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Materials Science and Engineering A 527 (2010) 6870–6878

Contents lists available at ScienceDirect

Materials Science and Engineering A

journal homepage: www.elsevier.com/locate/msea

Microwave and conventional sintering of 90W–7Ni–3Cu alloys with premixed

and prealloyed binder phase
Avijit Mondal a , Anish Upadhyaya a,∗ , Dinesh Agrawal b
a
Department of Materials Science and Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India
b
The Pennsylvania State University, University Park, PA 16802, USA

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

Article history: The present study investigates the possibility of consolidating premixed 90W–7Ni–3Cu alloy – desig-
Received 9 April 2010 nated as 90W–PM (Ni–Cu) – through microwave sintering. An attempt has been made to compare the
Received in revised form 8 June 2010 results between microwave and conventionally sintered samples. This study also compares the sintering
Accepted 22 July 2010
behavior of 90W–7Ni–3Cu with prealloyed 90W–PA (Ni–Cu) in both conventional as well as microwave
furnace at various temperatures. The comparative analysis is based on the sintered density, densifica-
tion parameter, hardness and microstructures of the samples. The present investigation also includes the
Keywords:
variation of matrix composition as a function of temperature by EPMA analysis. The results show that
Microwave sintering
Conventional sintering
microwave sintering requires about 75% less processing time than required by conventional method and
Tungsten heavy alloys still provides better physical and mechanical properties.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction
Tungsten heavy alloy (WHA) is a group of two-phase
composites, based on W–Ni–Cu and W–Ni–Fe alloys.
Tungsten–nickel–copper alloys are widely used for ordinance
application, electrical contacts of switches, radiation shielding,
mass balances, etc. In general the tungsten heavy alloys have been
processed through powder metallurgy route since 1930s [1]. These
heavy alloys contain mainly pure tungsten as principal phase in
association with a binder phase containing transition metals (Ni,
Fe, Cu, Co) [2]. In W–Ni–Cu alloys, normally the nickel-to-copper
ratio ranges from 3:2 to 4:1. Price et al. [3] were the first to propose
Ni–Cu as the binder for tungsten heavy alloys. Over the last several
years, these alloys have been extensively investigated for den-
sification mechanism, microstructural evolution and properties
[4–7].
The effect of tungsten and copper powder size variation on
the sintered properties of W–Ni–Cu heavy alloys was carried out
by Srikanth and Upadhyaya [8,9]. The effect of composition and
sintering temperature on the densification and microstructure of
W–Ni–Cu heavy alloys was studied by Ramakrishnan and Upad-
hyaya [10]. Kuzmic [11] proposed that rapid cooling from the
sintering temperature prevents the formation of brittle phase in
∗ Corresponding author at: Materials Science and Engineering, Indian Institute of
Technology Kanpur, P.O. IIT Kanpur, Kanpur 208016, UP, India.
Tel.: +91 512 2597672; fax: +91 512 2597505.
E-mail address: anishu@iitk.ac.in (A. Upadhyaya).
order to obtain good mechanical properties. Ariel et al. [12] corre-
lated the mechanical properties of W–Ni–Cu system with sintered
microstructure. Their study showed that the mechanical properties
are a function of mean free path between tungsten grains, volume
fraction of tungsten grains and the contiguity of tungsten spheroids.
The solubility of tungsten in the liquid binder plays a domi-
nant role in determining the mechanical properties of the sintered
W–Ni–Cu alloys. The solubility of tungsten in copper is negli-
gible. Even at temperatures as high as 1350 ◦ C only 0.04 at.% of
tungsten goes in solution with copper [13]. In contrast, tungsten
exhibits appreciable solubility (up to 40 wt.%) in nickel. It is there-
fore possible to tailor the tungsten solubility, wetting and the
dihedral angle and thereby, the accompanying sintering response
and properties of the system by varying the Ni:Cu ratio [10,14].
Nowadays, W–Ni–Cu alloys are also being consolidated by employ-
ing prealloyed powders [15]. Use of prealloyed powder improves
homogeneity. The homogenization process accelerates sintering
and promotes densification. The alloy formation during sintering
decreases the material viscosity and, hence, stimulates material
flow under the action of capillary forces [16].
Despite widespread application, difficulties still exist in the
manufacture of liquid phase sintered tungsten heavy alloys. In
order to avoid thermal shock, processing of tungsten heavy alloys in
conventional furnace involves heating at a slower rate (<10 ◦ C/min)
and with isothermal holds at intermittent temperatures. This not
only increases the process time, but also results in significant
microstructural coarsening during sintering, leading to the degra-
dation of mechanical properties. This problem is further aggravated
when the initial powder size is extremely fine. Hence, it is envis-

0921-5093/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2010.07.074
 Author's personal copy
A. Mondal et al. / Materials Science and Engineering A 527 (2010) 6870–6878
Table 1
Powder characteristics of as-received elemental W, Ni, Cu and prealloyed Ni–Cu powder.
Property W Ni
Supplier Widia
Processing technique Chemical reduction
Powder shape Irregular
Powder size (␮m)
D10 2.0
D50 4.2
D90 6.2
aged that a fast heating rate would mitigate this problem. One of
the techniques to achieve fast and relatively uniform sintering is
through microwaves [17]. The W–Ni–Cu alloys are usually pre-
pared by mixing the constituent powders. One of the challenges
in the processing of these alloys is to ensure homogenous melt
distribution [15]. Nickel and copper are known to interdiffuse at
temperatures higher than 900 ◦ C. However, in case of rapid sinter-
ing in microwave this may not be readily feasible.
Microwave heating is much more uniform at a rapid rate result-
ing in reduction of processing time and energy consumption. Also
rapid heating leads to finer microstructure enhancing the mechan-
ical properties. Clark and Sutton [18] cited many other benefits of
the process such as precise and controlled heating, environmen-
tally friendly etc. Microwave heating is a very sensitive function
of the material being processed and depends on several factors,
such as sample size, as-pressed density, its mass and geometry
[19,20]. Though there have been attempts to explain microwave
heating of metal powders, still there is not yet any consensus on a
comprehensive theory to explain the mechanism [21].
Applicability of microwave sintering to metals was ignored due
to the fact that they reflect microwaves. Roy et al. [22] reported
that particulate metals can be heated rapidly in microwaves. This
has led to the use of microwaves to consolidate a range of partic-
ulate metals and alloys [23–25]. While researchers have reported
microstructural refinement due to rapid heating in microwaves, the
effect of microwave sintering on the microstructural homogene-
ity and mechanical properties seem to be system specific [23–25].
Researchers have also attempted to consolidate refractory materi-
als such as pure W, W–Cu, W–Ni–Fe and W–Ni–Cu [26–33] using
microwave energy and reported significant reduction in process
time, elimination of brittle intermetallic formation and superior
mechanical properties.
This paper reports the sintering behavior of premixed and pre-
alloyed 90W–7Ni–3Cu powders in both, microwave as well as
in a conventional (radiatively heated) furnace. The comparative
analysis is based on the sintered density, densification parameter,
hardness and microstructures of the samples.
2. Experimental procedure
The as-received powders were characterized for their size, size
distribution and morphology. Table 1 summarizes the charac-
teristics of the as-received elemental W, Ni, Cu and prealloyed
Ni–Cu powder used for this study. For investigating the densifi-
cation response and compaction studies of various compositions,
cylindrical pellets (diameter: 16 mm and height 8 mm) were
pressed at 200 MPa using a uniaxial semi-automatic hydraulic press
(model: CTM 50, supplier: FIE, India) of 50 T capacity. To facilitate
compaction and subsequent removal of compacted samples, zinc-
stearate powder was applied as die-wall lubricant. The as-pressed
green compact density varied from 56% to 58% of the theoretical
density of the alloy, where the theoretical density was calculated
using the inverse rule of mixtures.
6871
Cu 69Ni–31Cu
Inco A Cu Powder International, LLC Ametek
Carbonyl process Gas atomization Gas atomization
Spiky Spherical Spherical
3.8 19.4 8.2
11.0 47.0 17.3
31.8 96.3 40.4
To study the densification behavior; the green (as-pressed) com-
pacts were sintered using conventional and microwave furnace.
The experimental details have been mentioned elsewhere [32].
The sintered density was obtained by both dimensional mea-
surements as well as Archimedes’ density measurement technique.
To compare the densification response of various compositions, the
sintered densities were normalized with respect to the theoretical
density. To take into account the influence of the initial as-pressed
density, the compact sinterability was also expressed in terms of
densification parameter which is calculated as follows:
sintered density − green density
densification parameter= (1)
theoretical density − green density
An Anter 1161 V vertical dilatometer was used for measuring
axial shrinkage and shrinkage rate during sintering with constant
heating rate of premixed and prealloyed 90W–7Ni–3Cu compacts.
It measures dimensional changes over the entire sintering cycle
with precision of 1 ␮m. The dilatometery studies were performed
at constant heating and cooling rate of 10 ◦ C/min. The sintered
samples were wet polished in a manual polisher (model: Lunn
Major, supplier: Struers, Denmark) using a series of 6 ␮m, 3 ␮m and
1 ␮m diamond paste, followed by cloth polishing using a 0.04 ␮m
colloidal SiO2 suspension. The scanning electron micrographs of as-
polished samples were obtained by a scanning electron microscope
(model: FEI quanta, Netherlands) in the secondary electron (SE)
mode. A quantitative analysis was also carried out on selected spec-
imens using EPMA equipment (model: JXA-8600 SX Super-Probe,
supplier: JEOL, Japan). Phase determination and phase evolution, if
any were studied for all the samples using an X-ray Diffractometer
(model: Rich. Seifert & Co., GmbH & Co., KG, Germany).
Bulk hardness measurements were performed on polished sur-
faces of sintered cylindrical compacts at a load of 5 kg using Vickers
hardness tester (model: V100-C1, supplier: Leco, Japan). The load
was applied for 30 s. Micro hardness tester (model: 8299, supplier:
Leitz, Germany) was used to evaluate the hardness of the matrix
phase. The load applied on matrix phase during the micro hard-
ness measurement was 15 g. The bulk hardness of the compact
and the micro hardness of the matrix phase for each sample were
an average of 5 readings taken at different locations on respec-
tive phases. Transverse rupture strength (TRS) measurements of
premixed and prealloyed samples were performed following the
procedure described in MPIF Standard 41 [34].
3. Results and discussion
3.1. Heating response and densification of W–Ni–Cu alloy
Fig. 1 compares the thermal profiles of 90W–7Ni–3Cu compacts
(prepared using premixed and prealloyed Ni–Cu binder) in a con-
ventional and microwave furnace. It is evident from the figure that
W–Ni–Cu alloys couple with microwaves and undergo rapid heat-
ing. In case of conventional furnace, in order to ensure uniform
heating, the compacts heating rate was restricted to 5 ◦ C/min and
isothermal holds were provided at intermittent temperatures. In
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6872 A. Mondal et al. / Materials Science and Engineering A 527 (2010) 6870–6878

Fig. 2. Photograph of 90W–7Ni–3Cu compacts conventionally sintered at various

temperatures ranging from 1200 ◦ C to 1450 ◦ C.

Fig. 1. Thermal profiles of 90W–7Ni–3Cu alloys heated up to 1450 ◦ C in conven-

tional and microwave furnace. The heating profile of W–Ni–Fe alloys prepared using
premixed and prealloyed Ni–Cu binder is shown separately in case of microwave
processing.

contrast, the overall heating rate achieved in the microwave fur-

nace was 22 ◦ C/min. Taking into consideration the slow heating rate
and isothermal holds associated with conventional sintering, the
compacts were consolidated through microwaves with significant
(∼75%) reduction in the processing time. Figs. 2 and 3 show the pho-
tograph of the 90W–7Ni–3Cu alloys sintered in the temperature
range of 1200–1450 ◦ C in conventional and microwave furnace,
respectively. Note that irrespective of the heating mode and the Fig. 3. Photograph of the 90W–7Ni–3Cu compacts prepared using (a) prealloyed
binder chemistry, none of the 90W–7Ni–3Cu compacts distorted and (b) premixed Ni–Cu binder and sintered in a microwave furnace at various
temperatures.
or developed any cracks during sintering even up to temperatures
as high as 1450 ◦ C. It is interesting to note that despite a fast heat-
ing rate, no macro cracking was observed in any of the microwave nace. It can therefore be inferred that the chemical state of the
sintered samples. This is attributed to the volumetric heating of alloying constituents influences the microwave coupling and the
the compacts, a unique feature of microwave heating. From the resultant heating. It is well recognized that microwave heating
microwave heating profile (Fig. 1), it is interesting to note that alloys is material dependent. Peelamedu et al. [36] and Roy et al. [37]
with premixed Ni–Cu binder heat at slightly faster rate than those demonstrated in multi-phase systems, the phases heat up at dif-
containing prealloyed matrix. Elsewhere, Sethi et al. [23] and Upad- ferent rates and lead to local an isothermal heating effect. Through
hyaya and Sethi [35] too have reported similar heating response of model experiments in systems, such as Y2 O3 –Fe3 O4 , BaCO3 –Fe3 O4 ,
the premixed and prealloyed Cu–12Sn bronze in microwave fur- and NiO–Al2 O3 , Peelamedu et al. [36] demonstrated that the hotter

Fig. 4. Effect of binder state (premixed vs. prealloyed), heating mode and sintering temperature on the (a) sintered density and (b) densification parameter of 90W–7Ni–3Cu
alloys. For the sake of comparison, the density and densification parameter data points (denoted by symbol ) for the same composition (in premixed state) sintered at
1300 ◦ C and 1400 ◦ C are also superimposed.
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A. Mondal et al. / Materials Science and Engineering A 527 (2010) 6870–6878 6873

Table 2
Composition as a function of temperature and heating mode of the matrix phase of liquid phase sintered 90W–7Ni–3Cu alloys prepared by (a) premixed and (b) prealloyed
powders.

(a) Premixed powders

Temperature (◦ C) Heating mode Elemental content (wt.%)

W Ni Cu

1200 Conventional 19.13 ± 1.93 53.15 ± 2.71 25.69 ± 0.92

Microwave 18.43 ± 0.37 55.03 ± 0.85 24.18 ± 0.61

1250 Conventional – – –
Microwave 20.41 ± 0.72 56.16 ± 0.89 20.77 ± 0.52

1300 Conventional 18.66 ± 0.42 56.04 ± 0.68 23.98 ± 0.88

Microwave 24.29 ± 4.65 54.01 ± 1.84 18.37 ± 5.72

1450 Conventional 22.06 ± 4.66 57.03 ± 1.02 20.27 ± 5.36

Microwave 23.57 ± 3.37 59.36 ± 0.35 14.41 ± 3.09

(b) Prealloyed powders

Temperature (◦ C) Heating mode Elemental content (wt.%)

W Ni Cu

Conventional 29.25 ± 0.73 53.62 ± 1.00 15.59 ± 0.13

1200
Microwave 27.26 ± 0.96 54.42 ± 0.65 15.20 ± 0.40

Conventional – – –
1250
Microwave 25.12 ± 0.57 55.68 ± 0.78 16.32 ± 0.55

Conventional 26.37 ± 0.38 56.36 ± 0.39 15.36 ± 0.22

1300
Microwave 28.73 ± 18.0 50.34 ± 6.99 17.08 ± 10.63

Conventional 23.25 ± 7.56 56.96 ± 2.3 18.80 ± 5.60

1450
Microwave 19.34 ± 3.09 57.97 ± 2.71 20.62 ± 5.80

species diffuse rapidly into the relatively colder ones and correlated
it with the very rapid diffusion rates observed in microwave pro-
cessed compacts. It is likely that a similar mechanism is also active
in the W heavy alloys system as well. The presence of such effect
will result in densification enhancement in the microwave sintered
components.
To test the above hypothesis, the densification responses of the
compacts consolidated at various temperatures was evaluated for
both the heating modes and is summarized in Fig. 4a and b. From
Fig. 4a, it is evident that the density of the compacts increases
with increasing sintering temperature. Since the green density
of all the compacts were the same, the densification parameter
results (Fig. 4b) closely follow the same trend as sintered den-
sity. Note that with the exception of 1200 ◦ C, for all other sintering
temperatures, microwave sintering results in better densification.
Since factors that contribute to enhanced diffusivity are known to
enhance densification during sintering, it can be inferred that the
atomic mass transport is higher in case of microwave sintering. This
will also result into less grain coarsening during microwave sinter-
ing. Consequently, the finer particle size is retained at the sintering
temperature which results in higher grain boundary diffusivity.
From the sintered density and the densification parameter
plots shown in Fig. 4, it is evident that for both heating modes
the densification increases with increasing temperature. For the
sake of comparison the sintered density and densification param-
eter results reported by Ramakrishnan and Upadhyaya [10] on
the similar alloy composition sintered at 1300 ◦ C and 1400 ◦ C has
been superimposed on Fig. 4a and b. Note that the densification
results from this study on 90W–PM (Ni–Cu) are similar to those
reported by Ramakrishnan and Upadhyaya [10]. Based on the sin-
tering studies on a range of W–Ni–Cu alloys, Makipiritti [38] and
Kothari [6] have confirmed that densification in this system is
diffusion-controlled. Kothari [6] and Crowson [39] have shown
that increasing sintering temperature results in enhanced diffu-
sivity and lower activation energy in W–Ni–Cu alloys. The same
will hold good for the present investigation as well and thereby
activate densification. Besides enhanced diffusivity at high tem-
perature, another factor that contributes to densification is the
solid-solubility of tungsten in the Ni–Cu matrix [38–40]. In one of
the very early works, Prill et al. [41] based on the sintering studies of
99W–1(Ni–Cu) alloys showed that the dissolution of the tungsten
grains in the matrix and their subsequent reprecipitation from the
supersaturated matrix on to the larger tungsten is a major con-
tributor to densification. To validate this, the effect of sintering
temperature, heating mode and the powder type on the matrix
composition was evaluated using EPMA. The corresponding results
for 90W–PM (Ni–Cu) and 90W–PA (Ni–Cu) compacts are summa-
rized in Table 2a and b, respectively. From Table 2a, it is obvious
that higher sintering temperature leads to higher tungsten solubil-
ity in the matrix for the samples prepared from premixed powder.
The matrix composition analysis is similar to those reported by Sail-
land et al. [42] and Xiong et al. [43] for the sintered W–Ni–Cu alloys.
On the other hand for the prealloyed compositions (Table 2b) the
tungsten solubility does not follow any specific trend as a function
of temperature. The complete explanation for this observation is
not readily available. It is hypothesized that this trend is possibly
due to the difference in diffusivity of tungsten in prealloyed Ni–Cu
matrix.
3.2. Dilatometric evaluation of 90W–7Ni–3Cu alloy
For better understanding the phenomenology of the densifi-
cation of the W–Ni–Cu compacts the dimensional changes were
measured in situ during sintering using dilatometry. However,
owing to the instrument’s limitations, dilatometric evaluation
could be performed through conventional heating mode only.
Fig. 5a and b plots the dilatometric data of shrinkage and shrinkage
rate vs. temperature for the as-pressed 90W–7Ni–3Cu compacts
prepared using premixed and prealloyed binder. From the figures,
it is evident that both compacts undergo gradual densification
during heating till 1280 ◦ C. Subsequent heating beyond 1280 ◦ C
results in sudden increase in the axial shrinkage and shrinkage rate.
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6874 A. Mondal et al. / Materials Science and Engineering A 527 (2010) 6870–6878
Fig. 5. Dilatometer plots showing the effect of Ni–Cu binder state (premixed vs. pre-
alloyed) on the (a) shrinkage and (b) shrinkage rate of 90W–7Ni–3Cu alloys heated
up to 1400 ◦ C at a constant heating rate of 10 ◦ C/min in reducing atmosphere.
This spurt in the densification is attributed to the onset of binder
melting which results in densification through capillary-induced
rearrangement and solution-reprecipitation. The rapid shrink-
age resulting from liquid phase sintering sustains until 1400 ◦ C
wherein nearly full densification (98%) was achieved. Elsewhere,
Wu et al. [44] and Martin et al. [15] too have reported simi-
lar dilatometric curves for 80W–14Ni–6Cu alloys and prealloyed
90W–6.9Ni–3.1Fe, respectively. For the range of compositions
used, both researchers [15,44] have demonstrated that the onset
of melt formation in the W–Ni–Cu system with Ni and Cu in
the ratio 7:3 occurs at 1282 ◦ C. From the binary phase dia-
gram [45] and the experiments [44] the solidus and the liquidus
temperatures of the 70Ni–30Cu matrix was determined to be
1345 ◦ C and 1380 ◦ C, respectively. However, in case of ternary
W–Ni–Cu system, due to substantial solubility of the tungsten
in the matrix the solidus and liquidus temperatures are lowered
[42].
From the dilatometric results (Fig. 5a and b), it can be dis-
cerned that the 90W–PA (Ni–Cu) alloy exhibits slightly higher
densification particularly at lower temperatures as compared to the
90W–PM (Ni–Cu) compact. This trend is similar to that reported
by Huang et al. [46] who investigated the influence of preal-
loyed Ni–Fe–Mo binder on the sintering behavior of tungsten
heavy alloys. They [46] noted that prealloying results in a more
Fig. 6. XRD plots showing the effect of heating mode and sintering temperature on
the phase evolution of 90W–7Ni–3Cu alloys prepared using (a) premixed and (b)
prealloyed Ni–Cu binder.
homogenous microstructure and lowers the interfacial energy of
the tungsten (solid)–matrix (liquid) phase providing a higher den-
sity compact. The analyses of matrix composition of the W–Ni–Cu
compacts in the present study (Table 2a and b) – particularly, the
ones sintered at 1200 ◦ C – are in accordance with this hypothe-
sis. At 1200 ◦ C, the dissolved tungsten amount in 90W–PM (Ni–Cu)
is lower than its prealloyed counterpart. Consequently, the lat-
ter exhibits higher densification (Fig. 4b). For compacts heated or
sintered at higher temperatures, the densification in both the com-
pacts is not too different and is attributed to homogenization of
the premixed matrix through interdiffusion. It is well known that
Cu and Ni have mutual intersolubility [45]. Using X-ray analysis,
Heckel et al. [47] have experimentally shown that significant inter-
diffusion and homogenization through in situ alloying occurs in the
Ni–52 at.% Cu compact after sintering at 950 ◦ C for 1 h. Since the
Cu:Ni ratio in the present system (90W–7Ni–3Cu) is much lower,
hence, it is quite reasonable to assume that the premixed Ni–Cu
powders will get completely homogenized during conventional
sintering.
3.3. Microstructural evolution and properties
Fig. 6a and b compares the effect of heating mode and
sintering temperature on the phase evolution in 90W–PM
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A. Mondal et al. / Materials Science and Engineering A 527 (2010) 6870–6878 6875

Fig. 7. SEM micrographs of 90W–7Ni–3Cu alloys prepared using prealloyed Ni–Cu binder and consolidated in a microwave furnace at (a) 1200 ◦ C, (b) 1250 ◦ C, (c) 1300 ◦ C
and (d) 1450 ◦ C, respectively.

(Ni–Cu) and 90W–PA (Ni–Cu) alloys, respectively. For all
XRD experiments, the sample size and other test parame-
ters were kept constant. It is therefore rather surprising to
note that in case of microwave sintered compacts some of
the peaks do not even register on the diffractogram. Sim-
ilar observations have also been reported by Padmavathi
[48] in case of microwave sintering of various aluminium
alloys.
The reduction in the intensity indicates that the microwave
sintered compacts have less perfect crystals and contain more
defects as compared to their conventionally sintered counter-
parts. Recently, many researchers, [37,49–51] have reported that

Fig. 8. SEM micrographs of (a) premixed and (b) prealloyed 90W–7Ni–3Cu alloys sintered at 1300 ◦ C in conventional (left) and microwave (right) furnace.
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6876 A. Mondal et al. / Materials Science and Engineering A 527 (2010) 6870–6878
Fig. 9. SEM micrographs of (a) premixed and (b) prealloyed 90W–7Ni–3Cu alloys sintered at 1450 ◦ C in conventional (left) and microwave (right) furnace.
exposure to microwave heating leads to decrystallization and
sometimes even amorphization in some of the ceramic and semi-
conducting systems. The defects within a crystalline structure are
known to activate sintering [52]. Hence, it may be possible that
in the present system too the defects generated on exposure to
microwaves contribute to densification enhancement.
The phenomenology of microstructural evolution in conven-
tionally sintered W–Ni–Cu alloys has been extensively investigated
by several researchers [3,10,15,40]. In the present study, the atten-
tion was focused on the microstructural response of microwave
sintered W–Ni–Cu system and its comparison with that obtained
through conventional sintering. Fig. 7a–d shows the effect of sinter-
ing temperature on the representative microstructure of 90W–PA
(Ni–Cu) alloy consolidated in a 2.45 GHz multimode microwave fur-
nace. It is quite evident that higher temperature not only results in
pore elimination but is also accompanied by redistribution of the
matrix and coarsening of tungsten grains. It is worth noting that
the microstructure of the compacts sintered in solid-state (1200 ◦ C
and 1250 ◦ C) is drastically different from the liquid phase sintered
counterparts (Fig. 7c and d). In case of compacts sintered at 1200 ◦ C,
the binder phase is inhomogenously distributed (Fig. 7a) and the
tungsten grains are faceted. In contrast, at 1250 ◦ C (Fig. 7b), while
the W-grains still remain faceted, the binder is more uniformly dis-
tributed. The well rounded and coarser grains associated with liquid
phase sintering (Fig. 7c and d) are associated with higher solid-
solubility (Table 2) and relatively faster solution-reprecipitation
kinetics.
Fig. 8a and b compares the effect of heating mode on the
microstructures of the 90W–PM (Ni–Cu) and 90W–PA (Ni–Cu)
alloys, respectively, sintered at 1300 ◦ C. The corresponding
microstructures of compacts liquid phase sintered at 1450 ◦ C are
shown in Fig. 9a and b. From Figs. 8 and 9, it can be discerned that
irrespective of the sintering temperature and the heating mode,
the prealloyed sintered compacts have slightly higher coarsening
than their premixed counterparts. This can be attributed to a more
homogenous microstructure and better spreading of the melt due
to the relatively lower tungsten (solid)–matrix (liquid) interfacial
energy in case of alloys prepared using prealloyed binder [46]. More
recently, Martin et al. [15] showed that the Ni–Cu additive phase
in 90W–6.9Ni–3.1Cu alloy with prealloyed matrix is more effec-
tively distributed within the tungsten grains during sintering and
contributes not only to densification but also leads to enhanced
tungsten grain coarsening as compared to premixed alloys.
One of the intriguing observations in the present study is the
dramatic difference between the microstructure of W–Ni–Cu com-
pacts sintered in conventional and microwave furnace (Fig. 8a and
b). In case of conventionally sintered compacts, the microstructure
at 1300 ◦ C is quite similar to that obtained through solid-state sin-
tering. Some of the earlier researchers [10,53,54] too have reported
similar findings at this temperature for premixed 90W–7Ni–3Cu
compacts. The larger tungsten grain size in microwave sintered
W–Ni–Cu compacts at 1300 ◦ C is contrary to the observations in
various systems that a fast heating rate will result in lower grain size
[30,55,56]. However, similar contrary results have recently been
reported by Zaspalis et al. [57] in microwave sintered Mn–Zn fer-
rites and by Kim et al. [58] in spark plasma sintered alumina. The
exact explanation of such observations is still lacking and further
detailed experiments need to be carried out in future to elucidate
this better. In contrast to 1300 ◦ C sintered compacts, both con-
ventional as well as microwave sintered 90W–7Ni–3Cu alloys (at
1450 ◦ C) exhibit well-defined liquid phase sintered microstructure
with rounded tungsten grains interspersed in the Ni–Cu matrix
(Fig. 9a and b). Table 3 summarizes the effect of heating mode
on the average tungsten grain size in premixed and prealloyed
90W–7Ni–3Cu alloys liquid phase sintered at 1450 ◦ C. From Fig. 9
and Table 3, it can be inferred that irrespective of the state of ini-
 Author's personal copy

A. Mondal et al. / Materials Science and Engineering A 527 (2010) 6870–6878 6877

Table 3
Effect of heating mode on the average tungsten grain size in 90W–7Ni–3Cu alloys
prepared using premixed and prealloyed Ni–Cu binder and sintered at 1450 ◦ C.

Composition Heating mode W grain size (␮m)

90W–PM Conventional 23 ± 10
(Ni–Cu) Microwave 21 ± 7

90W–PA Conventional 26 ± 8
(Ni–Cu) Microwave 20 ± 7

Table 4
Effect of heating mode and sintering temperature on the bulk hardness (in kgf/mm2 )
of 90W–7Ni–3Cu alloys prepared using premixed and prealloyed binder.

Heating mode 90W–PM (7Ni–3Cu)a 90W–PA (7Ni–3Cu)

1300 ◦ C 1450 ◦ C 1300 ◦ C 1450 ◦ C

Conventional 276 ± 21 301 ± 16 290 ± 19 330 ± 13

Microwave 309 ± 17 328 ± 13 330 ± 18 350 ± 12
a
As a note of comparison in one of the previous reports [10] the bulk hardness of
the same composition has been listed as 175VHN and 220VHN for compacts sintered
at 1300 ◦ C and 1400 ◦ C, respectively.
Fig. 10. Effect of heating mode and sintering temperature on the transverse rupture
strength of 90W–7Ni–3Cu alloys prepared using premixed and prealloyed binders.

tial binder chemistry (premixed vs. prealloyed), the microwave

sintered compacts have relatively more refined microstructure
as compared to those consolidated in a conventional (radiatively
heated) furnace. Elsewhere, Upadhyaya et al. [30] has reported
similar findings in liquid phase sintered W–Ni–Fe system.
The differences in the sintered microstructure of alloys consol-
idated through conventional and microwave furnace is bound to
influence the mechanical properties. Table 4 summarizes the effect
of heating mode and powder chemistry (prealloyed vs. premixed)
on the bulk hardness of 90W–7Ni–3Cu alloys sintered at 1300 ◦ C
and 1450 ◦ C, respectively. To provide a basis of comparison, the
bulk hardness of premixed 90W–7Ni–3Cu alloy sintered at 1300 ◦ C
and 1400 ◦ C reported by Ramakrishnan and Upadhyaya [10] is also
provided in Table 4. It is remarkable to note that the hardness
achieved in the present study is far superior to those reported in
earlier work [10,59]. From Table 4, it is worth noting that for all
conditions, microwave sintering results in up to 13% improvement
in the bulk hardness. This can be attributed to the increased densi-
fication and a more refined microstructure in case of microwave
sintered alloys. Previous report from Upadhyaya et al. [30] has
shown that the hardness of tungsten grains per se does depend
on the heating mode. However, on account of the varying tungsten
solid-solubility, the hardness of the matrix phase is expected to
be dependent upon the heating mode. To test this, Table 5 summa-
rizes the corresponding matrix hardness measurements performed
on compacts consolidated in both the heating modes at 1300 ◦ C and
1450 ◦ C. It is interesting to observe that in case of compacts con-
solidated at 1300 ◦ C, the matrix hardness is higher for microwave
processed compacts (Table 5). This can be correlated to the higher
tungsten solubility observed in microwave sintered alloys (Table 2a
and b). In contrast, the trend is reversed for compacts sintered at
1450 ◦ C. In case of prealloyed compacts, this can be correlated to
the higher W-solubility in conventionally sintered alloys. However,
further tests need to be performed to gain detailed insight for this.
Table 5
Effect of heating mode on the micro hardness (in kgf/mm2 ) of the matrix phase in
sintered 90W–7Ni–3Cu alloys.
Heating mode 90W–PM (7Ni–3Cu) 90W–PA (7Ni–3Cu)
◦ ◦
1300 C 1450 C 1300 ◦ C
Conventional 260 ± 20 333 ± 13 250 ± 25
Microwave 290 ± 23 312 ± 15 280 ± 21
Fig. 10 shows the effect of heating mode and powder chem-
istry on the transverse rupture strength of the 90W–7Ni–3Cu alloy
sintered at 1300 ◦ C and 1450 ◦ C. One of the very interesting observa-
tions is that microwave sintered compacts have higher transverse
rupture strength as compared to those sintered conventionally. The
enhancement of strength is as high as up to threefolds (∼211%) in
case of alloys processed at 1300 ◦ C. This can be correlated to a less
contiguous microstructure consisting of rounded tungsten grains
that result in alloys microwave sintered at 1300 ◦ C (Fig. 8). Else-
where, Chermant and Osterstock [60] have demonstrated similar
influence of microstructure on the fracture toughness of WC–Co
system. The transverse rupture strength of the conventionally sin-
tered 90W–PM (Ni–Cu) system is similar to that reported earlier
by Kalina et al. [61]. Another observation that can be inferred from
Fig. 10 is that the transverse rupture strength of alloys prepared
with prealloyed Ni–Cu is marginally higher than those prepared
using premixed binder. This could be due to better homogeneity of
the alloying additives in case of the prealloyed system.
4. Conclusions
90W–7Ni–3Cu alloys, compacts were prepared using both
premixed and prealloyed Ni–Cu binder and were sintered at
temperatures ranging between 1200 ◦ C and 1450 ◦ C. As com-
pared to conventional sintering, both premixed and prealloyed
90W–7Ni–3Cu alloys were microwave sintered in significantly
(∼75%) less time. In spite of higher heating rate in microwave sin-
tering, no micro- or macro-cracking was observed in all microwave
sintered samples. Dilatometric analysis of the 90W–7Ni–3Cu alloy
at slower heating rates (<10 ◦ C/min) reveals that – unlike the W–Cu
system – the W–Ni–Cu system exhibits significant solubility of
tungsten in the matrix. Consequently, a major portion of the overall
densification in this alloy occurs prior to melt formation. Due to the
inter-diffusivity between nickel and copper, by the time the sinter-
ing temperature was attained, both Cu and Ni form a homogeneous
solid solution. Hence, the sintering response of the 90W–7Ni–3Cu
alloy was per se independent of the initial matrix type (premixed
vs. prealloyed). An interesting finding in the present study was the
observation of the heating mode effect on the microstructure of the
compacts sintered at 1300 ◦ C. While the conventionally processed
1450 ◦ C
alloy had a typical solid-state sintered structure, the microwave
320 ± 16 processed samples had a well-developed microstructure, typically
290 ± 12
associated with liquid phase sintering. Consequently, as compared
 Author's personal copy
6878 A. Mondal et al. / Materials Science and Engineering A 527 (2010) 6870–6878
to conventional sintering, microwave sintering resulted in about
9% improvement in hardness (to ∼350VHN) and about threefold
(∼211%) enhancement in flexural strength to around 1625 MPa.
Acknowledgement
This collaborative research was done as a part of the Center for
Development of Metal–Ceramic Composites through Microwave
Processing which was funded by the Indo-US Science and Tech-
nology Forum (IUSSTF), New Delhi.
References
[1] S.G. Caldwell, in: P.W. Lee, R. Lacocca (Eds.), Powder Metal Technologies and
Applications, vol. 7, Materials Park, OH, USA, 1998, pp. 914–921.
[2] A. Upadhyaya, Mater. Chem. Phys. 67 (2001) 101–110.
[3] G.H.S. Price, C.J. Smithells, S.V. Williams, J. Inst. Met. 62 (1938) 239–264.
[4] A.L. Prill, Trans. AIME 230 (1964) 769–772.
[5] J.H. Brophy, H.W. Hayden, J. Wulff, Trans. TMS-AIME 224 (1962) 797–803.
[6] N.C. Kothari, J. Less Common Met. 13 (1967) 457–468.
[7] R. Makarov, O.K. Teodorovich, I.N. Fruntsevich, Sov. Powder Metall. Met. Ceram.
4 (1965) 554–559.
[8] V. Srikanth, G.S. Upadhyaya, Int. J. Ref. Hard Met. 2 (1983) 49–54.
[9] V. Srikanth, G.S. Upadhyaya, Powder Technol. 39 (1984) 61–65.
[10] K.N. Ramakrishnan, G.S. Upadhyaya, J. Mater. Sci. Lett. 9 (1990) 456–459.
[11] J.F. Kuzmic, in: H.H. Hausner (Ed.), Modern Development in Powder Metallurgy,
vol. 3, Plenum Press, New York, 1966, pp. 166–171.
[12] E. Ariel, J. Batra, D. Brandon, Powder Metall. Int. 5 (1973) 125–128.
[13] V.N. Eremenko, R.V. Minakova, M.M. Churakov, Sov. Powder Metall. Met. Ceram.
15 (1976) 283–286.
[14] Y.V. Naidich, I.A. Lavrinenko, V.A. Evdokimov, Sov. Powder Metall. Met. Ceram.
16 (1977) 276–280.
[15] J.M. Martin, J.L. Johnson, R.M. German, F. Castro, in: E. Daver, C.J. Trombino
(Eds.), Advances in Powder Metallurgy and Particulate Materials, vol. 1, Metal
Powder Industries Federation, Princeton, NJ, 2006, pp. 5.43–5.57.
[16] A.P. Savitskii, Sci. Sinter. 37 (2005) 3–17.
[17] K.J. Rao, P.D. Ramesh, Mater. Bull. Sci. 18 (1995) 447–465.
[18] D.E. Clark, W.H. Sutton, Ann. Rev. Mater. Sci. 26 (1996) 299–331.
[19] R.M. Hutcheon, M.S. De Jong, F.P. Adams, Microw.: Theor. Appl. Mater. Proc. III,
Ceram. Trans., Am. Ceram. Soc. 59 (1995) 215.
[20] A. Mondal, D. Agrawal, A. Upadhyaya, J. Microw. Power. Electromagn. Energy
(JMPEE) 43 (2009) 5–10.
[21] M.W. Porada, Microw.: Theor. Appl. Mater. Proc. III, Ceram. Trans., Am. Ceram.
Soc. 80 (1997) 153.
[22] R. Roy, D.K. Agrawal, J.P. Cheng, S. Gedevanishvili, Nature 399 (1999) 668–670.
[23] G. Sethi, A. Upadhyaya, D. Agrawal, Sci. Sinter. 35 (2003) 49–65.
[24] R.M. Anklekar, D.K. Agrawal, R. Roy, Powder Metall. 44 (2001) 355–362.
[25] K. Saitou, Scripta Mater. 54 (2006) 875–879.
[26] M. Jain, G. Skandan, K. Martin, K. Cho, B. Klotz, R. Dowding, D. Kapoor, D. Agar-
wal, J. Chang, Int. J. Powder Metall. 42 (2006) 45–50.
[27] G. Prabhu, A. Charkraborty, B. Sarma, Int. J. Ref. Met. Hard Mater. 27 (2009)
545–548.
[28] S.D. Luo, J.H. Yi, Y.L. Guo, Y.D. Peng, L.Y. Li, J.M. Ran, J. Alloys Compd. 473 (2009)
L5–L9.
[29] A. Mondal, A. Upadhyaya, D. Agrawal, J. Microw. Power Electromagn. Energy
(JMPEE) 43 (2009) 11–16.
[30] A. Upadhyaya, S.K. Tiwari, P. Mishra, Scripta Mater. 56 (2007) 5–8.
[31] A. Mondal, D. Agrawal, A. Upadhyaya, J. Microw. Power Electromagn. Energy
(JMPEE) 44 (2010).
[32] A. Mondal, D. Agrawal, A. Upadhyaya, Mater. Sci. Technol. (2008) 2502–2515.
[33] A. Mondal, Modeling of microwave heating of particulate metals and its appli-
cation in sintering of tungsten-based alloys, Ph.D. Thesis, The Indian Institute
of Technology, Kanpur, 2009.
[34] MPIF Standard 41, Determination of transverse rupture strength of powder
metallurgy materials, standard test methods for metal powders and powder
metallurgy products, MPIF, Princeton, NJ, USA, 2002, pp. 55–57.
[35] A. Upadhyaya, G. Sethi, Scripta Mater. 56 (2007) 469–472.
[36] R.D. Peelamedu, R. Roy, D. Agrawal, Mater. Res. Bull. 36 (2001) 2723–2739.
[37] R. Roy, Y. Fang, J. Cheng, D.K. Agrawal, J. Am. Ceram. Soc. 88 (2005) 1640–1642.
[38] S. Makipiritti, Powder Metall. 4 (1961) 97–111.
[39] A. Crowson, Modern Developments in Powder Metallurgy, vol. 15, Metal Pow-
der Industries Federation, Princeton, NJ, 1985, pp. 507–520.
[40] G. Sethi, S.J. Park, J.L. Johnson, R.M. German, Int. J. Ref. Met. Hard Mater. 27
(2009) 688–695.
[41] A.L. Prill, H.W. Hayden, J.H. Brophy, Trans. AIME 233 (1965) 1960–1964.
[42] F. Sailland, J.M. Chaix, C.H. Allibert, Colloquium on Controlling the Properties
of Powder Metallurgy Parts Through Their Microstructures, Societe Francaise
de Metallurgie, Paris, 1990, pp. 4.1–4.6.
[43] H. Xiong, L. Zhang, Q. Shen, R. Yuan, J. Mater. Sci. Technol. 15 (1999) 94–96.
[44] Y. Wu, R.M. German, B. Marx, R. Bollina, M. Bell, Mater. Sci. Eng. A344 (2003)
158–167.
[45] P.R. Subramaniam, D.J. Chakrabarti, D.E. Laughlin (Eds.), Monograph Series on
Alloy Phase Diagram-10: Phase Diagram of Binary Copper Alloys, ASM Interna-
tional, Materials Park, OH, 1994, pp. 276–286.
[46] J.H. Huang, G.A. Zhou, C.Q. Zhu, S.Q. Zhang, H.Y. Lai, Mater. Lett. 23 (1995) 47–53.
[47] R.W. Heckel, R.D. Lanam, R.A. Tanzilli, in: J.S. Hirschhorn, K.H. Roll (Eds.),
Advanced Experimental Techniques in Powder Metallurgy, Plenum Press, New
York, 1970, pp. 139–188.
[48] C. Padmavathi, Liquid phase sintering of 2712, 6711 and 7775 aluminum alloys
and their properties, Ph.D. Thesis, The Indian Institute of Technology, Kanpur,
2009.
[49] R. Peelamedu, R. Roy, L. Hurtt, D. Agrawal, A.W. Fliflet, D. Lewis III, R.W. Bruce,
Mater. Chem. Phys. 88 (2004) 119–129.
[50] D.C. Dube, M. Fu, D. Agrawal, R. Roy, A. Santra, Mater. Res. Innovat. 12 (2008)
119–122.
[51] J. Cheng, D. Agrawal, Y. Zhang, R. Roy, A.K. Santra, Synthesis of amorphous Si-Ge
alloys using microwave energy, J. Alloys Compd. 491 (2010) 517–521.
[52] W. Schatt, E. Friedrich, Powder Metall. 28 (1985) 140–144.
[53] A. Upadhyaya, Distortion in liquid phase sintered tungsten heavy alloys, M.S.
Thesis, The Pennsylvania State University, University Park, PA, 1996.
[54] A. Upadhyaya, J.L. Johnson, R.M. German, Tungsten and Refractory Metals-1995,
Metal Powder Industries Federation, Princeton, NJ, 1995, p. 18.
[55] C. Zhou, J. Yi, S. Luo, Y. Peng, L. Li, G. Chen, J. Alloys Compd. 482 (2009) L6–L8.
[56] K. Rödiger, K. Dreyer, T. Gerdes, M. Willert-Porada, Int. J. Ref. Met. Hard Mater.
16 (1998) 409–416.
[57] V.T. Zaspalis, S. Sklari, M. Kolenbrander, J. Magn. Mater. 310 (2007) 28–36.
[58] B.N. Kim, K. Hiraga, K. Morita, H. Yoshida, J. Eur. Ceram. Soc. 29 (2009) 323–327.
[59] G.S. Upadhyaya, V. Srikanth, Modern Developments in Powder Metallurgy, vol.
17, Metal Powder Industries Federation, Princeton, NJ, 1985, pp. 51–75.
[60] J.L. Chermant, F. Osterstock, J. Mater. Sci. 11 (1976) 1939–1951.
[61] M.M. Kalina, Z.G. Soboleva, V.N. Gorokhov, E.M. Rabinovich, Powder Metall.
Met. Ceram. 29 (1990) 406–409.
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Journal of Alloys and Compounds 509 (2011) 301–310

