Freeze Drying

A solution of metal salt is broken up by an atomizer into fine droplets,

which are then frozen rapidly by being sprayed into a cold bath of
immiscible liquid such as hexane and dry ice or directly into liquid nitrogen
The frozen droplets are then placed in a cooled vacuum chamber and the
solvent is removed, under the action of a vacuum, by sublimation without
any melting.
The technique produces spherical agglomerates of fine primary particles
with the agglomerate size being the same size as that of the frozen
droplets.
The size of the primary particles (in the range of 10500 nm) depends on
the processing parameters such as the rate of freezing, the concentration
of metal salt in the solution, and the chemical composition of the salt.
After drying, the salt is decomposed at elevated temperatures to produce
an oxide.

Synthesis of Powders
The solubility of most salts decreases with temperature and the rapid
cooling of the droplets in freeze drying produces a state of supersaturation
of the droplet solution very rapidly.
Particle nucleation is therefore rapid and growth slow so that the size of
the particles in the frozen droplet can be very fine.
When compared to the evaporation of the liquid in spray drying, the
approach to supersaturation is relatively faster so that freeze drying
produces much finer primary particles with a higher surface area per unit
mass.
Freeze drying of solutions has been used on a laboratory scale for the
preparation of ferrite and other oxide powders.
Finally, as we outlined for spray drying, the freeze drying technique is also
used for drying slurries.

Gel Routes
The formation of the gel or resin, mixing of the constituents occurs on the
atomic scale by a polymerization process.
Provided none of the constituents are volatilized during the
decomposition and calcination steps, then the cation composition of the
pow- der can be identical to that of the original solution.
A drawback is that the decom- position product is commonly not in the
form of a powder but consists of charred lumps.
These lumps have to be ground and calcined to achieve the desired
powder characteristics.
Gel routes to ceramic powders are currently used mainly at the laboratory
scale.

SolGel Processing
1. The Pechini Method
The method has since been applied to many complex oxide
compositions
Metal ions from starting materials such as carbonates, nitrates, and
alkoxides are complexed in an aqueous solution with -carboxylic acids
such as citric acid.
When heated with a polyhydroxy alcohol, such as ethylene glycol,
polyesterification occurs, and on removal of the excess liquid, a
transparent resin is formed.
The resin is then heated to decompose the organic constituents,
ground, and calcined to produce the powder.

2. The Citrate Gel Method

The citrate gel method was developed by Marcilly et al. and can be
illustrated by the synthesis of the ceramic superconductor YBa2Cu3O7-x.
Nitrate solu- tions of Y, Ba, and Cu were added to citric acid solution, and
the pH was kept at 6 to prevent precipitation of barium nitrate.
Heating the solution at 75C in air produced a viscous liquid containing
polybasic chelates.
Further heating at 85C in a vacuum produced an amorphous solid that was
pyrolyzed in air at 900C to produce a crystalline powder.
3. The Glycine Nitrate Process
The glycine nitrate process is one of a general class of combustion
methods for the preparation of ceramic powders.
A highly viscous mass formed by evaporation of a solution of metal
nitrates and glycine is ignited to produce the powder.
Glycine, an amino acid, forms complexes with the metal ions in solution
which increases the solubility and prevents the precipitation of the metal
ions as the water is evaporated.
Glycine also serves another important function: it provides a fuel for the
ignition step of the process since it is oxidized by the nitrate ions.

 The reactions occurring during ignition are highly explosive, and extreme care
must be exercised during this step.Normally, only small quantities should be
ignited at a time.
Under well controlled conditions, a loose mass of very fine, crystalline powder
(particle size less than a tens of nanometers) is obtained after ignition.
When compared to the Pechini method, grinding and calcination of the
product are not required.
The very fine size and crystalline nature of the powder is believed to be a direct
result of the short exposure to high temperatures during the ignition step.
With adequate process control, the glycine nitrate process offers a relatively
inexpensive route to the preparation of very fine, chemically homogeneous
powders.
It has been used for the preparation of simple oxides as well as
complexoxides(e.g.,manganites,chromites,ferrites,andoxidesuperconductors).

Nonaqueous Liquid Reaction

Reactions involving nonaqueous liquids have been used for the synthesis of
Si3N4 and other nonoxide powders.
The advantage of these methods is the higher purity and finer particle size
of the powder compared with methods that involve grinding of a solid
product.
The reaction between liquid SiCl4 and liquid NH3 has been used on an
industrial scale by UBE Industries (Japan) to produce Si3N4 powder.
SiCl4 + NH3
Si(NH)2 + NH4Cl
A more involved sequence of reactions occurs, involving the formation of
poly- meric silicon diimide and ammonium chloride triammoniate,
NH4Cl3NH3. Silicon diimide decomposes according to the overall reaction
3Si(NH)2
Si3N4 + N2 + 3H2
In the UBE process, the products formed by the interfacial reaction
between the SiCl4 and NH3 liquids are collected and washed with liquid
NH3 and calcined at 1000 C to produce an amorphous Si3N4 powder.
Subsequent calcination at 1550 C in N 2 yields a crystalline powder with a
particle size of 0.2 mm.