Transcript Materials Research Science and Engineering Center University of

NATIONAL SCIENCE FOUNDATION
MATERIALS RESEARCH SCIENCE AND
ENGINEERING CENTER ON POLYMERS
Thomas P. Russell, Director
Shaw Ling Hsu, Associate Director
NSF Criteria
MRSECs support interdisciplinary and multi-disciplinary materials
research and education of the highest quality while addressing
fundamental problems in science and engineering that are important to
society.
Requirements
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outstanding research quality
intellectual breadth
interdisciplinarity
flexibility
research infrastructure support
foster integration of research and education
Expectations
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fundamental materials research of intellectual and societal importance
foster collaborations between academia and other sectors
enable research that requires a center
basis for a national network of university-based centers
outreach, education
Scope of Center
3 Interdisciplinary Research Groups
IRG-I
IRG-II
IRG-III
Seed-1
Seed-2
Tailored Interfaces
Structured Materials in Supercritical Fluids
Aqueous Polymer Assembly
Heterojunction Photovoltaics
Engineering Hierarchical Polymer Interfaces
32 faculty from 7 departments
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Biochemistry, Chemical Engineering, Plant Biology, Chemistry, Physics, Mechaniccal
and Industrial Engineering and Polymer Science and Engineering
Collaborations
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Seagate, Kodak, Honeywell, Rhodia, IBM, NIST, BNL, ORNL, ANL, Cambridge U, U
of Halle, U of Bayreuth, LRSP-Paris, Ecole Normal Superiore de Lachar, Max Planck
Institut (Halle), Kyushu U, HOMRC, KAIST, Gangwon U, Pohang U, UTK, UPenn,
UMass-Worcester, U Texas Austin, U Vermont, UCSB, UCLA, U South Carolina,
Howard U, Mt Holyoke College, Smith College and Harvey Mudd College
Complements ongoing research with 45 other industrial sponsors
Enhancements Under MRSEC Sponsorship
Undergraduate Research
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Smith College, Mount Holyoke College Harvey Mudd College, and Howard
University
Educational Outreach
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Established REU program
Established RET program
Middle school curricula
On-site laboratory program (ASPIRE)
