CHAPTER 1

Introduction to Colloid Chemistry and Sol-gel Process

1.1 Colloid Chemistry: Introduction

A colloid is defined as a dispersion of finely divided particles in a homogeneous
medium. By convention, colloidal particles are considered to range from 1 to 1000
nm in size and consist of 103 to 109 atoms. Due to their small size, these particles are
small enough that they remain suspended indefinitely due to Brownian motion, a
random walk resulting from momentum imparted by collision with molecules of the
suspending medium. A dispersion of solid particles in a liquid medium is termed a
sol. Sols can be prepared by two techniques, condensation and dispersion.
Condensation proceeds by nucleation and growth of particles to the appropriate size,
whereas dispersion involves the reduction of large particles down to the colloidal
dimensions. Dispersion of a precipitate by chemical means, such as the introduction
of an electrolyte or washing with a solvent, to form a sol is referred to as peptization.
While this approach has been used in sol-gel chemistry, this method is not as
convenient as condensation and will not be described at length in this report.
Condensation proceeds in two stages: (1) nucleation or the formation of
crystallization centers and (2) the growth of the crystals. The size and properties of
the resulting particles depends on the relative rates of these two processes. Sol
formation is favored when the rate of nucleation is high and the rate of crystal
growth is low. Depending on the degree of crosslinking and the growth process by
which they are formed, the inorganic clusters can be either colloidal or polymeric in
nature and can range from 10 to 200 A⁰in diameters.
Gelation is the process whereby a free flowing sol is converted into a 3D solid
network enclosing the solvent medium. The point of gelation is typically identified by
an abrupt rise in viscosity and an elastic response to stress. For preparation of
aerogels, the gelation is most conveniently induced through a change in the pH of the
reaction solution. Under controlled conditions, the pH change reduces the
electrostatic barrier to agglomeration and promotes inter-cluster crosslinking,
leading to the formation of the 3D network.
A colloidal system is made up of two phases. The substance distributed as a
colloidal particle is called the dispersed phase (analogous to solute) and the phase
1
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

where the colloidal particles are dispersed is called the dispersion medium
(analogous to solvent). A colloidal solution can form eight different types based upon
the physical state (solid, liquid, gas) of dispersed phase / dispersion medium. The
common examples of colloids are milk, curd, cheese, clouds, paint etc. The properties
of these colloidal solution are in many ways different from that of true solution.The
Scottish chemist Thomas Graham [1,2] found that certain materials, which are
dispersed through the solvent, are very much larger than the molecules of the
solvent, such systems are called as colloidal dispersion. The following two conditions
are essential to form a colloidal dispersion of a solid in a given liquid;

True Solution Colloidal Sol

(a) (b)
Fig. 1.1 shows scattering of light by a (a) true solution and (b) colloidal
dispersion (Tyndall Effect).

(a) The solid must be insoluble in the liquid.

(b) The solid must have certain definite size of the particles.
Hence, depending upon the particle sizes the solutions are classified into three
types as below and their properties are listed in table 1.1.
(1) True solution (common salt dissolved into water)
(2) Colloidal solution
(3) Suspension
Fig. 1.1 shows scattering of light by true solution and colloidal sol. In a true
solution the size of the particles of dissolved substance and that of molecules of the
liquid are comparable i.e. smaller than the colloidal particles. Whereas in suspension,
2
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

the particles are much larger (>1000 nm) than the colloidal particles. Colloidal
particles are usually of the order of 1 to 1000 nm in size [3-5].

Properties Colloidal solution True solution Suspension

Size 1nm-1 m Less than 1nm More than 1 m
Diffusion Diffuses slowely Diffuses rapidly Will not diffuse
Settling of particles Will not settle by Will not settle at all Settles by just
gravity but settles gravity
by centrifugation
Filterability Cannot be filtered Cannot be filtered Can be filtered
Appearance Transluscent Very clear Opaque
Nature Heterogeneous Homogeneous Heterogeneous
Tyndall effect Will show tyndall Does not show Will show tyndall
effect effect
Number of Particle is the Particle is single Particle is the
molecules are in aggregate of few molecule or ion aggregate of
one particle hundreds of millions of
molecules molecules

Table1.1: Difference between Colloidal solution, true solution and Suspension

In the case of substances like glue, gum and gelatin the molecules are very big
in size compared to the colloidal particles. Therefore, in the dissolved state these
substances are in molecular form and they exhibit the properties of colloids. One way
of classifying the colloids is to group them according to the phase (solid, liquid or
gas) of the dispersed substance and that of the dispersion medium. There are two
basic methods of forming a colloid: (i) reduction of larger particles to colloidal size
and (ii) condensation of smaller particles (e.g. molecules) into colloidal particles.
Some substances like gelatin or glue are easily dispersed (in a proper solvent) to
form a colloid. This spontaneous dispersion is called peptization. A metal can be
dispersed by evaporating it in an electric arc, if the electrodes are immersed in water,
colloidal particles of the metal form as the metal vapour gets cooled. A solid like paint
pigment can be reduced to colloidal particles in a colloid mill. This is a mechanical

3
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

device, which uses a shearing force to break the larger particles in to smaller ones.
Table 1.3 gives the various types of colloidal systems with a common example [6].

