, only small material erosion takes
place during etching.
The first compact sample was produced with maximum sinter-
ing temperature of 850 °C and pressure of 67 MPa. Under these
conditions a body of high porosity was obtained, where the shapes
of origin powder particles are well preserved (Fig. 5). The original
shape of particles retains up to sintering temperature of 1100 °C,
even if the densification is higher. This is in good agreement with
isothermal sintering of molybdenum, where a grain structure at
1100 °C does not appear [19].
At temperatures of 1400 °C or higher, the original shapes of the
powder particles get lost and the formation of a polyhedral micro-
553
structure is observed. The sample still exhibits open porosity, the
pores are irregularly shaped and exist mainly between the grains.
The average grain size is larger than the initial average grain size.
Further increasing of temperature initiates a strong grain growth,
which was not expected in such a manner at short-time sintering.
For sintering temperatures higher than 1600 °C, the porosity is
lower than 5%, i.e. closed porosity appears. The pore size decreases
and pores exhibit a more and more spherical shape. Pores are dis-
connected from grain boundaries during grain growth and are lo-
cated mainly inside the grains.
At the highest temperatures, an agglomeration of pores at grain
boundary triples can be observed. Plane grain faces and grain
boundary angles of about 120° are observed, which is typical for
polycrystalline metals, since the surface stress of the most grain
boundaries is similar. In contrast to isothermal sintering of molyb-
denum in [19], no abnormal grain growth was observed.
To investigate accurately the relationship between grain growth
and temperature, the chord length distribution of the grains was
measured in samples sintered with 67 MPa. Fig. 7 shows the rela-
tive frequency of chord length depending on sintering tempera-
ture. A continuous grain growth starts at temperatures higher
than 1400 °C. This is closely related to a broadening of the grain
spectrum. Also, during isothermal sintering this effect occurs, but
in contrast, it depends on sintering time [10]. When plotting the
mean chord length vs. the sintering temperature in a log–log scale,
two straight lines of different slope can be adapted to the date
points (Fig. 8). The straight lines intersect at the initial temperature
554 R. Ohser-Wiedemann et al. / Int. Journal of Refractory Metals & Hard Materials 28 (2010) 550–557
Fig. 6. Preparation steps of cross sections: (a) mechanical grinded and polished; (b) electrolytic polished; (c) etched and (d) deformation layer after mechanical grinding and
polishing. Hardness indentation marks the equal position on sample surface.
Fig. 7. Grain growth of molybdenum by SPS process.
Fig. 8. Log–log plot of grain growth (67 MPa pressure) vs. sintering temperature.
for the grain growth. For pure molybdenum the initial temperature
is about 1330 °C, which corresponds to a homologous temperature
of 0.56 Tm.
Fig. 9 shows the grain size as a function of the sintering temper-
ature of our experiments compared with those obtained for iso-
thermal sintering [19,20]. The data are normalized by the initial
Fig. 9. Grain size, normalized by initial grain size, as a function of the sintering
temperature of our experiments compared with those obtained for isothermal
sintering.
grain size. Up to about 1700 °C the grain sizes of SPS samples are
smaller than those of isothermal sintering. This effect is due to
the shorter sintering times of SPS. Finally, the starting temperature
of grain growth was calculated from the slope of the curves for iso-
thermal sintering (as in Fig. 8). The grain growth starts at temper-
atures between 950 and 1035 °C, which are lower than the SPS
starting temperature of 1330 °C. The huge difference is a conse-
quence of the fast heating up in the SPS process.
The contact of molybdenum powder with the graphite die and
sheets leads to diffusion of carbon inside the samples, although
the spark plasma sintering is a short time process. The micrograph
(Fig. 10) shows a sharp transition between carburized region and
uninfluenced molybdenum body. The thickness of the layer de-
pends on temperature and can reach 200 lm at 2000 °C. The layer
grows in a parabolic manner, which allows a rough estimation of
the activation energy of carbon diffusion in molybdenum. We give
an estimate of 180 kJ mol 1, which is in agreement with the values
of literature, e.g. in [25]. The carburization kinetics is comparable
with the boriding kinetics in molybdenum under SPS conditions,
investigated in [26].
 R. Ohser-Wiedemann et al. / Int. Journal of Refractory Metals & Hard Materials 28 (2010) 550–557 555

Fig. 11. Experimental and corrected piston travel and the corresponding baseline
during sintering of molybdenum powder under a pressure of 67 MPa. The piston
travel, caused by the applied pressure before sintering, was subtracted.

