coprecipitation
TRANSCRIPT
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, HClPolar 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 hydroxidThe adding is often done by titration
Simultaneous precipitation
1. Formation of TiOC2O4 (Ti : C2O4 ratio 1:1, pH ≤ 2)(C4H9O)4Ti + H2C2O4·2H2O → TiOC2O4 + 4C4H9OH2. 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 oxalatesTiO(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 number of processes compete. In this generalized example metal ions were added to an oxalate-diethylamine media
The competing precipitants are Ox and OH-:
• 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-diethylamine media in the preparation of YBa2Cu3Oy superconductor, Chen et al, 1992
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 lengthr = center to center particle distanceZ = constant surface chargeλB= 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 concentrationsSimilar 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