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jallcom

Effect of heating mode and sintering temperature on the consolidation of

90W–7Ni–3Fe alloys
Avijit Mondal a , Anish Upadhyaya b,∗ , Dinesh Agrawal c
a
NTPC Energy Technology Research Alliance (NETRA), National Thermal Power Corporation Ltd., Greater Noida 201308, India
b
Department of Materials Science and Engineering Indian Institute of Technology, Kanpur 208016, India
c
The Pennsylvania State University, University Park, PA 16802, USA

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

Article history: The present study compares the sintering response of 90W–7Ni–3Fe alloys consolidated in a 2.45 GHz
Received 6 April 2010 microwave furnace and a conventional furnace. The W–Ni–Fe compacts were sintered in a temperature
Received in revised form 28 August 2010 range of 1200–1500 ◦ C corresponding to solid-state as well as liquid phase sintering. The compacts were
Accepted 2 September 2010
successfully sintered in a microwave furnace with about 80% reduction in the overall processing time.
Available online 21 September 2010
For both the heating modes, the W–Ni–Fe alloys exhibited significant densification prior to melt for-
mation through solid-state sintering. The in situ dilatometric studies revealed that the contribution to
Keywords:
densification from solid-state sintering is higher at lower heating rates. In comparison to conventional
Sintering
Microwave heating
sintering, microwave sintered compacts showed relatively refined microstructure and higher hardness
Tungsten heavy alloy and flexural strength.
Microstructure © 2010 Elsevier B.V. All rights reserved.

1. Introduction and found that ductility of the alloys continuously decreases

Tungsten heavy alloys (WHAs) belong to a group of two-phase
composites, based on W–Ni–Cu and W–Ni–Fe alloys. Although
WHAs with Ni–Cu binder were initially developed, attention has
now been focussed on heavy alloys with Ni–Fe binder because of
their superior mechanical properties [1–3]. WHAs possess unique
combination of properties, such as high density (16–18 g/cm3 ), high
strength (1000–1700 MPa) and high ductility (10–30%) [3], ther-
mal conductivity and corrosion resistance. This makes them unique
in many applications such as radiation shields, vibration dampers,
kinetic energy penetrators and heavy-duty electrical contacts.
The highly dense W–Ni–Fe heavy alloys could be fabricated
only by liquid phase sintering [4]. Dzykovich et al. [5] have quan-
titatively analyzed the distribution of individual elements in the
tungsten grains and matrix phase in sintered W–Ni–Fe alloys. They
observed that addition of Fe decreases the solubility of W in Ni
and prevents the formation of an intermetallic phase. To avoid this,
the matrix composition is restricted to an optimal nickel to iron
ratio of 7:3 [5,6]. The sintered properties of WHAs exhibit a com-
plex dependence on particle size, matrix composition, sintering
time, temperature and atmosphere, heating/cooling rate, and post-
sintering heat-treatment. Rabin et al. [7] correlated the strength
and ductility of W–Ni–Fe heavy alloys with the microstructure
∗ Corresponding author. Tel.: +91 512 2597672; fax: +91 512 2597505.
E-mail address: anishu@iitk.ac.in (A. Upadhyaya).
with increasing tungsten content and an optimal combination of
strength and ductility is achieved at about 93 wt.% tungsten. Bel-
hadjhamida and German [8] too confirmed the decrease in ductility
with increasing tungsten content. However, they found that the
strength of W–Ni–Fe alloy increases with an increasing tungsten
content and attains a maximum at about 85 vol.% (93 wt.%) tung-
sten. Besides tungsten powder size and distribution, the properties
of W–Ni–Fe alloys are also influenced by sintering time and tem-
perature. Bourguignon and German [9] reported lower strength
and higher ductility of 93W–4.9Ni–2.1Fe alloy liquid phase sin-
tered at higher temperature. The strength decreased from 924 MPa
to 899 MPa and the ductility increased from 14% to 27% when the
sintering temperature was increased from 1465 ◦ C to 1580 ◦ C. This
was attributed to the rate of tungsten grain growth, which results
in proportionately higher fraction of matrix phase between the
grains. In yet another study, Bose et al. [10] reported similar effect
of temperature on strength and ductility of liquid phase sintered
90W–7Ni–3Fe system.
German et al. [11] studied the effect of sintering time on the
microstructure and mechanical properties of tungsten heavy alloys.
They reported that increasing sintering time obviously resulted in
microstructural coarsening, which degraded the mechanical prop-
erties. During the heating process, substantial changes in terms
of thermodynamics and microstructure occur with the tempera-
ture to minimize the free energy. Clearly, the changes are time and
heating rate dependent. Recently, Bollina and German [12] have
critically examined the effect of heating rate in conventional tech-

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doi:10.1016/j.jallcom.2010.09.008
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302 A. Mondal et al. / Journal of Alloys and Compounds 509 (2011) 301–310

Fig. 1. SEM micrographs of as-received (a) W, (b) Ni, and (c) Fe powder.

nique in a range from 1 ◦ C/min to 15 ◦ C/min, on densification during
liquid phase sintering of a range of W–Ni–Fe alloy compositions.
Conventional sintering requires long soaking time for W–Ni–Fe
alloys which results in undesired grain growth and precipitation of
brittle intermetallic phases. Microwave sintering of W–Ni–Fe com-
positions was studied by Upadhyaya et al. [13]. They investigated
the sintering response of a 92.5W–7.5(Ni–Fe) alloy – with a non-
optimal matrix composition – consolidated through microwaves
and compared its densification, microstructure and mechanical
properties with those of conventionally sintered compacts. Many
studies on microwave sintering of tungsten and its alloys have
been conducted earlier by several researchers [14–23]. Zhou et
al. [20] investigated the effect of heating rate on the microwave
sintered 90W–7Ni–3Fe heavy alloys, with the heating rate in the
range from 10 ◦ C/min to 112 ◦ C/min. They have shown that a faster
heating rate results in smaller W grain size and larger W–W con-
tiguity. The heating rate of 80 ◦ C/min has the best combination of
the microstructure and mechanical performance. The present study
evaluates the effect of heating mode and sintering temperature on
the sintering of 90W–7Ni–3Fe alloys.
was carried out in a MoSi2 -heated horizontal tubular furnace (model: OKAY 70T-7,
supplier: Bysakh, Kolkata, India) at a constant heating rate of 5 ◦ C/min. The sinter-
ing temperatures selected for the solid and liquid phase sintering of 90W–7Ni–3Fe
alloys were 1200 ◦ C, 1250 ◦ C, 1300 ◦ C, 1450 ◦ C and 1500 ◦ C, and sintering time was
kept constant at 60 min. All samples were processed in flowing H2 atmosphere
with dew point −35 ◦ C. Microwave sintering of the green compacts was carried out
using a multi-mode cavity, 2.45 GHz, 6 kW commercial microwave furnace (model:
RC/20SE, supplier: Amana Radarange). Further details of the microwave furnace and
experimental arrangements have been described elsewhere [17].
The sintered density was obtained by both dimensional measurements as well
as Archimedes principle. In order to take into account the influence of the ini-
tial as-pressed density, the compact sinterability was also expressed in terms of
densification parameter which is calculated as follows:
(Sintered density − green density)
Densification parameter = (2)
(Theoretical density − green density)
To compare the densification response of various compositions, the sintered
densities were normalized with respect to the theoretical density. The formulae

2. Experimental procedure

The as-received powders were characterized for their size, size distribution
and morphology. Table 1 summarizes the characteristics of the as-received W, Ni,
Fe powders used in the present study. Fig. 1 shows the scanning electron micro-
graphs of the precursor powders. The chemically reduced tungsten powder has
irregular, faceted morphology. Nickel powder, which was produced by carbonyl
decomposition, resulted in a rounded morphology with spiky appearance. Iron pow-
der was also produced by carbonyl decomposition. The alloy compositions were
prepared by mixing the required proportions of each powder in a turbula mixer
(model: T2C Nr 921266, supplier: Bachofen AG, Switzerland) for 60 min to ensure
complete homogeneity in the resultant powder mixture. For investigating the densi-
fication response and compaction studies of various compositions, cylindrical pellets
(diameter: 1.6 cm and height 0.8 cm) were pressed at 200 MPa using a uniaxial, semi-
automatic hydraulic press (model: CTM 50, supplier: FIE, Ichalkaranji, India) and
zinc-stearate powder as die-wall lubricant. The as-pressed green compact density
varied from 54% to 56% of the theoretical density of the alloy, calculated using the
inverse rule of mixtures.
To study the densification behavior, the green compacts were sintered using Fig. 2. Thermal profile of 90W–7Ni–3Fe alloy consolidated in a radiatively heated
conventional and microwave furnace. The conventional sintering of green compacts (conventional) and microwave furnace.
 Author's personal copy

A. Mondal et al. / Journal of Alloys and Compounds 509 (2011) 301–310 303

Table 1
Characteristics of the as-received powders used in the present study.

Powders W Ni Fe

Supplier Kennametal Widia India Ltd. INCO Kennametal Widia India Ltd.
Processing route Chemical reduction Carbonyl process Carbonyl process
Powder shape Irregular Spiky Spherical
Flow rate (s/50 g) Non-flowing Non-flowing 5.5

(Powder size, ␮m)

D10 2.0 3.8 1.4
D50 4.2 11.0 7.0
D90 6.2 31.8 19.0

Apparent density, g/cm3 (%theoretical) 4.8 (25%) 2.2 (25%) 3.1 (39%)
Tap density, g/cm3 (%theoretical) 6.3 (33%) 3.1 (35%) 3.7 (47%)

used for calculation of axial (ıA ) and radial shrinkage (ıR ) of the sintered cylindrical are similar to those reported by Upadhyaya et al. [13] in case of
compacts are given below: 92.5W–6.4Ni–1.1Fe alloys and more recently by Zhou et al. [20] in
  case of 90W–7Ni–3Fe system. Fig. 3 compares the temporal power
hs
ıA = 1− × 100% (3)
hg consumption in heating the 90W–7Ni–3Fe alloys. It is interesting to
  note that heating of the same compact in microwaves is achieved at
rs
ıR = 1− × 100% (4) much lower power consumption. This can be attributed to the fact
rg
that in microwaves only the sample per se heats up and acts as the
where hg and hs are heights; and rg and rs are radii of the green and sintered compact, source of heat. As a result, energy is primarily consumed in heat-
respectively.
ing up the sample only. Consequently, the effective thermal mass
For understanding the phenomenology of phase evolution, differential scanning
calorimetry (DSC) was used. The W–Ni–Fe compacts were heated to 1500 ◦ C at a reduction lowers the required power input. Despite such high heat-
constant rate of 10 ◦ C/min and subsequently cooled at a controlled rate (10 ◦ C/min) ing rate, no micro- or macro-cracking and distortion was observed
in a DSC unit (model: SDT2960, supplier: TA Instruments, New Castle, DE, USA). in microwave sintered samples (Fig. 4). This further underscores the
For measuring in situ axial shrinkage and shrinkage rate during sintering efficacy of unique volumetric heating associated with microwaves.
dilatometry experiments were performed using a vertical push rod dilatometer
in reducing atmosphere. The temperature inside the dilatometer (model: 1161V,
Anter, Pittsburgh, PA, USA) was accurate to ±2 ◦ C. It measures dimensional changes 3.2. Effect of heating mode and sintering temperature on
over the entire sintering cycle with precision of 1 ␮m. The dilatometry studies were densification
conducted at various heating rates (2 ◦ C/min, 5 ◦ C/min, and 10 ◦ C/min) and constant
cooling rate of 10 ◦ C/min. Metallographic techniques were employed on the sintered
samples. The sintered samples were wet polished in a manual polisher (model: Lunn Fig. 5a and b show the effect of sintering temperature on the
Major, supplier: Struers, Denmark) using a series of 6 ␮m, 3 ␮m and 1 ␮m diamond density and densification parameter of 90W–7Ni–3Fe alloy con-
paste, followed by cloth polishing using a suspension of 0.04 ␮m colloidal SiO2 sus- solidated in conventional and microwave furnaces, respectively.
pension. The scanning electron micrographs of as-polished samples were obtained
In case of conventional sintering the compacts were sintered up
by a scanning electron microscope (model: Quanta, supplier: FEI, The Netherlands)
in the secondary electron (SE) mode. Grain size measurement was done by line to 1500 ◦ C for 1 h. However, owing to slight distortion that was
intercept method. During the measurement it was assumed that there were no sub discerned in microwave sintering the compacts sintering tempera-
grain boundaries inside the tungsten grain. In the present study, quantitative anal- ture in microwave furnace was restricted to 1450 ◦ C, 30 min. In fact,
ysis was carried out on selected specimens using an EPMA (model: JXA-8600 SX microwave sintered compacts attained nearly full (>98.5%) density
Super-Probe, supplier: JEOL, Japan). Phase determination and phase evolution, if any
were studied for all the samples using X-Ray Diffractometer (model: Rich. Seifert
at 1450 ◦ C, 30 min. Prolonged soaking time in microwave led to
& Co., GmbH & Co. KG, Germany). Bulk hardness measurements were performed distortion of the compact and therefore was not employed.
on polished surfaces of sintered cylindrical compacts at a load of 5 kg using Vick- For both the heating modes, the sintered density increases with
ers hardness tester (model: V100-C1, supplier: Leco, Japan). The load was applied sintering temperature. Since the green density of the compacts was
for 30 s. Micro hardness tester (model: 8299, supplier: Leitz, Germany) was used to
evaluate the hardness of tungsten grains and the matrix phase. The loads applied on
tungsten grain and matrix phase during the micro hardness measurement were 50 g
and 15 g, respectively. The bulk hardness and the micro hardness values of tungsten
grain and matrix phase reported for each sample were an average of five read-
ings taken at different locations on respective phases. Transverse rupture strength
(TRS) measurements of sintered samples were performed following the procedure
described in MPIF Standard 41 [24].

3. Results and discussion

3.1. Heating response of W–Ni–Fe alloy

Fig. 2 compares the thermal profiles for 90W–7Ni–3Fe alloy con-

solidated in conventional and microwave furnaces, respectively.
From the figure, it is quite evident that 90W–7Ni–3Fe samples
effectively couple with the microwaves and undergo rapid heating.
The overall heating rate observed in case of microwave heating
was 29 ◦ C/min. It is also interesting to note that due to the less
thermal mass, the cooling rate in microwave furnace is relatively
higher. Taking into consideration the slow heating rate (5 ◦ C/min)
and isothermal holds at intermittent temperatures in conventional
furnace, microwave sintering results in about 80% reduction in Fig. 3. Input power variation with time in heating of 90W–7Ni–3Fe alloy compacts
the overall process time. These scales of the time compression in a conventional and microwave furnace.
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304 A. Mondal et al. / Journal of Alloys and Compounds 509 (2011) 301–310

Fig. 4. Photographs of the 90W–7Ni–3Fe compacts sintered in (a) conventional and (b) microwave furnace at temperatures ranging between 1200 ◦ C and 1450 ◦ C.

maintained the same, the densification parameter follows the sim-
ilar trend as sintered density. For all the sintering temperatures
microwave sintering resulted in enhanced densification. In fact,
microwave sintered compacts attained nearly full (>98.5%) density
at 1450 ◦ C. The increase in densification with increasing tempera-
ture can be attributed to the greater diffusivity of W in the binder. It
has been reported [25,26] that the diffusivity of tungsten in nickel
shows a drastic increase from 10−10 cm2 /s to about 10−5 cm2 /s as
the temperature increases from 1200 ◦ C to 1350 ◦ C.
Fig. 6a and b show the variation in the radial and axial shrinkage
with sintering temperature for the 90W–7Ni–3Fe alloys consol-
idated in conventional and microwave furnace, respectively. As
evident from the figure, for both the heating modes, shrinkage of
the cylindrical compacts in radial direction is invariably higher than
that measured axially. The shrinkage trend correlates well with the
densification results summarized in Fig. 5a. As compared to the
conventional sintering, the dimensional shrinkage in both radial as
well as axial direction is higher for compacts sintered in microwave
furnace. Elsewhere, similar results have been reported in other sys-
tems as well by Lenel et al. [27] and El-Shanshoury and Nazmy [28].
The anisotropy in the shrinkage has been attributed to the asym-
metry of the pore shape and its curvature that results due to the
compaction of the powders. As a result the radial direction under-
goes more shrinkage due to pore rounding. From Fig. 6, it can also be
inferred that the above trend (i.e. more radial shrinkage) is more
accentuated in case of microwave sintered compacts. While the
exact reason for this is not clear, however, based on the modeling
results [22] and literature report [29], it is hypothesized that the
curvature difference of the pores in the cylindrical compacts may
have resulted in differential microwave coupling, which, in turn,
may result in asymmetric dimensional change during heating.
To understand phenomenology of densification during sinter-
ing, it is important to first evaluate the phase changes that occur in
the premixed W–Ni–Fe powder compacts during thermal cycling.
To isolate the influence of tungsten addition on the associated phase
changes, DSC analysis was conducted separately for 70Ni–30Fe
and 90W–7Ni–3Fe system. The corresponding DSC curves are pre-
sented in Figs. 7 and 8, respectively. For the 90W–7Ni–3Fe compact,
two sequential endothermic peaks are formed at 1419 ◦ C and
1441 ◦ C during heating (Fig. 7a), and the corresponding exother-

Fig. 5. Effect of sintering temperature on the (a) density and (b) densification parameter of 90W–7Ni–3Fe alloys consolidated in conventional and microwave furnace.
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A. Mondal et al. / Journal of Alloys and Compounds 509 (2011) 301–310 305

Fig. 6. Effect of sintering temperature and heating mode on the (a) axial and (b) radial shrinkage of 90W–7Ni–Fe alloys.

mic peak upon cooling occurs at 1436 ◦ C and 1445 ◦ C, respectively
(Fig. 7b). According to the Fe–Ni phase diagram [30], iron and
nickel are mutually soluble over a wide temperature range. The
30:70 ( Fe, Ni) alloy melts congruently at 1445 ◦ C. The endother-
mic peak at 1441 ◦ C is related to the melting temperature of
Ni–Fe alloys. The depression in the solidification temperature under
non-equilibrium processing condition is well known [31]. Com-
pared with 7Ni–3Fe, the 90W–7Ni–3Fe compact exhibits a much
similar temperature range for liquid-phase formation and solidifi-
cation. During heating (Fig. 8a), the endothermic peak at 1477 ◦ C
represents the melting of the Ni–Fe matrix. In accordance, the
exothermic peak appears at 1471 ◦ C (Fig. 8b) corresponds to the
solidification of the binder melt. It is evident that the melting tem-
perature of the Ni–Fe matrix is well above the melting point of
elemental nickel and does not significantly change with the in situ
alloying among elemental Ni, Fe, and W powders. This agrees well
with the equilibrium conditions in Fe–Ni and Fe–Ni–W phase dia-
grams [30,32]. According to the Fe–Ni phase diagram [30], iron and
nickel are mutually soluble over a wide temperature range. The
30:70 ( Fe, Ni) alloy melts congruently at 1445 ◦ C. In the Fe–Ni–W
ternary alloys phase diagrams [32], ( Fe, Ni) also acts as one of the
main phases between 800 ◦ C and 1500 ◦ C, and the eutectic Ni–Fe–W
liquid phase forms at 1465 ◦ C. Besides liquid-phase formation, the
sintering process in the W–Ni–Fe alloy system may also involve
some other phase changes, most of which relate to the forma-

Fig. 8. DSC analysis of 90–7Ni–3Fe powder mixture during (a) heating and (b) cool-
Fig. 7. DSC analysis of 70Ni–30Fe alloy powder during (a) heating and (b) cooling ing at a constant rate of 10 ◦ C/min. The powders were heated up to 1500 ◦ C in
at a constant rate of 10 ◦ C/min. The powders were heated up to 1500 ◦ C in argon. argon.
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306 A. Mondal et al. / Journal of Alloys and Compounds 509 (2011) 301–310

Fig. 9. Dilatometric shrinkage and shrinkage rate curve of 90W–7Ni–3Fe compacts

heated up to 1500 ◦ C at a constant heating rate of 10 ◦ C/min.

tion of intermetallics [33,34]. As evident in Fig. 8, an endothermic

peak forms at 1253 ◦ C for the 90W–7Ni–3Fe compact during heat-
ing (Fig. 6a), and an exothermic peak appears at 1174 ◦ C upon its
cooling (Fig. 8b). These two peaks are very likely resulted from the
transformation of Fe7 W6 , which is the sole intermetallic phase in
the Fe–Ni–W alloy system above 1150 ◦ C [32]. The results from
the present study correspond well with those reported elsewhere
[12,35,36]. Unlike the previous reports [33,34], the alloy used in the
present study had a stoichiometric binder composition (Ni:Fe 7:3),
hence, formation of the intermetallic is not expected. However, as
the composition in the present study was prepared by powder mix-
ing, it is likely that this may have caused some local inhomogeneity Fig. 10. Dilatometric plots showing the effect of heating rate on the (a) linear shrink-
that may have resulted in formation of small amounts of inter- age and (b) shrinkage rate of 90W–7Ni–3Fe alloy heated up to 1500 ◦ C in reducing
atmosphere.
metallic phases which sensitive equipment such as DSC can readily
detect. To ensure good homogeneity, it would be interesting to con-
duct further studies using prealloyed Ni–Fe powders instead of the ature measurement and the differences in the atmosphere used,
premixed ones. this closely corresponds with the melt formation temperature of
From the DSC curves, it can be inferred that out of the five tem- this alloy determined using DSC (Fig. 8) and reported by others
peratures selected for conventional sintering, lower temperatures [12,35,36]. The enhanced densification at the onset of melting is
(1200 ◦ C, 1250 ◦ C and 1300 ◦ C) correspond to solid-state sintering, due to the capillary-induced arrangement. In addition, melt forma-
and the higher ones (1450 ◦ C and 1500 ◦ C) to liquid phase sintering. tion also results in enhanced tungsten solubility. The tungsten is
It is well known that due to faster diffusion rate and capillary-
induced stresses the densification kinetics is higher during liquid
phase sintered compacts [37]. The densification response of the
alloys in the present study (Fig. 5b) confirms that they are in accor-
dance with this. Another factor that contributes to densification
during liquid phase sintering is that the newly formed wetting melt
spreads to fill the small pores and preferentially penetrates the
grain boundaries [37,38]. Since tungsten has substantial solubility
into the Ni–Fe matrix, hence the melt tends to dissolve the interpar-
ticle necks and spreads out [39], this results in the decrease of the
solid–liquid interfacial energy below that of the equilibrium value
[40] and further contributes to densification in the initial period
just after melt formation.
To obtain a better insight about the densification response of
the 90W–7Ni–3Fe compacts, Fig. 9 plots the shrinkage and shrink-
age rate data of the alloy at various temperatures during heating at
a rate of 10 ◦ C/min in a dilatometer. The compact did not show
any significant dimensional change till about 1000 ◦ C. From the
figure, it is quite evident that up to 900 ◦ C the compact does not
undergo any significant shrinkage. Subsequently, a substantial por-
tion of the densification (10% linear shrinkage) occurs prior to the
melt formation. This is in agreement with the similar observations
Fig. 11. The peak shrinkage rate of 90W–7Ni–3Fe alloy at the onset of liquid forma-
reported by other researchers [41–43]. From the shrinkage rate
tion temperature plotted as a function of heating rate. The temperature at which the
curve (Fig. 9) it is evident that there is a sudden increase in the peak shrinkage occurs is also indicated on the plot. The data from Bollina and German
densification at 1463 ◦ C. Taking into account the error in temper- [12] on 88W–Ni–Fe (7:3) have also been superimposed for the sake of comparison.
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A. Mondal et al. / Journal of Alloys and Compounds 509 (2011) 301–310 307

Fig. 12. SEM micrographs of 90W–7Ni–3Fe compacts sintered in a conventional furnace (left) and microwave furnace (right) at (a) 1200 ◦ C, (b) 1250 ◦ C, 1300 ◦ C and (b)
1450 ◦ C, respectively.

preferentially dissolved from the interparticle necks and/or sharp
curvatures. This results in disruption of the solid-state sintered
W–W bonds and causes grain shape accommodation. Both results
in activating densification kinetics and accounts for the greater
shrinkage rates observed in Fig. 9.
In the above section, dilatometric investigation aided in under-
standing the influence of temperature on the phenomenology of
densification. Besides temperature, heating rate is also an impor-
tant parameter that influences the densification since it influences
not only the diffusivity but also alters the phase transforma-
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308 A. Mondal et al. / Journal of Alloys and Compounds 509 (2011) 301–310
tion temperature. Unfortunately, owing to the limitation of the
dilatometer used in the present investigation, the fast heating
rates obtained in microwave heating could not be achieved. Hence,
to evaluate the influence of heating rate on the sinterability, the
90W–7Ni–3Fe compacts were heated up to 1500 ◦ C at three heat-
ing rates, namely 2 ◦ C/min, 5 ◦ C/min and 10 ◦ C/min in a dilatometer.
The corresponding shrinkage and shrinkage rate variation at the
three heating rates are summarized in Fig. 10a and b, respectively.
It is interesting to note that the contribution to densification from
solid-state sintering is higher at lower heating rates (Fig. 10a). In the
temperature range corresponding to onset of melting, the effect of
heating rate is better reflected in the shrinkage rate plot (Fig. 10b)
since it is more sensitive to small changes in temperature. Inter-
estingly, the contribution of liquid phase sintering to densification
is higher for alloys sintered at higher heating rate. Similar effect
of heating rate on the shrinkage and shrinkage rate were observed
by Bollina and German [12] in 88W–Ni–Fe alloy (Ni/Fe ratio 7:3).
The shrinkage rate results near binder melting temperature (plot-
ted as inset to Fig. 10b) reveals that both the shrinkage rate and
matrix melting temperature shift to higher values as the heating
rate increases [Fig. 10b (inset)]. Fig. 11 shows the peak tempera-
ture corresponding to the maximum shrinkage rate in the present
alloy at various heating rates and along with the results from Bollina
and German [12] in a similar alloy system.
At any temperature the shrinkage rate is lower for a slower
heating rate. The point of maximum shrinkage rate indicates the
dissolution of solid-solid bonds by liquid phase and densification
due to rearrangement. If the solid-state densification is suppressed,
then melt formation significantly contributes to densification of
the compact. The shrinkage at any given temperature is higher for
the slower heating rate of 2 ◦ C/ min, since the slower heating rate
gives more time for solid-state diffusion prior to liquid formation.
As the compact becomes more dense prior to reaching the liquid
formation temperature, hence the contribution from liquid phase
sintering proportionately decreases at slower heating rates [44]. By
extending this argument it is hypothesized that during microwave
sintering the major contribution to densification stems from liquid
phase sintering. It is envisaged that the fast heating rates achieved
through microwaves restrict the W–W bond formation prior to
melting and thereby making the contribution to densification from
rearrangement more effective. Elsewhere too, researchers [44–46]
have proposed that slow heating rates are detrimental to rearrange-
ment.
3.3. Microstructural evolution during conventional and
microwave sintering
Fig. 12a–d compare the effect of heating mode on the
microstructure of the 90W–7Ni–3Fe compacts sintered at 1200 ◦ C,
1250 ◦ C, 1300 ◦ C, and 1450 ◦ C, respectively. At 1500 ◦ C, the
W–Ni–Fe compacts were only conventionally sintered and the cor-
responding microstructure is presented in Fig. 13. As expected,
for both conventional as well microwave heating, higher sinter-
ing temperatures, result in reduced porosity, more homogenous
distribution of the binder phase and coarser tungsten grains.
For compacts sintered at 1200 ◦ C and 1250 ◦ C, the microstruc-
tures are typical of those expected from solid-state sintering. In
case of conventional sintering, the compacts sintered at 1300 ◦ C,
again corresponds to solid-state sintering. In comparison, while
the microstructure of compacts conventionally sintered at 1450 ◦ C
exhibit significant grain coarsening, the tungsten grains still have
irregular shape which underscores solid-state sintering. Further
increase in the sintering temperature to 1500 ◦ C results in a typ-
ical liquid phase sintered microstructure with well-rounded and
less contiguous tungsten grains interspersed in a Ni–Fe matrix
(Fig. 13). These results when looked in isolation are as per
Fig. 13. Representative microstructure of 90W–7Ni–3Fe alloy liquid phase sintered
at 1500 ◦ C in a conventional furnace.
expected and correlate well with the DSC (Fig. 7) and dilatometric
(Fig. 8) observations. However, the corresponding microstructures
of 90W–7Ni–3Fe alloys microwave sintered at 1300 ◦ C and 1450 ◦ C
(Fig. 12c and d) are very intriguing. The samples microwave sin-
tered at these temperatures show significantly coarse tungsten
grains and the microstructure is similar to that expected of a typ-
ically liquid phase sintered W–Ni–Fe alloy! In view of the fact
that the matrix melting temperature in these alloys is elevated as
the heating rate increases (Fig. 11), this is even more perplexing.
This finding was validated by several repeated experiments. These
results are similar to those reported in 90W–7Ni–3Cu system [19]
and need to be more critically investigated.
One of the probable cause of this observation can be attributed
to the inherent problem in accurately measuring temperature
during microwave sintering. The temperature measurement for
the present study was done by optical pyrometer. To address
this inherent limitation, temperature was also measured using a
more accurate emmissivity-based infra-red pyrometer, wherein,
the emmissivity at various elevated temperatures was calibrated
(for the same composition compacts) in a conventional furnace.
Even in this, same results were obtained. One of the probable rea-
sons for this observation is also the critique that the pyrometer
based temperature measurements are an average of the surface
temperature only. It may be likely that – for multi-component sys-
tem, such as W–Ni–Fe alloys – the temperature in the interior of
the sample may be slightly higher. However, no gradient in the
microstructure was obtained in the sintered samples. One of the
likely explanations for such an observation therefore could be the
differential coupling of the constituents with microwave thereby
leading to anisothermal heating effect that has been reported to
cause rapid diffusion rates and onset of liquid phase sintering at
lower temperatures [47,48]. Besides microstructural coarsening,
as a consequence of this enhanced diffusion, the densification is
expected to be high, which is indeed the case (Fig. 5). This is further
confirmed by the EPMA results summarizing the effect of heating
mode and sintering temperature on the composition of the matrix
phase. Note that irrespective of the temperature, the amount of dis-
solved tungsten in microwave sintered alloy is higher than those
consolidated conventionally (Table 2).
Fig. 14a and b compare the XRD patterns of the samples sintered
at various temperatures in conventional and microwave furnace,
respectively. As discussed earlier, the choice of a stoichiometric
binder ratio (7:3) obviates intermetallic formation in any of the
sintered compact. The microwave sintered 90W–7Ni–3Fe alloys are
characterized by a change in the peak intensity and absence of some
of the matrix diffraction peaks. Such observations have also been
noticed in other systems as well and have been attributed to the
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A. Mondal et al. / Journal of Alloys and Compounds 509 (2011) 301–310 309

Table 2
Effect of heating mode and sintering temperature on the composition of the matrix phase in 90W–7Ni–3Fe alloys.

