1. MATERIALS RESEARCH SCIENCE AND ENGINEERING CENTER ON POLYMERS Thomas P. Russell, Director Shaw Ling Hsu, Associate Director NATIONAL SCIENCE FOUNDATION

2. 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 outstanding research quality l intellectual breadth l interdisciplinarity l flexibility l research infrastructure support l foster integration of research and education Expectations l fundamental materials research of intellectual and societal importance l foster collaborations between academia and other sectors l enable research that requires a center l basis for a national network of university-based centers l outreach, education NSF Criteria

3. 3 Interdisciplinary Research Groups IRG-I Tailored Interfaces IRG-II Structured Materials in Supercritical Fluids IRG-III Aqueous Polymer Assembly Seed-1Heterojunction Photovoltaics Seed-2 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 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 l Complements ongoing research with 45 other industrial sponsors Scope of Center

4. Undergraduate Research l Smith College, Mount Holyoke College Harvey Mudd College, and Howard University Educational Outreach l Established REU program l Established RET program l Middle school curricula l On-site laboratory program (ASPIRE) l Graduate student K-12 l National Plastics Center and Museum l Graduate Student Career Programs l VISUAL Shared Experimental Facilities CharacterizationComputingElectron Microscopy Molecular Weight X-ray ScatteringRheology Surface ScienceOptical Microscopy Spectroscopy Nanostructures Laboratory Nuclear Magnetic Resonance l Managed by Director with Internal Advisory Committee l Annual Review by External Advisory Board Enhancements Under MRSEC Sponsorship

5. Center Investigators S. BakerChemHMC M. BarnesChemUMass S. BhatiaChemEUMass S. BrowneChem MHC K. CarterPSEUMass W. ChenChem MHC E. B. CoughlinPSEUMass A. CrosbyPSE UMass A. DinsmorePhysUMass N. EaswarPhysSmith T. EmrickPSEUMass R. FarrisPSEUMass S. GidoPSEUMass R. HallockPhysUMass R. HaywardPSEUMass D. HoaglandPSEUMass S. L. HsuPSEUMass A. LevinePhys UMass A. LesserPSEUMass W. MacKnightPSEUMass T. McCarthy PSEUMass N. MenonPhys UMass M. MuthukumarPSEUMass J. PenelleChemLRSP,Paris D. RaghavanChem Howard S. RobertsChemE UMass V. RotelloChem UMass J. RothsteinM&I EUMass T. RussellPSEUMass M. SantorePSEUMass H. StreyPSEUMass G. TewPSEUMass S. ThayumanavanChemUMass M. TuominenPhysUMass J. WatkinsChemE UMass R. WeisChemUMass H. H. WinterChemE UMass

6. Shared Experimental Facilities

7. 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)

8. l Heterogeneous structures - Functionalized surfaces - Nanoparticle assemblies l Gradient surfaces - Lateral variations l Long-range order - Lateral registry l Topography - Enhanced surface area l Decorating in 3-D - Directional particles Interdisciplinary Research Group I Tailored Interfaces - Projects

9. Thermal Annealing UV Exposed Interdisciplinary Research Group I Balanced Interfacial Interactions

10. Process of Record at IBM Interdisciplinary Research Group I Templating: Technology Transfer

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

12. Interdisciplinary Research Group I Overcoming Interfacial Interactions cNcN f

13. Wet Dry: PS-b-PEO Interdisciplinary Research Group I Long-Range Order Patterned Topography

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 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

15. First Nanoscopic Template: Semicrystalline Polymers G. Strobl, The Physics of Polymers, Springer-Verlag: Heidelberg, 1996 scCO 2 Poly(methylpentene) T c = 31 °C P c = 1070 psi PMP: 70% crystalline Dissolves ~15 wt.% CO 2

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 10 7 ) - 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 0 C, 123 bar (Pai et al., Science, 303, 507, 2004)

18. Interdisciplinary Research Group III Aqueous Polymer Assembly Objective: to tune interactions among water-soluble polymers and cosolutes so as to induce their assembly into useful microstructures Co-coordinators: Hoagland, Muthukumar 10 Participating Faculty: Bhatia, Coughlin, Emrick, Gido, Hoagland, Hsu, Muthukumar, Roberts, Santore, Tew 9 Graduate students; 1 Post-doctoral fellow

19. Morphology of Polyelectrolyte-Surfactant Complexes Pm3n cubic spherical micelles cylindrical micelles HCP-C Increasing surfactant- to-polymer charge ratio soluble: insoluble: IRG activities: phase map, thermodynamics functions, variation of polymer structure, applications (sequestering oils; controlled delivery) + Sequence of Structures:

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 low activity, high activity, high selectivity low selectivity copolymers optimize properties Measure thermodynamics and structure R h, nm Time, min 500 250 0 0 10 20 30 - monitoring disruption with DLS - Polymer 3  intact, possibly aggregated vesicles Polymer 2 1 2 3