1.2 Dispersed phase and dispersing medium

If a substance A, is insoluble in substance B then it will be usually possible to
break the substance A into very small particles that can be distributed more or less
uniformly throughout the substance B. Substance A is then called the dispersed phase
and the substance B is called the dispersing medium. The colloidal solution is not
homogeneous but it is an heterogeneous system, since the colloidal solution has two
phases, one phase is continuous (liquid) and the other phase is discontinuous
(particles) for example, colloidal solution of sulfur in water, sulfur is discontinuous
and water is a continuous phase. In a colloidal solution, the continuous phase
corresponds to solvent and is called the dispersing medium.

1.3 Lyophilic and lyophobic colloidal systems

Depending on the extent to which the dispersion medium (solvent) is able to
interact with the atoms of the suspended particles, the colloidal systems are
classified as lyophilic and lyophobic sols. The lyophilic and lyophobic colloids have
different characteristics, which is given in Table.
1.3.1 Lyophilic colloidal system
The particles in a lyophilic colloidal system have a great affinity for the
solvent, and are readily solvated (combined, chemically or physically) with the
solvent and dispersed even at high concentrations. Lyophilic sol can be prepared
from the substances containing large molecules simply by mixing them with the
dispersing medium under a suitable catalytic condition [7]. If the dispersing medium
is water then the term hydrophilic is used. The lyophilic colloid solution is
thermodynamically stable since there is reduction in the Gibbs free energy when the
solute is dispersed. The strong interaction between solute and solvent usually
supplies sufficient energy to break up the disperse phase and there is often increase
in the entropy as well.
1.3.2 Lyophobic colloidal system
In a lyophobic colloidal system the particles resist solvation and dispersion in
the solvent, and the concentration of particles is usually relatively low. For the
lyophobic colloid, the Gibbs free energy increases when the disperse phase is

4
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

distributed throughout the dispersion medium. The lyophobic dispersion can be

prepared by grinding the solid with the dispersing medium in a colloidal mill, which
over a prolonged period of time reduces the substance to a size in the colloidal range
(i.e. between 102 to 103 nm). In general, the lyophobic sol is produced by
precipitation reactions under catalytic conditions in which a large number of nuclei
are produced while limiting their growth for example: - by oxidation, reduction,
hydrolysis, double decomposition etc. Particles in a lyophobic system are readily
coagulated and precipitated, and the system cannot easily be restored to its colloidal
state. When the dispersion medium of a system is water, the term hydrophobic
system is used.

1.4 Forces of interaction between the colloidal particles

The stability of suspensions and emulsions against coagulation is governed by
the forces between the particles. Dispersion is said to be stable when the particles
are permanently free. In dispersions of fine particles in a liquid, frequent encounters
between the particles occur due to Brownian movement. Such encounters may result
in permanent contact or the particles become free depend upon the forces between
them. The different types of forces between the particles are:-
a) Van der Waals forces: - Van der Waals forces are always attractive between
particles of the same nature. Hamaker [8] derived equations for these forces on
the basis of additivity of Vander Waals energies between pairs of atoms or
molecules, and assuming these energies to be proportional to the inverse sixth
power of the distance.
b) Electrostatic forces:- Electrostatic forces, due to the interaction of the electrical
double layers surrounding the particles, always lead to a repulsion between
particles if they are of the same chemical nature and have surface charges and
surface potentials of the same sign and magnitude.
When the surface charge is generated by the adsorption of potential determining
ions, the surface potential, o, is determined by the activity of these ions and remains
constant during interaction at least if complete adsorption equilibrium is maintained.
In that case, interaction occurs at constant surface potential.
The Van der Waals forces fall off as an inverse power of the separation
between the particles and have a range comparable to the particle size, whereas the

5
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

electrostatic repulsion falls off as an exponential function of the distance and has a
range of the order of the thickness of the electric double layer.

