1

IV (5)

Synthesis of Nanoparticles
Methods and Techniques
2
Materials Synthesis by Combustion
Using fuels
(A) Flame Synthesis (gas phase)
(a) Optical fiber
(b) Diamond film
(c) Fine particles
carbon particles (carbon black)
oxide ceramic powders
(SiO
2
, TiO
2
, Al
2
O
3
)
non-oxide ceramic powders
(AIN, Si
3
N
4
)
(B) Solution Combustion Synthesis
3
Using no fuels (one reactant serves as fuel)
Combustion Synthesis
Self-Propagating High-Temperature Synthesis (SHS)
(A) solid solid
(B) solid liquid
(C) solid gas
(D) gas gas
ceramics, composites, elements,
intermetallics,
polymers.
4
I. Flame Synthesis
(A) General Scheme for Flame Synthesis of Fine Powders
flame
(Chem. rxn,
nucleation,
growth)
Combust gases
Particles
+
Fuel (e.g., H
2
or CH
4
)
Oxidizer
(e.g., O
2
or air)
particles
collection
product
powder
combust
gases
pollution
control
exhaust
gases
Reactants
(e.g., SiCl
4
or AlCl
3
)
(burner)
5
(B) Particle Formation Processes in a Flame
SiCl
4(g)
H
2
O, O
2
SiO
2(g)
AlCl
3(g) Al
2
O
3(g)
H
2
O, O
2
TiCl
4(g)
H
2
O, O
2
TiO
2(g)
Condensing species
(flame)
Nucleation
Initial Particles
Initial Particles
(flame)
Growth
Product Particles
Reactants
Chemical reaction
(flame)
Condensing Species
(particle forming species)
6
(C) Flame Structure and Burner Design
flame serves as the medium or environment
for the formation of particles
Burner
Design
Flame Structure
temp dist
conc dist
flow pattern
residence time
Formation
of
Particles
Properties
of
Powders
chemical reaction, nucleation and growth all
occur in the flame.
7
Classification of Flame (or flame structures)
flame
premixed flame
(fuel and
oxidizer are
premixed before
feeding into
burner)
diffusion flame
(fuel and
oxidizer are fed
separately into
burner)
parallel flow
diffusion flame
counter flow
diffusion flame
F 1
F 3
F 2
F 7
8
Premixed flame characteristics
ignition
Rate of Comb. Rxn = f (T, [F], [O], [inert])
For ignition
= ( ,[ ])
rxn
Q f T radicals
radicalsH, OH, CH, CH
2
,
rxn loss
Q Q >
ignition occurs when
9
(a) by increasing temperature
e.g., by using a hot metal stick

(b) by creating radicals
e.g., by UV illmination

(c) by both increasing temperature and creating radicals
e.g., pilot flame (math, lighter,)
techniques for ignition
10
Extinction
by decreasing temperature
e.g., water spraying, blowing

by decreasing radical concentration
e.g., increasing contact surface area with solid.
F 4
11
Flash Back
combustion velocityV
com
stationary flame

flash back

blow off

V
gas
V
com
| V
com
| | V
gas
|
V
gas
V
com




F + O
(stay still) V
gas
=0
bot plate
flame
12
(D) Rate of fusion of an Agglomerate in a Flame
1/ 3
(1 ) 1
dR
dt
o o

( +

=
Rprimary particle radius
number of neighbors
t time
surface tension
viscosity
Frenkel (1945)
13

f (Temp, mixing with other oxides)
strong
Temp or/and
mixing of SiO
2
and Al
2
O
3

