Advanced Powder Technology 20 (2009) 480487

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Advanced Powder Technology

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

Original research paper

Metal injection molding of pure molybdenum

Duxin Li *, Haitao Hou, Zhaoqiang Tan, Kun Lee
State Key Laboratory for Powder Metallurgy, Central South University, Changsha 410083, PR China

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

Article history: In this work the processing steps for producing molybdenum parts by means of metal injection molding
Received 13 January 2009 technique, including milling, mixing, debinding and sintering, were investigated in detail. Different feed-
Received in revised form 1 May 2009 stocks were prepared from received and milled molybdenum powder and a thermoplastic binder based
Accepted 28 May 2009
on parafn wax. The feedstock including 50% by volume of milled molybdenum powder had better rhe-
ological property and was injected successfully at low pressure. The molded specimens were debinded by
two different processes, direct thermal debinding and solventthermal debinding. The content of carbon
Keywords:
and oxygen were respectively less than 0.060% and 0.0042% after the parts were sintered under hydrogen
Molybdenum
Metal injection molding
atmosphere. The parts sintered at 1850 C for 120 min exhibited a highest density of 9.70 g/cm3,mean-
Rheology behavior while the tensile strength and hardness was 229 MPa and 193 HV10, respectively.
Debinding Crown Copyright 2009 Published by Elsevier B.V. on behalf of The Society of Powder Technology Japan.
Sintering All rights reserved.

1. Introduction In this work, the complete processing of pure molybdenum

parts by metal injection molding with a popular binder based par-
Molybdenum has long been used in electronic application of its afn wax was investigated. The rheology behavior of prepared
unique set of physical and mechanical properties. Molybdenums feedstocks was studied and the best one was selected for injection
low coefcient of thermal expansion (CET) relative to most other molding. Thermal debinding and solventthermal debinding were
metals, and the ability of its oxide to bond well with glass, also used for removing binder from specimens and nally sintering pro-
made it useful for glassmetal seals [14]. The toxicity of molybde- cess was studied. The nal goal was to produce the optimum prop-
num is low, reducing concerns about the presence of trace erties of the MIM molybdenum parts.
amounts in water and soils which may enter the human food
chain. Further, this low toxicity enables molybdenum to play a sig-
2. Experimental
nicant part in lubricants, molybdenum-containing catalysts and
treat pollutants, minimizing the consequences of accidental con-
2.1. Materials
tamination [5].
Molybdenum has high melting point and its ductile-to-brittle
The metal powder used in this work was reduced molybdenum
transition temperature (DBTT) can be at or below room tempera-
powder supplied by Xiamen Tungsten CO. Ltd., China. Characteris-
ture, making it difcult to manufacture by methods such as casting
tics and morphology of the powder (Table 1 and Fig. 1a) reveals
and machine [6,7]. MIM (Metal Injection Molding) is a relatively
that this powder has a high carbon and oxygen content and irreg-
new manufacturing process, modied from the plastic injection
ular shape with slight agglomeration phenomenon which goes
molding process where a signicant volume fraction of the plastic
against packing and densication in processing steps.
is replaced by small metal particles [8]. Its success versus estab-
The binder ingredients used in this work included parafn wax
lished processes like die-compaction, machining, and investment
(PW) as a major component, high density polyethylene (HDPE) and
casting lies in producing intricate shapes at high production rates.
ethylene-vinyl acetate (EVA) as minor components and stearic acid
For refractory metals, MIM as shaping process has a relative cost
(SA) as a surface active agent. The composition of the binder sys-
advantage since it uses the same powders at the same price as used
tem used is given in Table 2.
in alternative processes [9]. Some work have been done in the pro-
cessing of molybdenum and via MIM, but the detailed processing
2.2. Procedure
wasnt reported [10,11].
For deagglomeration of the applied powder, the milling pro-
* Corresponding author. Tel.: +86 731 8830526; fax: +86 731 8876204. cessing was carried out in low energy mill (XQM-4) using stainless
E-mail address: liduxin6404@yahoo.com (D. Li). steel balls (18 and 6 mm; 33:100) and vial at rotational speed of

0921-8831/$ - see front matter Crown Copyright 2009 Published by Elsevier B.V. on behalf of The Society of Powder Technology Japan. All rights reserved.
doi:10.1016/j.apt.2009.05.005

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 D. Li et al. / Advanced Powder Technology 20 (2009) 480487 481

Table 1
Characteristics of asreceived molybdenum powder.

