Particle Processing

Research
Terry A. Ring
Chemical Engineering
University of Utah
Presentation Goals
Introduce My Work to NSF
Show Breadth of Coverage
Fundamentals of Ceramic Powder Processing
and Synthesis
Product Box
Show Depth of Coverage in One Area
Nano-sized Cluster Nucleation
NSF - Program Vision

Ceramic Particle
Processing Research
Crystallization
Inhibitors -
Trane Corp.
Nifedipine (Heart
Drug) Sintering-
Pfizer, Bayer
Scaling Chemicals-
Spa Natural
Bio-Cements as Bone
Replacement
Materials - Sultzer,
Mathis
Ceramic Thin Films As
Chemical Sensors -
RMA Associates
BaTiO
3
Multi-layer
Capacitors-
Phillips(Taiwan)

Ceramic Particle
Processing Research-cont
Multi-layer Chip
Support Sintering -
Metalor, IBM, Dupont
Vermiculite Based
Insulation Materials -
ABB
Silica Aerogels for
Building Insulation -
Airglass, SA
Nitride coating for
Al
2
O
3
Platelets for
Cutting Tools -
Amysa, SA
Pultrusion Process for
Carbon Fiber
Reinforced Composite
- Easton

Precipitation Research
Agglomeration in CSTR
Reactant A Reactant B
Outlet
Overflow
Mixing
Shaft Baffles
Nano-sized Cluster
Nucleation
Introduction
Classical Nucleation Theory & Limitations
New Theory & Findings
Introduction
Unique Properties of Nanosized Particles
Plasmon Resonance -color due to size, color
change due to adsorption-sensors
Between Bulk and Atomic Electrical
Properties
Catalytic Properties
Magic Cluster Sizes
C60, C70, C nanotubes,
Na clusters of 8, 20, 40, 58 and 92

Silicon Particles
Stimulated Emission CdS
Nano-Clusters-Laser
Lasing only when quantum
dot concentration is
sufficiently high.
Stimulated emission>Auger
recombination

Klimov, V. Mikhailovsky,
A.,Xu, S., Hollingswork, J.,
Malko, A., Bawendi, M.,
Eiser, H-J., Leatherhead,
C.A.
Science 290,314 (2000)
Science 287,1011 (2000)
Semiconductor Nanocrystals
Breakdown Organic Pollutants
- Environmental remediation
- Solar photocatalysis/fuel production
0
100
200
300
400
500
600
700
800
3 4 5 6 7 8
A
b
s
o
r
b
a
n
c
e

(
2
5
0

n
m
)

Elution Time (min)
MoS
2
Photocatalyst
alkyl chloride
t=1 hour
t = 0
3 nm MoS
2
nanocrystals photo-oxidize
an alkyl chloride in solution using only
visible room light
Fullerene Synthesis
Fullerene Synthesis
odd vs. even clusters
Nanoparticle Synthesis
Desperate Need to Control
and Scale-up!!
Nanoparticle Synthesis =
Nucleation (no Growth!!)
Classical Nucleation Theory
Free Energy in two pieces
G(r) = -(|
v
r
3
/Vm)RT ln(S)+ |
a
r
2
G(i) = - i k
B
T lnS+ |
a
a
o
2
i
2/3

where v(=|
v
r
3
) is the volume and
a(=|
a
r
2
) is the area of the aggregate,is
the molar volume of the precipitate, is
the surface free energy per unit area.
X(atom) +X(r*-atom)<----> X(r*)
0 10 20 30 40 50
324.897
0
G( ) , i 1
.
kB T
G( ) , i 10
.
kB T
G( ) , i 50
.
kB T
G( ) , i 100
.
kB T
G( ) , i 500
.
kB T
G( ) , i 1000
.
kB T
G( ) , i 5000
.
kB T
G( ) , i 10000
.
kB T
i
Critical
Size, r*
G(i)
S|
New Nucleation Theory
Multi-Atom Addition
Free Energy Driving Force for Diffusion and
Addition
New Attributes
Predicts transients of Cluster Size Distribution
Predicts Induction Time

Population Balance
- Multi-atom Addition

Numerical solution required except

ij
= 1 C
k
=
Smoluchowski, Physik Zeits, 17,557(1916)

ij
= i+j C
k
= , u= 1-exp(-t)
Scott, W.T., J. Atmos. Sci., 25,54(1968)

ij
=i*j C
k
= t
k-1
k
k-2
exp(-k t)/k!, t 0
McLeod, J.B., Quant, J. Math Oxford, 13,119 and 193(1962).


