Journal of Materials Processing Technology 119 (2001) 199±202

Production of large size parts by MIM process

T. Shimizua,*, A. Kitazimaa, M. Noseb, S. Fuchizawab, T. Sanoa
a
Mechanical Engineering Laboratory, AIST, MITI, Namik 1-2, Tsukuba, Ibaraki 305, Japan
b
Utsunomiya University, Utsunomiya, Japan

Abstract

Extraction method using supercritical carbon dioxide is an ef®cient and safe extraction method, and began to use many industrial ®elds.
Supercritical ¯uid has high density like liquid and low viscosity like gas. It can solve solute like liquid and it can go into porous body like
gas. Carbon dioxide becomes supercritical state at relatively low temperature and low pressure, and it is harmless to human health and
environment. This extraction method is adopted to the debinding process of metal injection moulding (MIM). On this method, powder is
mixed with binder and parts are moulded by injection moulding. After moulding, binder is removed from the parts and these are sintered.
On these processes, the debinding process is most dif®cult and time consuming. On conventional thermal debinding, it need several days for
debinding process, and it is dif®cult to produce the part which has the thickness more than 10 mm. Applying this extraction method to the
debinding process, production of large parts is possible. # 2001 Elsevier Science B.V. All rights reserved.
Keywords: Carbon dioxide; Supercritical; MIM; Debinding; Large size

1. Introduction order of typical physical parameters for liquid, supercritical

On metal injection moulding (MIM), powder is mixed with
binder and parts are moulded by injection moulding. After
that, binder is removed from moulded parts and the parts are
sintered. In these processes, the thermal debinding is still used
as conventional method, this method has many problems. For
example, a long debinding time and problem of oxidation of
metal powder may be encountered during the process, and the
products are limited to small size by this process. To overcome
these problems, an extraction technique by organic solvent
is used. However, these solvents are harmful for human body
and environment. Because of these reasons, an extraction
method using supercritical carbon dioxide was investigated.
Due to its importance, there are some patents which are
available for this process [1,2]. Recently, this method is used
for binder extraction of the ceramic compound as reported in
[3,4]. The rate of the binder extraction is also discussed in [5].
Also, this process is applied to the MIM [6±8] and the binder
for this method is examined. In the present study, large size
MIM parts are produced using supercritical debinding, and
the binders used on this process are investigated.
2. Supercritical carbon dioxide
Supercritical ¯uid is a physical state above the critical
point and assume the state between liquid and gas. In Table 1,
*
Corresponding author.
¯uid, and gas are compared. From this table, it is realised
that supercritical ¯uid has density and diffusion coef®cient
like a liquid and viscosity like a gas. It suggest that the
supercritical ¯uid can enter into a porous body like gas, and
dissolves solute like liquid. A phase diagram of carbon
dioxide is shown in Fig. 1.
In this diagram, a point where boiling point curve dis-
appears is the critical point. Carbon dioxide can change the
physical state without latent heat at the pressure and the
temperature above the critical point. Such supercritical
carbon dioxide has a character that it dissolves non-polar
molecules or low molecules organic materials like the
paraf®n wax (PW). However, it does not dissolve the polar
molecules like bee-wax or the high molecular materials like
polyethylene (PE) or polypropylene (PP).
3. Supercritical debinding process
3.1. Debinding apparatus
Extraction method using supercritical carbon dioxide
is applied to the debinding on MIM. On MIM, if all the
binder is removed from the specimen, only the powder
remains, and the specimen cannot keep its moulded shape.
On this process, the binder has to contain components which
are soluble and insoluble to supercritical carbon dioxide,
and insoluble component keep the moulded shape after

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200 T. Shimizu et al. / Journal of Materials Processing Technology 119 (2001) 199±202

Table 1 mantel heater, (5) reducing valve, (6) wax trapper, (7) ¯ow
Physical parameter of gas, supercritical fluid and liquid meter.
Physical Diffusion coefficient Viscosity Density For debinding, the specimens are settled in the vessel, and
state (cm2 s 1) (g cm 1 s 1) (g cm 3) liquid carbon dioxide is driven from the cylinder. High
Gas 10 1 10 4 10 3 pressure pump for liquid chromatography is used as the
Supercritical fluid 10 3±10 4
10 3±10 4
0.3±0.8 hydraulic pump. While for driving the carbon dioxide, the
Liquid 10 5 10 2 1 plunger head is cooled from 5 to 58C using cooling
circulator. The vessel has 100 cm3 capacity and it can heat
from RT to 2008C. Also, it can bear 30 MPa pressure.

3.2. Debinding condition

In previous reports [6±8], carbon dioxide is carried into

the vessel while the debinding, and extracted binder is
captured from ¯owing out carbon dioxide at the binder
trapper. However, it takes long time for the debinding of
large size parts, and consumption of the carbon dioxide while
the debinding is not so small. Therefore, ``Batch method'' is
used for the large size parts debinding [9]. On Batch method,
carbon dioxide is not carried after that the vessel becomes
desired pressure and temperature, and the extracted binder is
absorbed to activated carbon which is kept inside the vessel.
If enough activated carbon is used, the ef®ciency of Batch
method is almost the same as the previous method.
Fig. 1. Phase diagram of carbon dioxide.

debinding. An apparatus used for this debinding process 4. MIM process

is shown in Fig. 2. This apparatus is composed of: (1)
liquid carbon dioxide cylinder, (2) high pressure hydraulic SUS316L stainless powder (Paci®c Metal) is used as
pump, (3) cooling circulator, (4) extraction vessel with metal powder, and moulding of large size parts is performed.