dR
dt

F 7 F 14.46 F 6 F 5 F 7.2 F 14.50
14
II. Combustion Synthesis
Self Propagating High Temperature Synthesis (SHS)
or Combustion Synthesis
A. IntroductionCharacteristics of SHS
Highly Exothermic Reaction
High Temperature(2000-4000K), Visible Radiation,
and Self-Propagation.
Rapid, Combustion Velocity1-10 mm/sec
Maximum Combustion Temperature
1 2 3
4 5
15
Why self-propagating
(1) large contact surface area between reactant particles
(a) compaction of reactants
(b) melting and capillary spreading
(2) high reaction temperature
(3) small heat losses
(heat retained due to compaction of reactants)
(4) assisted by liquid and/or gas formation
16
(B) Types of SHS Reactions
(A) Metals
(a)
( ) 4
4
g
Na SiCl +
( ) ( )
4
l g
Si NaCl +
(b)
( )
( ) 5
5/ 2
g g
Mg NbCl +
( )
( )
2
5/ 2
l
g
Nb MgCl +
Examples for Combustion Synsthesis
17
(B) Oxides
2 3 2 2
0.5 2 3 Y O BaO Cu O + + +
2 3 6 x
YBa Cu O
+
(C) Carbides
(a) Ti+C TiC
(b) N
b
+(1-x)/2 N
2
+ xC NbN
1-x
C
x
(c) Si+C SiC
18
(D) Nitrides
(a) 2Al+N
2
2AlN
(b) 3Al+NaN
3
3AlN+Na
(c) 3Si+2N
2
Si
3
N
4
(E) Intermetallics
(a) Ti+Al TiAlx
(b) Ni+Al NiAl
19
(F) Composites
(c) 3TiO
2
+ 4Al + 3xC + yAl
2
O
3
3TiC

+ 2(1+y)Al
2
O
3
(b) 3TiO
2
+ 10Al

+ 3B
2
O
3
5Al
2
O
3
+ 3TiB
2
(a) Al + Fe
3
O
4
Al
2
O
3
+ Fe

30
Typical Solution Methods
Preparation
of Solution
Precipitation
of Solute
Species
Filtration of
Precipitates
Washing Calcination
Precise control of components, e.g., Ce(NO
3
)
2
:ZrO(NO
3
)=0.75:0.25 for Ce
0.75

Zr
0.25
O
2
powder.
Complete solution or complete mixing on molecutar level. (otherwise, e.g., single
phase CeO
2
or ZrO
2 will form instead of
Ce
0.75
Zr
0.25
O
2
)
*Solution-precipitation method: OK
*Coprecipitation method: OK
*Sol-gel method: OK
*Spoay pyrolysis: OK
*Freeze drying: OK
*Solution combustion: OK
31
Precipitation of Solute Species

Simultaneous precipitation (or simultaneous nucleation or Co-precipitation)
of all desired species to form uniform composition, e.g., 0.75Ce+0.25Zr for
Ce
0.75
Zr
0.25
O
2

Uniform and short growth duration to obtain nanoparticales.
=abrupt (rapid) charge in conditions to bring about precipitation
=short processing duration
*Solution-evaporation: too slow
*Solution-precipitation, coprecipitation: too slow [adjustment of PH by adding
acids or bases (or addition of precipitation agentes) with mixing is slow and
not uniform)
*Sol-gel method: OK
*Spray pyrolysis, freeze drying: OK
*Solution combustion: OK
32
Abrupt occeurence of ignition, rapid propagation of combustion, short
combustion duration
Generation and evolution of large amounts of gases carry away large
grantities of heat, create pores in the product and causes rapid cooling of
the product=shorter the time for growth, generating nano size particles
with large specific surface area.
High combustion temperature (900): (1). dry powders; (2). desired
crystalline structure; (3). high purity (impurities are decomposed and
raporiad) (4). does not need filtration, washing and calcination.
*Microwave-assisted solution combustion synthesis
same ao solution combustion with even better uniform temperature
distribution and additional control of temperature
33
possible microwave effects:
34
Sol- Gel Auto- Combustion Synthesis Method
(Sol gel method + SHS)
Example I
Synthesis of nanocrystalline LaFeO
3
(magnetic materials with
potential applications in sensors and monitoring)
Fe(NO
3
) 9H
2
O
La(NO
3
) 6H
2
O
C
6
H
8
O
7
H
2
O
dissol
d.i.H
2
O
Clear solution
NH
3
soln
sol
130C
brown dried gel
ignition
combustion
LaFeO
3
Example II
Synthesis of NiCuZn Ferrite(Ni0.25Cu0.25Zn0.25Fe2O4, magnetic
material having potential applications in multilayer chip inductor (MLCI))
metal nitrates
citric acid
disso
d.i.H
2
O
NH
3
soln
sol
130C
gel
ignition
combustion
NiCuZn Ferrite
nanopowder
47
SHS
Various Materials
ceramics
intermetallics
elements
composites
polymers
SHS
Commercialization ???

advantages:
fast reaction
low energy consumption
simple processing
48
Commercialization of SHS Processes

high values (market prices) of the products
other synthesis methods: difficult or high
production costs
low prices of the raw materials for the SHS
Economics