Sr.No. Property Lyophilic colloids Lyphobic colloids

1. Preparation Easily be prepared Need some special methods
to prepare
2. Affinity Solvent attracting Solvent heating
3. Coagulation Coagulation requires A small quantity of
large quantity of electrolyte is sufficient
electrolytes
4. Detection through Cannot be easily Can be easily detected
ultramicroscope detected
5. Viscosity Very much different Almost the same as that of
from that of the the dispersion medium
dispersion medium
6. Surface tension Very much different Almost the same as that of
from that of the dispersion medium
dispersion medium
7. Density Very much different as Almost the same as that of
that of the dispersion the dispersion medium
medium
8. Electrophoresis Particles migrate in Migrate in particular
either direction direction
9. Reversibility The reaction is Irreversible
reversible
10. Example Starch solution, Soap Colloidal gold, colloidal
solution silver

Table1.2: Distinction between lyophilic and lyophobic colloids

For molecules of a simple monatomic liquid the interaction energy between a

pair of molecules is given by equation (1.1). The interaction only depends on the
separation between the centers of the molecules. At large separations, r > the

6
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

interaction is attractive, u(r) <0. At smaller separations, overlap of the electron

orbital of the two molecules is giving rise to a repulsion that increases very rapidly as
the separation decreases.
u(r) = 4 [ ( /r) 12 ( /r)6 ] (1.1)
Where and give the measure of size and the strength of interaction between the
molecules respectively. Fig (1.2) shows the curve of potential energy of interaction
against distance r.

Dispersed Dispersing Technical

Notation Examples
phase medium name
Smoke
Solid Gas S/G Aerosol

Hairspray, mist, fog

Liquid Gas L/G Aerosol etc.

Sol or Printing ink, paint

Solid Liquid S/L
dispersion
Milk, Lubricants,
Liquid Liquid L/L Emulsion crude petroleum

Foam
Gas Liquid G/L Foam

Ruby glass (Au in

Solid
Solid Solid S/S glass), some alloys
dispersion

Ice-cream, moist soil,

Solid
Liquid Solid L/S adsorbents
emulsion

Gas Solid G/S Solid foam Insulating foam

Table 1.3: Types of colloidal systems

7
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

At short distances, a deep potential energy minimum occurs, the position of which
decides the distance of closest approach, r0. At intermediate distances the
electrostatic repulsion makes the largest contribution and hence a maximum occurs
in the potential energy curve, Vm. At larger distances, the exponential decay of the
electrical double layer term causes it to fall off more rapidly than the power law of
the attractive term and a second minimum appears in the curve Vsm.

Repulsive Energy U2= B / r12

Potential energy U (r)

6 12
U (r) = ( A / r ) + (B / r )

ro
6
Umin Attractive Energy U1= A / r
nnn

Interparticle distance (r)

Fig. 1.2 Potential energy (P. E.) U(r) of two particle system as a function of
distance (r) between them. 'ro' is equilibrium distance where the
P. E. is minimum (Umin).

1.5 Charge on the colloidal particles

It is well known that most of the colloidal particles are electrically charged
and will migrate in one or other direction when subjected to an electric field. It has
been observed that there is a tendency for charges to accumulate at any interface
between two phases, because, the relative affinities of the cations and anions for the
8
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

two phases are, in general, different, one phase acquires a positive and the other a
negative charge.
Therefore, the potential curve drops steeper at places where there are more
compensating counter ions. The potential at the outer surface of the double layer
(plane AB) is still higher than that of the solution which accounts for the
electrokinetic properties of the sol and is called as electrokinetic or zeta potential.
The state of the charge on the electrolyte molecules is also determined by the pH
(concentration of H+ and OH– ions) of the sol. Thus a molecule having positive charge
at low pH may acquire a negative charge at higher pH values and there is an
intermediate pH called the isoelectric point at which the molecule will be electrically
neutral [9]

H+

2
H+ (SiO3) H+

2
2 (SiO3)
(SiO3)
H+ H+

2 SiO2
(SiO3) 2
(SiO3)
+ H+
H
2 2
(SiO3) (SiO3)

2
H+ (SiO3) H+
H+
H+

Fig. 1.3 Formation of electric double layer on a particle of an aqueous sol of

silicon dioxide due to ionization

1.6 Shape of colloidal particles

It is a general observation that the colloidal particles acquire spherical shape.
This is explained by the excess of free energy. It is known that among the bodies of
different geometrical shapes, a sphere has the smallest surface energy, and the
process of sphere formation occurs spontaneously in accordance with the second law
9
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

of thermodynamics. In a spherical drop, all the surface molecules are

indistinguishable from one another and also differ from the bulk ones in their
orientation.

Fixed layer

+ B Mobile layer
+ +
+ +
+
+
+ +
+ +
Potential

+
+ +
+
+ + Zeta
+ + Potential
+ +
+
+
+
+
+
+ +
+ A +

Distance
Particle surface

Fig. 1.4 Variation of attractive potential due to the charge on the particle
surface and Zeta potential ( ).

