Dennis Smith, Ph.D - US grants

A new family of polyarylene derivatives is proposed which are of interest and potentially useful in a variety of high performance, optoelectronic, and high yield carbon applications. Polyarylenes, in general, are currently limited by poor melt and solution processability and traditional strategies to improve processability typically sacrifice performance. To enable the use of polyarylenes as fabricated high performance materials and as functional hybrid molecular composites, the proposed research will provide access to polyarylene networks from processable intermediates. The recently discovered synthetic approach consists of three steps starting from commercial bisphenols and affords bis-ortho-diynylarene(BODA) monomers in high yield. When heated, BODA tetraynes undergo Bergman cyclopolymerization and further thermal cure results in high performance networks, optoelectroactive materials, and high yield semiconductor glassy carbon. As a significant extension to this projects preliminary results, this work seeks to: (1) Prepare new BODA compounds and determine structure/property relationships for both thermal and catalytic/initiated routes. (2) Combine monomers and reactive intermediates with inorganic spacers, metal complexes, sol-gel precursors, and polymer electrolytes. (3) Expand preliminary microfabrication and pyrolysis studies to tailored semi-conductive glassy carbon and carbon/inorganic hybrid molecular composites.

This project offers a new approach to processable and property-timable architectures for advanced application such as light emitting diodes, optical waveguides, low dielectric insulators, polymer electrolyte membranes, membrane electrode assemblies, and bipolar plates for batteries and fuel cells, microelectro/magnetomechanical systems, and microsemiconductors for optical signal processors, sensors, and switches. An inter-disciplinary approach spanning synthesis, materials science, polymer physics, and device fabrication is planned. Over the next five years, the proposed education and outreach plan will: (1) Establish an interdisciplinary basic polymer science curriculum that complements the rich variety of applied polymer studies currently offered at Clemson University. (2) Expose undergraduate and graduate students to inter-disciplinary collaborations on campus and industrial cooperative education/internships. (3) Team with the Intersociety Polymer Education Council (IPEC) and education faculty to implement a plan for teacher training workshops in polymer chemistry. (4) Use current and future positions at the national ACS level to enhance the local ACS section and extend leadership to the student affiliate programs.

0076257
Harrison

This IMR grant supports the acquisition of an extensional rheometer in the Chemical Engineering department at Clemson University. The instrument will support the research of two young and two midcareer scientists in the investigation of extensional viscosity in polymers and polymer blends. The study facilitated by this instrument will allow a more complete characterization of a broad class of materials and lead to the development of new materials engineered with particular extensional properties. The rheometer will also enable current and future students to study extensional properties and investigate the influence of these properties on materials processing. Examples of materials to be studied are highly entangled polymer solutions and melts, polymer blends, composite materials and suspensions.

Plastics and rubbers have extraordinary properites when they are squeezed or stretched. Pulling them apart involves measures such as extensional viscosity which play a vital role in the mechanical properties of these materials. The instrument acquisition supported by this grant is to help study the mechanical propertis of these technologically critical materials.

This one-year exploratory research project proposes to develop a new family of carbon-aerogel-based nanomaterials for use as electrodes in high-performance proton exchange membrane (PEM) fuel cell power sources. The proposed materials consist of electrically conductive mesoporous carbon aerogel supports having internal porosity of nanoscopic dimensions, with fluorinated polymeric electrolytes grafted onto the interior surface of the aerogel mesopores. The high surface area and high porosity of aerogel materials are desirable in fuel cell electrodes because they allow for dispersion of a maximum amount of catalyst particles per unit volume of support while also providing sufficient physical structure in the support to allow for access of fluoropolymer electrolyte to catalyst particles without also blocking transport of fuel, oxidant, and water to and from catalyst particles. Fluorinated electrolytes are essential in fuel cell electrodes because only fluorinated materials can provide the needed long-term chemical stability for a practical device. Grafting of fluoropolymer electrolytes inside of carbon aerogel mesopores has never been attempted but will be essential to operation of a PEM fuel cell electrode since it offers the only means for making robust electrodes that provide for electrolyte access to catalyst particles anchored inside the aerogel mesopores. Electrode materials designed with these considerations in mind are expected to exhibit maximum activity for fuel cell reactions (e.g., electrochemical oxygen reduction, hydrogen oxidation, methanol oxidation) and could form the basis of a new generation of power sources exhibiting much higher performance than existing devices.

The specific scientific objectives of the proposed research are twofold: (1) explore methods for synthesizing carbon aerogels with grafted fluoropolymer electrolytes and dispersed nanoparticulate catalysts in the pores, with particular focus on methods amenable to eventual high-volume manufacturing; and (2) characterize the resulting materials to demonstrate their potential utility in PEM fuel cell technology. In addition to the interdisciplinary training of graduate students, this project will have broad impacts in several areas of importance to the national interest. It will contribute to making more effective utilization of energy resources, minimizing long-term environmental problems associated with depletion of fossil fuels, helping to make more viable a sustainable energy economy based on hydrogen gas as an energy carrier, and helping to make our nation more secure by providing our military forces with more options for lightweight portable electric power.

