Annual Report Table of Contents Cover Sheet for Proposal

2005 Annual Report Table of Contents Cover Sheet for Proposal to the National Science Foundaion I. General Info Executive Summary II. Research III. Education IV. Knowledge Transfer V. Partnerships VI. Diversity VII. Management VIII. Center-Wide Outputs & Issues CERSP, Page 1 of 230 COVER SHEET FOR PROPOSAL TO THE NATIONAL SCIENCE FOUNDATION PROGRAM ANNOUNCEMENT/SOLICITATION NO /CLOSING NSF 98-13 FOR NSF USE NSF PROPOSAL FOR CONSIDERATION BY NSF ORGANIZATIONAL UNIT(S) NSF Science & Technology Center DATE NUMBER DIVISION FUND DUNS # (Data FILE LOCATION 003203213 EMPLOYER SHOW PREVIOUS IS THIS PROPOSAL BEING IDENTIFICATION AWARD NO. IF THIS IS SUBMITTED TO ANOTHER NUMBER (EIN) OR FEDERAL TAXPAYER AGENCY? YES NO x IF x A RENEWAL IDENTIFICATION YES, LIST ACRONYM(S) NUMBER (TIN) 566001393 AN ACCOMPLISHMENTBASED RENEWAL NAME OF ORGANIZATION TO University of North Carolina @ AWARDEE ORGANIZATION CODE 0029744000 NAME OF PERFORMING PERFORMING ORGANIZATION ADDRESS OF AWARDEE ORGANIZATION, 300 Bynum Hall CB 4100 Chapel Hill, NC 27599 ADDRESS OF PERFORMING ORGANIZATION, IS AWARDEE (See GPG II D 1 For Definitions) FOR-PROFIT ORGANIZATION TITLE OF PROPOSED PROJECT NSF Science & Technology Center for REQUESTED AMOUNT PROPOSED DURATION (1-60 MONTHS) 12 REQUESTED STARTING DATE 11/1/2003 $ SMALL SHOW RELATED PREPROPOSAL NO., IF APPLICABLE months CHECK APPROPRIATE BOX(ES) IF THIS PROPOSAL INCLUDES ANY OF THE ITEMS LISTED BELOW BEGINNING INVESTIGATOR (GPG VERTEBRATE ANIMALS DISCLOSURE OF LOBBYING HUMAN SUBJECTS (GPG II.D.12) PROPRIETARY & PRIVILEGED Exemption NATIONAL ENVIRONMENTAL POLICY INTERNATIONAL COOPERATIVE HISTORIC PLACES (GPG II.D.10) SMALL GRANT FOR EXPLOR. FACILITATION FOR RESEARCH OPPORTUNITY AWARD PI/PD DEPARTMENT PI/PD POSTAL ADDRESS Department of Chemistry CB #3290 Venable & Kenan Laboratories CERSP, Page 2 of 230 PI/PD FAX NUMBER 919-962-5467 NAMES (TYPED) PI/PD NAME J.M. DeSimone CO-PI/PD Ruben G. Carbonell CO PI/PD NSF Form 1207 (10/99) UNC Chapel Hill, NC 27599-3265 High Yr of Telephone Ph.D. Ph.D. 1990 1973 919-962919-515- Electronic Mail Address desimone@unc.edu ruben@ncsu.edu Page 1 of 2 CERSP, Page 3 of 230 CERTIFICATION PAGE Certification for Principal Investigators and Co-Principal Investigators I certify to the best of my knowledge that: (1) the statements herein (excluding scientific hypotheses and scientific opinions) are (2) the text and graphics herein as well as any accompanying publications or other signatories or individuals working under their supervision I agree to accept required project reports if an award is made as a result of this proposal I understand that the willful provision of false information or concealing a material fact criminal offense (U S Code Title 18 Section 1001) Name (Typed) Signature Social Security No * Date PI/PD Joseph M. July 29, 2005 Co-PI/PD Ruben G. Carbonell July 29, 2005 Co-PI/PD Co-PI/PD Co-PI/PD Certification for Authorized Organizational Representative or Individual Applicant By signing and submitting this proposal the individual applicant or the authorized are true and complete to the best of his/her knowledge; and (2) agreeing to accept the made as a result of this application Further the applicant is hereby providing workplace and lobbying activities (see below) as set forth in the Grant Proposal and its supporting documents or in reports required under an ensuing award is a In addition if the applicant institution employs more than fifty persons the authorized implemented a written and enforced conflict of interest policy that is consistent with the knowledge all financial disclosures required by that conflict of interest policy have satisfactorily managed reduced or eliminated prior to the institution’s expenditure of interest policy Conflicts that cannot be satisfactorily managed reduced or eliminated Debt and Debarment Certifications (If answer “yes” to either, please provide Is the organization delinquent on any Federal debt? Yes No x Is the organization or its principals presently debarred suspended or voluntarily excluded from covered transactions by any Yes No x Federal Department or agency? Certification Regarding Lobbying This certification is required for an award of a Federal contract grant or cooperative a commitment providing for the United States