1
1
) 2 / 1 (
) 2 / (
+

+
k
k
t
t
!
) exp( ) )( 1 (
1
k
ku ku u
k

i
i
k i k i k i
k
i
i k i k
C C C C t C

+ = c c
1
,
1
1
,
2 / 1 /
Collision Frequency
J
ij
= -(Dij C
i
)/(ri+rj)*4
t
(r
i
+r
j
)
2
*C
j
*exp(-
A
Gij/kBT)) =

ij
C
i
C
j
This Collision Frequency compares to others by various Mechanisms:
Collision Frequency

ij
=
J
ij
C
i
C
j

Kolmogorov
microlength
scale =
v
/u
eddy size =

Tank size = L
Diffusion D
ij
*4
t
(r
i
+r
j
)
Free Energy
-D
ij
exp(
T k
G
B
ij
A
) 4
t
(r
i
+r
j
)
Viscous Shear
4/3

(r
i
+r
j
)
3 6
v
/u <

Transition
2.36*
c
5/12

v
-1/4
(r
i
+r
j
)
8/3
6
v
/u <

< 25
v
/u
Inertial
6.87*
c
1/3
(r
i
+r
j
)
7/3 25
v
/u<

< L/2
macro
7.09*(
c
L)
1/3
(r
i
+r
j
)
2 L/2<

~L
D
ij
=

T k
B
t 6
*[
1
r
i
+
1
r
j
] r
i
=a
o
*i
1/3
Collision Free Energy, AG
ij
AG
ij
=G(i+j)-(G(i)+G(j))
G(i) = - i k
B
T lnS + |
a
a
o
2
i
2/3

i or j > 1
AG
ij
=G(i+j)-(G(i)+G(j))=

|
a
a
o
2
|(i+j)
2/3
- i
2/3
- j
2/3
]
i = 1, any j
AG
ij =
- i k
B
T lnS + |
a
a
o
2
|(i+j)
2/3
- j
2/3
]
j = 1, any i
AG
ij =
- j k
B
T lnS + |
a
a
o
2
|(i+j)
2/3
- i
2/3
]

Effect of exp(-AGij/k
B
T) on Nucleation

ij
=(i+j)exp(-AGij/k
B
T),
Numerical Solution- C

ij
=(i+j),
Analytical Solution, N
Binding Energy per Li atom
Kouteckky, J. and Fantucci, P., Chem. Rev., 86,539-87(1986).
0 10 20
18. 3358
-0
( ) GS
is
.
. . .
4 t a1
2

.
kB T
ig
2
3
1
ig
.
0 ig
20 1 , is ig
Li
n
Optimal Geometry
BE/n
(eV)
Li
3
3.2 (C
2v
) 0.35
Li
3
3.3 (C
2v
) 0.34*
Li
4
4.2(D
4h
) 0.51
Li
4
4.3(T
d
) 0.41
Li
5
5.2(D
3h
,C
3v
) 0.56
Li
5
5.3(C
4v
) 0.53
Li
5
5.4(D
5h
) -
Li
6
6.2(C
5v
) 0.62
Li
6
6.3(O
h
) 0.60
Li
6
6.4(D
3h
) 0.63**
Li
7
7.2(C
3v
) 0.61
Li
7
7.3("fcc") 0.61
Li
7
7.4(??) -
Li
8
8.2(C
2v
) 0.71
Li
8
8.3("fcc") 0.65
Li
8
8.4("bcc") 0.60
Li
8
8.5(??) -
Cluster Binding Energy
Activation Energy for i+j Cluster
Calculated from EA
i,j
= [
j i
BE
+
*
] -
j i
j
j
BE
i
i
BE
o o
+
+ ] [
, [
j i
BE
+
*
]
values are taken from Table 3 using
BE*
i
+.
j
BE*
corresponding
to a deformed structure of each cluster.
i / j 1 2 3 4 5 6 7 8
1 -k
B
T lnS 0.34 0.51 0.56 0.62 0.61 0.71 0.65
2 - 0.41 0.53 0.60 0.61 0.65 0.65 -
3 - - 0.63 0.61 0.60 0.65 - -
4 - - - 0.60 0.65 - - -
Structural Classical
0 1 10
6
2 10
6
3 10
6
0
0. 5
1
C
, m 1
N( ) ,
.
m At 1
C
, m 2
N( ) ,
.
m At 2
.
m At
0 0. 05 0. 1
0
0. 5
1
C
, m 1
N( ) ,
.
m At 1
C
, m 2
N( ) ,
.
m At 2
.
m At
0 1 2 3 4 5 6 7 8 910
0. 9999
4. 63056e-33
N ,
.
tmax
2
At k
C
,
tmax
2
k
N( ) ,
.
tmax At k
C
, tmax k
9 k
0 1 2 3 4 5 6 7 8 910
1 10
14
1 10
13
1 10
12
1 10
11
1 10
10
1 10
9
1 10
8
1 10
7
1 10
6
1 10
5
1 10
4
0. 001
0. 01
0. 1
1
,
.
tmax
2
At k
,
tmax
2
k
( ) ,
.
tmax At k
, tmax k
1
k
New Nucleation Theory
Dramatic effect for stable clusters,
k=2,4,8, Magic Clusters
Magic Clusters Affects Synthesis Path
Not One but Multiple Critical Cluster Sizes
Nucleation Rate, I= dC
k*
/dt
Depends on Synthesis Path
Crystalloluminescence
0 2 4
0
0.2
0.4
0.6
0.8
Col lision Trajectory, R/r e
B
E
/

