NATIONAL SCIENCE FOUNDATION MATERIALS RESEARCH SCIENCE AND ENGINEERING

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 l l l outstanding research quality intellectual breadth interdisciplinarity flexibility research infrastructure support foster integration of research and education Expectations l l l 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-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 l Biochemistry, Chemical Engineering, Plant Biology, Chemistry, Physics, Mechaniccal and Industrial Engineering and Polymer Science and Engineering Collaborations l l 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 l Smith College, Mount Holyoke College Harvey Mudd College, and Howard University Educational Outreach l l l l 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 l l Managed by Director with Internal Advisory Committee Annual Review by External Advisory Board

Center Investigators S. Baker Chem M. Barnes Chem S. Bhatia Chem. E S. Browne Chem K. Carter PSE W. Chen Chem E. B. Coughlin A. Crosby PSE A. Dinsmore N. Easwar Phys T. Emrick PSE R. Farris PSE S. Gido PSE R. Hallock Phys R. Hayward D. Hoagland S. L. Hsu PSE A. Levine Phys HMC UMass MHC PSE UMass Phys Smith UMass PSE UMass UMass A. Lesser PSE W. Mac. Knight T. Mc. Carthy N. Menon Phys M. Muthukumar J. Penelle Chem D. Raghavan S. Roberts Chem. E V. Rotello Chem J. Rothstein T. Russell PSE M. Santore H. Strey PSE G. Tew PSE S. Thayumanavan M. Tuominen J. Watkins Chem. E R. Weis Chem H. H. Winter UMass PSE UMass LRSP, Paris Chem Howard UMass M&I E UMass PSE UMass Chem UMass Phys UMass Chem. E 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. Mc. Carthy, 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 l Heterogeneous structures - l Gradient surfaces - l Lateral registry Topography - l Lateral variations Long-range order - l Functionalized surfaces Nanoparticle assemblies Enhanced surface area Decorating in 3 -D - 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 c N f

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. Mc. Carthy, 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, highlyordered 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 sc. CO 2 Poly(methylpentene) Tc = 31 °C Pc = 1070 psi PMP: 70% crystalline Dissolves ~15 wt. % CO 2

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 miscible with other gases - hydrogen dissolves most small molecule organics and organometallics compatible with cosolvents increases diffusivity in solid polymers (~X 107) - RRL chemis variable (with T&P) density (solubility parameter) near critica another “knob to turn” - diffusion vs. thermally activated proc 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 F 108 Template, 60 0 C, 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 + + + + + + + + + + + + + + + + + + + + +

Morphology of Polyelectrolyte-Surfactant Complexes + Sequence of Structures: soluble: spherical micelles insoluble: cylindrical micelles Increasing surfactantto-polymer charge ratio HCP-C Pm 3 n cubic IRG activities: phase map, thermodynamics functions, variation of polymer structure, applications (sequestering oils; controlled delivery)

Polyamphiphiles + Vesicles: Antimicrobial Polymers + Selectivity: activity against bacterial cells divided by that against mammalian cells structure + hydrophobicity + charge Three candidates made by ROMP: 2 3 Measure thermodynamics and structure - monitoring disruption with DLS Polymer 3 Rh, nm 1 Understanding Response: low activity, high selectivity high activity, low selectivity copolymers optimize properties 500 250 0 Polymer 2 0 10 20 Time, min 30 intact, possibly aggregated vesicles