Chapter - 1

Introduction to colloid
and sol-gel chemistry
Introduction to colloid and … 1 Chapter - 1

Chapter - 1
Introduction to colloid and sol-gel chemistry

1.1 Introduction
Solution is an intimate mixture of two or more chemical substances. In
solution, the dissolving agent is the solvent (dispersion medium) and the
substance which dissolves is the solute (dispersed phase). The state of
matter of a solution may be solid, liquid or gas which are in the form of
atoms, ions, or molecules.
According to Scottish chemist Thomas Graham (1861), depending on
the size of solute particles, the solutions are classified as given in fig. 1.1.

Fig. 1.1 Types of solutions

1.1.1True solutions
A true solution is a homogeneous solution in which the solute
particles have diameters lesser than 1 nm i.e., the solute particles are of
molecular dimensions. Such dispersed particles dissolve in solution to form a
homogenous system. These do not settle down when the solution is left
standing. The particles are invisible even under powerful microscopes and
cannot be separated through filter paper, parchment paper or animal
membranes, e.g. sodium chloride in water, sugar in water.

1.1.2 Suspensions
Suspensions consist of particles of a solid suspended in a liquid
medium. Suspensions are systems with two distinct phases. The particles in
suspensions are bigger than 1000 nm. The particles of a suspension are
Introduction to colloid and … 2 Chapter - 1

visible to the naked eye or under a microscope. Suspensions are

heterogeneous systems. They stay only for a limited period i.e. these are not
stable as the particles have a tendency to settle down under the influence of
gravity. The particles of a suspension can neither pass through ordinary filter
paper nor through animal membranes, e.g. sand in water, oil in water.

1.1.3 Colloids
Colloids or Colloidal solutions, represent an intermediate kind of a
mixture between true solution and suspension [1]. The size of a colloidal
particle lies roughly between 1-1000 nm [2, 3]. Colloids are also a two-phase
heterogeneous system consisting of the dispersed phase (internal or
discontinuous phase) and dispersion medium (external or continuous
phase). Since the dispersed phase in a colloidal system is uniformly
distributed in the dispersion medium, the colloidal state appears
homogenous to the naked eye or even an ordinary microscope (due to
particles being invisible). However it is a heterogeneous dispersion of two
immiscible phases by viewing it under an ultra-microscope, where the light
reflected by colloidal particles can be seen. Colloidal particles do not settle
down under gravity. Colloids can pass through ordinary filter paper but do
not pass through animal membranes, e.g. a colloidal solution of gold.
Total interface area of the colloidal dispersed particles is very large due
to their submicroscopic size. The huge area-to-volume ratio determines
specific properties and behavior of colloids. In other words, as in the colloids
the amount of dispersed particles is very large, their overall surface is very
large too and by consequence the interaction of the two phases is important.
Because of the wide surface of contact between the two phases, often the
colloids are studied with the surface phenomena. Adsorption processes
occurring on the interface between the dispersed and continuous phases
exert considerable effect on the colloid physical properties, chemical
reactions in the system and its stability. Surface active substances added to
a colloid modify its properties.
Colloidal solutions, depending upon the nature of interactions
between dispersed phase and the dispersion medium, are classified into two
types as lyophilic (solvent loving) and lyophobic colloids (solvent hating).
Introduction to colloid and … 3 Chapter - 1

(a) Lyophilic colloids: “The colloidal solution in which the particles of the
dispersed phase have a great affinity for the dispersion medium, are called
lyophilic collodis.” In such colloids, the dispersed phase does not precipitate
easily and the colloids are quite stable. If the dispersion medium is
separated from the dispersed phase, the colloids can be reconstituted by
simply remixing with the dispersion medium [4]. Hence, these colloids are
reversible in nature, e.g. colloids of gum, polymers in organic solvents.
(b) Lyophobic colloids: “The colloidal solution in which there is no affinity
between particles of the dispersed phase and the dispersion medium are
called lyophobic colloids.” These colloids are easily precipitated on addition
of small amount of electrolytes, by heating or by shaking and therefore are
not stable. Once precipitated, it is not easy to reconstitute the colloid by
simple mixing with the dispersion medium. Hence these colloids are
irreversible in nature, e.g. colloids of metals.

