Overview of Nanoparticle Materials John Texter College of Technology, Eastern Michigan University, Ypsilanti, MI
Particle Synthesis, Particle Modification Particle Characterization ParticleBased Materials
Synthesis and Modification Gas Phase (Pratsinis)
Synthesis and Modification Gas Phase (Pratsinis)
Synthesis and Modification Liquid Feed FlameSpray Pyrolysis (Laine)
Synthesis and Modification Segmented Flow Tube Reactor (Hoffman)
Synthesis and Modification Hydrothermal (Matijevic)
Synthesis and Modification Binary Metal Oxides Nonaqueous Sol Gel (Niederberger) General Synthesis Protocol: 1) Metal Alkoxide Benzyl Alcohol (C 6 H 5 CH 2 OH) 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 C250 C Ta 2 O 5
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 M w small Add solvent (oil) for polymer swell with oil
Synthesis and Modification Barium Sulfate Morphogenesis (Coelfen, Qi) 2μm PEGbPEI PEISO 3 H 0.5μm PEGbPMAA PMAAAspAsp 0.5μm 2μm No additive 2μ m PEGbPEI PEICOOH PEGbPMAA PMAAPOPO 3 H 2
Synthesis and Modification SIP (Advincula)
Synthesis and Modification Block Copolymers as Nanoreactors (Advincula) Cationic polyelectrolytes Dendrimers (PAMAM) Amphiphilic block copolymers (PSbP2VP)
Synthesis and Modification Microgels by Dispersion Polymerization (Lyon) HN O HN HN O O X O SDS APS 70 o C >4 hrs. Precipitation Polymerization Oligoradical Precursor Particle Growing Particle Microgel
Synthesis and Modification Functionalization (Hoffman)
Synthesis and Modification Ligand Coated Metal Nanoparticles (Stellacci) HS Metal Salt (AuHCl 4 ) HS Reducing Agent (NaBH 4 ) Direct mixed ligands reaction ** Ligand exchange reaction *
Synthesis and Modification Quantum Dots in Frogs (Norris) hydrophilic shell hydrophobic core H 2 O H 2 O Me 2 Cd Se CdSe NCs micelle 320 C diameters between 2nm to 12nm size distributions <35%
Synthesis and Modification in Reverse Micelles (Pinna)
Synthesis and Modification Microemulsion Polymerization (Kaler) M Initiation by IM IM M M M M Chain Transfer P M M M M M I M M M PM Propagation M M M M M M Initiation by M M M M M # Micelle # Particles 3 ~ 10 5 nm
Synthesis and Modification Templating in Matrices (Braun) y x z 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 silica spheres 8 9 10 11 11 4 5 6 7 silicacoated PMMA spheres 8 9 10 11 11
Synthesis and Modification Colloidal Molecules (Pine) 2 3 4
Synthesis and Modification Encapsulation (Velev)
Characterization Confocal Microscopy (Wiltzius) illuminating aperture photomultiplier tube confocal 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)
Characterization TEM Image Analysis (Coelfen) Number frequency % 20 15 10 5 350 counts 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)
ParticleBased 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) Grounded F DEP 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 Fourier transform Diffraction pattern 5 s 15 s
Particle Assembly Domain sizes too small (Wiltzius)
Particle Assembly Convective Crystallization (Xia)
Particle Assembly Convective Assembly (Velev) cm 2 coatings from μl drops in minutes 1.1 μm latex crystal viewed with: Ambient light Low angle Light transmission 1cm
Particle Assembly CCAs to closepacked photonic xtals (Wiltzius) no salt Charge Stabilized Screened electrostatics dominate add salt screened electrostatics u(r) electrostatic repulsion u(r) screening r van der Waals attraction r VdW s attraction guide adhesion salt
Particle Assembly Modifying interactions and annealing in microgel photonic materials (Lyon)
Particle Assembly Strategies for Assembling Anisotropic Structures (Niederberger)
Particle Assembly SelfAssembly of Nanoparticles (Niederberger)
Particle Assembly Chains with Given Handedness (Xia)
Particle Assembly Colloidal Crystalline Arrays (Asher) ~ 10 13 spheres/cm 3 spacing dependent only upon particle number density and crystalline structure Dialysis / Ion Exchange Resin Selfassembly Crystalline Colloidal Array FCC
Particle Assembly Mechanism of Convective Crystallization (Norris) 800nm spheres immersion oil 100X real time video microscope objective CCD 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 CaCO 3 removal removal SEM of SEM mature mussel developing shell mussel shell
Particle Assembly Magnetically Driven Assembly (Asher) 240 FCC (111) plane spcaing / nm 220 200 180 Relative intensity 6 4 2 NaCl Concentration (From left to right) 4.0mM, 2.0mM, 1.0mM, 0.67mM, 0.33 mm,0.16 mm, 0mM 0 350 400 450 500 550 600 650 700 wavelength (nm) 160 0 1 2 3 4 NaCl concentration / mm
Particle Assembly Balancing Interfacial Interactions (Coelfen) Nucleation clusters Crystal growth Primary nanoparticles > 3 nm Amplification Temporary Stabilization Mesoscale assembly Mesoscale assembly Mesocrystal Single crystal Isooriented crystal
Particle Assembly Balancing Interfacial Interactions (Hoffman)
Particle Assembly Copper Oxalate Assembly (Hoffman)
Functional Materials Flame Pyrolysis (Laine) Pure nano αal2o3 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 5 20 Oe 9 Oe 9 Oe 20 Oe 6 5 Relative Intensity (a.u.) 4 3 2 S 686 nm 549 nm N N S 4 3 2 Relative Intensity (a.u.) 1 1 500 600 700 Wavelength /nm 120 90 60 30 0 30 60 90 120 H / Oe
Functional Materials Metal Cation Sensors (Asher) 54 μm 0.5 mm 2 mm 5 mm Diffraction intensity / a.u. 0.54 μm 1 μm 1 μm 0.54 μm 54 μm 0.5 mm 2 mm 5 mm 11 nm No Cu 2 buffered saline 11 nm 500 550 600 650 700 750 800 λ / nm
Functional Materials Glucose Sensing (Braun) HO GlucosePBA complex HO OH B R HO HO OH B R HO O OH O O OH B R PBA (phenylboronic acid) [Glucose] 0 mm 100 mm Inflow from syringe pump Outflow 0 mm glucose Flow cell Hydrogel SEM of templated hydrogel 10x Objective Beamsplitter Photodiode Array Detector Optical fiber Pinhole Light source 1 mm glucose
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. Positively charged pigment particles. Suspended in a clear oil. Addressed with electrodes. Sony s LIBRie EBR1000EP from E Ink and Phillips Electronics
Functional Materials Electrochromic Devices (Kotov)
Functional Materials DonorAcceptor 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