PREPARATION, PROPERTIES PREPARATION OF METALLIC PARTICLES
AND
APPLICATIONS • Phase ‘break down’ - Milling/grinding
- Atomization
OF
• Phase ‘transformation’ - Thermolysis/Pyrolysis
HIGHLY DISPERSED METALLIC - Reduction
PARTICLES • Phase ‘build-up’ - Condensation in gas phase (Me0)g
- Condensation in liquid phase (Me0)l
Dan Goia
Clarkson University
PHASE ‘BREAK DOWN’ / MILLING PHASE ‘BREAK DOWN’ / ATOMIZATION
Spraying/pulverization of molten metals
Size reduction of coarse/agglomerated metallic powders
• Large particles, broad size distributions
- Mechanical energy (shear, collision)
- Dispersion media (liquid or gas) - Monodispersed particles
- Dispersing agents - Sub-micrometer size
- Controlled atmosphere and temperature frequently required
• Capable to produce a large variety of alloy powders
• Suitable for some applications (mechanical alloying) • Low manufacturing costs
• Rarely yields highly monodispersed, spherical particles
• Inert carrier gases may be required
1
PHASE TRANSFORMATION PHASE TRANSFORMATION
AEROSOL AEROSOL
THERMOLYSYS REDUCTION
MeX2 MeX2
Metallic T, ne-
particle
T +2 e-
- 2X
+n e-
- Difficult to control the size distribution of precursor droplets -nX
- Agglomeration of droplets/particles due to collisions
Wide particle size distribution Metallic compounds Metallic particles
SPRAY PYROLYSIS/AEROSOL THERMOLYSIS
PHASE ‘BUILD UP’ / CONDENSATION
Decomposition of liquid precursors in gas phase
Condensation from Condensation from liquids
gas phase (Chemical Precipitation)
>1200C >8500C >1,0000C
CVD Plasma (Men+)l
(MeX)g (Me0)s
Pd(NO3)2 droplet Pd(NO3)2 crystal Polycrystalline Highly crystalline + ne-
Pd particle Pd particle
-X
T T
Size, uniformity, and degree of agglomeration of Me particles depends on:
a) Size and size distribution of droplets (Me0)l
(Me0)g
- Droplet generation → pneumatic/spraying
→ ultrasonic Nucleation
- Size control → pressure
→ transducers’ frequency, size ~ ν and
- Size distribution → various approaches (momentum, gravitation force) Growth
b) Stability of the aerosols (droplets, intermediates, and final particles)
- Laminar flow during the process
- Working below the critical concentration) (Me0n)gas (Me0n)liquid
2
CHEMICAL PRECIPITATION
2.0
MnO4- + 4H- + 3 e- → MnO2 + 2H2O
Au3+ + 3 e- → Au0
Metal atoms generated ‘via’ redox reactions:
Pt2+ + 2 e- → Pt0
1.0 Pd2+ + 2 e- → Pd0
Me n+ + Red → Me 0 + Ox Ag+ + e- → Ag0
Cu+ + 2 e- → Cu0
Driving force: 0.0 H+ + e- → ½ H2
Co2+ + 2 e- → Co0
∆ E0 = E01 - E02 C6H8O6 → C6H8O6 + 2 e- + 2H+ Fe2+ + 2 e- → Fe0
Zn2+ + 2 e- → Zn0
ln Ke = nF⋅ ∆ E0 /RT R-CH2OH → R-COH + 2e- + 2H+
-1.0
N2H4 + 4OH- → N2 + 4 e- + H2O V2+ + 2 e- → V0
∆ E0 → critical supersaturation
Ti2+ + 2 e- → Ti0
→ nucleation rate Al3+ + 3 e- → Al0
-2.0
TAILORING ∆E0 TAILORING ∆E0
Ag+ + 1e- → Ag0 E0 = +0.799V • Effect of the pH
• Precipitation Ag+ + Cl- → AgCl Ksp = 1.82 x 10-10 → Whenever H+ or OH- species are involved in the reaction
AgCl + 1e- → Ag0 + Cl- Examples
E0AgCl = E0Ag+ - 0.059/1 log[Cl-]/Ksp = 0.799 - 0.059(log[Cl-] – logKsp) = 0.222V
a) C6H6O6 + 2e- + 2H+ → C6H8O6 E0 = -0.244V
AgI Ksp = 3.0 x 10-17 E0 = -0.152V
Ag2S Ksp = 6.3 x 10-50 E0 = -0.710V
E0 = E0 - 0.059/2 log[C6H8O6]/[H+]2[C6H6O6] = -0.244 - 0.059 (pH)
• Complexation Ag+ + 2NH3 → Ag[NH3]2+ pKf = 10-7.4
[H+] ↑ , pH ↓ ⇒ C6H8O6 less strong reductant
Ag[NH3]2+ + 1e- → Ag0 + 2NH3