to insure or guarantee a loan exceeding Certification for Contracts, Grants, Loans and Cooperative Agreements The undersigned certifies to the best of his or her knowledge and belief that: (1) No Federal appropriated funds have been paid or will be paid by or on behalf of influence an officer or employee of any agency a Member of Congress an officer or connection with the awarding of any federal contract the making of any Federal grant agreement and the extension continuation renewal amendment or modification of (2) If any funds other than Federal appropriated funds have been paid or will be paid employee of any agency a Member of Congress and officer or employee of Federal contract grant loan or cooperative agreement the undersigned shall Activities ” in accordance with its instructions (3) The undersigned shall require that the language of this certification be included in subcontracts subgrants and contracts under grants loans and cooperative This certification is a material representation of fact upon which reliance was placed certification is a prerequisite for making or entering into this transaction imposed by required certification shall be subject to a civil penalty of not less than $10 000 and not AUTHORIZED ORGANIZATIONAL SIGNATURE DATE NAME/TITLE (TYPED) CERSP, Page 4 of 230 Robert P. Lowman, Ph.D. Associate Vice TELEPHONE ELECTRONIC MAIL ADDRESS 919-966-5625 lowman@unc edu 7/29/05 FAX NUMBER 919-962-6769 *SUBMISSION OF SOCIAL SECURITY NUMBERS IS VOLUNTARY AND WILL NOT AFFECT THE ORGANIZATION’S ELIGIBILITY FOR AN AWARD. HOWEVER, THEY ARE AN INTEGRAL PART OF THE NSF INFORMATION SYSTEM AND ASSIST IN PROCESSING THE PROPOSAL. SSN SOLICITED UNDER NSF ACT OF 1950, AS AMENDED. CERSP, Page 5 of 230 I. GENERAL INFORMATION Date submitted Reporting period Name of the Center Name of the Center Director Lead University Contact information Address July 29, 2005 August 1, 2004-July 31, 2005 Science and Technology Center for Environmentally Responsible Solvents and Processes Prof. Joseph M. DeSimone University of North Carolina-Chapel Hill Prof. Joseph M. DeSimone, Director CB# 3290 Department of Chemistry University of North Carolina Chapel Hill, NC 27599-3290 (919) 962-2166 (919) 962-5467 desimone@unc.edu Phone Number Fax Number Email Address of Center Director Center URL www.nsfstc.unc.edu Names of participating institutions, role, and (for each institution) name of contact person and other contact information Institution 1 Name University of North Carolina-Chapel Hill Address Phone Number Fax Number Email Address Role of Institution at Center Institution 2 Name Address CB# 3290 Department of Chemistry University of North Carolina Chapel Hill, NC 27599-3290 (919) 962-2166 (919) 962-5467 desimone@unc.edu Lead administrative institution, chemistry initiatives North Carolina State University Prof. Ruben G. Carbonell, Co-Director Kenan Institute, 3200 Partners Bldg. I, Box 7006, NCSU, Raleigh, NC 27695 CERSP, Page 6 of 230 Phone Number Fax Number Email Address of CoDirector Role of Institution at Center (919) 515-5118 (919) 515-5831 Ruben@ncsu.edu Engineering initiatives, K-12 outreach partnership through Science House, technology transfer through industrial consortia, and social science programs North Carolina A &T State University Prof. Leonard Uitenham (called to active duty 2005, temporarily replaced by Prof. Vinayak N. Kabadi) Chairman, Dept of Mechanical and Chemical Engineering, NC A&T, Greensboro, NC 27411 (336) 334-7620 ext 310 (334) 334-7417 U10ham@ncat.edu or kabadi@ncat.edu Institution 3 Name Address Phone Number Fax Number Email Address of Site Leader Role of Institution at Center HMU, lead undergraduate minority mentoring and recruiting, and lead thermodynamic measurements Institution 4 Name Address University of Texas-Austin Prof. Keith Johnston Dept. of Chemical Engineering, 26th & Speedway, University of Texas-Austin, Austin, TX 78712 (512) 471-4617 (512) 471-7060 kpj@che.utexas.edu Phone Number Fax Number Email Address of Site Leader Role of Institution at Center Nanotechnology, surface science/engineering and theory, technology transfer through Separations Research Program, lead in Hispanic mentoring and recruiting Institution 5 Name Address Georgia Institute of Technology Prof. William Koros Dept. of Chemical and Biomolecular Engineering CERSP, Page 7 of 