Institute for Macromolecules and Interfaces (IMI)

1. Institute for Macromolecules and Interfaces (IMI) A proposed Virginia Tech initiative presented to the NRC committee on Engineering and Materials October 7, 2003 Coordinator James E. McGrath, PhD University Distinguished Professor Ethyl Chair National Academy of Engineering JMCGRATH@VT.EDU

2. Outline for Today • Who are we and what have we done? • Current situation - a crossroads • Faculty, equipment, space • Proposed research and education thrusts • Proposed investments • Payoffs • University • Commonwealth • Nation • Appendix

3. Proposed Institute for Macromolecules and Interfaces at Virginia Tech Evolution of the Polymer Program leading to the proposed Institute for Macromolecules and Interfaces (IMI) Polymer Materials & Interfaces Laboratory (1978-present) Center for Adhesive & Sealant Science (1982-present) DEPARTMENTS Materials Research Institute (1987 - present) NSF Science & Technology Center on High Performance Polymeric Adhesives & Composites (1989 - 2000) Macromolecular Science and Engineering, MS and PhD, 2001-present

4. Selected Major Research and Education Programs • Adhesive and Sealant Council support for the Center for Adhesive and Sealant Science: $4MM • NSF Science and Technology Center for High Performance Polymeric Adhesives and Composites: $20MM over 11 Years • NSF IGERT in Macromolecular Science and Infrastructure Engineering: $3MM • Army Research Office MURI “Macromolecular Architecture for Performance (MAP)”: $5MM • Advanced Materials for Fuel Cells: >$3MM from DoE, NSF, DoD, NASA • NSF IGERT on Macromolecular Interfaces with Life Sciences (MILES): pending $3MM • Preproposal for NSF Science and Technology Center on Fuel Cell Performance (joint with UConn): pending $20MM • Preproposal for NSF Science and Technology Center on Self-Assembled Organic Optoelectronic Nanostructures and Devices: $11.5MM • Inflatable, durable large aperture composite space structures, NASA Langley

5. MACR Graduate Program • In 3rd Year (28 graduate students enrolled) • University granted degree program • Flexibility in tailoring interdisciplinary programs of study • Core courses (8 hrs.) focus on Polymer Fundamentals and Communication skills • Additional coursework requirements are based on a modular approach http://www.macro.vt.edu

6. Accomplishments provide the base for a Premier Program in Advanced Polymer Technologies… • National/international reputation in Polymer Science and Engineering • Broad, interdisciplinary research and education with 47 Ph.D. degrees awarded in 2000-2003 • Graduates are leaders in U.S. industries and academe • Established industrial collaborations with 25 years of affiliate programs • National leaders in educational outreach to U.S. and Virginia Commonwealth industries • Economic development potential is high

7. October, 2003: Program is at a CROSSROADS Polymer science and engineering has evolved, and the IMI is poised to take advantage of the science and engineering base to address 4 key proposed technologies. Synergies with other Commonwealth initiatives are envisioned Several senior critical faculty who have been major program contributors have retired (or perhaps should have). Successes will not continue unless this issue is addressed!

8. The proposed IMI will facilitate the transition toFour Key Integrated Polymer Research-Education Thrusts… Advanced Materials and Processes for Proton Exchange Membrane (PEM) Fuel Cell Energy Systems High Performance Adhesives and Composites for The 21st Century IMI Nanostructured Materials Based on Self-Organization and Solvent-Free Processing Advanced Materials for Biomaterials, Membranes, Sensors and Actuators

9. Vision for Interdisciplinary Fuel Cell Research PEMs PEMs and MEAs and MEAs Gas Diffusion Medium Adhesives and Sealants Adhesives and Sealants J.E. McGrath, T. Long J.E. McGrath, T. Long J. Dillard, J. McGrath, J. Dillard, J. McGrath, High Performance Materials J. Riffle, D. Dillard J. Riffle, D. Dillard Catalysis, Catalysis, Buildings, Cars; Buildings, Cars; Conductivity ,Transport Conductivity ,Transport FUEL CELL Performance Systems Integration and Systems Integration and J. Morris J. Morris Analysis Analysis Catalyst M. von Spakovsky M. von Spakovsky M. Ellis, D. Nelson M. Ellis, D. Nelson Composite System Composite System Polymer Membrane Composite bipolar plates PMC/Carbon Injection PMC/Carbon Injection Packaging Packaging Composite Manifold Molded Bipolar Plates Molded Bipolar Plates J. Lesko, S. Case J. Lesko, S. Case D. Baird, A D. Baird Loos Knowledge Transfer Knowledge Transfer Industry, Government Industry, Government

