Spray drying and Spray pyrolysis

Spray Drying

• Powder preparation method involving liquid solutions

• evaporation of the liquid bring a solution to supersaturation,
thereby causing the nucleation and growth of particles
• Commonly aqueous solutions of metal salts used
• Sulfates and chlorides are often used because of their high
solubility
• Maximum temperature (typically less than 300C)
• Key solution parameters -size of the droplet, concentration and
composition of the metal salt
• Advantages: High purity, small particle size, composition control,
chemical homogeneity
• Disadvantage: Expensive, poor for nonoxides, powder
agglomeration commonly a problem
Spray Drying
•A solution is broken up
into fine droplets by a
fluid atomizer and
sprayed into a drying
chamber
•Contact between the
spray and drying medium
(commonly hot air) leads
to evaporation of
moisture.
•The product, consisting
of dry particles of the
metal salt, is carried out
in the air stream leaving
the chamber and
collected using a bag
collector or a cyclone.
 Spray Drying

• A variety of atomizers are available

• Rotary atomization (centrifugal atomization) – liquid is
centrifugally accelerated to high velocity by a spinning
disk
• Pressure atomization, pressure nozzles atomize the
solution by accelerating it through a large pressure
difference and injecting it into the chamber.
• Pneumatic atomization occurs when the solution is
impacted by a stream of high-speed gas from a nozzle.
• Ultrasonic atomization involves passing the solution
over a piezoelectric device that is vibrating rapidly.
 Spray Drying

• Droplet sizes ranging from less than 10 µm to over 100 µm

can be produced by these atomizers.
• Under suitable conditions, spherical agglomerates with a
primary particle size of 0.1 µm or less can be obtained
• Temperature in the drying chamber is commonly
insufficient to cause decomposition of salt or solid-state
reaction.
• Hence, additional processing steps such as calcination and
milling become essential.
• E.g. Ni-Zn ferrite
• Used to produce pressing-grade ceramic powders and for
numerous other applications in the foods, chemicals, and
materials industries
 Spray Pyrolysis
(spray roasting, spray reaction, or evaporative decomposition of solutions)

• Describe all synthesis processes in which a solution is

atomized and thermolyzed to attain the requisite phase
• By using a higher temperature and a reactive (e.g.,
oxidizing) atmosphere in the chamber, solutions of
metal salts can be dried and decomposed directly in a
single step.
• Mixed metal oxide, non-oxide, and composite particles
that are solid, hollow, porous, or fibrous can be
produced by modifying the precursor characteristics,
solution properties, and process parameters
• Controlled synthesis of advanced ceramic powders and
films is possible.
Pyrolysis (i.e., thermal decomposition)
Oxidation, nitridation, or reduction-based thermal processes are also included
 Spray Pyrolysis
• Differs from spray drying in the use of solutions, the
consequent process of precipitation or condensation within a
droplet, and the use of significantly higher temperatures (e.g.,
>3OOoC) to form the desired inorganic phase by thermolysis.
•Solution is atomized into a series of reactors (Fig. 1) where the aerosol
droplets undergo evaporation and solute condensation within the droplet,
drying, thermolysis of the precipitate particle at higher temperature to form a
microporous particle, and, finally, sintering of the microporous particle to form
a dense particle.
•Uniquely control the particle formation environment by compartmentalizing
the solution into droplets. In this manner, SP ensures complete stoichiometry
retention on the droplet scale
 Mechanism

Droplet undergoes evaporation and the solute concentration in the outer layer
increases above the supersaturation Limit

Precipitation of fine particles.

Precipitation is followed by a drying stage in which the vapor diffuse through

the pores in the precipitated layer.

Decomposition of the precipitated salts produces a porous particle made up of

very fine grains

Finally heated to produce a dense particle

Variety of particle
morphologies
produced

For the fabrication of

advanced ceramics,
dense particles are
preferred over those
with highly porous or
hollow shell-like
morphologies because a
subsequent milling step
is normally unnecessary.
Zirconyl
hydroxychloride
(ZHC)
If dense particles are required, we
must first achieve homogeneous
nucleation and growth in the droplet
(volume precipitation)

Facilitated by a small droplet size and

slow drying

A large difference between the

supersaturation concentration Css and
the saturation concentration Cs of the
solute in solution increases the
nucleation rate (Lamer diagram)

A high Cs (i.e., a high solute solubility)

and a positive temperature coefficient
of solute solubility desired so that
sufficient solute is available to form
filled agglomerates of touching
primary particles.

Precipiitated solids should not be

thermoplastic or melt during the
decomposition stage
 Drying of a droplet containing fine precipitates
• Drying of a droplet containing fine precipitates is quite
different from that of a liquid droplet.
• Fine precipitates provide a resistance to the mass
transport of the solvent vapor
• If the temperature of the drying chamber is too high,
boiling of the solution may occur leading to inflation or
disintegration of the droplet.
• Combination of fine pores between the precipitates
and rapid drying of the droplet can lead to high
capillary stresses and fracture of the particle
• It is important to achieve complete decomposition of
the dried salts prior to sintering.
 Types of solutions used
• Laboratory scale-nitrates and acetates are preferable to
sulfates because of their lower decomposition
temperatures
• However, acetates have a low solubility, while nitrates,
acetates and sulfates can introduce impurities into the
powder.
• Chlorides and oxychlorides are used industrially because of
their high solubilities, but the corrosive nature of the gases
produced during decomposition and the deleterious effect
of residual chlorine on subsequent sintering is problematic.
• The particles should be sintered in situ to take full
advantage of the spray pyrolysis process.
• The fine pores between the primary particles and the short
interparticle collision time in the process favor the
formation of dense individual particles if exposure to a high
enough temperature can be achieved.
Spray Drying of Suspensions
Spray drying of suspensions is used
on a large scale industrially
for granulating fine powders to
control their flow and compaction
characteristics
during die pressing

liquid is removed in such a

way as to limit the
agglomeration of the dried
powder to a scale equal to or
less than the size of the
droplet.

Limiting scale of the agglomeration

provide benefits like better overall
uniformity of the compacted body