The excess free energy makes the disperse systems thermodynamically

unstable. The process of lowering the excess free energy and reducing the dispersity
is the fundamental characteristics of all dispersed systems. If a dispersed system
remains unchanged in its chemical composition, but changes its free energy
characteristic then this will result in a change in colloidal properties.

10
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

1.7 Molecular-kinetic properties of colloidal systems

1.7.1 Brownian motion
The first macroscopic observation of the rapid and erratic motion of small
particles was made by Robert Brown, an English Botanist, who was examining the
pollen grains. The motion was thought to be caused by the bombardment of the
particles by the surrounding molecules of the solvent. The intensity of the
bombardment would vary from moment to moment on one side or other of the
particle and this was the cause of erratic motion. When viewed under microscope, by
putting few such grains on a drop of water, he found that they are continuously
moving in random directions but along straight-line paths as shown in Fig (1.5). The
zig-zag motion of colloidal particles along straight-line path in random directions is
called the Brownian motion [10].

Fig. 1.5 Brownian motion of colloidal particles.

When the particles are very small, they can be viewed only under ultra
microscope. Because of the Brownian motion the particle remains suspended or
dispersed in the medium and do not settle down as precipitate. The motion is
characterized by the mean displacement x of a particle during the time t. Therefore,
, the root mean square value of projection of displacement of a particle on X-axis
parallel to the selected direction is given by
2 2
....
( 1 2
)1 / 2 (1.2)
n
Where 1, 2, …..... = Projections of displacements of a particle on X- axis and n=
number of such projections taken for calculation.

11
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

1.7.2 Diffusion
In the absence of any external fields, the chemical potential, i, of the substance
within a phase at equilibrium is constant. If for some reason the value of i varies
from place to place, then the substance 'i' will tend to diffuse in such a way as to
equalize the value of through out the phase. The driving force for the diffusion
process is the gradient of i – larger it is, the faster is the diffusion process. For one
dimensional process:
Fd = d i / dx (1.3)
Where Fd is the driving force for the diffusion process. Diffusion is a
spontaneous equalization of the concentration of molecules, ions or colloidal
particles in a system as a result of their thermal random motion. Hence, diffusion is a
macroscopic exhibition of thermal motion of molecules, and therefore the more rapid
it is, the higher is the temperature. Diffusion is irreversible, it occurs until
concentrations are completely equalized because the maximum entropy of a system
corresponds to the random distribution of the particles.
Diffusion can be best understood by the Fick 's first law, given by
Ji = - D (dc/dx) (1.4)
Where Ji= flux of the material, D= diffusion coefficient which depends on the
properties of the diffusing particles and the medium, dc/dx = concentration gradient.
The significance of negative sign is that the derivative dc/dx has a negative value as
the quantity c decreases with an increase in the value of x. The diffusion coefficient is
directly proportional to the absolute temperature and inversely proportional to the
viscosity of a medium and the particle radius, as given below:
RT 1 KT
D (1.5)
NA 6 r 6 r
where R is the gas constant, T is temperature, NA is Avogadro's number, is viscosity
and r is the particle radius. The diffusion coefficient is small in colloidal systems
because the dimensions of colloidal particles are very large in comparison with those
of ordinary molecules.
1.7.3 Osmosis
When two solutions of different concentrations are separated by a semi
permeable membrane, a flow of the solvent appears from the lower concentration to
the higher one that levels out the concentrations. The flow is balanced by counter
12
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

pressure gradient developed due to the excess number of impacts of the solvent
molecules against the membrane from the side of the more dilute solution.
The osmotic pressure P of very diluted colloidal solutions is given by
ms RT RT
P KT (1.6)
m pVN A NA

Where ms= mass of the solute, mp =mass of the particle, V= volume of the system, NA=
Avogadro's number, T= absolute temperature, = numerical constant. The
molecular-kinetic equations that are suitable for true solutions can be applied also to
colloidal solutions, the only difference being that the mass of a mole of a substance is
replaced by the mass of particles in them. The osmotic pressure of a disperse system
is determined only by the numerical concentration and does not depend on the
nature and dimensions of particles. Hence, the osmotic pressure is very low for
colloidal systems since the numerical concentration of a colloidal system is always
far less than that of a true solution.
1.7.4 Tyndall effect (optical property)
When a beam of light is passed through a true solution, and observed at right
angles to the direction of the beam, the path of the light is not clear. At the same time,
if the beam of light is passed through a colloidal solution, the path of the light is quite
distinct due to scattering of light by the colloidal particles. If an electric potential is
applied across two platinum electrodes immersed in a colloidal solution, the colloidal
particles move in a particular direction, depending upon the charge of the particles.
The phenomenon of scattering of light by the colloidal particles is known as “Tyndall
effect”.
1.7.5 Electrophoresis (electrical property)

If an electric potential is applied across two platinum electrodes immersed in

a colloidal solution, the colloidal particles move in a particular direction, depending
upon the charge of the particles. Thus the migration of colloidal particles under the
influence of electric field is called electrophoresis.
This phenomenon can be demonstrated by placing a layer of arsenic sulphide
solution under two limbs of a U-tube. When current is passed through the limbs, it
can be observed that the level of the colloidal solution decreases at one end of the
limb and rises on the other end.

