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