Overview of Nanoparticle
Materials
John Texter
College of Technology, Eastern Michigan University, Ypsilanti, MI
Particle Synthesis, Particle Modification
Particle Characterization
Particle-Based Materials
Synthesis and Modification
Gas Phase (Pratsinis)
Synthesis and Modification
Gas Phase (Pratsinis)
Synthesis and Modification
Liquid Feed Flame-Spray Pyrolysis
(Laine)
Synthesis and Modification
Segmented Flow Tube Reactor
(Hoffman)
Synthesis and Modification
Hydrothermal (Matijevic)
Synthesis and Modification
Binary Metal Oxides - Nonaqueous SolGel (Niederberger)
General Synthesis
Protocol:
1) Metal Alkoxide + Benzyl Alcohol
(C6H5CH2OH)
Metal Alkoxides:
VO(OiPr)3, Nb(OEt)5, Hf(OEt)4,
Ta(OEt)5, Sn(OtBu)4, In(OiPr)3
2) Heat Treatment in Autoclave at
200°C-250°C
Ta2O5
Synthesis and Modification
Monodisperse Particles from
Aggregation of Nanoparticles (Matijevic)
Synthesis and Modification
Monodisperse Emulsions (Pine)
monomer
liquid
polymer
particles
polar fluid
+ surfactant
swell with
monomer
polymerize
monomers
Mw small
Add
solvent
(oil) for
polymer
swell
with
oil
Synthesis and Modification
Barium Sulfate Morphogenesis (Coelfen, Qi)
2μm
0.5μm
PEG-b-PEI-SO3H
PEG-b-PMAA-Asp
0.5μm
2μm
No additive
2μ
m
PEG-b-PEI-COOH
PEG-b-PMAA-PO3H2
Synthesis and Modification
SIP (Advincula)
Synthesis and Modification
Block Copolymers as Nanoreactors
(Advincula)
Dendrimers
(PAMAM)
Cationic
polyelectrolytes
Amphiphilic
block copolymers
(PS-b-P2VP)
Synthesis and Modification
Microgels by Dispersion Polymerization
(Lyon)
O
O
HN
HN
+
+
HN
SDS
70 oC
APS
>4 hrs.
O
X
O
Precipitation Polymerization
Oligoradical
Precursor
Particle
Growing
Particle
Microgel
Synthesis and Modification
Functionalization (Hoffman)
Synthesis and Modification
Ligand Coated Metal Nanoparticles
(Stellacci)
HS
Metal Salt (AuHCl4) +
+
Reducing Agent (NaBH4)
HS
Direct mixed
ligands
reaction**
Ligand
exchange
reaction*
Synthesis and Modification
Quantum Dots in Frogs (Norris)
hydrophobic core
hydrophilic shell
H2O
H2O
Me2Cd
Se
CdSe NCs
320 °C
• diameters between 2nm to 12nm
• size distributions <3-5%
micelle
Synthesis and Modification
in Reverse Micelles (Pinna)
Synthesis and Modification
Microemulsion Polymerization (Kaler)
M
Initiation by IM•
M
P•
IM•
M
M•
M
M
M
PM•
MPropagation
M
M
M
Chain
Transfer
M
I•
M
M
M
M
M
M
M
Initiation
by M•
M
M
M
M
# Micelle
~ 10 3
# Particles
5 nm
Synthesis and Modification
Templating in Matrices (Braun)
y
x
zz
5 mm
Synthesis and Modification
Replacement of Ag by Au (Xia)
Synthesis and Modification
Stretching Polymer Beads (Xia)
Synthesis and Modification
Dimeric Colloids (Xia)
Synthesis and Modification
Geometrical Clusters (Pine)
3
4
5
6
7
8
9
10
11
11
4
5
6
7
9
10
11
11
8
silica spheres
silica-coated
PMMA spheres
Synthesis and Modification
Colloidal Molecules (Pine)
2
3
4
Synthesis and Modification
Encapsulation (Velev)
Characterization
Confocal Microscopy (Wiltzius)
photomultiplier tube
confocal aperture
illuminating aperture
laser
dichroic beamsplitter
in focus
out of focus
sample
objective lens, e.g. 100x
focal plane
Characterization
Surface Charge in Heterocoagulation
(Matijevic)
Characterization
Analytical Ultracentrifugation (Coelfen)
Characterization
HRTEM (Pinna)
Number frequency %
Characterization
TEM Image Analysis (Coelfen)
20
350 counts
15
10
5
0
0.8 1.2 1.6 2.0 2.4 2.8 3.2 3.6
particle diameter [nm]
Characterization
Particle Interaction Potentials (Yodh)
