Binders in water-based tape casting

MULTILAYER Tape casting workshop Karlsruhe 2010-03-17 12/6/07 Elis Carlstrm

Why water-based tape casting?

Advantages
No fire hazard No toxic solvents Reduced greenhouse gas emissions Better economy Easier handling

Problems
Less knowledge requires more development Water soluble powders Slower drying Prone to cracking

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Binder types
Latex
dispersion of polymer

PVA
water soluble polymer

HPMC
water soluble polymer

-[-CH2-CH-]nOH

CH2OCH3 H H O H OH H

O H

H H OCH2CHCH3 OH n

surfactant anionic, nonionic or cationic polymer e.g. acrylic, PMMA

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-[-CH2-CH-]nOH C=O CH3

Multilayer Worshop on Tape Deverlopment

Viscosity for different binder types

HPMC Hydroxy propyl methyl cellulose PVA Polyvinyl acolhol

Latex binders

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Latex binders in water-based tape casting

Latex

Latex

Latex binders
Latex

Low viscosity
Latex

Al2O3

Thicker tapes without cracking Lamination at room temperature

Al2O3

Latex

Latex

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Latexes
Particle size range 30-500 nm Solids content 0.4 - 0.7 (polymer concentration) o Tg range -50 -120 C Polymer eg. Acrylic, PMMA insoluble in water

Surfactant anionic, nonionic or cationic

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Surfactants

Hydrophilic head group

Hydrophobic tail
Alkyl group 6-16 C atoms

Anionic surfactant
Carboxylate COO- Sulfate OSO3Sulfonate SO3- or Phosphate PO32- groups

Nonionic surfactant
Typically oxyethylene units [O-CH2-CH2-] with 5-10 units

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With and without latex addition

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Optimizing dispersion with an nonionic or anionic latex binder

1000 0.2% D3021 0.3% D3021 0.5% D3021

4 0.2% D3021 Relative viscosity 3 0.3% D3021 0.5% D3021 2

Relative viscosity

100

10

0.1 0.01 1 100

0 0.01 1 Shear rate (s )

-1

100

Shear rate (s-1)

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Slip casting with latex binder

Slip casting mould

0% latex

1% latex

3% latex

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Latex influences plasticty and strength

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Critical cracking thickness

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Critical cracking thickness

System SiC, DM760, lignosulphonate SiC, DM765, lignosulphonate Al2O3, AKP30, 7% DM765, Dispex Al2O3, AKP30, 10% DM765, Dispex Al2O3, AKP30, 7% DM765, D3021 Al2O3, AKP30, 7% LDM 7651, D3021 Al2O3, A16SG, B1001, D3021 Al2O3, A16SG, B1035, D3021 Mullite, SACR193, DM765, Dispex Mullite, SACR193, DM765, Dispex Solids volume fraction 59 wt% 63 wt% 48 vol% 48 vol% 53.6 vol% 53.6 vol% 55 vol% 55 vol% 45 vol% 51 vol% Latex particle size [nm] 20200 100200 100200 100200 100200 <300 320 370 100200 100200 16 240 Tg of latex [C] 1 16 16 16 16 10 6 40 16 CCT [m] 60 75 410 370 460 700 ~800 ~800 125 Viscosity in mPas [Shear rate, s1] 623 (5) 2410 (5) 522 (11.2) 1020 (11.2) 463 (11.2) 350 (11.2) 400 (11.6) 400 (11.6) -

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Phase Separation in anionic latexes

Vertical channels formed in green tapes using anionically stabilized latex. These effects have also been observed in paint systems. Due to phase separation between surfactant and polymer in latex during the drying process, surfactant migrates to interfaces, e.g. air/liquid. The surfactant stabilises the pores forming during drying. Anionic surfactant is not soluble in the latex particle Nonionic surfactant is soluble (no phase separation)

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Sintered Density
Tape-cast materials using different alumina powders and latex binders Sintering at 1600C Sintered density (% of T.D.) Alumina powder
Latex Anionic latex Nonionic latex A16SG 93.1 98.4 AKP30 94.3 98.5(99.7) AA04 92.6 98.4

Value in bracket with 0.05% MgO addition

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Green ,icrostructures Showing Pores from Phase Separation of Latex

Anionic B1035 Latex

A16SG AKP30 AA04

Nonionic DM765 Latex

A16SG AKP30 AA04

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Polyvinyl alcohol as a ceramic binder

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Comparision of binder effect in granules/tapes

Granulation and pressing
Viscosity of slip in spray drying Plasticity of granules in pressing Stickiness of powder on dies in pressing Flowabillity and fill density of powder

Tape casting and embossing

Viscosity of slip in tape casting Plasticity of tapes in embossing Lamination of tapes Stickiness on rolls in calendering

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Moisture sensitivity of pressing additive

All water-soluble additives are plasticized by moisture
Fray and Halloran, J. Am. Ceram Soc. 67(3) 199 (1984)

A dried out granulate often becomes hard and brittle A moist granulate is generally softer and easier to press
DiMillia and Reed, Am. Ceram Soc Bull. 62(4) 484-488 (1983)
Summary by Elis Carlstrm Surface Chemistry in Dry pressing, pp.245-278 in Surface and Colloid Chemistry in Advanced Ceramics Processing, Surfactant Science Series, vol 51

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Adding a plastiziser
A plasticizer such as PEG can be used to make PVA plasticized regardless of humidity Nies and Messing J. Am. Ceram Soc. 67(4) 301 (1984) The drawback is that a plastic granulate can increase in stickiness. This lowers the fill density of the granulate.

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Moisture adsorption of PVA

Spray dried granulate with 2.7% PVA 2.2% PVA 1.0% PVA

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PVA is plasticized by moisture adsorption

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Plasticizing effect depends on PVA content

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Apparent yield point as function of H2O content

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PEG (polyethylen glycol) as plasticizer of PVA

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Granule yield point with PEG additions

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Pressed density vs pressing temperature

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Adhesion cemented carbide: granule substrate from L. Bergstrm (Euroceramics VII)

Effect of PEG on adhesion

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Friction cemented carbide: granule - substrate from L. Bergstrm (Euroceramics VII)

Effect of PEG on friction

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Moisture content of a commercial presspowder (PVA-binder) 0.7

M oisture content of powder (%) 0.6 0.5 0.4 0.3 0.2 0.1 0.0 10 20 30 40 50 60 70 80 90 Humidity in climate chamber (%)

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Green strength of pressed granulate

0.115 1.4 1.2 Green strength (M Pa) 1.0 0.8 0.6 0.4 0.2 0.0 10 20 30 40 50 60 70 80 90 Humidity in climate chamber (%) 50 MPa 100 MPa 150 MPa 0.215 Moisture content of powder (%) 0.315 0.415 0.515 0.615 0.715

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Comparision of latex and PVA

Latex binder Small influence on viscosity No addition of plasticier Lamination and embossing at room temperture possible Nonionic latex can adsorb some dispersant Aninionic latex can create pores on drying No redispersion of powder
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PVA-binder Increases viscosity Moisture sensitive Plasticiser necessary Heating for embossing or lamination PVA reacts with soluble divalent ions Redispersion easier