n

(
e
V
)
BE
(i+j)
o
BE
j
o
BE
i
o
+
BE
j
BE
i
+
*
*
E
EA
Crystallo-
luminescence
Figure 3 Collision trajectory for collision between i=3 and j=4 clusters,
showing ground state energies before and after collision, as well as the
activiation energy of collsion.
Crystalloluminesent Spectrum
Intensity vs Energy
Intensity =
collisions/per unit time =
photons/unit time
Wavelength E = hc/l

Human eye detection
@ 3x10
4
photons/cm
2
/s at
510 nm
0 0. 5 1 1. 5 2 2. 5
1 10
14
1 10
13
1 10
12
1 10
11
1 10
10
1 10
9
1 10
8
1 10
7
1 10
6
1 10
5
1 10
4
0. 001
0. 01
0. 1
I
, i k
AE
, i k
eV
Similar to Line Spectra
Is this another cold fusion?
An effect produced by a barely detectable cause.
Data on the edge of detectability
Measurements are attributed to greater accuracy
Fantastic theories are offered.
Criticisms are met by ad hoc excuses thought up
on the spur of the moment.
The ratio of supporters to critics rises up to
~50% and then falls gradually to oblivion.

From1953 Lecture by Irving Langmuir
Another cold fusion? Cont.
Researcher avoids designing experiments that
would confirm whether or not an effect actually
exists. (D. Rousseau, 1982).
Pressures to publish prematurely (Broad, W. and
Wade, N., 1982.)
Being scooped.
Notoriety.
Potential for money to be made.
More common in fields with reliance on
statistically weak data. (N. Turro, 2001)
Crystalloluminescence
Term Schoenwald in 1786
30 References 1786 and 1957
An understanding of crystalloluminescence in not too
satisfactory at the present time, E.N. Harvey 1957
Examples: NaCl, KCl, NaF, AsCl
3
, K
2
SO
4
, As
3
O
3
, Sr(NO
3
)
2,
, CoSO
4
, K
2
CO
3
, KHSO
3
, NaKSO
4
,
NaKCrO
4
, NaKSeO
4
, Na
2
SO
4
, benzoic acid, and ice, water.
16 References 1957-1991 (15 Russian, 1 US + 1 Italian Review)
It is not possible to provide either a unifying physical picture of the microscopic mechanism
governing (crystalloluminescence) or a physical rule that allows conditions...where the
phenomenon is stronger, Barsanti, M. & Maccarrone,F., 1991
3 References from 1991-2000 (2 India, 1 Russian) - Experiments
Experimental Observations
Delay time is a function
of concentration & mixing
Flashes are Short
< 80 ns
Peak Count rates
~5-8x10
5
photons/s
Temporal & Spatial
Bunching of Flashes
340nm<<380 nm
Faint Blue White Light
Gibbon, M.A., Sopp, H. , Swanson, J., and Walton, A.J., J. Phys. C. 21,1921(1988).
Saturated NaCl + Conc. HCl - 120 s observation time
Spectra Has Series of Peaks
Lines are Different from
Thermal
Luminescence
Photoluminescence
Impurities in Crystal have
a Big Effect on Spectrum
Rabinerson, A.I. Wladimirskaya, M.A., Acta Physicochimica URSS, 10,859(1939)
BaSO
4
Crystallization
(20 min. exposure)
Lines
1935-1945
1976-1991
2021-2037
2145-2165
2228-2300
2300-2326
New Theorys Predictions
Predicts Crystalloluminescent Spectrum
Method to Quantitatively Measure Nucleation

Potential Real World Examples
H
2
O Condensation Nucleation
Interstellar Dust Nano-nucleation
Light from Deep Sea Vents


Super Novae
Nanocluster, Ti
14
C
13

with emission peak at 20.1 microns
is seen in Egg Nebula by
A.G.G.M. Thielens and M.A. Duncan
Science 288,313(2000)

this joins some 120 other small molecules
identified in the vicinity of stars,
interstellar gas and dust clouds
Experimental Verification
Interstellar Dust Clouds - Light from the Fringe
- Crystalloluminescence due to Nanocluster Nucleation
NSF
Particulate and Multiphase Program
1. Aerosols and colloids
2. Nanostructures
3. Granular flows
4. Multiphase processes related to particles,
droplets, and bubbles
5. Hydrodynamical multiphase analysis
6. Specific tools
Nanotechnology has
acquired National Status
National Nanotechnology
Initiative $500M proposed
for FY01 Federal Budget
Usher in the Next Industrial
Revolution
Develop and explore the
rules and tools of
nanotechnology
Education and Societal
Implications

President Clintons Jan. 21, 2000 announcement
of a National Nanotechnology Initiative
in a speech from the California Institute
of Technology.

