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Sol-Gel Process
Hydrolyses
Polymerization
Growth of
nanostructures
Agglomeration
Variation of PH
Temperature
Time
Concentration of Reagent
Concentration of Catalyzor
H2O/Si
Phase transition Sol
Gel
Drying
Sol
For example
(C 2 H 5 ) SiO4 C 2 H 5 OH HCl H 2 O
aerosol
SiO2
Homogeneous mixture
With diameter20-50nm
Gel
Xerogel
Drying in air
Glass of Nanoparticles
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
Some
real
example
s
Reaction Characteristics
More Characteristics
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
600
500
Diameter (nm)
Effect of
different solvents
on particle size
(silica)
PA, PB =
polarity of
solvents A, B
A, B volume
fraction
400
300
200
100
TEOS=0.28M
0
4.00
4.25
4.50
4.75
5.00
5.25
5.50
5.75
P P A P B
'
AB
'
A
'
B
Problem
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
Gel Characteristics
Low
coordination
number
large pore
inside
structure;
high CN
dense
structure
Theoretical composition
During
formation
of gels,
sample
may
adhere to
wall and
cause
crack
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
PRODUCT OF FUTURE
Precursors:
catalyst:
solvent:
various alcohols
water
UNIT IV LECTURE 3
32
SOL-GEL SCIENCE
Mix the reactives
Sol
Gelification
Aging
Soaking
Gelification
Gel
Aging
Drying
Gel
Aerogel
Gelification
OR
Si
OR
Mix reactives
OR
OR
OR
H2O
OR
OR
OR
OR
Si
OR
OR
HO
Si
OR
Gelification
Gel
OR
HO
OR
OR
Aging
Gel
Si
OR
Si
OR
OR
OR
OR
ROH
H2O
OR
OR
Si
ROH
OR
OR
OR
OH
OR
OR
Si
OR
OR
Sol
Si
HO
OR
Si
Si
OR
OR
Designing Nanomaterials
First Step
Silica Solution
Precursor: Tetraetilortosilicate
Si(OCH2CH3)4
Solvent: Ethanol
Catalyst: OxalicAcid
Modifications
pH (final product)
Temperature (crystal phase)
Precursor (Type of material)
Time (Strength)
etc
(I)
Aerogels are a unique, nanostrutured material derived from gels. Gels are a
novel class of material exhibiting solid-like behavior although consisting predominantly
of a liquid phase. Their solidity derives from a continuous interpenetrating framework
that, in essence, acts like a molecular scaffold extending throughout the liquid. This
perspective of a gel as a molecular web in a liquid has found many industrial
applications.
Figure 1:
Gelification
OR
Si
OR
Mix reactives
OR
OR
OR
H2O
OR
OR
OR
OR
Si
OR
OR
HO
Si
OR
Gelification
Gel
OR
HO
OR
OR
Aging
Gel
Si
OR
Si
OR
OR
OR
OR
ROH
H2O
OR
OR
Si
ROH
OR
OR
OR
OH
OR
OR
Si
OR
OR
Sol
Si
HO
OR
Si
Si
OR
OR