Depending upon the physical state of dispersed phase and

dispersion medium whether these are solids, liquids or gases, eight types of
colloidal systems are possible as given in the table 1.1 [5].

Table 1.1 Types of colloidal systems

Dispersed phase
Medium / Phases
Gas Liquid Solid
NONE Solid aerosol
Liquid aerosol
(All gases are Examples: smoke,
Gas Examples: fog,
mutually cloud, air
hair sprays
miscible) particulates
Emulsion Sol
Foam
Dispersion Examples: Examples:
medium Liquid Example:
milk, hand pigmented ink,
Shaving cream
cream blood

Solid foam Gel

Solid sol
Solid Examples: Examples: jelly,
Example: glass
aerogel, silica gel
Introduction to colloid and … 4 Chapter - 1

1.2 Formation of Colloids

There are two basic methods for formation of colloids:
(i) Dispersion method where in the reduction of larger particles to colloidal
size occurs, e.g. by mechanical subdivision of larger particles or by
dissolution in the case of lyophilic sols.
(ii) Condensation method where in condensation of smaller particles (e.g.,
molecules) into colloidal particles occurs, e.g. from supersaturated solutions
or as the product of chemical reactions.
Some substances (e.g. glue) are easily dispersed (in the proper
solvent) to form a colloid; this spontaneous dispersion is called peptization.
Condensation of smaller particles to form a colloid usually involves chemical
reactions—typically displacement, hydrolysis, or oxidation and reduction.
When a condensation method is applied, molecules (or ions) are deposited
on nuclei, which may be of the same chemical species as the colloid
(homogeneous nucleation) or different (heterogeneous nucleation).

1.3 Shape of colloidal particles

It is general observation that the colloidal particles acquire spherical
shape. This is explained by the excess free surface 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 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.
The excess free energy makes the colloidal solutions
thermodynamically unstable. The process of lowering the excess free energy
and reducing the dispersity are the fundamental characteristics of all
colloidal solutions. If a colloidal solution remains unchanged in its chemical
composition, but changes its free energy characteristics, then this will result
in a change in colloidal properties.

1.4 Origin of charge on colloids

The origin of charges on colloidal particles arises due to friction
between the colloidal particles and molecules of the dispersion medium,
Introduction to colloid and … 5 Chapter - 1

preferential adsorption of ions from the solutions, dissociation of surface

molecules and by the simple process of electron capture. An ionic solution
adsorbs ions common to its own lattice structure e.g. AgCl particles can
absorb Cl- ions if excess of KCl solution is used for its preparation.
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 two phases are, in general,
different, one phase acquires a positive and the other a negative charge.
The charge on the colloidal particle is due to the presence of an electric
double layer of ions on its surface. Fig. 1.2 shows formation of electric
double layer on a particle of an aqueous sol of silicon dioxide due to
ionization.

H+
2−
(SiO3)
H+ H+

2−
2− (SiO3)
(SiO3)
H+ H+

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

2−
H+ (SiO3) H+
H+
H+

Fig. 1.2 Formation of electric double layer around a particle of silicon

dioxide in water

This charge gives rise to a potential gradient, called as Zeta potential

(ζ) in the sol as shown schematically in Fig. 1.3.
Introduction to colloid and … 6 Chapter - 1

Fixed layer

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

− + +
− +
− + + Zeta
− + +
ζ Potential
+
− + +
− +
− + +
− + + +
− + A +

Distance
Particle surface

Fig. 1.3 Variation of attractive potential due to the charge on the

ζ)
particle surface and Zeta potential (ζ

The double layer originates either upon selective adsorption of one

type of the ions of an electrolyte in a solution or owing to ionization of the
surface molecules of substances. The adsorbed ions repel the ions
possessing similar charge. These counter ions which compensate the
particle charge, are distributed non-uniformly throughout the solution.
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 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 [6].
Introduction to colloid and … 7 Chapter - 1

