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Advanced Electronic Ceramics I (2004)
Starting Point in Tape Casting: Surface
D. J. Shanefield, Organic Additives & Ceramic Processing
Greendensity
Surfaceenergy
Fireddensity
Homogeneousslurry formationusing small amount of organic additive to the active(small)powder
Advanced Electronic Ceramics I (2004)
Tape Casting
Ceramic Powder Binder Plasticizer Solvent Dispersent
Ball milling in the jar
Deairing
Tape Casting
Drying
Cutting
Electroding
Lamination
Co-firing
Packaging
Advanced Electronic Ceramics I (2004)
Tape Casting
http://www.algonet.se/~keram/pdf/Tape%20Casting.pdf
Advanced Electronic Ceramics I (2004)
Tape Casting Machine 1
http://yoojintech.co.kr/frame1.htm
Tape casting machine
Slurry feeder
Advanced Electronic Ceramics I (2004)
Tape Casting Machine 2
http://www.glass-ceramics.uni-erlangen.de/Staff/Research/Functceramics/
http://www.nrel.gov/ncpv/pdfs/26122.pdf
Advanced Electronic Ceramics I (2004)
Multi-Layer Casting
R.E.Mistler, Am.Ceram.Bull., 52(11), 850-854 (1973)
Advanced Electronic Ceramics I (2004)
Control Parameters: Thickness
♦ Thickness of the film1. Casting thickness (t)2. The thickness after drying(td) : 0.5t ~ 0.8t3. The thickness after sintering(Ts) : 0.5td ~ 0.7td
* The overall thickness variation due to the change in the pool level(constant feed can be employed to achieve constant pool height)
* The thickness variation at the edge of the casting
Window region RecycleRecycle
Carrier film
Ceramic green sheet
Advanced Electronic Ceramics I (2004)
Control Parameters: Casting Velocity
R. E. Mistler and E. R. Twiname, Tape Casting, Theory and Practice
Advanced Electronic Ceramics I (2004)
Control Parameters: Drying
♦ Designing the temperature-profile for drying (in order to keep thehomogeneity of the tape after sintering)
1. Thickness of the casting film2. The volatility and content of organic (especially solvent) in the slurry3. The total length of the drying line4. Feeding rate for casting
[Key items]1. Employ the Azeotropic Mixture, : solution that contains the same ratio of chemical constituents after itis distilled (see distillation). The most common example is a solutionof 4.43% water and 95.57% ethyl alcohol.
2. Controlling drying
Advanced Electronic Ceramics I (2004)
Binary Azeotropic Mixtures
R. Moreno, Am.Ceram.Soc.Bull., 71(10), 1521 (1992)
Advanced Electronic Ceramics I (2004)
Drying
First stage1. The solvent diffuse through the body to the surface, and then the
solvent waits for the right number of calories to diffuse to it via the random motion of warm molecules (fast)
2. It then evaporates (slowest)3. It swept away by moving air (slow)It is usually useful to nearly saturate the air with solvent vaporto prevent quick drying. Quick drying can promote skin formation or
cracking.
