Overview of Nanoparticle MaterialsJohn Texter

College of Technology, Eastern Michigan University, Ypsilanti, MI

Particle Synthesis, Particle Modification

Particle Characterization

Particle-Based Materials

Synthesis and ModificationGas Phase (Pratsinis)

Synthesis and ModificationGas Phase (Pratsinis)

Synthesis and ModificationLiquid Feed Flame-Spray Pyrolysis (Laine)

Synthesis and ModificationSegmented Flow Tube Reactor (Hoffman)

Synthesis and ModificationHydrothermal (Matijevic)

Synthesis and ModificationBinary Metal Oxides - Nonaqueous Sol-Gel (Niederberger)

General Synthesis General Synthesis ProtocolProtocol::

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 ModificationMonodisperse Particles from Aggregation of Nanoparticles (Matijevic)

Synthesis and ModificationMonodisperse Emulsions (Pine)

polar fluid+ surfactant

polymer particles

monomerliquid

swell with monomer

polymerize monomers Mw small

swell with oil

Add solvent (oil) for polymer

Synthesis and ModificationBarium Sulfate Morphogenesis (Coelfen, Qi)

2μm

0.5μm

0.5μm

2μm

PEGPEG--bb--PEIPEI--SOSO33HH

PEGPEG--bb--PMAAPMAA--POPO33HH22

PEGPEG--bb--PMAAPMAA--AspAsp

2μm

PEGPEG--bb--PEIPEI--COOHCOOH

NoNo additiveadditive

Synthesis and ModificationSIP (Advincula)

Synthesis and ModificationBlock Copolymers as Nanoreactors (Advincula)

Cationicpolyelectrolytes

Amphiphilicblock copolymers

(PS-b-P2VP)

Dendrimers(PAMAM)

Synthesis and ModificationMicrogels by Dispersion Polymerization (Lyon)

Oligoradical Precursor Particle

Growing Particle Microgel

Precipitation Polymerization

NHO NH

NH

O

OX

O+ +SDS

APS

70 oC

>4 hrs.

Synthesis and ModificationFunctionalization (Hoffman)

Synthesis and ModificationLigand Coated Metal Nanoparticles (Stellacci)

Metal Salt (AuHCl4) + HS

Reducing Agent (NaBH4)+HS

Ligand exchange reaction*

Direct mixed ligands reaction**

Synthesis and ModificationQuantum Dots in Frogs (Norris)

Me2Cd Se CdSe NCs

320 °C

• diameters between 2nm to 12nm• size distributions <3-5%

micelle

hydrophobic corehydrophilic shell

H2OH2O

Synthesis and Modificationin Reverse Micelles (Pinna)

Synthesis and ModificationMicroemulsion Polymerization (Kaler)

P•

MM M M

PM•

MM

M

M M

MM

M

M

MM

M

M

I•

IM•M•

310~Particles#Micelle#

Initiation by IM•

Propagation

Initiationby M•

ChainTransfer

M

M

M

M

M

5 nm

Synthesis and ModificationTemplating in Matrices (Braun)

z 5 mmzz

x

y

zzzzzz

xx

yy

xx

yy

xx

yy

xx

yy

Synthesis and ModificationReplacement of Ag by Au (Xia)

Synthesis and ModificationStretching Polymer Beads (Xia)

Synthesis and ModificationDimeric Colloids (Xia)

Synthesis and ModificationGeometrical Clusters (Pine)

silica spheres

11

silica-coatedPMMA spheres

11

4 5 6 7

8 9 10 11

118 9 10

3 4 5 6 7

Synthesis and ModificationColloidal Molecules (Pine)

2 3 4

Synthesis and ModificationEncapsulation (Velev)

CharacterizationConfocal Microscopy (Wiltzius)

photomultiplier tube

objective lens, e.g. 100x

laser

illuminating aperture

dichroic beamsplitter

confocal aperture

focal planesample

in focusout of focus

CharacterizationSurface Charge in Heterocoagulation (Matijevic)

