Ceramic Freeze Casting Technique

with Sublimable Vehicles

Kiyoshi Araki and John Halloran

University of Michigan
Department of Materials Science and Engineering

105th Annual Meeting of the ACerS, 4/29/2003

Disadvantages
of Complex-shape Forming Techniques for Ceramics

1. Slip Casting
- time-consuming consolidation
- inevitable green density distribution

2. (Wax-based) Injection Molding http://www.ngk.co.jp

- troublesome and time-consuming wax burnout

3. Gel Casting
- toxic chemicals
- troublesome and time-consuming polymer burnout

4. Freeze Casting
- low temperature (~ -40°C)
Conventional Freeze Casting (Aqueous Vehicle)

No binder burnout process

Freeze Drying
Casting or Injection Molding Freezing at around - 40°C (Sublimation of Ice)

e.g., Quickset™ Process

- SiC preform for Al-SiC composites
- AlN substrates
…but, still needs extremely cold temp.
http://www.alsic.com

Objective of our work

To develop a new freeze casting technique
capable of manufacturing near room temperature
What vehicle is appropriate for room temperature manufacturing?

Vehicle : Water ?
Operating Temperature : -40°C Room Temperature

1. Solidification Temperature 3. Volume Change during Solidification

- higher than R.T., but not too high - as small as possible, ideally zero.
(< 100°C) ( < 3-5%?, cf. +11% for water)

Freeze Casting
around Room Temperature

2. Liquid Viscosity 4. Solid Vapor Pressure

- preferably as low as water - preferably as high as ice
(1mmHg for ice under freeze drying)
Candidates for Vehicle instead of Water

Camphene (C10H16, Tsolidification= 47°C)

• a cyclic hydrocarbon
• a crystalline material at room temperature
• natural material, terpenoid (from pine trees)
• pine aroma

10mm

Camphene Water
(C10H16) (H2O)
Solidification
47°C 0°C
Temp.

Viscosity (liquid) 1.4mPa·sec (47°C) 1.0mPa·sec (20°C)

Volume Change
during -3.1% +11% CH2
Solidification
CH CH2
Vapor Pressure
3 mmHg (25°C) 1 mmHg (-20°C) CH2 C
(solid)
CH
CH2 C CH3
CH3
Experimental Procedure

Camphene Al2O3 Powder Dispersant *1

(Vehicle,Solid) (Alcoa, 0.40µm) (liquid) *1 amine derivative of fatty acid polymer
(Perfad9100, Uniqema, Belgium)

Warm ball-milling (55°C, 20hrs)

Warm Slurry (55°C)

Casting, Solidification (at Room Temp.)

Rigid Cast Body (RT)

Sublimation *2
(Freeze Drying) *2 at ambient atmosphere

Sintering *3 *3 ex 1600°C-4hrs
Rheological Behavior of the Slurry

Al2O3 (0.4µm) / Camphene / Dispersant (2wt% to 100wt%Al2O3)

after ball-milled at 55°C for 20hrs. Data measured at 55°C

1.0
50.8vol%
0.9
Viscosity (Pa-sec) , η

0.8 Shear-thinning Behavior

0.7 48.9vol%
0.6
Cross Model
0.5 M.M. Cross
0.4 J. Colloid Interface Sci., 20, 417-37 (1965)

0.3 47.0vol% at high shear rate region

where bγ& p >>1
0.2 45.4vol%

0.1 43.0vol% η0 − η∞
η = η∞ + γ& − p
0.0 33.1vol% b
10 100 1000 η : viscosity
Shear rate (1/sec), γ& γ& : shear rate
η0 : viscosity at low shear rate limit
η∞ : viscosity at high shear rate limit
b,p : constants (p=2/3 by Cross)
 Rheological Behavior of the Slurry (continued)

200
180
, ηr

160
140 at 55°C
Relative Viscosity
from the Cross model)
(at the high shear limit

120
100
80 (Modified) Krieger-Dougherty Model
60 I.M. Krieger and T.J. Dougherty
Trans. Soc. Rheol., 3, 137-52 (1959)
40
20 −n
 φ 
0 η r = 1 − 
0 0.1 0.2 0.3 0.4 0.5 0.6  φm 
Volume Fraction of Solids, Φ ηr : relative viscosity (high shear)
Φ : volume fraction of solids
Φm,n : fitting parameters
(Φm :max. volume fraction of solids)

Φm = 0.61, n = 2.9
Sublimation (Freeze Drying) Behavior
50.6 vol.% Al2O3 (0.4µm)
after ball-milled at 55°C for 20hrs

Weight Change of the Cast Body

55°C

Percent Residual Camphene

102
100 100%
98
Relative Weight (%)

Room Temp.
96
94
92 50%
90 Rapid Solidification ( < 30 sec.)
Cast bodies can be demolded soon
88
86
84 0%
82
0 10 20 30 40 50 60
Φ55mm-5t
Time (Hours)

Camphene Sublimation
(Freeze Drying)
in ambient atmosphere
Density of the Sintered Body

98.4 99.2
100

90
Relative Density (% T.D.)

80

green body
70
1600C-4hrs
58.0
60
50.6
50

40

New Freeze Casting Uniaxially-pressed at 200MPa

- sintered at 1600°C for 4hrs

- with ramping rate of 5°C/min
- without special burnout process for organics
- Φ10mm -t2mm
Microstructure of the Sintered Body

10µm

Fracture surface of Al2O3 sintered body with over 98%T.D.,

made by the novel freeze casting technique
Demo-casting for Fine Features 10mm

US 1¢ coin

1mm 1mm

US penny (1¢ coin) replica made of Al2O3 sintered body

with the novel freeze casting technique
Prospective Expansion 1 - the sublimable vehicles -

Vehicle properties can be modified by

1. Using another vehicle
e.g., Menthol…etc.

2. Alloying components
e.g., Camphene - Camphor liquid
180°C
Temp.

47°C
solid

Camphene Camphor
(C10H16) (C10H16O)

3. Using some eutectic systems

e.g., Camphor - Naphthalene 180°C

Liquid
Temp. 85°C

32°C

Camphor Naphthalene
(C10H16O) (C10H18)
Prospective Expansion 2 - process availability -

Injection Molding + Freeze Casting Solid Freeform Fabrication

cf. Quickset™ Process - Direct Ink Jet Printing
Disadvantages of conventional vehicle
No freezing system is required alcohol – dilute suspension
wax – burnout process
- Concentrated slurry is obtained
- No burnout is required
Summary

1. A New Freeze Casting technique capable of

manufacturing near room temperature has been
developed by using sublimable materials,
such as camphene, C10H16, as a vehicle.

2. The proposed advantage includes

1) Elimination of extremely low temperature
2) Elimination of troublesome burnout process
3) Fast manufacturing cycle (Rapid Solidification)