TECHNICAL SUMMARY

The proposed research describes a new family of polyarylenes and hybrid molecular composites useful in a variety of high performance, thin film network, and high yield carbon applications. As a general class, polyarylenes are currently limited by poor melt and solution processability and traditional strategies to improve processability typically sacrifice performance. In an effort to overcome these issues, prior NSF funding has enabled the development of a versatile family of polyarylene networks from processable intermediates. The general synthetic approach requires three steps from commercial bisphenols and affords bis-ortho-diynylarene (BODA) monomers in high yield. When heated, BODA tetraynes undergo Bergman cyclopolymerization to branched - and thus processable - intermediate reactive oligomers. Solution or melt fabrication and further thermal cure results in high performance networks, electroactive and light emissive materials, and high yield semiconductor glassy carbon. The synthesis of new BODA derived materials is proposed targeted for applications in important emerging areas including fuel cells, photo-voltaics, light emissive devices, photonic sensors, and inorganic / carbon hybrid composites.

NON-TECHNICAL SUMMARY

The proposed research describes synthesis and study of a new family of plastics which have potential applications in emerging and strategically important fields such as solar energy, hydrogen fuel cells, light emitting devices, and chem/bio sensors. The unique advantage of this technology includes the ability to form coatings and molded parts while forming the plastic structure at the same time. Plastic structures of this type have been very difficult to process in the past. The project also includes many broader impacts focused on the promotion of multi-disciplinary graduate training, project stewardship from an industrial mentor, and K-12 teacher and student outreach.
Specifically, outreach activities will be focused in three areas: K-12 teacher training workshops on using everyday plastics to convey scientific concepts, K-12 chemistry demonstration road shows, and the Clemson Emerging Scholars Program. The latter is a three week program at Clemson for several hundred economically disadvantaged and primarily minority high school students in South Carolina. A special element of the project is the management plan which will include faculty and graduate student project stewardship through the current NSF Discovery Corps Fellowship Grant under the direction of one of the Discovery Corps Sr. Fellows as industrial mentor.

SUMMARY. Funds are requested from the National Science Foundation (NSF) for
attendee / speaker support for the title symposium. The ACS Division of Polymer
Chemistry has established a unique and diverse team of organizers from industry,
academia, and government focused on the important topic of entrepreneurship in polymer
science and technology. Polymer science and technology is an important component of
materials research which overlaps with many current NSF initiatives. The global
competitive demands on polymer chemists today require that they be well trained in
science and that they behave more like entrepreneurs to feed an insatiable technologically
innovative economy. An entrepreneur transforms creative ideas into successes and many
of the entrepreneurial success are directly related to NSF programs. This symposium will
focus on breakthrough inventions enabled by experimentation on novel, emerging, and
pioneering technologies oriented toward materials research. Closer collaboration
between industry, academia and government should increase the number, speed and
impact of success stories and place prominent emphasis on the necessity of
entrepreneurship.
The symposium will cover basic research leading to new technology development and
commercialization. Entrepreneurial activities ranging from identifying a need, to basic
research, to developing novel and useful technology, to protecting the invention, to
obtaining funding, to becoming a self-sustaining business will be reviewed. Our objective
is to provide current, practical information that is based on scientific breakthroughs
leading to real world experiences. The symposium will begin with a tutorial on
entrepreneurship. Discussions will focus on fundamental polymer and related science,
challenges and opportunities for scientists and engineers in the market to facilitate an
understanding of entrepreneurship. Scientists, engineers and technologists interested in
the latest developments and advances in this diverse and growing area are invited to
contribute oral and poster presentations.

SUMMARY: Support is requested for the first joint IUPAC / ACS Conference on Macromolecules for a Sustainable, Safe and Healthy World (IUMACRO-07) to be held June 10-14, 2007 in Brooklyn, New York (for program details, see: http:www.polyacs.org). IUMACRO-07 is cosponored by the Division of Polymer Chemistry (POLY) and the Division of Polymeric Materials: Science & Engineering (PMSE) of the Amecian Chemical Socity (ACS). In addition, the conference is supported by donations from industry including: LUBRIZOL, DOW CHEMICAL, TETACORE, INC. ABTECH SCIENTIFIC, INC., APPLIED BIOPHYSICS, INC.; as well as other government agencies including: ONR and AFRI. Joint sponsorship provides an interdisciplinary forum for the presentation and discussion of new and previously unpublished results on advances in polymer chemistry and materials science relevant to NSF initiatives and global macromolecular technology.