1.5 Forces of interaction between 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:

1.5.1 Van der Waals forces

If the particles don't have a permanent dipole, fluctuations of the
electron density gives rise to a temporary dipole in a particle. This
temporary dipole induces a dipole in particles nearby. The temporary dipole
and the induced dipole are attracted to each other. This is known as van der
Waal's force, and is always present, is short range, and is attractive. Van
der Waal's forces refer to the tendency of particles in nature to attract each
other weakly if they have no charge. Van der Waals forces are always
attractive between particles of the same nature. Hamaker [7] derived
equations for these forces on the basis of additivity of Van der Waals
energies between pairs of atoms or molecules, and assuming these
energies to be proportional to the inverse sixth power of the distance.

1.5.2 Electrostatic forces

The particles of a colloid selectively absorb ions and acquire an
electric charge. All of the particles of a given colloid take on the same charge
(either positive or negative) and thus are repelled by one another, due to the
interaction of the electrical double layers surrounding the particles, 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, φo, 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
Introduction to colloid and … 8 Chapter - 1

to the particle size, whereas the 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. For molecules of a simple monoatomic
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 > δ the interaction is
attractive, u(r)<0. At smaller separations, overlap of the electron orbital of the
two molecules give rise to a repulsion that increases very rapidly as the
separation decreases.

u(r) = 4∈ [ (δ/r) 12 − (δ/r)6 ] --- (1.1)

Where δ and ∈ give the measure of size and the strength of interaction
between the molecules respectively.

Repulsive Energy U2= B / r12

Potential energy U (r)

−A / r6) + (B / r12)
U (r) = (−

Umin ro Attractive Energy U1= −A / r6

Inter particle distance (r)

Fig. 1.4 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).

Fig. 1.4 shows the curve of potential energy of interaction against

distance r. At short distances, a deep potential energy minimum occurs, the
Introduction to colloid and … 9 Chapter - 1

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.

1.6 Molecular kinetic and optical properties of colloids

1.6.1 Brownian movement

Brownian movement was first discovered by Robert Brown, a
botanist, in 1827. He observed that pollen grains in water do not remain at
the rest but move continuously and randomly. This random continuous
movement (Brownian motion) was observed in colloidal sol when the sol was
viewed under an ultra microscope. Brownian motion is phenomena whereby
small particles suspended in a liquid tend to move in psuedo-random paths
through the liquid, even if the liquid is calm. Brownian motion in colloidal sol
arises due to the impact of the molecules of the dispersion medium with the
colloidal particles. It has been postulated that the impact of the molecules of
the dispersion medium on the colloidal particles are unequal. This leads to
the zig-zag (random) motion of the colloidal particles [8] as shown in fig. 1.5.
This random movement decreases as the size of the particles increases
because the effect of the impact average out. When the size of the dispersed
particles increases beyond the colloidal range, Brownian motion stops, i.e.
no Brownian movement is observed.

Fig. 1.5 Brownian motion

Introduction to colloid and … 10 Chapter - 1

The significant of Brownian movement is that

• It provides a direct demonstration of ceaseless motion of molecules as
postulated by kinetic theory.
• It counters the force of gravity acting on the colloidal particles and hence
helps in providing the stability to the colloidal sols by not allowing them to
settle down.
The scientist who made Brownian motion famous is Albert Einstein,
who brought the phenomenon to the attention of the larger physics
community.
The motion is characterized by the mean displacement ∆x of the
particle during time t. The chaotic motion of a particle occurs in a definite
volume of space that grows with time. Unlike the real path of a particle,
which changes its direction up to 1020 times a second, the averaged
quantity, ∆x will be zero since both positive and negative displacements are
equally probable. Hence, the mean square displacement ∆X2 is calculated
proceeding from the statistical laws. It is given by

∆X12 + ∆X22 + ∆X32 + ……

∆X2 = ---- (1.2)
n

Where, n is the number of particles considered and ∆Xi2 is the square of the
displacement of the ith particle.
For a spherical particle of radius r, the mean square displacement is
directly proportional to the absolute temperature, T, the duration of
observation, t and inversally proportional to the coefficient of hydrodynamic
resistance of the medium, ω= 6πηr, where η is the coefficient of viscosity.