13
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

1.7.6 Surface Tension and Surface Energy

The existence of surface tension can be expected from the difference between
the molecules in the bulk and molecules at the surface. The force which acts per unit
length of an interface and causes a diminution of the liquid surface is known as
surface tension which is always tangential to liquid surface and is measured in
Newton / meter. In order to increase the liquid surface, work must be done to
overcome forces which cause internal pressure is called surface energy. Surface
tension is also regarded as a free energy per unit area i.e. the work required to bring
molecules from the interior of the phase on to the surface region to form more
surface and the corresponding unit is joule/meter2 which is dimensionally equal to
N/m. Surface energy is equal to surface tension only for a single-component liquid.
The surface tension decreases with the increase in temperature. This relation is
shown by the Gibbs - Helmholtz equation [11] as
S= T (d / dT) V (1.7)
Where S = Total surface energy per unit area of the layer (for a homogeneous surface
at V= constant) and = Surface tension.

Fig 1.6 Temperature dependence of the surface tension and the total
surface energy S for carbon tetrachloride [12].

From Fig (1.6), it is clear that as the temperature rises, the surface tension of the
liquid diminishes almost according to the linear law. This means that the
temperature coefficient d /dT has almost constant negative value upto temperatures
14
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

which are close to critical temperature. At the critical temperature, the difference
between boundary phases disappears and surface tension becomes zero. This applies
not only to the liquid-vapour system, but also to the liquid-liquid system when
surface tension disappears at the critical temperature of solubility.

1.8 Coagulation of colloids

The entire colloidal particles are electrically charged; all are positively
charged or negatively charged. Therefore every colloidal particle repel each other
and remains stable. In order to coagulate a colloid, these charges have to be nullified.
This can be done in three ways:
(I) By adding a double salt (electrolyte)
(ii) By introducing an electrode of opposite charge
(iii) By introducing another colloid of opposite charge
After nuetralising the charges, the colloidal particles are brought
together and they are large enough to settle down. Thus the process of precipitating a
colloidal solution is called coagulation.

1.9 Stability of colloidal systems

If the colloidal particles do not aggregate at a significant rate, the system is
said to be colloidally stable. An aggregate is, in general, a group of particles (atoms or
molecules) held together in any way. When a sol is colloidally unstable, the formation
of aggregates is called coagulation or flocculation. Specifically, if the aggregation is
compact, it is called as coagulation and a formation of a loose or open network
implies flocculation.
The reversal of coagulation i.e. dispersion of aggregates to form a colloidally
stable suspension or emulsion is called as deflocculation or peptization. The rate at
which a sol coagulate depends on the frequency with which the particles encounter
one another and the probability that their thermal energy is sufficient to overcome
the repulsive potential energy barrier to coagulation when these encounters take
place. The rate at which the particles aggregate is given by,

dn
k2n 2 (1.8)
dt

15
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

Where 'n' is the number of particles per unit volume of sol at time’t’ and 'k2' is a
second order rate constant. The negative sign stands for a decrease in number of free
particles. During the course of coagulation, k2 usually decreases and the sol may
become only partially coagulated – due to the height of the repulsion energy barrier
increasing with increase in particle size.
In lyophilic sol, the colloidal particles experience short range repulsive forces
and also, as they are surrounded by several solvent molecules, lyophilic sols can be
stable even at their isoelectric point [13]. Whereas, lyophobic sols are stable due to
the electric double layer at the surface of the colloidal particles [14]. If two particles
of an insoluble material do not have a double layer, they can come close due to the
attractive van der Waals forces (refer equation 1.1). On the other hand, if the
particles possess a double layer, the overall effect is that they repel one another at
large distances of separation. This repulsion prevents the close approach of the
particles and stabilizes the colloid.
Coagulation can be brought about in lyophobic sols by changing the
electrolyte concentration. The size of the repulsion barrier between colloidal
particles depend upon the magnitude of the surface charge and on the extent of the
electrical double layer which in turn depends on the total electrolyte concentration.
The electrolyte concentration at which slow coagulation gives way to rapid
coagulation is called as the Critical Coagulation Concentration. Addition of small
amounts of a lyophilic colloidal sol to a lyophobic sol may make the latter more
sensitive to flocculation by electrolyte. This phenomenon is called as Sensitization.
The disappearance of the boundary between the aggregated particles followed by
change of shape leading to a reduction of the total surface area is called as
Coalescence.
Settling of suspended particles under the action of gravity is called as
sedimentation. Sedimentation depends on the radius of the particle (r), which is given
by the formula,
9 H
r ( )1 / 2 (1.9)
2T (d d 0 ) g
Where, : viscosity of the medium, H: height, T: time for settling, d: density of the
particle, do: density of the medium and g: acceleration due to gravity.