Temperature, ◦ C Heating mode Elemental content, wt. %

W Ni Fe

Conventional 8.11 ± 5.85 24.65 ± 17.85 67.48 ± 24.34

1200 ◦ C
Microwave 19.14 ± 10.9 45.24 ± 12.41 35.63 ± 24.62

Conventional 27.38 ± 5.8 57.67 ± 0.81 11.21 ± 6.35

1250 ◦ C
Microwave 30.23 ± 4.58 58.45 ± 0.38 10.18 ± 5.17

Conventional 21.04 ± 3.65 53.96 ± 4.00 23.19 ± 7.48

1300 ◦ C
Microwave 28.43 ± 0.5 51.07 ± 0.12 20.65 ± 0.41

Conventional 23.19 ± 1.05 52.63 ± 0.58 21.3 ± 0.34

1450 ◦ C
Microwave 25.62 ± 0.66 51.48 ± 0.28 21.7 ± 0.27

Conventional 22.96 ± 1.71 52.5 ± 0.76 21.77 ± 0.34

1500 ◦ C
Microwave – – –

Table 3
Effect of heating mode and sintering temperature on the average grain size, transverse rupture strength (TRS) and hardness (bulk and micro) of the 90W–7Ni–3Fe compacts.

Sintering temperature , ◦ C Heating mode Grain size, ␮m Hardness HV5 Vickers microhardness TRS MPa

WHV0.05 MatrixHV0.015

CON – 161 ± 27 – – 212

1300
MW 17 ± 7 325 ± 15 – – 751

CON 18 ± 11 289 ± 23 – – 782

1450
MW 20 ± 7 352 ± 11 475 ± 15 403 ± 14 1800 ± 11

1500 CON 26 ± 14 329 ± 17 454 ± 8 402 ± 14 1796 ± 19

creation of defects upon interaction with the microwaves [48,49].

The presence of such defects and their nature needs to be investi-
gated further through transmission electron microscopy (TEM) and
orientation imaging microscopy (OIM/EBSD) techniques.

3.4. Mechanical properties of sintered W–Ni–Fe alloys

Table 3 summarizes the effect of heating mode and sintering

temperature on the average grain size, bulk and micro-hardness
and the flexural strength of the 90W–7Ni–3Fe alloys. Owing to
the fine and contiguous microstructure, it is rather difficult to
accurately measure the tungsten grain size in solid-state sintered
compacts. For conventional sintering, the grain size measurements
were performed for samples sintered at 1450 ◦ C and 1500 ◦ C. In
case of microwave sintering, the grain sizes were quantified for
compacts sintered at 1300 ◦ C and 1450 ◦ C. Note that as compared to
conventionally liquid phase sintered alloys, the grain size was lower
for compacts consolidated in microwave furnace. This, along with
a higher sintered density, resulted in significantly higher hardness
and the bend strength in microwave sintered alloys. The hardness
values are similar or better than those reported previously [50,51].
The higher transverse rupture strength in microwave sintered sam-
ples can be attributed with the spheroidal tungsten grains which
are less contiguous and hence provide higher mean free path for
crack propagation [52–54]. It is well-recognized that the mechan-
ical properties of the as-sintered W–Ni–Fe alloys can be further
improved by heat-treatment [55,56]. In view of the high tungsten
solubility in the matrix, anomalous microstructural and phase evo-
lution during sintering, a future extension of the present set of study
could be to evaluate critically the detailed DSC analysis of the com-
position and also the effect of thermo-mechanical treatment on
the mechanical properties of microwave sintered tungsten heavy
alloys.

4. Conclusions
Fig. 14. XRD plots showing the effect of sintering temperature on the phase evolu-
tion in 90W–7Ni–3Fe alloy sintered in (a) conventional and (b) microwave furnace. In this study, 90W–7Ni–3Fe alloys were successfully sin-
tered both through solid-state as well as liquid phase sintering
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310 A. Mondal et al. / Journal of Alloys and Compounds 509 (2011) 301–310
in microwave furnace. As compared to conventional sintering,
microwave sintering resulted in about 80% reduction in the overall
processing time. To evaluate the influence of heating rate on the sin-
terability, the 90W–7Ni–3Fe compacts were heated up to 1500 ◦ C
at three heating rates, namely 2 ◦ C/min, 5 ◦ C/min and 10 ◦ C/min in
a dilatometer. The W–Ni–Fe alloys exhibit significant densification
prior to melt formation through solid-state sintering. The in situ
dilatometric studies reveal that the contribution to densification
from solid-state sintering is higher at lower heating rates. By corol-
lary, the contribution of liquid phase sintering to densification is
higher for alloys sintered at higher heating rate. It is also interesting
to note that microwave sintered compacts had a well-developed
liquid phase sintered structure at about 50 ◦ C lower temperature
as compared to conventional sintering. Accordingly, microwave
sintered compacts had about 23% lower tungsten grain size and
22% improvement in the bulk hardness (352 VHN). As compared to
90W–7Ni–3Fe alloys sintered at 1450 ◦ C in a conventional furnace,
microwave sintering led to significant (∼130%) improvement in the
transverse rupture strength from 782 MPa to 1800 MPa.
Acknowledgement
This collaborative research was done as a part of the Center
for Development of Metal-Ceramic Composites through Microwave
Processing which was funded by the Indo-US Science and Technol-
ogy Forum (IUSSTF), New Delhi.
References
[1] A. Upadhyaya, Trans. Indian Inst. Met. 55 (2002) 51–69.
[2] E. Lassner, W.D. Schubert, Tungst: Properties, Chemistry, Technology of the
Elements, Alloys, Chemical Compounds, Kluwer Academic/Plenum Publishers,
New York, NY, USA, 1999.
[3] V. Srikanth, G.S. Upadhyaya, Int. J. Refract. Hard Met. 5 (1986) 49–54.
[4] R.M. German, Liquid Phase Sintering, Plenum Press, NY, 1985.
[5] I.Y. Dzykovich, R.V. Makarova, O.K. Teodorovich, I.N. Frantsevich, Sov. Powder
Metall. Met. Ceram. 4 (1965) 655–660.
[6] S.G. Caldwell, in: A. Bose, R.J. Dowding (Eds.), Tungsten and Tungsten
Alloys—1992, Metal Powder Industries Federation, Princeton, NJ, 1992, pp.
89–96.
[7] B.H. Rabin, A. Bose, R.M. German, Int. J. Powder Metall. 25 (1989) 21–27.
[8] A. Belhadjhamida, R.M. German, in: E.S. Crowson, Chen (Eds.), Tungsten and
Tungsten Alloys—Recent Advances, The Minerals, Metals & Materials Society,
Warrendale, PA, USA, 1991, pp. 3–19.
[9] L.L. Bourguignon, R.M. German, Int. J. Powder Metall. 24 (1988) 115–121.
[10] A. Bose, D. Sims, R.M. German, Metall. Trans. A 19 (1988) 487–494.
[11] R.M. German, A. Bose, S.S. Mani, Metall. Trans. A 23 (1992) 211–219.
[12] R. Bollina, R.M. German, Int. J. Refract. Met. Hard Mater. 22 (2004) 117–
127.
[13] A. Upadhyaya, S.K. Tiwari, P. Mishra, Scripta Mater. 56 (2007) 5–8.
[14] M. Jain, G. Skandan, K. Martin, K. Cho, B. Klotz, R. Dowding, D. Kapoor, D. Agar-
wal, J. Chang, Int. J. Powder Metall. 42 (2006) 53–57.
[15] M. Jain, G. Skandan, K. Martin, K. Cho, B. Klotz, R. Dowding, D. Kapoor, D. Agar-
wal, J. Chang, Int. J. Powder Metall. 42 (2006) 45–50.
[16] G. Prabhu, A. Charkraborty, B. Sarma, Int. J. Refract. Met. Hard Mater. 27 (2009)
545–548.
[17] A. Mondal, A. Upadhyaya, D. Agrawal, J. Microwave Power Electromagn. Energy
JMPEE 43 (2009) 11–16.
[18] S.D. Luo, J.H. Yi, Y.L. Guo, Y.D. Peng, L.Y. Li, J.M. Ran, J. Alloys Compd. 473 (2009)
L5–L9.
[19] A. Mondal, A. Upadhyaya, D. Agrawal, Mater. Sci. Eng. A 527 (2010) 6870–6878.
[20] C. Zhou, J. Yi, S. Luo, Y. Peng, L. Li, G. Chen, J. Alloys Compd. 482 (2009) L6–L8.
[21] A. Mondal, D. Agrawal, A. Upadhyaya, J. Microwave Power Electromag. Energy
JMPEE, 44, in press.
[22] A. Mondal, Modeling of Microwave Heating of Particulate Metals and its Appli-
cation in Sintering of Tungsten-Based Alloys, Ph.D. Thesis, The Indian Institute
of Technology, Kanpur, 2010.
[23] D. Agrawal, J. Cheng, M. Jain, G. Skandan, R. Dowding, K. Cho, B. Klotz, D. Kapoor,
Eighth Int. Conf. Sci. Hard Mater., 2004, pp. 143–144.
[24] MPIF Standard 41, Standard Test Methods for Metal Powders and Powder Met-
allurgy Products, MPIF, Princeton, New Jersey, USA, 2002, pp. 55–57.
[25] G.E. Murch, C.M. Bruff, Diffus. Solid Met. Alloys 26 (1990) 279–371.
[26] J.P. Leonard, T.J. Renk, M.O. Thompson, M.J. Aziz, Metall. Mater. Trans. A 35
(2004) 2803–2807.
[27] F.V. Lenel, H.H. Hausner, E. Hayashi, G.S. Ansell, Powder Metall. 8 (1961) 25–36.
[28] I.A. El-Shashoury, M.Y. Nazmy, Powder Metall. 11 (1968) 63–72.
[29] M. Wllert-Porada, Microwave: Theory and Applications in Materials Processing
IV, 1998, pp. 158–164.
[30] J.I. Goldstein, Alloy Phase Diagram, ASM Metals Reference Book, American Soci-
ety for Metals, Metals Park, OH, 1981.
[31] D.M. Stefanescu, Science and Engineering of Casting Solidification, 2nd ed.,
Springer, New York, NY, USA, 2009, pp. 1–20.
[32] P. Villars, A. Prince, H. Okamoto, Handbook of Ternary Alloy Phase Diagrams,
ASM International, Materials Park, OH, 1997.
[33] B.C. Muddle, Metall. Trans. A 15 (1984) 1089–1098.
[34] J.B. Posthill, D.V. Edmonds, Metall. Trans. A 17 (1986) 1921–1934.
[35] S.S. Mani, R.M. German, Advances in Powder Metallurgy, vol. 1, Metal Powder
Industries Federation, Princeton, NJ, 1990, pp. 453–467.
[36] Y. Wu, R.M. German, B. Marx, P. Suri, R. Bollina, J. Mater. Sci. 38 (2003)
2271–2281.
[37] V.L. Yupko, R.V. Minakova, O.P. Kolchin, L.S. Vodopyanova, N.I. Monastyreva,
V.L. Voitenko, Sov. Powder Metall. Met. Ceram. 22 (1983) 44–47.
[38] R.M. German, P. Suri, S.J. Park, J. Mater. Sci. 44 (2009) 1–39.
[39] L. Ekbom, A. Eliasson, Processing of Powder Metallurgy World Congress PM’94,
vol. II, European Powder Metallurgy Association, Shrewsbury, UK, 1994, pp.
1565–1572.
[40] I.A. Aksay, C.I. Hoge, J.A. Pask, J. Phys. Chem. 78 (1974) 1178–1183.
[41] A. Upadhyaya, J. Mater. Chem. Phys. 67 (2001) 101–110.
[42] W.E. Gurwell, in: A. Bose, R.J. Dowding (Eds.), Tungsten and Refractory Metals,
vol. 2, Metal Powder Industries Federation, Princeton, NJ, 1994, pp. 65–75.
[43] F. Akhtar, Int. J. Ref. Met. Hard Mater. 26 (2008) 145–151.
[44] R.M. German, S. Farooq, in: S. Sōmiya, M. Shimada, M. Yoshimura, R. Watanabe
(Eds.), Sintering’87, vol. 1, Elsevier Science Publishing Co. Inc., New York, NY,
1988, pp. 459–464.
[45] G.J. Shu, K.S. Hwang, Mater. Trans. 46 (2005) 298–302.
[46] B.D. Storozh, P.S. Kislyi, Powder Metall. Met. Ceram. 13 (2005) 712–716.
[47] R.D. Peelamedu, R. Roy, D. Agrawal, Mater. Res. Bull. 36 (2001) 2723–2739.
[48] R. Roy, Y. Fang, J. Cheng, D.K. Agrawal, J. Ceram. Am. Soc. 88 (2005) 1640–1642.
[49] R. Peelamedu, R. Roy, L. Hurtt, D. Agrawal, A.W. Fliflet, D. Lewis III, R.W. Bruce,
Mater. Chem. Phys. 88 (2004) 119–129.
[50] V. Srikanth, G.S. Upadhyaya, J. Mater. Sci. Lett. 7 (1988) 195–197.
[51] M. Debata, A. Upadhyaya, J. Mater. Sci. 39 (2004) 2539–2541.
[52] G.S. Upadhyaya, V. Srikanth, Modern Developments in Powder Metallurgy, vol.
17, Metal Powder Industries Federation, Princeton, NJ, 1985, pp. 51–75.
[53] I.S. Humail, F. Akhtar, S.J. Askari, M. Tufail, X. Qu, Int. J. Refract. Met. Hard Mater.
25 (2007) 380–385.
[54] S.H. Islam, X. Qu, S.J. Askari, M. Tufail, X. He, Rare Met. 26 (2007) 200–204.
[55] S.G. Caldwell, Int. J. Powder Metall. 39 (2003) 43–51.
[56] W.H. Baek, M.H. Hong, E.P. Kim, J.W. Noh, S. Lee, H.S. Song, S.H. Lee, Solid State
Phenom. 118 (2006) 35–40.
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Int. Journal of Refractory Metals and Hard Materials 28 (2010) 597–600

Contents lists available at ScienceDirect

Int. Journal of Refractory Metals and Hard Materials

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / I J R M H M

Effect of heating mode on sintering of tungsten

Avijit Mondal a, Anish Upadhyaya a,⁎, Dinesh Agrawal b
a
Department of Materials and Metallurgical Engineering, Indian Institute of Technology, Kanpur 208016, India
b
The Pennsylvania State University, University Park, PA 16802, USA

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

Article history: Microwave heating is recognized for its various advantages, such as time and energy saving, very rapid
Received 4 February 2010 heating rates, considerably reduced processing cycle time and temperature, fine microstructures and
Accepted 5 May 2010 improved properties. The present paper investigates the feasibility of consolidating tungsten powders
through microwave sintering. A comparative analysis has also been attempted between the sintering
Keywords: response of pure tungsten powder compact in a microwave and conventional furnace.
Microwave sintering
© 2010 Elsevier Ltd. All rights reserved.
Tungsten
Microstructures

1. Introduction
Tungsten belongs to Group VIB of periodic table. As a refractory
metal, tungsten is characterized by its very high melting point
(3420 °C), high density (19.3 g/cm3), low coefficient of thermal
expansion (4.4 ppm/K at 20 °C) and superior mechanical properties
at elevated temperatures, which render it highly suitable for many
engineering applications such as lighting filaments, heating source,
aerospace, electronic devices, sports and military uses, etc. [1]. Owing
to very high fusion point, the consolidation of a conventional
microcrystalline W powder is difficult and generally requires a
temperature in excess of 1700 °C through solid-state sintering in
electrical resistance sintering furnace under hydrogen atmosphere.
Achievement of near theoretical sintered densities for pure tungsten
at temperatures below 1650 °C is typically not feasible [2]. Densification
of refractory metals, such as tungsten, can be enhanced greatly by
activating the sintering process wherein the sintering temperature is
appreciably lowered. Activated sintering refers to combination of
processing approaches that reduce the activation energy for sintering.
One such technique to activate sintering is by addition of small amounts
(b1 wt.%) of Group VIII transition metals [3–6]. It has been reported that
the sintering temperature of tungsten can be brought down from
2800 °C to 1400 °C by less than 1 wt.% addition of transition metals, such
as palladium and nickel [6]. German and Munir [5,6] have extensively
investigated the role of various transition metal additions in densifica-
tion activation of tungsten powder compacts. From their study, it is quite
evident that some transition metals (e.g. Pd, Ni) enhance densification,
while others (e.g. Ag, Cr) have little influence. Densification enhance-
ment in tungsten by transition metal additives was attributed to
⁎ Corresponding author. Tel.: + 91 512 2597672; fax: + 2597505.
E-mail address: anishu@iitk.ac.in (A. Upadhyaya).
enhanced solubility and mass transport kinetics. The additives which
remain segregated to the W–W powder interface and in which tungsten
has appreciable solubility, act as short-circuit diffusion pathways,
thereby promoting densification.
Another important approach to activate sintering of tungsten is
through selection of submicron or nano-sized precursor tungsten
powder. However, such powders are expensive and are prone to
contamination [7]. Many studies have shown that sintering temper-
ature is related to the powder size, when the size is in nano-scale, the
sintering temperature can be decreased up to several hundreds of
degrees. The reduction of sintering temperature for nano tungsten has
been reported by several researchers [7–10]. Bose et al. [7] have also
shown that pressure assisted process such as plasma pressure
compaction helps in the reduction of process temperature. The
reported sintering temperature of nano-sized tungsten produced by
high energy mechanical milling was drastically decreased from
conventional temperature of 2500 °C to 1700 °C [8]. Other processes
such as hot-isostatic processing [10], and spark plasma sintering [11],
too result in further reduction in the processing temperature.
Because of the characteristic feature and obvious advantages,
application of microwave energy in consolidating particulate materi-
als has become a preferred method over conventional (resistant
heating) technique. The application of microwave energy in consol-
idating tungsten powders was first studied by Jain et al. [12]. A
comprehensive study on microwave sintering of tungsten and its
alloys were also conducted by several researchers [13–21]. This paper
reports the consolidation of nano-sized tungsten powder through
microwave and conventional sintering methods. To evaluate the
interaction of microwaves, tungsten powder with a median particle
size of 72 nm was subjected to 2.45 GHz microwaves in a multimode
furnace. For comparing the effect of heating mode, in a parallel set of
experiments, tungsten powder compacts pressed to similar green
density levels were consolidated in a conventional furnace.

0263-4368/$ – see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijrmhm.2010.05.002
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598 A. Mondal et al. / Int. Journal of Refractory Metals and Hard Materials 28 (2010) 597–600
2. Experimental procedure
Tungsten of average crystallite size of 72 nm powders was
supplied by NEI Corporation, New Jersey, USA. The as-received
powders were pressed in a die of 1.6 cm inner diameter to make the
green compacts of approximately 0.3 to 0.4 cm in height. The green
density was around 49% of theoretical. To study the densification
behavior the green (as-pressed) compacts were sintered using
conventional and microwave furnace. The conventional sintering of
green compacts was conducted in a MoSi2 heated horizontal tubular
sintering furnace (model: OKAY 70T-7, supplier: Bysakh, Kolkata,
India). Microwave sintering of the green compacts was carried out
using a multimode cavity 2.45 GHz, 6 kW microwave furnace. Further
details of the microwave furnace and experimental arrangements
have been described elsewhere [19]. For each set of experiments
(conventional and microwave sintering) four samples were investi-
gated and the as-sintered samples were characterized for sintered
density through both dimensional measurements as well as Archi-
medes' density measurement techniques. To take into account the
influence of the initial as-pressed density, the compact sinterability
was also expressed in terms of densification parameter which is
calculated as follows:
ðsintered density−green densityÞ
Densification parameter = ð1Þ
ðtheoretical density−green densityÞ
Metallographic techniques were employed on the sintered
samples. The sintered samples were wet polished in a manual
polisher (model: Lunn Major, supplier: Struers, Denmark) using a
series of 6 µm, 3 µm and 1 µm diamond paste, followed by cloth
polishing using a suspension of 0.04 µm colloidal SiO2 suspension.
Murakami's reagent was used for etching the sintered tungsten
samples. The scanning electron micrographs of as-polished samples
were obtained by a scanning electron microscope (model: FEI quanta,
Netherlands) in the secondary electron (SE) and back scattered (BSE)
mode. Bulk hardness measurements were performed on polished
surfaces of sintered cylindrical compacts at a load of 5 kg using Vickers
hardness tester (model: V100-C1, supplier: Leco, Japan).
3. Results and discussion
3.1. Effect of heating mode on sintering of tungsten
Fig. 1 compares the thermal profiles for tungsten powder compacts
heated in conventional and microwave furnace. It is interesting to
note that W compact couples with microwaves and gets heated up
Fig. 1. Comparison of the thermal profiles of tungsten compact sintered in a radiatively-
heated (conventional) and microwave furnace.
quite rapidly. Tungsten powders owing to their fine size are
susceptible to oxidation and hence need to be processed in reducing
(hydrogen) atmosphere. Due to the poor thermal shock resistance of
the alumina tube used, the heating rate of the conventional sintering
was restricted to 5 °C/min. Furthermore, to ensure homogenization of
the temperature, isothermal hold at intermediate sintering tempera-
tures was provided. Unlike conventional sintering, in a microwave
furnace, the tungsten powder compact per se acts as a source of heat
since it couples directly with microwaves. Consequently, the overall
heating rate achieved in microwave furnace was ∼25 °C/min for the
tungsten compacts. Taking into consideration the lower heating rate
and the intermittent isothermal holds in conventional furnace
sintering, there is about 90% reduction in the overall processing
time during microwave sintering.
Unlike ceramic materials microwave interaction with metals is
restricted to its surface only. This depth of penetration in metals, also
known as skin depth (δ), is defined as the distance into the material at
which the incident power drops to 1/e (36.8%) of the surface value.
The skin depth is mathematically expressed as follows:
1
δ = pffiffiffiffiffiffiffiffiffiffiffiffi ð2Þ
πf μσ
where, f is the microwave frequency (2.45 GHz), μ is the magnetic
permeability, σ is the electrical conductivity, and ρ is the electrical
resistivity of the metals. From Eq. (2), it is evident that metals with
higher electrical conductivity have lower skin depths. For metals, as
the resistivity increases with increase in temperature, the skin depth
too increases. Resistivity as a function of temperature has been
considered from the literature [22] and Fig. 2 plots the effect of
temperature on the skin depth of tungsten. For the sake of comparison
similar graphs have been plotted for various other conductive metals
as well. It is interesting to note as compared to some other metals, the
skin depth of tungsten is relatively higher. Since the initial tungsten
powder size is lower hence the compacts undergo relatively
homogenous heating despite the heating rate being so high. Since
the objective of the present work was to restrict the temperature to
1600 °C, owing to the small size of the initial powder the temperature
was achieved in just applying 900 W of power. In comparison, to heat
the similar compact in a conventional furnace wherein the heat
transfer was indirect and limited by the radiative losses, the input
power was on an average 2.1 kW. While it is possible to increase the
heating rate in the conventional sintering by increasing the power
throughput, it will be at the expense of overall furnace life. One such
experiment was tried; however, the as-pressed compact could not
withstand the thermal gradient and pulverized during processing.
Recently, Prabhu et al. [14] too have reported microwave sintering
of tungsten powders prepared by high energy milling. However, as
compared to our study, they could achieve 93% theoretical density at
1800 °C with a heating rate of 7.8 °C/min and at a power throughput
Fig. 2. The variation in the skin depth of tungsten subjected to 2.45 GHz microwave. For
comparison, the skin depths of some common metals have been plotted for various
temperatures.
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A. Mondal et al. / Int. Journal of Refractory Metals and Hard Materials 28 (2010) 597–600
Fig. 3. Effect of heating mode on (a) the sintered density and densification parameter and (b) the axial and radial shrinkage of tungsten compact. All compacts were pressed at
100 MPa and sintered at 1600 °C in reducing atmosphere.
of 16 kW. Furthermore, they did not compare their sintering results
with the conventionally sintered W powder compacts.
3.2. Densification response of sintered tungsten
Fig. 3a compares the effect of heating mode on the sintered density
and densification parameter of tungsten powder compact. It is worth
noticing that irrespective of the heating mode the compacts undergo
significant densification during sintering. This can be attributed to the
ultra-fine particle size of the powder used for this investigation.
Elsewhere, Wang et al. [10] too reported similar sintering response of
ultra-fine sized tungsten powder. The sintered density of the W
powder compacts in microwave increased from 90% to 95% for pure
tungsten compacts when compared with conventional heating. The
densification parameter is a normalized parameter which takes into
consideration the initial variation of the green density on the
densification response. Since, the initial density of the W powder
compact was kept the same hence the densification parameter follows
a similar trend as the sintered density.
Usually, the sintering characteristics of the tungsten powders have
been investigated in micron-sized powders [10]. For achieving small
sizes, these powders were usually milled [8]. Due to the contamina-
tion from the milling media and high defect structure within the
crystallites, proper evaluation of the sintering response of the
tungsten powder is usually difficult. However, the general consensus
in the literature has converged to the fact that for submicron/nano
Fig. 4. SEM photomicrograph of (a) the as-pressed tungsten powder and the powder compact sintered at 1600 °C for 30 min in (b) conventional and (c) microwave furnace.
599
particle sizes the onset of densification occurs at lower temperatures
of 0.2–0.4Tm (Tm — melting temperature in K) as compared to 0.5–
0.8Tm for micron-sized powders [23]. Moreover, it has been
established that for nano-structured powders, grain boundary sliding
and rotation and viscous flow significantly contribute to densification
enhancement [24–27]. In the present study, due to the chemical
processing route, the tungsten powders were prepared in nano-scale
in strain free condition. The sintering temperature selected for the
present study corresponds to 0.46Tm.
Jain et al. [12] also reported about 10 to 12% higher density in case
of microwave sintered compacts over the conventional heating. More
recently, Prabhu et al. [14] have also investigated microwave sintering
of high energy milled tungsten powder compacts. However, in their
experiments the compacts were sintered under nitrogen atmosphere
and at a high temperature (1800 °C). Despite consolidating at such a
high temperature, the sintered density was less than that achieved in
this study. It can therefore be inferred that for effective utilization of
the microwave heating, the powder compacts must be sintered in
reducing atmosphere.
Fig. 3b shows the axial and radial shrinkage of the cylindrical
tungsten compacts sintered in a conventional and microwave furnace.
Due to the low green density (49%), the compacts heated in both the
modes undergo substantial shrinkage. In case of conventional
sintering, however, the radial shrinkage is more than that observed
in the longitudinal (axial) direction. In contrast, the shrinkage in both
the directions is nearly similar for microwave sintered compacts
 Author's personal copy
600 A. Mondal et al. / Int. Journal of Refractory Metals and Hard Materials 28 (2010) 597–600
Table 1
Average grain size and bulk hardness of conventionally and microwave sintered
tungsten powder compacts.
Heating mode Grain size, µm Hardness, HV5
Conventional 2.9 ± 1.1 412 ± 12
Microwave 2.6 ± 1.0 441 ± 9
which indicates more isotropic shrinkage behavior. This further
confirms that the compact heating in microwaves is more uniform
despite the high heating rate. This is attributed to the volumetric
heating microwave provides.
3.3. Effect of heating mode on microstructure and hardness
To investigate the effect of heating mode on the microstructural
coarsening and its homogeneity, the as-sintered compacts were
metallographically prepared. Fig. 4a shows the SEM micrograph of the
as-pressed tungsten powder. Fig. 4b and c shows the photomicro-
graphs of compacts sintered in conventional and microwave furnace,
respectively. It is worth noticing that as owing to the initial low as-
pressed density, sintering results in significant microstructural
coarsening in tungsten powder compacts. For both the heating
modes, the as-sintered compacts attain well-developed polyhedral
grains. The average tungsten grain size was measured using intercept
method and is summarized in Table 1. From Fig. 4 and Table 1, it is
evident that varying heating modes have not significantly influenced
the microstructures.
Table 1 also compares the effect of heating mode on the bulk
hardness of the sintered tungsten compacts. As expected, the
microwave sintered compacts have higher hardness. This can be
attributed to the higher density and a more refined microstructure of
the tungsten grains in case of microwave sintering. The hardness of W
compact achieved through microwave sintering in this study is higher
than those reported earlier by Upadhyaya et al. [15] and Kim et al.
[28]. The hardness results achieved in microwave sintered W
compacts in the present study is 30% higher than the best values
(303VHN) achieved by Prabhu et al. [14] by microwave sintering
tungsten compact at 1800 °C.
4. Conclusions
In this study, tungsten powder compact was successfully consol-
idated through microwave sintering. It is interesting to note that
tungsten compact strongly couples with microwaves and gets heated
very rapidly. This result in the drastic reduction in the sintering cycle
time over the conventional process: up to as high as 90%. Despite
being heated at high heating rates, none of the tungsten powder
compacts displayed any distortion or cracking during microwave
heating. This underscores the volumetric heating aspects of micro-
waves. Moreover, due to the low thermal mass, microwave heating
was less energy (power) consuming as compared to the equivalent
volume of material being consolidated conventionally. Another
common observation is that the microwave sintered compacts
undergo more densification as compared to their conventionally
processed counterparts. Because of the rapid heating rates achieved in
microwave furnace, the microstructure coarsening was relatively
lower. Consequently, as compared to conventional sintering, the
mechanical properties of the microwave sintered compacts were
higher.
Acknowledgement
The authors would like to acknowledge NEI Corporation, New
Jersey, USA for supplying the powder used for this investigation. This
study was also partially supported by the Indo-US Science and
Technology Forum (IUSSTF), New Delhi and the Institute for Plasma
Research (IPR), Ahmedabad.
References
[1] Lassner E, Schubert WD. Tungsten: properties, chemistry, technology of the
elements, alloys, and chemical compounds. New York, NY, USA: Kluwer Academic/
Plenum Publishers; 1999.
[2] German RM. Critical developments in tungsten heavy alloys. In: Bose A, Dowding
RJ, editors. Tungsten and tungsten alloys — 1992. Princeton, NJ, USA: Metal
Powder Industries Federation; 1992. p. 3–13.
[3] Hayden HW, Brophy JH. The activated sintering of tungsten with Group VIII
elements. J Electrochem Soc 1963;110(7):805–10.
[4] Shaler AJ. Activated sintering — a review. In: Kuczynski GC, editor. Sintering and
related phenomena. New York, NY, USA: Gordon and Breach; 1967. p. 807–23.
[5] German RM, Munir ZA. Systematic trends in the chemically activated sintering of
tungsten. High Temp Sci 1976;8:267–80.
[6] German RM, Munir ZA. Enhanced low-temperature sintering of tungsten. Metall
Mater Trans A 1976;7A:1873–7.
[7] Bose A, Klotz BR, Kellogg FR, Cho KC, Dowding RJ. Nanocrystalline Tungsten
Powder Synthesis Using High Energy Milling. Proc. 2008 Intl Conf on W, Refract &
Hardmetals VII, Publ MPIF, 5-35 – 5-48.
[8] Malewar R, Kumar KS, Murty BS, Sarma B, Pabi SK. On sinterability of
nanostructured W produced by high-energy ball milling. J Mater Res 2007;22
(5):1200–6.
[9] Johnson JL. Progress in Processing Nanoscale Refractory and Hardmetal Powders.
Proc. 2008 Intl Conf on W, Refract & Hardmetals VII, Publ MPIF, 5-57 – 5-71.
[10] Wang H, Fang Z, Siddle D. Study of size-dependent sintering behavior of tungsten
powders. Tungsten, Refractory & Hardmetals VII. Princeton: Metal Powder
Industries Federation; 2008. 5-72 – 5-77.
[11] Oda1 E, Ameyama K, Yamaguchi S. Fabrication of nano grain tungsten compact by
mechanical milling process and its high temperature properties. Mater. Sci.
Forum; 2006. 503-504, 573-578.
[12] Jain M, Skandan G, Martin K, Cho K, Klotz B, Dowding R, et al. Microwave sintering:
a new approach to fine-grain tungsten-II. Int J Powder Metall 2006;42(2):53–7.
[13] Jain M, Skandan G, Martin K, Cho K, Klotz B, Dowding R, et al. Microwave sintering:
a new approach to fine-grain tungsten-I. Int J Powder Metall 2006;42(2):45–50.
[14] Prabhu G, Charkraborty A, Sarma B. Microwave sintering of tungsten. Int J Refract
Hard Met 2009;27:545–8.
[15] Upadhyaya A, Tiwari SK, Mishra P. Microwave sintering of W–Ni–Fe alloy. Scripta
Mater 2007;56:5–8.
[16] Luo SD, Yi JH, Guo YL, Peng YD, Li LY, Ran JM. Microwave sintering W–Cu
composites: analyses of densification and microstructural homogenization. J
Alloys Comp 2009;473:L5–9.
[17] Zhou C, Yi J, Luo S, Peng Y, Li L, Chen G. Effect of heating rate on the microwave
sintered W–Ni–Fe heavy alloys. J Alloys Comp 2009;482:L6–8.
[18] Mondal A, Agrawal D, Upadhyaya A. Microwave Sintering of Refractory Metals/
Alloys: W, Mo, Re, W–Cu, W–Ni–Cu and W–Ni–Fe Alloys. J. Microwave Power
Electromagnetic Energy in press;44.
[19] Mondal A, Agrawal D, Upadhyaya A. Microwave and conventional sintering of
premixed and prealloyed tungsten heavy alloys. Mater Sci Tech 2008:2502–15.
[20] Mondal A, Upadhyaya A, Agrawal D. Microwave sintering of W–18Cu and W–7Ni–
3Cu alloys. J Microw Power Electromagn Energy 2009;43(1):11–6.
[21] Mondal A, “Modeling of Microwave Heating of Particulate Metals and its
Application in Sintering of Tungsten-Based Alloys”, Ph.D. Thesis, The Indian
Institute of Technology, Kanpur, submitted.
[22] Brandes EA, Brook GB. Smithells metals reference book7th ed. . Oxford, UK:
Butterworth Heinemannn; 2000.
[23] Groza JR. Sintering of nanocrystalline powders. Int J Powder Metall 1999;35:59.
[24] Hahn H. Microstructure and properties of nanostructured oxides. Nanostructured
Mater 1993;2:251.
[25] Averbach RS, Zhu H, Tao R, Hofler HJ. In: Bourell DL, editor. Sintering of
nanocrystalline materials: experiments and computer simulations. synthesis and
processing of nanocrystalline powder. Warrendale, PA: TMS; 1996. p. 203–16.
[26] Bourell L, Groza JR. Consolidation of ultra fine and nanocrystalline powder. ASM
handbook, vol. 7. Metals Park, OH: American Society of Metals; 1998. p. 583–9.
[27] Groza JR. Nanocrystalline powder consolidation methods. In: Koch CC, editor.
Nanostructured materials—processing, properties and potential applications. New
York, NY: Noyes; 2002. p. 115–78.
[28] Kim YM, Hong MH, Lee SH, Kim EP, Lee S, Noh JW. The effect of yttrium oxide on
the sintering behavior and hardness of tungsten. Met Mater Int 2006;12(3):
245–8.
Comparative study of densification and
microstructural development in W–18Cu
composites using microwave and
conventional heating
A. Mondal*1, A. Upadhyaya2 and D. Agrawal3
Tungsten based composites such as W–Cu have been widely used as electrical contacts,
especially in heavy duty applications and as spark erosion electrodes. The lack of solubility
between tungsten and copper makes it very difficult to achieve full densification through liquid
phase sintering. Higher sintering temperatures or longer holding times always help to improve the
densification but Cu may leach out from the skeleton which leads to Cu segregation and results in
non-homogeneous microstructure and poor product performance. Microwave heating has been
increasingly gaining popularity in the field of sintering of particulate materials. As compared to
conventional heating, microwave heating is more rapid resulting in substantial reduction in the
overall sintering time. In addition to the energy efficiency, the faster heating rate achieved in
microwave furnaces minimises microstructural coarsening and improves homogeneity. This study
examines the effect of heating mode (conventional and microwave) and temperature on the
consolidation of specially prepared commercial W–Cu powder. Near theoretical density has been
achieved under optimum conditions in microwave sintering. The bulk hardness and electrical
conductivity of the samples sintered by two methods have been determined and the data
compared.
Keywords: Liquid phase sintering, Microwave sintering, Powder consolidation, Synthesis and processing