2
bTt
∆X = ---- (1.3)
6πηr
For the proportionality factor b Einstein theory gives the expression:

b = 2R/ NA = 2K ---- (1.4)

where, R is the molar gas constant, NA is the Avogadro constant and k is the
Boltzmann constant. Consequently, the final expression for the mean square
displacement is:
Introduction to colloid and … 11 Chapter - 1

kTt
∆X2 = ---- (1.5)
3πηr

Hence it showed that motion became more rapid and the particles moved
farther in a given time interval when the temperature of the water was raised,
when the viscosity of the fluid was lowered, or when the size of the particles
was reduced.

1.6.2 Diffusion
Diffusion is a spontaneous, natural process leading to the transport of
atomic, ionic or molecular species, across a gradient of concentration.
Random walks under the ever-present thermal fluctuations let the species
undergo a statistical displacement or diffusion down the concentration setup
in the medium. Through the process an inhomogeneous system at local
equilibriums return to its overall equilibrium by homogenization of the values
of the intensive parameters. So, the phenomenon of diffusion basically
involves mass transfer.
In the absence of any external fields, the chemical potential, µi, of the
substance within a phase at equilibrium is constant. If for some reason the
value of µi vary from place to place, then the substance 'i' will tend to diffuse
in such a way as to equalize the value of µ through out the phase. The
driving force (Fd) for the diffusion process is the gradient of µi – larger it is,
the faster is the diffusion process. For one dimensional process the force Fd
is given as

Fd = −dµi / dx ---- (1.6)

Further, Fick’s first law describes steady state diffusion of atomic or

molecular species under their concentration gradients. The diffusion flux in
one dimensional case is expressed as,

J = - D ( ∂C/∂x ) ---- (1.7)

where, J is the diffusion flux (quantity of material that crosses a plane of unit
area perpendicular to the diffusion direction for time unit); D is the diffusion
Introduction to colloid and … 12 Chapter - 1

coefficient or diffusivity of the dispersed phase; ∂C/∂x is the concentration

gradient in the diffusion direction.
Fick’s second law describes the diffusion under non-steady state
solution, when the concentration of diffusing species is time (t) dependent.
Within a volume element inside the medium, any accumulation or release
can be accounted by the imbalance of incoming or outgoing fluxes of
diffusing species and is expressed as,

∂C/∂t – D (∂2C/∂x2) = 0 --- (1.8)

The equation being asymmetric in time flow expresses irreversibility in

diffusion process.
Due to Brownian motion the colloidal particles are capable to move
(diffuse) from the regions with higher concentration to the regions with lower
concentration of the dispersed phase. Because of their bigger sizes colloidal
particles move slowly and diffuse at a slower rate. Since the diffusion
coefficient is lower for the greater particles the concentration gradient is
smaller for the colloids with finer dispersed phase. The diffusion coefficient
for colloidal system:

D = kBT /(6πµr) ---- (1.9)

where, kB is Bolzman constant (1.38X10-3 J/K), T is the temperature (K), µ

is the dynamic viscosity of the dispersion media (Pas) and r is the radius of
the particles.
Outside force applied to the colloidal particles causes their
sedimentation towards the force direction and gravity force causes the
dispersed particles to sediment to the bottom. But, diffusion counteracting to
any directed force prevents complete concentration of the dispersed phase
at the bottom.