16
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

1.10 Sol-gel process

Sol-Gel process is a colloidal route used to synthesize aerogels or coatings
with an intermediate stage of a sol or a gel state. It generally consists of the
preparation of a colloidal suspension of a solid into liquid; viz (sol) and then three
dimensional structures of solid enclosing the liquid (gel). The gel on further removal
of liquid results in the final material which will be in the hydroxylated state [2,15].
The starting material used in the preparation of the sol is usually inorganic metal
salts or metal organic compounds such as metal alkoxides. In a typical sol gel process
the precursor is subjected to a series of hydrolysis and polymerization reactions to
form a colloidal suspension or sol. The sol when cast into mould results in the
formation of a gel. With further drying and heat treatment, the gel is converted into
dense ceramics or glass articles. If the liquid in a wet gel is removed under
supercritical conditions; a highly porous and extremely low density material called
aerogel is obtained. Applying sol-gel process, it is possible to fabricate ceramic or
glass materials in a wide variety of forms, ultra fine or spherical shaped, powders,
thin film coatings, ceramic fibers, microporous inorganic membranes, monolithic
ceramics and glasses or extremely porous aerogel materials. In the sol-gel process,
simple molecular precursors are converted into nanometer-sized particles to form a
colloidal suspension, or sol. The colloidal nanoparticles are then linked with one
another in a 3D, liquid-filled solid network. This transformation to a gel can be
initiated in several ways, but the most convenient approach is to change the pH of the
reaction solution. Even the method used to remove liquid from a solid will affect the
solgel’s properties.

1.10.1 Sol
A sol is a stable suspension of colloidal solid particles within a liquid [16].
Particles of a sol are small enough to remain suspended indefinitely by Brownian
motion. Sols are classified as lyophobic if there is a relatively weak solvent particle
interaction and lyophilic if the interaction is relatively strong. Lyophobic sols exhibit
well defined Tyndall effect. In lyophilic sols the particles are largely solvated and this
lowers the differences in refractive indices of two phases. The Tyndall effect is due to
the scattering of light from the surface of colloidal particles.

17
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

1.10.2 Stability of sols

Sol particles are held by Van der Waals forces of attraction or dispersion
energy.
Van der Waals force is propotional to the polarisabilities of the atoms and inversely
related to the sixth power of their separation. This Van der Waals force results from
transitory dipole-transitory dipole interactions (London forces). It is this London
forces that produce long range attraction between the colloidal particles. The
attractive potential for two infinite slabs separated by distance, h is given by
A
VA (1.10)
12 h 2

For atoms, VA 1
h6
Where A is a material property called Hamaker’s constant. Since this attractive force
extends over distances of nanometers, sols are thermodynamically unstable [17,18].
Aggregation can be prevented by erecting necessary barriers of comparable
dimensions.
i) Electrostatic stabilization
Electrostatic stabilization is explained by DLVO theory. According to this
theory the net force between particles in suspension is assumed to be the sum of the
attractive Van der Waals forces and electrostatic repulsion created by charges
adsorbed on particles. The repulsive barrier depends on two types of ions that make
up the double layer, charge determining ions that controls the charge on the surface
of the particle and counter ions that are in solution in the vicinity of the particle and
act to screen charges of potential determining ions [2]. A schematic representation of
electrostatic stabilization is provided in Fig. 1.7.
For hydrous oxides the charge determining ions are H+ and OH- which establish
the charge on the particle by protonating or deprotonating the MOH bonds on the
surface of the particle.
M-OH + H M - OH2+ (1.11)
M-OH + OH- M – O- + H2O (1.12)
The ease with which the protons are added or removed from the oxide depends
on the metal atom. The pH at which the particle is neutrally charged is called the
Point of Zero Charge (PZC). At pH greater than PZC equation (1.12) predominates
and the particle is negatively charged, whereas at pH less than PZC equation (1.11)
18
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

gives the particle a positive charge. The magnitude of the surface potential depends
on the departure of the pH from the PZC, and that potential attracts oppositely
charged ions (counter ions) that may be present in the solution.