10. Composites in Virginia’s Highway Infrastructure Interstate 81 Deck Test Bed Troutville Weigh Station FRP Pilings Rt. 40 Tom’s Creek Bridge Dickey Creek Bridge Hawthorne Street Bridge Hawthorne St. Bridge Tilghman Island Troutville Weigh Station Tom’s Creek Bridge Rt. 351 Dickey Creek Bridge Rt. 40

11. 100 nm Advanced Materials for Biomaterials, Membranes, Sensors and Actuators Cell-complex interactions U.O. Hafeli Cleveland Clinic Foundation Cleveland, OH Synthesis of biomaterial complexes J.S. Riffle VA Tech Blacksburg, VA Magnetic PDMS Fluids for Treating Retinal Detachments Permanent magnet Magnetic Materials for Medical Applications Ocular applications J.P. Dailey Hamot Medical Center Erie, PA Characterization of material and magnetic properties T.G. St. Pierre Univ. Western Australia

12. Cationic polymers bind DNA The binding between the cationic polymer and plasmid occurs through electrostatic interactions. Advantages of Polycations as Therapeutic Gene Carriers A Gene Transfer Agent is a carrier molecule of genetic material (DNA or RNA)…. Gene Therapy is the primary target, which treats inherited or acquired genetic deficiencies by introducing DNA which encodes for a therapeutic protein. Types of Gene Transfer Agents? • Viral Vectors 2) Non-viral vectors (homo- and block copolymers) poly(2-(dimethylamino)ethyl methacrylate) poly(ethylene oxide-b-ethyleneimine) polymer plasmid Condenses the size of the plasmid after binding by shielding the negative charge on the phosphate backbone of DNA

13. Advanced Membranes and Films • Gas separations • Water purification • Sensors and actuators

14. Nanostructured Materials Based on Self-Organization and Solvent-Free Processing Phase and Intensity Control of Light OUTPUT Phase and Intensity Control of Electrical INPUT Light IN Electrodes NLO Film material C60 electron acceptor Conducting polymer Heating Interdiffusion Bulk heterojunction Photovoltaic device with concentration gradient Electro-optic Modulators for Rapid Conversion of Electrical Signals to Modulated Optical Signals (water-based processing) Polymer-Based Solar Cells with Interdiffused C60 Next-generation optical communications systems and computers Renewable energy sources

15. Macromolecular Architecture for Performance “MAP” MURI Responsive Surfaces and Adhesives 70°C T. E. Long, PI Well-Defined Topology and Chemical Functionality THREE RESEARCH THRUST AREAS Macromolecular Design Molecular Rheology and Topology Functional Surfaces and Sensors Controlled Rheology Functional Fibers New Sensing Materials www.chem.vt.edu/chem-dept/mapmuri

16. Proposed Investments Four chaired professorships (2 in science, 2 in engineering) - $8 million Six start-up packages for new macromolecules and interfaces faculty (3 in science, 3 in engineering) - $2.4 million Basic and specialized equipment to support four thrust areas - $4.6 million TOTAL: $15 MILLION Complementary support from Virginia Tech: • Renovated/New Common Space for Advanced Materials • Faculty Positions in Polymer Science and Engineering

17. Impact on the University, Commonwealth and the Nation • Educated workforce for the 21st century • Research and knowledge transfer to industry and government with a focus on polymeric materials for • Energy • Infrastructure, aerospace and defense • Healthcare • Environment • Economic development in the Commonwealth, especially through the Southside VA polymer processing institute IALR Under Construction

18. Institute for Macromolecules and Interfaces (IMI) APPENDIX

19. Web Links for More Information • Institute for Macromolecules and Interfaces (under development): http://www.imi.vt.edu • Polymer Materials and Interfaces Laboratory: http://www.chem.vt.edu/PMIL • Center for Adhesive and Sealant Science: http://www.cass.vt.edu • Center for Composite Materials and Structures: http://www.research.vt.edu/ccms • MACRO degree program: http://www.macro.vt.edu

20. Participating Faculty

21. Equipment Needs

22. Economic Growth Potential A Profile of the Materials Industry in Virginia, prepared for CIT by Chmura Economics and Analytics, Nov. 2001

23. Staff Summary

24. Student Participation Summer Undergraduate Research Program (SURP)

25. Student Participation Recent Graduate Degrees

26. Research Awards Summary

27. Research Awards Summary [1] Sponsored awards with an inception date before FY2000 include only those funds received since FY2000. Totals for continuing projects include only those funds authorized to date.