230 Phone Number Fax Number Email Address of Site Leader Role of Institution at Center Separations research 0100, Georgia Institute of Technology, Atlanta, Georgia 30332 (404) 385-2845 (404) 385-2683 bill.koros@chbe.gatech.edu 1b. Research Staff Additions Appendix A1. Biographical Sketches of Research Staff Additions (none this period) Appendix A2. Biographical Sketches of External Advisory Board Additions CERSP, Page 8 of 230 2. EXECUTIVE SUMMARY VISION AND GOALS The vision for the Center for Environmentally Responsible Solvents and Processes (CERSP) is to enable a revolution in sustainable technology through cutting-edge integrated science/engineering and educational programs. Our mission is (1) to support multi-disciplinary, fundamental research to identify and enable sustainable processes and products using CO2-related technology and (2) to enable our science and technology to have broad societal benefit by understanding and applying social processes that foster collaboration and innovation; attracting and educating diverse students at all levels; and by promoting the benefits of sustainability. Our goals are to create a strong body of integrated basic knowledge and activities meant to: • Provide underlying science in selected areas of application and technology • Identify new areas of relevant basic science and technology for future focus • Develop and apply fundamental understanding of social processes Promote innovative, collaborative science education • Inform academia, industry, public and government sectors regarding opportunities for CO2 • Integrate research and education, with a strong focus on diversity, to realize our vision RESEARCH We converged to three Thrust Areas, plus Separations as an overarching technology: (1) Macromolecular Synthesis and Engineering, (2) Functional Materials and Devices, and (3) Nanostructures. The guiding principle for these selections remains consistent with our mission: select high-risk areas with potential for high impact, applying fundamental science and technology that are strengths of the Center. It is our belief that the Center’s mission is consistent with taking such risks rather than remaining in our “comfort zone” established during our first five years. It is the only way we can have high impact. However, rather than targeting incumbent technology broadly, we have now decided to focus on few steps with higher probability of success. Meanwhile, we will seek other applications from emerging studies in our laboratories. RESEARCH HIGHLIGHTS Macromolecular Synthesis and Engineering • A new catalytic procedure has potential to provide a much improved general reduction process of C-X bonds avoiding use of toxic reagents and simplifying separations. CERSP, Page 9 of 230 • Kinetics of polymerization is reaction-controlled in dilute regime, and is diffusion-controlled in semi-dilute regime. These results may be used to design novel elastomers. • For hexafluoropropylene/vinylidene fluoride copolymers, those with high HFP content can be polymerized in scCO2 solution, while those with low HFP must use precipitation methods. Intermediate compositions can use either technique depending upon conditions. • Proton exchange membranes have been developed that have ultra highconductivity and good mechanical stability, both surpassing commercially available fuel cell membranes. • CO2-mediated dispersion polymerizations produce nanocomposites at high yields without the need for extra surfactant to stabilize the system. • Novel methods to make superabsorbent polymers with supercritical CO2 technology have been developed using post-polymerization neutralization of the cross-linked polymer. • We have obtained partially resolved 19F and 1H spectra of the cross-linked networks in “liquid Teflon”, and are preparing to monitor polymerization kinetics in situ. • PEO-b-PFOMA block copolymer thin films in CO2 are disordered at high temperatures, become ordered as the temperature is reduced, and at still lower temperatures become disordered again. This type of behavior, to our knowledge, is previously unreported. Functional Materials and Devices • Soft lithography has been demonstrated using curable liquid PFPE-based materials and found to be a solvent-free high performance lithographic process. • Films deposited from liquid CO2 were much thinner, more