Sol-gel Processing

Sol & gel

Particulate gel
Polymeric gel
 Sol-gel processing : Basics

colloidal particles (1 to 1000 nm)

A sol is a suspension of colloidal particles in a liquid or a solution of

polymer molecules.

The term gel refers to the semirigid mass formed when the colloidal
particles are linked to form a network or when the polymer molecules
are cross-linked or interlinked.
Sol–gel process: --- A solution of metal compounds or a suspension of
very fine particles in a liquid (referred to as a sol) is converted into a
highly viscous mass (the gel).
Sol–gel processes:  two major kind

Starting with a sol, the gelled
material consists of identifiable
colloidal particles that have been
joined together by surface forces to
form a network (Fig-a).
When a solution is used, typically a
solution of metal-organic
compounds (such as metal
alkoxides), the gelled material in
many cases may consist of a
network of polymer chains formed
by hydrolysis and condensation
reactions (Fig-b).

Schematic diagram of the structure of (a) a particulate gel formed from a

suspension of fine particles and (b) a polymeric gel from a solution.
 Basic flow chart of sol-gel processing

From a suspension
From a solution
of fine particles
 Sol-gel process in brief

Polymerization of the species formed by the hydrolysis and

condensation reactions together with interlinking and cross-linking of
the polymer chains eventually leads to a marked increase in the
viscosity of the reaction mixture and the production of a gel. The gel
has a continuous solid network and a finite shear modulus.
Normally, excess water and alcohol are used in the reactions so that the
amount of solid matter in the gel (i.e., the solids content of the gel) can
be quite low, being 5–10 vol% in many cases. The remainder of the
volume consists of liquid that must be removed prior to firing.

This ‘‘solution sol–gel process’’ is receiving considerable research interest;

however, the sol–gel process based on the gelling of suspensions sees
more widespread industrial application.
 Type of Gels
Particulate gel & Polymeric gel

Particulate gels consist of a skeletal network of essentially anhydrous

particles held together by surface forces, with the structure of the
particles normally corresponding to that of the bulk solid with the same
composition.

Example,
colloidal SiO2 particles have the same structure as bulk silica glass
produced by melting. Hydroxyl groups are present only on the surface of
the particles.
More on Particulate gels

Because of the larger pores, the permeability of colloidal gels is higher,

and this, combined with the lower capillary pressure, means that
colloidal gels are less likely to crack during drying. The structure of the
dried gel is characterized by a relatively high porosity (70–80%) and
pores that are relatively large compared with the size of the particles
(i.e., the average pore size is typically 1–5 times.
By a schematic below a comparison between particulate gel and
polymeric gel has been shown.
 Polymeric gel
Polymeric gels consist of a skeletal network of polymer chains that form
by the entanglement and cross-linking of growing polymer chains or
polymer clusters resulting from the hydrolysis, condensation and
polymerization of precursors in solution.

The polymerization of silicon alkoxide, for example, can lead to complex

branching of the polymer as shown in the figure below.

Fractal polymer made by

branching of polyfunctional
monomer. (Computer
simulation of two-dimensional
aggregation.)
 More on Polymeric gel
Gelation is accompanied by a sharp increase in the viscosity that
essentially ‘‘freezes-in’’ the polymer structure at the point of gelling. At
this stage, the gel consists of a weak amorphous solid structure and an
interconnected network of very fine pores filled with liquid. The volume
of the liquid-filled pores is very high, typically 90–95% of the total
volume, and the diameters of the pore channels are typically of the order
of 2 to 10 nm. The frozen-in structure can change appreciably during
subsequent aging of the gel and during removal of the liquid from the gel
(drying). Under certain conditions, the aging gel can shrink considerably
while expelling liquid.
 Cont…

Because of the very fine pores, huge capillary stresses are developed
during normal evaporation of the liquid so that polymeric gels are very
prone to cracking. Removal of the liquid by evaporation therefore
collapses the weak polymer network and results in additional
crosslinking of the polymer structure. Cross-linking and collapse of the
gel continues until the structure can withstand the compressive action
of the capillary stresses.
Depending on the structure of the gel, the porosity of the dried gel can
be anywhere between 30 and 70%.
 Difference in dried Particulate gel and dried Polymeric gel

Compared to the particulate gel case, structural effects of the dried gel
on sintering are more pronounced as well as more complex. The average
pore size of polymeric gels is usually much finer than that of colloidal
gels so that the driving force for sintering (which varies inversely as the
radius of the pore) is usually much higher. The result is a lowering of the
sintering temperature for polymeric gels. For example, in the case of
SiO2, viscous sintering of polymeric gels occurs generally between 800
and 1000 oC.
 Polymeric gel route: significance

While there are many potential applications of the polymeric gel route,
the preparation of thin films is by far the most important use.
Thin films benefit from most of the advantages of the method while
avoiding most of the disadvantages.
However, even films suffer from problems (e.g., cracking) if attempts are
made to prepare films thicker than 1 μm.
SOL–GEL PROCESSING OF
AQUEOUS SILICATES

Introduction
Effect of pH
 Ranges 2 to 7
 Above pH 7
 Below pH2
 Introduction
Silicon is hydrolyzed even in dilute acid and as shown in Fig.

silicic acid [Si(OH)4], often referred to as

monosilicic acid, orthosilicic acid,

Distribution of of aqueous silicate species at 25 oC in (a) 0.1 m Si(IV) and

(b)10-5 m Si (IV). Ionic strength, I = 3 m.
Sol to gel transformation in Aqueous silicates
Cont…

Polymerization behavior of
silica. In basic solution (B)
particles in sol grow in size
with decrease in numbers; in
acid solution or in presence
of flocculating salts (A),
particles aggregate into
three-dimensional networks
and form gels.
Polymerization in the pH range 2 ̶ 7
Effect of pH in the colloidal silica-water system.
Polymerization above pH 7
Polymerization below pH 2