Coprecipitation
December 16
2008

 
 
Archy, OK, Jesper and Maria
Outline

 
 Precipitation

“The forming of a solid phase within a liquid

phase”

Ex. Fe(OH)3, AgCl, BaSO4

http://www.dartmouth.edu/~chemlab/chem3-5/qual_cat/graphics/procedure/proc6.gif
 Coprecipitation

Mechanisms
• Surface adsorption
• Mixed-crystal formation
• Occlusion
• Mechanical entrapment
 Overview of process

1. Atomic mixing
2. Adding of precipitation agent
3. Calcination

Analytical Study of Oxalates Coprecipitation, Marta et al

 1. Atomic mixing of precursors

Metaloxides or metalsalts are common precursors. The solubility of

the salts or MOs are limiting.
An acid or a polar solvent is usually employed.
Common acids: HNO3, HAc, HCl
Polar solvents are traditionally alcohols or water or a mixture of the
two.
 2. Adding of precipitating agent

Temperature range 0-80°C

Precipitating agents are typically oxalic acid, ammonium oxalat or
ammonium hydroxid
The adding is often done by titration
 Simultaneous precipitation

1. Formation of TiOC2O4 (Ti : C2O4 ratio 1:1, pH ≤ 2)

(C4H9O)4Ti + H2C2O4·2H2O → TiOC2O4 + 4C4H9OH
2. Conversion of TiOC2O4 to soluble Na2TiO(C2O4)2 (Ti : C2O4 ratio
1:2)
TiOC2O4 + Na2C2O4 → Na2TiO(C2O4)2
pH range 2.5-3.5: TiO(C2O4)22-
3. Addition of Ba(CH3COO)2 resulting in simultaneous precipitation
of (Ba + Ti) in the form of oxalates
TiO(C2O4)22- + 2H2O → TiOC2O4(H2O)2 ↓ + C2O42-
Ba2+ + C2O42- → BaC2O4↓

Chemical coprecipitation of mixed (Ba + Ti) oxalates precursor leading to BaTiO3 powders,
Potdar et al, 1998
 Simultaneous precipitation

4. BaTiO3 powders are produced after pyrolysis in air of the mixed

oxalates [BaC2O4 + TiOC2O4(H2O)2] precursor

Chemical coprecipitation of mixed (Ba + Ti) oxalates precursor leading to BaTiO3 powders,
Potdar et al, 1998
 Parameters

• pH
• Solubility
• Temperature
 pH
Constant vs variable pH
Layered Double Hydroxides (LDHs)
cation pairs: Mg(II)-Al(III) and Zn(II)-Cr(III)
anions: terephthalate (TA) and dodecylsulfate (DS)
• varying the cation combination, interlamellar anion and pH
control, with or without submission to hydrothermal treatment

Comparative study of the coprecipitation methods for the preparation of Layered Double
Hydroxides, Crepaldi et al, 2000
 pH - Crystallinity

Comparative study of the coprecipitation methods for the preparation of Layered Double Hydroxides,
Crepaldi et al, 2000
 pH – Specific Surface Area and
average pore diameter

Comparative study of the coprecipitation methods for the preparation of Layered Double Hydroxides,
Crepaldi et al, 2000
pH - dependence

Journal of Materials Science 25 (1990) 3634-3640

 Competing reactions

In the coprecipitation process, a The competing precipitants are

number of processes compete. In Ox and OH-:
this generalized example metal
ions were added to an oxalate-
diethylamine media

• pH
• pOx
• Solubility

Studies of theoretical and experimental precipitation conditions of Y +3, Ba+2, and Cu+2 ions in oxalate-
diethylamine media in the preparation of YBa2Cu3Oy superconductor, Chen et al, 1992
 pH region and Solubility

Studies of theoretical and experimental precipitation conditions of Y +3, Ba+2, and Cu+2 ions in oxalate-
diethylamine media in the preparation of YBa2Cu3Oy superconductor, Chen et al, 1992
Studies of theoretical and experimental precipitation conditions of Y +3, Ba+2, and Cu+2 ions in oxalate-
diethylamine media in the preparation of YBa2Cu3Oy superconductor, Chen et al, 1992
 Aggregation rates

Aggregation rate depends on:

• pH
• Concentration
• Ionic strength

The generally accepted theory for agglomoration of particles comes

from the DLVO-theory

Studies of theoretical and experimental precipitation conditions of Y +3, Ba+2, and Cu+2 ions in oxalate
Derjaguin Landau Verwey Overbeek

The DLVO-theory was first presented in the 1940's. It describes the

force between charged particles interacting through a liquid medium.
It combines the van der Waals attractive forces with the counterion
double layer repulsive forces.

β − 1 = kBT, the thermal energy scale.

κ − 1 = Debye-Hückel screening length
r = center to center particle distance
Z = constant surface charge
λB= is the Bjerrum length
 Aggregation rate, Ionic strength

Ionic strength: measure of the particle concentration of all ions in a

solution.
Fe2O3 particles were held @ pH 5.7. 1-200 mM NaCl was employed
as a variator of ionic strength.

Aggregation rate increases with increased ionic strength

Kinetic stability of hematite nanoparticles: the effect of particle size, He et al, 2007
 Aggregation rate, pH

FeO3 particle solution ranged from pH 5-9.

Aggregation rate increases with pH increase, the result is more

obvious close to the IEP of the particles.
The same is has shown to be true in similar experiments using Y2O3
particles in solution.

Kinetic stability of hematite nanoparticles: the effect of particle size, He et al, 2007
 Aggregation rate, particle
concentration
13, 44, 132 and 440 mg/L of 65 nm Fe2O3 particles was used.

Aggregation rate is increased with increasing concentrations

Similar experiments indicating the same results have been done
with kaolinite particles as well as colloidal polystyrene particles

Kinetic stability of hematite nanoparticles: the effect of particle size, He et al, 2007
 Coprecipitation

Chemical precipitation is widely used in industry. Especially to

synhesize complex metaloxides.

Common metal oxides: BaTiO3,Y3Al5O12,YBa2Cu3O7

Advantages of
Coprecipitation
• Technical simplicity
• Low manufacturing
costs
• High reproducability
• Fine particle size
Challenges
• Difficult to control chemical
composition
• Time consuming
• Upscaling issue