Graduate student K-12
National Plastics Center and Museum
Graduate Student Career Programs
VISUAL
Shared Experimental Facilities
Characterization
X-ray Scattering
Spectroscopy
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Computing
Electron Microscopy
Molecular Weight
Rheology
Surface Science
Optical Microscopy
Nanostructures Laboratory
Nuclear Magnetic Resonance
Managed by Director with Internal Advisory Committee
Annual Review by External Advisory Board
Center Investigators
S. Baker
M. Barnes
S. Bhatia
S. Browne
K. Carter
W. Chen
E. B. Coughlin
A. Crosby
A. Dinsmore
N. Easwar
T. Emrick
R. Farris
S. Gido
R. Hallock
R. Hayward
D. Hoagland
S. L. Hsu
A. Levine
Chem
Chem
ChemE
Chem
PSE
Chem
PSE
PSE
Phys
Phys
PSE
PSE
PSE
Phys
PSE
PSE
PSE
Phys
HMC
UMass
UMass
MHC
UMass
MHC
UMass
UMass
UMass
Smith
UMass
UMass
UMass
UMass
UMass
UMass
UMass
UMass
A. Lesser
W. MacKnight
T. McCarthy
N. Menon
M. Muthukumar
J. Penelle
D. Raghavan
S. Roberts
V. Rotello
J. Rothstein
T. Russell
M. Santore
H. Strey
G. Tew
S. Thayumanavan
M. Tuominen
J. Watkins
R. Weis
H. H. Winter
PSE
UMass
PSE
UMass
PSE
UMass
Phys
UMass
PSE
UMass
Chem LRSP,Paris
Chem
Howard
ChemE UMass
Chem
UMass
M&I E
UMass
PSE
UMass
PSE
UMass
PSE
UMass
PSE
UMass
Chem
UMass
Phys
UMass
ChemE UMass
Chem
UMass
ChemE UMass
Shared Experimental Facilities
Interdisciplinary Research Group I
Tailored Interfaces
Thomas P. Russell, Coordinator
K.Carter, A. Dinsmore, T. Emrick, S. Gido, R. Hallock,
D. Hoagland, T. McCarthy, N.Menon, M. Muthukumar, V.
Rotello, T. Russell, M. Santore, S.Thayumanavan,
M. Tuominen and R. Weis
11 Graduate Students, 1 Postdoctoral Fellow
Goal
To tailor interfacial interactions and surface
topography so as to manipulate polymer structure and
morphology that will open new avenues of science and
technology (solid to liquid surfaces)
Interdisciplinary Research Group I
Tailored Interfaces - Projects
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Heterogeneous structures
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Gradient surfaces
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Lateral registry
Topography
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Lateral variations
Long-range order
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Functionalized surfaces
Nanoparticle assemblies
Enhanced surface area
Decorating in 3-D
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Directional particles
Interdisciplinary Research Group I
Balanced Interfacial Interactions
Thermal Annealing
UV Exposed
Interdisciplinary Research Group I
Templating: Technology Transfer
Process of Record at IBM
Interdisciplinary Research Group I
Technology Transfer
Standard Flash
Memory Cell
Top View
Side View
Control Gate
Floating Gate
Substrate
(a)
Nanostructured Flash
Memory Cell
Patterned
using a block
copolymer
film
Better retention and endurance
IBM Press Release
December 2003
On the line…..
Interdisciplinary Research Group I
Overcoming Interfacial Interactions
Solvent
Evaporation
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Highly Mobile
Surface
cN
cN
Ordered
Disordered
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APS/03
Interdisciplinary Research Group I
Long-Range Order
Dry: PS-b-PEO
Wet
Patterned Topography
IRG II: Preparation of Structured Materials in Supercritical Fluids
J. Watkins (IRG Coordinator), K. Carter, A. Dinsmore,
S. Gido, A. Lesser, T. McCarthy, T. Russell, G. Tew
Collaborators: C. Ober (Cornell MRSEC), B. Vogt (NIST Polymers Division),
Rajesh Naik, AFRL
Premise:
SCFs uniquely enable the preparation of functional, highly-ordered materials
through the modification of pre-organized polymer templates
Fundamentals:
Transport and thermodynamics in polymer/SCF systems are examined in
support of this work and to exploit the unique properties of SCF solvents to
answer broader questions in polymer physics
First Nanoscopic Template: Semicrystalline Polymers
G. Strobl, The Physics of Polymers,
Springer-Verlag: Heidelberg, 1996
scCO2
Poly(methylpentene)
Tc = 31 °C Pc = 1070 psi
PMP: 70% crystalline
Dissolves ~15 wt.% CO2
The unique properties of SCF carbon dioxide
 swells all organic polymers (to varying degrees)
 doesn’t dissolve 99.99% of polymers
 inert to most reagents (not to strong nucleophiles or reducing agents)
 miscible with other gases - hydrogen
 dissolves most small molecule organics and organometallics
 compatible with cosolvents
 increases diffusivity in solid polymers (~X 107) - RRL chemistry
 variable (with T&P) density (solubility parameter) near critical point
 another “knob to turn” - diffusion vs. thermally activated processes
 a solvent with no L-V interface
 no “interface” with glassy or semicrystalline polymers
 can quench from a SC to V state with no L intermediate
 sneaky
Fabrication of Thick Films – TEOS / Pluronic F108 Template, 60 0C, 123 bar
(Pai et al., Science, 303, 507, 2004)
Interdisciplinary Research Group III
Aqueous Polymer Assembly
Co-coordinators: Hoagland, Muthukumar
10 Participating Faculty: Bhatia, Coughlin, Emrick, Gido, Hoagland, Hsu,
Muthukumar, Roberts, Santore, Tew
9 Graduate students; 1 Post-doctoral fellow
Objective: to tune interactions among water-soluble polymers and cosolutes so
as to induce their assembly into useful microstructures
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Morphology of Polyelectrolyte-Surfactant
Complexes
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Sequence of Structures:
soluble:
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spherical
micelles
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insoluble:
cylindrical
micelles
Increasing surfactantto-polymer charge ratio
HCP-C
Pm3n
cubic
IRG activities: phase map, thermodynamics functions, variation of polymer structure,
applications (sequestering oils; controlled delivery)
Polyamphiphiles + Vesicles: Antimicrobial Polymers
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Selectivity: activity against bacterial cells divided
by that against mammalian cells
structure + hydrophobicity + charge
Three candidates made by ROMP:
1
2
3
Understanding Response:
Measure thermodynamics and
structure
O
- monitoring disruption with DLS N
+
NH3
O
O
N
O
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NH3
low activity,
high selectivity
O
N
O
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NH3
high activity,
low selectivity
copolymers optimize properties
Polymer 3
Rh, nm
O
500
250
0
Polymer 2
0
10
20
Time, min
30
 intact, possibly aggregated vesicles