Polymer Nanomaterials W. Marshall Ming Department of Chemistry, Georgia Southern University Statesboro, GA 30460, USA
[email protected]; (912)478-5043
Synthetic Polymers Are Ubiquitous!
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Natural Polymers: as Early as Life Began
Cellulose
Chitin CH3
H
Natural Rubber cis-Polyisoprene
C C CH2
DNA
CH2 n
Naturally Occurring Polymeric Nanomaterials
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What are Polymers? • Poly + Meros = “many” + “parts or units” (Poly – mer!) • Long-chain-like polymers consisting of many repeating units (monomers) that are covalently linked • Molecular weight higher than ~10,000 g/mol
Teflon!
Plexiglass
Other Typical Polymers
Nylon
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Polymer Nobel Laureates 1953
1963
H. Staudinger
K. Ziegler,
Macromolecular chemistry
G. Natta
Chemistry and technology of high polymers
1974
1991
P.J. Flory
P.G. de Gennes
Physical chemistry of macromolecules
Ordering in liquid crystal and polymer
2000
2005
A. Heeger, A. MacDiarmid, H. Shirakawa Conductive polymer
Y. Chauvin,
R.H. Grubbs, R.R. Schrock
Metathesis in organic/polymer synthesis
States of Matter
Melt/Crystallize Tm Tc
Sublime/Deposit Solid
Vaporize/Condense Liquid
Gas Fourth state: plasma
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States of A Polymer
Melt/Crystallize Tm/Tc Tg
Sublime/Deposit
Solid
Vaporize/Condense Liquid
No gaseous state
Polymer Properties
• Physical network • Chemically cross-linked network
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Polymer Property: Rheological Behavior
shock-absorbing materials Joachim Bublath, Second German Television
d3o materials
Polymer-Related Nanomaterials
Spheres
Rods
Disks/Platelets
Polymer (latex)
Carbon nanotube (1 nm diameter)
Clay
•Inorganic Silica Magnets •Carbon Fullerene Carbon black
•Inorganic Rods Wires
Graphene (1 atom thick)
Hybrid nanomaterials are often used!
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From Polymer Nanoparticles to Microparticles 1-20 m
10-100 nm
Miniemulsion/ Emulsion Polymerization Dispersion Polymerization
Microemulsion Polymerization
80-1000 nm Ming, et al. Macromolecules 1996, 29, 7678; 2005, 38, 3653; Macromol. Chem. Phys. 1998, 199, 1075; Polym. Bull. (Berlin) 1998, 40, 749; Colloid Polym. Sci. 1998, 276, 655.
Film Formation from Polymer Particles
Particle Packing Stage
Particle Deformation Stage
Film Coalescence Stage
L.E. Scriven, et al. ACS Symposium Series 2001, 790, 29; 174.
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Hybrid Polymer/Silica Nanoparticles
Much improved flame retardancy
Super-hard transparent coating
Schmid et al. Macromolecules 2009, 42, 3721
Magnetic Hybrid Particles
Surface can be modified for diagnostic applications... Ugelstad J, et al. Prog Polym Sci 1992, 17, 87 Lindlar B, Boldt M, Eiden-Assmann S, Maret G Adv Mater 2002, 14, 1656
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Photonic Crystals from Nanoparticles From colloidal template
Template colloidal particles
Vos et al. Nature 2004, 430, 654
Raspberry-like Particles Self-Cleaning lotus leaf: “rising out of muddy water, untainted”
Self-cleaning
Surface roughness
Bar = 20 m
Barthlott, et al. Planta 1997, 202, 1
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Synthesis of Raspberry-like Particles O
O OH OCH3 HO
SiO2
OH
+
CH3O
Si
O CH2
O
O
OCH3
O O
OH
O
(Stöber method)
O
O
NH2 NH2
H2N
O
+ O
NH2
O O
Nano-raspberry! Ming, Wu, van Benthem, de With, Nano Lett. 2005, 5, 2298.
Self-Cleaning Raspberry-like Surface Smooth surface
+ Big particles
a/r = 107°/67° a/r = 151°/94° CAH = 40°
CAH = 57°
+ Raspberry particles
a/r = 165°/163° CAH = 2°
Ming, Wu, van Benthem, de With, Nano Lett. 2005, 5, 2298.
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Functional Materials: Self-healing Nanocomposites
White, et al. Nature 2001, 409, 794.
Block Copolymers: Unique Nanoscale Morphologies
Nano-lithography
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Polymer/Clay Nanocomposites
Functional Nanostructured Coatings: A Few Examples Self-cleaning
Antimicrobial coatings
Smart coatings for early corrosion detection
Anti-fogging
“Self-healing” corrosion protection via on-demand release of corrosion inhibitor
Control
https://sites.google.com/a/georgiasouthern.edu/ming-lab
0.1% BTA in our particles
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