Characterization
SANS (Kaler)
Characterization
Rheology (Weitz)
Particle-Based Materials
Particle Assembly
Thermodynamics
Functional Materials
Devices
Particle Assembly
Thermodynamics (Wiltzius)
Particle Assembly
Entropy Drives Growth (Weitz)
Particle Assembly
Entropy and Other Forces (Yodh)
Particle Assembly
Dielectrophoretic
Microwire Assembly
(Velev)
FDEP
Grounded
AC
Voltage
Particle Assembly
2D Epitaxy (Yodh)
Particle Assembly
Template Assisted Assembly
(Niederberger)
Particle Assembly
Templated Clusters (Xia)
Particle Assembly
2D Dielectrophoretic Assembly (Velev)
Optical micrograph
5s
15 s
Fourier transform
Diffraction pattern
Particle Assembly
Domain sizes too small (Wiltzius)
Particle Assembly
Convective Crystallization (Xia)
Particle Assembly
Convective Assembly
(Velev)
cm2 coatings from
μL drops in minutes
1.1 μm latex crystal
viewed with:
- Ambient light
- Low angle
Light transmission
1cm
Particle Assembly
CCAs to close-packed photonic xtals
(Wiltzius)
no salt
electrostatics
dominate
Charge Stabilized
Screened
add salt
u (r)
electrostatic
repulsion
r
screened
electrostatics
u (r)
screening
r
VdW’s attraction
“guide” adhesion
van der Waals
attraction
salt
Particle Assembly
Modifying interactions and annealing in
microgel photonic materials (Lyon)
Particle Assembly
Strategies for Assembling Anisotropic
Structures (Niederberger)
Particle Assembly
Self-Assembly of Nanoparticles
(Niederberger)
Particle Assembly
Chains with Given Handedness (Xia)
Particle Assembly
Colloidal Crystalline Arrays (Asher)
Dialysis /
Ion Exchange
Resin
- + ++ - + +- - -+ +
- ++-- +-+
+ -+
+
+
- -- - +++ +
- - + - +
+
+
Self-assembly
FCC
~ 1013 spheres/cm3
-+- - +
+
+
+--+
+ - - +
+- +
- - +
-- --+
- +
++ +-
-- - +
-+ - - +
-
+
+ ++ -+
- - - + - - - -+
- - -- - - - -+ + -- +
+
- - - - - -+- - ++
+
+ - - -+ - - +- - + + +- - - - ++
+
+
+
+ - +
++ --+
-+
+
- -- - +
+
+
- - -- - - + - - ++
- - +-- - +
+
+ - -- - +
- +- - + +-+- - - + + -+- +
- + +
+- ++
+
+
-- --- - -+ - ++
+
+
- - - -+
-- --+- - +
+
Crystalline Colloidal Array
z spacing dependent only upon
particle number density and
crystalline structure
Particle Assembly
Mechanism of
Convective
Crystallization
(Norris)
800nm spheres
microscope
objective
real time video
CCD
100X
immersion
oil
video camera
Particle Assembly
Biomineralization (Coelfen)
SEM of broken mussel
shell
TEM thin cut of
developing
mussel shell
SEM of broken mussel SEM of broken mussel
shell after protein
shell after CaCO3
removal
removal
SEM of
SEM mature mussel
developing
shell
mussel shell
Particle Assembly
Magnetically Driven Assembly (Asher)
6
220
Relative intensity
FCC (111) plane spcaing / nm
240
200
NaCl Concentration (From left to right)
4.0mM, 2.0mM, 1.0mM, 0.67mM, 0.33 mM,0.16 mM, 0mM
4
2
0
350
400
450
500
550
600
650
700
wavelength (nm)
180
160
0
1
2
NaCl concentration / mM
3
4
Particle Assembly
Balancing Interfacial Interactions (Coelfen)
Nucleation
clusters
Crystal growth
Primary
nanoparticles
> 3 nm
Temporary
Stabilization
Mesoscale
assembly
Mesocrystal
Amplification Mesoscale
assembly
Single crystal Iso-oriented
crystal
Particle Assembly
Balancing Interfacial Interactions (Hoffman)
Particle Assembly
Copper Oxalate Assembly (Hoffman)
Functional Materials
Flame Pyrolysis (Laine)
•
•
•
•
•
•
•
Pure nano α-Al2O3
Abrasives
–Chemical mechanical polishing
Transparent ceramics
–Sodium vapor lamps
–Ti:Sapphire lasers among other things.