Second stageA. Ceramic green body becomes stiffB. 1 becomes much slower (it becomes controlling step)
- drying rate is dependent upon T and remaining solvent (that affect diffusion rate)
the temperature can be greatly increased without damage
Advanced Electronic Ceramics I (2004)
Tape Casting: examples
http://www.umr.edu/~rahaman/Forming.pdf
Advanced Electronic Ceramics I (2004)
Solvent
D. J. Shanefield, Organic Additives & Ceramic Processing
Desirable properties of solvents1. Ability to dissolve other additives2. Low viscosity at high solid loading3. Low tendency to form bubbles during milling4. High evaporation rate5. Safe, including
(a) nonflammability(b) nontoxicity
6. Low cost7. Lack of chemical attack on the ceramic powder
Advanced Electronic Ceramics I (2004)
Reported Solvent Systems
R. E. Mistler and E. R. Twiname, Tape Casting, Theory and Practice
1. Methyl ethyl ketone(MEK)2. MEK/95% ethanol3. MEK/anhydrous ethanol4. Xylenes/95% ethanol5. Xylene/anhydrous ethanol6. MEK/toluene7. Toluene8. 1,1,1 trichloroethane(TCE)9. TCE/ anhydrous ethanol10. TCE/MEK/ethanol11. TCE/acetone12. Toluene/95% ethanol13. MEK/95% ethanol/toluene14. MEK/methanol/buthanol
Advanced Electronic Ceramics I (2004)
Various Solvents
D. J. Shanefield, Organic Additives & Ceramic Processing
n↑ in alkane⇒ density, m.p., b.p. ↑ex) methane, ethane - gas
octane - liquid
HCH
H H
n=8
H
C
H
H
H
C
OH
H
C
H
H
CH3
O
C C2H5
Isopropanol
Methyl Ethyl Ketone (MEK)- flammable
Trichloroethylene (TCE)- not flammable- probable carcinogen- slowly being phased out due to environmental problem
C
Cl
C Cl
Cl
C
Advanced Electronic Ceramics I (2004)
Various Solvents
D. J. Shanefield, Organic Additives & Ceramic Processing
Benzene- carcinogen- leukemia, liver cancer- remain in the blood streamafter exposure
CH3 Toluene- less toxic than benzene- human body can metabolizetoluene into carbon dioxideand water
- flammable
CH3 CH3CH3
CH3
CH3
CH3
CH3
CH3
Ortho-Xylene Meta-Xylene Para-Xylene Mixture
- don not remain in the human body for a long time
Advanced Electronic Ceramics I (2004)
Physical Properties of Some Usual Solvents
R. Moreno, Am.Ceram.Soc.Bull., 71(10), 1521 (1992)
Advanced Electronic Ceramics I (2004)
Solvent: H-bond
D. J. Shanefield, Organic Additives & Ceramic Processing
m.w. of H2O ≅ m.w. of liquefied CH4
viscosity of H2O > viscosity of liquefied CH4
⇒ H-bonding
H-bonding between ceramic (covered with OH group adsorbed from air) and water molecule⇒ tends to raise the viscosity of slip
In order to achieve low porosity in the fired state⇒ solid loading as high as possible⇒ minimize the shrinkage during drying and firing to full density⇒ minimize the warpage and cracking
H-bonding is major cause for high viscosity ⇒ non-aqueous solvent such as toluene are used
Advanced Electronic Ceramics I (2004)
Solvent: H-bond
D. J. Shanefield, Organic Additives & Ceramic Processing
m.w. of H2O ≅ m.w. of liquefied CH4
viscosity of H2O > viscosity of liquefied CH4
surface tension of H2O > surface tension of liquefied CH4
⇒ high surface tension stabilize bubbles ⇒ bubble can be a serious problem in water system
(ex.1) glazeone stable bubble can ruin the appearance of the fired ceramics
(ex.2) single bubble of the same diameter as the thickness of the fired sheet can result problem
Advanced Electronic Ceramics I (2004)
청자상감운학문매병(해강유근영)
국보제68호청자상감운학문매병을그대로재현한작품이다.
Advanced Electronic Ceramics I (2004)
Evaporation rate
D. J. Shanefield, Organic Additives & Ceramic Processing
Solvent
waterEtOHTolueneTCEHeptane
∆Hvap.(cal/g)580204955776
b.p.(oC)10078
1118798
Flash point(oC)
203
- 1
Explosive limit(vol%)
3-191-7
1-7
1) Energy for drying2) The length of drying line(30 m line for full drying in Toluene system.Then, how long will it be for the water system?)
TCE + EtOH → non-flammable(chloro carbon such as PCB, DDT, CFC)
Advanced Electronic Ceramics I (2004)
Binder
Binder gives green strength for machining, inspection, and storage.