1.6.3 Tyndall effect and Rayleigh scattering

The optical properties of the colloidal substance are of practical
importance for studying their structure, determining size and shape of the
particles and also their concentration.
 Introduction to colloid and … 13 Chapter - 1

Although a colloidal solution appears to be homogeneous because

the dispersed particles are too small too be seen, it can be distinguished
from a true solution by its ability to scatter light. The scattering of light by
colloidal particles is called the Tyndall effect. This effect was first observed
by Tyndall in 1869. When a strong beam of light was passed through a
colloidal sol placed in a dark place, then the path of beam got illuminated
and this illuminated path is called Tyndall cone. Tyndall effect is not shown
by true solutions because the ions or solute molecules are of such minute
sizes that they cannot reflect light. Fig. 1.6 shows scattering of light by a (a)
true solution and (b) colloidal dispersion. The Tyndall effect can therefore be
used to distinguish between a true solution and a colloidal solution. The hazy
illumination of the light beams from the headlights of a car on a dusty road is
a familiar example of Tyndall effect. Blue colour of sky and seawater,
twinkling of stars and visibility of tails of comets are also due to scattering of
light of Tyndall effect.

True Solution Colloidal Solution

(a) (b)

Fig 1.6 Scattering of light by (a) true and (b) colloidal solutions (Tyndall Effect)

The theory of light scattering was developed by Lord Rayleigh for

spherical non-conducting particles that do not absorb light. This scattering
results from the interaction of light with inhomogenities in solid, liquid, or
gaseous materials. The actual entities that causes scattering, called
scattering center, can be as small as single large molecules arranged in a
non-uniform way. However, scattering becomes more effective when the
size of scattering center is similar to wavelength of incident light. When a
light wave passes through a medium containing non-conducting particles,
the time varying electromagnetic field polarizes them. The so formed dipoles
become source of light emission. In a homogeneous medium, the light
Introduction to colloid and … 14 Chapter - 1

emitted by all the dipoles propagates only in the initial direction due to
interference. On the other hand, if the medium containing heterogeneities
with a different refractive index, as in colloidal systems with density
fluctuations, the value of the dipole moment at these nodes becomes
different and dipole emit non-compensated radiation in the form of scattered
light. According to Rayleigh, the intensity of the scattered light, I, is given by
the equation;

24 νπ3 v 2 n12 – n02

I= I0 ---- (1.10)
λ4 n12 + 2n02

Where, n and n0 are refractive indices of the dispersed phase and the
dispersing medium; λ is the wavelength; v is the volume of the particle and ν
is the particle concentration.

1.7 Coagulation of colloidal particles

Coagulation is the process of formation of aggregates of colloidal
particles, which stick together under the action of forces of molecular
attraction, in the course of Brownian motion. Coagulation can be either rapid
or slow. Rapid coagulation occurs when all the particles in Brownian motion
stick together as they approach each other. In slow coagulation, only some
particles stick together upon approach because the electric double layer
partially remains on the surface of colloidal particles. The reversal of
coagulation or flocculation is the dispersion of aggregates to form a
colloidally stable suspension or emulsion is called deflocculation or
peptization. The rate of aggregation is determined by the frequency of
collisions and the probability of cohesion during collision. If the collisions are
caused by Brownian motion, the process is called perikinetic aggregation, if
by hydrodynamic motion (i.e. convection or sedimentation), the process is
called orthokinetic aggregation.
Coagulation causes the destabilization of colloids by neutralizing the
electric charge of the dispersed phase particles, which results in aggregation
of the colloidal particles. The purpose of most coagulant chemicals is to
neutralize the negative charges on the turbidity particles to prevent those
Introduction to colloid and … 15 Chapter - 1

particles from repelling each other. The amount of coagulant which should
be added to the water will depend on the zeta potential, a measurement of
the magnitude of electrical charge surrounding the colloidal particles. It is
the amount of repulsive force which keeps the particles in the water. If the
zeta potential is large, then more coagulants will be needed. Coagulants
tend to be positively charged. Due to their positive charge, they are
attracted to the negative particles in the water. The combination of positive
and negative charge results in a neutral, or lack, of charge. As a result, the
particles no longer repel each other.

