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Materials%20Research%20Science%20and%20Engineering%20Center%20%20University%20of%20Massachusetts%20at%20Amherst

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... in Supercritical Fluids IRG-III Aqueous Polymer Assembly Seed-1 Heterojunction Photovoltaics Seed-2 Engineering Hierarchical ... Nanostructured Flash Memory Cell ... – PowerPoint PPT presentation

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Title: Materials%20Research%20Science%20and%20Engineering%20Center%20%20University%20of%20Massachusetts%20at%20Amherst


1
NATIONAL SCIENCE FOUNDATION
MATERIALS RESEARCH SCIENCE AND ENGINEERING CENTER
ON POLYMERS
Thomas P. Russell, Director Shaw Ling Hsu,
Associate Director
2
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
  • outstanding research quality
  • intellectual breadth
  • interdisciplinarity
  • flexibility
  • research infrastructure support
  • foster integration of research and education
  • Expectations
  • 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

3
Scope of Center
  • 3 Interdisciplinary Research Groups
  • IRG-I Tailored Interfaces
  • IRG-II Structured Materials in Supercritical
    Fluids
  • IRG-III Aqueous Polymer Assembly
  • Seed-1 Heterojunction Photovoltaics
  • Seed-2 Engineering Hierarchical Polymer
    Interfaces
  • 32 faculty from 7 departments
  • Biochemistry, Chemical Engineering, Plant
    Biology, Chemistry, Physics, Mechaniccal and
    Industrial Engineering and Polymer Science and
    Engineering
  • Collaborations
  • 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

4
Enhancements Under MRSEC Sponsorship
  • Undergraduate Research
  • Smith College, Mount Holyoke College Harvey Mudd
    College, and Howard University
  • Educational Outreach
  • 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 Computing Electron Microscopy
    Molecular Weight
  • X-ray Scattering Rheology Surface
    Science Optical Microscopy
  • Spectroscopy Nanostructures Laboratory
    Nuclear Magnetic Resonance
  • Managed by Director with Internal Advisory
    Committee
  • Annual Review by External Advisory Board

5
Center Investigators
  • A. Lesser PSE UMass
  • W. MacKnight PSE UMass
  • T. McCarthy PSE UMass
  • N. Menon Phys UMass
  • M. Muthukumar PSE UMass
  • J. Penelle Chem LRSP,Paris
  • D. Raghavan Chem Howard
  • S. Roberts ChemE UMass
  • V. Rotello Chem UMass
  • J. Rothstein MI E UMass
  • T. Russell PSE UMass
  • M. Santore PSE UMass
  • H. Strey PSE UMass
  • G. Tew PSE UMass
  • S. Thayumanavan Chem UMass
  • M. Tuominen Phys UMass
  • J. Watkins ChemE UMass
  • R. Weis Chem UMass
  • S. Baker Chem HMC
  • M. Barnes Chem UMass
  • S. Bhatia ChemE UMass
  • S. Browne Chem MHC
  • K. Carter PSE UMass
  • W. Chen Chem MHC
  • E. B. Coughlin PSE UMass
  • A. Crosby PSE UMass
  • A. Dinsmore Phys UMass
  • N. Easwar Phys Smith
  • T. Emrick PSE UMass
  • R. Farris PSE UMass
  • S. Gido PSE UMass
  • R. Hallock Phys UMass
  • R. Hayward PSE UMass
  • D. Hoagland PSE UMass
  • S. L. Hsu PSE UMass
  • A. Levine Phys UMass

6
Shared Experimental Facilities
7
Interdisciplinary Research Group ITailored
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)
8
Interdisciplinary Research Group ITailored
Interfaces - Projects
  • Heterogeneous structures
  • Functionalized surfaces
  • Nanoparticle assemblies
  • Gradient surfaces
  • Lateral variations
  • Long-range order
  • Lateral registry
  • Topography
  • Enhanced surface area
  • Decorating in 3-D
  • Directional particles

9
Interdisciplinary Research Group IBalanced
Interfacial Interactions
Thermal Annealing
UV Exposed
10
Interdisciplinary Research Group ITemplating
Technology Transfer
Process of Record at IBM
11
Interdisciplinary Research Group ITechnology
Transfer
12
Interdisciplinary Research Group IOvercoming
Interfacial Interactions
cN
f

13
Interdisciplinary Research Group ILong-Range
Order
Dry PS-b-PEO
Patterned Topography
Wet
14
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
15
First Nanoscopic Template Semicrystalline
Polymers
Tc 31 C Pc 1070 psi
PMP 70 crystalline Dissolves 15 wt. CO2
16
The unique properties of SCF carbon dioxide
  • ? swells all organic polymers (to varying
    degrees)
  • ? doesnt 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 TP) 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

17
Fabrication of Thick Films TEOS / Pluronic F108
Template, 60 0C, 123 bar
(Pai et al., Science, 303, 507, 2004)
18
Interdisciplinary Research Group IIIAqueous
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
19
Morphology of Polyelectrolyte-Surfactant Complexes

Sequence of Structures
IRG activities phase map, thermodynamics
functions, variation of polymer structure,
applications (sequestering oils controlled
delivery)
20
Polyamphiphiles Vesicles Antimicrobial Polymers
Selectivity activity against bacterial cells
divided by that against
mammalian cells Three candidates made by
ROMP Understanding Response
structure hydrophobicity charge
1 2
3
Measure thermodynamics and structure
- monitoring disruption with DLS -
Polymer 3
500 250 0
Rh, nm
Polymer 2
low activity, high activity, high
selectivity low selectivity
0 10 20 30

Time, min
? intact, possibly aggregated vesicles
copolymers optimize properties
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