POWDER PREPARATION BY CHEMICAL METHODS

we shall start by dividing the methods into three fairly

broad categories:
(i) preparation by solid-state reactions
(ii) preparation from liquid solutions
(iii) preparation by vapor-phase reactions
A. Solid-state Reactions

Chemical decomposition reactions, in which a solid

reactant is heated to produce a new solid plus a gas,
are commonly used for the production of powders of
simple oxides from carbonates, hydroxides, nitrates,
sulfates, citrates (C6H5O73-), acetates (CH3COO-),
oxalates (C2O42-), alkoxides and other metal salts. The
reaction is strongly endothermic, which is typical for
decomposition reactions. This means that heat must be
supplied to the reactant to sustain the decomposition.

MgCO3(s)  MgO(s) + CO2(g)

Chemical reactions between solid starting materials,
usually in the form of mixed powders, are common
for the production of powders of complex oxides such
as titanates, ferrites, and silicates.

BaCO3(s) + TiO2(s)  BaTiO3(s) + CO2(g)

MnO + ZnO + Fe203  (Mn,Zn)Fe204

MgO + Al203  MgAl204

These reactions, involving decomposition of solids or

chemical reactions between solids, are referred to in
the ceramic literature as calcination (Thermolysis). It
is a process in which a material is heated to change or
transform it to a more thermodynamically stable form
so that the chemical/physical processes that are
involved do not occur during sintering.
Reasons for calcining powders
Depending on the chemical nature of the reactant and the
temperature, the kinetics of the decomposition may be
controlled by any one of three processes:
(i) the reaction at the surface,
(ii) heat transfer to the reaction surface, or
(iii) gas diffusion or permeation from the reaction
surface through the porous product layer.

Figure 2.10 Schematic of the decomposition of calcium carbonate.

Assuming constant temperature and spherical reactant

particles for which the reaction initiates on the surface
and moves inward uniformly at a fixed rate, the reaction
kinetics are given by

1 - (1-)1/3 = Kt

where  is the fraction of the reactant decomposed after

a time t and K is the thermally activated rate constant
obeying an Arrhenius relationship.
A feature of decomposition reactions;

• extremely fine particle size (e.g., in case of the

production of MgO from MgCO3 or from Mg(OH)2,
the particle size of the MgO can be as low as 2-3 nm
when the decomposition is carried out in vacuum.
• pseudomorphic; i.e., the initial size and shape of the
reactant particles are retained. The product therefore
consists of agglomerates of very fine particles
separated by porosity.

The atmosphere can have a strong influence on

the characteristics of the powder produced.

If MgO is produced from MgCO3 or from Mg(OH)2 in

the ambient atmosphere rather than in a vacuum, the
water vapor in the atmosphere catalyzes the sintering of
the very fine particles to produce larger particles. High
decomposition temperatures and long decomposition
times can lead to the sintering of the particles and
agglomerates, giving a highly agglomerated, low surface
area powder.
Specific surface area as
high as 100 m2/g with
particle and pore sizes
smaller than 10 nm.

Surface area is
only 3–5 m2/g

Fig 2.12 Scanning electron micrographs of CaO produced by

decomposing CaCO3 powder at 650C in (a) vacuum (particles
are same apparent size and shape as parent CaCO3 particles) and
(b) dry N2 at atmospheric pressure.
Chemical reactions between solids: Reactions
between mixed powders are technologically important for
powder synthesis.

For solid-state reactions between two single crystals (A

and B), the reaction is diffusion-controlled as long as the
parabolic rate law applies:

x = K’ t1/2

where x is the thickness of the reaction product formed

after a time t and K’ is a constant at a fixed temperature.
(K’ increases with temperature according to the
Arrhenius relation)

Reaction product (C)

Figure 2.13 Schematic of solid-state reaction in single crystals

A+BC
After the initiation of the reaction, A and B are separated by the
solid reaction product C. Further reaction involves the transport
of atoms, ions, or molecules by several possible mechanisms
through the phase boundaries and the reaction product C.
 For reactions in mixed powders,

Reaction product

powders Partially reacted Fully reacted

Figure 2.15 Schematic of solid-state reaction in mixed powders.