Fig. 1.7 Electrostatic stabilization

According to the standard theory, from Fig.1.8. the potential drops linearly
through the tightly bound layer of water and counter ions, called the Stern layer.
Beyond the Helmholtz plane h=H, that is, in the Gouy layer, the counter ions diffuse
freely. In this region the repulsive electrostatic potential of the double layer varies
with distance from the particle, h, approximately according to
K (h H )
VR e ,h H (1.13)
Where1/K is called the Debye Huckel screening length. When the screening length is
large (i.e. K is small), the repulsive potential extends far from the particle. This
happens when the counterion concentration is small. When counterions are present,
the potential drops more rapidly with distance. Since the repulsive force is
propotional to the slope of the potential,

dVR K (h H )
FR Ke (1.14)
dh
The repulsive force increases with small additions of electrolyte. (i.e FR increases
with K). Large amounts of counter ions collapse the double layer. As the
concentration of counter ions increases, the double layer is compressed because the
same numbers of charges are required to balance the surface charge and they are
now available in a smaller volume surrounding the particle. On further increase in
the concentration of counter ions , the double layer repulsions are reduced to the
point that net particle potential is attractive and the colloid will coagulate
immediately. When an electric field is applied to a colloid, the charged particles move
19
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

towards the electrode with the opposite charge. This phenomenon is called
electrophoresis. When the particle moves it carries along the adsorbed layer and part
of the cloud of counter ions, while the more distant portion of the double layer is
drawn towards the opposite electrode. The slip plane or plane of shear separates the
region of fluid that moves with the particle from region that flows freely. The rate of
movement of particles in the field depends on the potential at the slip plane, known
as zeta potential. The pH at which zeta potential is zero is called the isoelectric point
(IEP). The stability of the colloid correlates with zeta potential to be around 30-50
mV [2].

Fig. 1.8 Schematic of Stern and Guoy layers. Surface charge on particle is
assumed positive

ii) Steric stabilization

Sols can be stabilized by steric hindrance. For example when short chain
polymers are adsorbed onto the surface of particles. There are two components to
this stabilization energy. As the sol particles approach one another, the adsorbed
polymer loses configurational entropy. This raises the Gibb’s free energy of the
system, which is equivalent to the development of a repulsive force between the
particles. In addition, as the polymer layers overlap the concentration of the polymer
in the overlap region increases. This leads to local osmotic pressure and a repulsive

20
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

force between the particles [19]. A schematic representation of steric stabilization is

provided in Fig. 1.9.

Fig. 1.9 Steric Stabilization

iii) Stability by solvation
Sol stability coming from energy of solvation is most effective in aqueous
system. Energy of solvation is the energy required to disrupt the ordered layer of
solvent surrounding the sol particles and to desolvate the surface to allow the
particles to come into contact with one another. Because of the energy of solvation,
lyophilic sols tend to be more stable than lyophobic sols [20].

1.10.3 Gel
A gel is a porous three dimensionally inter-connected solid network that
expands in a stable fashion throughout the liquid medium and is only limited by the
size of the container [21]. Gel results when the sol loses its fluidity. An important
criterion for gel formation is that at least part of the solvent is bound. If the solid
network is made up of colloidal particles, the gel is said to be colloidal (particulate). If
the solid network is made up of sub colloidal chemical units the gel is called
polymeric. In particulate gels, the sol gel transition is caused by physio-chemical
effect and in the latter by chemical bonding [20]. The Schematic representation of
sol-gel process is shown in Fig. 1.10.

1.10.4 Sol-Gel Precursors

The based on the data concerning the development of sol-gel technologies,
one can say that a very important moment is the choice of appropriate precursors.
Most often these are alkoxides, soluble metal salts, polymers, colloids which
depending on their nature, may be combined with suitable solvents, and the
aggregation processes stimulating solid phase formation can be controlled. Fig. 1.11

21
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

shows schematically the most used variant of the sol-gel process. The more general
interpretation is given by Kakihana [22], according to which a chemical process
starting from solutions and leading to a solid phase without a precipitate is a sol-gel
process even if the system does not represent an infinite solid network. One of the
methods leading to colloid dispersions (sols) is based on inorganic salts, water and
occurrence of hydrolysis processes at a definite pH. A classical example is the
formation of gel of SiO2 whose detailed description is given in the monograph of Iler
[23]. Metal salts and alkoxides are the two main groups of precursors. The general
formula of metallic salts is MmXm where M is the metal, X is the anionic group.
M(OR)n is the general formula of alkoxides. Sol-Gel precursors undergo chemical
reactions both with water and other species present in the solution.

Fig. 1.10 Schematic Representation of Sol-Gel Process

22
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

Fig. 1.11 Different routes of the sol-gel processing

1.10.5 Application of Sol-Gel Process

Monoliths, fibers, films and nano-sized powders obtained directly from the gel
state combined with compositional and microstructural control and low processing
temperature finds applications in various fields. Thin films and coatings find
applications for optical, electronic, protective and porous thin films or coatings.
Monoliths find applications as optical components, transparent super insulation and
ultra low expansion glasses. Powders, grains and spheres used as ceramic precursors
or abrasive grains. Fibers drawn from viscous sols are used primarily for
reinforcement or fabrication of refractory textiles. Gels can be used as matrices for
particle-reinforced composites and as hosts for organic, ceramic or metallic phases.
Porous gels and membranes found application in filtration, separations, catalysis and
chromatography.