b) N2 + 4e- + 4H2O → N2H4 + 4OH- E0 = -1.160V
E0Ag[NH3]2 = E0Ag+ - 0.059/1 log[Ag+][NH3]2/[Ag(NH3)2]+ = 0.799 - 0.059(pKf) = 0.373V
Ag(SO3)23- + 1e- → Ag+ + 2SO32- pKf = 8.68 E0 = 0.430V
E0 = E0 - 0.059/4 log1/[OH-]4 = -1.160 + 0.059 (14 - pH)
Ag(S2O3)23- + 1e- → Ag+ + 2S2O32- pKf = 13.46 E0 = 0.010V
Ag(CN)2- + 1e- → Ag+ + 2CN- pKf = 19.85 E0 = -0.290V
[H+] ↑ , pH ↓ ⇒ Hydrazine becomes a less strong reductant
• Concentration
E = E0 - 0.059 log [Ag0]/[Ag+] = 0.799 + 0.059 log[Ag+]
[Ag+] = 103M E0 = 0.777V
3
REDOX DIAGRAMS
CONDENSATION FROM LIQUID PHASE
E (V) METAL IONS/COMPLEXES
Pd2+ + 2e- → Pd0 Reduction
+
Ag+ + e- → Ag0 METAL ATOMS (~3Å)
CLUSTERS
Ag[NH3]2+ + 1e- → Ag0 + 2NH3
NUCLEI (~8-10Å)
pH
0
Pd[NH3]42+ + 2e- → Pd0 + 42NH3 Diffusional growth
NANOSIZE
C6H6O6 + 2e- + 2H+ → C6H8O6 PRIMARY PARTICLES (1-30 nm)
Diffusional growth/
Effective Stabilization Aggregation
Coagulation
+ 4H2O → N2H4 +
- N2 + 4e- 4OH-
LARGE PARTICLES TRUE AGGREGATED
(Crystalline / Polycrystalline) NANOSYSTEMS NANOSIZE SYSTEMS
EXPERIMENTAL
CRITICAL PROPERTIES
‘DIRECT’ ADDITION ‘REVERSED’ ADDITION ‘DOUBLE-JET’ ADDITION
Red Men+/MeXmn Red Men+/MeXmn
• Particle size and size distribution
MeXmn + Red • Internal structure
Men+ Disp. Disp.
Disp.
• Particle morphology
C C C
• Internal composition
Red
Men+ Men+ • Surface properties
Red Men+ Red
Tn Tf Time Tn Tf Time Tn Tf Time
4
Platinum Particles (~ 2.0 nm)
PREPARATION OF NANOSIZE METALLIC PARTICLES
a) Generate a large number of nuclei
b) Involve a large fraction (f) of atoms in the nucleation step
Final size in the nanosize range Rp = rn × (100/f )1/3
→ Provide high supersaturation (large ∆ E)
→ Use suitable dispersion media
→ Work in dilute systems
→ Use surfactants
c) Prevent the aggregation of primary particles
→ Maximize electrostatic repulsive forces (dilute systems)
→ Minimize/screen attractive forces (dispersing agents)
PREPARATION OF LARGE PARTICLES
A. CRYSTALLINE → diffusion growth
- Slow nucleation (small ∆E, strong metallic complexes)
- Slow addition of precursors in the system
- Use of seeds
- Very effective stabilization
B. POLYCRYSTALLINE PARTICLES → aggregation
- Control the attractive/repulsive forces by adjusting:
- Ionic strength
- pH
- Activity of the dispersant/protective colloid
- More versatile in controlling the size of the particles
Nanosize Silver Particles (~90 nm)
5
CRYSTALLINE GOLD POWDER
INTERNAL PARTICLE STRUCTURE
Diffusional Growth
Effective colloid stabilization
Small ∆ E, supersaturation
Crystalline
0.15 µm 0.30 µm Particles
Nanosize
Primary Particles
Coagulation/Aggregation
Poor colloid stabilization
Large ∆ E, supersaturation
Polycrystalline
0.5 µm 1.0 µm Particles
AgPd Spherical Alloy Particles
6
INTERNAL PARTICLE
METAL PARTICLES STRUCTURE
FORMATION IMPORTANCE OF PARTICLE STRUCTURE
Crystalline Polycrystalline
Monodispersed Gold Monodispersed Gold A. Electronics/Thick film
Due to the absence of internal grain boundaries, highly crystalline particles
of PM yield dense, continuous, thinner, and more conductive ‘fired’ films.
B. Electronics/Oxidation of base metals
Highly crystalline base metals (Cu, Ni) are more resistant against oxidation
when used as precursors for thick film conductors.
C. Medicine/Biology
Highly crystalline, dense gold particles are more effective as carriers of
drugs/vaccines through biological tissues.