Fig. 10. Carburized region after sintering at 1800 °C.

In the carburized layer, the microhardness rises up to 1300 HV

0.1 and cracks are created. The carbon concentration amounts ca.
7 wt% which is consistent with the carbon content of Mo2C-car-
bide. The results of X-ray phase analyses detected, that the carbu-
rized region was completely converted in the hexagonal Mo2C-
carbide.
The measured diffraction pattern shows a preferred orientation
of the (0 0 2) reflection. Texture measurements verify occurrence
of a (0 0 1) fibre texture modified by a coarse grain structure. The
fibre texture is caused by columnar grain growth, which was ob-
served by light microscopy.

3.4. Densification behaviour

Fig. 12. Corrected piston travel vs. sintering time for different heating rates
The force adjustment of our SPS equipment is starting with a (pressure of 67 MPa).
load of 5 kN. At this point, the motion of piston is recorded during
whole sintering process. The so called ‘‘relative piston travel” con-
Table 2
tains information about linear intrinsic shrinkage of every sample. Values of sample high before sintering.
For interpretation of the records, the experimental data must be
Batch Final height after Final corrected piston Height before
corrected by subtracting the contribution of piston motion caused
sintering lf (mm) travel Dlf (mm) sintering, l0 (mm)
by compression during applied pressure before sintering starts (see
3.1 7.74 0.37 8.11
Fig. 2). This is necessary, because this first compaction depends on
3.2 6.43 0.97 7.40
the applied pressure as well as on the die filling behaviour of pow- 3.3 4.18 2.06 6.24
der varying with every batch. Furthermore, the thermal expansion 3.4 3.89 2.54 6.43
of sample, die and graphite sheets must be subtracted. For this cor- 3.5 4.62 3.79 8.41
rection, which is explained in [6], baselines were determined 3.6 4.65 3.86 8.51
3.7 3.71 3.43 7.14
experimentally. The baselines were recorded with heating rate of
200 K/min, maximal temperature of 2000 °C and pressure of 67
and 57 MPa, respectively. Each baseline can be described by a poly-
nomial, and this is valid for all experimental data recorded at the slopes in parts II and III indicate that the consolidation takes place
same pressure and with the same die. Fig. 11 shows the experi- mainly during fast heating up of SPS.
mental and corrected piston travel and the corresponding baseline Linear shrinkage Dl/l0 can be calculated basing on the corrected
during sintering of molybdenum powder under a pressure of piston travel, where Dl is corrected piston travel depending on sin-
67 MPa. tering time and temperature, respectively. The sample height l0 be-
Fig. 12 gives examples of corrected piston travels depending on fore sintering starts (in our investigation after the cold pressing
different heating rates vs. sintering time. The curves of all samples step) can not be estimated exactly. It can be approximated by
are very similar in their shape but they differ in their slopes the sum of the final sample height lf (after sintering) and the final
depending on the heating rates. On the curves one can observe typ- corrected piston travel Dlf (values see Table 2).
ical points (in Fig. 12 marked by arrows) where the slope changes If this linear shrinkage plotted vs. temperature during heating
considerably. These points are visible in particular for higher sin- up, the curves of all samples, compacted with the same pressure,
tering temperatures (cf. Fig. 12, 1800 °C). By these points, each cover each other with slight deviations (Fig. 13). As pointed out
curve can be divided into parts in the following denoted with Ro- in Section 3.1, the densification of molybdenum by SPS process de-
man numerals. Parts I–III are related to the heating up, the flat part pends strongly on the acting temperature, generated by resistance
IV is controlled by holding time at sintering temperature. The large heating in the powder.
556 R. Ohser-Wiedemann et al. / Int. Journal of Refractory Metals & Hard Materials 28 (2010) 550–557
Fig. 13. Corrected piston travel of different sintered batches (pressure of 67 MPa)
vs. temperature during heating up.
The parts I up to III marked in Fig. 12 can be observed again and