Introduction through LPS, sufficient amount of melt and its

Tungsten–copper alloys are one of the most important
alloys of tungsten which have widespread use as
electrical contact materials, in strategic applications
(e.g. shape chargers) and for thermal management
applications.1,2 On account of the refractoriness of the
major phase (Wmp: 3420uC), these alloys are usually
processed through liquid phase sintering. There are two
ways used to form W–Cu composites: copper infiltration
of a porous tungsten skeleton and liquid phase sintering
(LPS) of mixed phase compacts. For economical
reasons, shape, complexity and large scale production
consideration, the latter technique is the only widely
adopted fabrication routes for W–Cu alloys. The lack of
solubility between tungsten and copper makes it very
difficult to achieve full densification through liquid
phase sintering. For ensuring complete densification
1
NTPC Energy Technologies and Research Alliance (NETRA), Greater
Noida-201306, INDIA
2
Department of Materials Science and Engineering Indian Institute of
Technology, Kanpur 208016, INDIA
3
Microwave Processing and Engineering Center, Materials Research
Institute, The Pennsylvania State University, PA 16802, USA
*Corresponding author, email avijit.mondal@gmail.com
homogeneous distribution is required.3 In the case of
W–Cu compacts, while high compaction pressures
increase the green density, it results in increased particle
contacts that limit particle rearrangement during LPS.4
Another approach for ensuring densification in the
W–Cu system is through the addition of transition metal
additives that activate the sintering kinetics.5–7 The
addition of small quantities of transition elements (such
as Ni, Co and Fe), activates tungsten skeletal sintering
and has a positive impact on the sinterability of the W–
Cu. Such activators remain segregated at the grain
boundaries and thereby result in poor mechanical
properties.8 Higher sintering temperature or longer
holding time always helps to improve the densification
but copper may leach out from the skeleton which leads
to non-homogeneous microstructure.9 Co-reduction of
oxides or other thermochemical processes are also
efficient methods to improve the densification of this
material.3,5,10 Novel sintering techniques have also been
explored to enhance W–Cu composite densifications
which include resistance sintering, plasma spraying and
laser sintering.11,12
Microwave sintering is a well known technique in the
field of sintering of particulate ceramic materials. But for

ß W. S. Maney & Son Ltd. 2010

Received 14 May 2010; accepted 25 May 2010
DOI 10.1179/143307510X12820854748638 Materials Research Innovations 2010 VOL 14 NO 5 355
 Mondal et al.
the metallic material it was not applied earlier because of
the fact that bulk metal reflects microwave. But recently
it has been shown that metals can also be coupled with
microwave and get heated provided they are in powder
form.13 This has resulted in wide spread interest in
sintering of many metallic compacts in microwave field.
As compared to conventional heating, microwave
heating is more rapid which results in reducing the
overall sintering time. In addition to the cost efficiency,
the faster heating rate achieved in microwave techniques
minimises microstructural coarsening. For powder
compacts sintering is usually associated with densifica-
tion as well as concomitant microstructural coarsening.
If the latter is restricted the mass atomic transport is
enhanced due to the availability of more grain bound-
aries. Recent review reports14 on various systems have
exhibited higher sintered density and better mechanical
properties in microwave sintered compacts as compared
to their conventionally sintered counterparts.
The application of microwave energy in consolidating
tungsten powders was first studied by Jain et al.15 A
comprehensive study on microwave sintering of tungsten
and its alloys were also conducted by several research-
ers.16–20 In a very recent report, Luo et al.21 studied the
microwave sintering of W–Cu alloys. However, their
assessment was qualitative, and the comparative analysis
was lacking in terms of properties concerned.
This study investigated the effect of heating mode as
well as temperature on the densification, microstructure
and properties of specially prepared commercial W–
18Cu powder compacts. Dilatometry measurements
have also been used to study the in situ linear shrinkage
behaviour as a function of temperature.
Experimental
Table 1 summarises the characteristics of the as received
W–18Cu power used in this investigation. The spatially
prepared powder was supplied by Osram Sylvania,
Towanda, PA, USA. Particle size analysis of the as
received powder was performed using Malvern
Instruments particle size analyser which works on the
principle of laser diffraction. The surface area of the as
received powder was measured by nitrogen adsorptions
method using a Brunauer–Emmett–Teller (BET) appa-
ratus. The BET equivalent spherical particle diameter
DBET was calculated for the powders using equation (1)
6 field and can even lead to measurement errors. The
DBET ~ (1)
rp A
where A is the specific BET surface area of the powder in
m2 g21 and rp is the pycnometer density of the powder
in g cm23 and DBET is in mm.
Figure 1 is a scanning electron micrograph of as
received powder. Powders were pressed in a die of
1?6 cm inner diameter to make the green compacts of
approximately 0?6–0?8 cm in height. The pressure was
Table 1 Powder characteristics of as received W–18Cu powder
Powder size, mm
Property Processing technique Powder shape D10
W–18Cu Chemical synthesis of Spherical 1.74
powder W–Cu oxides
Densification and microstructural development in W–18Cu composites
1 Scanning electron micrograph of as received W–18Cu
powder: a and b are at different magnifications
applied uniaxially in a 50 t hydraulic press (model
CTM-50, FIE, Ichalkaranji, India) with floating die,
using zinc stearate as a die wall lubricant.
All the samples were compressed at pressures of
200 MPa. The as pressed green compact density varied
from 52 to 54% of the theoretical density of the
composites, where the theoretical density rT was
calculated using the inverse rule of mixtures as follows
1 X
N
wi
~ (2)
rT i~1 ri
where N is the number of elements in the mixture, wi is
the weight fraction of the ith component and ri is the
theoretical density of the ith element. To study the
densification behaviour, the green (as pressed) compacts
were sintered using conventional and microwave fur-
nace. The conventional sintering of green compacts was
carried in a MoSi2 heated horizontal tubular sintering
furnace (model OKAY 70T-7, Bysakh, Kolkata, India)
at a constant heating rate of 5uC min21. To ensure
uniform temperature distribution during heating, inter-
mittent isothermal hold for 30 min was provided at 500
and 900uC. The sintering temperatures selected for the
solid state and LPS were 1000, 1200, 1300 and 1400uC
respectively. Sintering was carried out for 60 and 30 min
in H2 atmosphere with dew point 235uC. Microwave
sintering of the green compacts was carried out using a
multimode cavity 2?45 GHz, 6 kW commercial micro-
wave furnace (model RC/20SE, Amana Radarange,
Benton Harbor, MI, USA).
Unlike a conventional furnace, the temperature of the
samples inside a microwave furnace cannot be mon-
itored by using a thermocouple. The presence of
thermocouples can locally distort the electromagnetic
temperature of the sample was monitored using an
optical pyrometer (Marathon Series, Raytek, Santa
Cruz, CA, USA) with the circular crosswire focused
on the sample cross-section. Further details of the
experimental set-up of microwave sintering are
described elsewhere.22
The sintered density was obtained by both dimen-
sional measurements as well as Archimedes’ density
measurement technique. To take into account the
Surface BET equivalent
D50 D90 area, m2 g21 particle size, mm
8.23 33.19 0.81 0.47
Materials Research Innovations 2010 VOL 14 NO 5 356
 Mondal et al.
2 Thermal profile of W–18Cu compact heated in radia-
tively heated and 2?45 GHz microwave furnace
influence of the initial as pressed density, the compact
sinterability was also expressed in terms of densification
parameter which is calculated as follows
Densification parameter~
sintered density{green density
theoretical density{green density (3)
The sintered samples were wet polished in a manual
polisher (model Major, Struers, Ballerup, Denmark)
using a series of 6, 3 and 1 mm diamond paste, followed
by cloth polishing using a suspension of 0?04 mm
colloidal SiO2 suspension. The scanning electron micro-
3 Photograph of W–18Cu compacts sintered at 1200uC in
a conventional and b microwave furnace
4 Effect of heating mode and sintering temperature on a sintered density and b densification parameter of W–18Cu alloy
Densification and microstructural development in W–18Cu composites
graphs of as polished samples were obtained by a
scanning electron microscope (model FEI Quanta, FEI
Company, Eindhoven, The Netherlands) in the second-
ary electron and backscattered mode. Phase determina-
tion and phase evolution, if any were studied for all the
samples with the help of X-ray diffractometer (model
ISO Debyeflex-2002, Rich Seifert & Co., Ahrensburg,
Germany) with a scan rate of 3u min21. Bulk hardness
measurements were performed on polished surfaces of
sintered cylindrical compacts at a load of 5 kg using a
Vickers hardness tester (model V100-C1, Leco, Tokyo,
Japan). The load was applied for 30 s. The Vickers bulk
hardness value for each sample was an average of 10
readings taken at random locations throughout the
sample. The electrical conductivity measurements of the
sintered samples were carried out using digital con-
ductivity meter (model 757, TechnoFour, Pune, India).
Results and discussion
Heating profiles
The W–18Cu powder compacts were sintered for 30 min
at temperatures corresponding to solid state (1000uC)
and liquid phase (1200, 1300 and 1400uC) sintering.
Figure 2 compares the thermal profiles of the compacts
heated in conventional and microwave furnace. It is
interesting to note that W–18Cu compact couples with
microwaves very efficiently and gets heated up rapidly.
The overall heating rate in microwave furnace was
y22uC min21; taking into consideration the slow
heating rate (5uC min21) and isothermal holds at
intermittent temperatures in conventional furnace, there
is y80% reduction in the overall process time during
sintering of W–18Cu compacts in microwave furnace.
Figure 3 shows the photograph of the conventionally
and microwave sintered W–18Cu compacts. From the
figure, it is evident that in both cases the sintered W–
18Cu compacts do not show any macrocracking or
dimensional distortion.
Densification response of W–18Cu
Figure 4a and b shows the effect of sintering tempera-
ture and heating mode on the sintered density and
densification parameter respectively. Since all compacts
were pressed to the same green density, hence, the
densification parameter response is similar to sintered
Materials Research Innovations 2010 VOL 14 NO 5 357
 Mondal et al.
5 Effect of heating mode and sintering temperature on
axial and radial shrinkage of W–18Cu alloy
6 Representative microstructure of W–18Cu compacts
solid state sintered at 1000uC in a conventional and
b microwave furnace
7 Scanning electron micrographs of W–18Cu alloys sin-
tered at a 1200uC, b 1300uC and c 1400uC in conven-
tional (left) and microwave (right) furnace
Densification and microstructural development in W–18Cu composites
density. For temperatures corresponding to LPS, both
microwave and conventional sintering methods result in
similar (nearly 100%) densification. In fact, at 1200uC
itself the compact attains full densification which
underscores the efficacy of capillary induced rearrange-
ment. It is, however, remarkable to observe the positive
influence of microwave heating on compacts consoli-
dated in solid state at 1000uC. These results are
contradictory to those reported by Ryu et al.23 who
showed that the overall densification in W–Cu alloys
consolidated through solid state conventional sintering
is higher for compacts heated at slower heating rates. As
compared to conventional heating, microwave heating
rate is nearly five times higher. Thus, microwave heating
not only lowers significantly the processing time but also
enhances the sintering kinetics.
Figure 5 compares the effect of heating mode and
sintering temperature on the axial and radial shrinkage
of the cylindrical compacts. Note that irrespective of the
sintering temperature and the heating mode dimensional
changes in the W–18Cu compacts are isotropic in
nature.
The as sintered W–18Cu alloys were metallographi-
cally prepared for microstructural observation. Figure 6a
and b compares the microstructures of the W–18Cu
alloys solid state sintered (1000uC) in a conventional and
microwave furnace respectively. Figure 7a–c compares
the effect of temperature on the microstructure of W–Cu
compacts consolidated in conventional and microwave
furnace through LPS. For both the heating modes,
higher sintering temperatures are expected to lead to
microstructural coarsening. In the case of conventionally
sintered W–18Cu compacts, microstructural coarsening
is distinctly observed. At 1400uC, the tungsten grains
appear in well defined spheroidal form. Figure 8 shows
the elemental distribution in W–Cu compacts sintered at
1400uC. It is to be noted that the distribution of W and
Cu phases is quite distinct corresponding to granular
structure and matrix region respectively in the sintered
body, while no intermixing was observed. This confirms
lack of mutual solubility between W and Cu. Unlike
systems such as W–Ni–Fe and W–Ni–Cu alloys, the lack
of solid solubility obviates solution reprecipitation in W–
Cu alloys during sintering.24,25 Hence, grain coarsening
in W–Cu alloys is restricted and coalescence is the sole
contributor to it.26 As compared to conventional
sintering, shorter processing time in microwave sintering
restricts microstructural coarsening still further.
X-ray diffraction (XRD) analysis
Figure 9 compares the XRD patterns of the composition
in both the heating modes at different temperatures.
From XRD patterns of both conventionally and
microwave sintered samples, no difference as far as
phase evolution is concerned was observed. However, it
is interesting to note that although the sample size and
other parameters were constant during the experiment
still relative intensity of the X-ray peaks was slightly
lower in microwave sintered samples than conventional
one. This difference dominates at higher temperature.
There is no plausible explanation for this observation
yet. One possible explanation may be that in microwave
the W phase may be undergoing a partial decrystallisa-
tion as had been observed in a single mode microwave
Materials Research Innovations 2010 VOL 14 NO 5 358
 Mondal et al.
b the variation in the sintered porosity. For both the
c wave furnace, better binder homogeneity achieved at
8 a scanning electron micrograph of W–18Cu alloy liquid
phase sintered at 1400uC, b and c corresponding ele-
mental maps
H-field processing of certain materials such as ferrites,
Si, etc.27,28
Bulk hardness and electrical conductivity
Figure 10 compares the effect of heating mode and
sintering temperature on the bulk hardness of W–18Cu
9 X-ray diffraction pattern of conventionally and micro-
wave sintered W–18Cu alloys
Densification and microstructural development in W–18Cu composites
10 Effect of heating mode and sintering temperature on
bulk hardness of W–18Cu alloys
alloys. The variation in the hardness closely is related to
heating modes, liquid phase sintered compacts have
significantly higher hardness as compared to those
consolidated at 1000uC through solid state sintering.
The size of the tungsten grains also seems to influence
the bulk hardness. In the case of W–18Cu alloys
conventionally processed through LPS, the hardness
decreases as the sintering temperature increases from
1200 to 1400uC. This can be correlated to the micro-
structural coarsening at higher temperatures (Fig. 7).
In the case of W–Cu compacts processed in micro-
higher temperature, causes a gradual improvement of
the bulk hardness as the sintering temperature increases.
Figure 11 compares the effect of heating mode and
sintering temperature on the electrical conductivity of
W–18Cu compacts. The trend in electrical conductivity
variation is similar to that observed for hardness
(Fig. 10). In general, microwave sintered compacts
exhibit improved conductivity. For both the heating
modes, as compared to solid state sintering, LPS
resulted in significant improvement in the conductivity.
This can be attributed to greater densification and more
11 Effect of sintering temperature on electrical conductiv-
ity of W–18Cu compacts consolidated in conventional
(radiatively heated) and microwave furnace
Materials Research Innovations 2010 VOL 14 NO 5 359
 Mondal et al.
uniform binder distribution in liquid phase sintered
compacts.
Conclusion
Compacts of W–18Cu alloys were successfully sintered in
a microwave furnace for temperatures corresponding to
solid and liquid phase sintering in relatively much shorter
time than in the conventional heating method. In spite of
higher heating rate in microwave sintering, no micro- or
macrocracks in the sintered samples were observed which
essentially supports the volumetric heating nature of
microwave sintering. Microwave sintering lowers the
sintering temperature to achieve the optimum densifica-
tion as well as optimum mechanical properties. Finer
particle size and more homogeneous distribution of
tungsten in the microstructure can be obtained by using
microwave energy for the consolidation of W–18Cu
composites leading to higher mechanical properties.
Acknowledgements
The authors would like to acknowledge Osram Sylvania,
Towanda, PA, USA, for supplying the powder used for
this investigation. Partial support from Indo–US Science
and Technology Forum (IUSSTF), New Delhi, India is
gratefully acknowledged.
References
1. A. Upadhyaya: Mater. Chem. Phys., 2001, 67, 101–110.
2. A. Upadhyaya: Trans. Indian Inst. Met., 2002, 55, 51–69.
3. J. L. Johnson, J. J. Brezovsky and R. M. German: Metall. Mater.
Trans. A, 2005, 36A, 1157–1165.
4. J. L. Johnson and R. M. German: Metall. Mater. Trans. B, 1996,
27B, 901–909.
5. D. G. Kim, G. S. Kim, M. J. Suk, S. T. Oh and Y. D. Kim: Scr.
Mater., 2004, 51, 677–681.
6. V. Gauthier, F. Robaut, A. Upadhyaya and C. H. Alliberta:
J. Alloys Compd, 2003, 361, 222–226.
Densification and microstructural development in W–18Cu composites
7. J. L. Johnson and R. M. German: ‘Advances in powder metallurgy
and particulate materials’, Vol. 4, 201–213; 1993, Princeton, NJ,
MPIF.
8. A. Upadhyaya and R. M. German: Int. J. Powder Metall., 1998, 34,
43–55.
9. J. L. Johnson, J. J. Brezovsky and R. M. German: Metall. Mater.
Trans. A, 2005, 36A, 2807–2814.
10. O. Ozer, J. M. Missiaen, S. Lay and R. Mitteau: Mater. Sci. Eng.
A, 2007, A460–A461, 525–532.
11. Z. J. Zhou, J. Du, S. X. Song, Z. H. Zhong and C. C. Ge: J. Alloys
Compd, 2007, 428, 146–150.
12. G. Pintsuk, S. E. Brünings, J. E. Döring, J. Linke, I. Smid and
L. Xue: Fusion Eng. Des., 2003, 66–68, 237–241.
13. R. Roy, D. K. Agrawal, J. P. Cheng and S. Gedevanishvili: Nature,
1999, 399, 668–670.
14. M. Oghbaei and O. Mirzaee: J. Alloys Compd, 2010, 494, 175–189.
15. M. Jain, G. Skandan, K. Martin, K. Cho, B. Klotz, R. Dowding,
D. Kapoor, D. Agarwal and J. Chang: Int. J. Powder Metall., 2006,
42, 45–50.
16. G. Prabhu, A. Charkraborty and B. Sarma: Int. J. Refract. Hard
Met., 2009, 27, 545–548.
17. C. Zhou, J. Yi, S. Luo, Y. Peng, L. Li and G. Chen: J. Alloys
Compd, 2009, 482, L6–L8.
18. A. Upadhyaya, S. K. Tiwari and P. Mishra: Scr. Mater., 2007, 56,
5–8.
19. A. Mondal, D. Agrawal and A. Upadhyaya: J. Microw. Power
Electromagn. Energy, 2010, 44, to be published.
20. A. Mondal: ‘Modeling of microwave heating of particulate metals
and its application in sintering of tungsten–based alloys’, PhD
thesis, Indian Institute of Technology, Kanpur, India, 2009.
21. S. D. Luo, J. H. Yi, Y. L. Guo, Y. D. Peng, L. Y. Li and J. M. Ran:
J. Alloys Compd, 2009, 473, L5–L9.
22. A. Mondal, D. Agrawal and A. Upadhyaya: J. Microw. Power
Electromagn. Energy, 2009, 43, 5–10.
23. S. S. Ryu, Y. D. Kim and I. H. Moon: J. Alloys Compd, 2002, 335,
233–240.
24. F. V. Lenel: Trans AIME, 1948, 175, 878–896.
25. W. J. Huppmann: Z. Metallkd, 1979, 70, 792–797.
26. E. G. Zukas, P. S. Z. Rogers and R. S. Rogers: Z. Metallkd, 1976,
67, 591–595.
27. R. Roy, Y. Fang, J. Cheng and D. K. Agrawal: J. Amer. Ceram.
Soc., 2005, 88, 1640–1642.
28. R. Peelamedu, R. Roy, L. Hurtt, D. Agrawal, A. W. Fliflet,
D. Lewis, III and R. W. Bruce: Mater. Chem. Phys., 2004, 88, 119–
129.
Materials Research Innovations 2010 VOL 14 NO 5 360
 Journal of Microwave Power and Electromagnetic Energy, 44 (1), 2010, pp. 28-44
A Publication of the International Microwave Power Institute

Microwave Sintering of Refractory

Metals/alloys: W, Mo, Re, W-Cu,
W-Ni-Cu and W-Ni-Fe Alloys
Avijit Mondal1, Dinesh Agrawal2, Anish Upadhyaya1
1
Department of Materials & Metallurgical Engineering
Indian Institute of Technology, Kanpur 208016, INDIA

2
Materials Research Institute
The Pennsylvania State University, University Park, PA 16802, USA

Received: August 5, 2009

Accepted: January 28, 2010

ABSTRACT
Refractory metals and alloys are well known for their high mechanical properties which
make them useful for wide range of high temperature applications. However, owing to the
refractoriness of these metals and alloys, it is very difficult to consolidate them under moderate
conditions. Conventional P/M processing is a viable sintering technique for these refractory
metals. One of the constraints in conventional sintering is long residence time which results in
undesirable microstructural coarsening. This problem gets further aggravated when using smaller
(submicron and nano) precursor powder sizes. Furthermore, conventional heating is mostly
radiative, which leads to non-uniform heating in large components. This review article describes
recent research findings about how these refractory metals and alloys (W, Mo, Re, W-Cu, W-Ni-
Cu and W-Ni-Fe) have been successfully consolidated using microwave sintering. A comparative
study with conventional data has been made. In most cases, microwave sintering resulted in an
overall reduction of sintering time of up to 80%. This sintering time reduction prevents grain
growth substantially providing finer microstructure and as a result better mechanical properties
have been observed.

KEYWORDS: Microwave sintering; Refractory metals/alloys; Microstrutures

INTRODUCTION
Refractory metals are known for their very high melting temperatures. Most refractory
metals used for various applications are tungsten with fusion point of 3420°C, molybdenum of
2620°C and rhenium of 3180°C. Because of their high melting point, most refractory metals and
alloys are consolidated through powder metallurgy (P/M) techniques, though for some specific
applications mechanical alloying and infiltration technique are also employed. Most commonly,
liquid phase sintering (LPS) is used for consolidating tungsten based alloys such as W-Cu, W-
Ni-Cu and W-Ni-Fe compositions [Upadhyaya, 2001]. The LPS offers an advantage of relatively
lower sintering temperature, enhanced densification, microstructural homogenization and near
theoretical density.

International Microwave Power Institute

28
Avijit Mondal et al., Microwave Sintering of Refractory Metals/alloys: W, Mo, Re, W-Cu, W-Ni-Cu and W-Ni-Fe ...
These refractory metals and alloys
offer a wide range of properties which make
them advantageous for high temperature
applications over other materials. Sintered
tungsten is an excellent material for many
applications such as lightings, heating,
aerospace, electronic, sports and military
uses due to its high melting point, high
density of 19.3 g/cm3, high hardness of 9.75
GPa, moderate elastic modulus of 407 GPa,
low coefficient of thermal expansion, good
thermal conductivity, and low vapor pressure.
Rhenium metal is interesting from a number
of standpoints. It is only second to tungsten,
among the metallic elements, in melting
point. Its density of 21.0 g/cm3 is higher
than that of tungsten. Annealed material has
exhibited tensile strengths of about 120,000
p.s.i. with 25% ductility at room temperature,
and it is somewhat harder and more resistant
to abrasion than tungsten. Other properties,
such as its corrosion resistance and electrical
properties make it promising for incandescent
lamp filaments and electrical contacts.
Molybdenum is a typical transition metal
element having a high melting point, high
mechanical strength, and high modulus of
elasticity. Most of the applications for pure
molybdenum metal and its alloys involve
as electrodes for electrically heated glass
furnaces and forehearths, nuclear energy
applications, missile and aircraft parts,
thermocouple sheaths, flame and corrosion
resistant coatings for other metals, and as an
alloying agent in steel.
An important class of tungsten based
material is tungsten heavy alloys (WHA). A
typical tungsten heavy alloy contains 60 to
98 wt. % tungsten. The balance is generally
a mixture of relatively low melting transition
elements, such as nickel, iron, copper, and
cobalt. Due to their unique combination
of properties WHAs have a wide range
of applications, such as radiation-shield,
counter-balanced weights etc.
Most important of all applications is
its potential to be a replacement of depleted
uranium within kinetic energy anti armor
Journal of Microwave Power and Electromagnetic Energy, 44 (1), 2010
International Microwave Power Institute
penetrators in ordnance industry. For most
of the applications, near theoretical density,
dimensional stability, higher hardness,
toughness and very high ductility are
important.
These metals and alloys in conventional
furnace are sintered at very high temperatures
(1500-2000°C) and to avoid thermal shock at
a slow heating rate (<10°C/min) and with an
isothermal hold at intermittent temperatures.
The high sintering temperature results in
significant microstructural coarsening in the
sintered material, leading to the degradation
of mechanical properties. This problem is
further aggravated when the initial powder
size is extremely fine. Hence, it is envisaged
that a sintering method that provides a rapid
heating rate, lower sintering temopertaure
and duration would mitigate this problem.
One of the techniques to achieve rapid
and relatively uniform sintering is through
microwaves [Rao et al., 1995; Clark and
Sutton, 1996; Agrawal, 1998].
Microwave sintering in the recent
times has emerged as an innovative technique
for high temperature material processing.
Microwave assisted synthesis is generally
faster, cleaner and more economical than
the conventional methods. The possibility of
ceramics processing by microwave heating
was first discussed over 50 years ago by Von
Hippel [Von Hippel, 1954], and experimental
studies started in the middle of the 1960s by
Tinga and co-authors [Tinga et al., 1968; Tinga
and Edwards, 1968]. Since then variety of
materials such as carbides, nitrides, complex
oxides, silicides, zeolieties apatite, etc. have
been synthesized using microwaves [Bykov et.
al., 2001; Booske et al., 1997; Sutton, 1992;
Agrawal, 1999; Agrawal et al., 2001; Rodiger
et al., 1998; Agrawal et al., 2000].
In 1999, for the first time Roy et al.
[Roy et al., 1999] reported that a porous
powder metal compact could be heated
and sintered in a microwave field. Their
work added a new dimension towards the
application of microwave energy for high
temperature material processing. The
29
 Avijit Mondal et al., Microwave Sintering of Refractory Metals/alloys: W, Mo, Re, W-Cu, W-Ni-Cu and W-Ni-Fe ...
results of many investigations in microwave
sintering and joining of ceramics, ceramic-
metal composites, metals and alloys have
been reported [Bykov et. al., 2001; Booske
et al., 1997; Sutton, 1992; Agrawal, 1999;
Agrawal et al., 2001; Rodiger et al., 1998;
Agrawal et al., 2000; Anklekar et al., 2001;
Saitou, 2006; Luo, J. et al., 2004; Anklekar
et al., 2005; Takayama et. al., 2006; Rybakov
et al., 2006; Mishra et al., 2006; Mondal
et al., 2008; Mondal et al., 2009]. In the
majority of the papers the authors claim
acceleration of microwave driven processes
as compared with the processes performed
using conventional heating. The acceleration
commonly manifests itself as a reduction in the
densification time of the powder compacts,
which is often accompanied by a decrease in
the temperature of sintering. High rates of
volumetric heating in microwave sintering,
not limited by thermal diffusion, prevent
recrystallization grain growth and result in
a finer and more uniform microstructure in
the sintered bulk materials. It is well known
that a fine, homogeneous, and fault-free
microstructure is a necessary prerequisite for
enhanced material performance. Similarly,
a decrease in the duration of the high-
temperature stage leads to reduced grain
growth as a result, to the higher mechanical
strength in the final product.
There are different mechanisms
by which microwaves can couple to a
material and a whole host of ways that the
microwave energy is subsequently absorbed
by the system. The main loss mechanisms are
electric, conduction (eddy current), hysteresis
and resonance (domain wall and electron spin
(FMR)). It is often difficult to ascertain which
loss mechanism, or combination of mechanisms
is occurring for a particular material in given
conditions. The different mechanisms do
however have different dependencies on
certain properties such as sample type and
microstructure, frequency and temperature.
A brief description of these different loss
mechanisms for ceramic material can be
found in the reference [Clark and Sutton,
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1996; Agrawal, 1998; Von Hippel, 1954; Tinga
et al., 1968; Tinga and Edwards, 1968; Bykov
et. al., 2001; Booske et al., 1997; Sutton,
1992; Agrawal, 1999; Agrawal et al., 2001;
Rodiger et al., 1998; Agrawal et al., 2000].
Microwave heating in metals is different from
that observed in dielectric materials (mostly
ceramics). Being good conductors, no internal
electrical field is induced in metals.
The induced electrical charge remains
at the surface of a bulk metallic sample. As a
consequence, bulk metals reflect microwaves
at room temperature; hence no bulk
absorption (heating) occurs, particularly, at
temperatures below 500°C. According to the
Faraday’s effect in a conductive material, a
varying magnetic field generates an electric
field that gives rise to eddy currents and
subsequently resistive losses. Additionally
during sintering of particulate metal
compact, each individual powder particle in
the compact is surrounded by a dielectric
oxide layer. The presence of such dielectric
“shell” on the powder particle prevents the
connectivity percolation between the particles
and increases significantly electromagnetic
power that can be absorbed by the compact.
In general, the skin depth is relatively small
in metals, since in the microwave regime,
the particle sizes are much smaller than the
wavelength of microwave radiation; the field
across the particle are uniform and causes
volumetric heating. However, for relatively
coarse particle (>100µm), the heating may be
conductive from outside to the interior of the
powder. Recent study confirms that magnetic
heating plays most important role for metallic
materials. Quite contrary to the fact that
electric heating predominates for dielectric
materials. The detailed microwave absorption
mechanism for metallic material can be found
in the reference already mentioned.
From the above discussion it is quite
clear that microwave processing has many
advantages over conventional methods,
especially for sintering applications. The
various advantages are: time and energy
saving, rapid heating rates, considerably
Avijit Mondal et al., Microwave Sintering of Refractory Metals/alloys: W, Mo, Re, W-Cu, W-Ni-Cu and W-Ni-Fe ...
reduced processing cycle time and
temperature, substantial enhancement
in reactivity and diffusion kinetics, fine
homogeneous microstructures and improved
mechanical properties which lead to better
product performance. Microwave-matter
interaction and anisothermal situations often
produce better quality and new materials that
are normally not possible with conventional
methods. These characteristics advantages
of microwave sintering can be exploited to
overcome the processing difficulties of the
refractory metals and alloys.
This review article describes recent
research findings about how certain refractory
metals and alloys (W, Mo, Re, W-Cu, W-Ni-
Cu and W-Ni-Fe) have been successfully
consolidated using microwave sintering and
a comparative study with conventional data
has been made. In most cases, microwave
sintering resulted in an overall reduction of
sintering time of up to 80%. This sintering time
reduction prevents grain growth providing
finer microstructure and as a result better
mechanical properties have been observed.
CONSOLIDATION OF TUNGSTEN
Usually the consolidation of W powder
by conventional heating is difficult and
requires very high temperature (2200°C or
more) in electrical resistance sintering under
hydrogen atmosphere. The requirement
of excessive high temperature and special
technique makes the process more expensive
and imparts a restriction in the sizes and
shapes of the sintered products.
Low-temperature brittleness is the
most crucial aspect in the manufacturing of
pure tungsten metal. Therefore, in the past
much effort has been directed at lowering
the ductile to- brittle transition temperature
(DBTT) and hence improving the fabricability
of the metal.
The brittleness of polycrystalline
tungsten at low temperature is attributed to
the weakness of the grain boundaries, which
leads to initiation of cracking in both wrought
and recrystallized tungsten. Pure, single
Journal of Microwave Power and Electromagnetic Energy, 44 (1), 2010
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crystalline tungsten (free of grain boundaries)
remains ductile down to at least 20K. Any
plastic deformation decreases the transition
temperature by fining the structure [Lassner
and Schubert, 1999]. The presence of small
amount of interstitial impurities such as O, C,
N and H2 has a detrimental effect on DBTT.
The solubility for such elements in
tungsten at room temperature is much lower
when compare to high temperature. So during
cooling segregation of such elements at the
grain boundary significantly weakens the grain
boundary strength. The ductilizing effect
of Re in tungsten have gained outstanding
importance in this regard. Addition of Re can
cause the transformation temperature to fall
below room temperature, even for slightly
deformed products. Many studies have shown
that sintering temperature is related to the
powder size, when the size is in nano-scale,
the sintering temperature can be decreased
up to several hundred degrees. The reduction
of sintering temperature for nano tungsten
has been reported by several researchers
[Sarma and Pabi, 2007; Oda et al., 2006;
Bose et al., 2008; Engleman et al., 2008;
Johnson, 2008; Wang et al., 2008; Jain
et al., 2006; Jain et al., 2006]. The reported
sintering temperature of nano sized tungsten
produced by high energy mechanical milling
was drastically decreased from conventional
temperature of 2500°C to 1700°C [Malewar
et al., 2007]. Researchers have also shown
that pressure assisted process such as spark
plasma sintering [Oda et al., 2006], plasma
pressure compaction [Bose et al., 2008],
and hot isostatic processing (HIP) [Engleman
et al., 2008] etc. helps in further reduction
in the processing temperature. Selection of
nano powders over microcrystalline powders
has certain distinct advantages. According to
the literature reported data for both metals
and ceramic nano particles was found to start
densification at temperatures of 0.2–0.4 Tm
(Tm - melting temperature) compared to 0.5–
0.8 Tm for the conventional powders.
It is believed that in the case of
nanostructured powders the grain boundary
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 Avijit Mondal et al., Microwave Sintering of Refractory Metals/alloys: W, Mo, Re, W-Cu, W-Ni-Cu and W-Ni-Fe ...
sliding, dislocation motion, grain rotation,
and viscous flow can significantly contribute
to the enhanced sintering kinetics [Hahn,
1993; Averbach et al., 1996; Bourell and
Groza, 1998; Groza, 1999; Groza, 2002].
Generally sintering theories hold that the
sintering temperature is often correlated
with melting point of the material. It is long
been know that the melting temperature
of very fine particles decreases with the
size of the particles [Couchman and Jesser,
1977]. Therefore in addition to the faster
sintering kinetics, the faster densification in
nano structured material could be attributed
to the lower melting temperature of nano
particles.
In addition to all the above mentioned
advantages, nano tungsten has two distinct
advantages over conventionally sized tungsten
powder. First, the thermal conductivity
of nano tungsten is much lower than that
of conventionally sized tungsten powder.
Secondly, as in nano dimension grain size are
close to dislocation length, no pinning or pile
up of dislocation occurs [Andrey et al., 2004].
The contribution of these two phenomenon
results in a material that exhibits a higher
propensity of adiabatic shear, which is very
important aspects of this material as a kinetic
energy penetrator application is concerned.
Wang [Wang et al., 2008] has studied the size
dependent sintering behavior of tungsten
powder.
They observed that the starting
particle size before milling plays an important
role in sinterability of this material, lower
the size higher will be the sinterability.
Although, the final crystallite size after
milling is same in both the cases. The reason
for this difference could be attributed with
the difference in particle size after milling.
Mohit et al. [Jain et al., 2006] studied
the application of microwave energy in
consolidating pure tungsten powder. They
found 10 to 12% higher sintered density in
microwave sintering as compare to their
conventional counter part. In another study
they have reported the role of HfO2 and
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Y2O3 as successful grain growth inhibitors.
They also observed that the introduction of
a secondary oxide (HfO2 and/or Y2O3) had a
significant effect on the powder morphology
and in reducing the primary particle size of
the as synthesized tungsten powders. The
particle size was reduced from 350 nm to 80-
100nm, and the crystallite size was reduced
from 48 nm to 25 nm with the addition of
dopents [Jain et al., 2006].
Prabhu [Prabhu et al., 2008] has also
investigated microwave sintering of pure
tungsten powder of as received grade and
tungsten powder activated by high energy
milling (HEM). Their study shows better
sinterability of activated tungsten powder in
compare to as received powder.
Mondal [Mondal et al., 2009] has also
reported the similar kind of accelerated
densification in microwave sintered tungsten
sample. They reported that more than 95%
Th density of microwave sintered samples
at 1600°C for 30 min holding in hydrogen
atmosphere.
Figure 1 describes typical thermal
profile used for their experiments in both
conventional as well as microwave heating
mode.
Figure 2 are the SEM micrograph
of both conventionally and microwave
Figure. 1. Typical thermal profiles of sintered W using
conventional and microwave furnaces [Mondal et al., 2009].
Avijit Mondal et al., Microwave Sintering of Refractory Metals/alloys: W, Mo, Re, W-Cu, W-Ni-Cu and W-Ni-Fe ...

Figure. 2. SEM micrographs of (left) conventional and (rigtj) microwave sintered W at 1600°C for 30 min in H2
atmosphere [Mondal et al., 2009].

Figure.3. Microwave sintering of complex shaped tungsten samples.

sintered samples. Figure 3 show some of an inert atmosphere (argon) or in a reducing

the commercial pure tungsten products that
have been successfully sintered in microwave
furnace at Penn State’s Microwave Processing
Center.
CONSOLIDATION OF MOLYBDENUM
Conventionally the sintering of
molybdenum powder is conducted using a
resistance or induction sintering furnace in
atmosphere (hydrogen) [Patrician et al.,
1985]. High temperatures in the range of
2000°C are employed, resulting in densities
of 90–95% of theoretical, depending upon the
sintering time. Huang [Huang and Hwang,
2002] reported the sintering of molybdenum
using vacuum furnaces and obtained densities
of 97 to 98.5% at a sintering temperature of
1750°C with times ranging from 10 to 40 h.