Nanoscience -- behavior of materials
at the nanoscale is Nothing like that at the
large scale
- Properties not predictable from those at large scale

- Different physics and chemistry emerges

- New phenomena associate with:

Lead to:
Measured Yield Point
Light from Si
Catalysis from Pd clusters
GPa strength from Au
Pyrene hydrogenation
Electronic confinement
Preponderance of surfaces
and interfaces
Quantized effects
New modes of electronic and thermal transport
Different manifestations of thermodynamic
properties, phase transitions, and collective
phenomena
New chemical reactivities
New mechanical properties--strength,
friction, wear
Many Particulate Problems
in Nanotechnology
Lasers, Catalysis
Photonic Crystals - optical computing
Photonic Light Pipes
Nano TiO
2
Solar Cells
Nanotubes - computer wires, transistors
Nanotube Light Emission - Displays
Nanocomposites - tunable lasers

Layered Structures
Taylored Materials
- Electronics/photonics
- Novel Magnets
- Tailored hardness
Defects in Ordered Arrays
Bend Light
Optical Semiconductors
Hexagonal Packing of
Spheres
Light Diffraction
Photonic Crystal Light Pipe
Light Pipe
Light Leaving Pipe
Quantum Computing-
poly-Si
Si substrate
Light Traps
Stopping Light without Absorption
Yablonovitch, E., 1986.
Coupling to Biology
Sol-gel (or Micelle structures) for drug
delivery
Diffusive Collisions ~ R
(D
F
+2-3)
Diffusing Species will Stay in Fractal when D
F
>1.0

Barbe, C., 2001 Australian Patent Application
Connection to Biology
Enzyme Binding
Surfaces
Particles
Better BioCatalysis
Protein Binding
Surfaces
Particles
Better Implants
1/4
th
of Catalyase Tetramer
Liver Enzyme
2 H
2
O
2
----> 2 H
2
O + O
2
(g)
Heam
Site
Nano-particles for
Bio Separations/Bio Sensing

Couple to Computation
Nanoparticle properties from
Computational QM
Particulate Generation in CFD
Molecular Adsorption
Molecular Binding
Fractals + Flow

Conclusion
Particulate and Multiphase Program
Bright Future
Many New Research Areas
Many New Phenomena
Collaboration is key to Success
Virtual Centers
Nano Property Prediction
Photonic Crystals
Enzyme/Particle Binding
Fractal Aggregates
Nano Particle Synthesis



New properties abound at this
small scale
microscale nanoscale
Inertia

Turbulence, convection, and
momentum are negligible

Surface and interfacial
properties play dominant
role

Electronics, optics,
mechanics, chemistry

Atomic forces and
chemical bonds dominate

Quantized effects
rule
New knowledge and understanding is needed
Nanostructuring is Key
to Novel/Enhanced Functionality
Layered-Structures Nanocrystals
Nanocomposites
- Electronics/photonics
- Novel Magnets
- Tailored hardness
- Novel catalysts
- Tailorable light emission
- Supercapacitors
- Separation membranes
- Adaptive/responsive behavior
- Pollutant/impurity gettering
Nanosciences will enable scientifically tailored materials
and lead to revolutionary advances in technology
Layered and 3-D Structures
Yield New Optical Properties
- The VCSEL is to photonics what the
transistor was to electronics. A key
21st century technology
- Most efficient, low-power light source
(57% in 97)
- Applications in optical
communications, scanners, laser
printing, computing...
Vertical Cavity Surface
Emitting Lasers (VCSELs)
Photonic Lattices
- Optical signals guided through narrow
channels and around sharp corners
- Near 100% transmission
- Key technology for
telecommunications and optical
computing
A
2-D
B
3-D
poly-Si
Si substrate
Water Condensation due to Shock Wave
Deep Sea
Life
Salt Lake Tribune, 2/13/97
National Geographic October 2000
Deep Sea Vents
C&E News 12/21/98
National Geographic October 2000
Deep Sea Vents
Deep Sea Vents Spew Solublized Salts into
the cold sea, causing Precipitation &
Crystalloluminescence
In the Deep Ocean Deep Sea Vents are the
only source of Chemical Energy and Food
Mobile Animals need to be able to locate
them - so they need eyes!!