their transitions can now be linked to characteristic values of tem-
perature, shrinkage, porosity and mean grain size, as demonstrated
in Fig. 13. The reason for the small shift of the curves of Fig. 13 is
not clear.
4. Discussion
As the densification process is thermally activated, a sigmoid
progression of sintering curve was expected, comparable with such
of isothermal sintering [27,28], where in our curves the part I
exhibits a linear relationship between Dl/l0 and temperature and
a sharp transition to second part starting at 900 or 950 °C, respec-
tively. This transition temperature is consistent with 0.4 Tm of Mo,
the temperature, where appreciable volume diffusion starts in so-
lid materials. The end of this part is related to a small shrinkage of
5% and a high porosity of 40%. The densification rate is low. As
shown in Section 3.3, grain growth and change in particle shape
were not observed.
Part II is characterised by the highest densification rate of sin-
tering process. The shrinkage achieves more than 30% and the
porosity decreases to 15%, where the micrographs do not show
any change in particle shape up to 1100 °C. Nevertheless, the den-
sity increases and the number and sizes of contact areas between
particles are enlarged. Furthermore, the particle strength decreases
further, which makes particle rotation and sliding easier. A phe-
nomenological description of the consolidation process during
parts I and II is an open problem.
The grain growth starts with the beginning of the third part at
1330 °C. At first the porosity amounts 10%, which marks the tran-
sition to closed porosity. During the third part the porosity reduces
to 5% and the densification rate decreases continuously.
The micrographs (Fig. 5, 1600 °C) show that the pores are
rounded and the grain boundaries are separated from pores. Both
processes are driven mainly by diffusion.
In part IV, where sintering temperature is constant, the densifi-
cation is comparable to isothermal sintering process. The material
transport is supported by the applied pressure and by the electric
field, which was demonstrated in [6,8].
5. Conclusions
The results of this investigation demonstrate that molybdenum
powder can be successfully consolidated by spark plasma sintering
in very short times. A relative density of 95% is achieved at sinter-
ing temperatures of 1600 °C and an external pressure of 67 MPa. It
can be concluded that the density is primarily controlled by exter-
nal pressure and temperature. In comparison with values from the
literature, the densities obtained by SPS exceed those by isother-
mal sintering.
The grain growth during spark plasma sintering was mainly
controlled by the sintering temperature. The grain growth starts
at 1350 °C, which corresponds to a homologous temperature of
0.56 Tm. A strong grain growth occurs at temperatures higher than
1600 °C. Due to the shorter sintering times of SPS the grain sizes of
our samples are smaller than those of isothermal sintering.
Nanohardness and indentation modulus was estimated by
nanohardness testing. It was shown that the porosity strongly
influences both values in spite of the marginal loads used at this
test. An average indentation hardness of 2057 ± 152 MPa and an
average indentation modulus of 297 ± 12 GPa were estimated,
which are in agreement with values for bulk molybdenum.
Based on the recorded relative piston travel, the linear shrink-
age of molybdenum powder during SPS process can be calculated.
The shrinkage of all batches, compacted with the same external
pressure, follow the same curve independent of heating rate. The
main part of compaction takes place during fast heating up by SPS.
In summary, our investigation shows that the best results of
molybdenum powder spark plasma sintering are achieved at
1600 °C and 67 MPa. The optimal sintering temperature corre-
sponds to that of Plasma Pressure Compaction, but a higher exter-
nal pressure is necessary for SPS.
Acknowledgments
The authors are grateful for the financial support of this work by
Dr. Erich Krüger Stiftung and for the abandonment of the molybde-
num powder by Dr. A. Hoffmann, Plansee Metall GmbH Reutte.
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