Coatings
High strength monoliths
–Ceramic prosthetics for example
Catalyst supports that do not sinter
Catalysts
Functional Materials
Microporous and Mesoporous
Materials (Stein)
Functional Materials
Inorganic Pigments (Stein)
Functional Materials
Photonic Crystals (Norris)
Functional Materials
Hierarchically Ordered Structures (Pine)
PDMS Master
(10 µm
structures)
Place on substrate
Place a drop of
suspension of
polystyrene spheres at
one end (1 µm
structures)
Fill channels by
capillary flow;
evaporate solvent.
Place sol droplet; fill
Space between latex
particles by capillary flow.
Allow to gel. Remove
PDMS master. Calcine.
Functional Materials
Two Photon Fab (Braun)
Functional Materials
Optical Switch (Asher)
6
6
-20 Oe
-9 Oe
+9 Oe
+20 Oe
5
4
686 nm
549 nm
4
3
3
N
S
S
N
2
2
1
1
500
600
700
Wavelength /nm
-120 -90 -60 -30
0
30
H / Oe
60
90 120
Relative Intensity (a.u.)
Relative Intensity (a.u.)
5
Functional Materials
Metal Cation Sensors (Asher)
54 μM 0.5 mM 2 mM 5 mM
Diffraction intensity / a.u.
1 μM 0.54 μM
11 nM No Cu2+
54 μM
0 .5 4 μ M
5 mM
11 nM
b u ffe re d
s a lin e
0 .5 m M
2 mM
1 μM
500
550
600
650
λ / nm
700
750
800
Functional Materials
Glucose Sensing (Braun)
OH
B
O
OH
HO B
HO
R
HO
PBA (phenylboronic acid)
[Glucose]
0 mM
100 mM
Inflow from
syringe pump
Glucose-PBA complex
HO
OH
R
Outflow
HO
OH
O
B
O
0 mM glucose
Flow cell
Hydrogel
10x Objective
Beamsplitter
Photodiode
Array
Detector
Optical fiber
Pinhole
Light source
SEM of templated hydrogel
1 mM glucose
R
Functional Materials
Gyricon Display (Morrison)
Charged,
bichromal
balls.
Suspended
in an oil.
Encased in
a plastic
sheet.
Addressed
with electrodes.
That Xerox
built.
Functional Materials
Electrophoretic Display (Morrison)
Negatively
charged
pigment
particles.
Addressed
with electrodes.
Positively
charged
pigment
particles.
Suspended
in a clear oil.
Sony’s LIBRie EBR-1000EP from E Ink and Phillips Electronics
Functional Materials
Electrochromic Devices (Kotov)
Functional Materials
Donor-Acceptor Tagging (Kotov)
Functional Materials
Insulin Incorporation and Release (Lyon)
Linear increase in
insulin content with
particle layer
number.
Functional Materials
Glucose Sensing (Asher)
Functional Materials
Lab on a Chip (Velev)
gold nanoparticles →
sulfate latex →
Functional Materials
Quantum Dots in Frogs (Norris)
Acknowledgments
• Liehui Ge, Swapnil Bondre,
Swapna Devireddy
• Lecturers
• Students for their participation and
stimulation
• Petroleum Research Fund ($$$$)
Overview of Nanoparticle
Materials
John Texter
College of Technology, Eastern Michigan University, Ypsilanti, MI