Planning Grant for an I/UCRC for the Ceramic, Composite and Optical Materials Center

0934300 Clemson University; Dennis Smith
0934258 Rutgers University; Richard Haber

The Center for the Ceramic, Composite and Optical Materials Center (CCOMC) will focus on providing a broader range of relevant technologies critical to materials-based companies. Clemson University and Rutgers University are collaborating to establish the proposed center, with Clemson University as the lead institution.

The Center for Ceramic Research (CRC) at Rutgers University, a past member of an ending NSF I/UCRC for Ceramic and Composite Materials Center, proposes to join with the Center for Optical Material Science and Engineering Technologies (COMSET) at Clemson University to form the proposed new Center (CCOMC) with new technological thrusts. COMSET has developed a strong industrial base, with three spin-off companies that, combined with Rutgers University, would provide a new and unique research program. The proposed Center (CCOMC) will focus on five thrust areas including ceramic materials and processing, nanoparticulates and processes, opaque and transparent armor ceramics, optical material synthesis and processing, and materials for energy conversion. The proposed research program across the five thrust areas will be carried out by an interdisciplinary group of faculty and across different academic disciplines. The PIs are well-qualified and have adequate resources to conduct the proposed research. Both institutions in this Center plan to use the NSF planning grant fund to hold a meeting with prospective industrial partners to establish the proposed Center's organizational framework, and to establish research projects of greatest relevance.

The proposed center (CCOMC) has the potential to improve sustainability and profitability of US manufacturing by developing new technologies in the ceramic, optic and composite material field. CCOMC has plans in place for involving under-represented groups, to recruit highly qualified faculty and graduate students, and to motivate undergraduate students through unique research experiences and fellowships. Results will be disseminated through semi-annual meetings, publications, and a website for information, results and accomplishments. CCOMC will continue to integrate research and education; and by providing hands-on experience to students, the Center will attempt to motivate students to go beyond common approaches towards learning by hands-on experiences in state-of-the-art facilities focusing on today's relevant materials issues.

Planning Grant for an I/UCRC for Energy Harvesting Materials and Systems

0856032 Virginia Polytechnic Institute and State University; Daniel Inman
0856046 Clemson University; Stephen Foulger
0855891 University of Texas, Dallas; Bruce Gnade

The proposal seeks a planning grant for a new multi-university Center for Energy Harvesting Materials and Systems to focus on recovery (harvesting) of unused energy from various sources such as radio and television towers, satellites and various portable electronics. Virginia Polytechnic Institute (VT), Clemson University (CU) and the University of Texas, Dallas (UTD) are collaborating to establish the proposed center, with VT as the lead institution. The research plan includes developing new products and designs in the following areas: Energy Harvesting for Vibration Measurement, PiezoCell and Panels for Harvesting Wind Energy, VLSI Circuit Design, Materials for "Self-Powered" Position and Speed Sensors and Electrical Energy Storage, Micro-Scale Thermal to Electric Energy Conversion, Magnetic to Electric Energy Conversion in Ocean Environments, On-Chip Energy Source Using Indium Nitride Quantum Dot Solar Cells, Piezoelectric Cantilevers Based Energy Harvesters, and Roll-to-Roll Printing of Organic Energy Harvesters. VT, CU and UTD plan to use the NSF planning grant fund to hold a meeting with prospective industrial partners, and to develop an initial research agenda for CEHMS of sufficient commercial interest that attendees will be willing to invest in and sustain the Center.

The proposed Center has the potential to improve sustainability and profitability of US manufacturing firms by developing new technologies that will reduce energy consumption and harvest energy that is normally wasted. Industrial members will benefit from the research conducted at the Center in areas of materials synthesis, thin-film deposition, energy conversion devices, micro/nano electronics, electrochemical storage systems, sensor development, system design, integrated hybrid architectures, computational and theoretical modeling, and nano-scale fabrication techniques. Students and faculty members of CEHMS will gain valuable experience by interaction with industry partners.

I/UCRC for the Ceramic, Composite and Optical Materials Center

1034979 Clemson University; Dennis Smith
1034978 Rutgers University; Richard Haber

The Center for the Ceramic, Composite and Optical Materials Center (CCOMC) will focus on providing a broader range of relevant technologies critical to materials-based companies. Clemson University and Rutgers University are collaborating to establish the proposed center, with Clemson University as the lead institution.