28. Research Awards Summary [1] Sponsored awards with an inception date before FY2000 include only those funds received since FY2000. Totals for continuing projects include only those funds authorized to date.

29. Recent Dissertations • Martin Drees, “Polymer/Fullerene Photovoltaic Devices - Nanoscale Control of the Interface by Thermally-controlled Interdiffusion,” Physics (Advisor: Heflin) • David Williamson, “Synthesis and Characterization of Well-defined Poly(1,3-cyclohexadiene) Homopolymers and Copolymers,” Chemistry (Advisor: Long), DuPont • Jeremy Lizotte, "Synthesis and Characterization of Tailored Macromolecules via Stable Free Radical Polymerization Methodologies,” Chemistry (Advisor: Long), Eastman • Kristen O’Brien “Synthesis of Functionalized Poly(dimethylsiloxane)s and the Preparation of Magnetic Nanoparticle Complexes and Dispersions,” Chemistry (Advisor: Riffle), National Research Council Fellow—NIST • Astrid Rosario, “The Chemistry of Dimethacrylate-Styrene Networks and Development of Flame-Retardant, Halogen-Free Fiber Reinforced Vinyl Ester Composites”, Chemistry (Advisor: Riffle), Assistant Professor—University of South Carolina-Spartanburg [1] Sponsored awards with an inception date before FY2000 include only those funds received since FY2000. Totals for continuing projects include only those funds authorized to date.

30. Recent Dissertations • Sandra Case, “Fundamental Importance of Fillers, Cure Conditions, and Crosslink Density on Model Epoxy Properties,” (Advisor: Ward), Lord Corporation • M. J. Bortner, “Melt Processing of Polyacrylonitrile Copolymers,” (Advisor: Baird), Nanosonic • Miguel Pando, “A Laboratory and Field Study of Composite Piles for Bridge Substructures,” Civil and Environmental Engineering (Advisor: Lesko), Assistant Professor—University of Puerto Rico • Amy Eichstadt, “Structure-Property Relationships and Adhesion in Polyimides of Varying Aliphatic Content,” Chemistry (Advisor: Ward), Procter and Gamble • Michael Hickner, “Transport and Structure in Fuel Cell Proton Exchange Membranes,” Chemical Engineering (Advisor: McGrath), Assistant Professor—University of California Davis [1] Sponsored awards with an inception date before FY2000 include only those funds received since FY2000. Totals for continuing projects include only those funds authorized to date.

31. Proposed NSF STC on Fuel Cell Performance Technology Technology Technology Technology Science Science Science Science Durability Durability Bipolar Plate Bipolar Plate Bipolar Plate Bipolar Plate Baird, Bergman, Case, Lesko Baird, Bergman, Case, Lesko Baird Baird Characterization Characterization And Modeling And Modeling Performance Performance Performance Performance Gas Diffusion Layer Gas Diffusion Layer Gas Diffusion Layer Gas Diffusion Layer Seal Seal Based Based Based Based Seal Seal Case, Lesko, Case, Lesko, Morris, Fenton, England Morris, Fenton, England Catalyst Catalyst Catalyst Catalyst Morris Morris Optimization Optimization Optimization Optimization Dillard, von Dillard, von von von Spakovsky Spakovsky , , Spakovsky Spakovsky , , High Performance Membrane High Performance Membrane High Performance Membrane High Performance Membrane McGrath, Long, Leo, Weiss, Shaw, McGrath, Long, Leo McGrath, Long, Leo, Weiss, Shaw, McGrath, Long, Leo Sammes Sammes Ellis, Nelson, Ellis, Nelson, Ellis, Nelson, Ellis, Nelson, Bergman Bergman Catalyst Catalyst Catalyst Catalyst Huang, Huang, Riffle, Long, Dillard Riffle, Long, Dillard Riffle, Long, Dillard, England Riffle, Long, Dillard, England Seal Seal Seal Seal Reifsnider Reifsnider , Chiu , Chiu Gas Diffusion Layer Gas Diffusion Layer Gas Diffusion Layer Gas Diffusion Layer Bipolar Plate Bipolar Plate Bipolar Plate Bipolar Plate