CharacterizationAnalytical Ultracentrifugation (Coelfen)

CharacterizationHRTEM (Pinna)

CharacterizationTEM Image Analysis (Coelfen)

0.80.8 1.21.2 1.61.6 2.02.0 2.42.4 2.82.8 3.23.2 3.63.600

55

1010

1515

2020350350 countscounts

particle diameterparticle diameter [nm][nm]

Num

ber f

requ

ency

%

CharacterizationParticle Interaction Potentials (Yodh)

CharacterizationSANS (Kaler)

CharacterizationRheology (Weitz)

Particle-Based Materials

Particle Assembly

Thermodynamics

Functional Materials

Devices

Particle AssemblyThermodynamics (Wiltzius)

Particle AssemblyEntropy Drives Growth (Weitz)

Particle AssemblyEntropy and Other Forces (Yodh)

Particle AssemblyDielectrophoreticMicrowire Assembly(Velev)

AC Voltage

Grounded

FDEP

Particle Assembly2D Epitaxy (Yodh)

Particle AssemblyTemplate Assisted Assembly (Niederberger)

Particle AssemblyTemplated Clusters (Xia)

Particle Assembly2D Dielectrophoretic Assembly (Velev)

Fourier transform Diffraction pattern

5 s

15 s

Optical micrograph

Particle AssemblyDomain sizes too small (Wiltzius)

Particle AssemblyConvective Crystallization (Xia)

Particle AssemblyConvective Assembly(Velev)

- Ambient light

- Low angleLight transmission

cm2 coatings from μL drops in minutes1.1 μm latex crystal viewed with:

1cm

Particle AssemblyCCAs to close-packed photonic xtals (Wiltzius) no salt

salt

electrostaticsdominate

screenedelectrostatics

VdW’s attraction“guide” adhesion

add salt

Charge Stabilized

u(r)

rvan der Waals

attraction

electrostaticrepulsion

Screened

u(r)

r

screening

Particle AssemblyModifying interactions and annealing in microgel photonic materials (Lyon)

Particle AssemblyStrategies for Assembling Anisotropic Structures (Niederberger)

Particle AssemblySelf-Assembly of Nanoparticles (Niederberger)

Particle AssemblyChains with Given Handedness (Xia)

Particle AssemblyColloidal Crystalline Arrays (Asher)

~ 1013 spheres/cm3

spacing dependent only upon particle number density and crystalline structure

-

Dialysis /Ion Exchange Resin

Self-assembly

Crystalline Colloidal Array

FCC--

----

- --

+

-

--

---

- --

+

--

---- -- -

--

--- ---

--

--- -

-

--

---

- --

-

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---

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--

---- --

++

--

-

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---

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---

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---

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--

-

-

-

--

++

+

++ + +

+

+

+

+

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+

+

+

++

+

+

+

++

+

+

++

+

+

+

+

+

+

+ +

++

+

++

+

++

+ +

--

---- --

+

++

+

--

---- --

+ +

+

++

+

+

+

+

+

+

+

+ +

++

+

+

+

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+

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- ---

--

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---- --+

+

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+

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---- --+

+

+

+--

--- --+

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-- -- ++

+

+

+

+

+

+

+

+

++

+

+-

-

--

-+

+

+

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---

----

-+

+-

- -

Particle AssemblyMechanism of Convective Crystallization(Norris)

100X

microscopeobjective

immersionoil

CC

D

video camera

800nm spheres

real time video

Particle AssemblyBiomineralization (Coelfen)

SEM ofSEM of broken mussel broken mussel shellshell

SEM ofSEM of broken mussel broken mussel shell after proteinshell after protein

removalremoval

SEM ofSEM of broken mussel broken mussel shell after shell after CaCOCaCO33

removalremovalTEM TEM thin cutthin cut ofofdeveloping developing mussel shellmussel shell

SEM ofSEM ofdeveloping developing mussel shellmussel shell

SEM SEM mature mussel mature mussel shellshell

Particle AssemblyMagnetically Driven Assembly (Asher)