The Center for Ceramic Research (CRC) at Rutgers University, a past member of an ending NSF I/UCRC for Ceramic and Composite Materials Center (CCR), proposes to join with the Center for Optical Material Science and Engineering Technologies (COMSET) at Clemson University to form the proposed new Center (CCOMC) with new technological thrusts. COMSET has developed a strong industrial base, with three spin-off companies that, combined with Rutgers University, would provide a new and unique research program. The mission of the proposed Center (CCOMC) is to develop new innovations that enable and sustain United States competitiveness in ceramic, particulate, composite and optical material science, technology and engineering. Furthermore, the CCOMC will transfer these new innovations to its industrial members for competitive reproducible ceramic, particulate, composite and optical materials, for advanced, high performance commercial products. The proposed center's research projects are integrated into five thrust areas: powder synthesis and processing, nanoparticulates and processes, optical material synthesis and processing, materials for defense sciences, and materials for energy conversion. The proposed research program across the five thrust areas will be carried out by an interdisciplinary group of faculty and across different academic disciplines. The PIs are well-qualified and have adequate resources to conduct the proposed research.

The proposed center (CCOMC) has the potential to improve sustainability and profitability of US manufacturing by developing new technologies in the ceramic, optic and composite material field. CCOMC has plans in place for involving under-represented groups, to recruit highly qualified faculty and graduate students, and to motivate undergraduate students through unique research experiences and fellowships. Results will be disseminated through semi-annual meetings, publications, and a website for information, results and accomplishments. CCOMC will continue to integrate research and education; and by providing hands-on experience to students, the Center will attempt to motivate students to go beyond common approaches towards learning by hands-on experiences in state-of-the-art facilities focusing on todays relevant materials issues.

I/UCRC for Energy Harvesting Materials and Systems

1035042 Virginia Polytechnic Institute and State University; Daniel Inman
1035024 University of Texas, Dallas; Bruce Gnade

The Center for Energy Harvesting Materials and Systems ((CEHMS) will focus on recovery (harvesting) of unused energy from various sources such as radio and television towers, satellites and various portable electronics. Virginia Polytechnic Institute (VT) and the University of Texas, Dallas (UTD) are collaborating to establish the proposed center, with VT as the lead institution.

The proposal seeks a grant for a new multi-university Center for Energy Harvesting Materials and Systems to focus on energy harvesting approaches. The focus of research within this center will be to investigate a wide range of potential energy harvesting opportunities in power systems, human activity, industrial machines, vehicles, vibrating structures and other such sources. While the energy harvested in any one of the opportunities is small, the accumulation effect can be very significant. The proposed researchers have identified some unique and creative opportunities to assess the value and potential for harvesting energy that would otherwise be untapped. The research is important to the US and much of the world in efforts to capture new sources of energy. The reduction in dependence on foreign oil is always of significant value. The PIs have excellent credentials for conducting the research effort, and the involvement of a number of qualified researchers from the two collaborative universities is impressive. The proposal is very well written and the project descriptions are clear and well documented. The research tasks are appropriate and appear to be very well conceived.

The proposed Center has the potential to improve sustainability and profitability of US manufacturing firms by developing new technologies that will reduce energy consumption and harvest energy that is normally wasted. The proposal uses a diverse group of researchers to develop new technologies that can be used in developing new industries, new jobs, new products and new services in the future. The research team is made up of various ethnic and gender groups that have a variety of educational and professional experiences including minority and disadvantage groups. The technologies that are developed by this proposal have the potential to have a large economical impact by producing jobs in new industries and reducing the need for existing fossil fuels. The plan for involving underrepresented students and faculty in the center is very well presented and appropriate. The research program will enhance the already impressive infrastructure at the two universities. Because of the wide range of topics, the dissemination of the results will be primarily through publications and industry meeting. The students involved with the program will be well prepared to enter the workforce and provide additional technology transfer.

With this award from the Major Research Instrumentation Program (MRI) that is co-funded by the Chemistry Research Instrumentation Program (CRIF), Professor Mihaela Iovu from University of Texas Dallas and colleagues A. Dean Sherry, John Ferraris, Dennis Smith and Jung-Mo Ahn will acquire a 500 MHz NMR spectrometer equipped with two probes. The proposal is aimed at enhancing research training and education at all levels, especially in areas such as (a) polythiophene-CdSe blends for bulk heterojunction solar cells, (b) perfluorocyclobutyl (PFCB) polymers for proton exchange membrane (PEM) fuel cells and gas separation applications, (c) fluorovinylene aryl ether telechelic polymers for thermal chain extension and tandem crosslinking, (d) lanthanide complexes and polymers as metabolic sensors for Magnetic Resonance Imaging, and (e) development of peptidomimetics for treatment of diabetes mellitus.

Nuclear Magnetic Resonance (NMR) spectroscopy is one of the most powerful tools available to chemists for the elucidation of the structure of molecules. It is used to identify unknown substances, to characterize specific arrangements of atoms within molecules, and to study the dynamics of interactions between molecules in solution. Access to state-of-the-art NMR spectrometers is essential to chemists who are carrying out frontier research. The results from these NMR studies will have an impact in synthetic organic/inorganic chemistry, materials chemistry and biochemistry. This instrument will be an integral part of teaching as well as research.