Desirable properties of binders1. Easy Burn-out2. Strong Green Body(a) Adhesion to Powder(b) Cohesive Strength
3. Solubility in Fluidizing liquid(solubility parameter)4. Low cost
D. J. Shanefield, Organic Additives & Ceramic Processing
Advanced Electronic Ceramics I (2004)
Reported Binder Systems
R. E. Mistler and E. R. Twiname, Tape Casting, Theory and Practice
- Vinyl polymer burns at elevated temperature and requires oxygen
- Should be fired at oxidizing atmosphere
- Acrylic polymers dissemble and evaporate
- Removal of binder in reducing or neutral atmosphere is possible
- Proper for SiC and AlNsystems requiring reducing or inert atm.
Advanced Electronic Ceramics I (2004)
Binder: PVA
- reaction can continue until all of the starting materials is used up- large molecule tends to be brittle solid- for desired(proper) molecule size, small amount of terminator is added- water ↑ ⇒ molecular weight↓- there is a variation in chain length (in molecular weight)- average molecular weight is usually used
B
D. J. Shanefield, Organic Additives & Ceramic Processing
Advanced Electronic Ceramics I (2004)
Polyvinyl Butyral(PVB)
Binder: PVBH
C
HH
H
C
O
H
C
OH
H
C
H
O
CH H
H
C
H
H
C
O
H
C
O
H
C
H
C
H H
H
C
HH
H
C
O
H
C
OH
H
C
H
C3H7
O
C H
H
C
H
H
C
O
H
C
O
H
C
H
C
H
H
C
H
H
C
H
H
C
H
Polyvinyl Alcohol(PVA)
FormaldehydePolyvinyl Formal
Butyraldehyde
Popular binderin ceramicprocessing
B
D. J. Shanefield, Organic Additives & Ceramic Processing
Advanced Electronic Ceramics I (2004)
Other Binders
Polymethacrylic Acid(PMA)
HCH
CH3
C
C O
OHn
HCH
CH3
C
C O
O-CH3
n
Poly(methylmethacrylate) (PMMA)
HOHCH
HCH
O Hn
Polyethylene Glycol (PEG)
D P BD B
B
Polypropylene
C Cn
C
B
D. J. Shanefield, Organic Additives & Ceramic Processing
Advanced Electronic Ceramics I (2004)
Polymer Characterization: molecular weight by GPC
HOHCH
HCH
O Hn
m.w. (n=1) = 1 x 44 + 18 = 62m.w. (n=2) = 2 x 44 + 18 = 106m.w. (n=n) = 44n + 18
GPC (Gel Permeation Chromatography)- a solution of the polymer diffuses through the inert gel- the smaller molecule (with low m.w.) diffuses fastest- get the m.w. distribution
relative amount median m.w.0.08 x 500 = 400.13 x 1500 = 1950.41 x 2500 = 10250.29 x 3500 = 10150.09 x 4500 = 405
total 1.00 2680/1 = 2680 # avg.m.w.
8% below 100013% between 1000 and 200041% between 2000 and 300029% between 3000 and 40009% between 4000 and 5000
D. J. Shanefield, Organic Additives & Ceramic Processing
Advanced Electronic Ceramics I (2004)
Polymer Characterization: m.w. by other methods
Light scattering- larger molecule scatter more ultraviolet light than the smaller one- large ones actually scatter much more than the smaller one- yields weight average molecular weight- Because the larger molecules count much more than the smaller one,usually weight avg.m.w. > number avg.m.w. by GPC
Other methods- viscosity- osmosis- sedimentation- ultracentrifuge
D. J. Shanefield, Organic Additives & Ceramic Processing
Advanced Electronic Ceramics I (2004)D. J. Shanefield, Organic Additives & Ceramic Processing
Polymer Characterization: Tg
Glass
RubberV
Tg
Temperature
TMA(Thermomehcanical analysis) : The height of polymer molecule is measured with a mechanical prove resting on its top surface during heating (similar with the dilatometery)
Below Tg : relatively hard and brittlelike glass
Above Tg: relatively soft and elasticlike rubber
The addition of plasticizer- lower the Tg
- for easy handling