1.8 Sedimentation of colloidal particles

Sedimentation is the settling of suspended particles under the action
of gravity or a centrifugal field. If the concentration of particles is high and
interparticle forces are strong enough, the process of sedimentation may be
better described as compaction of the particle structure with pressing out of
the liquid. This particular kind of settling is also called subsidence.
The rate of sedimentation can be greatly increased using high speed
ultra centrifuge. The force of gravity, F, is directly proportional to the effective
mass, (m-m0), of the particle. Then, F= g (m-m0) where m is the mass of the
particle, m0 is mass of the dispersing medium in the volume of the particle
and g is the acceleration due to gravity. Sedimentation also depends on the
radius of the particle, r, which is given by the equation:

r = [ 9ηh/ 2t( d-d0) g]1/2 ---- (1.11)

where η, is the viscosity of the medium, h is height, t is the time for setting
(sedimentation time), d is the density of the particle and d0 is the density of
the medium. Hence, a growth in dispersity is followed by a sharp decrease in
the setting speed and for colloidal particles the setting time is months and
years. The following table gives the settling time of a sand particle in water to
a depth of 10 cm.

Radius (µm) 50 10 5 1 0.1

Time 12 Sec 5 min 20 min 8.3 hrs > 1 month
Introduction to colloid and … 16 Chapter - 1

1.9 Sol-Gel Processing

Sol-gel synthesis encompasses a wide range of organic, inorganic
and organic-inorganic porous materials which share a common preparation
strategy. Generally, the sol-gel process involves the evolution of inorganic
networks through the formation of a colloidal suspension (sol) and gelation of
the sol to form a network in a continuous liquid phase (gel). The sol-gel
process always consists in selecting the precursor of the required material,
water and catalysts.
• Precursor : It is the precursor that, by its chemistry, leads the reaction
towards the formation of colloidal particles. The precursors for
synthesizing these colloids consist of a metal or metalloid element
surrounded by various reactive ligands. Alkoxides are most popular
because they react readily with water. For example Tetraethoxysilane
(TEOS), Tetramethoxysilane (TMOS). Also, the inorganic precursor
Sodium silicate (Na2SiO3) is also used in sol-gel processing.
• Water : The complete hydrolysis and polycondensation of the precursor
takes place in presence of water only. Further, water is a side product of
condensation and, hence, its excess should promote the reverse reaction,
i.e., the hydrolysis of siloxane bonds.
• Catalyst : The kinetics of the reaction are impracticably slow at room
temperature, often requiring several days to reach completion. For this
reason acid or base acatlysts are added to the formulation. The amount
and type of catalyst used play key role in the microstructural, physical and
optical properties of final product. Catalysts promote the hydrolysis of the
precursors and render it more complete. Various mineral and carboxylic
acids can be applied in the sol-gel synthesis.
Sol-Gel processing designates a type of solid materials synthesis
procedure, performed in a liquid and at low temperature (typically T < 100
°C). The solid is formed as the result of a polymerization process which
involves the establishment of M-OH-M or M-O-M bridges between the
metallic atoms M of the precursor molecules. Such transformations are the
equivalent of the polymerization process well-known to occur in organic
chemistry and which consists of the establishment of direct bonds between
Introduction to colloid and … 17 Chapter - 1

the carbon atoms of organic precursors. Regarding inorganic gels, that is to

say mostly oxides, independent solid colloidal particles (i.e., nanoparticles
with a size below a micrometer) are often formed, in a first step of the
process. Each colloidal particle has a more or less densely crosslinked
internal structure, as illustrated in fig. 1.7 a. It is usually easy to maintain
such particles in a dispersed state in the solvent, in which case a colloidal
suspension also termed a sol is obtained. In a second step, these colloidal
particles can be made to link with each other, while they are still in the
solvent, so as to build a three-dimensional open grid, termed a gel (fig. 1.7
b). The transformation of a sol to a gel constitutes the gelation process [9].

