Precipitation from Solution

Two basic steps

nucleation of fine particles
their growth by addition of more material to the surfaces.

Control of the powder characteristics requires

control over both
Nucleation
Homogeneous nucleation
No foreign inclusions in the solution or on the walls of the
reaction vessel
Is the most common case

Heterogeneous nucleation
Inclusions are present and act to assist the nucleation
Good for coated particle and monodispersed particles

Nucleation
Density fluctuations produce clusters of atoms
referred to as embryos, which can grow by
addition of atoms
Embryos with a radius r less than a critical
radius rc cannot grow whereas embryos with r
rc can.
formation of nuclei (i.e.,embryo) requires an
energy barrier to be surmounted.
spherical nucleus of radius r is assumed.

Unstable/
dissolution

Stable/growth

Free energy on second phase formation

S
the contribution by the
bulk free energy change
Intrinsically positive contribution
of the surface free energy

r=particle size
=Specific surface energy
(solid liquid interphase)
S=Degree of supersaturation,
S=K/Keq
K=Reaction constant
Keq=Equilibrium reaction
constant

Is the most important

term we control in
particle systhesis from
solution

Supersaturation
For the limiting cases
Supersaturation ratio S =1, the bulk term
vanishes and Gn increases monotonically
as a parabola.
For S<1, the Gn curve rises more steeply
because a fractional S makes the second
term on the right go positive, reinforcing
the effect due to the surface free energy
barrier.
For S>1, the second term is negative and
this assures the existence of a maximum
in Gn at some critical radius rc,
The critical radius rc is obtained by
putting d(Gn)/dr = 0,

Unstable/
dissolution

Stable/growth

Sufficient increase in the supersaturation ratio S finally serves to increase the

atomic (molecular) bombardment rate in the new enbriyo to reduce Gc and rc
to such an extent that the probability of subcritical embryo growing to
supercritical size in a short time approaches unity. Homogeneous nucleation
to form liquid droplets now becomes an effective process.

Nucleation Rate
Nucleation rate of particles from solution
Supersaturation

N= is the number of ions per unit volume in the solution

s is the volume of a molecule in the solid phase
is the specific energy of the solidliquid interface
Ga is the activation energy for the transport of an ion to the solid surface
Css is the supersaturated concentration,
Cs is the saturated concentration of the ions in the solution.
S= Css/Cs
The nucleation rate is strongly dependent on the supersaturation ratio
Css/Cs

Particle Growth by Solute

Precipitation
Nuclei formed in a supersaturated solution can grow by
transport of solute species (ions or molecules) through the
solution to the particle surface, desolvation, and alignment on
the particle surface.

The rate-determining step in the growth of the particles

Diffusion towards the particle (Diffusion-controlled growth)
Addition of new material to the particle by a form of
surface reaction

Diffusion-controlled growth
The diffusion of solute species towards the particle (assumed
to be spherical of radius r) can be described by Ficks first
law
The flux J through any spherical shell of radius x is given by
D is the diffusion coefficient for the solute through the solution and C is its
concentration.

The rate of growth of the particle radius is then:

or
Vs is the molar volume of the solid precipitating on the particle

For diffusion controlled growth, d(r2)/dt is the same for particles of

any size

Surface-reaction-controlled
growth
Each new layer around the particle has to be nucleated first
by a process that is different from the homogeneous
nucleation discussed earlier.

Main Difference
In the mononuclear growth
mechanism, once a nucleation
step is formed on the particle
surface, a layer has the time to
achieve its completion before a
new step appears.

mononuclear growth

polynuclear growth

Therefore,
In the mononuclear growth
Growth proceeds layer by
layer and the particle
surface may appear
faceted on a macroscopic
scale.

Controlled Particle Size

Distribution, LaMer diagram
Nuclaetion Time

t0
t1

t2
t3

To produce particles with a fairly

uniform size, then one short burst of
nucleation should occur in a short
time interval, t2 and t1, so that all
particles grow to the same size in
the same time interval.

Particle size distribution

If continuous nucleation occurs

wide range of particle size
distribution is obtained because
growth interval for each particle
is different

Controlled Particle Size

Distribution, LaMer diagram
As the reaction proceeds, the concentration of the solute to be
precipitated, Cx, increases to or above the saturation 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
concentration 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 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.