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This also results in abnormal grain growth. sintering times and temperatures produce
Microwave sintering of molybdenum metal bars of high yield and small grain size with
powder has been reported for the first time the same homogeneity attainable by electron
by Chillar [Chhillar et al., 2008]. In their beam or arc melting. Subsequent fabrication
work, the authors reported sintering of nano is performed by swaging, rolling, forging and
molybdenum powder to obtain submicron grain drawing with intermediate annealing.
size microstructure using microwave energy. Some of these operations may have to
As received Mo powder was agglomerated be conducted at elevated temperatures. The
with a mean agglomerate size of 1.6 um, optimum sequence of these operations varies
but equivalent surface area based on N2 for rhenium and it alloys and depends on the
adsorption suggests an average particle size final end form. Microwave sintering of rhenium
of 200 nm. Sintering was carried out using the pallet has been successfully conducted at
as received powder. Samples with densities as Penn State’s microwave processing center.
high as 98% of theoretical density (TD) were
obtained with limited grain growth in 5 min
of sintering time in microwaves, compared to
10–20 h in a conventional process.
The highlight of this research was
achieving 98%TD in 1 min at 1650°C with a
submicron grain size. Microwave sintering
result showed that near theoretical
densities can be obtained at much reduced
temperatures, and with much reduced
sintering times, as compared to conventional
sintering.
Conventionally sintered samples at
1400°C for 10 h resulted in 98%TD. However,
using microwave energy 99%TD could be
obtained at 1400°C in just 30 min. This
conclusively shows that microwave sintering
is much faster than conventional sintering.

CONSOLIDATION OF RHENIUM
Arc melting of rhenium in an inert
atmosphere or vacuum is possible but the
metal produced tends to have coarse grain
size and may have segregation of rhenium
oxides at the grain boundaries. These issues
are a problem for further fabrication of a
product and therefore powder metallurgy has
shown to mitigate some of these problems.
Rhenium powder is consolidated using pressure
techniques to a density of approximately 60%
of the theoretical density.
The pressed compacts are then pre-
sintered in a hydrogen atmosphere to facilitate Fig. 4: SEM micrographs of Re pallet in (above) as
handling before final sintering. Proper choice pressed and (below) microwave sintered at 2000°C for
of powder sizes, careful blending and adequate 10 min [Mondal et al., 2009].

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Relatively high sintered density in the order enhance W-Cu composite densification which
of 95% of theoretical has been achieved in includes resistance sintering, plasma spraying
microwave heating at 2000°C, 20 min soaking and laser sintering. Microwave sintering
time. Figure 4 shows a SEM micrograph of of W-Cu has also been successfully reported
as-pressed and microwave sintered rhenium by several researchers [Mondal et al., 2008;
compact. Mondal et al., 2009; Mondal et al., 2007].
Mondal showed that full densification can be
CONSOLIDATION OF W-Cu achieved by microwave sintering of W-15Cu
There are two ways used to form composition. In spite of higher heating rate in
W–Cu composites: copper infiltration of a microwave sintering, cracking in the sintered
porous tungsten skeleton and liquid phase samples was not observed. This is attributed
sintering (LPS) of mixed phase compacts. For to the volumetric heating nature of microwave
economical reasons, shape, complexity, and sintering. They also reported that microwave
large scale production consideration, the sintering lowers the sintering temperature
latter technique is the only widely adapted to achieve the optimum densification as
fabrication routes for W-Cu alloys. However, well as optimum mechanical properties.
the lack of solubility between tungsten and
copper makes it very difficult to achieve full
densification through liquid phase sintering.
In the LPS approach, high compaction
pressures increase the green density, but
result in increased particle-particle contacts
that limit particle rearrangement during
LPS. Other than rearrangement shrinkage,
the sintering shrinkage is due to solid state
sintering of the tungsten skeleton, even after
liquid formation. Smaller tungsten powders
induce faster skeletal sintering or allow
for a lower sintering temperature, which is
desirable since copper evaporation occurs at
high temperatures. The mutual insolubility of
the W–Cu system denies solution precipitation
controlled LPS densification. On the other
hand, the addition of small quantities of
transition elements (such as Ni, Co and Fe),
activate tungsten skeletal sintering and have
a positive impact on the sinterability of
the W–Cu system. However, these additions
degrade electrical and thermal conductivity.
Higher sintering temperature or longer
holding time always help to improve the
densification but copper may diffuse out from
the skeleton which leads to non homogeneous
microstructure. Slow heating rate, co
reduction of oxides or other thermo chemical
processes are all efficient method to improve Figure 5. SEM micrographs of (above) conventional and
the densification of this material. Novel (below) microwave sintered W-30Cu alloys, sintered at
sintering technique has also been explored to 1200°C for 30 min in H2 atmosphere.

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Finer particle size and more homogeneous
distribution of tungsten in the microstructure
have been reported in microwave sintered W-
15Cu composites. Figure 5 exhibits finer grain
size and homogeneous distribution of both
the phases in microwave and conventionally
sintered W-30Cu composites.
TUNGSTEN HEAVY ALLOYS (WHAs)
Tungsten heavy alloy (WHA) is a group
of two-phase composites, based on W-Ni-Cu
and W-Ni-Fe. Price [Price et al., 1938] proposed
liquid phase sintering as a viable technique
for consolidating the W-Ni-Cu alloy. The W-
Ni-Cu system provided an important basis for
understanding the phenomenology of liquid
phase sintering. In fact Cannon [Cannon and
Lenel, 1953] referred the mechanism of liquid
phase sintering as ‘heavy alloy mechanism’.
WHA possesses unique combination of
properties such as high density (16-18 g/
cm3), high strength (1000-1700 MPa) and high
ductility (10-30%).
WHAs can be classified into two main
groups based on the binder composition: W-
Ni-Cu and W-Ni-Fe. Besides the high density
and unique combination of high strength and
ductility, there are other attributes, which
make WHA a versatile product [Lassner and
Schubert, 1999]:
• The high modulus of elasticity
• Excellent vibration damping stages of sintering: (i) rearrangement and (ii)
characteristics
• Its good machinability
• The high absorption ability for of tungsten was studied by Prill [Prill, 1964].
x-rays and γ-rays
• Good thermal and electrical the acceleration of sintering of tungsten
conductivities
• Low electrical erosion and the densification and grain growth kinetics
welding tendency
• Good corrosion resistance
The combination of density, ductility,
strength, thermal conductivity and corrosion
resistance makes them unique in many
applications such as radiation shields,
vibration dampers, kinetic energy penetrators
and heavy-duty electrical contacts. Being a
strategic material, all the details regarding
the processing are not available in the open
literature. These alloys are very structure
sensitive and therefore a firm understanding
of the processing and their physical metallurgy
are very critical for attaining better product
performance. In the past, substantial
work has been focused on modifying the
matrix composition and post-sintering heat
treatment to achieve full densification and
optimal mechanical properties. Residual
porosity greater than 0.5% drastically reduces
the mechanical properties, especially the
toughness and ductility.
CONSOLIDATION OF W-Ni-Cu ALLOYS
In W-Ni-Cu alloys, normally the nickel-
to-copper ratio ranges from 3:2 to 4:1. Price
[Price et al, 1938] were the first to propose
Ni-Cu as the binder for tungsten heavy alloys.
They have shown that highly dense W-Ni-Cu
heavy alloys could only be obtained by liquid
phase sintering.
Subsequently, researchers looked
at full densified W-Ni-Cu composites by
solid state sintering. Solid state activated
sintering of tungsten powder with various Ni-
Cu additions was studied by Brophy [Brophy
et al., 1966]. Their study was mainly confined
to densification mechanism. They proposed
that shrinkage occurs during the initial two
solution-reprecipitation stages. The role of
phase relationships on the activated sintering
They proposed that at lower Ni:Cu content,
diminishes. Kothari [Kothari, 1967] studied
of W-Ni-Cu heavy alloys with different Ni:Cu
ratios.
The rate constant for the sintering
process was evaluated from the volume
change as a function of sintering period. The
activation energy was found to be independent
of binder composition. Grain growth rate was
proportional to the sintering period. Makarov

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[Makarov et al., 1965] studied the coalescence
phenomenon in W-Ni-Cu alloys during liquid
phase sintering. The effect of tungsten and
copper powder size variation on the sintered
properties of W-Ni-Cu heavy alloys was carried
out by Srikanth [Srikanth et al., 1983; Srikanth
and Upadhyaya, 1984]. They found enhanced
sintered properties with finer particle size of
the constituent with increasing nickel content
in the binder. The effect of composition and
sintering temperature on the densification
and microstructure of W-Ni-Cu heavy alloys
was studied by Ramakrishanan [Ramakrishnan
and Upadhyaya, 1990]. Kuzmic [Kuzmic, 1966]
proposed that rapid cooling from the sintering
temperature prevent the formation of brittle
phase in order to obtain good mechanical
properties. Ariel [Ariel et al., 1973] correlated
the mechanical properties of W-Ni-Cu system
with sintered microstructure. Their study
showed that the mechanical properties are a
function of mean free path between tungsten
grains, volume fraction of tungsten grains and
the contiguity of tungsten spheroids.
The solubility of tungsten in the liquid
binder plays a dominant role in sintered W-
Ni-Cu alloys. The solubility of W in the Ni-Cu
additive can be regulated by an appropriate
selection of Ni:Cu ratio. Nowadays, W-Ni-
Cu alloys are also being consolidated by
employing prealloyed powders [Martin et al.,
2006]. Use of prealloyed powder improves
homogeneity.
The homogenization process
accelerates sintering and promotes
densification. The alloy formation during
sintering decreases the material viscosity and,
hence, stimulates material flow under the
action of capillary forces [Savitskii, 2005]. In
the binary Ni-W system either solid tungsten
or a Ni-base solid solution can co-exist in
equilibrium with a liquid phase [Hansen and
Anderko, 1957; Eremenko et al., 1977],
which depends upon temperature and relative
amount of components in the system.
Despite widespread application,
difficulties still exist in the manufacture of
liquid phase sintered tungsten heavy alloys.
Large dimensional change takes place during
sintering. The linear shrinkage can be as large
as 20%, which causes slumping to occur. The
distortion behavior of 80W-20 (Ni, Cu) alloy
was studied by Upadhyaya [Upadhyaya, 1998
]. He found that high dihedral angle minimize
compact slumping. Researchers have also
attempted to consolidate W-Ni-Cu alloys using
microwave energy. Mondal showed that at
relatively low temperature (1300°C) prealloyed
compositions gave better densification but at
relatively higher temperature (1450°C) which

Figure 6. SEM micrographs of (left) conventional and (rigth) microwave sintered W-7Ni-3Cu alloys. The compacts
were sintered at 1450°C [Mondal et al., 2008].

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corresponds to the liquid phase sintering of compacts. Taking into consideration the
this system, there is no difference between slow heating rate (5°C/min) in conventional
premixed and prealloyed compositions of furnace, there was about 75% reduction in
90W-7Ni-3Cu alloys, as far as densification the process time of W-Ni-Fe compacts in
is concerned irrespective of the heating microwave furnace. Figure 7 shows a typical
mode. Figure 6 exhibits SEM micrographs of thermal profile used in their experiments. It
conventionally and microwave sintered 90W- was interesting to note that heating of the
7Ni-3Cu alloys. They also reported about 75% same compact in microwaves was achieved
reduction in process time, elimination of at much lower power consumption. This can
brittle intermetallic formation and superior be attributed to the fact that in microwaves
mechanical properties in microwave sintered the sample per se heats up and acts as the
samples. source of heat. Consequently, the effective
thermal mass reduction lowers the required
CONSOLIDATION OF W-Ni-Fe ALLOYS power input. Furthermore, for both heating
Although WHAs with Ni-Cu binder were modes, no distortion was observed in the
initially developed, attention was eventually
focussed on heavy alloys with Ni-Fe binder
because of their better mechanical properties
[25]. Conventional sintering of W-Ni-Fe alloys
results in grain growth and long sintering time
results in precipitation of brittle intermetallic
phases. To avoid this, the matrix composition
is restricted to an optimal nickel to iron ratio
of 7:3 [25]. Microwave sintering of W-Ni-Fe
composition were first studied by Upadhyaya
et al. [70]. They investigated the sintering
response of a 92.5W-7.5(Ni-Fe) alloy - with a
non-optimal matrix composition - consolidated
through microwaves and compared its
densification, microstructure and mechanical
properties vis a vis conventionally sintered

Fig. 8: SEM micrographs of (above) conventional and

Figure 7. Typical thermal profiles used for sintering (below) microwave sintered 92.5W-6.4Ni-1.1Fe alloys.
of 92.5 W -6.1Ni-1.1Fe alloys using conventional and The compacts were sintered at 1500°C [Upadhyaya et
microwave furnaces [Upadhyaya et al., 2007]. al., 2007].

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sintered samples. Both conventional as well alloys for structural and high performance
as microwave sintered samples attained applications. Similar study on 90W-7Ni-3Fe
>98.5% density. alloys were conducted by Mondal [Mondal and
Figure 8 compares the microstructures Upadhyaya, 2007; Mondal and Upadhyaya,
of conventional and microwave sintered alloy. 2006]. They also observed the reduction in
Their observed trend is in accordance with the sintering time during the consolidation of
earlier reports of microwave advantage in this alloys. They also observed the lowering
producing finer grains, since microstructural of sintering temperature in microwave mode.
coarsening in W-Ni-Fe alloys occurs through The W-Ni-Fe alloys were sintered to equivalent
solution-reprecipitation and its kinetics level in microwaves with 75% reduction in the
is time-dependent. Hence, sintering-time sintering time.
compression in microwave furnace will Figures 10 and 11 compare the SEM
restrict W grain growth. microstructure of conventional and microwave
Figure 9 compares the XRD patterns of sintered alloys at different temperature. The
conventional and microwave sintered alloys. microwave sintered W-Ni-Fe microstructure
As expected, since the matrix was not in is less contiguous than conventional
stoichiometric proportion, therefore, phase microstructure. Microwave sintered compacts
analysis of conventionally sintered 92.5W-
6.4Ni-1.1Fe alloy shows presence of brittle
intermetallic phases (NiW, Fe7W6). Remarkably,
these phases are absent in microwave
sintered compacts. It is conjectured that
the precipitation of intermetallic phase in
conventionally sintered compacts promotes
cleavage fracture and thereby leads to
degradation of mechanical properties.
Based on the above results, it is evident
that microwave sintering offers a potentially
viable means to consolidate tungsten heavy

Figura 9. XRD analysis of microwave as well as Figure 10. SEM micrographs of (above) conventional
conventionally sintered 92.5W-6.4Ni- 1.1Fe alloy and (below) microwave sintered 90W-7Ni-3Fe alloys
[Upadhyaya et al., 2007]. sintered at 1300°C.

Journal of Microwave Power and Electromagnetic Energy, 44 (1), 2010

39
International Microwave Power Institute
 Avijit Mondal et al., Microwave Sintering of Refractory Metals/alloys: W, Mo, Re, W-Cu, W-Ni-Cu and W-Ni-Fe ...
Figure 11. SEM micrographs of (above) conventional
and (below) microwave sintered 90W-7Ni-3Fe alloys
sintered at 1450°C.
Figure 12. XRD analysis of microwave as well as
conventionally sintered 90W-7Ni-3Fe alloy.
Journal of Microwave Power and Electromagnetic Energy, 44 (1), 2010
40
International Microwave Power Institute
have higher hardness and tensile properties
as compared to their conventionally sintered
counterparts. Figure 12 represents the XRD
analysis of conventionally and microwave
sintered samples. This analysis does not
reveal the presence of any intermetallic
phase formation irrespective of the heating
mode for this particular composition.
FINAL REMARKS
Pure refractory metals such as, W,
Re and Mo can be effectively sintered using
microwave energy to high densification.
Microwave sintering provides about 80%
reduction in total processing time. Microwave
sintering leads to higher sintered densities
(of as high as 98% of theoretical density).
Finer grain sizes and superior mechanical
properties have been achieved in microwave
sintering irrespective of the material. In case
of W sintering addition of Y2O3 and HfO2 (grain
growth inhibitors) have been successfully
used to restrict grain growth. W-based
alloys have been very effectively sintered in
microwaves without causing any micro- and
macro-cracking. In general finer particle
size and higher mechanical properties are
achieved through microwave sintering. Non-
stoichiometric compositions can be sintered
using microwaves. This opens the possibility
for tailoring a wide variety of compositions
for high performance applications.
ACKNOWLEDGEMENTS
This collaborative research was done
as a part of the Center for Development of
Metal-Ceramic Composites through Microwave
Processing which was funded by the Indo-US
Science and Technology Forum (IUSSTF), New
Delhi. The present project was also partially
funded by Institute of Plasma Research,
Department of Atomic Energy.
REFERENCES
Agrawal, D. (1999). “Microwave
Sintering of Ceramics, Composites, Metals,
and Transparent Materials.” J Mater. Edu. vol.
19 (4, 5, 6), pp. 49-58.
Avijit Mondal et al., Microwave Sintering of Refractory Metals/alloys: W, Mo, Re, W-Cu, W-Ni-Cu and W-Ni-Fe ...
Agrawal, D., J. Cheng, P. Seegopaul,
and L. Gao (2000). “Grain Growth Control
in Microwave Sintering of Ultrafine WC-
Co Composite Powder Compacts.” Powder
Metal., vol. 43(1), pp. 15-16.
Agrawal, D.K. (1998). “Microwave
Processing of Ceramics: A Review.” Current Opinion
in Solid State & Mat Sci, vol. 3 (5), pp. 480-86.
Agrawal, D.K., A.J. Papworth, J.
Cheng, H. Jain, and D.B. Williams (2001), “
Microstructural Examination by TEM of WC/
Co Composites Prepared by Conventional and
Microwave Processes.” Proc. 15th International
Plansee Seminar, vol.2, G. Kneringer, P.
Rodhammer and P. wilhartitz (eds.),Plansee
AG, Reutte, Austria, pp. 677-684.
Andrey, L.M., Eugene A. Olevsky
(2004). “Effective Diffusion Coefficients in
Solid-State Sintering.” Acta Materialia, vol.
52, pp. 2953–2963.
Anklekar, R.M., D.K. Agrawal, and
R. Roy (2001). “Microwave Sintering and
Mechanical Properties of P/M Steel.” Powder
Metal., vol. 44[4], pp. 355-362
Anklekar, R.M., K. Bauer, D.K. Agrawal,
and R. Roy (2005). “Improved Mechanical
Properties and Microstructural Development
of Microwave Sintered Copper and Nickel
Steel PM Parts.” Powder Metallurgy, vol. 48,
no. 1, pp. 39-46.
Ariel, E., J. Batra, and D. Brandon
(1973). “Activated Sintering.” Powder
Metallurgy International, vol. 5, pp 125-128.
Averbach, R.S., H. Zhu, R. Tao, and H.J.
Hofler (1996). “Sintering of Nanocrystalline
Materials.” Experiments and Computer
Simulations, in Synthesis and Processing
of Nanocrystalline Powder, edited by D.L.
Bourell, pp. 203–216.
Booske, J. H., R.F. Cooper, S.A.
Freeman (1997). “Microwave Enhanced
Reaction Kinetics in Ceramics.” Mat. Res.
Innovat., vol. 1, pp. 77–84.
Bose, A., B.R. Klotz, F.R. Kellogg, K.C.
Cho and R.J. Dowding (2008). “Nanocrystalline
Tungsten Powder Synthesis Using High Energy
Milling.” Proc. 2008 Intl Conf on W, Refract &
Hardmetals VII, Publ MPIF, pp. 5-35 – 5-48.
Journal of Microwave Power and Electromagnetic Energy, 44 (1), 2010
International Microwave Power Institute
Bourell, L., and J.R. Groza
(1998). “Consolidation of Ultra Fine and
Nanocrystalline Powder.” in ASM Handbook
7 (American Society of Metals, Metals Park,
OH), pp. 583–589.
Brophy, J.H. and A.L. Prill (1966).
“A Reanalysis of Data on the Solution-
Reprecipitation Stage of Liquid Phase
Sintering.” Trans. AIME, vol. 236, pp. 85-91.
Bykov, Yu. V., K.I. Rybakov and
V.E. Semenov (2001). “High-Temperature
Microwave Processing of Materials.” J. Phys.
D: Appl. Phys., vol. 34, pp. R55–R75.
Cannon, H.S. and F.V. Lenel (1953).
“Some Observations on the Mechanism of
Liquid Phase Sintering.” Proceedings of
Plansee Seminar, F. Benesovsky (ed.), Plansee
Metallwerk, Reutte, Austria, pp. 106-122.
Chhillar, P., D. Agrawal and J.H. Adair
(2008). “Sintering of Molybdenum Metal
Powder using Microwave Energy.” Powder
Metallurgy , vol. 51, no. 2, pp. 182-187
Clark, D.E. and W.H. Sutton (1996).
“Microwave Processing of Materials.” Ann.
Rev. Mater. Sci., vol. 26, pp. 299-331.
Couchman, P.R. and W.A. Jesser (1977).
“Thermodynamic Theory of Size Dependence
of Melting Temperature in Metals,” Nature,
vol. 269, no.6, pp. 481-483.
Engleman, G., J. Nable, A.J. Sherman,
L.O. Vatamanu, B. Doud and J. Stiglich (2008).
“Development and Characterization of Nano-
Tungsten Powder.” Proc. 2008 Intl Conf on W,
Refract & Hardmetals VII, Publ MPIF, pp. 5-49
– 3-56.
Eremenko, V.N., R.V. Minakova, and
M.M. Churakov (1977). “Solubility of Tungsten
in Copper-Nickel Melts.” Soviet Powder
Metallurgy and Metals Ceramics, vol. 16, pp.
283-286.
Groza, J.R. (1999). “Sintering of
Nanocrystalline Powders.” Int. J. Powder
Metall. vol. 35, 59
Groza, J.R. (2002). “Nanocrystalline
Powder Consolidation Methods.” Nanostructured
Materials-Processing, Properties and Potential
Applications, edited by C.C. Koch Noyes, New
York, NY, pp. 115–178.
41
 Avijit Mondal et al., Microwave Sintering of Refractory Metals/alloys: W, Mo, Re, W-Cu, W-Ni-Cu and W-Ni-Fe ...
Hahn, H. (1993). “Microstructure
and Properties of Nanostructured Oxides.”
Nanostruct. Mater. vol. 2, pp. 251.
Hansen, M., and K.P. Anderko (1957).
“Constitution of Binary Alloys.” McGraw-Hill,
New York.
Huang, H., and K. Hwang (2002).
“Deoxidation of Molybdenum during Vacuum
Sintering.” Metall. Mater. Trans. A, vol. 33A,
pp. 657–664.
Jain, M., G. Skandan, K. Martin, K. Cho,
B. Klotz, R. Dowding, D. Kapoor, D. Agarwal,
and J. Chang (2006). “Microwave Sintering:
A New Approach to Fine-Grain Tungsten-I.”
International Journal of Powder Metallurgy,
vol. 42, no. 2, pp. 45-50. Materials Transactions B, vol. 37b, pp.839-
Jain, M., G. Skandan, K. Martin, K. Cho,
B. Klotz, R. Dowding, D. Kapoor, D. Agarwal,
and J. Chang (2006). “Microwave Sintering:
A New Approach to Fine-Grain Tungsten-II.”
International Journal of Powder Metallurgy,
vol. 42, no. 2, pp. 53-57.
Johnson, J.L. (2008). “Progress
in Processing Nanoscale Refractory and
Hardmetal Powders.” Proc. 2008 Intl Conf on
W, Refract & Hardmetals VII, Publ MPIF, pp.
5-57 – 5-71.
Kothari, N.C. (1967). “Densification
and Grain Growth during Liquid Phase
Sintering of Tungsten-Nickel-Copper Alloys.”
Journal Less-Common. Metals, vol. 13, pp.
457-461.
Kuzmic,J.F.(1966).“ModernDevelopment
in Powder Metallurgy.” Ed. H.H. Hausner, Plenum
Press New York, vol. 3 , pp. 166-171
Lassner, E., and W.D. Schubert (1999).
“Tungsten: Properties, Chemistry, Technology
of the Elements, Alloys, and Chemical
Compounds.” Kluwer Academic/Plenum
Publishers, New York
Luo, J., C. Hunyar, l. Feher, G. Link,
M. Thumm, and P. Pozzo (2004). “Theory and
Experiments of Electromagnetic Loss Mechanism
for Microwave Heating of Powdered Metals.”
Appl. Phys. Lett., vol.84, no.24, pp. 5076-79.
Makarov, R., O.K. Teodorovich, and
I.N. Fruntsevich (1965). “The Coalescence
Phenomena in Liquid Phase Sintering in the
Journal of Microwave Power and Electromagnetic Energy, 44 (1), 2010
42
International Microwave Power Institute
Systems W-Ni-Fe and W-Ni-Cu.” Soviet Powder
Metallurgy and Metal Ceramic, vol. 4, pp.
554-559.
Malewar, R., K.S. Kumar, B.S. Murty, B.
Sarma, and S.K. Pabi (2007). “On Sinterability
of Nanostructured W Produced by High-Energy
Ball Milling.” Journal of Material Research,
vol. 22, no. 5, pp.1200-1206.
Martin, J.M., J.L. Johnson, R.M.
German, and F. Castro (2006). “Microstructural
Evolution of Tungsten Heavy Alloys during
Heating.” San Diego.
Mishra, P., G. Sethi, and A. Upadhyaya
(2006). “Modeling of Microwave Heating
of Particulate Metals.”Metallurgical and
845.
Mondal, A., A. Upadhyaya and B. Sarma
(2007). “Microwave Sintering of Tungsten
Heavy Alloys.” International Conference on
Metals and Alloys: Past, Present and Future,
Kanpur, December
Mondal, A., A. Upadhyaya and D.
Agarwal (2009). “Microwave Sintering of
W-Cu, W-Ni-Cu and W-Ni-Fe Alloys.” 17th
International Plansee Seminar, 25 to 29th
May , Reutte, Austria
Mondal, A., A. Upadhyaya and D.
Agarwal (2009). “Sintering Advances in
Consolidating W and its Alloys.” TMS 2009
Annual Meeting and Exhibition, February 15-
19, San Francisco, California.
Mondal, A., A. Upadhyaya and D.
Agrawal (2009). “Microwave Sintering of
W-18Cu and W-7Ni3Cu Alloys,” Journal of
Microwave Power & Electromagnetic Energy,
vol. 43, no. 1, pp. 43-1-11 – 16.
Mondal, A., and A. Upadhyaya (2006).
“Sintering Advances in Consolidating W-Based
Alloys.” PMRM workshop, organized by Heavy
Alloy Penetrator Project, Tiruchirappalli.
Mondal, A., and A. Upadhyaya (2007).
“Microwave Sintering of Tungsten Heavy
Alloys.” PMAI Conference organized by Powder
Metallurgical Association of India, Delhi
Mondal, A., D. Agrawal and A.
Upadhyaya (2008). “Effect of Microwave and
Conventional Heating on Sintering Behavior of
Avijit Mondal et al., Microwave Sintering of Refractory Metals/alloys: W, Mo, Re, W-Cu, W-Ni-Cu and W-Ni-Fe ...
Tungsten Coated Copper Powder.” Proc. 2008
Intl Conf on W, Refract & Hardmetals VII, Publ
MPIF, pp. 3-134 – 3-140.
Mondal, A., D. Agrawal and A.
Upadhyaya (2008). “Microwave and
conventional Sintering of Premixed and
Prealloyed Tungsten Heavy Alloys.” Materials
Science and Technology, Oct 5-9, Pittsburgh,
pp. 2502-2515.
Mondal, A., D. Agrawal and A.
Upadhyaya (2008). “Microwave Heating of
Pure Copper Powder with Different Particle
Size and Porosity.” Global Congress on
Microwave Energy Application, Japan, pp.
517-520
Mondal, A., D. Agrawal and A.
Upadhyaya (2008). “Microwave Sintering of
Tungsten Based Alloys.” Proc. 2008 Intl Conf
on W, Refract & Hardmetals VII, Publ MPIF,
pp. 3-122 – 3-132.
Mondal, A., D. Agrawal and A.
Upadhyaya (2008). “Sintering Advances
in Consolidating W Based Alloys.” Global
Congress on Microwave Energy Application,
Japan, pp. 301-304.
Mondal, A., D. Agrawal and A.
Upadhyaya (2009). “Microwave Heating of
Pure Copper Powder with Varying Particle Size
and Porosity.” Journal of Microwave Power &
Electromagnetic Energy, vol 43, no. 1, pp. 43-
1-5 – 10.
Mondal, A., D. Agrawal, A. Upadhyaya,
P. Chhillar, J. Cheng, and R. Roy (2009).
“Microwave Sintering of Refractory Metals: W,
Mo, Re, W-Cu, W-Ni-Cu and W-Ni-Fe Alloys.”
International Conference on Materials for
Advanced Technology, 28th June to 3rd July,
Singapore.
Oda, E., K. Ameyama, S. Yamaguchi
(2006). “Fabrication of Nano Grain Tungsten
Compact by Mechanical Milling Process and
its High Temperature Properties.” Materials
Science Forum, vol. 503-504, pp 573-578.
Patrician, T., V. Sylvester and R. Daga
(1985). Proc. Symp. On “Physical Metallurgy
and Technology of Molybdenum and its Alloys”;
Ann Arbor, MI, USA, AMAX Materials Research
Center, 1–11.
Journal of Microwave Power and Electromagnetic Energy, 44 (1), 2010
International Microwave Power Institute
Prabhu, G., A. Chakraborty, B. Sarma
(2008). “Microwave Sintering of Tungsten.”
Int. Journal of Refractory Metals & Hard
Materials,
Price, G.H.S., C.J. Smithells, and
S.V. Williams (1938). “Sintered Alloys. Part I.
Copper-Nickel-Tungsten Alloys Sintered with
a Liquid Phase Present.” Journal of Institute.
Metals, vol. 62, pp. 239-264.
Prill, A.L. (1964). “The Role of Phase
Relationships in the Activated Sintering of
Tungsten.” Transaction AIME, vol. 230, pp.
769-772.
Ramakrishnan, K.N., and G.S.
Upadhyaya (1990). “Effect of Composition
and Sintering on the Densification and
Microstructure of Heavy Alloys Containing
Copper and Nickel.” Journal of Materials
Science Letters, vol. 9, pp. 456-459.
Rao, K.J. and P.D. Ramesh (1995).
“Use of Microwaves for the Synthesis and
Processing of Materials.” Bull. Mater. Sci.,
vol.18, no.4, pp. 447-465.
Rodiger, K., K. Dreyer, T. Gerdes, and
M.W. Porada (1998). “Microwave Sintering
of Hardmetals.” International Journal of
Refractory Metals & Hard Materials, vol.16,
pp. 409-416.
Roy, R., D.K. Agrawal, J.P. Cheng, and
S. Gedevanishvili (1999). “Full Sintering of
Powdered Metals Using Microwaves.” Nature,
vol.399, no.17, pp. 668-670.
Rybakov, K.I., V.E. Semenov, S.V.
Egorov, A.G. Eremeev, I.V. Plotnikov, and
Y.V. Bykov (2006). “Microwave Heating of
Conductive Powder Materials.” J. Appl. Phys.,
vol. 99, pp. 023506-09.
Saitou, K. (2006). “Microwave Sintering
of Iron, Cobalt, Nickel, Copper and Stainless
Steel Powders.” Scripta Materialia, vol. 54,
no. 5, pp. 875-879.
Savitskii, A.P (2005). “Scientific
Approaches to Problems of Mixtures Sintering.”
Science of Sintering, vol. 37, pp. 03-17.
Srikanth, V. and G.S. Upadhyaya
(1983). “Properties of Sintered Heavy Alloys.”
International Journal of Refractory and Hard
Metals, vol. 2, no 3. pp. 49-54.
43
 Avijit Mondal et al., Microwave Sintering of Refractory Metals/alloys: W, Mo, Re, W-Cu, W-Ni-Cu and W-Ni-Fe ...

Srikanth, V. and G.S. Upadhyaya Upadhyaya, A. (2001). “Processing

(1984). “Effect of Tungsten Particle Size on
Sintered Properties of Heavy Alloys.” Powder
Technology, vol. 39, pp. 61-65.
Sutton, W. (1992). “Microwave
Processing of Ceramics-an Overview.” Mater
Res Sot Symp Proc, vol. 269, pp. 3-l 9.
Takayama, S., G. Link, S. Miksch, M.
Sato, J. Ichikawa, and M. Thumm (2006).
“Millimetre Wave Effects on Sintering
Behavior of Metal Powder Compacts.” Powder
Metallurgy, vol.49, no.3, pp. 274-280.
Tinga, W.R. and A.G. Voss (1968).
“Microwave Power Engineering.” New York:
Academic
Tinga, W.R. and E.M Edwards (1968).
“Dielectric Measurements Using Swept
Frequency Techniques.” Journal of Microwave
Power, vol.3, no. 3, p.p.114-125.
Strategy for Consolidating Tungsten Heavy
Alloys for Ordnance Applications.” Materials
Chemistry and Physics, vol. 67, pp. 101-110.
Upadhyaya, A., (1998). “A
Microstructure-Based Model for Shape
Distortion during Liquid Phase Sintering.”
Ph.D.Thesis, Penn State, USA.
Upadhyaya, A., S. K. Tiwari, and P.
Mishra (2007). “Microwave Sintering of W-Ni-
Fe Alloys.” Scripta Materialia, vol.56, pp. 5-8.
Von Hippel, A. (1954). “Dielectric
Materials and Applications,” Technology Press
of M.I.T, p.p.301
Wang, H., Z.Z. Fang and D. Siddle
(2008). “Study of Size-Dependent Sintering
Behavior of Tungsten Powders.” Proc. 2008
Intl Conf on W, Refract & Hardmetals VII, Publ
MPIF, pp. 5-72 – 5-77

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 Science of Sintering, 42 (2010) 169-182
________________________________________________________________________

doi: 10.2298/SOS1002169M

UDK 622.785:546.56
Effect of Porosity and Particle Size on Microwave Heating
of Copper
A. Mondal1, A. Shukla1, A. Upadhyaya1, *), D. Agrawal2
1
Department of Materials & Metallurgical Engineering Indian Institute of
Technology, Kanpur 208016, India
2
Materials Research Institute, The Pennsylvania State University, University Park,
PA 16802, USA

Abstract:
The present study investigates the effect of varying particle size and porosity on the
heating behavior of a metallic particulate compact in a 2.45GHz multimode microwave
furnace. Experiments on copper suggest that unlike monolithic (bulk) materials, metallic
materials do couple with microwaves when they are in particulate form. The powder
compacts having higher porosity and smaller particle sizes interact more effectively with
microwaves and are heated more rapidly. A dynamic electromagnetic-thermal model was
developed to simulate the temporal temperature distribution using a 2-D finite difference time
domain (FDTD) approach. The model predicts the variation in temperature with time during
heating of copper powder compacts. The simulated heating profiles correlate well with those
observed from experiments.
Keywords: Finite Difference Modelling (FDM); Microwave heating; Sintering; Numerical
Modeling, Heat Transfer

Introduction

Microwaves are primarily coherent, polarized electromagnetic waves which lie

between the radio-waves and visible light in the electromagnetic spectrum. Their frequency
lies between 0.3 to 300 GHz and wavelength varies from 1 mm to 1 m range. One of the key
applications of microwaves is to heat materials. For such applications, however, only few
frequencies are allowed, namely 915 MHz, 2.45 GHz, 5.8 GHz and 28 GHz [1]. Out of these
2.45 GHz multimode microwaves are most commonly used. For engineering applications,
microwaves are known to interact strongly with a range of ceramics – both in bulk as well as
particulate form - and heat them to high temperatures (up to 1800°C) [2]. Unlike conventional
heating, wherein the heat-transfer is limited by radiative and conductive mode, microwaves
directly couple with ceramics result in rapid and uniform heating. Microwave heating of
ceramic and other dielectrically lossy materials have been widely investigated and the
mechanism of microwave-material interaction is well documented [2-4]. Microwave
penetrates and propagates through dielectric material. Thus, in effect, the material per se
becomes the source of heat. Consequently, at times, the flow of heat is the reverse of that
observed in conventional heating.
Unlike ceramics, bulk or monolithic metallic materials are known to reflect
_____________________________
*)
Corresponding author: anishu@iitk.ac.in
170 A. Mondal et al. /Science of Sintering, 42 (2010) 169-182
___________________________________________________________________________

microwaves at room temperature. Being good conductors, no internal electrical field is

induced in metallic materials. The induced electrical charges remain restricted at the surface
of a bulk metallic sample. This causes the eddy currents and subsequently resistive losses.
Roy et al. [5] were the first to recognize that this can be exploited to heat metals too to high
temperatures provided they are in particulate form. This opened the possibility of
consolidating the particulate metal compacts to full density through sintering using
microwaves. Subsequently, several researchers [6-19] have demonstrated that a range of
particulate metals and alloys can be heated using microwaves and can result an overall 60 to
90% reduction in the processing time. Besides cost advantage, a reduced processing time
restricts microstructural coarsening that occurs concomitantly with densification during
sintering. Hence, as compared to compacts processed in a conventional (radiatively-heated)
furnace, microwave sintered compacts have more homogenous and refined microstructure
which leads to an improved mechanical properties [8-19].
While the efficacy of microwaves to sinter metals is now well recognized, a
systematic evaluation of factors influencing the microwave interaction with the particulate
compact and its influence on the heating rate is as yet lacking. Recently, Saitou [10]
systematically investigated microwave heating of several metal powder compacts and
reported that the sintering mechanism per se remain the same both in conventional as well as
microwave heating. In recent years, using single-mode microwaves where the electric (E) and
magnetic (H) fields were separated; researchers [20-23] have demonstrated experimentally
that the effect of microwave frequency, sample conductivity, and green density on heating
efficiency of metallic compacts. However, from an industrial materials processing standpoint,
single-mode microwaves have limited application. Mishra et al. [24] modeled microwave
heating in metallic systems by solving the Maxwell’s equation and using a two-dimensional
finite difference time domain (FDTD) technique. However, their model ignored the influence
of the initial compact porosity and was not validated experimentally.
From the preceding discussion, it is evident that while microwave heating of ceramics
is well-understood and many models have been attempted, there is still an uncertainty about
the exact mechanism and mode of microwave heating in case of particulate metals. This study
therefore sets out to systematically investigate - both experimentally as well as through a
thermal-electromagnetic model - the effect of initial powder size and the as-pressed porosity
on the heating response of a copper compact in a multimode (2.45 GHz) microwave furnace.