Apparent density (g/cm3) Tap density (g/cm3) True density (g/cm3) Particle size (lm) Shape Chemical content (ppm)
D10 D50 D90 C O
0.89 2.27 10.22 2.33 5.87 14.13 Irregular 490 7000

Fig. 1. Scanning electron micrograph of molybdenum powder. (a) Before milling, (b) After milling.

Table 2
The characterization of polymeric binder used in this study.

Binder constituent Density (g/cm3) Melting temperature (C) Decomposition temperature (C) Weight (%)
PW 0.91 58 182370 74
HDPE 0.98 139 413.5550 5
EVA 0.96 80 380539 20
SA 0.96 66 160435 1

258 rpm for 4 h. The weight ratio of the ball to the powder was 5 to
1 and powder charge ratio was 30%. The Scanning electron micro-
graph (Fig. 1) and powder particle size distribution (Fig. 2) before
and after milling have been prepared. These pictures indicate a
reduction in particle size for the milled powder and the powder
of sponge-like agglomerates was broken down to smaller pieces.
The milled powder and the binder was mixed in home-made
torque rheometer at 140 C for 3 h and three different feedstocks
with the received and milled molybdenum powder in a designed
powder loading (47% received, 47% milled, 50% milled) were pre-
pared. In the mixing process, the binder was put into the mixer
rst and completely melted. Then the powder was added slowly.
Subsequently, the mixer was covered to prevent evaporation of
the wax. At last, the feedstock was allowed to cool and granulated
in the mixer, after which it was suitable for injection molding. The
tensile specimens of 50.00 mm  9.50 mm  3.15 mm were injec-
tion molding in BOY50T2 injection molding machine. The injection
molding parameters were optimized. Mold and injection molding
temperature were 50 C and 160 C, respectively, and injection
pressure was 75 MPa.
The organic binder was removed through direct thermal
debinding and solventthermal debinding. Solvent immersion
debinding was carried out by immersing the parts in n-heptane
(supplier: yuyao sanjin manufacturing Inc.) at different tempera-
tures from 40 to 55 C without stirring. Parts with a thickness of
3.15 mm were placed on perforated steel trays and dipped into
heptane once the temperature reached the set temperature. When
nished, parts were transferred to loft drier for drying at about
40 C. Thermal debinding was performed in H2 in a tubular furnace.
The heating cycle was designed on the basis of thermogravimetrial

Fig. 2. Particle size distribution of received and milled molybdenum.

482 D. Li et al. / Advanced Powder Technology 20 (2009) 480487

analysis of the feedstock. Specimens were sintered at 1000 C for

30 min and then heated to sintering temperatures (1550, 1750,
1850, and 1900 C) for different holding time (60,120 and
180 min) in a Cerorr Series 60 high temperature furnace. In all
cases, the heating rate was 10 C/min to the sintering
temperatures.

2.3. Property measurement

Rheological properties were measured by RH7D capillary rhe-

ometer with a 0.5 mm diameter orice and 16 mm long. Thermal
degradation properties were determined by Perkin Elmer, thermal
gravimetrical analyzer, under nitrogen atmosphere and heating
rate of 10 C/min. A scanning electron microscope (Cambridge-
S360) was used to observe the micrograph of specimens. Density
of sintered parts was determined by the Archimedes method. Coke
and oxygen residue after sintering were measured by CS/44 and
TC/436 analyzer, respectively. The hardness and strength of the
specimens were determined on the Hardness tester and the Tensile
tester. The thermal conductivity of sintered specimens were mea- Fig. 4. The dependence of rheological behavior on temperature.
sured by Laser Flash Apparatus JR-3.

