Synthesis of Powders 83

FIGURE 2.18 Nucleation of layers around a particle for (a) mononuclear growth and
(b) polynuclear growth.

and increases in the ratio r/r0. In the polynuclear growth mechanism, formation
of nucleation steps on the particle surface is fast enough to create a new layer
before the previous one has been completed. The growth rate is independent of
the surface area of the existing particles and is given by (40)

dr
= K2 (2.34)
dt
where K2 is a constant. In this case, the relative width of the distribution decreases
according to

∆r r0 ∆r0
=
r r r0 (2.35)

Controlled Particle Size Distribution

The basic principles for obtaining particles with a fairly uniform size by precipita-
tion from solution were put forward nearly 50 years ago by LaMer and Dinegar
(52). The main features may be represented in terms of the diagram shown in
Fig. 2.19, often referred to as the LaMer diagram. As the reaction proceeds, the
concentration of the solute to be precipitated, Cx, increases to or above the satura-
tion value Cs. If the solution is free of foreign inclusions and the container walls
are clean and smooth, then it is possible for Cx to exceed Cs by a large amount
to give a supersaturated solution. Eventually a critical supersaturation concentra-
tion Css will be reached after some time t1 and homogeneous nucleation and
growth of solute particles will occur, leading to a decrease in Cx to a value below
84 Chapter 2

FIGURE 2.19 Schematic representation of the solute concentration versus time in the
nucleation and growth of particles from a solution. (From Ref. 52.)

Css after a time t2. Further growth of the particles occurs by diffusion of solute
through the liquid and precipitation on to the particle surfaces. Finally, particle
growth stops after a time t3 when Cx = Cs.
It is clear that if we wish to produce particles with a fairly uniform size,
then one short burst of nucleation should occur in a short time interval, t2 ⳮ t1.
One way of achieving this is through the use of a fairly low reactant concentration.
Furthermore, uniform growth of the particles requires that the solute be released
slowly to allow diffusion to the particles without buildup of the solute concentra-
tion and further bursts of nucleation. This mechanism of nucleation followed by
diffusion-controlled growth does not apply to the formation of particles that are
aggregates of finer primary particles. Instead, it may apply only to the primary
particles.
Particle Growth by Aggregation
High-resolution electron micrographs of particles synthesized by several routes
involving precipitation from solution show that the particles consist of aggregates
of much finer primary particles. Titania particles prepared by the Stober process
show primary particle features that are smaller than ⬃10 nm (Fig. 2.20a). The
TEM of CeO2 particles synthesized by hydrolysis of cerium nitrate salts in the
presence of sulfate ions (53) show that the hexagonal particles consist of smaller
primary particles with a spherical shape (Fig. 2.20b). Based on studies of SiO2
particle synthesis by the Stober process, Bogush et al. (54,55) put forward a
model in which particle growth occurs by aggregation of fine particles rather
than by diffusion of solute to existing particles. Using the DLVO theory for
Synthesis of Powders 85

FIGURE 2.20 (a) Scanning electron micrograph of TiO2 particles prepared by the Stober
process showing that the particles consist of much finer primary particles. (Courtesy of
A. M. Glaeser.) (b) Transmission electron micrograph of hexagonal CeO2 particles synthe-
sized by hydrolysis of cerium nitrate salts in the presence of sulfate ions showing that the
hexagonal particles consist of much smaller primary particles with a spherical shape.
(From Ref. 53.)

colloid stability (see Chapter 4), they showed that under identical surface charge
densities, the barrier to aggregation increases with the size for two equal-size
particles so that their rate of aggregation decreases exponentially. However, fine
particles aggregate more quickly with large particles than they do with themselves.
According to the model, during a precipitation reaction, the first nuclei grow
rapidly by aggregation to a colloidally stable size. These particles then sweep
through the suspension, picking up freshly formed nuclei and smaller aggregates.
The formation of particles with uniform size is thus achieved through size-depen-
dent aggregation rates.
Particle Growth by Ostwald Ripening
Particles in a liquid can also grow by a process in which the smaller particles
dissolve and the solute precipitates on the larger particles. This type of growth,
better described as coarsening, is referred to as Ostwald ripening. The coarsening
of precipitates in a solid medium can occur by a similar process and the theory of
Ostwald ripening, sometimes referred to as the Lifshitz-Slyozov-Wagner (LSW)
theory, is described in detail in Chapter 10. Matter transport from the smaller
particles to the larger particles can be controlled by (1) diffusion through the
86 Chapter 2

liquid or (2) an interface reaction (dissolution of the solid or deposition of the

solute onto the particle surfaces). The average radius ⬍r⬎ of the particles (as-
sumed to be spherical) is predicted to increase with time t according to

〈 r 〉 m = 〈r0 〉 m + Kt (2.36)

where 〈r0典 is the initial average radius of the particles, K is a constant that obeys
the Arrhenius relation, and m is an exponent the depends on the mechanism (m =
2 for interface reaction control and m = 3 for diffusion control). Regardless of
the initial size distribution, the particle size distribution reaches a self-similar
distribution since it depends only on r/〈r典 and is independent of time. The maxi-
mum radius of the distribution is 2〈r典 for the interface reaction mechanism and
(3/2)〈r典 for the diffusion mechanism. Ostwald ripening by itself cannot therefore
lead to a monodisperse system of particles.
Procedures for Precipitation from Solution
The most straightforward use of precipitation is for the preparation of simple
oxides or hydrous oxides (also referred to as hydroxides or hydrated oxides).
Precipitation is commonly achieved by hydrolysis reactions. Two main routes
can be distinguished:
1. Hydrolysis of metal-organic compounds (e.g., metal alkoxides) in al-
coholic solution, generally referred to as the Stober process and
2. Hydrolysis of aqueous solution of metal salts (where considerable
work has been done by Matijevic)
Hydrolysis of Solutions of Metal Alkoxides
Metal alkoxides have the general formula M(OR)z, where z is an integer equal
to the valence of the metal M, and R is an alkyl chain (see Chapter 5). They can
be considered as derivatives of either an alcohol, ROH, in which the hydrogen
is replaced by the metal M, or of a metal hydroxide, M(OH)z, in which the
hydrogen is replaced by an alkyl group. The reactions involve hydrolysis:

M ( OR)z + xH2 O → M (OR)z − x ( OH )x + xROH (2.37)

followed by condensation and polymerization by dehydration:

− M − OH + HO − M − → − M − O − M − + H2 O (2.38)

Stober et al. (56) carried out a systematic study of the factors that control the
preparation of fine, uniform SiO2 particles by the hydrolysis of silicon alkoxides
in the presence of NH3. The NH3 served to produce pH values in the basic range.
For the hydrolysis of silicon tetraethoxide, Si(OC2H5)4, referred to commonly as
TEOS, with ethanol as the solvent, the particle size of the powder was dependent