Freeze Casting of Porous Ceramics

Dr. xxxxxxxxxx 31.01.2012

Colloidal Near-Net-Shaping Techniques

Colloidal Near-Net-Shaping Techniques

Prozessschritte von Freeze Casting berblick

J.Ceram.Soc.Jpn. 2011, 119, 147-160

Kristallwachstum

Einfluss der Einfriergeschwindigkeit

Phil. Trans. R. Soc. A 2010 368, 2099-2121

Einfluss der Gefriereinrichtung

Einfluss des Lsungsmittels (LMi)

Flssiges Wasser

Wasser als Eis

Temperaturausdehnung (TAD) beim Einfrieren

+9% !!!

Bildung von Eiskristallen

H2O: Water (m.p.= 0C)

TAD= +9%

Adv.Eng.Mater. 2008, 10, 3, 155-169

Anderes LMi Andere Struktur

Camphene (m.p.= 45-46C)

TAD= -3,1%

Solidified camphene dendrites

tert-Butanol (m.p.= 26C)

TAD= +2%
Prismatic Channels

Einfluss der Partikelgre an Porenmorphologie

Freeze Casting: Vorteile

Low shrinkage Independent on material Easy control through sintering step Porosity design Relatively high mechanical properties in the green state Environmentally friendly

Freeze Casting: Bestimmende Parameter

Solid content of the suspension (1050 vol% = 2085wt%) Particle size (20nm 6.5m) Solvent (pure solvents and eutectic mixtures; aqueous and non-aqueous
techniques: viscosity, thermal conductivity, surface tension, melting point, volume change, vapor pressure, crystal structure)

Freezing direction, rate and temperature (velocity of freezing

front, temperature gradient)

Freezing device and cryoprotector additions

(isotropic/anisotropic cooling = homogeneous/direction solidification)

Pressure and temperature of freeze-dryer (sublimation step)

Freeze Casting: Probleme und Grenzen

During the whole process the slurry must be absolutely stable against sedimentation Solid load is limited (breakthrough concentration) Most investigations reported 13 cm (lab scale). Homogeneity of the temperature filed and the freezing kinetics will become problematic for larger bodies (wrmeleitfhigkeit und viscositt des LMi, temperaturgradient) mgliche Losung -> Einfrieren unterm Druck Temperaturausdehnung may become critical during freezing and lead to cracks and flaws Flaws during sublimation of the solvent has been never optimized terra incognita Larger particles will lower the critical velocity (cv the particles become encapsulated by solid)

Beispiele aus Literatur

Materials Alumina Alumina Alumina Alumina Alumina Glass Powder Particle Size 700 nm 700 nm 400 nm 400 nm 200 nm 6.5 m Solvent Silica Sol Silica Sol Camphene Water t-BuOH Water Cooling Conditions Cold Plate, -30C Metallic Mould, -40C Mould, from 55 to 22C From 22 to -100C From 0 to -15 Mould, -55C Mould, from 60 to 20C Mould, -40C Cold support, -18C Pore Size 80 m 50 m 5-20 m 2-200 m 50 m 100-150 m Sintering Temperature No sintering 1100-1500 1600C 1500C 1500C 620C

Bioglass
SiC TiO2

16 m 150 nm

Camphene
Water Water

20-40 m
300 m 15 m

700-1100C
No sintering 1000C