uniform, and exhibited much fewer drying defects and better surface roughness than films from typical organic solvents. • CO2 has been found to improve drying in several steps of the lithographic process used to manufacture computer chips. In addition, a process using CO2 has been demonstrated that results in rapid development rates while maintaining critical dimensional control and potentially improving line edge roughness control. • We have spun-cast 5nm films of PVDF-TrFE and have characterized optical properties and dielectric constants both for as-prepared and for vacuumannealed films up to 150oC. • Using 193 nm radiation we observed time–resolved electron paramagnetic resonance spectra in aqueous solution involving both sulfate radicals and CERSP, Page 10 of 230 hydroxyl radicals. Both redox and H–atom abstraction chemistry were observed. • Molecular dynamics simulations comparing perfluoro surfactants and polyether analogues at the H2O/CO2 interface show that parameters related to chain rigidity determine whether the surfactant has "good" or "bad" properties for creating microemulsions. • We have shown that HF/CO2 etching of SiO2 films on single crystal Si does not affect the electronic integrity of the Si for slow and moderate etch rates. • We are applying technology (especially time-resolved EPR) developed in earlier studies to understand radical-based decomposition of fuel cell membranes. Nanostructures • PRINT (Particle Replication In Non-wetting Templates) can produce monodisperse organic nanoparticles of any shape and size; e.g., selfassembled or biological molecules. • Activation barrier energies decrease and electron hopping rates increase in 1.1 nm films of monolayer-protected Au38 nanoparticles when contacted by high pressure gaseous CO2. • We have designed a helical peptide, whose secondary structure is induced by the nonpolar nature of the CO2 solvent, thus making it CO2-soluble. • Sterically-stabilized organic monolayer coated metal nanocrystals can be dispersed in CO2 at low solvent densities. • Ordered monolayers of metal nanocrystals can be deposited from CO2 with better surface coverage than when using conventional solvents. • We are developing new ligand chemistry to enable liquid CO2 dispersibility for nanocrystal deposition and processing. • The analysis of the molecular interactions underlying interactions between modified surfaces at nanoscale geometries will provide the basis for rational surfactant design for future technology development. • Carbon dioxide may be used to control the morphology of dodecanethiol capped gold nanoparticles in polystyrene and polymethylmethacrylate thin films cast on SiOx substrates. CO2 may be utilized to anneal diblock copolymers to form templates to order nano-crystals selectively in one of the two phases. • A rapid deposition process for antireflective and superhydrophobic coatings from silica nanoparticles has potential to improve performance of solar cells and windows. CERSP, Page 11 of 230 • Micron-sized inorganic particles can be electrostatically stabilized at long range (several microns) in liquid and scCO2 despite the ultra-low dielectric constant, as low as 1.5. • Experiments show that CO2 facilitates dispersion of metal nanocrystals into porous materials, especially in pore sizes <5 nm. This simple method allows for facile production of nanocrystal/silica composites for applications like catalysis and optoelectronics. • Protein activities comparable to conventional lyophilization are achieved with surface areas greater than 35m2/gm with the spray freezing into liquid process. • We have formed CO2-in-water (C/W) emulsions using hydrocarbon tertiary amines, a new class of surfactants for CO2-based dispersions. • Organically-modified clays are amenable to melt intercalation in polydisperse polymer matrices containing short chains that effectively serve as dispersants. Extended annealing of these nanocomposites at elevated temperatures where polymer degradation takes place can affect clay microstructure and increase nanocomposite modulus substantially. Separations • Zeolite-polyvinyl acetate composites were prepared and are being evaluated as membranes for high-pressure separation of CO2 from monomers. We have demonstrated levels previously unachieved (50%) and are attempting to reach levels up to 