32. History of Program

33. History of Program

34. Vision Statement • The Institute will serve as a primary and integrating source of guidance to the University administration with respect to educational and research programs and opportunities in polymeric materials and interfaces at VA Tech. • The principal goal will be to maintain and advance the national and international ranking of the polymer program at VA Tech. • The Institute will outline needs and suggest mechanisms for enhancing personnel, space, and equipment issues required to achieve this goal. [1] Sponsored awards with an inception date before FY2000 include only those funds received since FY2000. Totals for continuing projects include only those funds authorized to date.

35. Mission Statement The Institute will be organized to serve the University in the following areas: • Recommend personnel needs via cluster hiring • Provide guidance and seek support for the MACRO and related graduate and undergraduate educational efforts • Recommend space and equipment needs to accomplish the Vision goals • Serve as a coordinating body for major multi-disciplinary polymer research proposals to Federal, State and industrial sources • The Institute will review opportunities and initiate proposals to the NSF, DoD, DoE, NASA, NIH • The Institute will conduct annual reviews focusing on VT capabilities and opportunities with industry and government [1] Sponsored awards with an inception date before FY2000 include only those funds received since FY2000. Totals for continuing projects include only those funds authorized to date.

36. Recent Publications • D.G. Baird and D.I. Collias, Polymer Processing: Principles and Design, Second Edition, John Wiley and Sons, March, 1998. • M. W. Ellis, Fuel Cell Cogeneration Technology Assessment Guide, Atlanta, GA: American Society of Heating, Refrigerating, and Air Conditioning Engineers, ISBN 1-931862, 2001. • Y. Seo, A. R. Esker, D. Sohn, H.-J. Kim, S. Park, and H. Yu, "Study of the Behavior of Different Polystyrene-block-Poly(methyl methacrylate) Diblock Copolymers Adsorbed on the Air/Water Interface," Langmuir, 19, 3313-3322, 2003. • S. Wendler and C.E. Frazier, “The Effects of Cure Temperature and Time on the Isocyanate-Wood Adhesive Bondline by 15N CP/MAS NMR,” Int. J. Adhesion and Adhesives, 16, 3, 179-186, 1996. • Zhao, Tiejun; Beckham, Haskell W.; Gibson, Harry W.. Quantitative Determination of Threading in Rotaxanated Polymers by Diffusion-Ordered NMR Spectroscopy. Macromolecules (2003), 36(13), 4833-4837. [1] Sponsored awards with an inception date before FY2000 include only those funds received since FY2000. Totals for continuing projects include only those funds authorized to date.

37. Recent Publications • M. Drees, K. Premaratne, W. Graupner, J. R. Heflin, R. M. Davis, D. Marciu, and M. Miller, “Creation of a Gradient Polymer-Fullerene Interface in Photovoltaic Devices by Thermally-Controlled Interdiffusion,” Applied Physics Letters, 81, 24, 2002. • D. Xu, M. Bluemle, E. M. Neyman, and J. G. Dillard, "Surface Modification of Coated Silicon Substrates for Adhesion to Epoxy Adhesives", Proceedings of the Adhesion Society, 2, 157-159, 2002. • K. M. Newbury and D. J. Leo, “Linear Electromechanical Model of Ionic Polymer Transducers, Part I & II,” Journal of Intelligent Material Systems and Structures, 14(6), 333-358, 2003. • A. J. Pasquale, T. E. Long, H. Truong, and R. D. Allen, “Investigations of the Adhesion of Maleic Anhydride/Cyclic Olefin Alternating Copolymers to Silicon Substrates: Improved Materials for 193 nm Lithography,” J. Adhesion, 78, 1, 1-3, 2002. • T. A. Bullions, J. E. McGrath, and A. C. Loos, “Thermal-Oxidative Aging Effects on the Properties of a Carbon Fiber-Reinforced Phenylethynyl-Terminated Poly(etherimide),” Composite Science and Technology, 63, 1737 – 1448, 2003.

