MATERIALS RESEARCH SCIENCE AND ENGINEERING CENTER ON POLYMERS
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Transcript of MATERIALS RESEARCH SCIENCE AND ENGINEERING CENTER ON POLYMERS
MATERIALS RESEARCH SCIENCE AND ENGINEERING CENTER ON POLYMERS
Thomas P. Russell, DirectorShaw Ling Hsu, Associate Director
NATIONAL SCIENCE FOUNDATION
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
NSF CriteriaNSF Criteria
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
Scope of CenterScope of Center
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 FacilitiesCharacterization Computing Electron Microscopy Molecular WeightX-ray Scattering Rheology Surface Science Optical MicroscopySpectroscopy Nanostructures Laboratory Nuclear Magnetic Resonance
Managed by Director with Internal Advisory Committee Annual Review by External Advisory Board
Enhancements Under MRSEC SponsorshipEnhancements Under MRSEC Sponsorship
Center InvestigatorsCenter Investigators
S. Baker Chem HMCM. Barnes Chem UMassS. Bhatia ChemE UMassS. Browne Chem MHCK. Carter PSE UMassW. Chen Chem MHCE. B. Coughlin PSE UMassA. Crosby PSE UMassA. Dinsmore Phys UMassN. Easwar Phys SmithT. Emrick PSE UMassR. Farris PSE UMassS. Gido PSE UMassR. Hallock Phys UMassR. Hayward PSE UMassD. Hoagland PSE UMassS. L. Hsu PSE UMass A. Levine Phys UMass
A. Lesser PSE UMassW. MacKnight PSE UMass T. McCarthy PSE UMassN. Menon Phys UMassM. Muthukumar PSE UMassJ. Penelle Chem LRSP,ParisD. Raghavan Chem HowardS. Roberts ChemE UMassV. Rotello Chem UMassJ. Rothstein M&I E UMassT. Russell PSE UMassM. Santore PSE UMassH. Strey PSE UMassG. Tew PSE UMassS. Thayumanavan Chem UMassM. Tuominen Phys UMassJ. Watkins ChemE UMassR. Weis Chem UMassH. H. Winter ChemE UMass
Shared Experimental FacilitiesShared Experimental Facilities
Interdisciplinary Research Group IInterdisciplinary Research Group ITailored InterfacesTailored Interfaces
Thomas P. Russell, CoordinatorK.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. Weis11 Graduate Students, 1 Postdoctoral Fellow
GoalTo 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)
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
Interdisciplinary Research Group IInterdisciplinary Research Group ITailored Interfaces - ProjectsTailored Interfaces - Projects
Thermal AnnealingThermal Annealing UV ExposedUV Exposed
Interdisciplinary Research Group IInterdisciplinary Research Group IBalanced Interfacial InteractionsBalanced Interfacial Interactions
Process of Record at IBMProcess of Record at IBM
Interdisciplinary Research Group IInterdisciplinary Research Group ITemplating: Templating: Technology TransferTechnology Transfer
Standard FlashMemory Cell
Floating Gate
Control Gate
Substrate
(a)Nanostructured Flash
Memory Cell
Better retention and endurance IBM Press Release December 2003On the line…..
Top View Side View
Patterned using a blockcopolymerfilm
Interdisciplinary Research Group IInterdisciplinary Research Group ITechnology TransferTechnology Transfer
Interdisciplinary Research Group IInterdisciplinary Research Group IOvercoming Interfacial InteractionsOvercoming Interfacial Interactions
SolventEvaporation
S
Ordered
Disordered
Highly MobileSurface
cN
fAPS/03
N
Wet
Dry: PS-b-PEO
Interdisciplinary Research Group IInterdisciplinary Research Group ILong-Range OrderLong-Range Order
Patterned Topography
IRG II: Preparation of Structured Materials in Supercritical FluidsIRG 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
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
Collaborators: C. Ober (Cornell MRSEC), B. Vogt (NIST Polymers Division), Rajesh Naik, AFRL
First Nanoscopic Template: Semicrystalline PolymersFirst 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% crystallineDissolves ~15 wt.% CO2
The unique properties of SCF carbon dioxideThe 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 Fabrication of Thick Films – TEOS / Pluronic F108 Template, 60 00C, 123 barC, 123 bar
(Pai et al., Science, 303, 507, 2004)
Interdisciplinary Research Group IIIInterdisciplinary Research Group IIIAqueous Polymer AssemblyAqueous Polymer Assembly
Objective: to tune interactions among water-soluble polymers and cosolutes so as to induce their assembly into useful microstructures
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Co-coordinators: Hoagland, Muthukumar 10 Participating Faculty: Bhatia, Coughlin, Emrick, Gido, Hoagland, Hsu, Muthukumar, Roberts, Santore, Tew9 Graduate students; 1 Post-doctoral fellow
Morphology of Polyelectrolyte-Surfactant Complexes
Pm3ncubic
sphericalmicelles
cylindricalmicelles
HCP-CIncreasing surfactant-to-polymer charge ratio
soluble:
insoluble:
IRG activities: phase map, thermodynamics functions, variation of polymer structure,
applications (sequestering oils; controlled delivery)
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Sequence of Structures:
Polyamphiphiles + Vesicles: Antimicrobial Polymers
N OO
O
NH3
+
N OO
NH3
+
N OO
NH3
+
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Selectivity: activity against bacterial cells divided by that against mammalian cells
Three candidates made by ROMP: Understanding Response:
structure + hydrophobicity + charge
low activity, high activity,high selectivity low selectivity
copolymers optimize properties
Measure thermodynamics and structure
Rh,
nm
Time, min
500
250
00 10 20 30
- monitoring disruption with DLS -
Polymer 3
intact, possibly aggregated vesicles
Polymer 2
1 2 3