80%. • A defect-free asymmetric hollow fiber membrane can be made using Torlon® polyimide polymer. This achievement encourages us that formation of an asymmetric membrane based on a hybrid zeolite-Torlon® blend is likely to be ultimately feasible. • It is necessary to “titrate” the tethering agent on the sieve surface to balance desirable adhesion vs. transport properties. EDUCATION CERSP continues to conduct a coordinated K-12 education outreach program. Through teacher workshops, presentations and demonstrations, we directly reached 533 teachers in NC and TX. Through distribution of exemplary learning materials, this program continues to reach indirectly an estimated 1000 teachers and 160,000 students per year in these states. Environmental Science laboratory books are being distributed for both high school and middle school grades, aligned with the NC and TX state science curricula. Science demonstrations “Fun with Polymers!” and “Fun with CO2!” are being used widely in North Carolina. The Center has partnered with several other education and service organizations to increase its reach and, especially, to increase access to students from underrepresented groups. CERSP, Page 12 of 230 Our redesigned website has been extremely successful. The monthly “hit rate” is up >10X (to 80,000/mo.) attributed a new section “Focus on A Scientist” and the site’s being more user friendly. Participation by CERSP personnel in K-12 activities remained high. K-12 events involving >50 Center faculty, staff and students directly reached >1700 students. Events included field trips, science demos, laboratory open houses, seminars, talks, workshops, mentoring, etc. Videoconference seminars reached an average of 40 students and faculty weekly, a total of 1500 contacts, down about 20% from last year. We are seeking means to revitalize these seminars. Conversely, impact of the Innovation Seminar Series has improved. Three nationally renowned speakers plus an Entrepreneurial Roundtable led by STC professors were very well received. Our collaboration workshop, led by Dr. Russ Osmond, was transformed to an ongoing leadership series to give students a “toolbox” of leadership skills. Much of the “toolbox” material from the workshop was put on our website for easy access and reference by the students. The workshop was modified from a “one time experience” to an ongoing educational process. Twenty-seven students and post-docs completed their studies and an additional five from 2004 were placed. Of 24 BS, MS and PhDs, 9 (38%) went to further education. Of the remaining 23, five went to university positions, one to high school teaching, one to a research institute, two to government positions, 12 to industry and two unknown. Sixty-seven percent of finishing BS, MS, and PhD students, but only 38% of finishing post docs, are U.S. citizens. KNOWLEDGE TRANSFER A total of 88 publications receiving full or partial CERSP support were issued or in press as of mid-June. This includes 72 papers (70 peer-reviewed) and five book chapters issued through June 2005 plus an additional 11 papers in press. In addition, six patents were issued and five applied for. A total of 110 external papers or posters were presented, including 68 presentations at conferences (4 abroad) and 42 invited lectures (11 abroad). Two of three organizers of the 7th International Symposium on Supercritical Fluids (attended by 400 including 250 oversees scientists) are STC faculty and 18 papers at ISSP were from CERSP. We are reorganizing our industrial consortium, the Kenan Center for Utilization of Carbon Dioxide in Manufacturing because (1) cost of administering patents in the old system exceeds the value and (2) interests of corporate members in the KCUCDM continue to evolve. CERSP, Page 13 of 230 PARTNERSHIPS Documented external collaborative partnerships increased from 123 to 126, with 16 new partnerships. Of these, 14 are government labs; 48, foreign institutions (from 23 different countries); 45 are with US universities, and 19 are from industrial concerns. DIVERSITY The EXperimental Program for Education in Research and Training (EXPERT) was implemented, led by a Discovery Corps Fellow, supporting 22 students; 100% of current EXPERT students are participating in summer research programs. EXPERT, which aims to increase the number of