(a) Sol (b) Gel

Fig. 1.7 The sol-gel process, (a) sol, (b) gel

The general hydrolysis and condensation reactions are given below:

Hydrolysis:
≡ M − X + H2O ≡ M −OH + HX ---- (1.12)

M = metal or Si ; X = reactive ligand like halogen, OR, NR2, acylate

Condensation:
Alcohol condensation
≡ M − OH + X−M ≡ ≡ M −O− M ≡ + HX ---- (1.13)
Water condensation
≡ M − OH + HO−M ≡ ≡ M −O− M ≡ + H2O ---- (1.14)
Introduction to colloid and … 18 Chapter - 1

1.9.1 Sol
A sol is a dispersion of colloidal particles suspended in Brownian
motion within a fluid matrix. Suspension of particles of linear dimensions
between 1nm (10 Ao) and 1µm (104Ao) are called colloids [10]. The particles
in this proper size range can be divided into three categories. They can be
either composed of subdivided parts of bulk mater (e.g. small particles of
alumina), or real macromolecules that are big enough to be colloidal (such
as proteins), or of small particles that can be considered both
macromolecules and as tiny parts of macroscopic matter (e.g. lacy particles).
In the case of subdivided parts of bulk material, there are two
thermodynamic phases and the sol is considered as lyophobic, or
hydrophobic if water is the main solvent used.

1.9.2 Gelation
Gelation occurs when links form between silica sol particles, produced
by hydrolysis and condensation reactions, to such an extent that a giant
spanning cluster reaches across the containing vessel. At this point,
although the mixture has a high viscosity so that it does not pour when the
vessel is tipped. Many sol particles are still present as such, entrapped and
entangled in the spanning cluster. This initial gel has a high viscosity but low
elasticity. There is no exotherm or endotherm, nor any discrete chemical
change at the gel point, only the sudden viscosity increase as shown in fig.
1.8.
Viscosity (mPas.s)

Elasticity (Pa)

Fig. 1.8 Change in viscosity and elasticity of the sol with time
Introduction to colloid and … 19 Chapter - 1

Following gelation, further cross-linking and chemical inclusion of

isolated sol particles into the spanning cluster continues, leading to an
increase in the elasticity of the sample. Precise definition of the term
“gelpoint” is the time interval starting from the moment of sol preparation to
the moment no more fluidity of the sol [11].
Fig. 1.9 depicts the bond formation between two colloidal silica
particles while gelation takes place.

Fig. 1.9 Bond between two colloidal particles

The kind of inorganic network formed by the condensation reactions

not only depends on the absolute rates of the individual reactions but also on
the relative rate of hydrolysis and condensation reactions as illustrated in fig.
1.10 [12].
Acidic conditions (pH 2–5) favor hydrolysis, and condensation is the
rate-determining step. A great number of monomers or small oligomers with
reactive Si–OH groups are simultaneously formed. Under these conditions,
reactions at terminal silicon atoms are favored, and chains with few
branches are formed. This results in polymer like networks with small pores.
Hydrolysis is the rate-determining step under basic conditions, which
favor reaction at central silicon atoms of an oligomer. The resulting network
has a particulate character with large particles and large pores (“colloidal”
gels). Hydrolyzed species are immediately consumed because of the faster
condensation reaction. Condensation of clusters with each other is relatively
Introduction to colloid and … 20 Chapter - 1

unfavorable. Therefore, the clusters mainly grow by the condensation of

monomers.

Fig. 1.10 Dependence of the relative hydrolysis and condensation

reaction on the pH of the sol

1.9.3 Gel
A gel is a porous 3-dimentionally interconnected semi-solid network
that expands in a stable fashion throughout a liquid medium and is only
limited by the size of the container. The nature of gels depends on the
coexistence between the solid network and the liquid medium. The liquid is
present between the mesh of the solid network that composes the gel; it
does not flow out spontaneously and is in thermodynamic equilibrium with
the solid network. A gel is a soft material that can be easily cut with a knife.
Finally, removal of the liquid phase leads to the xerogel or aerogel which
depends upon the drying conditions of the gel.