2. Modeling approach

Modeling of microwave heating involves solving Maxwell equations of

electromagnetism simultaneously with the heat transfer equation [25]. The detailed approach
which has been adapted in this study to calculate the electro-magnetic absorption (PEM) by
metal powder compact has been discussed elsewhere [24].
In the present study, the calculated power absorbed is correlated with the temperature
rise in the compact. The latter requires solving the heat transfer equation for the boundary
conditions defined by the dimensions of the sample and its physical, thermal and dielectric
properties. The dependency of these parameters on temperature necessitates the need for a
dynamic simulation. Figure 1 shows the modeling approach adopted in this study through a
schematic flow-chart.
Microwaves interaction with metals is restricted to its surface only. This depth of
penetration in metals, also known as skin-depth (δ), is defined as the distance into the material
at which the incident power drops to 1/e (36.8%) of the surface value. The skin depth is
mathematically expressed as follows [26]:

δ = 1
= 0 . 029 ρλ o (1)
π f μσ
 A. Mondal et al./Science of Sintering, 42 (2010) 169-182 171
___________________________________________________________________________

where, ƒ is normal microwave frequency, μ is magnetic permeability, σ is electrical

conductivity, ρ is electrical resistivity, λo is incident wavelength (12.24 cm for 2.45 GHz
waves). The skin-depth in metals typically varies between 0.1 to 10 μm. From Equation 1, it
is evident that metals with higher electrical conductivity have lower skin depths. For metals,
as the resistivity increases with increase in temperature, the skin depth too increases. In
general, the skin depth is relatively small in metals; however, most metallic powders typically
have equivalent dimensions. In metal powders, the surface area and thereby the ‘effective
skin’ (portion of metal powder that couples with microwaves) is high enough to contribute to
its heating. Thus, it is likely that some of the submicron and nano-sized metal powders
undergo volumetric heating when subjected to microwaves. The skin depth of the metal plays
an important role in governing the power loss during the microwave-metal interaction which
leads to its heating [25]. The tangential component of the magnetic field, Ht, of microwaves
induces an electrical field, E, at the metal powder surface. The induced electrical field
generates surface current which causes the resistive Joule heating in metal powders.
Assuming spherical metal powder of radius, rp, the electro-magnetic power density (PEM) can
be expressed as [25]:
2
6 Rs Ε o
Ρ EM = 3Ρ
rp = η o 2 ⋅r p
(2)

where, Rs is surface resistivity ( Rs = 1/σδ, σ is electrical conductivity and δ is skin depth); Eo

is electric field amplitude at surface; and ηo is impedance of free space (377 Ω). In our
approach Eo is considered as a tunning parameter to fit the experimental data. In our earlier
work [24] the effect of porosity and particle size has not been considered whereas in this
model it has been considered.

2.2. Assumptions

To make the problem tractable and simplistic for modeling, following assumptions
are made:
• Since the particle size is much smaller than the wavelength of the microwave
radiation, the field across the particle is assumed to be spatially uniform and periodic in time.
• Powder coarsening is not assumed during heating.
• Monosized powders are assumed so that the calculated EM-power density generated
in a powder will be same when integrated over bulk aggregate.
• All metal powders within a compact are assumed to heat-up at the same rate so no
heat conduction between particles occurs.
• A heat-factor is considered to account for the presence of susceptor.
• Effect of oxide layer formation is not considered in the present model.
As shown schematically through Fig. 1, Eo which is the electric field amplitude at surface are
in turn fed as input parameter into the thermal model.

2.3. Thermal Model for Predicting Temperature Rise

Thermal Model for Cylindrical Geometry Compact has been defined as following:

∂T 1 ∂ ⎛ ∂T ⎞ ∂ ⎛ ∂T ⎞
ρC P = ⎜ Kr ⎟+ ⎜K ⎟ + PEM (3)
∂t r ∂r ⎝ ∂r ⎠ ∂z ⎝ ∂z ⎠

where
172 A. Mondal et al. /Science of Sintering, 42 (2010) 169-182
___________________________________________________________________________

ρ : Density of the material, which is time dependent and increases as densification

increases.
K: Thermal conductivity of the material (temperature dependent)
C P : Specific heat of the material (temperature dependent)
PEM : Power density due to microwave effect (temperature dependent)

Fig. 1. Flow chart of the dynamic model proposed for simulating the thermal profile in the
present study.

Typically, in the initial stage of heating, the metal powder compacts require
susceptor-assisted heating [27]. The susceptors usually couple very well with the microwaves
and are used for initially raising the temperature of the compact. Beyond a critical
temperature, the heating occurs primarily due to microwave-metal powder surface interaction.
Besides, assisting heating in the initial stage, the main role of susceptor is to prevent heat loss
 A. Mondal et al./Science of Sintering, 42 (2010) 169-182 173
___________________________________________________________________________

from the surface of the powder compact to the surrounding through radiation. In the present
modeling scheme, the contribution of SiC as susceptor for compact heating was also included.
Hence, the boundary condition at the surfaces of the compact can be formulated as following:

∂T
= h(T − Ta ) + K SUC (T − TSUC ) + σεF (T 4 − Tencl )
4
−K (4)
∂r

where
H: Heat Transfer Coefficient for convective heat transfer to surrounding
TSUC : Temperature of the SiC suspector
Tencl : Temperature of the enclosure in which compact is put
Ta : Ambiant Air temperature
K SUC : Susceptor constant
σ : Stefens-Boltzman’s constant
ε : Emissivity
F : View Factor
When no thermal gradient inside the compact exists, above equations may be written as
following:

⎛ V ⎞ ∂T ⎛V ⎞
− ρC P ⎜ ⎟ = h(T − Ta ) + K SUC (T 4 − T 4 SUC ) + σεF (T 4 − Tencl ) − PEM ⎜ ⎟
4
(5)
⎝ A ⎠ ∂t ⎝ A⎠

where
V πR 2 H
=
(
A 2πRH + 2πR 2 )
h is convective heat transfer coefficient of incoming gas,
A/V is surface area to volume ratio for compact,
σ is Stefan Boltzman constant,
ε is effective emissivity of metal powder, and
Ta is surrounding temperature.
Above equation may be discretisized with respected to time in following manner:
Tn +1 − Tn ∂T
= (6)
Δt ∂t
In Equation 6, Δt should not be too small as it increases the number of iterations, hence, the
round-off error is also increased. However, too large a Δt should also be avoided as it causes
an increase in the truncation error per step. Therefore, a suitable value of Δt is chosen which
satisfies stability criterion given below:
0.05 ≤ ∆t٠K ≤ 0.1 (7)
where, K is upper bound of following expression:
⎧ A ⎫ 1
d ⎨ ρC p ( (h(T − Ta ) + K SUC (T − TSUC ) + σεF (T 4 − Tencl
4
) − PEM )⎬
⎩ V ⎭ dT

3. Experimental setup to validate model

The as-received gas-atomized copper powders (supplier: American Chemet Corp.

USA) of different particle size were characterized for their size, size distribution and
174 A. Mondal et al. /Science of Sintering, 42 (2010) 169-182
___________________________________________________________________________

morphology. Tab. I summarizes the characteristics of the as-received powders used for this
study. Fig. 2 shows the scanning electron micrographs of the powders in as-received
condition. The particle size analysis of the as-received powders was performed using a
Malvern Instruments particle size analyzer which works on the principle of laser diffraction.

Tab. I. Characteristics of the as-received Cu powders used for the present study.

Cu Powder Grade A B C D E
Purity, % ~99 >99.5 >99.2 >99.2 >98
Particle size, µm
D10 2 6 8 26 231
D50 6 12 18 63 383
D90 36 20 33 118 560
Specific surface area, 2.5 1.4 0.5 0.3 0.3
2
/

Fig. 2. SEM micrograph Cu powders used in the present study and having average particle
size of (a) 6 µm, (b) 12 µm, (c) 18 µm, (d) 63 µm and (e) 383 µm, respectively.

The surface areas of the as received powders were measured using a BET apparatus.
The morphological analyses of the powders were carried out using SEM imaging. Tab. II
summarizes the physical and thermal properties of the copper powder used for the present
investigations, which are the input parameters in the model. The total experimental approach
consists of two sub sets. First experiment is all about the effect of particle size during the
 A. Mondal et al./Science of Sintering, 42 (2010) 169-182 175
___________________________________________________________________________

heating of powder particle in a multimode microwave furnace. Second experiment includes

the role of initial density/porosity during the heating of metal powders in a multimode
microwave furnace. For the first experiment powders were uniaxially pressed at 400 Mpa in
to compacts with green densities ranging between 60 to 83%Th. The sintering response on
densification and microstructures were evaluated on cylindrical pellets (12.7 mm diameter
and 5 mm average height). For the second set of experiments cylindrical pellets of the same
dimensions of as-received copper powder (particle size 18 µm) were compacted using the
varying compaction pressure in the range of 90 to 350 Mpa to obtain green densities ranging
between 56 to 76%Th.

Tab. II. Physical and thermal properties of Cu used for simulation of the thermal profile
[28,29].
Density, gcm-3 8.9
Heat capacity (Cp), Jkg-1K-1 92•10-3T + 355.9
Electrical resistivity, μΩ-cm 6.9×10-3 (T-273) + 1.5
Emissivity 0.65

Fig. 3. Schematic diagram showing the inside of the multimode microwave furnace used in
the present study.

Microwave heating of the as-pressed compacts was carried out using 2.45 GHz
multimode microwaves in a 6kW capacity furnace. The experimental setup for the furnace is
shown in Figure 3. A multi- layered insulation package was used to provide sufficient
insulation to obtain high and uniform temperatures throughout the sample. The outer package
was made up of thick ceramic fiber (aluminum silicate) sheets. A mullite tube was placed at
the centre of the package, and samples were placed inside this mullite tube. The entire
package was placed on a turntable to ensure uniform exposure of the sample to the microwave
field. Further details about the experimental setup are described elsewhere [27]. The
temperature of the sample was monitored using an infrared pyrometer (Type: RAYMA25CCF
Manufacturer: Raytek Co., Santa Cruz, CA, USA). Temperature measurement through
pyrometer is emissivity-based. Typically, emissivity varies with temperature. However, as
176 A. Mondal et al. /Science of Sintering, 42 (2010) 169-182
___________________________________________________________________________

very little variation in the emissivity was reported in the temperature range used in the present
study, hence, the effect of variation in emissivity was ignored in the present investigation.
The sintered density was obtained by both dimensional measurements as well as
Archimedes density measurement technique. The sinterability of the compact was also
determined through densification parameter which is expressed as:
(sintered density - green density)
Densification parameter = ……… (8)
(theoretical density - green density)

4. Results and discussion

In the preceding sections, a theoretical approach has been formulated to predict the
heating profile of metal powder compacts in microwave furnace. One of the first objectives
was to test the efficacy of the model to predict the temperature distribution within the
compact during heating. To test this, thermal profiles was simulated for Cu powder compact
(particle size 18 µm) having radius 6.5 mm and 6.5 cm respectively (Fig. 4).

Fig. 4. Simulated isothermal contours as a function of time in cylindrical Cu compacts(Avg.

particle size 18 µm) having dimensions (a) 6.5 mm radius and 5.5 mm height; and (b) 6.5 cm
radius and 5.5 cm height, respectively.
 A. Mondal et al./Science of Sintering, 42 (2010) 169-182 177
___________________________________________________________________________

As is evident from Figs. 4a and 4b, for copper powder compacts, irrespective of the compact
size, the temperature remains homogenous throughout its cross-section. It is also interesting to
note that for both cases, the temperature homogenization is achieved within a few seconds.
Therefore the assumption that the temperature is uniform inside the compact is valid.
1200

1000
Temperature, (°C)

800

600
6 µm
12 µm
400 18 µm
63 µm
383 µm
200 bulk Cu

0
0 10 20 30 40 50 60 70
Time, (min)

Fig. 5. Effect of varying particle size on the heating behavior of Cu compacts in a microwave
furnace. For comparison the thermal profile of bulk Cu under microwave is also
superimposed.

1200

1000
Temperature, (°C)

800

600 % Porosity
44
400 35
29
24
200

0
0 2 4 6 8 10 12 14
Time, (min)

Fig. 6. Effect of varying initial porosity on the heating behavior of Cu compacts (avg. size: 18
µm) in a microwave furnace.

Figs. 5 and 6 compare the effect of the initial powder size and the as-pressed porosity
on the thermal profiles of cylindrical copper compacts exposed to microwaves. For the sake
of comparison, the thermal profile on bulk copper is also superimposed in Figure 5. As
expected, the bulk copper does not heat up at all in microwave. In contrast, particulate
compacts show strong interaction with microwaves. It is evident from the figures that the
microwave heating is more effective for compacts having smaller particle size and high
178 A. Mondal et al. /Science of Sintering, 42 (2010) 169-182
___________________________________________________________________________

porosity levels. Elsewhere, Ma et al. [23] too have reported similar observations in copper
powder compacts heated in single-mode microwaves.
As particle size increases the heating rate decreases and after certain time for a
particular particle size; heating rate becomes constant at a particular power setting. It is well
known that microwaves for electrically conducting materials such as copper do not penetrate
a bulk sample beyond the skin depth. The skin depth expression in Equation 1 can be
rewritten as:
2
δ= (9)
μσω
where, µ is the real part of the permeability taken to be 4 ×10-7 T m/A for nonmagnetic
materials. σ and ω are the dc electrical conductivity and angular frequency, respectively. At
2.45 GHz, the skin depth of bulk copper is about 1.3 µm. However, in case of porous
compacts, the electrical conductivity correspondingly decreases. Thus, from the above
equation effective skin depth also increases proportionately. The variation in the heating rates
therefore can be attributed to the difference in skin depth and also the change in surface area
per unit volume with the varying particle sizes. This effect is further manifested to a larger
extent for coarser particle sizes on account of their higher compressibility. This is confirmed
by recently report from Ma et al. [23] who have experimentally shown that the electrical
conductivity of the as-pressed copper powder compacts with 22 µm powder is 104 times
higher than those prepared using 3 µm powder.

Tab. III: Densification response of Cu powder of different particle under microwave heating.

Average Cu Powder Size (µm) 6 12 18 63 383

sintered density (% theoretical) 95.4 90.4 90.0 89.8 90.0

densification parameter 0.88 0.54 0.48 0.43 0.39

Tab. IV. Effect of compaction pressure on the densification response of Cu powder compact
having average particle size of 18 µm.
Compaction Pressure (MPa) 90 210 280 350
green density (% theoretical) 56 65 71 76

sintered density (% theoretical) 78 82 87 90

densification parameter 0.50 0.49 0.55 0.58

Tab. III compares the densification response of all the sintered copper compacts of
different particle sizes in microwave furnace. In case of smallest particle compacts,
densification during microwave sintering is highest and the trend is similar for the rest of
other particle sizes. This is also validated by comparing the densification parameters which
follows similar trend as sintered density. Tab. IV compares the densification response of
different initial green density copper compacts sintered in microwave furnace. Although the
heating rate is faster for lower green density samples than the higher green density compacts
but densification during microwave sintering is higher in case of higher green density
compacts and the densification trend is also similar. This can be attributed to the difference in
the initial density.
 A. Mondal et al./Science of Sintering, 42 (2010) 169-182 179
___________________________________________________________________________

Fig. 7. Effect of varying initial particle size [(a) 6 µm, (b) 12 µm, (c) 18 µm, (d) 63 µm, (e)
383 µm] on the actual and predicted thermal profiles (left) and their correlation assuming a
linear fit (right).

Figs. 7a to 7e compare the actual and predicted thermal profile of copper powder
compact with increasing powder size. For all the five powder sizes, the trends in experimental
and predicted heating profile are self-similar. The differences in experimental and simulated
heating profiles can partly be attributed to the fact that power input was kept constant in
modelling, whereas, in the actual experiment, it was changed from 0.5 kW to 1.3 kW during
this experiment. An interesting observation for both experimental and simulation of thermal
profile is that for a particular choice of experimental variables, the temperature rise is
180 A. Mondal et al. /Science of Sintering, 42 (2010) 169-182
___________________________________________________________________________

restricted to a certain level. This can be attributed to the fact that the heat generated in the
compact (due to electromagnetic power absorbed) is balanced by the convective and radiative
heat losses. The figures to the right are the corresponding regression fit for the actual and
predicted temperatures for each time interval. The figures and the corresponding coefficient
of correlation (R2) values suggest that for lower particle sizes the model prediction are closer
to those measured experimentally because smaller particles which size is comparable with the
skin depth undergoes volumetric heating and much better microwave effect whereas powders
with larger particle size undergoes only surface heating and lesser microwave induced heating
effect. Smaller particle attains higher maximum temperature as compared to the larger
particle.

Fig. 8. Effect of varying initial porosity in a Cu compact [(a) 44%, (b) 35%, (c) 29%, (d)
24%] on the actual and predicted thermal profiles (left) and their correlation assuming a linear
fit (right).
 A. Mondal et al./Science of Sintering, 42 (2010) 169-182 181
___________________________________________________________________________

Figs. 8a to 8d compare the experimental and simulated thermal profiles of copper

powder compacts (particle size: 18 µm) having initial porosity of 44%, 35%, 29% and 24%,
respectively. The figures to the right are the corresponding predicted and actual temperature
correlation plots. It is worth noticing that for varying porosity levels the model predictions are
quite close to the experimental observations. For all the cases the correlation coefficient is
greater than 0.95.
Unlike microwave heating, for conventional furnace sintering, high green density
compacts are preferred so as to ensure homogenous heat transfer. The high green density
requires larger compaction pressure which results in lower tool life. The relatively longer
sintering time during conventional sintering is accompanied by microstructural coarsening
that is detrimental to the mechanical properties. For small sized particle compacts, the
problem is further compounded during conventional sintering since they have poor
compressibility and are also more prone to grain coarsening. From the above discussion, it is
logical to conclude that a finer powder size and higher as-pressed porosity compacts will
respond more favourably when subjected to microwave heating. The present study therefore
provides guidelines for effective design and optimization of process parameters to attain
greater microwave heating efficacy.

5. Conclusions

This study shows that copper powder compacts strongly couple with micowaves and
can be rapidly heated to high temperatures. The heating rate of the particulate compacts
increases as the particle size and green density decrease. A two-dimensional FDTD approach
was employed to simulate the heating response of the powder compacts that incorporated both
the electromagnetic and thermal model. A special feature of this approach is that it considers
the temperature-dependency on the physical and thermal properties. The predicted thermal
profiles correlate well with the experimental observations.

6. Acknowledgements

This work has been partially supported by Indo-US Joint Centre on Microwave
Applications funded under the program of Indo-US Public-Private Networked Joint Center
Program, India, and National Institute for Fusions Science, Japan.

7. Reference

1. A.C. Metaxas: Foundation of Electroheat: A Unified Approach, J. Wiley & Sons

Inc., New York, NY, 1996.
2. W. Sutton,: Mater. Res. Soc. Symp Proc. 269 (1992) 3.
3. D.E. Clark, W.H. Sutton, Ann. Rev. Mater. Sci. 26 (1996) 299.
4. D.K. Agrawal, Current Opinion in Solid State Mater. Sci. 3 (1998) 480.
5. R. Roy, D.K. Agrawal, J.P. Cheng, S. Gedevanishvili, Nature 399 (1999) 668.
6. D. Agrawal, J. Cheng, P. Seegopaul, L. Gao, Powder Metall. 43 (2000) 15.
7. K. Rödiger, K. Dreyer, T. Gerdes, M.W. Porada, Int. J. Ref. Metals Hard Mater.
16 (1998) 409.
8. R.M. Anklekar, D.K. Agrawal, R. Roy, Powder Metall, 44 (2000) 355.
9. G. Sethi, A. Upadhyaya, D. Agrawal, Sci. Sintering 35 (2003) 49.
10. K. Saitou, Scripta Mater. 54 (2006) 875.
182 A. Mondal et al. /Science of Sintering, 42 (2010) 169-182
___________________________________________________________________________

11. S. Takayama, G. Link, S. Miksch, M. Sato, J. Ichikawa, M. Thumm, Powder

Metall. 49 (2006) 274.
12. A. Upadhyaya, S.K. Tiwari, P. Mishra, Scripta Mater. 56 (2007) 5.
13. W.L. Wong, M.Gupta, Composites Sci. Tech. 67 (2007) 1541.
14. P. Chhillar, D. Agrawal, J.H. Adair, Powder Metall. 51 (2008) 182.
15. A. Mondal, D. Agrawal, A. Upadhyaya, in Proc. 2008 Int. Conf. Tungsten,
Refractory Hardmetals VII, Metal Powder Industries Federation, Princeton, NJ, v.
3, pp. 122-132.
16. A. Mondal, D. Agrawal, A. Upadhyaya, Mater. Sci. Tech. 2008, 2502.
17. A. Mondal, A. Upadhyaya, D. Agrawal, J. Microwave Power Electromag. Energy
43 (2009) 11.
18. A. Mondal, D. Agrawal, A. Upadhyaya, J. Microwave Power Electromag.
Energy, 44 (2010) (in press).
19. G. Prabhu, A. Chakraborty, B. Sarma, Int. J. Ref. Metals Hard Mater. 27 (2009)
545.
20. J. Cheng, R. Roy, D. Agrawal, Mat. Res. Innovations 5 (2002) 170.
21. J. Luo, C. Hunyar, I. Feher, G. Link, M. Thumm, P. Pozzo, Appl. Phy. Lett. 84
(2004) 5076.
22. K.I. Rybakov, V.E. Semenov, S.V. Egorov, A.G. Eremeev, I.V. Plotnikov, Y.V.
Bykov, J. Appl. Phy.99 (2006) 023506.
23. J. Ma, J.F. Diehl, E.J. Johnson, K.R. Martin, N.M. Miskovsky, C.T. Smith, G.J.
Weisel, B.L. Weiss, D.T. Zimmerman, J. Appl. Phy. 101 (2007) 074906.
24. P. Mishra, G. Sethi, A. Upadhyaya, Metall. Mater. Trans. B 37B (2006) 839.
25. J.H. Hill, T.R. Merchant, Appl. Mathematical Modelling 20 (1996) 3.
26. M. Pozar, Microwave Engineering, 2nd ed., J. Wiley & Sons Inc., Toronto,
Canada, 2001.
27. A. Mondal, D. Agrawal, A. Upadhyaya, J. Microwave Power & Electromag.
Energy 43 (2009) 5.
28. E.A. Brandes, and G.B. Brook: Smithells Metals Reference Book, 7th ed.,
Butterworth Heinemannn, Oxford, UK. 2000.
29. A. Cezairliyan, J.L. McClure, J. Res. National Bureau of Standards 75A (1971)
283.

Садржај: У овом раду проучен је утицај варирања величине честице и порозности на

понашање компакта металног партикулата током загревања у 2.45 GHz
мултимодалној микроталасној пећи. Експерименти вођени на бакру предлажу да за
разлику од монолитичних (балк) материјала, метални материјали се куплују са
микроталасима када су у форми партикулата. Компакти праха са већом порозношћу и
мањим величинама ћестица реагују ефективније са микроталасима и загревају се
брже. развијен је динамички електромагнетни-термички модел за симулирање
темпоралне расподеле температуре коришћењем приступа дводимензионалних
коначним разликама временских домена. Модел предвижа варијацију температуре са
временом током загревања компакта од бакарног праха. Симулирани профили
загревања су добро корелисани са експерименталним подацима.
Кључне речи: Моделирање коначним разликама, микроталасно загревање,
синтеровање, нумеричко моделовање, пренос топлоте.
 MICROWAVE HEATING OF PURE COPPER POWDER
WITH VARYING PARTICLE SIZE AND POROSITY

Avijit Mondal1*, Dinesh Agrawal2 and Anish Upadhyaya1

Department of Materials & Metallurgical Engineering
1

Indian Institute of Technology, Kanpur 208016, India

2
The Pennsylvania State University, University Park, PA 16802, USA
*
avijitm@iitk.ac.in

In recent years, microwave processing of metal/alloy powders have gained considerable

potential in the field of material synthesis. Microwave heating is recognized for its various advan-
tages such as: time and energy saving, rapid heating rates, considerably reduced processing cycle
time and temperature, fine microstructures and improved mechanical properties, better product
performance, etc. Microwave material interaction for materials having bound charge are well es-
tablished, but for highly conductive materials like metals, there is not much information available to
interpret the mechanism of microwave heating and subsequent sintering of metallic materials. The
present study describes how the thermal profile of electrically conductive powder metal like copper
changes with particle size and also with porosity content; in other words, initial green density when
the material is exposed to 2.45 GHz microwave radiation in a multimode microwave furnace.

Submission Date: 5 August 2008

Acceptance Date: 29 December 2008
Publication Date: 16 January 2009

INTRODUCTION graded materials, metals and alloys [Rodiger et

Microwave processing technology has been
developed in the field of ceramics and compos-
ites. Microwave heating allows an instantaneous
volumetric, and therefore a more rapid, heating
in comparison with the conventional heating
process. It also provides enhanced sintering
kinetics. As a result, it allows a reduction of
process temperature and time which leads to
an increased productivity and a reduction of
energy consumption. During the last decade, the
microwave has been used for sintering particu-
late metals. The reported materials of interest
included hard metals, metal–ceramic functional
Keywords: Cu metal powder, microwave sintering,
particle size, porosity
Guest Editor: Dr. Satoshi Horikoshi, Tokyo University of
Science, Chiba, Japan
al., 1998; Porada and Borchert, 1996-97; Jain
et al., 2006; Sethi et al., 2003; Anklekar et al.,
2001].
Microwave sintering of metal powders
which have high electrical conductivity is a
new area with growing interest. It was first
reported in 1999 by Roy and coworkers [1999]
that a porous, powder metal compact could be
heated and sintered in a microwave field. At that
time, this was considered surprising because the
electrically conducting materials were supposed
to reflect microwave radiation. Later, other
researchers also demonstrated that all powder
metals at room temperature absorb microwaves
and only bulk metals reflect the microwaves,
allowing only surface penetration.
However, these empirical studies did not
attempt to explain the observed heating trends
and presently there are few reports regarding

International Microwave Power Institute 43-1-5

the details of the direct interaction of micro-
waves with powder metal compacts. Sintering
mechanisms and activation energy for diffusion
were studied by Saitou [2006] and he concluded
that microwave radiation does not change the
sintering mechanism for diffusion in the case
of metallic material sintering. Thus, there is not
much information available by which to inter-
pret the mechanism of microwave heating and
subsequent sintering of metallic materials.
Microwave heating of ceramic and other
dielectrically lossy materials have been widely
investigated and the mechanism of micro-
wave-material interaction is well documented.
Microwave penetrates and propagates through
dielectric material, such as SiC. This generates
an internal electric field (E) within a specific
volume, which in turn induces polarization and
movement of charges. The resistance to these
induced motions due to internal, electric and
frictional forces attenuates the electric field.
These losses result in volumetric heating.
The microwave-metal interaction is quite
different than that of ceramics. Being good
electrical conductors, no internal electrical field
is induced in metals. Microwave interaction
with metals is restricted to its surface only. The
depth of penetration in metals, also known as
skin depth, is defined as the distance into the
material at which the incident power drops to
1/e (36.8 %) of the surface value. In general,
the skin depth is relatively small in metals, since
in the microwave regime, the particle sizes are
much smaller than the wavelength of microwave
radiation; the field across the particle is uniform
and causes volumetric heating [Takayama et al.,
2006]. However, for relatively coarse particle
(>100μm), the heating may be conductive from
outside to the interior of the powder. According
to the Faraday’s effect in a conductive material,
a varying magnetic field generates an electric
field that gives rise to eddy currents and sub-
sequent resistive losses. Hence a metal powder
compact will start absorbing more microwave
radiation with an increase in temperature due to
43-1-6 Journal of Microwave Power & Electromagnetic Energy ONLINE
an increase in skin depth.
Many researchers have addressed the role of
several parameters such as sample conductivity
and frequency [Ma et al., 2007], and effect of E
and H field [Rybakov et al., 2006] upon thermal
profile which affect the microwave absorption
by pure powdered metals. In the literature, the
researchers have also addressed the role of par-
ticle size and initial porosity upon the thermal
profile during microwave heating of different
conductive metal powders [Rybakov et al., 2006;
Mishra et al., 2006; Vaidhyanathan and Rao,
1997].
This paper reports how the thermal profile
of electrically conductive metal like copper
changes with particle size and also with poros-
ity content (i.e., initial green density) when the
material is exposed to 2.45 GHz microwave
radiation in a multimode microwave furnace.
EXPERIMENTAL PROCEDURE
For the present study gas-atomized copper
powders of different particle sizes were sup-
plied by American Chemet Corporation, USA.
The average (d50) particle sizes were 6, 12, 18,
63 and 383 μm respectively. The experimental
part consists of two subsets. The first experiment
investigates the effect of particle size during
the heating of powder particle in a multimode
microwave furnace. The second experiment
evaluates the role of initial density during the
heating of metal powder in a multimode micro-
wave furnace. In the first experiment powders
were uniaxially compacted at 400 MPa in to
a cylindrical pellet (12.7 mm diameter and 5
mm average height) of green densities ranging
between 60 to 83% of the theoretical density
(8.9 g/cm3). For the second part of the experi-
ment, cylindrical pellets of the same dimensions
of as-received gas-atomized copper powders
(particle size 18 μm) were compacted using the
same compaction press at 90 to 350 MPa in to
a green densities ranging between 56 to 76%
of the theoretical density. Microwave sintering
Vol. 43, No. 1, 2009
 Figure 2. Thermal profiles of copper compacts as a function of particle size.

temperature. However, as very little variation in
the emissivity was reported in the temperature
range used in the present study, hence, the ef-
fect of variation in emissivity was ignored in the
present investigation.
RESULT AND DISCUSSION
Figure 2 compares the thermal profiles of the
copper powder compacts of varying particle size,
sintered in multimode microwave furnace. It is
interesting to note that the porous metal compact
couple with microwaves heats rapidly. As par-
ticle size increases the heating rate decreases and
after certain time heating rate becomes constant
at a particular power setting. It is well known that
microwaves for electrically conducting materials
such as copper do not penetrate a bulk sample
beyond the skin depth. The skin depth is given
by the well-known expression:
 Another factor that influences the heat-



 
Here, μ is the real part of the permeability taken
to be 4 × 10-7 Tm/A for nonmagnetic materials.
In the above expression, σ and ω are the DC
electrical conductivity and angular frequency,
respectively. At 2.45 GHz, the skin depth of bulk
copper is about 1.3μm. But, as in case of porous
material, electrical conductivity decreases with
an increase in porosity. Therefore, based on the
above equation, effective skin depth should also
increase. So the difference in the heating rates
can be attributed to the difference in skin depth
and also the change in surface area per unit vol-
ume with the change of particle size. The effect
is more pronounced for the larger size powders
because they do not retain their single-particle
status when pressed into a compact and are
more likely to form electrical contacts during
die pressing, making them effectively much
larger. This was experimentally proved by Ma
et al. [2007]. They measured the conductivity of
a green sample made from 22 μm powder and
found that it was 104 times as great as one made
from 3 μm powder.
ing behavior is the initial green density of the
metal powder compacts. Figure 3 shows the
experimental temperature rise with time in pure
copper compacts with 56%, 65%, 71% and 76%

43-1-8 Journal of Microwave Power & Electromagnetic Energy ONLINE Vol. 43, No. 1, 2009
 and D. T. Zimmermana (2007). “ Systematic Study of
Microwave Absorption, Heating and Microstructure
Evolution of Porous Copper Powder Metal Com-
pacts.” J. Appl. Phys., 101, pp.074906-08.
Mishra, P., G. Sethi, and A. Upadhyaya (2006). “Model-
ing of Microwave Heating of Particulate Metals.”
Metallurgical and Materials Transactions B, 37(b),
pp.839-845.
Nayer, P. (1997). The Metals Data Book. McGraw-Hill,
New York.
Pert, E., Y. Carmel, A. Birnboim, T. Olorunyolemi, D.
Gershon, J. Calame, I.K. Lloyd, and O.C. Wilson Jr.
(2001). “Temperature Measurement during Micro-
wave Processing: The significance of Thermocouple
Effects.” J. Am. Ceram. Soc., 84(9), pp.1981-1986.
Porada, M.W., and R. Borchert (1996-1996). “Microwave
Sintering of Metal-Ceramic FGM.” Proceedings of
the 4th International Symposium on Functionally
Graded Materials, AIST Tsukuba Research Center,
Tsukuba, Japan, October 21- 24, pp. 349-354.
Rodiger, K., K. Dreyer, K. Gerdes, and M.W. Porada
(1998). “Microwave Sintering of Hardmetals.” In-
ternational Journal of Refractory Metals & Hard
Materials, 16, pp. 409-416.
Roy, R., D.K. Agrawal, J.P. Cheng, and S. Gedevanishvili
(1999). “Full Sintering of Powdered Metals Using
Microwaves.” Nature, 399(17), pp.668-670.
Rybakov, K.I., V. E. Semenov, S. V. Egorov, A. G. Ere-
meev, I. V. Plotnikov, and Yu. V. Bykov (2006). “Mi-
crowave Heating of Conductive Powder Materials.”
J. Appl. Phys., 99, 023506-09.
Saitou, K. (2006). “Microwave Sintering of Iron, Cobalt,
Nickel, Copper and Stainless Steel Powders.” Scripta
Materialia, 54(5), pp.875-879.
Sethi, G., A. Upadhyaya, and D. Agrawal (2003). “Micro-
wave and Conventional Sintering of Premixed and
Pre-alloyed Cu-12Sn Bronze.” Science of Sintering,
35, pp.49-65.
Takayama, S., G. Link, S. Miksch, M. Sato, J. Ichikawa,
and M. Thumm (2006). “Millimetre Wave Effects
on Sintering Behavior of Metal Powder Compacts.”
Powder Metallurgy, 49(3), pp.274-280.
Vaidhyanathan, B. and K.J. Rao (1997). “Microwave
Assisted Synthesis of Technologically Important
Transition Metal Silicides.” J. Mater. Res., 12(12),
pp.3225-29.