R: initial radius of the particle

y : thickness of the reaction layer

Assumptions: the reaction product forms coherently

and uniformly on the reactant particles and the
particles are spherical and have the same size.
The reaction rate is

[1 – (1 - )1/3]2 = Kt / R2

Assuming that y grows according to the parabolic

relationship given by x as in the single crystals
For powder reactions, the variables that can
influence the reaction rate are fairly numerous;
• chemical nature of the reactants and the products,
• the particle size and the particle size distribution,
• the relative sizes of the powders in the mixture,
• the uniformity of the mixing,
• the reaction atmosphere,
• the temperature (Arrhenius relation of K) and the time.

For example, the reaction rate will decrease with an

increase in particle size of the reactants because the
diffusion distances will increase.

FIGURE 2.16 Kinetics of

reaction between spherical
particles of ZnO and Al2O3
to form ZnAl2O4 at 1400C
in air
Powder preparation by solid-state reactions
generally has an advantage in terms of
production cost.

BUT
• normally agglomerated
• grinding step is required (contamination with
impurities)
• incomplete reactions
• the particle shape of ground powders is usually
difficult to control.
Decomposition reactions

G° = - RT In PCO2
 G = G° + RTlnK
G < 0 reaction occurs
G = 0 at equilibrium, G° = - RTInK
G > 0 reaction does not occur

Note for hydroxides, e.g.,

Mg(OH)2 (s) =MgO(s) + H20(g)

G° = - RT In PH20

We can now obtain the decomposition temperature and

pressure.
Other powder precursors such as sulfates or nitrates are
not limited by the atmosphere when fired in air as their
product gases are not typically present in large
concentrations except locally. However, organic
precursors (oxalates [C204-2], acetates [CH3C00-], citrates
[C6H507-3] usually decompose to H20, CO and CO2.
For example: nickel–manganese oxalate

NiMn2(C2O4)3 .6H2O  NiMn2(C2O4)3 + 6H2O dehydration step

NiMn2(C2O4)3 + 2O2  NiMn2O4 + 6CO2 decomposition step

 Figure 2.8

PH2O
 CaO + CO2

Equilibrium reaction line

G° (CaCO3, CaO, CO2)
CaCO3 + CO2

Temperature, K

Rate of decomposition of CaCO3 in CO2 atmosphere

As PCO2   decomposition becomes more difficult

WHY?
J. Am. Ceram. Soc., 41, 70 (1958).
Processing and Electrical Properties in Lead-Based
(Pb(Mg1/3Nb2/3)O3, Pb(Yb1/2Nb1/2)O3, PbTiO3) Systems Full paper is attached
Erdem Akça, Huseyin Yilmaz, and Cihangir Duran
J. Am. Ceram. Soc., 93 [1] 28–31 (2010)
 Full paper is attached

2ZrSiO4 + 3Al2O3  3Al2O3.2SiO2 + 2ZrO2 (ZrSiO4  SiO2 + ZrO2)

(zircon) (Alumina) (Mullite) (Zirconia)
Seed: Aluminum borate (9Al2O3·2B2O3) whiskers
Additives: TiO2 and MgO

Figure 2 XRD patterns of the

⊥-cut MZ-TMA samples after
sintering for 2 h.
A: Alumina,
Zn: Zircon,
M: Mullite,
AB: Aluminum borate,
m: monocliniczirconia.

Figure 4 Phase formation of mullite

(β) as a function of composition and
sintering temperature.
B. Liquid Solutions

There are two general routes for the

production of a powdered material from
a solution:

(i) evaporation of the liquid

(ii) precipitation by adding a chemical

reagent that reacts with the solution.

We need to understand the phenomena

occurring during the precipitation process
in order to produce the desired powder
characteristics.
 t1 t2 t3
Figure 2.19. Schematic representation of the solute concentration versus time
in the nucleation and growth of particles from solution-LaMer Diagram
Evaporation of the liquid and addition of a chemical reagent to the
solution;
The concentration of the solute to be precipitated, Cx increases to or
above the saturation value, Cs if the solution is free of dirt particles
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, is reached
after some time t1, and homogeneous nucleation and rapid growth of
solute particles occurs, 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 onto the particle
surfaces. Finally, particle growth stops after a time t3 when Cx = Cs.
Precipitation of powders from Solutions:

Precipitation -The process of producing a separable solid

phase within a liquid medium or the formation of a new
condensed phase (either a liquid or solid) from the vapor.

The most straightforward use of precipitation is for the

preparation of simple oxides.

Powders are prepared by:

i. the hydrolysis of metal organic compounds (e.g.,
metal alkoxides) in alcoholic solutions or
ii. the hydrolysis of metal salt solutions.

