Che5700

Sol-Gel Process

More and more applications, become an independent

category;
Use metal alkoxide, to go through hydrolysis reaction,
then condensation polymerization, to obtain desired
colloids
During process, system viscosity increase with time, it
can also be used for coating into films, or even directly
forming into desired objects variety;
Most common example: TEOS (tetraethyl orthosilicate)
hydrolysis to make silica; (OC2H5)4Si + H2O
(OC2H5)3SiOH + C2H5OH . Gradual hydrolysis and
then condensation reactions

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Advantages of Sol-Gel Processes

In general:
Able to get uniform & small sized powder
Can get at low temperature high density glass, without
high temperature re-crystallization
Can get new compositions of glass
New microstructure and composition
Easy to do coating for films
Can get objects or films with special porosity
For improved adhesion
Can get metal (inorganic) organic composites
Can coat onto large area or complex shape objects
Can get fibers
High uniformity, multicomponent systems

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More Process Characteristics

Mixing of reacting system: all alkoxide precursor, or 1

alkoxide + 1 metal salt; Things to consider: (a) cost of
precursor; (b) relative hydrolysis rate; (c) compatibility
of chemicals (uniform mixing)
Colloidal sol & polymerized sol;
Peptization: adding proper solvent or adjust pH, to redisperse weak agglomerates back into sols
M(OR)n mostly derived from MCln ; often sensitive to
light, moisture, temprature etc.;
M-O bonding: ionic nature mostly solids; covalent
nature - liquids
To decompose alkoxide: (a) add water; (b) heat (to
decompose)

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Some statistic data on Alkoxide synthesis

Source: Am. Cer. Soc. Bull., 72(10), 73, 1993;

Some
real
example
s

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Reaction Characteristics

In simple terms, whole process control is on control of

relative rate between (a) hydrolysis ; (b) polycondensation
M-OH + M-OR M-O-M + ROH; Yet M-OH & M-OH
condensation rate, and whether M-OR & M-OR can
condense; whether linear condensation or branched
form affect microstructure
Effect of catalyst: acid or base
Effect of temperature: e.g. Al(OR)3 low temperature
hydrolysis amorphous form, further aging
hydroxide; at high temperature (> 80 oC) crystalline
boehmite AlO(OH), sintering behavior different
Zr(OR)4 hydrolysis, easy to get oxo bond, instead of
hydroxy bond

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More Characteristics

Alcohol as solvent, same as alcohol in alkoxide, one can

also use different alcohols (or co-solvent), may affect
reaction; sometime the steric effect
Additive with carbonate groups, will get esterfication (
), and polyesterification to get gel-like product; (e.g.
Pb acetate; Pb(C2H3O2)2 . 2H2O for synthesis of BaTiO3
powder)
Another reason for gelation: solvent evaporation,
increase of concentration; mostly due to reaction;
end result 3D network structure, system viscosity
increase continue aging, stronger structure, begin to
shrink, expel solvent.

Taken
from TA
Ring,
1996;
Three
different
network
structures

Taken from
TA Ring,
1996; sol
characteristi
cs also affect
film structure
and
properties

Acid or base
(catalyst)
and /or salt:
will change
surface
charge
and final
structure

Polarity Effect
700

Ethanol & Ethylene glycol (NH3=1M)

600

Methanol & Ethanol (NH3=1M)

Methanol & Ethylene glycol (NH3=1M)

500

Diameter (nm)

Effect of
different solvents
on particle size
(silica)
PA, PB =
polarity of
solvents A, B
A, B volume
fraction

1,2-Dichloroethane & Ethanol (NH3=1M)

Methanol & Ethanol (NH3=0.5M)

400
300
200
100

TEOS=0.28M

0
4.00

4.25

4.50

4.75

5.00

5.25

Polarity index of cosolvent

5.50

5.75

P P A P B
'
AB

'
A

'
B

A Proposal

Si(OC2H 5)4-X (OH)X

high polarity
cosolvent
Cmax*
Cmax*
Cmin*
Cmin*

low polarity
cosolvent

Cs
Cs
Time

Adding
solvent of
different polarity,
change solubility
of precursor
species, change
supersaturation,
nucleation to
get more nuclei
smaller final
particle size

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Gel Characteristics

Gel stage: time to form film, fiber, etc. forming period.

Due to proper viscosity to work with.
Gel densification:
Continuous cross-linking & dehydration to expel solvent
Reduce free volume (relaxation of microstructure)
Reduce surface area
Capillary contraction: due to solvent evaporation
All above mechanisms shrink structure, may cause
crack, especially as films (constrained by substrate)
Sol gel can be considered as phase transition

Low
coordination
number
large pore
inside
structure;
high CN
dense
structure

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Theoretical composition

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Filtration of ordinary small particles, may

also form gel layer

During
formation
of gels,
sample
may
adhere to
wall and
cause
crack

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Gel Drying

Gel drying period, can get kinetic data from weight loss
Similar to ordinary drying process, classified as (a)
constant rate drying period; (b) reach a critical point
(prone to cracking); (c) first falling rate period; (d)
second falling rate period
To prevent cracking during drying, control drying rate
(slow during certain period), some proposed to add
drying control chemical additive (DCCA) objective:
to lower capillary pressure, to lower solvent pressure;
or to use supercritical evaporation method

skeletal
densification,
structural
relaxation may
be
polymerization
reaction
III zone little
change in
weight,
viscous
sintering
cause
shrinkage
I zone de-hydration, solvent evaporation,
slight capillary contraction
II zone continue to dehydrate, molecule

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Decomposition and Sintering

Up to 150oC, continuous dehydration, some ligand may

desorb and leave, micropores will limit its movement
Over 250oC, molecule begin to decompose, continue to
loss weight. Decomposition affected by gel structure,
extent of cross-linking; atmosphere also important,
incomplete decomposition may have residual char;
Skeleton collapse, particle sintering and densification,
mostly by viscous sintering (faster than conventional
diffusion mechanism), I.e. can be achieved at lower
temperature (one advantage of sol-gel process); if fast
heating, may contain residual pores.

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Sol to Gel to Glass

sol- gel- glass: one advantage no need of

high temperature treatment, can obtain special
composition, high purity, high uniformity

Difficult to make one whole piece glass without

crack, often very slow (because of slow drying
to avoid cracking)
Ref: Am Cer. Soc. Bull., 64(11), 1463, 1985

* TEOS + boric acid + phosphoric acid + acid

catalyst + glycerol + formamide PE or teflon
container room temperature; B+P content may
reach 12 wt%

Example of Reverse Micelle Method

Micelle = oil in water; reverse micelle = water in oil