49
One Possibility for SHS Commercialization: AlN
current market prices: 30-150 USD/kg
current industrial processes
direct nitridation (ART, USA)
2Al+N
2

carbothermal reduction (Tokuyama, Japan)

disadvantages:
high energy consumption slow production rate
additional steps to remove highproduction costs
residual reactants
raw materials for SHS
Al powder: 2-15 USD/kg N
2
gas: ~0.5 USD/kg
>1200k
several hrs
2AlN
1300~2000k
several hrs
2AlN+3CO
Al
2
O
3
+N
2
+3C
50
Properties of AlN
high thermal conductivity
Al:300,, Si:148, AlN:130260,SiO
2
:1.4, Al
2
O
3
:20(w/m-k)
high electrical resistivity
(10
13
O cm)
low thermal expansion coefficient
Si:4, AlN:4.3, Al
2
O
3
:7.2, SiO
2
:15(PPM/)
low dieletric constant (8.0 9.0)
good mechanical strength
good corrosion resistance
good thermal-shock resistance


51
Applications of AlN
semiconductor substrates
IC packages
IC encapsulant
heat sinks
thermal grease
thermally conductive filler
high thermally conductive composites
heat radiation plates
Si-Al-O-N compounds
Molten metal crucibles and liners
Corrosion resistant parts



52
D-1 Particle Formation Processes in a Flame
(1) Reactants
Chemical reactions
(flame)
Condensing Species
SiCl
4

(g)

H
2
O, O
2
SiO
2

(g)
AlCl
3(g)
Al
2
O
3 (g)
H
2
O, O
2
TiCl
4(g)
H
2
O, O
2
TiO
2(g)
(2) Condensing species
Nucleation
Initial Particles
(3) Initial Particles
Growth
Product Particles
53
solution of sodium
aluminate (NaAlO
2
)
+ waste
seeding
with fine
Al(OH)3
particles
hydrolyzed
cooling
Temp
agitation
aluminum gydroxide
(precipitated)
time
filtration washing
Aluminum hydroxide(Al(OH)
3
)
calcination
1200
cooling
(size, texture, purity)
40~100 m particles
size reduction
1 m or finer
54
2 BaTiO
3
()
Ba+2C
3
H
7
OH B(OC
3
H
7
)
2
+H
2
82
TiCl
4
+4C
3
H
7
OH+4NH
3
Ti (OC
3
H
7
)
4
+4NH
4
Cl
C
6
H
6
5
Ti(OC
4
H
7
)
4
4C
5
H
11
OH
reflux

24h
C
4
H
6
Ti (OC
5
H
11
)
4
4C
3
H
7
OH
Ba(OC
3
H
7
)
2
Ti(OC
5
H
11
)+3H
2
O BatiO
3
+ BaTiO
3
+2C
3
H
7
OH+4C
5
H
11
OH
(C) Solvent Extraction-Piltration
to reach supersaturation or to esceed the solubility product
(D) Sol-Gel Techniques
(E) solvent combustion
(F) Hydrothermal Precipitation
55
. Using fuelsFlame Synthesis
(A)Optical fiber
(B)Diamond film
(C)Fine particles
carbon particles (carbon black)
oxide ceramic powders
(SiO
2
, TiO
2
, Al
2
O
3
......)
non-oxide ceramic powders
(AlN, Si
3
N
4
.............)
Materials Synthesis by Combustion
56
. Using no fuels (one reactant serves as fuel)

Combustion Synthesis

Self-Propagating High-Temperature Synthesis (SHS)

(A)solid solid
(B)solid liquid
(C)solid gas
(D)gas gas

ceramics

intermetallics
composites
polymers
elements
57
General Scheme for Flame Synthesis of Fine Powders
flame
(Chem. rxn,
nucleation,
growth)
reactants
(e.g., SiCl
4
or AlCl
3
)
fuel (e.g., H
2
or CH
4
)
combust gases

particles
particles
collection
product
powder
combust
gases
pollution
control
exhaust
gases
Oxidizer
(e.g., O
2
or air)
58
A. Formation Process of Powder Particles

reactants
Chem. Rxn.
Particle Forming Species
Nucleation
Nuclei (Initial particles)
Growth
Product Particles
Particle Forming Species
(a) Vapor atoms or molecules in gas phase.
(b) Solute atoms, molecules, or ions in liquid solution; pure melt;
atoms, molecules, or ions in a melt solution.
(c) Solute atoms, molecules, or ions in a solid solution
(d) Newly formed phase materials.
Phys. Rxn.