analyzed shear rate range, viscosity increases when powder load-

3. Results and discussion
3.1. Feedstock rheology
In MIM, the rheological properties are quite important as it con-
cerns the ow ability of the feedstock during injection molding.
Generally, it is desired to incorporate a maximum amount of metal
powder to minimize subsequent sintering shrinkage and increase
dimensional precision while maintaining sufcient binder to retain
good ow behavior. Rheological analysis can be used to quantify
the stability of the feedstock during the molding process [12].
The shear rates encountered in the gates and the mold range from
100 to 1000 s1 for this reason most of rheological studies are
made in this interval. However, shear rates during injection mold-
ing can occasionally reach 10,000 s1, which is still considered
suitable for injection molding.
Figs. 3 and 4 show the variation of the feedstocks viscosity with
the shear rate at 150 C and with the temperature at 354.91 s1 for
the three prepared feedstocks. Viscosity of the powder-binder mix-
ture is very sensitive to solid content and milling process. In the
ing increases as expected, and the viscosity of the feedstock com-
posed of milled powder is smaller, compared with feedstock
composed of received powder. This proves that the milling process
of agglomerated powder improves the rheological properties of
feedstock. In all cases, the viscosity decreases as the shear rate
and temperature increases according to a pseudoplastic behavior.
For a pseudoplastic uid, there is:
g kcn1 1
where c is the shear rate, k is a constant, g is viscosity of the feed-
stock, and n is a ow behavior exponent. The value of n indicates the
degree of shear sensitivity. The lower the value of n, the higher the
shear sensitivity, and hence the viscosity decreases faster with
shear rate increasing, which is commonly range from 0.5 to 0.7
[13]. From the Arrhenius equation:
 
E
gT g0 exp 2
RT
where E is the ow activation energy, R is the gas constant, T is tem-
perature, and g0 is reference viscosity, it shows the dependence of
viscosity on temperature. The value of E expresses the inuence
of temperature on the viscosity of the feedstock. If the value of E
is low, the viscosity is not so sensitive to temperature variation,
and it means a small uctuation of temperature during injection
molding will not result in a sudden viscosity change which is the
cause of undue stress concentration in the molded parts [14].
Hence, weaker temperature dependence is desired to minimize
problems due to a uctuating molding temperaturethereby mini-
mizing stress concentration, cracks, and shape distortion.
Table 3 details the parameters of n and E related to the three
feedstocks viscosity model. Comparing the viscosity and the
parameters n and E of three feedstocks, the feedstock composed
of milled powder with powder loading 50% was preferred in injec-
tion molding.

Table 3
Parameters of n and E related to the feedstock viscosity model.

Feedstock 47% Before milling 47% After milling 50% After milling
n 0.49186 0.6289 0.52008
E (kJ/mol) 13.84 17.38 11.24
Fig. 3. The dependence of rheological behavior on shear rate.
 D. Li et al. / Advanced Powder Technology 20 (2009) 480487 483

3.2. Thermal degradation properties

The thermal degradation properties of the feedstock with

50 vol% milled molybdenum powder are given in Fig. 5. The TGA
curve shows two stages decomposition. The rst weight loss takes
place between 180 and 340 C and it corresponds to PW and SA
elimination, while the second step degradation, occurring from
400 to 490 C, corresponds to HDPE and EVA elimination. This
gradual and wide decomposition temperature range is benecial
from a technological point of view at least for two reasons: rst,
in the initial stage, the remaining binder component will serve to
retain the shape of the part and allow a smooth way out of decom-
position products; second, the rst main component, PW, decom-
posed in a wider temperature range, avoids the formation of
cracks during the process because at the beginning of the process
no pores or free space are present, while when the decomposition
of HDPE takes place there will be a interconnected pore channels
that serve as escape paths for decomposition gases [15]. Fig. 6. The heating cycle of direct thermal debinding.
As it is shown, binder degradation starts at 180 C, thus the pro-
cessing temperatures such as the mixing and injection molding
temperatures must be lower in order that binder degradation
doesnt occur.

3.3. Debinding

Binder removal was carried out by two different processes, di-

rect thermal debinding and solventthermal debinding.