LaMer diagram explanation

Particle Growth by
Ostwald Ripening/Coarsening
Smaller particles dissolve and the solute precipitates on the larger
particles.
Matter transport from the smaller particles to the larger particles can be
controlled by (1) diffusion through the liquid or (2) an interface reaction
(dissolution of the solid or deposition of the solute onto the particle
surfaces).
The average radius <r>
<r0> 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).
The maximum radius of the distribution is 2<r> for the interface reaction
mechanism and (3/2)<r> for the diffusion mechanism.
Ostwald ripening by itself cannot, therefore, lead to a monodisperse
system of particles.

Procedures for Precipitation

from Solution
Hydrolysis of Solutions of Metal Alkoxides

Most metal alkoxides hydrolyze readily in the presence of water, so that

stringent conditions must be maintained to achieve powders with
controlled characteristics.
The reactions are sensitive to the concentration of the reactants, the pH,
and the temperature. Oxide or hydrated oxide powders are produced.
The precipitated particles are commonly amorphous and can be
agglomerates of much finer particles

Procedures for Precipitation

from Solution
Hydrolysis of Solutions of Metal Salts
wider range of chemical compositions, including oxides or hydrous
oxides, sulfates, carbonates, phosphates, and sulfides.
Requires control over concentration of the metal salts, the chemical
composition of the salts used as starting materials, the temperature,
the pH of the solution, and the presence of anions and cations that
form intermediate complexes.
A variety of particle sizes and shapes can be produced

Procedures for Precipitation

from Solution
Ceramic powder precursors (sufates, carbonates, oxalates,
hydroxades, etc) are produced by precipitation, later they are
thermally decomposed to their oxides in a separate step.
These precipitated precursors are Sparingly Soluble (almost
insoluble) in the liquid medium. This is how supersaturation is
achieved for precipitation.

First
A soluble precursor is dissolved (nitrites, chlorides,etc.)

Then
a chemical compound (NaOH, Nh4OH, urea, oxalate etc) is added to the
solution that forms sparingly soluble metal precursors (metal-hyrdroxide, or
metal-carbonate, or metal oxalate),
Precipitated precursor is separated out

Last
Thermal decomposition to the desired phase (Calcination)

Procedures for Precipitation

from Solution
Example
Precipitation Aluminum hyroxide from AlCl3
aluminium chloride+sodium hydroxide=aluminium hydroxide+ sodiumchloride
AlCl3(aq)
+
3NaOH(aq) =
Al(OH)3(s)
+
3NaCl(aq)
The ionic equation is Al3+(aq) + 3OH-(aq) = Al(OH)3(s)
Al2(SO4)3(aq) + 6NaOH(aq) = 2Al(OH)3(s) + 3Na2SO4(aq)

Precipitation Calcium Carbonate

Ca(NO3)2(aq) + K2CO3(aq) = CaCO3(s) + 2KNO3(aq)

Soluble in H2O

CALCINATION is
required

Precipitation Aluminum hyroxide from Al2(SO4)3

Sparingly soluble in H2O

Therefore, precipitation due to

supersaturation
Pure solid product is obtained impurities are rejected to supernatant

Precipitation of Complex Oxides

Such as titanates, ferrites, and aluminates that contain more than
one type of metal in the chemical formula.
Coprecipitation from a solution of mixed alkoxides, mixed salts, or
of a combination of salts and alkoxides
A common problem in coprecipitation is that the different reactants
in the solution have different hydrolysis rates, which results in
segregation of the precipitated material.
MgAl2O4 by coprecipitation
AlCl3(aq)
+
3NaOH(aq) =
Al(OH)3(s)
+
3NaCl(aq)
MgCl2(aq)
+
2NaOH(aq) =
Mg(OH)3(s) +
2NaCl(aq)
An intimate micture of Al(OH)3 and Mg-Al double hydroxide 2Mg(OH)2
Al(OH)3 is produced at pH of 9.510.
Calcination of the precipitated mixture above 400C yields stoichiometric
MgAl2O4 powder with high purity and fine particle size.

Usually, with coprecipitation the final compound is NOT obtained,

requires an extra heat treatment (calcination)

Coprecipitation, Important note

The co-precipitation technique generally produces an intimate
mixture of precipitates.
In many cases, the mixture has to be calcined at elevated
temperature in order to produce the desired chemical composition.
One serious consequence is the need for milling of the calcined
powder, which can introduce impurities into the powder.
The preparation of lead lanthanum zirconium ttiatante (PLZT)
powders is a good example illustrating the combined use of coprecipitation, calcination, and milling.
There are many more powder synthesis methods like sol-gel, gas
phase reaction etc.
Each method is not applicable to all ceramic powders
Each method has its own advantages and disadvantages

Coprecipitation, Important note