2 µm 2 µm
PARTICLE MORPHOLOGY PARTICLE MORPHOLOGY
Hexagonal Gold platelets Crystalline Pd Particles
7
INTERNAL COMPOSITION SURFACE PROPERTIES
Bimetallic particles → electronics (wide range of properties attainable) IMPACT
→ catalysis (enhanced catalytic activity) • Dispersibility in liquids
• Self assembly properties
•Core/Shell structure • Sintering characteristics
• Catalytic activity
E01 ≠ E02 → the most electropositive element will form the core • Adhesion properties
→ the most electronegative element will form the shell • Corrosion
⇒ Precipitation order can be tailored by appropriate complex formation TAILORING SURFACE BEHAVIOR
• ‘Solid solutions’/Alloys • Selection of precipitation environment (reductant, dispersant, solvent)
• Subsequent surface treatment (performed on either wet or dry powders)
E01 ≅ 2E0 → similar reduction rates
∆E01 , ∆E02 >> → fast reactions - Coating with organic compounds
- Coating with inorganic compounds
⇒ Uniformly mixed crystalline lattices - Coating with metals
ELECTROLESS PLATING ELECTRODISPLACEMENT
Ag+
Nucleation Growth Ag+ Cu2+
e- e- Ag0 Ag0Ag0Ag0
Homogeneous Heterogeneous Ag0
Cu0
Ox Ox Ox Ox
e- Ag+ Ag+ e-
Red Red Red Red
Ag+ Ag+
e- Ag+ Ag+ e- Cu2+
e- e- e-
e- Copper e-
e-
e- e- Ag+
Agn 0 e- Agn 0 Ag+
Ag+ Ag+
Agn 0 Ag+
Ag+ Ag+ e- Cu2+
Metal e-
Ag0Ag0 Ag0Ag0Ag0Ag0
cluster
Cu0
Red: C6H8O6, N2H4 Substrate
8
APPLICATIONS OF THICK FILM TECHNOLOGY
MONODISPERSED METALLIC PARTICLES Conductive layers
a) ‘Fired’/Sintered films
• Electronics
• Catalysis Metal
‘Green’ layer Metallic layer
paste
• Biology and medicine Drying Sintering
• Pigments
• Obscurant smokes substrate
b) ‘Non-Fired’ films
• Nonlinear optics
Metal-filled polymer film
• Transparent conductive coatings Metal
paste
• Ferromagnetic fluids Drying/Curing
• High density magnetic storage
substrate
ULTRATHIN METALLIC LAYERS SECTION THROUGH A MLCC
(Up to 800 alternative layers)
dielectric layers (~ 6 µm) metallic layers (~ 1 µm)
Human
hair
(~ 60 µm)
Dielectric Tape Electrode film
1.0 µm
9
HIGH PERFORMANCE METAL POWDERS
• Spherical
• Monodispersed
Ag/Pd Ni Cu
• Size : 0.1 - 1.0 µm
• Non-agglomerated particles
• Easily dispersible
• Controlled composition (metals ratio, impurities)
• Highly crystalline
• Controlled sintering behavior
2.0 µm 1.0 µm 2.0 µm
ULTRATHIN METALLIC FILMS
140
10% = 131 nm
50% = 153 nm
90% = 179 nm
120
100% = 240 nm
100 Φ SEM = 130 nm
Intensity
80 I A = 1.1
60
40
20
0
0 100 200 300 400 500
Particle Diameter (nm)
Monodispersed Co particles
Monodispersed AgPd Particles
10
Monodispersed Ag Particles Monodispersed Nanosize Gold Particles
Applications Applications:
• Antimicrobial activity
• Medicine and Biology
- Antimicrobial coatings
- Water purification
- Delivery of anti-tumor drugs
- Vaccine delivery
• SPR Biosensing
- Biosensing and bioassays (SPR)
• Transparent conductive coatings
• Pigments for functional glasses
- Coating of CRT screens
- Potential replacement for ATO
50 nm 50 nm
SUPPORTED METALLIC CATALYSTS
NANOSIZE METALS IN CATALYSIS
• ‘Adhesion technique’
Decreasing particle size → larger specific surface area
→ larger fraction of surface atoms
Benefits : → Increased catalytic activity
→ Significant cost reduction
• ‘On-support’ precipitation
Difficulties : → Separation of reaction products
→ Propensity for sintering Support
Dispersant
Supported metal catalysts Metallic particle
11
PEM FUEL CELLS
Pt/Ru/C Electrodes: - 2.0 – 3.0 nm Pt and Pt/Ru particles supported on carbon
- Up to 60% metal loading
Catalyst
For
Pt, PtRu/Carbon H2 / H2 O
PEM Fuel Cells
2 e-
Anode
PEM 2 H+
Cathode 2 O2- 2 e-
Pt/Carbon
O2/Air
H2 O
CONCLUSIONS
• Chemical precipitation is a versatile technique capable to yield
non-agglomerated monodispersed metallic particles with:
- wide range of modal diameters (1 nm to several microns)
- controlled internal structure and morphology
- controlled composition
- controlled surface characteristics
Materials for many existing and emerging fields of high technology
CHALLENGE:
Assembly of fine particles (nanoparticles) into ordered mono, bi,
and three-dimensional complex structures structures
12
