PHASE TRANSFORMATION METHODS

Fine particles of metallic compounds  converted into metallic particles

MeXn : oxides, carbonates, chlorides, nitrates, etc.

MeXn Me

Types of transformations:

THERMOLYSYS REDUCTION

MeXn MeXn
Metallic
particle
T +n e-
- nX - nX

Advantages: - The size and shape of the precursors can be preserved

- Preparation of highly crystalline metallic particles
- Preparation of composite alloy metallic particles (Me xMeyMez)
 PHASE TRANSFORMATION

T, ne-

+n e-
-nX

Metallic compounds Metallic particles

 1 m
Haematite particles Iron particles
 THERMAL DECOMPOSITION
Precursors particles thermodynamically unstable at elevated temperatures

MeXn  Me0 + nX

Liquid: Chlorides, nitrates

Solid: Oxides, carbonates, organic and organometallic compounds

> 6000C Ag2O  2Ag + ½ O2

AgNO3 Ag0

> 8200C PdO  Pd + ½ O2

PdO Pd0

Continuous phase Gas - Reducing

- Reacting
- Inert

Liquid - High temperature liquids (polyols, mineral oil)

- Salt-melts (300 – 5000C)
- Low temperature transformations (Ag2O , SnO2 , Bi2O3*)

Solid - Inorganic compounds (ceramics, salts)

*Preparation of colloidal bismuth particles in polyols, J. Mater. Res., Vol. 20, No. 6, Jun 2005
 CHEMICAL TRANSFORMATION / REDUCTION

- Precursors particles in direct contact with a reducing agent

- Electron transfer from a reducing agent to the precursors
Men+ + ne-  Me0
Reducing agent

Gas - Reducing carrier gas

- Reducing gases (H2) mixed with an inert carrier gas (N2)

Mechanisms: - Diffusion of gas molecules into the precursor lattice

- ‘Electron hopping’

Liquid - The molecules of the liquid in which the precursor particles are dispersed (polyol)
- Reducing agent molecules dissolved in the dispersion medium

Mechanisms: - Dissolution/Precipitation
- ‘Electron hopping’ (reduction of copper oxide)*

Transformation temperature Depends on - The ‘strength’ or concentration (H2) of the reducing agent
- The stability of the precursors 

*"Formation of Uniform Colloidal Copper Particles in Polyols by Aggregation of Nanosize Precursors",

Goia, D.V.*, Crnjak-Orel, Z., Matijevic, E., J. of Mater. Res., Vol 18, 4, 2003.
 METALLIC PRECURSORS

• State of aggregation - Liquid  Solution droplets in either a gas or liquid medium

- Solid  Particles - in gas phase (aerosols)
- in liquid phase (suspensions)
- in solid phase (mixed salts, blends)

• Degree of dispersion - Dispersed particles - agglomerated

- non-agglomerated
- Bulk powders

• Size Nanosize to micron size

• Shape - Spheres, rods, platelets, etc.

- Various aspect ratios

• Chemical nature - Inorganic salts (oxides, carbonates, nitrates, chlorides, etc.)

- Organometallic compounds*

Processes  Transformations in gas phase/Spray pyrolysis

 Transformations in high temperature liquids
 Transformations in refractory solid phases

*Formation of uniform colloidal ceria in polyol", D. Andreescu, E. Matijević, D.V. Goia*,

Colloids and Surfaces A: Physiochemical and Engineering Aspects, 291 (2006) 93-100.
 SPRAY PYROLYSIS/AEROSOL THERMOLYSIS
Decomposition of liquid precursors in gas phase

>1200C >8500C >1,0000C

Pd(NO3)2 droplet Pd(NO3)2 crystal Polycrystalline Highly crystalline

Pd particle Pd particle

Size, uniformity, and degree of agglomeration of Me particles depends on:

a) Size and size distribution of droplets

- Droplet generation  pneumatic/spraying
 ultrasonic
- Size control  pressure
 transducers’ frequency, size ~ 
- Size distribution  various approaches (momentum, gravitation force)

b) Stability of the aerosols (droplets, intermediates, and final particles)

- Laminar flow during the process
- Working below the critical concentration)
'Method of making metallic powders by aerosol thermolysis, Ranade, M.B.,
Goia, D.V., Varga, G.J., Gamson, B.W., Bara, J., US 5,928,405, July 27,1999.
 SPRAY PYROLYSIS/AEROSOL THERMOLYSIS

Carrier gas - air  thermal decomposition (non-oxidizing metals)

- inert  thermal decomposition (oxidizing metals)
- reducing  chemical reduction

Heat sources - Plasma (plasma pyrolysis)

- Flame (flame pyrolysis)
- Hot wall/furnace

Particle properties
- Highly crystalline (severe internal sintering, even melting)  excellent sintering properties
 ‘inter-particles’ shrinkage only
- Size: - from nanosize to micron size particles
- Size distribution: - wide (due to droplet and particle collisions)
- classification required to obtain narrow size distributions (methods)
- Shape: - spherical
- Cost: - high capital investment
- increases with the decrease in size

Examples a) Preparation of noble metals - simple (Au, Ag, Pd) and composite
(Ag/Pd)
- decomposition of salts in air or inert gases
b) Preparation of non-noble metals (Cu, Co, Ni, etc.)
- decomposition of salts in reducing atmosphere

Applications - Electronics (Shoei/Japan)

- Thousand of tons of powders (Ag/Pd, Ni, Cu)
 PHASE TRANSFORMATIONS IN LIQUID PHASE

Precursors  Finely divided solids well-dispersed in liquids with high boiling temperatures
 Metallic compounds unstable at temperatures below Tb

Example
Polyol, ~1800C Polyol, >2100C

Bi2(CO3)3 Bi2(Poly)3 Bi particles

(various shapes possible)

Liquids Organic - Mineral oil

- Polyols
Inorganic - Melted salts

Advantage - May preserve the size and shape of the precursor particles
- The liquid phase more effective in preventing inter-particle collisions

Challenge - Prevent the aggregation of the resulting particles (easier with polyols)

Solution - Particle encapsulation in temperature resistant coatings

- Use of effective dispersants
- Deagglomeration via ‘media milling’
 PHASE TRANSFORMATIONS IN SOLID PHASE
• Precursors  Finely divided solids well-dispersed in a solid continuous phase
 Metallic compounds unstable at temperatures below Tm

• Transformations: Both chemical and thermal

• Examples H2 (4500C) Air >850

NiCl2 Ni particles PdO Pd particles

• Continuous phase - Inorganic salts

• Precursor dispersion: - Evaporation of dispersions in concentrated salt solutions

- dispersion technique, choice of solvent is very important
- solvent evaporation (under mixing, spray drying, etc.)
- Milling of precursor particles with inorganic salts

• Advantages - Very low cost

- May preserve the size and shape of the precursor particles
- The solid phase the most effective in preventing inter-particle collisions

• Challenges - Prevent the aggregation of the resulting particles (dispersion of precursor particles)
- Find a salt which is not reacting with the precursors or the final particles

- Deagglomeration via ‘media milling’

 BULK POWDER TRANSFORMATIONS
• Concept T, Red

• Limitation  Only nonagglomerated metallic precursors

• Type of transformation  Both chemical reduction and thermal decomposition eventually possible
• Advantage  low cost
• Challenge  prevent particle aggregation due to sintering

Solution  encapsulate the precursor particles with thin films of refractory ceramics (0.1 – 1%)

• Example

PdO/ZrO2 Pd/ZrO2
• Steps dispersion  coating  drying  transformation

- PSD can be very effectively preserved during the process

- Post-transformation milling can be eventually used to break any agglomerates formed