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A new ceramic freeze-casting technique capable of manufac- freeze-drying. Other than these requirements, the vehicle should be
turing near room temperature with a sublimable vehicle was safe and inexpensive.
accomplished. Fluid-concentrated slurries of Al2O3 powder in There could be many potential candidates for such a vehicle. In
molten camphene (C10H16) were prepared at 55°C. These this paper, we discuss an organic molecular compound, camphene
slurries were quickly solidified (frozen) at room temperature (C10H16, 2,2-dimethyl-3-methylenebicyclo[2.2.1]heptane, CAS
to yield rigid solid green bodies, followed by frozen camphene 79-92-5), as a vehicle. Camphene is a cyclic hydrocarbon as shown
removal by sublimation (freeze-drying) with negligible in Fig. 1. At room temperature it is a soft crystalline solid material.
shrinkage. Sintering without any special binder burnout It is a natural material, a terpenoid, and commonly used in
process yielded sintered bodies with over 98% theoretical fragrance compounds. Camphene has a melting temperature
density. The proposed advantages include (1) elimination of around 44°– 48°C, low liquid viscosity of 1.4 mPa䡠s at 47°C 12 and
extremely cold temperatures, (2) elimination of troublesome manageable solidification shrinkage of ⫺3.1%.12 Solid camphene
binder burnout process, and (3) fast manufacturing cycle has a vapor pressure of 1.3 kPa 13 just below the melting
due to quick solidification. temperature, high enough for convenient freeze-drying at room
temperature. It is safe and inexpensive. Thus, camphene seems a
good candidate for a vehicle of new freeze-casting capable of
I. Introduction near-room-temperature manufacturing.
1859
1860 Journal of the American Ceramic Society—Araki and Halloran Vol. 87, No. 10
Table I. Fitting Parameters Using Equation (2) for Table II. Fitting Parameters, m (Maximum Volume
Steady Shear Data in Figure 4 Fraction of Solids) and n (Exponent),
Using Equation (3), with Reported Values in
Solid Correlation
content ⬁ (0䡠⬁)/b p factor (R2) Other Nonaqueous Ceramic Slurries
m n Powder Vehicle Ref.
0.508 0.261 5.1653 2/3 0.9750
0.489 0.170 2.6145 2/3 0.9909 0.61 2.9 Al2O3 Camphene This work
0.470 0.0851 1.3256 2/3 0.9975 0.64 1.6 Al2O3 Acrylate monomer Ref. 19
0.454 0.0673 0.9239 2/3 0.9656 0.565 1.7 Al2O3 Acrylic triblock copolymer Ref. 20
0.430 0.0495 0.3327 2/3 0.9843 0.53 2 Al2O3 Paraffin wax Ref. 21
0.54 2.4 Si3N4 Decalin Ref. 18
冉
r ⫽ 1 ⫺
m 冊⫺n
(3)
thickness. After demolding (within 1 min after casting), the green
body was placed in a fume hood to sublime the frozen camphene
from the green body. Ambient temperature was kept 25 ⫾ 2°C and
where r is the relative high shear viscosity, is the volume the airflow rate of ambient atmosphere was 0.01– 0.05 m/s. The
fraction of the solids, and both m and n are fitting parameters, the cast body was placed on pins so that the sublimation occurs also
values of m ⫽ 0.61 and n ⫽ 2.9 for the Al2O3/camphene/ from the bottom side. Sublimation was measured from mass loss.
Shrinkage during the freeze-drying process was negligible.
Figure 6 shows the relative mass change of the cast body as a
function of time. Due to the sublimation of the frozen camphene in the
cast body, the mass decreases rapidly initially and reaches steady
value, about 84 wt% of the initial weight, after 24 h. This weight loss
Fig. 9. Sintered density (in theoretical density (TD)) of Al2O3 cast bodies as
a function of solid content in slurries. Sintering temperature was 1600°C.
Fig. 11. Fracture surface of a sintered Al2O3 body with over 98% TD,
fabricated by the new freeze-casting technique.
(3) Sintering
After freeze-drying, green bodies without vehicle were obtained
with negligible shrinkage. Figure 7 shows the microstructure of
Fig. 8. Weight changes of (a) the freeze-dried body during an early stage freeze-dried Al2O3 green body made from the slurry with 45.4
of the sintering process and (b) the dispersant, Perfad 9100, during thermal vol% solid content. No macroscopic defects, cracks, or hard
decomposition. agglomeration were observed.
October 2004 New Freeze-Casting Technique for Ceramics with Sublimable Vehicles 1863
IV. Summary