3.3.1. Direct thermal debinding

Fig 6 shows the optimized heating cycle designed on the basis
of this thermal gravimetric analysis. From room temperature to
160 C, since no decomposition took place, a heating rate of 2 C/
min was selected. From 160 to 350 C, the heating rate was critical
and had to be slow to prevent blistering and bloating since the low
melting binder component decomposed and the pores were
opened. Best results were found using lower heating rates (1 C/
min) to 250 C and holding for 120 min, then up to 350 C with
heating rate of 2 C/min. Therefore, the last heating up to 500 C
took place at 3 C/min. Finally, the specimens were pre-sintered Fig. 7. Correlation of binder removal efciency and debinding temperature and
time by solvent debinding.
at 900 C. The optimized thermal cycle lasted about 14 h.

3.3.2. Solventthermal debinding Fig. 7 shows the correlation of binder removal efciency with
In order to reduce the total debinding time, solvent debinding temperature (4055 C) and debinding time (16 h). A higher ef-
was conducted by immersing the parts in a bath with n-heptane ciency was achieved as bath temperature increased due to a larger
where PW and SA are soluble. solubility and diffusivity of the components on n-heptane with

Fig. 5. Thermal gravimetric analysis (TGA) of feedstock with 50 vol% milled

molybdenum powder. Fig. 8. The heating cycle of thermal debinding cycle after solvent debinding.
484 D. Li et al. / Advanced Powder Technology 20 (2009) 480487

temperature. In addition, the debinding rate was reduced when the
debinding time increased and also debinding rate was also faster at
short times for higher temperatures. From this analysis, solvent
debinding was performed at 55 C during 1 h. In general 60% (mass
based) of the binder could be extracted. But the debound parts had
defects such as cracking, slumping and sagging. After immersed for
2 h at 50 C, the parts achieved 68% binder removal without de-
fects. It is considered that after removing 40% of binder, there exits
some interconnected capillary porosity inside of specimen which
makes leaving of gaseous products in subsequent thermal debind-
ing easy in short time [16]. Since nearly 60% of parafn wax was
removed in solvent debinding step, subsequent thermal debinding
could be performed with higher speed in comparison with usual
thermal debinding process. The heating curve was given in Fig 8.
The whole debinding process including solvent performed at
50 C for 2 h and thermal debinding, lasted around 10.7 h, much
less than the direct thermal debinding time 14 h. Moreover, all
the pieces were free of defect.
Fig. 9 shows the schematics of binder distributions at the (a) as-
molded, (b) initial of solvent debinding and (c) nal stage of sol-
vent debinding based on n-heptane extraction. In as-molded parts,
the particles were enwrapped by the binder equably. When as-
molded parts were immersed in the solvent bath with preheated
heptane, the solvent, heptane, diffused into the PW, then the

Fig. 9. The schematics of binder distributions at different stage by stage of solvent debinding based on n-heptane extraction. (a) as-molded (b) initial stage of solvent
debinding (c) nal stage of solvent debinding.

Fig. 10. Scanning electron micrograph of debound and pre-sintered specimens at 900 C. (a) thermal debinding (b) solventthermal debinding.

Fig. 11. Effect of sintering temperature and time on density of molybdenum. (a) sintering temperature, (b) holding time.
 D. Li et al. / Advanced Powder Technology 20 (2009) 480487 485

heptane content decreased with the depth of specimen because the
heptane diffused into the specimen from the exterior to interior
slowly through the pores. Only PW at the surface began dissolving
into the solvent at this stage. As debinding continued, owing to the
increase of heptane content in the interior of specimen, the sol-
vent-debound depth increased with the debinding time. As the
debinding time continued to 2 h, the pore size and pore volume in-
creased and the distribution of pores broadened obviously. At the
nal stage of solvent debinding, the interconnected pore channels
were formed from exterior to interior, leaving the insoluble binders
in the contact region and the pore channels could serve as escape
paths for decomposed gas during subsequent thermal debinding
for insoluble binders.
Fig. 10 gives the SEM of rupture pre-sintered specimen by two
different debinding processes, showing that all binder were de-
bound and sinter-necks were grown between particles.
3.4. Sintering
Two process parameters (sintering temperature and holding
time) were considered to describe the sintering behavior of the
injection molded molybdenum.
Fig. 11 shows the effect of the temperature and time on the sin-
tered density. A maximum density of 9.70 g/cm3 is attained with a
120 min holding time at 1850 C, A decrease in density is observed
when the temperature is increased to 1900 C. Little difference of
density is seen between 120 min and 180 min holding time at
1850 C.
Fig. 12 shows the microstructure of specimens sintered at differ-
ent temperatures for 120 min. It was found that grains and pores
were coarsened as temperature increasing. Pores on the grain edge
disappeared at 1850 C. But there were lots of pores inside the
grains going against full densication. The effects of sintering