350 400 450 500 550 600 650 7000

2

4

6

NaCl Concentration (From left to right)4.0mM, 2.0mM, 1.0mM, 0.67mM, 0.33 mM,0.16 mM, 0mM

Rel

ativ

e in

tens

ity

wavelength (nm)

0 1 2 3 4

160

180

200

220

240FC

C (1

11) p

lane

spc

aing

/ nm

NaCl concentration / mM

Particle AssemblyBalancing Interfacial Interactions (Coelfen)

Nucleationclusters

Primary nanoparticles> 3 nm

Crystal growth

Amplification Mesoscale assembly

Single crystal Iso-orientedcrystal

TemporaryStabilization Mesoscale

assembly

Mesocrystal

Particle AssemblyBalancing Interfacial Interactions (Hoffman)

Particle AssemblyCopper Oxalate Assembly (Hoffman)

Functional MaterialsFlame 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 MaterialsMicroporous and Mesoporous Materials (Stein)

Functional MaterialsInorganic Pigments (Stein)

Functional MaterialsPhotonic Crystals (Norris)

Functional MaterialsHierarchically 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; fillSpace between latex particles by capillary flow.

Allow to gel. RemovePDMS master. Calcine.

Functional MaterialsTwo Photon Fab (Braun)

Functional MaterialsOptical Switch (Asher)

S NN S

500 600 700

1

2

3

4

5

6

Rel

ativ

e In

tens

ity (a

.u.)

-20 Oe -9 Oe +9 Oe +20 Oe

Rel

ativ

e In

tens

ity (a

.u.)

Wavelength /nm-120 -90 -60 -30 0 30 60 90 120

1

2

3

4

5

6

686 nm 549 nm

H / Oe

Functional MaterialsMetal Cation Sensors (Asher)

500 550 600 650 700 750 800

bu ffe red sa line

5 m M

2 m M0.5 m M

54 μM0.54 μM

1 μM

11 nM

Diff

ract

ion

inte

nsity

/ a.

u.

λ / nm

No Cu2+11 nM0.54 μM1 μM

54 μM 0.5 mM 2 mM 5 mM

Functional MaterialsGlucose Sensing (Braun)

HydrogelFlow cell

Inflow from syringe pump

10x ObjectiveBeamsplitter

Optical fiberPinhole

Light source

PhotodiodeArray

Detector

Outflow

RBOH

OHRB

OHOHOH

O

RBOH

OO

OH

OH

OH

Glucose-PBA complex

PBA (phenylboronic acid)

1 mM glucose

0 mM glucose[Glucose]0 mM 100 mM

SEM of templated hydrogel

Functional MaterialsGyricon Display (Morrison)

Charged,bichromalballs.

Suspendedin an oil.

Encased ina plasticsheet.

Addressedwith electrodes. That Xerox

built.

Functional MaterialsElectrophoretic Display (Morrison)

Sony’s LIBRie EBR-1000EP from E Ink and Phillips Electronics

Negativelychargedpigmentparticles.

Positivelychargedpigmentparticles.

Suspendedin a clear oil.

Addressedwith electrodes.

Functional MaterialsElectrochromic Devices (Kotov)

Functional MaterialsDonor-Acceptor Tagging (Kotov)

Functional MaterialsInsulin Incorporation and Release (Lyon)

Linear increase in insulin content with

particle layer number.

Functional MaterialsGlucose Sensing (Asher)

Functional MaterialsLab on a Chip (Velev)

gold nanoparticles →

sulfate latex →

Functional MaterialsQuantum Dots in Frogs (Norris)

Acknowledgments

• Liehui Ge, Swapnil Bondre, Swapna Devireddy

• Lecturers• Students for their participation and

stimulation• Petroleum Research Fund ($$$$)

Overview of Nanoparticle MaterialsJohn Texter

College of Technology, Eastern Michigan University, Ypsilanti, MI