AfricanAmericans with STEM graduate degrees, is being used by NCA&T as a recruiting tool to improve caliber of applicants. In 2005 the number of African-American under-graduates supported by CERSP has tripled. In addition, by actively recruiting African-American students at NCA&T we have increased percentage of US citizens seeking MS from 29 to 72%. Although not tracked explicitly, faculty members report a significant increase in the frequency of communication with summer students regarding attending graduate school at STC universities. Thirty-nine faculty, 18 post-docs, 75 graduate students, 41 undergraduates, and eight staff members received support from the Center this year; 60% of 182 reporting Center participants were from historically underrepresented groups, including 39% of faculty, 68% of post-docs, 54% of graduate students and 83% of undergraduates; 36% of CERSP students and post-doctoral associates are African-Americans and only 19% are Caucasian males. MANAGEMENT We have expanded documentation of our strategic plan to include philosophical and operational elements to describe better how our plan is implemented. We adopted a new icon illustrating how all aspects of CERSP— technical and social—interact and contribute to the Center. CERSP, Page 14 of 230 II. RESEARCH 1a. Overall Research Objectives Research objectives and performance measures have been revised slightly this year. Details of the revision are discussed in Section VII under Strategic Plan. Revised objectives and performance measures are stated here for completeness. Research Objectives • Develop fundamental understanding of o Macromolecular synthesis and engineering: kinetic and transport mechanisms, thermodynamics, phase equilibria; factors affecting polymeric structure of materials and function in CO2-related systems, including catalytic and post-polymerization processes o Functional materials and devices: phenomena involved in dissolution and removal of materials, formation of thin films and coatings, dimensional control of structures, and photochemical conversions o Nanostructures: beneficial properties of supercritical CO2 that enable control of synthesis, stabilization, deposition and self-assembly of nano-scale structures o Separations: phenomena specific to separation science and technology needed for CO2 processing • Integrate fundamental understanding in these areas to demonstrate processes for functional materials; e.g., for electronic, optical, energy and therapeutic applications in order to identify and demonstrate feasibility of sustainable processes, materials, and devices as candidates for further development. • Explore new frontiers in relevant basic science in order to identify new areas for application of sustainable technology • Develop fundamental understanding of key factors impacting leadership, knowledge exchange, education and diversity in order to facilitate the innovation process 1b. Performance and Management Indicators include the following: • Number of peer-reviewed publications in professional journals • Presentations at major professional meetings, invited lectures and seminars, etc. • Number and quality of external collaborative interactions • Matching funds attracted CERSP, Page 15 of 230 • Effective utilization (and sharing) of facilities • Number of effective tools to facilitate cross-disciplinary research, such as those for full-text data mining 1c. Research Problems and Issues There have been no unresolved problems. However, evolution of program organization continued. In our Renewal Proposal we modified two implementation domains; “Dissolution and Deposition” became “Microelectronics”, and “Small Molecule Systems” became “Nanostructures”. Adoption of microelectronics mainly anticipated transition of the industry to 157nm irradiation technology. When the industry leader, Intel, dropped 157 nm programs so did many other companies who had invested hundreds of millions of dollars in 157nm lithography. It soon became clear that we were about to embark upon a Sisyphean effort. At the same time we were trying, without much success, to develop an industrial consortium focused on microelectronics. Several months down this path we revised our strategic plan (to the one described in Section VII) to reflect this reality. Microelectronics was broadened to become “Functional Materials