43-1-10 Journal of Microwave Power & Electromagnetic Energy ONLINE Vol. 43, No. 1, 2009
 MICROWAVE SINTERING OF W-18CU AND
W-7NI-3CU ALLOYS
Avijit Mondal1*, Anish Upadhyaya1 and Dinesh Agrawal2
Department of Materials & Metallurgical Engineering
1

Indian Institute of Technology, Kanpur 208016, India

2
The Pennsylvania State University, University Park, PA 16802, USA
*
avijitm@iitk.ac.in

Microwave processing is emerging as an innovative and highly effective material processing

method offering many advantages over conventional methods, especially for sintering applications.
It is recognized for its various advantages, such as: time and energy saving, rapid heating rates,
considerably reduced processing cycle time and temperature, fine microstructures and improved
mechanical properties which lead to better product performance. Major constraints in conventional
sintering of refractory material such as tungsten and its alloys are high sintering temperatures and
long soaking times which cause abnormal grain growth and lead to poor mechanical properties.
They get further aggravated at smaller (submicron and nano) tungsten powder sizes. This study
describes recent research findings; W-18Cu and W-7Ni-3Cu alloys have been successfully con-
solidated using microwave heating which resulted in an overall reduction of sintering time of up
to 80%. The microwave sintered samples exhibited finer microstructure and superior mechanical
properties when compared with the conventional samples.
Submission Date: 6 August 2008
Acceptance Date: 7 January 2009
Publication Date: 16 January 2009

INTRODUCTION processed via sintering at temperatures ranging

Tungsten is a refractory metal with a melting
point of 3420°C. Because of its high melting
point, tungsten and its alloys are mostly consoli-
dated through powder metallurgy (P/M) tech-
niques, though for some specific applications
mechanical alloying and infiltration techniques
are also employed. Most commonly, liquid phase
sintering (LPS) is used for consolidating these
alloys. The technique offers the advantage of rel-
atively lower sintering temperatures, enhanced
densification, microstructural homogenization
and near theoretical density. These alloys are
Keywords: Tungsten heavy alloys, microwave sintering,
microstrutures
Guest Editor: Dr. Satoshi Horikoshi, Tokyo University of
Science, Chiba, Japan
from 1200°C to 1500°C when at least one of the
constituents melts and facilitates the sintering
process.
Depending upon the composition, these
alloys also offer a favorable combination of
high thermal conductivity, low thermal expan-
sion coefficient, high density, high strength and
ductility, good corrosion resistance and ease of
machinability. These alloys, because of their
wide range of properties, are strategically very
important and have a wide range of applications,
such as electrical contact, heat spreaders, elec-
tronic packaging, radiation-shield, counter-bal-
anced weights, and kinetic energy penetrator in
defense industry [Upadhyaya, 2001]. Because of
technological demands and strategic concerns,
there is considerable interest worldwide in con-
solidating the tungsten based alloys for thermal

International Microwave Power Institute 43-1-11

management and defense industry applications.
Each application has its own specific require-
ments as far as the properties are concerned.
In general for most of the applications, near
theoretical density, dimensional stability, high
hardness, toughness and very high ductility are
important [German, 1996].
In order to avoid thermal shock, processing
of tungsten heavy alloys in a conventional fur-
nace involves heating at a slower rate (<10°C/
min) and with an isothermal hold at intermittent
temperatures. This not only increases the process
time, but also results in significant microstruc-
tural coarsening (W grain growth) during sinter-
ing, leading to the degradation of mechanical
properties. This problem is further aggravated
when the initial powder size is extremely fine.
Hence, it is envisaged that a fast heating rate
would mitigate this problem. One of the tech-
niques to achieve fast and relatively uniform
sintering is through microwaves. Microwaves
interact with individual particulates within the
pressed compacts directly, and thereby provide
rapid volumetric and uniform heating [Clark
and Sutton, 1996]. This technique offers many
advantages over conventional methods for con-
solidation. The main advantages include rapid
sintering, fine microstructure, energy savings
and improvements in the mechanical properties
of the sintered products. Until recently, micro-
wave processing was mostly restricted to ceram-
ics, cemented carbides and ferrites [Clark and
Sutton, 1996; Gerdes et al., 1996; Agrawal et al.,
2001; Rodiger et al., 1998; Porada and Borchert,
1996-97; Tsay et al., 2001]. Applicability of
microwave sintering to metals was ignored due
to the fact that they reflect microwaves. Roy et
al. [1999] reported that particulate metals can
be heated rapidly in microwaves. This has led
to the use of microwaves to consolidate a range
of particulate metals and alloys. Researchers
have reported microstructural refinement due
to rapid heating, significant reduction in pro-
cess time, elimination of brittle intermetallic
formation and superior mechanical properties
43-1-12 Journal of Microwave Power & Electromagnetic Energy ONLINE
in microwaves [Saitou, 2006; Jain et al., 2006;
Upadhyaya et al., 2008; Mondal et al., 2008].
The present study describes the consolidation of
tungsten based alloys using microwave energy.
Conventional sintering has also been conducted
to compare the effectiveness of the microwave
process.
EXPERIMENTAL PROCEDURE
For the present study the W-18Cu powders were
supplied by Osram Sylvania, Towanda, USA.
The elemental W (d50: 4.2μm) , Ni (d50: 11.0 μm)
and Cu (d50: 47.0 μm) powders were supplied
by Kennametal-Widia India Ltd., Bangalore;
International Specialty Products (INCO), USA;
and ACu Powder International, LLC, USA re-
spectively. The detailed powder characteristics
have been reported elsewhere [Mondal et al.,
2008]. The elemental W, Ni and Cu powders
were mixed in a required proportion in a turbula
mixer for about 60 min to prepare 90W-7Ni-3Cu
(wt.%) alloy composition. Powders were pressed
in a die of 16 mm inner diameter to make the
green compacts of approximately 6 to 8 mm in
height. The pressure was applied uniaxially in a
50T hydraulic press with floating die, using zinc
stearate as a die wall lubricant. All the samples
were compressed at pressures of 200 MPa.
To study the densification behavior, the green
compacts were sintered using conventional and
microwave furnaces. The sintering temperatures
selected for the liquid phase sintering of W-18Cu
and 90W-7Ni-3Cu were 1300°C and 1450°C,
respectively. Sintering was carried out with a
constant heating rate 5°C/min in a flowing H2
atmosphere. Microwave sintering of the green
compacts was carried out using a multi-mode
cavity 2.45 GHz, 6 kW commercial microwave
furnace. The temperature of the sample was
monitored using an optical pyrometer with the
circular crosswire focused on the sample cross-
section.
The sintered density was obtained by both di-
mensional measurements as well as Archimedes’
Vol. 43, No. 1, 2009
 (a)
Figure 1. Thermal profiles of (a) W-18Cu and (b) W-7Ni-3Cu alloys sintered using conventional
and microwave furnaces.
density measurement technique. Metallographic
techniques were employed on the sintered
samples. The scanning electron micrographs of
as-polished samples were obtained by a scanning
electron microscope (model: FEI quanta, Neth-
erlands) in the secondary electron (SE) and back
scattered (BSE) mode. Phase determination and
phase evolution, if any were studied for all the
samples with the help of X-Ray Diffractometer
(Model: RICH. SEIFERT & Co., GmbH & Co.
KG, Germany). The experimental variables of
the XRD are as follows: scan rate-3°/min, tar-
get-Cu, and power-30kVx20 mA. Bulk hardness
measurements were performed on polished sur-
faces of sintered cylindrical compacts at a load
of 5 kg using Vickers hardness tester (model:
V100-C1, supplier: Leco, Japan). The load was
applied for 30 s. Micro-hardness tester (model:
Leitz 8299, Germany) was used to perform the
micro-hardness tests on the tungsten grains and
matrix phases. The loads applied for micro-hard-
ness test was 50 g for 15 s. Ten measurements
were taken at random locations for each macro
and micro-hardness test to determine statistically
accurate results.
International Microwave Power Institute
(b)
RESULTS AND DISCUSSION
Figs. 1(a) and 1(b) compare the thermal profiles
for both the compositions heated in both the
conventional and microwave furnace. It is in-
teresting to note that for both, the compositions
couple with microwaves and heat up rapidly.
The overall heating rates in the microwave fur-
nace were 15° and 22°C/min for W-18Cu and
90W-7Ni-3Cu, respectively. Taking into con-
sideration the slow heating rate (5°C/min) and
isothermal holds at intermittent temperatures in
conventional furnace, there is about a 70 to 80%
reduction in the process time during sintering of
all the compositions in the microwave furnace.
Despite such a fast heating rate, no micro- or
macro-cracking was observed in all microwave-
sintered samples. This underscores the efficacy
of volumetric heating associated with micro-
waves. Figs. 2(a) and 2(b) show the effect of
the heating mode upon the sintered density and
densification parameter for both the composi-
tions. It is noteworthy to mention that in both, a
heating mode more than 98% of its theoretical
density has been achieved. Microstructural ob-
servation was made to confirm the effect of the
heating mode on grain coarsening phenomenon
and microstructural homogeneity.
43-1-13
 Table 1. Effect of heating mode on the hardness of W-18Cu and 90W-7Ni-3Cu compacts.
Heating mode W-18Cu
Bulk hardness
Conventional 325±12
Microwave 376±15
For both the compositions, microwave sintering
results in a more refined microstructure, which
in turn, leads to enhancement of hardness.
ACKNOWLEDGMENTS
This collaborative research was done as a part of
the Center for Development of Metal-Ceramic
Composites through Microwave Processing,
funded by the Indo-US Science and Technol-
ogy Forum (IUSSTF), New Delhi. The authors
thank Dr. D. Houcke and Mr. P. Sedor of Osram
Sylvania, Towanda, USA for supplying the
powders.
REFERENCES
Agrawal, D.K., A.J. Papworth, J. Cheng, H. Jain, and
D.B. Williams (2001). “ Microstructural Examina-
tion by TEM of WC/Co Composites Prepared by
Conventional and Microwave Processes.” Proc. 15th
International Plansee seminar, v.2, G. Kneringer, P.
Rodhammer and P. wilhartitz (eds.), Plansee AG,
Reutte, Austroa, pp.677-684.
Clark, D.E and W. H. Sutton (1996). “Microwave Pro-
cessing of Materials.” Ann. Rev. Mater. Sci., 26, pp.
299-331.
Gerdes, T., M. W. Porada, K. Rodiger, and K. Dreyer
(1996). “Microwave Sintering of Tungsten Carbide
– Cobalt Hardmetals.” Mater. Res. Soc. Symp. Proc.,
430, pp.175-180.
German, R.M. (1996). Sintering Theory and Practice. J.
Wiley, New York.
Jain, M., G. Skandan, K. Martin, K. Cho, B. Klotz, R.
Dowding, D. Kapoor, D. Agarwal, and J. Chang
(2006). “Microwave Sintering: A New Approach to
Fine-Grain Tungsten-I.” International Journal of
Powder Metallurgy, 42(2), pp.45-50.
Mondal, A., D. Agarwal, and A. Upadhyaya (2008).
“Microwave Sintering of Tungsten Based Alloys.”
43-1-16 Journal of Microwave Power & Electromagnetic Energy ONLINE
90W-7Ni-3Cu
Bulk hardness Micro-hardness
W grains Matrix
301±21 445±15 333±13
328±12 442±9 312±18
International Conference on Tungsten,Refractory and
Hardmaterials VII , Washington DC, USA.
Mondal, A., and A. Upadhyaya (2008). “Phase Evolution
of Tungsten Alloys during Microwave Sintering.”
unpublished research.
Porada, M.W., and R. Borchert (1996-1997). “ Microwave
Sintering of Metal-Ceramic FGM.” Proceedings of
the 4th International Symposium on Functionally
Graded Materials, AIST Tsukuba Research Center,
Tsukuba, Japan, October 21–24, 1996-1997, pp.
349-354.
Rodiger, K., K. Dreyer, T. Gerdes, and M. W. Porada,
(1998). “Microwave Sintering of Hardmetals.” In-
ternational Journal of Refractory Metals & Hard
Materials, 16, pp.409-416.
Roy, R., D.K. Agrawal, J.P. Cheng, and S. Gedevanishvili
(1999). “Full Sintering of Powdered Metals Using
Microwaves.” Nature, 399(17), pp.668-670.
Saitou, K. (2006). “Microwave Sintering of Iron, Cobalt,
Nickel, Copper and Stainless Steel Powders.” Scripta
Materialia, 54(5), pp.875-879.
Tsay, C.Y., K.S. Liu, and I.N Lin, (2001). “Co-firing Pro-
cess Using Conventional and Microwave Sintering
Technologies for MnZn- and NiZn-Ferrites.” Journal
of European Ceramic Society, 21, pp.1937-40.
Upadhyaya, A. (2001). “Processing Strategy for Con-
solidating Tungsten Heavy Alloys for Ordnance
Applications.” Materials Chemistry and Physics,
67, pp.101-110.
Upadhyaya, A., S. K. Tiwari, and P. Mishra (2007).
“Microwave Sintering of W-Ni-Fe Alloys.” Scripta
Materialia, 56, pp.5-8.
Vol. 43, No. 1, 2009
 Science of Sintering, 42 (2010) 99-124
________________________________________________________________________

doi: 10.2298/SOS1001099S

UDK 675.92.027:54-732
Numerical Modeling of Microwave Heating

A. K. Shukla, A. Mondal, A. Upadhyaya*)

Department of Materials & Metallurgical Engineering
Indian Institute of Technology, Kanpur 208016, India

Abstract:
The present study compares the temperature distribution within cylindrical samples
heated in microwave furnace with those achieved in radiatively-heated (conventional)
furnace. Using a two-dimensional finite difference approach the thermal profiles were
simulated for cylinders of varying radii (0.65, 6.5, and 65 cm) and physical properties. The
influence of susceptor-assisted microwave heating was also modeled for the same. The
simulation results reveal differences in the heating behavior of samples in microwaves. The
efficacy of microwave heating depends on the sample size and its thermal conductivity.
Keywords: Microwave heating; Heat Transfer, Finite Difference Modelling (FDM)

1. Introduction

Microwaves are now well-recognized mode of heating material. In the beginning (late
40’s) 2.45 GHz microwaves were first used for heating food products up to 100-150°C [1].
Subsequently, they were used in rubber industry for aiding vulcanization [1]. Later on,
microwaves were utilized for heating ceramic bodies [2]. It was reported that microwaves
interact both with bulk as well as particulate ceramics and can cause rapid increase in their
temperature to up to 1700°C [3]. The coupling of particulate ceramics elicited keen interest
among researchers as it provided means to rapidly sinter the ceramic powder compacts [4]
without significant microstructural coarsening. Unlike conventional heating, microwaves
directly couple with the material, which leads to rapid and uniform heating. In the context of
sintering this is particularly important. Over the years, a variety of materials such as carbides,
nitrides, complex oxides, silicides, and apatites, etc. have been synthesized using microwaves.
Despite the widespread application of microwaves for thermal processing of materials, their
use till recently restricted for metals. This was on account of the fact that bulk metals tend to
reflect most of the microwaves incident on them, and only heat over a localized surface. Such
an interaction frequently results in arcing that eventually causes the failure of the magnetron.
However, in 1999, for the first time Roy et al. [5] demonstrated that most of the particulate
metals very effectively couple with microwaves and can be heated to high temperatures at
significantly faster rates. This has opened the possibility of consolidating particulate metal
compacts to full density through microwave sintering [6]. Several researchers [7-16] in recent
years have demonstrated the efficacy of microwave sintering in a range of materials that
include Cu, Sn, bronzes, stainless steel and tungsten heavy alloys.
Despite the widespread use of microwaves for heating materials, there is still no
unanimity regarding its interaction mechanism with the materials, particularly, metallic ones
_____________________________
*)
Corresponding author: anishu@iitk.ac.in
100 A.K. Shukla et al. /Science of Sintering, 42 (2010) 99-124
___________________________________________________________________________

[17-21]. The main loss mechanisms during microwave-material interaction are electric,
conduction (eddy current), hysteresis and resonance (domain wall and electron spin (FMR)).
It is often difficult to ascertain which loss mechanism, or combination of mechanisms is
occurring for a particular sample in given conditions. The different mechanisms do however
have different dependencies on certain properties such as sample type and microstructure,
frequency and temperature.
Recently, Mishra et al. [22] modeled the heating of particulate metal compacts by
solving the Maxwell equation and using a 2D-Finite Difference Time Domain (FDTD) model.
While their model showed good correlation between the experimental and simulated
temperature profiles of Cu, Sn and W, it had several limitations. Their model ignored the
effect of compact size and its thermal conductivity and assumed a uniform temperature
distribution within the compact. Furthermore, it failed to compare the thermal profile of
microwave heated compact with those achieved using a conventional (radiatively heated)
furnace. In case of microwave heating, since the sample per se acts as the source of heat,
hence, it is hypothesized that the compact should have an inverse thermal profile with the
central (inside) portion having higher temperature than the peripheral regions. Furthermore, at
times, a low temperature the coupling between microwaves and the compact is poor. To
address these issues, in practice, microwave heating is usually done by surrounding the
compact with susceptors such as SiC that gets preferentially heated at lower temperatures.
The present study, therefore systematically investigates the evolution of temperature
profile with time within a cylindrical material as a function of its size (0.65 cm, 6.5 cm, 65
cm) and conductivity under both conventional as well as microwave heating mode. The latter
has been examined both in the presence and absence of susceptor. The objective of current
study is to device a well defined strategy for the selection of most effective sintering process
(conventional versus microwave) for the given conditions. To achieve this, 2-D finite
difference mathematical model has been formulated to examine the role of various process
variables.

2. Mathematical Formulation

For the present simulation, the material was considered to interact with 2.45 GHz
multimode microwaves. Fig. 1 shows the schematic of a sample configuration in a multimode
microwave furnace. For facilitating the modeling an axio-symmetric (cylindrical) sample
geometry was assumed with the radius (R) to height (H) ratio of unity. Three different radii
(0.65, 6.5 and 65 cm) cylinders were considered in the present study for simulation. To
simulate the effect of thermal conductivity on the heating behavior for each size the
simulation was performed for a low and high thermal conductivity condition, respectively.
The present configuration was constructed so as to enable the placement of SiC
susceptors for assisting microwave heating. Microwaves penetrate and propagate through a
dielectric material like SiC. This generates an internal electric field (E) within a specific
volume, which in turn, induces polarization and movement of charges. The resistance to these
induced motions due to internal, elastic and frictional forces attenuates the electric field.
These losses result in volumetric heating. The resulting electromagnetic power absorbed per
unit volume (PEM) [Wm-3] by a material is given by [23]:

PEM = 2ω {εoεr′′ (T) |Erms|2 + µoµr′′ (T) |Hrms|2} (1)

where,
ω is frequency of the microwave radiation (2.45 GHz)
ε0 is absolute permittivity of free space (8.85×10-12 C2N-1m-2)
εr′′ is relative imaginary component of the dielectric constant
µ0 is absolute permeability of free space (4π×10-7 NA-2)
 A. K. Shukla et al./Science of Sintering, 42 (2010) 99-124 101
___________________________________________________________________________

µr′′ is relative imaginary component of permeability constant

Erms and Hrms are root mean square values of electric and magnetic field amplitudes,
respectively.

Fig. 1. Schematic of the microwave setup used in the present study.

This heat generation rate per unit volume in the material during microwave sintering
can be designated as the source term, S. For the sake of simplification, for constant power and
frequency input, the magnetic permeability, electrical conductivity and permittivity are
assumed to be linear function of temperature. Elsewhere too, this approximation has been
considered [24]. The entire source term ‘S’ therefore can be expressed as:
S = ASOURCE + BSOURCE ×T (2)
where, ASOURCE and BSOURCE are the constants and are specific to the materials and microwave
operating parameters (frequency and power).
The differences between conventional and microwave heating can be described
mathematically using unsteady state heat transfer equation with a volumetrically distributed
heat source and is expressed as:
∂T 1 ∂ ⎛ ∂T ⎞ ∂ ⎛ ∂T ⎞
ρc p = ⎜ kr ⎟ + ⎜k ⎟+S (3)
∂t r ∂r ⎝ ∂r ⎠ ∂z ⎝ ∂z ⎠
where, S is local density of heat sources. For conventional heating ‘S’ is non-existent,
whereas for microwave processing it can be determined using the Equations 1 and 2. Having
calculated the source term, the heat transfer for the cylindrical geometry was done using a 2D
finite difference explicit model. Fig. 2 shows the flowchart of the entire modeling scheme.
For formulating the model, the following assumptions have been made
(i) A cylindrical coordinate system has been assumed.
(ii) Physical properties, such as density, specific heat, thermal conductivity, resistivity
are assumed to be uniform throughout the calculation domain.
(iii) Heat source is uniformly distributed.
102 A.K. Shukla et al. /Science of Sintering, 42 (2010) 99-124
___________________________________________________________________________

Fig. 2. Flow diagram of the 2-D finite difference model used for cylindrical geometry.

Rearranging the governing heat transfer Equation 3:

∂T
ρc p
∂t = ∂ T + 1 ∂T + ∂ T + S
2 2
(4)
k ∂r 2 r ∂r ∂z 2 k

For the finite difference modeling, the cylindrical sample geometry is subdivided into
radial and axial grids. The total number of grid points in the radial and axial directions has
been designated as M and N, respectively (Fig. 3). The grid spacing in both the directions, Δr
and Δz, can be expressed as following:
 A. K. Shukla et al./Science of Sintering, 42 (2010) 99-124 103
___________________________________________________________________________

R
Δr = (5)
( M − 1)

H
Δz = (6)
( N − 1)

Fig. 3. (a) Discretization of the calculation domain of the cylindrical compact having the
radius to height ratio of unity. (b) Highlighted area in represents the section for which axial
and radial temperature profiles and isothermal contours were calculated.

The temperature within the sample at any grid point (m,n) at a specific time step (l) can be
designated as T (m,n,l), where
m = radial grid points 1, 2, 3, 4…..M (7.1)
n = axial grid points 1, 2, 3, 4…..N (7.2)
l= time step number 1, 2, 3… max t (7.3)
After discretizing, Equation (4) can be expressed as:
1 T (m, n, l + 1) − T (m, n, l ) T (m + 1, n, l ) − 2T (m, n, l ) + T (m − 1, n, l )
⋅ =
α Δt (Δr )2 (8)
1 T (m + 1, n, l ) − T (m, n, l ) (T (m, n + 1, l ) + T (m, n − 1, l ) − 2T (m, n, l )) S
+ + +
(m − 1)(Δr ) (Δr ) (Δz ) 2 k

After rearranging, the expression becomes

α .Δt T (m + 1, n, l ) − 2T (m, n, l ) + T (m − 1, n, l ) α .Δt ⎡ T (m + 1, n, l ) − T (m, n, l ) ⎤

T (m, n, l + 1) = +
(Δr ) 2 (Δr ) 2 ⎢⎣ m −1 ⎥
⎦ (9)
α .Δt (T (m, n + 1, l ) + T (m, n − 1, l ) − 2T (m, n, l )) S k
+ + . + T (m, n, l )
(Δz ) 2 k ρc p
The above equation is valid only for the inner nodes {m: 1, 2, 3 …..M-1 and n:
2…..N-1}. For writing the finite difference equation for the nodes lying on the outer surface
and edges the equations have to be reformulated. Fig.s 4a and 4b show the section view of
side and top/bottom surface, respectively of the cylindrical geometry. For the various
locations of the cylinder the nodal points can be expressed as following:
Side Surface m = M; n = 2, 3……….N-1 (10.1)
Top & Bottom Edges m = M; n = 1,N (10.2)
Top & Bottom Surface M = 1,2…..M; n = 1,N (10.3)
104 A.K. Shukla et al. /Science of Sintering, 42 (2010) 99-124
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Fig. 4. Section of the cylindrical compact showing (a) the side surface and (b) top/bottom
surface node.

2.1. Heat Transfer at Side Surface Boundary

In Fig. 4a, the heat balance in control volume centered at location corresponding to
node ‘O’ can be expressed as the summation of the rate of heat flow from various adjacent
nodes as following:

Rate of heat accumulation in control volume at the side surface

⇒
Rate of heat flow through conduction from {node 1→ node O + 2→O + 4→O + 5→O +
6→O}
+
Rate of heat flow through convection from 3→O
+
Rate of heat flow through radiation from 3→O
+
Rate of heat flow through susceptor 3→O
+
Rate of heat generation in control volume (11)

The above expression can be expressed mathematically as following:

 A. K. Shukla et al./Science of Sintering, 42 (2010) 99-124 105
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{k .(Δθ .Δz )( R − Δr ). T (m − 1, n, l ) − T (m, n, l ) + h.(Δθ .Δz ).R.(Tamb − T (m, n, l ))

2 Δr
Δr T (m, n − 1, l ) − T (m, n, l )
+ k SiC .(Δθ .Δz ).R.(TSiC − T (m, n, l )) + k .(Δθ . ).R.
2 Δz
(12)
Δr T (m, n + 1, l ) − T (m, n, l )
+ k .(Δθ . ).R. + σ .ε .F .(Δθ .Δz ).R.(Tend
4
− T 4 (m, n, l ))
2 Δz
Δr ⎫ Δr
+ S .( R.Δθ ).Δz. ⎬Δt = ρc p . .( R.Δθ ).Δz.[T (m, n, l + 1) − T (m, n,.l )]
2⎭ 2
Rearranging Equation 12,
2 k .Δt ⎡ Δr T (m − 1, n, l ) − T (m, n, l ) ⎤ h (Tamb − T (m, n, l ))
T ( m, n, l + 1) = T (m, n, l ) + . ⎢( R − ) ⎥ + .R.
r ρc p ⎣ 2 (Δr )2 ⎦ k (Δr )
k SiC (T 4 − T 4 ( m, n, l )) σ .ε .F (T 4 − T 4 (m, n, l )) (T (m, n − 1, l ) − T (m, n, l ))
+ .R. SiC + .R. end + R.
k (Δr ) k (Δr ) 2(Δz ) 2
(T (m, n + 1, l ) − T (m, n, l )) S .Δt
+ R. +
2(Δz ) 2 ρc p
(13)

2.2 Heat Transfer at Top/Bottom Edge Boundary

As done with the surface nodes, the heat balance in control volume centered at the top
and the bottom edges (Fig. 4b) location corresponding to node ‘O’ can be expressed as the
summation of the rate of heat flow from various adjacent nodes to it as following:

Rate of heat accumulation in control volume at top/bottom edge

⇒
Rate of heat flow through conduction from {1→O + 2→O + 4→O + 6→O}
+
Rate of heat flow through convection from {3→O + 5→O}
+
Rate of heat flow through radiation from {3→O + 5→O}
+
Rate of heat flow through susceptor {3→O + 5→O}
+
Rate of heat generation in control volume (14)

The above expression is mathematically expressed as:

4 k .Δt ⎡1 Δr T ( m − 1, n, l ) − T ( m, n, l ) ⎤ h (Tamb − T (m, n, l )) 1 ⎡ 1 1⎤

T (m, n, l + 1) = T ( m, n, l ) + . ⎢ (R − ) ⎥ + .R. . .⎢ + ⎥
r ρc p ⎣ 2 2 (Δ r )2
⎦ k 2 ⎣ Δ r Δ z⎦
k SiC (T − T ( m, n, l )) 1 ⎡ 1 1 ⎤ σ .ε .F (T 4 − T 4 (m, n, l )) 1 ⎡ 1 1⎤
+ .R. SiC . .⎢ + ⎥ + .R. end . .⎢ + ⎥
k ( Δr ) 2 ⎣ Δr Δz ⎦ k ( Δr ) 2 ⎣ Δr Δz ⎦
(T ( m, n + 1, l ) − T (m, n, l )) (T (m, n − 1, l ) − T ( m, n, l )) S .Δt
+ R. + R. +
2( Δz ) 2 2 ( Δz ) 2 ρc p
(15)
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2.3. Heat Transfer at Top/Bottom Surface Boundary

Rate of heat accumulation in control volume at top/bottom surface

⇒
Rate of heat flow through conduction from {1→O + 2→O + 3→O + 4→O + 6→O}
+
Rate of heat flow through convection from {5→O}
+
Rate of heat flow through radiation from {5→O}
+
Rate of heat flow through susceptor {5→O}
+
Rate of heat generation in control volume (16)

The above expression can be mathematically formulated as:

{k .(Δθ . Δz )(r − Δr ) T (m − 1, n, l ) − T (m, n, l ) + h.(Δθ .Δr ).r.(Tamb − T (m, n, l ))
2 2 Δr
T (m, n − 1, l ) − T (m, n, l ) T (m, n + 1, l ) − T (m, n, l )
+ k .(Δθ .Δr ).r. + k .(Δθ .Δr ).r.
Δz Δz (17)
+ k SiC .(Δθ .Δr ).r.(TSiC − T (m, n, l )) + σ .ε .F .(Δθ .Δr ).r.(Tend − T (m, n, l ))
4 4

Δz ⎫ Δz
+ S .(r.Δθ ).Δr. ⎬Δt = ρc p . .(r.Δθ ).Δr.[T (m, n, l + 1) − T (m, n, l )]
2⎭ 2
Rearranging the above,
2 k .Δt ⎡ Δr T (m − 1, n, l ) − T (m, n, l ) ⎤ h (Tamb − T (m, n, l ))
T (m, n, l + 1) = T (m, n, l ) + . ⎢( r − ) ⎥ + .r.
r ρc p ⎣ 2 (Δr )2 ⎦ k Δz
k (T − T (m, n, l )) σ .ε .F (Tend − T (m, n, l ))
4 4 (18)
+ SiC .r. SiC + .r.
k (Δz ) k (Δz )
(T (m, n − 1, l ) − T (m, n, l )) (T (m, n + 1, l ) − T (m, n, l )) S .Δt
+ r. + r. +
2(Δz ) 2 2(Δz ) 2 ρc p

2.4. Error Analysis and Establishing Stability Criteria

The finite difference model involves numerically solving the equation using Taylor
series expansion and hence consists of some inherent errors [25]. One such error is the
truncation error which can be attributed to the computation of derivatives that are used in
place of the finite difference equations. Another prevalent error in such formulation is the
numerical round-off error that is a consequence of finite significant digit restriction [26]. For
the explicit forward Euler method used in the present study, it is therefore pertinent to
establish the stability criterion. The time step, Δt, for the temporal temperature simulation
within the sample is expressed as [27]:
αΔt 1
Fo = ≤ (19.1)
1 2
(Δr 2 + Δz 2 )
2

After rearranging, the above equation Δt can be expressed as

 A. K. Shukla et al./Science of Sintering, 42 (2010) 99-124 107
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Δr 2 Δz 2
Δt ≤ + (19.2)
8α 8α
The stability criterion calculated in the above equation is valid only for the inner nodes.
Similarly, calculations can be made for the boundary nodes as well and are expressed in terms
of Biot number (Bi) as following:
1
heff . (Δz + Δr )
Bi = 2 (20.1)
k
where,
heff = h + k SiC + σε (TSiC
2
+ Tamb
2
).(TSiC + Tamb ) (20.2)

1
Fo ≤ (20.3)
2.(2 + Bi )
For the present simulation, assuming a 50×50 (M,N) mesh, irrespective of the sample size and
its conductivity Δt ≤ 0.0015s was found to satisfy the stability criterion.

2.5. Calculation Procedure

Tab. I provides a summary of the physical properties and other parameters used as
inputs for the simulation. To obtain the thermal profiles within the compact at various time
intervals, the mathematical formulation of the heat transfer model was done using a
FORTRAN based computer program run under UNIX environment. The simulation was run
for 180 seconds time duration for both conventional as well as microwave heating. The result
output from the compiled program was in the form of a three-dimensional matrix providing
the temperature at each node within the compact at various time steps. The data from the
output files were plotted using MATLAB (ver. 2008a).

Tab. I. Summary of the physical properties and other parameters used as inputs for
thesimulation.

Density (Kgm-3) 5000

Specific heat (Jkg-1 K-1) 400
Heat Transfer Coefficient (Wm-2 K-1) 50
100
Susceptor Constant (Wm-2 K-1) 40 (high) and 1(low)
Thermal Conductivity (Wm-1K-1) 3.0 × 106
Heat source coefficient, ASource (Wm-3)
Heat source coefficient ,BSource (Wm-3 K-1) 1.5× 104
Number of grids in radial direction (M) 50
Number of grids in axial direction (N) 50

3. Results and Discussion

Fig. 5 compares the effect of heating mode on the axial and radial thermal profile at
various time steps for a high thermal conductivity cylindrical compact having radius of 0.65
cm. Fig.s 6a to 6c show the corresponding isothermal contours within cylindrical section half
108 A.K. Shukla et al. /Science of Sintering, 42 (2010) 99-124
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(Fig. 3b) for conventional heating, only microwave heating, and susceptor-assisted
microwave heating, respectively. Tab. II summarizes the maximum temperature predicted
from our simulation for various combinations of heating, compact size and its conductivity.

Tab. II. Effect of compact size and its conductivity on the maximum predicted temperature in
conventional and microwave heating. The latter was simulated both with and without
susceptor.

Total time for

Compact Size Thermal Conductivity
Heating Mode Tmax, K Tmax calculation
Conventional 1200 1.8
High k MW without susceptor 434 180
MW with susceptor 906 180
0.65 cm
Conventional 1200 18
Low k MW without susceptor 479 180
MW with susceptor 978 180
Conventional 1200 180
High k MW without susceptor 1198 180
MW with susceptor 1523 180
6.5 cm Conventional 1200 180
Low k MW without susceptor 1597 180
MW with susceptor 1876 180
Conventional 1200 180
High k MW without susceptor 1695 180
MW with susceptor 1787 180
65 cm Conventional 1200 180
Low k MW without susceptor 1700 180
MW with susceptor 1761 180

It is worth noticing that for high conductivity small-sized compacts, at the very initial
stages (t=0.15s, 0.30s), the temperature at the center of the sample is lower than that on the
outside surface (top, bottom and side surface) (Fig. 5a). For conventional heating, the
simulations were performed for ambient surface temperature of 1200K. It is worth noticing
that for such small samples having high conductivity the temperature soon attains a steady
state condition in just 1.8s (Fig. 6a). In comparison with conventional heating, during
microwave heating the heat generation occurs within the sample per se. However, due to high
conductivity of the sample, the temperature is uniform both across the radial and axial
directions. However, even after 180s the maximum temperature attained within the compact is
below 1200K. The only difference observed is that in the presence of the susceptor the
maximum temperature attained is more than twice as much as that observed for similar
timeframe when the compacts are heated only in microwaves.
 A. K. Shukla et al./Science of Sintering, 42 (2010) 99-124 109
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Fig. 5. Simulated axial and radial temperature distribution in a high thermal conductivity
cylindrical compact having 0.65 cm radius under (a) conventional and MW heating without
(b) and with (c) susceptor assistance.

The effect of heating mode on the simulated thermal profile and isothermal contours
of a relatively low conductivity cylindrical compact to 0.65 cm radius is shown in Fig.s 7 and
8, respectively. As compared to the high conductivity counterparts, for similar dimensions,
the low conductivity samples when heated conventionally (Figs. 7a and 8a) show more
pronounced thermal gradient for the first 10s. Consequently, it takes more time for the
temperature to attain steady state condition. In contrast, for microwave heating (Fig. 7b) the
samples temperature is much more uniform (Fig. 8b). The trend remains the same even in the
presence of the susceptor. However, the maximum temperature attained is significantly higher
in susceptor-assisted microwave heating (Figs. 7c and 8c).
110 A.K. Shukla et al. /Science of Sintering, 42 (2010) 99-124
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Fig. 6. Simulated temperature distribution showing isothermal contours as a function of time

in a high conductivity cylindrical compact having 0.65 cm radius under conventional heating
(a), MW heating without susceptor (b) and susceptor-assisted MW heating (c).
 A. K. Shukla et al./Science of Sintering, 42 (2010) 99-124 111
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Fig. 7. Simulated axial and radial temperature distribution in a low thermal conductivity
cylindrical compact having 0.65 cm radius under (a) conventional and MW heating without
(b) and with (c) susceptor assistance.

Figs 9 and 10 show the effect of heating mode on the temporal thermal profile and
contours for high conductivity compacts of 6.5 cm radius. In spite of the high conductivity,
because of its relatively large size, conventional heating reveals steep temperature gradient in
the beginning (Figs. 9a,10a). Consequently, to homogenize the temperature distribution one
has to heat it for a longer duration. In actual systems, both these situations are detrimental to
the properties [5]. In case of microwave heating, the temperature is evenly distributed across
the section (Figs. 9b,10b). However, it does take about 180s for the temperature to reach
1200K. The same samples when subjected to microwaves in presence of SiC reveal very
interesting trend (Fig. 9c). As evident from Table II and Fig. 10c the maximum temperature
attained in the presence of the susceptor is much higher and even exceed that attained through
conventional heating. This underscores the efficacy of susceptor-aided microwave heating.
112 A.K. Shukla et al. /Science of Sintering, 42 (2010) 99-124
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Interestingly, initially, the susceptor couples more strongly than the sample. As a result the
outside surface of the sample has a higher temperature. With time however the contribution of
the same which too acts as a heat source becomes predominant. As a result at 180s, the
temperature profile becomes inverse with the sample temperature at the center being higher
than that attained outside.

Fig. 8. Simulated temperature distribution showing isothermal contours as a function of time

in a low conductivity cylindrical compact having 0.65 cm radius under conventional heating
(a), MW heating without susceptor (b) and susceptor-assisted MW heating (c).
 A. K. Shukla et al./Science of Sintering, 42 (2010) 99-124 113
___________________________________________________________________________

Fig. 9. Simulated axial and radial temperature distribution in a high thermal conductivity
cylindrical compact having 6.5 cm radius under (a) conventional and MW heating without (b)
and with (c) susceptor assistance.
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Fig. 10. Simulated temperature distribution showing isothermal contours as a function of time
in a high conductivity cylindrical compact having 6.5 cm radius under conventional heating
(a), MW heating without susceptor (b) and susceptor-assisted MW heating (c).
 A. K. Shukla et al./Science of Sintering, 42 (2010) 99-124 115
___________________________________________________________________________

Fig. 11. Simulated axial and radial temperature distribution in a low thermal conductivity
cylindrical compact having 6.5 cm radius under (a) conventional and MW heating without (b)
and with (c) susceptor assistance.

Fig.s 11a and 12a show the thermal profile and contours in a cylindrical compact of
6.5 cm having low conductivity heated in a conventional furnace. The thermal profile is
remarkably different than those obtained for the high conductivity samples (Fig. 9a). As
expected for low conductivity samples both the axial as well as radial thermal gradients are
very steep. While the maximum temperature is 1200K, for the timeframe used in the
simulation, the samples fail to attain a steady state condition. In contrast, for microwave
heating condition (Figs. 11b and 12b), the temperature attained is relatively uniform
throughout the samples. For longer time, the compacts do tend to get an inverse thermal
profile. Interestingly, in the presence of the susceptor the samples exhibit a mixed heating
mode. For smaller time duration the temperature at the surface is higher than that in the inside
region. For longer durations, the thermal profile becomes inverse in a more pronounced
manner.
116 A.K. Shukla et al. /Science of Sintering, 42 (2010) 99-124
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Fig. 12. Simulated temperature distribution showing isothermal contours as a function of time
in a low conductivity cylindrical compact having 6.5 cm radius under conventional heating
(a), MW heating without susceptor (b) and susceptor-assisted MW heating (c).
 A. K. Shukla et al./Science of Sintering, 42 (2010) 99-124 117
___________________________________________________________________________

Experimental results showing such a behavior has been reported by Binner and
coworkers [28]. From a design consideration, while it is recommended for medium-sized
components – particularly, those having lower conductivity – to have susceptors, the time
should be optimized so as to prevent the temperature runaways and inverse gradient.

Fig. 13. Simulated axial and radial temperature distribution in a high thermal conductivity
cylindrical compact having 65 cm radius under (a) conventional and MW heating without (b)
and with (c) susceptor assistance.

Figs 13 and 14 show the simulated temporal variation of temperatures within a high
conductivity cylindrical samples having 65 cm radius along its radius and height. Note that
despite the high conductivity, owing to the large sample size there is a thermal gradient during
conventional heating. In fact, for all the heating modes, the behavior of this sample is akin to
that shown by the medium sized sample (6.5 cm radius) having lower conductivity (Figs. 11
and 12). As shown in Fig. 15a, for such large sized cylinders, the thermal gradients are much
steeper when the samples have poor conductivity. In fact, for the same level of power setting
118 A.K. Shukla et al. /Science of Sintering, 42 (2010) 99-124
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and simulation time, the results prove that conventional heating is virtually ineffective with
only the surface region being heated (Fig. 16a).

