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Sol Gel
Sol Gel
Hydrolysis
Sol-gel process:
Condensation
Gelation
Ageing
Drying
Densification
Sol-Gel Methods
Sol-Gel Methods
Agglomeration = covalent bonds, van der Walls, hydrogen bonds, polymeric chain
entanglement
Sol-Gel Methods
Sol-Gel Methods
Sol-Gel Methods
M Colloid Route
metal salts in aqueous solution, pH and temperature control
Hydrolysis
M(H2O)bZ+ [M(H2O)b-1OH](Z-1)+ + H +
Condensation-polymerization
M(H2O)bZ+ [(H2O)b-1M(OH)2M(H2O)b-1](2Z-2)+ + 2H+
Sol-Gel Methods
Sol-Gel Methods
M Metal-organic Route
metal alkoxide in alcoholic solution, water addition
Acid catalysed hydrolysis
OR
RO
H
H
O
Si
RO
H
H
Si
RO
OR
+ ROH + H
Si
OR
R
RO
OR
OR
RO
Si
OR
OR
Si
H O
+ RO
Si
OR
RO
RO
RO
OR
Sol-Gel Methods
OR
Sol-Gel Methods
Sol-Gel Methods
Sol-Gel Methods
Effects on hydrolysis rate:
pH
substituents
solvent
water
Sol-Gel Methods
Sol-Gel Methods
Precursor substituent effect
Steric effects: branching and increasing of the chain length LOWERS the
hydrolysis rate
Si(OMe) 4 > Si(OEt)4 > Si(O nPr )4 > Si(O iPr)4 > Si(O nBu)4 > Si(OHex)4
Sol-Gel Methods
Sol-Gel Methods
Acidic conditions:
reaction rate decreases as more alkoxy groups are hydrolyzed
reaction at terminal Si favored, linear polymer products, fibers
RSi(OR) 3 more reactive than Si(OR)4
Basic conditions:
reaction rate increases as more alkoxy groups are hydrolyzed
reaction at central Si favored, branched polymer products,
spherical particles, powders
RSi(OR) 3 less reactive than Si(OR) 4
Sol-Gel Methods
Water:alkoxide ratio (R w) effect
stoichiometric ratio for complete hydrolysis = 4
Si(OR)4 + 4 H2O
Si(OH)4 + 4 ROH
Si-O-Si + H2O
Small amount of water = slow hydrolysis due to the reduced reactant conc.
Large amount of water = slow hydrolysis due to the reactant dilution
Sol-Gel Methods
10
Sol-Gel Methods
Hydrophobic effect
Sol-Gel Methods
11
Sol-Gel Methods
Sintering mechanisms
solid, liquid, gas phase
1. Evaporation-condensation and dissolutionprecipitation
2. Volume diffusion
3. Surface diffusion
4. Grain boundary diffusion
5. Volume diffusion from grain boundaries
6. Volume diffusion from dislocations
Sol-Gel Methods
12
Sol-Gel Methods
Sol-Gel Methods
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