and Devices.” Several projects were redirected within months of their start, but without significant loss of momentum or student research time. As we have now dropped Microelectronics as a stand-alone domain, we also dropped our plans to have a stand-alone consortium in this area in favor of a broader group of industrial affiliates. This recent foray into and out of microelectronics is consistent with our strategic plan outlined in Section VII. The strategy was appropriate, but our understanding of industry structure was flawed. While processes evolve rapidly (fitting our strategy), the underlying technology is firmly embedded. A frontal assault across the entire range of process steps to “revolutionize” the industry is too expensive and not supported by industry. Rather than trying to displace incumbent technology broadly, we have now decided to focus on few steps with higher probability of success. Meanwhile, we will seek other applications for emerging studies in our laboratories. Rather than closing this domain entirely, we have broadened its view to related topics applying similar technology not directly associated with microelectronics. For example, studies in photo-lithography have lead to discovery of “soft lithography” capable of replicating nanostructures and to technology that might be applicable to fuel cells. Both of these areas fall within our vision and mission and early research will be funded. Supplemental funding is being sought in these areas. Our NSF Discovery Corps Program, initiated last fall in part to help address the disconnection between researchers at NCA&T and the other universities, has CERSP, Page 16 of 230 begun to integrate NCA&T undergraduates into Center research. Research results are just beginning to flow, but the educational value has been substantial. See Section III. Several 2004 projects scheduled to be terminated in 2005 were carried for the entire year in order to allow for students to complete their theses or to allow PIs to identify alternative funding sources. As noted above several other projects were redirected out of microelectronics areas. No students were left unfunded. Despite all the changes, there was no disruption of Center activities or to students’ or associates’ careers. A complete listing of projects for FY2005 is given in Table II following Section II.2b. 2a. Research Projects II.2a.1 Project Team I: Macromolecular Synthesis and Engineering Institution NC State 1 2 3 4 5 6 7 8 9 10 11 NCA&T 1 2 3 4 PERSONNEL Researcher's Name Classification Tamer Ahmed Nathaniel Cain Coray Colina John Derek Tao Liu Vincent Morehead Lauriane Scanu Shaun Tanner Dawei Xu Saad Khan George Roberts Sureshkumar Gutti Derek Jones Connerly Stewart Rashawn Washington Graduate student (PhD) Graduate student (PhD) Post-doctoral associate Undergraduate Graduate student (PhD) Undergraduate Post doctoral associate Graduate student (PhD) Graduate student (PhD) Faculty Faculty Graduate (MS) Undergraduate Graduate (MS) Undergraduate CERSP, Page 17 of 230 5 Vinayak Kabadi UNC-Chapel Hill 1 Jonathan Alford 2 Erik Anderson 3 Emily Anderson 4 Carrie Betts 5 David DeLeon 6 Philip DeSimone 7 Guo, Ji 8 Jennifer Kelly 9 Lou Madsen 10 Benjamin Maynor 11 Evan Paul 12 Lauren Portnow 13 Jacina Redden 14 David Shirvanyants 15 Zuowei Wang 16 Kyle West 17 Bin Xu 18 Jian Yang 19 Zhilian Zhou 20 Qian Zhao James Darkwa 21 22 Maurice Brookhart 23 Joe DeSimone 24 Michael Rubinstein 25 Edward Samulski UT-Austin 1 Howard Abramowitz 2 Yuan Li 3 Xiaoyan Wang 4 Peter Green 5 Keith Johnston 6 Lynn Loo 7 Issac Sanchez Faculty Undergraduate High school senior Undergraduate Undergraduate Undergraduate High School Graduate student (PhD) Graduate student (PhD) Post doctoral associate Post doctoral associate Undergraduate Undergraduate Undegraduate Graduate student (PhD) Post doctoral associate High School Graduate student (PhD) Graduate student (PhD) Graduate student (PhD) Graduate student (PhD) Visiting scientist Faculty Faculty Faculty Faculty Graduate student (MS) Graduate student (PhD) Post doctoral associate Faculty Faculty Faculty Faculty Some faculty and students listed above participate in more than project area. CERSP, Page 18 of 230 Funding (reporting year) NSF DeSimone DeSimone Brookhart Khan Khan and G. Roberts Korgel Murray Murray Murray Rubinstein Other than