1.10.6 Advantages of sol-gel process

Advantages of sol-gel process are given below [24].
_ Increased chemical homogeneity in multicomponent system.
_ High surface area for the gels or powders produced.
_ High purity can be maintained because of the absence of grinding and pressing
steps.
_ A range of products in the form of fibers, powders, coatings and spheres can be
prepared with relative ease starting from simple solutions.

23
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

_ Low temperatures for sol-gel process, saving energy and minimizing evaporation
losses.
_ Gels can be molded in the shape of the final desired object, with dimensions
enlarged to allow for shrinkage during drying and sintering.

1.10.7 Disadvantages of sol-gel process

_ Hydrolysable organic derivatives of the metals used in sol-gel processing are
expensive [24].
_ The moulded body tends to crack during drying and sintering due to considerable
shrinkage [24].
_ Long processing times [25].

24
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

References:
[1] T. Graham, J. Chem. Soc., 17 (1864) 318.
[2] C. J. Brinker, G. W. Scherer, “Sol-gel science: the physics and chemistry of sol-gel
processing “, Academic Press, New York (1990)
[3] G. I. Brown, “Introduction to Physical Chemistry”, 3 ed. Longman Group (F.E.)
Ltd. Hong Kong (1983)
[4] A. Sheludko, ‘Colloid Chemistry’, Elsevier, Amsterdam, (1966)
[5] P.A. Rehbinder and G.J. Fuchs (eds.): “Uspekhi Kolloidnaya Khimii (Advances in
Colloid Chemistry)”, Nauka, Moscow (1973).
[6] R. J. Hunter, Foundations of Colloid Science, 2nd edition, Oxford University Press,
(2001).
[7] D. V. S. Jain, S. P. Jauhar "Physical chemistry: Principles and problems", Tata Mc
Graw Hill Publishing Company Ltd., New Delhi, (1988).
[8] H. C. Hamker, Rec, Trav. Chim., 55 (1936) 1015.
[9] J. Lyklema, Disc. Faraday Soc., 52 (1971) 318.
[10] M. V. Smoluchowski, Z. Phys. Chem., 92 (1917) 129.
[11] D. A. Fridrikshberg , "A Course in Colloid Chemistry" Mir Publishers, Moscow
(1984).
[12] J. Escobedo, G.A. Mansoori, AIChE Journal, 42(5) (1996) 1425
[13] G. Frens , J. Th. G. Overbeek, J. Colloid. Interface Science, 38 (1972) 376
[14]E. Matijevic, “Twenty Years of Colloid and Surface Chemistry”, the Kendall
Award Addresses, (eds. K.J. Mysels, C.M. Samour and J.H. Hollister) Amer.
Chem. Soc., Washington D.C. (1973) p 283
[15] A.C Pierre, Introduction to Sol-Gel Processing, Kluwer Academic publishers,
The Netherlands (1998).
[16] P.C. Hiemenz, R. Rajagopalan, ‘Principles of Colloidal and Surface Chemistry’,
Marcel Dekker, New York (1997).
[17] C.K. Narula, ‘Ceramic Precursor Technology and its Applications’, Marcel Dekker,
New York (1995).
[18] G.Y. Onoda and L.L. Hench eds. Ceramic Processing Before Firing, John Wiley
and Sons, New York (1978).
[19] C.W. Turner, Am. Ceram. Soc. Bull. 70 (1991)1487.
[20] C.F. Baes, R. E. Mesmer, ‘The Hydrolysis of Cations’, Wiley, New York (1976).

25
 Chapter 1 Introduction to Colloid Chemistry and Sol-gel Process

[21] Y.O. Roizin, S.A. Gevelyuk, L.P. Prokopovich, D.P. Savin, E. Rysiakiewicz-Pasek, K.
Marczuk, J. Porous Mater. 4 (1997) 151.
[22] M. Kakihana, J.Sol Gel Sci. Tech. 6 (1996) 7.
[23] R. K. Iler, ‘The Chemistry of Silica’, Wiley Interscience, Publ. N. Y. (1979).
[24] H. Schmidt, A. Kaiser, M. Rudolph and A Lentz in “Science of Ceramic Chemical
Processing”, ed. By L. L. Hench and D. R. Ulrich, Wiley, New York (1986).
[25] B.E. Yoldas, J. Mater. Sci. 21 (1986) 1080.

26