• One of the most common synthesis procedures (eg.

reagent grade chemicals-sulfates, chlorides, acetates etc.)
are first made by precipitation.
• Fundamental to almost all solution processes.
• Particle size ranges from nanometers to millimeters.
• Nucleation + growth determine particle size.
i. 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. They can be considered derivatives of either an
alcohol, ROH, in which the proton is replaced by the metal
M, or of a metal hydroxide, M(OH)z.

Examples:
titanium alkoxides (e.g., titanium tetraethoxide, Ti(OC2H5)4)
silicon tetraethoxide , Si(OC2H5)4

CnH2n+1

http://antoine.frostburg.edu/chem/senese/101/organic/faq/yl-ending.shtml

The reactions involve hydrolysis:

followed by condensation and polymerization by dehydration:

For example, silica spheres produced by the hydrolysis
of a solution of silicon tetraethoxide [Si(OC2H5)4] in
ethanol.

FIGURE 2.22

Very uniform particle size in the range of

0.05 to 0.90 µm.
Solution synthesis of (Pb0.85La0.1)(Zr0.8Ti0.2)O3 powder
For example, hydrolysis of titanium alkoxides (e.g., titanium
tetraethoxide, Ti(OC2H5)4) in overall;

Ti(OC2H5)4 + (2 + x)H2O TiO2.xH2O + 4C2H5OH

The value of x was found by thermogravimetric analysis to be

between 0.5 and 1. Precipitation of Ti02 powder occurred in 5
s at 25.5°C to produce particles with a mean size of =0.38
m. Hydrolysis of other titanium alkoxides produced fine
particles that were not spherical but equiaxial and
agglomerated.

The preparation of powders by the hydrolysis of metal

alkoxides is generally carried out above room temperature.

The variables that control the precipitation of

particles are;
• concentration of the reactants
• pH of the solution,
• temperature.

Oxide or hydrated oxide powders are produced.

The precipitated particles can be agglomerates of
much finer particles.
ii. The hydrolysis of metal salt solutions has the ability to
produce a wider range of chemical compositions, including
oxides or hydrated (or hydrous) oxides, sulfates, carbonates,
phosphates, and sulfides. However, the number of
parameters that must be controlled can, in some cases, be
higher;
• concentration of the metal salts,
• chemical composition of the salts used as starting
materials,
• temperature,
• pH of the solution,
• presence of anions and cations that form intermediate
complexes.

• The overall precipitation of hydrated metal oxides

can be represented as

Mz+(aq) + zOH-(aq) M(OH)z(s)

• Amorphous as well as crystalline particles can be

produced.
 Examples of sizes and shapes for some powders
prepared by precipitation form metal salt solutions.

Cadmium
-Fe2O3
sulfide

Iron (III) oxide Cadmium

carbonate
Figure 2.23.
The particle characteristics depend on the pH and the nature
of the anions present in solution. Soluble complexes
involving such anions must act as precursors to the
nucleation of the particles.

For example, solutions of Al2(S04)3, KAl(S04)2, a mixture of

Al(N03)3 and Al2(S04)3, or a mixture of Al2(S04)3 and
Na2S04 can be used for the preparation of spherical hydrated
aluminum oxide particles with a narrow size distribution.

For example, precipitation of yttrium basic carbonate

particles from a solution of yttrium chloride, YCl3 ,and urea,
(NH2)2CO (see next page)
For example, precipitation of yttrium basic carbonate particles
from a solution of yttrium chloride, YCl3 ,and urea, (NH2)2CO.
Aqueous solutions of urea yield
ammonium and cyanate ions:
In acid solutions:
In neutral and basic solutions:

The precipitation of spherical particles in acid solution:

The precipitation of rodlike particles in basic solution:

Figure 2.2.4. Particles obtained (a) by aging for 2.5 h at 90°C a solution
of 1.5x10-2 mol/dm3 YCl3 and 0.5 mol/dm3 urea and (b) by aging for 18
h at 115°C a solution of 3.0x10-2 mol/dm3 YCl3 and 3.3 mol/dm3 urea.
For example
The largest use of precipitation is the Bayer process for
the industrial production of Al2O3. The raw material
bauxite is first beneficiated, then digested in the
presence of NaOH at an elevated temperature.
During digestion, most of the hydrated alumina goes
into solution as sodium aluminate:

-
Al(OH)3 + NaOH → Na+ + Al(OH)4

And insoluble impurities are removed by settling and

filtration. After cooling, the solution is seeded with fine
particles of gibbsite, Al(OH)3. Gibbsite particles
provide nucleation sites for the growth of Al(OH)3. The
precipitates are continuously classified, washed to
reduce the sodium and then calcined at 1100-1200°C,
followed by grinding and classification (see SEM
pictures on the next page).
 For the preparation of complex oxides (e.g., titanates,
ferrites and aluminates)  coprecipitation (or cohydrolysis)
from a solution

A solution of mixed alkoxides, mixed salts, or of a

combination of salts and alkoxides is generally used. 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.
Suitable conditions (pH, T, concentration) must therefore
be found in order to achieve homogeneous precipitation.