Fig. 2. Apparatus for supercritical debinding.

 T. Shimizu et al. / Journal of Materials Processing Technology 119 (2001) 199±202 201

Fig. 3. Dimensions of: (a) conical specimen and (b) cylinder part.

Compound for moulding is made by mixing the powder and Table 3

New binders for large size specimens
the binder. The compound is moulded to conical specimen.
Dimensions of specimen are shown in Fig. 3(a). Moulded Binder PW …Tm ˆ 43 C† SA PE EVA
specimens are extracted by supercritical carbon dioxide. (wt.%) (wt.%) (wt.%) (wt.%)
Debinding pressure is 20 MPa. Temperature and processing C 70 5 25 0
time is changed depending on experiments. The specimens D 60 5 15 0
are sintered by hydrogen condition at 13508C. E 75 0 20 5
The binders used in supercritical debinding must consist F 75 0 15 10
of a component which is soluble into supercritical carbon
dioxide and a component which is not soluble into it. The
remaining component takes a role to keep the moulded
Table 4
shape. Already, the binders for supercritical carbon dioxide Specimen conditions after debinding and sintering
debinding are examined [8]. In this report, the binder which
consists of PW, PE and stearic acid (SA) is examined. SA is Binder Surface condition Condition after sintering
after debinding
added as dispersing agent. However, it remained after Surface Inside
debinding, and it is harmful to mechanical properties of
C No cracks No cracks Cracks
the products. Therefore, the binder which use ethylene vinyl D No cracks No cracks Cracks
acetate copolymer (EVA) is recommended. EVA has polar E No cracks No cracks No cracks
functional group and these work as the dispersing agent [10]. F Cracks Cracks No cracks
Used binder is shown in Table 2. About the binders in
Table 2, PW is extracted and EVA is remaining after
debinding.
The specimens have cracks after debinding, and the crack The conditions after debinding and sintering are shown in
becomes large depending on the EVA content. These cracks Table 4. From the table, the binder system E which contains
will be made by the swelling of EVA, while the debinding 5% EVA, 20% PE, 75% PW is recommended. Using binder
process, and these binders are not suitable for the MIM of F and changing the powder contents in the compound, the
large parts. specimens are moulded. These are extracted at the same
For the production of large parts, new binders are condition as the previous experiment. Results are shown in
designed and evaluated. Components of new binders are Table 5. All specimens have cracks, however, size of crack
given in Table 3. The binders and the powder are mixed becomes small according to increase of powder content.
42:58 in volume, and moulded to the conical specimens. EVA is a crystal polymer. It has a softening point at about
These specimens are kept in the supercritical carbon dioxide 508C, and it causes the swelling. It is the reason for the crack
with activated carbon for 6 h. The temperature and the during the debinding process. So, same debinding experi-
pressure are 558C and 20 MPa, respectively. Extracted ments are performed at 458C. Results are shown in Table 5,
specimens are sintered in 13508C in hydrogen gas and it is known that the decreasing of debinding temperature
for 2 h. is effective to prevent the crack while the debinding.
Also, production of larger size parts is performed using
supercritical debinding. Binder E and the stainless powder
Table 2 are mixed 38:62 in volume, and the compound is moulded to
Binders which consist of PW and EVA the part. Dimensions of the part are shown in Fig. 3(b). The
Binder PW …Tm ˆ 43 C† (wt.%) EVA (wt.%) part is extracted at 458C and 20 MPa carbon dioxide for
48 h. Debinding rate becomes about 65%. The sintering
A 85 15 condition is same as the condition of previous experiment.
B 65 35
This part can be sintered soundly on these conditions.
202 T. Shimizu et al. / Journal of Materials Processing Technology 119 (2001) 199±202

Table 5
Effect of powder content and temperature for the specimens condition (binder F is used)

Powder:binder Debinding Surface condition Condition after sintering

(vol.%) temperature (8C) after debinding
Surface Inside

58:42 55 Cracks Cracks No cracks

63:37 55 Cracks Cracks Cracks
68:32 55 Cracks Cracks No cracks
58:42 45 No cracks No cracks No cracks
63:37 45 No cracks No cracks No cracks
68:32 45 No cracks No cracks No cracks

5. Conclusions [2] S. Nakashima, M. Ishihara, S. Yasuhara, Method for removing binder

Supercritical debinding method can remove the binder in
short time as compared to the thermal debinding method or
other debinding methods. Using this method, debinding time
1 [4] M. Enoshima, Producing method of debinded ceramics molding,
can be reduced to 50 . Also, this method is adequate for
debinding a large size parts. For the production of large size
particles by this debinding method, new binder which con-
tains 5% EVA, 20% PE and 75% PW is designed. In this
binder, EVA works as the remaining component and disper-
sing agent. However, too much EVA causes swelling during
debinding, and the volume content of EVA should be
limited. Also, high powder rate compound is desirable to
prevent the swelling of binder, and debinding should be
performed in the temperature lower than the EVA softening
point. Using this new binder, large parts can be produced
soundly, and production ability of MIM can be extended.
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