MATERIALS RESEARCH SCIENCE AND ENGINEERING CENTER ON POLYMERS

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. 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 A. Lesser PSE UMass W. MacKnight PSE UMass T. McCarthy PSE UMass N. Menon Phys UMass M. Muthukumar PSE UMass J. PenelleChem LRSP,Paris D. Raghavan Chem Howard S. Roberts ChemE UMass V. Rotello Chem UMass J. RothsteinM&I E UMass T. Russell PSE UMass M. Santore PSE UMass H. StreyPSE UMass G. Tew PSE UMass S. ThayumanavanChem UMass M. Tuominen Phys UMass J. Watkins ChemE UMass R. Weis Chem UMass H. H. Winter ChemE UMass Center Investigators

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 Standard Flash Memory Cell Top View Side View Control Gate Floating Gate Substrate Patterned using a block copolymer film (a) Nanostructured Flash Memory Cell Better retention and endurance IBM Press Release December 2003 On the line…..

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. G. Strobl, The Physics of Polymers, Springer-Verlag: Heidelberg, 1996 scCO2 Poly(methylpentene) 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) 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

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. Morphologyof Polyelectrolyte-Surfactant Complexes soluble: spherical micelles insoluble: cylindrical micelles HCP-C Increasing surfactant- to-polymer charge ratio Pm3n cubic + 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