• Generally produce an intimate mixture of precipitates.

• In many cases, calcination required at elevated temperature to
produce the desired chemical composition.
• One serious consequencemilling of the calcined powder can
introduce impurities into the powder.
• Desirable to produce a precipitate that does not require the use of
elevated temperature calcination and subsequent milling.
Homogeneous nucleation in solutions
As S*   dN/dt  1 
2 1062 years
3 103 years
4 0.1 sec
5 10-13 sec
4.7x10-9 / 5.6x10-12 = 840

34
Precipitation occurs when a solution is supersaturated (S>1)

ksp= 1.9x10-33

1.9x10-33

3.8x10-12

35
https://users.stlcc.edu/gkrishnan/ksptable.html
 Particle characteristics are controlled by the effect of the degree
of supersaturation on nucleation and growth processes

The more area, the more growth

Average length of crystals, mm

Rate of process 

Nuclei formation  Sx (x=2-3)

As S   bigger particles
Particle growth  S
As S   smaller particles

a b c
S S

As S   more nucleation sites, thus growth is limited

37
As S   less nucleation sites, thus growth is favored
 Effect of S on precipitate morphology

Freeze drying and spray drying:

Possible to remove the solvent quickly; then, S increases  fine particles

Methods for homogeneous generation of anions

Embryo: collection of atoms by
chance. Problem is whether it will
shrink or grow?
rembryo < r*  redissolve
rembryo > r*  grow because G
will decrease  nucleus

Heterogeneous nucleation
Homogeneous nucleation (on inclusions, mold surface, etc)

A AB A
B AB
B
MB
MB< AB  otherwise B does not
nucleate on the mold (M) surface
 Heterogeneous Nucleation

Some heterogeneities lower the energy for nucleation by reducing

the interfacial energy (AB). By understanding the parameters that
lower the energy we can then intentionally add materials (i.e., seeds)
that serve as known sites for nucleation. For two dissimilar materials
consider their ‘wetting’ properties which is described by the contact
angle ().

Cos = (ML- SM)/SL

Heterogeneous nucleation of spherical cap on a flat mold

 Interface coherency

Homoepitaxy
 on 

Strain free coherent interfaces. (a) Each crystal has a different

Heteroepitaxy chemical composition but the same crystal structure. (b) The two
phases have different lattices.
 on  a

 

 
A coherent interface with slight mismatch leads a
to coherency strains in the adjoining lattices A semicoherent interface. The misfit parallel to the
interface is accommodated by a series of edge dislocations

An incoherent interface.
 Schematic microstructure evolution for conditions of

A. Unseeded system  constant nucleation rate

B. Seeded system  site saturation, nucleation rate=0

Controlled
particle size

Each seed corresponds to one particle, regulating nucleation frequency

Criteria for nucleation control by seeding (epitaxy)
(isostructural)

(to obtain finer grain size)

(no formation of different phase other than desired)

As f , D 

D

f
We can control particle size by seeding
Seeding controls grain size

-Al2O3  -Al2O3 transformation

Seeding  to control phase
transformation during calcination
(not for powder synthesis)
 Seeding  to control
Acicular seed particles microstructure during sintering
(not for powder synthesis)

C. Duran, G. L. Messing, and S. Trolier-

McKinstry, “Molten salt synthesis of
anisometric particles in the SrO-Nb2O5-BaO
system,” Materials Research Bulletin Vol.
39/11, pp. 1679-89 (2004).

Microstructure without seed

A duplex microstructure consisting
of bigger (in excess of 100 m for
some grains) and smaller grains
develops  Cracking occurs due
to high internal stress caused
excessively by abnormal grain
growth in the microstructure.

Microstructure with seed

A very uniform microstructure
despite the fact that it was sintered
at higher temperature.
Uniform microstructure  neither
abnormal grain growth nor cracking
is observed.