38. Recent Publications • S. R. Trenor, A. E. Suggs, and B. J. Love, “An Examination of Transdermal Drug Delivery Using a Model Polyisobutylene Pressure Sensitive Adhesive”, J Materials Science Letters, 21, 1321-1323, 2002. • Y. S. Kim, F. Wang, M. Hickner, T. A. Zawodzinski, and J. E. McGrath, “Fabrication and Characterization of Heteropolyacid (H3PW12O40)/Directly Polymerized Sulfonated Poly(arylene ether sulfone) Copolymer Composite Membranes for Higher Temperature Fuel Cell Applications,” Journal of Membrane Science, 121(1-2), 263-282, 2003. • F. Wang, M. Hickner, Y. S. Kim, T. A. Zawodzinski, and J. E. McGrath, “Direct Polymerization of Sulfonated Poly(arylene ether sulfone) Random (Statistical) Copolymers: Candidates for New Proton Exchange Membranes,” Journal of Membrane Science, 197, 231-242, 2002. • S. Shuler and J. R. Morris, "Energy Transfer in Rare Gas Collisions with Hydroxyl- and Methyl-Terminated Self-Assembled Monolayers," Journal of Chemical Physics, 116, 9147-9150, 2002. • N. Siegel, M. W. Ellis, D. J. Nelson, and M. R. von Spakovsky, “A Single Domain PEMFC Model Based on Agglomerate Catalyst Geometry,” J. Power Sources, 115(1), 81 – 89, 2003.

39. Recent Publications • M. J. Sumner, M. Sankarapandian, J. E. McGrath, J. S. Riffle and U. Sorathia, “Flame Retardant Novolac- Bisphthalonitrile Structural Thermosets,” Polymer, 43(19), 5069-5076, 2002. • K. E. Van Cott, M. Guzy, P. Neyman, C. Brands, J. R. Heflin, H. W. Gibson, and R. M. Davis, “Layer-by-Layer Deposition and Ordering of Low-Molecular Weight Dye Molecules for Second-Order Nonlinear Optics,” Angew. Chem. Int. Ed., 41(17), 3236-3238, 2002. • S. Xu and D. A. Dillard, “Environmental Aging Effects on Thermal and Mechanical Properties of Electrically Conductive Adhesive Joints,” J. of Adhesion, 79, 699-723, 2003. • K-T. Wan, V. Chan, D. A. Dillard, “Constitutive Equation for Elastic Indentation of a Thin-walled Bio-mimetic Microcapsule by an Atomic Force Microscope Tip,” Colloids and Surfaces B: Biointerfaces, 27, 241-248, 2002. • K. L. Reifsnider and S. W. Case, Damage Tolerance and Durability in Material Systems, John Wiley and Sons, New York, 2002.

40. Recent Publications • S. R. Patel and S. W. Case, “Durability of Hydrothermally Aged Graphite/Epoxy Woven Composites Under Combined Hydrothermal Conditions,” International Journal of Fatigue, 24, 1295-1301, 2002. • C. E. Bakis, L. C. Bank, V. L Brown, E. Cosenza, J. F. Davalos, J. J. Lesko, A. Machida, S. H. Rizkalla, and T. C. Triantafillou, “Fiber-Reinforced Polymer Composites for Construction—State-of-the-Art Review,” ASCE Journal of Composites for Construction, 150th Anniversary Paper, 73-87, May 2002. • S. Case and T.C. Ward, "Physical Properties of a Bisphenol-F Epoxy Containing a Silica Filler Treated with Silane Coupling Agents", Journal of Adhesion, 79, 105-122 2002. • E. O'Brien, T. C. Ward, S. Guo and D. Dillard, "Strain Energy Release Rates of a Pressure Sensitive Adhesive Measured by the Shaft-Loaded Blister Test", Journal of Adhesion, 79, 69-97, 2003. • Matthew J. O'Sickey, Bruce D. Lawrey, Garth L. Wilkes, “Structure-property relationships of poly(urethane urea)s with ultra-low monol content poly(propylene glycol) soft segments: I. Influence of soft segment molecular weight and hard segment content,” Journal of Applied Polymer Science, 84, 229-243, 2002.

41. The Virginia Tech Chemistry Complex Hahn Davidson Apr. 22, 2003 Hahn New Chemistry-Physics