Fig. 14. Simulated temperature distribution showing isothermal contours as a function of time
in a high conductivity cylindrical compact having 65 cm radius under conventional heating
(a), MW heating without susceptor (b) and susceptor-assisted MW heating (c).
 A. K. Shukla et al./Science of Sintering, 42 (2010) 99-124 119
___________________________________________________________________________

This implies that for attaining the steady state condition the process time has to be
significantly increased. In case of microwave heating however, the effective thermal mass of
the sample which acts as the heat source is high. Hence, except the edges, the temperature
remains homogenous throughout the sample (Figs. 15b and 16b). In fact owing to the large
sample size, the presence of susceptor does not significantly influence the temperature
distribution within the compact (Figs. 15c and 16c). This is also reflected in the maximum
predicted temperature (Tab. II) which shows only 3.5% increase when microwave heating is
done in conjunction with susceptor.

Fig. 15. Simulated axial and radial temperature distribution in a low thermal conductivity
cylindrical compact having 65 cm radius under (a) conventional and MW heating without (b)
and with (c) susceptor assistance.
120 A.K. Shukla et al. /Science of Sintering, 42 (2010) 99-124
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Fig. 16. Simulated temperature distribution showing isothermal contours as a function of

time in a low conductivity cylindrical compact having 65 cm radius under conventional
heating (a), MW heating without susceptor (b) and susceptor-assisted MW heating (c).
 A. K. Shukla et al./Science of Sintering, 42 (2010) 99-124 121
___________________________________________________________________________

Fig. 17. Effect of heating mode on the temporal thermal profile at the center of cylindrical
compact (Fig. 3b) of radius (a) 0.65 cm, (b) 6.5 cm and (c) 65 cm having high (left) and low
(right) thermal conductivity.

Fig.s 17a to 17c compare the effect of heating mode and conductivity on the
temperature variation at various time steps at the center of cylindrical compacts (Fig. 3b)
having radius of 0.65 cm, 6.5 cm and 65 cm, respectively. It is evident that irrespective of the
conductivity, for small-sized compacts (0.65 cm) conventional heating is most effective. For
medium sized compacts (6.5 cm) having higher thermal conductivity both conventional and
microwave heating results in similar maximum temperature. In the presence of the susceptor
122 A.K. Shukla et al. /Science of Sintering, 42 (2010) 99-124
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though the temperature attained is higher. For low-conductivity medium-sized cylindrical

samples (Fig. 17b) though conventional heating is hardly effective. In comparison, microwave
(both with and without susceptor) result in significant enhancement of the sample
temperature. The most significant difference is observed for large-sized compacts (Fig. 17c)
wherein microwave are the most effective means to heat the samples in a short time span. The
above results amply demonstrate the response of varying compact size and its conductivity to
the various heating modes. It is envisaged that this will enable the design of an optimum
heating methodology customized to the physical dimensions and thermal attributes of the
specific system.

4. Conclusions

The present study investigates the effect of the sample dimension and its physical
properties on the temporal temperature evolution in microwave heating. Using a 2-D finite
difference approach the temperature distribution in cylindrical samples of varying radii (0.65,
6.5, 65 cm) and thermal conductivites was simulated for microwave as well as conventional
heating. The influence of susceptor on the sample heating behaviour in microwaves was also
modeled. In microwave heaing, it is possible to have an inverse thermal profile wherein the
temperature at the core is higher than those achieved at the surface. The tendency to exhibit
inverse thermal gradient increases with heating time and is higher for large sizes and lower
conductivity samples. Use of susceptor aids is homogenization of temperature within the
samples. For smaller-sized samples (0.65 cm) – irrespective of their thermal conductivity –
microwave heating is ineffective. In contrast, samples are uniformly heated to higher
temperatures in conventional heating in a relatively short duration. To effectively heat such
samples in microwaves susceptor is essential. For high conductivity medium-sized samples
(6.5 cm) the heating behaviour is independent of the heating mode. The beneficial effect of
microwave heating is realized for lower conductivity samples which further manifest itself in
the presence of susceptor. For much larger sample size (65 cm) – irrespective of its thermal
conductivity – microwave heating is a more practical option for attaining a uniform
temperature within a short duration. For such large sample dimensions, susceptor does not
influence the heating efficacy. Unlike microwave heating, conventional heating is restricted
only to the sample surface. This implies a more prolonged heating period which may not
always be the best option from the processing consideration. It is envisaged that the findings
from the present study can be used as a guiding tool to customize optimum heating
methodology that takes into consideration the thermal attributes and the physical dimensions
of the sample.

5. Acknowledgments

The authors thank Professor Deepak Gupta and Professor Bramha Deo of Department
of Materials and Metallurgical Engineering at IIT Kanpur for their valuable comments and
insights. The authors also gratefully acknowledge the assistance from Mr. Bijoy Sarma of
Defense Metallurgical Research Laboratory (DMRL) Hyderabad, India. This study was
supported by grants from the Indo-US Science and Technology Forum (IUSSTF) and Defense
Research and Development Organization (DRDO), India.
 A. K. Shukla et al./Science of Sintering, 42 (2010) 99-124 123
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6. References

1. A.C. Metaxas, Foundation of Electroheat: A Unified Approach, J. Wiley & Sons

Inc., New York, NY, 1996.
2. W.R. Tinga, W.A.G. Voss, Microwave Power Engineering, E.C. Okress (ed.),
Academic Press, New York, NY, 1968, p. 189-199.
3. D.K. Agrawal, Current Opinion in Solid State Mater. Sci. 3 (1998) 480.
4. R. Roy, D.K. Agrawal, J.P. Cheng, S. Gedevanishvili, Nature 399 (1999) 668.
5. D. Agrawal, J. Mater, Education 19 (1999) 49.
6. G. Sethi, A. Upadhyaya, D. Agrawal, Sci. Sintering 35 (2003) 49.
7. R.M. Anklekar, D.K. Agrawal, R. Roy, Powder Metall. 44 (2000) 355.
8. K. Saitou, Scripta Mater. 54 (2006) 875.
9. M. Jain, G. Skandan, K. Martin, K. Cho, B. Klotz, R. Dowding, D. Kapoor, D.
Agrawal, J. Chang, Int. J. Powder Metall. 42 (2006) 45.
10. A. Upadhyaya, S.K. Tiwari, P. Mishra, Scripta Mater. 56 (2007) 5.
11. A. Mondal, D. Agrawal, A. Upadhyaya in: “Proc. of 2008 Int. Conf. on Tungsten,
Refractory & Hardmetals VII,” Metal Powder Industries Federation, Princeton, NJ,
2008, p. 3.134-3.140.
12. A. Mondal, D. Agrawal, A. Upadhyaya, Ibid., p. 3.122-3.132.
13. A. Mondal, D. Agrawal, A. Upadhyaya, Mater. Sci. Tech. 2502.
14. A. Mondal, A. Upadhyaya, D. Agrawal, J. Microwave Power Electromag. Energy
43 (2009) 11.
15. G. Prabhu, A. Chakraborty, B. Sarma, Int. J. Ref. Metals Hard Materials 27 (2009)
545.
16. A. Mondal, D. Agrawal, A. Upadhyaya, P. Chhillar, J. Cheng, R. Roy, J.
Microwave Power Electromag. Energy, 44 (2010).
17. J. Luo, C. Hunyar, I. Feher, G. Link, M. Thumm, P. Pozzo, Appl. Phys. Lett. 84
(2004) 5076.
18. S. Takayama, G. Link, S. Miksch, M. Sato, J. Ichikawa, M. Thumm, Powder
Metall. 49 (2006) 274.
19. K.I. Rybakov, V.E. Semenov, S.V. Egorov, A.G. Eremeev, I.V. Plotnikov, Y.V.
Bykov, J. Appl. Phys. 99 (2006) 023506.
20. J. Ma, J.F. Diehl, E.J. Johnson, K.R. Martin, N.M. Miskovsky, C.T. Smith, G.J.
Weisel, B.L. Weiss, D.T. Zimmerman, J. Appl. Phys. 101 (2007) 074906.
21. A. Mondal, D. Agrawal, A. Upadhyaya, J. Microwave Power Electromag. Energy
43 (2009) 5.
22. P. Mishra, G. Sethi, A. Upadhyaya, Metall. Mater. Trans. B 37B (2006) 839.
23. M. Pozar, Microwave Engineering, 2nd ed., J. Wiley & Sons Inc., Toronto, Canada,
2001.
24. J.H. Hill, T.R. Merchant, Appl. Mathematical Modelling 20 (1996) 3.
25. D.R. Poirier, G.H. Geiger, Transport Phenomena in Materials Processing, 2nd ed.,
TMS, Warrendale, PA, 1996.
26. R.J. Schilling, S.L. Harries, Applied Numerical Methods for Engineers, Thompson
Asia Pvt. Ltd. , Singapore, 2002.
27. S.C. Chapra, R.P. Canale, Numerical Methods for Engineers, 4th ed., Tata McGraw-
Hill Pub., New Delhi, India.
28. J.G.P. Binner, B. Vaidyanathan, Key Eng. Mater. 264 (2004) 725.

Садржај: У овом раду поређен је температурни распоред у цилиндричним узорцима

загреваним у микроталасној пећи са оним загреваним у радијално загрејаној
(конвенционалној). Коришћењем дводимензионог коначног приступа температурни
124 A.K. Shukla et al. /Science of Sintering, 42 (2010) 99-124
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профили су симулирани за цилиндре са различитим презницима (0.65, 6.5 и 65 см) и за

разлизита физичка својства. Резултати симулације указују на разлике и понашању
узорака у микроталасима. Ефикасност микроталасног загревања зависи од величине
честица и термалне проводности.
Кључне речи: Микроталасно загревање, пренос топлоте, моделирање коначном
разликом.
Hindawi Publishing Corporation
Indian Journal of Materials Science
Volume 2013, Article ID 603791, 7 pages
http://dx.doi.org/10.1155/2013/603791

Research Article
Effect of Heating Mode and Copper Content on
the Densification of W-Cu Alloys

Avijit Mondal,1 Anish Upadhyaya,2 and Dinesh Agrawal3

1
NTPC Energy Technology Research Alliance (NETRA), NTPC Ltd., E-III, Echotech-2, Greater Noida 201308, India
2
Department of Materials Science and Engineering, Indian Institute of Technology, Kanpur 208016, India
3
Materials Research Institute, The Pennsylvania State University, University Park, PA 16802, USA

Correspondence should be addressed to Avijit Mondal; avijit.mondal@gmail.com

Received 18 June 2013; Accepted 13 July 2013

Academic Editors: D. Das and Y. Ge

Copyright © 2013 Avijit Mondal et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

This study investigates the effect of heating mode on the sintering of tungsten-copper alloys containing up to 30 wt.% Cu. The
sinterability of the W-Cu system consolidated in a 2.45 GHz multimode microwave furnace has been critically compared with that
processed in a radiatively heated (conventional) furnace. The as-pressed W-Cu alloys can be readily sintered in microwave furnace
with substantial (sixfold) reduction in the processing time. As compared to conventional sintering, microwave processing results
in greater densification, more homogenous distribution of the binder phase, and smaller tungsten grain size. The densification in
compacts increases with increasing Cu content. For all compositions, the electrical conductivity and hardness of microwave sintered
W-Cu alloys are higher than those of their conventionally sintered counterparts. This study investigates the effect of heating mode
on the sintering of tungsten-copper alloys containing up to 30 wt.% Cu. The W-Cu alloys were sintered in a 2.45 GHz microwave
furnace with substantial (sixfold) reduction in the processing time. As compared to conventional sintering, microwave processing
results in greater densification, more homogenous distribution of the binder phase, and smaller tungsten grain size. This results in
higher electrical conductivity and hardness of the microwave sintered W-Cu alloys.

1. Introduction enhance densification during sintering [7]. However, such a

Tungsten-copper alloys are widely used for a range of
applications, such as electrical contact materials, thermal-
management devices, and in ordnance applications [1–3].
On account of the refractoriness of the major phase (Wm.p. :
3420∘ C), these alloys are usually processed through liquid
phase sintering [4]. Due to lack of solubility between W
and Cu, it is rather difficult to attain full densification in
this system. For ensuring complete densification through
liquid phase sintering, sufficient amount of melt and its
homogeneous distribution are required [5]. Unfortunately,
due to the density difference between the constituents, it
is rather difficult to ensure Cu homogeneity. Thus, the W
and Cu powders are often comilled, which, in turn, results
in contamination from the milling media and results in
subsequent degradation of property, such as conductivity [6].
Alternatively, Cu coating over the tungsten has shown to
technique is not economically viable for upscaling. Another
approach for ensuring densification in the W-Cu system
is through the addition of transition metal additives that
activate the sintering kinetics [8–10]. Such activators though
remain segregated at the grain boundaries and thereby result
in poor mechanical properties [11]. Consequently, most of the
efforts are in consolidation of W-Cu alloys through the use of
ultrafine constituent powders [12]. Such powders are prone
to contamination and therefore require careful handling.
Most importantly, when processed through a convention-
ally adopted technique, the compacts from these powders
undergo significant microstructural coarsening. It is there-
fore well recognized that a faster sintering cycle would restrict
microstructural coarsening. However, because sintering is
a diffusion-driven process, the effect of high heating rate
on the densification response is not that straightforward
[13]. Furthermore, most conventional sintering furnaces are
2 Indian Journal of Materials Science
resistance heated and the heat transfer is limited by radiation
and conduction. Hence, to ensure uniformity of temperature
distribution, the samples are usually heated at a slower rate
and for longer times.
In the recent years, on account of the interaction of
microwaves with the particulate material, microwave sinter-
ing has been widely used for consolidating a range of materi-
als [14]. Till very recently, the application of microwaves was
restricted to ceramics and cermets [15]. However, Roy et al.
[16] demonstrated that particulate metals too can effectively
interact with microwaves and get heated up. This has opened
the possibility for consolidating a range of particulate metals
and their alloys through microwaves sintering [17]. So far, for
the metallic systems, microwave sintering has been applied
either for pure metals or for multicomponents systems which
have mutual interaction, such as Fe-Cu, Cu-Sn, and W-
Ni-Fe alloys [18–24]. This study evaluates the feasibility of
microwave sintering of W-Cu system where the constituents
are chemically noninteractive.
2. Experimental Section
For the current study, the sintering of W-Cu particulate
compacts having 10, 20, and 30 wt.% copper was investigated.
The starting powder in as-mixed condition was supplied by
NEI Corporation, Somerset, NJ, USA. The tungsten powder
size was 70 nm. The as-received powders were uniaxially
compacted in a 50 T hydraulic press (model: CTM-50,
supplier: FIE, Ichalkaranji, India) equipped with a floating
die. To facilitate compaction, zinc stearate was used as die-
wall lubricant. Cylindrical compacts having 16 mm diameter
and 8 mm height were pressed at 200 MPa. To take into
account the variability of the density of the compacts due
to the variation in the composition, the as-pressed (green)
and the sintered densities were normalized with respect
to the theoretical density which was calculated using the
inverse rule of mixture. The green density for all the three
compositions was nearly the same and varied 50 to 53% with
the theoretical density.
The as-pressed compacts were sintered using both a
radiatively heated (conventional) as well as a 2.45 GHz
multimode microwave furnaces. The former was carried in a
MoSi2 -heated horizontal tubular furnace (model: OKAY 70T,
supplier: Bysakh Inc., Kolkata, India) at a constant heating
rate of 5∘ C/min. To ensure uniform temperature distribution
during heating, intermittent isothermal hold for 30 min was
provided at 500∘ C and 900∘ C. For microwave sintering, a
6 kW microwave furnace (model: RC/20SE, supplier: Amana
Radarange) was employed. Further details of the microwave
sintering unit are provided elsewhere [20, 21]. All W-Cu
compacts were sintered at 1200∘ C in hydrogen atmosphere
with dew point −35∘ C. At the sintering temperature, the
compacts were kept isothermally for 30 min.
The density of the sintered compacts was evaluated both
through dimensional measurements as well as Archimedes’
density measurements. To take into account the effect of the
initial as-pressed density variation, the compact sinterability
1400
Microwave Conventional
1200
1000
Temperature (∘ C)
800
600
400
200
0
0 100 200 300 400 500
Time (min)
W-10Cu
W-20Cu
W-30Cu
Figure 1: Comparison of heating profile of conventionally and
microwave sintered W-Cu alloys.
was also expressed in terms of a normalized, dimensionless
densification parameter which is expressed as follows:
densification parameter
(sintered density − green density) (1)
= .
(theoretical density − green density)
The samples of sintered W-Cu alloys were prepared for
microstructural investigation using standard metallographic
practices. The samples were wet-polished in a manual pol-
isher (model: Lunn Major, supplier: Struers, Denmark) using
a series of 6 𝜇m, 3 𝜇m, and 1 𝜇m diamond pastes, which
was followed by cloth-polishing using an 0.04 𝜇m colloidal
silica suspension. The microstructural observations were
done using a scanning electron microscope (model: Quanta,
supplier: FEI, The Netherlands) both in secondary as well as
back-scattered imaging modes.
The bulk hardness of the conventional and microwave
sintered W-Cu alloys was assessed using a Vickers hardness
tester (model: V100-C1, supplier: Leco, Japan) under 50 N
load. To take into account the variability, for each sample, on
an average, ten hardness indentations were taken randomly
across the cross-section. The electrical conductivity of the
sintered W-Cu alloys was evaluated using a digital conduc-
tivity meter (model: 757, supplier: TechnoFour, Pune, India).
3. Results and Discussion
Figure 1 compares the thermal profiles of the W-Cu compacts
consolidated in a conventional and microwave furnace. It is
interesting to note that all compacts (W-10Cu, W-20Cu, and
W-30Cu) exhibit very strong coupling with microwaves and
undergo very rapid heating. As compared to conventional
Indian Journal of Materials Science
100
Sintered density (%theoretical)
90
80
70
60
50
W-10Cu W-20Cu
Cu content (wt.%)
Conventional
Microwave
(a)
Figure 2: Effect of heating mode on the (a) sintered density and (b) densification parameter of W-Cu alloys containing varying amounts of
Cu. All compacts were sintered at 1200∘ C.
sintering, microwave heating results in about more than six-
fold decrease in the heating time. For conventional sintering,
to ensure uniform homogenous heat transfer during heating
and prevent thermal shock to the furnace assembly (tube
and heating elements), the heating rate was restricted to
5∘ C/min. In comparison, because of the direct coupling of the
microwaves with the powder, an overall high heating rate of
about 35∘ C/min was achieved. From Figure 1, it is evident that
W-Cu compacts can be consolidated in microwave furnace
in significantly (∼85%) lower time that those achieved in a
conventional furnace. Mishra et al. [25] have modeled the
microwave heating of metals and have elucidated its mech-
anism in metallic system as mainly joule heating. Usually, for
conductive materials, such as metals, the interaction with the
microwaves is restricted at the surface and results in eddy
currents. This depth of penetration in metals, also known as
skin-depth (𝛿), is defined as the distance into the material
at which the incident power drops to 1/e (36.8%) of the
surface value. This skin depth is indirectly proportional to the
conductivity of the metals and increases with temperatures.
Usually, for most common metallic systems, the skin depth
varies in the range of 0.5 to 20 𝜇m. By corollary, therefore,
microwaves will interact volumetrically if the metallic system
is in particulate form and contains porosity [26]. For W
and Cu, the skin depth varies between 2.5–6 𝜇m and 1.75–
2.25 𝜇m, respectively. For tungsten, the initial particle sizes
are much smaller as compared to the skin depth, hence
it is reasonable to assume that all the tungsten powders
get homogenously and volumetrically heated up. The W-
Cu powder due to its poor compressibility and had up to
50% porosity in the green state. This coupling with the small
powder size ensures good interaction of the compact with the
microwaves. Elsewhere, other researchers too have reported
3
1.0
0.9
Densification parameter
0.8
0.7
0.6
0.5
W-30Cu W-10Cu W-20Cu W-30Cu
Cu content (wt.%)
Conventional
Microwave
(b)
similar interaction of microwaves with tungsten-based alloys
[24, 27–29].
Figure 2(a) compares the effect of Cu content and the
heating mode on the sintered density of the W-Cu compacts.
The corresponding densification parameters are summarized
in Figure 2(b). From Figure 2, it is interesting to note that the
densification of the W-Cu alloys is enhanced with increasing
copper content. It can also be inferred that, irrespective of the
copper content, the density of microwave sintered compacts
is higher than that achieved through conventional sintering.
This underscores the efficacy of microwaves processing not
only from the viewpoint of sintering time compression but
also in densification enhancement standpoint as well. The
role of increasing copper content on the densification can
be attributed to the greater capillary stresses induced grain
rearrangement [30]. During conventional sintering, however,
prior to Cu melt formation, substantial solid-state densifica-
tion also occurs which results in W-W particle bonding which
results in formation of a skeletal structure [31, 32]. In most
multiphase systems, the occurrence of such structure is a
common occurrence [33, 34]. However, upon melt formation,
the liquid chemically dissolves the interparticle bonds and
disintegrates the skeletal structure. In W-Cu system, owing
to the insolubility of W in copper [35], the Cu melt does
not chemically dissolve the W-W interparticle neck formed
during solid-state sintering. In addition to poor solubility, the
W-Cu has a high dihedral angle (∼90∘ ) [30, 36]. The dihedral
angle can be expressed as a balance of the interfacial W-Cu
melt and W-W energy as well as geometrically in terms of
the interparticle W-W neck size (𝑋) to the W-grain size (𝐺W )
ratio as follows [37]:
𝛾 𝑋
𝜙 = 2cos−1 ( WW ) = 2sin−1 ( ). (2)
𝛾W-Cu 𝐺W
4 Indian Journal of Materials Science

SEM micrograph

Conventional Microwave
(a)
SEM micrograph

Conventional Microwave
(b)
SEM micrograph

Conventional Microwave
(c)

Figure 3: SEM photomicrographs of (a) W-10Cu, (b) W-20Cu, and (c) W-30Cu alloys consolidated in a radiatively heated (conventional)
and microwave furnaces.

In the W-Cu system, the W-W interfacial energy is rela-
tively low (2.79 J/m2 ) [38]; this entails that the interparticle
tungsten bonds that form through solid-state sintering are
energetically favoured and therefore stable. Thus, on account
of both poor intersolubility as well as high dihedral angles,
the W-Cu system is fundamentally not predisposed for
densification due to capillary-induced rearrangement. To
circumvent this problem, it is essential that the W-W bond
formation prior to melting is restricted. The rapid heating in
microwaves helps in achieving this. Thus, it is not surprising
that, as compared to conventional heating, microwave
sintering results in higher densification. Elsewhere also,
Indian Journal of Materials Science
W grains Cu pool
Conventional
(a)
Figure 4: Microstructure of W-30Cu alloys sintered at 1200∘ C in (a) conventional and (b) microwave furnaces.
Table 1: Effect of Cu content and heating mode on the grain size, bulk hardness, and electrical conductivity of sintered W-Cu alloys.
Composition (in wt.%) Heating mode∗ Grain Size (nm)
CON
W-10Cu
MW
CON
W-20Cu
MW
CON
W-30Cu
MW
∗
CON: conventional; MW: microwave.
researchers [13, 38, 39] have proposed that slow heating rates
are detrimental to rearrangement. However, in conventional
resistance heated furnace where the heat transfer mode
is predominantly radiative and convective, high heating
rates are not readily and economically feasible. Microwave
consolidation therefore offers a viable alternative to process
W-Cu alloys through liquid phase sintering.
Figures 3(a) to 3(c) compare distribution of the binder
(Cu) phase in the microstructures of conventionally and
microwave sintered W-Cu alloys with varying Cu content.
Figures 4(a) and 4(b) compare microstructures (at higher
magnification) of liquid phase sintered W-30Cu alloys con-
solidated in a conventional and microwave furnace, respec-
tively. From Figures 3 and 4, it is evident, that in con-
ventional sintering, copper is more inhomogeneously dis-
tributed. Moreover, there is evidence of binder pools which
is indicative of poor rearrangement of the bonded skeletal
structure that results in densification during liquid phase
sintering occurring through pore-filling effect [40]. In a very
recent report, Luo et al. [28] also made similar observations.
However, their assessment was qualitative and the reason
for this was not clearly elaborated. Table 1 summarizes the
W grain sizes measured in the sintered compacts. For both
sintering modes, the tungsten grain size reduces as the copper
content increases. Similar observations were also reported by
5
SEM micrograph
Microwave
(b)
Electrical Conductivity (% IACS) Hardness (HV5 )
511 ± 91 16.0 ± 0.5 224 ± 19
362 ± 104 21.2 ± 0.3 248 ± 12
496 ± 108 32.6 ± 0.2 280 ± 16
403 ± 105 35.2 ± 0.5 349 ± 19
499 ± 75 40.0 ± 0.3 258 ± 8
302 ± 63 43.1 ± 0.7 322 ± 9
Upadhyaya and German [30] and Mondal et al. [29, 41] on liq-
uid phase sintered W-Ni alloys containing Fe and Cu. How-
ever, unlike W-Ni-Fe and W-Ni-Cu systems, due to lack of
W solubility in Cu, solution reprecipitation is not expected to
contribute to the tungsten grain coarsening [42]. For the W-
Cu system, the grain growth primarily occurs through coa-
lescence for which W-W particle contact is a prerequisite. A
higher Cu volume fraction in the alloys reduces the tungsten
contiguity in the structure and thereby results in less coarsen-
ing [43]. In case of microwave sintering, besides the less time
available for microstructural coarsening, a more uniform
melt distribution also contributes towards restricting the
grain growth by further reducing the interparticle contacts.
Table 1 also compares the effect of heating mode and the
Cu content on the tungsten grain size, electrical conductivity,
and the hardness. As expected, a Cu content in general results
in an increase in the electrical conductivity. However, it has
an opposing effect on the compact hardness. It is rather
interesting to note that, as compared to conventional sinter-
ing, the microwave sintered compacts have higher electrical
conductivity and greater hardness. This can be correlated to
a sintered density, more uniform binder distribution, and
a smaller tungsten grain size achieved in the W-Cu alloys
consolidated in microwave furnace.
6 Indian Journal of Materials Science
4. Conclusions
In summary, this study shows that the W-Cu alloys with
varying Cu content can be successfully consolidated through
microwave sintering. As compared to conventional sintering,
the W-Cu alloys were consolidated in microwaves with about
85% reduction in the overall processing time. Irrespective
of the Cu content, microwave sintered compacts had higher
densification and a more uniform microstructure with lower
tungsten grain size. Consequently, the electrical conductiv-
ity and the bulk hardness of W-Cu sintered alloys using
microwaves were higher than those of their counterparts
processed through conventional (radiatively heated) furnace.
Acknowledgments
The authors thank NEI Corporation, Somerset, NJ, USA,
for supplying the powder used for this investigation. The
financial support from the Indo-US Science and Technology
Forum (IUSSTF), New Delhi, for this study is gratefully
acknowledged.
References
[1] A. Upadhyaya, “Processing strategy for consolidating tungsten
heavy alloys for ordnance applications,” Materials Chemistry
and Physics, vol. 67, no. 1–3, pp. 101–110, 2001.
[2] A. Upadhyaya, “Processing strategy for consolidating tungsten
heavy alloys for ordnance and thermal-management applica-
tions,” Transactions of the Indian Institute of Metals, vol. 55, no.
1-2, pp. 51–69, 2002.
[3] R. M. German, K. F. Hens, and J. L. Johnson, “Powder
metallurgy processing of thermal management materials for
microelectronic applications,” International Journal of Powder
Metallurgy, vol. 30, no. 2, pp. 205–215, 1994.
[4] A. Belhadjhamida and R. M. German, “Tungsten and tungsten
alloys by powder metallurgy: a status review,” in Tungsten and
Tungsten Alloys Recent Advances, A. Crowson and E. S. Chen,
Eds., pp. 3–20, TMS, Warrendale, Pa, USA, 1991.
[5] J. L. Johnson, J. J. Brezovsky, and R. M. German, “Effect of
liquid content on distortion and rearrangement densification
of liquid-phase-sintered W-Cu,” Metallurgical and Materials
Transactions A, vol. 36, no. 6, pp. 1557–1565, 2005.
[6] J.-C. Kim, S.-S. Ryu, Y. D. Kim, and I.-H. Moon, “Densification
behavior of mechanically alloyed W-Cu composite powders by
the double rearrangement process,” Scripta Materialia, vol. 39,
no. 6, pp. 669–676, 1998.
[7] A. Upadhyaya and C. Ghosh, “Effect of coating and activators
on sintering of W-Cu alloys,” Powder Metallurgy Progress, vol.
2, no. 2, pp. 98–110, 2002.
[8] J. L. Johnson and R. M. German, “A theory of activated liquid
phase sintering and its application to the W-Cu system,” in
Proceedings of the International Conference & Exhibition on
Powder Metallurgy & Particulate Materials, vol. 3 of Advances in
Powder Metallurgy and Particulate Materials, pp. 35–46, Metal
Powder Industries Federation, June 1992.
[9] D.-G. Kim, G.-S. Kim, M.-J. Suk, S.-T. Oh, and Y. D. Kim, “Effect
of heating rate on microstructural homogeneity of sintered
W-15 wt% Cu nanocomposite fabricated from W-CuO powder
mixture,” Scripta Materialia, vol. 51, no. 7, pp. 677–681, 2004.
[10] V. Gauthier, F. Robaut, A. Upadhyaya, and C. H. Allibert, “Effect
of Fe on the constitution of Cu-W alloys at 1200∘ C,” Journal of
Alloys and Compounds, vol. 361, no. 1-2, pp. 222–226, 2003.
[11] J. L. Johnson and R. M. German, “Factors affecting the ther-
mal conductivity of W-Cu composites,” in Proceedings of the
International Conference & Exhibition on Powder Metallurgy &
Particulate Materials, vol. 4 of Advances in Powder Metallurgy
and Particulate Materials, pp. 201–213, Metal Powder Industries
Federation, May 1993.
[12] J. L. Johnson, J. J. Brezovsky, and R. M. German, “Effects
of tungsten particle size and copper content on densification
of liquid-phase-sintered W-Cu,” Metallurgical and Materials
Transactions A, vol. 36, no. 10, pp. 2807–2814, 2005.
[13] R. M. German and S. Farooq, “An update on the theory of liquid
phase sintering,” in Sintering’87, S. Sōmiya, M. Shimada, M.
Yoshimura, and R. Watanabe, Eds., vol. 1, pp. 459–464, Elsevier
Science, New York, NY, USA, 1988.
[14] M. Gupta and W. L. E. Wong, Microwaves and Metals, John
Wiley & Sons, Singapore, 2007.
[15] K. Rödiger, K. Dreyer, T. Gerdes, and M. Willert-Porada,
“Microwave sintering of hardmetals,” International Journal of
Refractory Metals and Hard Materials, vol. 16, no. 4–6, pp. 409–
416, 1998.
[16] R. Roy, D. Agrawal, J. Cheng, and S. Gedevanishvili, “Full
sintering of powdered-metal bodies in a microwave field,”
Nature, vol. 399, pp. 668–670, 1999.
[17] K. Saitou, “Microwave sintering of iron, cobalt, nickel, copper
and stainless steel powders,” Scripta Materialia, vol. 54, no. 5,
pp. 875–879, 2006.
[18] R. M. Anklekar, D. K. Agrawal, and R. Roy, “Microwave sin-
tering and mechanical properties of PM copper steel,” Powder
Metallurgy, vol. 44, no. 4, pp. 355–362, 2001.
[19] M. Gupta and W. L. E. Wong, “Enhancing overall mechan-
ical performance of metallic materials using two-directional
microwave assisted rapid sintering,” Scripta Materialia, vol. 52,
no. 6, pp. 479–483, 2005.
[20] S. S. Panda, V. Singh, A. Upadhyaya, and D. Agrawal, “Sintering
response of austenitic (316L) and ferritic (434L) stainless steel
consolidated in conventional and microwave furnaces,” Scripta
Materialia, vol. 54, no. 12, pp. 2179–2183, 2006.
[21] S. S. Panda, V. Singh, A. Upadhyaya, and D. Agrawal, “Effect
of conventional and microwave sintering on the properties
of yttria alumina garnet-dispersed austenitic stainless steel,”
Metallurgical and Materials Transactions A, vol. 37, no. 7, pp.
2253–2264, 2006.
[22] C. Padmavathi, A. Upadhyaya, and D. Agrawal, “Corrosion
behavior of microwave-sintered austenitic stainless steel com-
posites,” Scripta Materialia, vol. 57, no. 7, pp. 651–654, 2007.
[23] A. Upadhyaya and G. Sethi, “Effect of heating mode on the
densification and microstructural homogenization response of
premixed bronze,” Scripta Materialia, vol. 56, no. 6, pp. 469–472,
2007.
[24] A. Upadhyaya, S. K. Tiwari, and P. Mishra, “Microwave sinter-
ing of W-Ni-Fe alloy,” Scripta Materialia, vol. 56, no. 1, pp. 5–8,
2007.
[25] P. Mishra, G. Sethi, and A. Upadhyaya, “Modeling of microwave
heating of particulate metals,” Metallurgical and Materials
Transactions B, vol. 37, no. 5, pp. 839–845, 2006.
[26] A. Mondal, D. Agrawal, and A. Upadhyaya, “Microwave heating
of pure copper powder with varying particle size and porosity,”
The Journal of Microwave Power and Electromagnetic Energy,
vol. 43, no. 1, pp. 5–10, 2009.
Indian Journal of Materials Science 7

[27] G. Prabhu, A. Chakraborty, and B. Sarma, “Microwave sintering

of tungsten,” International Journal of Refractory Metals and Hard
Materials, vol. 27, no. 3, pp. 545–548, 2009.
[28] S. D. Luo, J. H. Yi, Y. L. Guo, Y. D. Peng, L. Y. Li, and J.
M. Ran, “Microwave sintering W-Cu composites: analyses of
densification and microstructural homogenization,” Journal of
Alloys and Compounds, vol. 473, no. 1-2, pp. L5–L9, 2009.
[29] A. Mondal, A. Upadhyaya, and D. Agrawal, “Microwave sin-
tering of refractory metals/alloys: W, Mo, Re, W-Cu, W-Ni-
Cu and W-Ni-Fe alloys,” The Journal of Microwave Power and
Electromagnetic Energy, vol. 44, no. 1, pp. 28–44, 2010.
[30] A. Upadhyaya and R. M. German, “Densification and dilation
of sintered W-CU alloys,” International Journal of Powder
Metallurgy, vol. 34, no. 2, pp. 43–55, 1998.
[31] J. L. Johnson and R. M. German, “Solid-state contributions to
densification during liquid-phase sintering,” Metallurgical and
Materials Transactions B, vol. 27, no. 6, pp. 901–909, 1996.
[32] V. V. Panichkina and N. I. Filipov, “Structure formation pro-
cesses in the sintering of disperse copper-tungsten pseudoal-
loys,” Science of Sintering, vol. 26, pp. 269–275, 1994.
[33] G. S. Upadhyaya, Sintered Metallic and Ceramic Materials, John
Wiley & Sons, New York, NY, USA, 2000.
[34] A. P. Savitskii, Liquid Phase Sintering of the Systems with
Interacting Components, Russian Academy of Sciences, Tomsk,
Russia, 1993.
[35] H. Okamoto, P. R. Subramaniam, and L. Kacprzak, Binary Phase
Diagrams, vol. 2, American Society for Microbiology, Materials
Park, Ohio, USA, 2nd edition, 1990.
[36] A. Upadhyaya and R. M. German, “Shape distortion in liquid-
phase-sintered tungsten heavy alloys,” Metallurgical and Mate-
rials Transactions A, vol. 29, no. 10, pp. 2631–2638, 1998.
[37] R. M. German, P. Suri, and S. J. Park, “Review: liquid phase
sintering,” Journal of Materials Science, vol. 44, no. 1, pp. 1–39,
2009.
[38] B. D. Storozh and P. S. Kislyi, “Sintering of tungsten-alumina
cermets in the presence of a liquid phase,” Soviet Powder
Metallurgy and Metal Ceramics, vol. 13, no. 9, pp. 712–716, 1974.
[39] R. Bollina and R. M. German, “Heating rate effects on
microstructural properties of liquid phase sintered tungsten
heavy alloys,” International Journal of Refractory Metals and
Hard Materials, vol. 22, no. 2-3, pp. 117–127, 2004.
[40] S.-M. Lee and S.-J. L. Kang, “Theoretical analysis of liquid-phase
sintering: pore filling theory,” Acta Materialia, vol. 46, no. 9, pp.
3191–3202, 1998.
[41] A. Mondal, A. Upadhyaya, and D. Agrawal, “Microwave sinter-
ing of W-18Cu and W-7Ni-3Cu alloys,” The Journal of Microwave
Power and Electromagnetic Energy, vol. 43, no. 1, pp. 11–16, 2009.
[42] W. J. Huppmann, “The elementary mechanisms of liquid phase
sintering: II. solution-reprecipitation,” Zeitschrift fuer Metal-
lkunde, vol. 70, pp. 792–797, 1979.
[43] S.-C. Yang, S. S. Mani, and R. M. German, “The effect of
contiguity on growth kinetics in liquid-phase sintering,” Journal
of Metals, vol. 42, no. 4, pp. 16–19, 1990.
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