1.10 Types of gel

Depending on the way of formation of gel network, the gels are
classified as colloidal and polymeric gels.
1.10.1 Colloidal gel : Systems containing colloidal particles (1-1000 nm) upon
aggregation and condensation are linked into a three dimensional network
Introduction to colloid and … 21 Chapter - 1

surrounded by liquid phase are termed as colloidal gels. Theses gels are
formed from sol particles and are also known as corpuscular gel.
1.10.2 Polymeric gel : These are considered as suspensions of highly
branched macromolecules in which individual particles cannot be
distinguished. If the solid network is made up of sub-colloidal chemical units
then the gel is polymeric. A polymer, as defined by the Flory is a group of
molecules whose structure can be generated through repetition of one or a
few elementary units [13]. The solubility of these macromolecules in a water-
alcohol acid medium prevents the transformation of these chains into
individual particles. They are directly formed gels from rather linear polymer
formed from a precursor solution, without the intermediate occurrence of
individual particles.
Further depending on the fluid present in the pores of gels, they are
classified as given in the table 1.3.

Table 1.3 Types of gel

Fluid Gel
Water Hydrogel / Aquagel
Alcohol Alcogel
Air Aerogel

1.11 Advantages of sol-gel processing

Sol–gel synthesis is one of the pursuits of modern materials science.
This method is widely used in practice owing to the large number of
advantages over the traditional synthesis of materials from powders. These
advantages are as follows [14]:
(i) the simplicity of purification of initial metal alkoxides (in the
case of synthesis of xerogels by hydrolysis and
polycondensation of alkoxides),
(ii) a high degree of homogeneity in a multicomponent system,
(iii) a considerable decrease in the expenditure of energy upon
sintering of colloidal particles due to their high surface energy,
Introduction to colloid and … 22 Chapter - 1

(iv) the possibility of producing noncrystalline systems whose

synthesis by traditional methods leads to the phase separation
or crystallization,
(v) the possibility of retaining the shape and volume from the
pouring of a liquid sol to the preparation of a final product, and
(vi) a sufficiently large amount of information in the field of
preparation technology.
Due to possibility of obtaining high surface area solids with
homogeneous compositions and controlled porosity, sol-gel methods have
been widely employed for the synthesis of micro and mesoporous materials.
There are three strategies that enable to control the pore size:
• Solvent-templating of the silica framework (Aerogel, Xerogel)
• The preparation of hybrid organic-inorganic membranes followed by the
extraction of the organic constituents that serves as micropore templates.
• Surface derivatization of preformed pore networks with well-defined
molecular species.
Introduction to colloid and … 23 Chapter - 1

References
[1] T. Graham, J. Chem., 17 (1864) 318
[2] G. I. Brown, “Introduction to Physical Chemistry”, 3 ed. Longman Group
(F.E.) Ltd. Hong Kong (1983)
[3] P.A. Rehbinder and G.J. Fuchs (eds.): “Uspekhi Kolloidnaya Khimii
(Advances in Colloid Chemistry)”, Nauka, Moscow (1973)
[4] D. V. S. Jain, S. P. Jauhar "Physical chemistry principles and problems",
Tata Mc Graw Hill Publishing Company Ltd., New Delhi, (1988)
[5] R. J. Hunter, Foundations of Colloid Science, 2nd edition, Oxford
University Press, (2001) 3
[6] J. Lyklema, Faraday Soc. Disc., 52 (1971) 318
[7] H. C. Hamker, Rec, Trav. Chim., 55 (1936) 1015
[8] M. V. Smoluchowski, Z. Physik Chem., 92 (1917) 129
[9] G. M. Pajonk, Heterog. Chem. Rev., 2 (1995) 129
[10] D. J. Shaw, “Colloid and Surface Schemistry”, Butterworth, 4th ed.,1992
[11] M. W. Colby, A. Osaka, J. D. Mackenzie, J. Non-Cryst. Solids,
82 (1986) 37
[12] J. Livage, M. Henry, C. Sanchez, Prog. Solid St. Chem., 18 (1988) 259
[13] J. P. Flory, Disc. Faraday Soc., 57 (1974) 7
[14] N. N. Khimich, Glass Phys. and Chem., 5 (2004) 430
Introduction to colloid and … 24 Chapter - 1