Fig. 12. The microstructure of parts sintered at different temperature for 120 min. (a) 1550 C, (b) 1750 C, (c) 1850 C, (d) 1900 C.

Fig. 13. Effect of sintering temperature on hardness and tensile strength. (a) hardness, (b) tensile strength.
486 D. Li et al. / Advanced Powder Technology 20 (2009) 480487
Table 4
Comparison of molybdenums properties made by MIM and press/sinter process (sintered at1 850 C for 120 min).
Process Density (g/cm3) Tensile strength (MPa)
MIM 9.70 229
Press/sinter 9.29 126
Table 5
Carbon and oxygen content of the debound and sintered parts.
Debinding method Debinded parts (%)
C O
Solventthermal debinding 0.036 0.120
Thermal debinding 0.100 0.078
temperature (120 min) on the ultimate tensile strength and hard-
ness of sintered Mo test bars are shown in Fig. 13. A optimum prop-
erties of tensile strength 229 MPa and hardness 193 HV10 were
achieved at 1850 C, which is better than those specimens made
by conventional press-sintering process including parts thermal
conductivity (Table 4). The sintering at 1900 C caused a reduction
in mechanical properties due to grain growth and pore coarsening.
3.5. Carbon and oxygen control
Molybdenum has a rather high ductile-brittle transition tem-
perature (DBTT), and this is a major limitation in its usefulness in
structural materials. The brittle fracture of molybdenum, especially
in a recrystallized and coarse-grained state, is intergranular and
markedly depends on impurities [17]. It has been reported that
the presence of impurities such as oxygen and carbon could have
a strong effect on the mechanical properties of molybdenum and
its alloy [18]. The impurities of oxygen and carbon would segregate
and precipitate at grain boundaries to enhance intergranular
embrittlement [19].
In this work, carbon control was even signicant because of the
addition of binder during injection molding. Binders are normally
hydrocarbon chains and act as the source for carbon. Table 5 shows
carbon and oxygen content of the debound and sintered parts. An
increase in carbon content was observed in the directly thermal
debound parts and a decreased in solventthermal debound parts,
compared with the as-received powder (Table 1). This is due to dis-
solution of wax during solvent debinding without any chemical
reactions, which doesnt obtain residual carbon. On the other hand
extraction by the thermal method gives a carbon residue owing to
thermal decomposition of polymers [20]. After sintering in reduc-
tive and decarburization H2 atmosphere, the carbon and oxygen
content gradually decreased respectively to less than 0.060% and
0.0042%. The removal of carbon not only depends on the sintering
temperature and time, but also on the oxygen content [21].
4. Conclusions
The milling process helped to improve the rheological property
of powders. As a result, injection molding of the feedstock includ-
ing 50% by volume of milled molybdenum powder was injected
successfully at low pressure.
Debinding of molded parts was carried out by two different pro-
cesses, direct thermal debinding and solventthermal debinding.
The later process took much less time and increased debinding
efciency.
The content of direct thermal debinding parts carbon was high-
er than solventthermal debinding parts. The content of carbon
Hardness (HV10) Thermal conductivity (W/(m K))
193 107.4
168 63.7
Sintered parts (%) (sintered atl 850 C for 120 min)
C O
0.025 0.0042
0.060 0.0030
and oxygen of both debinding processes decreased signicantly
and were respectively less than 0.060% and 0.0042% after the parts
were sintered under hydrogen atmosphere. The parts sintered at 1
850 C for 120 min exhibited a density of 9.70 g/cm3,tensile
strength of 229 MPa and hardness of 193HV10.
Acknowledgement
The authors wish to thank the State Key Laboratory for Powder
Metallurgy for the support of this work under the project
(2008112016).
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