NSF DeSimone (EPA) DeSimone (Office of Naval Research) DeSimone (DuPont) DeSimone (University of Texas-Austin) DeSimone (NIH) pending DeSimone (DoE) DeSimone (DuPont) Brookhart (DuPont ) Brookhart (NIH) Khan (Dept. of Energy) Khan (Lawrence Berkeley Labs) G. Roberts (Army Research Office) G. Roberts (Dept. of Energy) Kabadi (Dept. of Energy) Green (Welch Foundation) Ilias (Dept. of Energy) Ilias (Dept. of Energy) Koros (NIST) Johnston (Welch Foundation) Johnston (Separations Research Program) Rubinstein (NASA) Samulski (NASA) $27,933 (1/02-12/05)* $22,749 (12/01-11/04) $355,000 (08/04-07/06)* $367,330 (9/01-8/05)* $361,679 (12/01-11/04) $1,500,000 (8/01-7/05) $53,478 (8/02-8/07)* $386,000 (03/04-02/07)* $ 87,938.00 8/02-8/07)* $400,000 (2001-05)* $349,966 (11/01-10/04) $280,580 (10/03-3/05) $150,000 (6/04-5/05) $184,935 (5/02-9/04) $300,000 (4/05-3/10)# $900,000 (6/05-5/08)# $150,000 (6/05-5/06)# $150,000 (10/04-9/05)# $680,000 03/05-02/09 )# $598,000 (11/01-12/04) $448,000 (5/01-4/05) $343,183 (7/01-6/06)# $593,257 (10/01-9/04) $196,000, 10/03-9/06# $150,000 (6/02-6/05) $199,981 (9/01-8/04) $199,996 (10/02-9/05)# $267,000 (7/01-8/04) $150,000 (6/02-5/05) $100,000 (1/03-12/04) $400,000 (2002-07)# $3,385,500 (8/02-8/07)# CERSP, Page 19 of 230 $360,000 (2004-2006)# Sanchez (Murray Endowed Chair) North Carolina Supercomputer Center CPU time Funding (anticipated for next year) NSF See funding marked with * above Other than NSF Brookhart (DuPont) $150,000 (10/05-9/06) See funding marked with # above Much of the support listed above also supplements projects under Application Domains II and III. Objective To enable engineering of CO2-based polymerization processes by developing a fundamental understanding of kinetic and transport mechanisms, thermodynamics, phase equilibria, and factors affecting structure and function in CO2-related systems, including catalytic and post-polymerization processes So that the viability of non-polluting CO2-based polymerization processes with low capital investment and low operating costs will be clear and attract commercial support. New Catalysts for Dehydropolymerization of Silanes to Polysilanes Principal Investigators: Maurice Brookhart and Edward Samulski with Jian Yang, PhD student Key finding: Identification of an efficient late metal catalyst for synthesis of high molecular weight, functionalized polysilanes is unlikely, and we have terminated the program to find one. Polysilanes are photodegradable and have potential for use in microlithographic processes. Synthesis of polysilanes is primarily carried out either by reduction of chlorosilanes by sodium metal (Wurtz coupling) or by dehydropolymerization of silanes (R2SiH2 or R3SiH) using highly oxophilic, unsaturated early transition metal complexes. Neither synthetic route is compatible with organic functional groups, thus greatly limiting the potential structural variation of polysilanes. There is one early report of dehydropolymerization of silanes using Pt(0) complexes. Encouraged by this report we designed a number on unsaturated, low valent late metal complexes of Rh(I), Ir(I) and Ir(III) which are functional group compatible and tested them in dehydropolymerization. Polymers were formed; CERSP, Page 20 of 230 however, NMR analysis suggested pure polysilanes were not formed and that clearly end groups and probably in-chain linkages contained siloxane linkages. The previously reported Pt(0) catalyst was reinvestigated and polymers from dialkyl silanes were formed, but again NMR analysis showed siloxane end groups. UV-vis analysis also established that the longest run of silane linkages could not exceed ca. 8 units, and thus the polymer seems likely to consist of Si-Si linkages together with Si-O-Si linkages. Traces of water provide the likely source oxygen. These results suggested that finding an efficient late metal catalyst for synthesis of high molecular weight, functionalized polysilanes was unlikely. Fortunately in the course of this work we discovered an Ir(III) complex that catalyzes the reduction of halocarbons, a valuable and environ-mentally attractive process. That is now the focus of the current work and is described below. Environmentally Attractive Metal-Catalyzed Reduction of Carbon-Halogen Bonds Principal Investigator: Maurice Brookhart with Jian Yang, PhD student Key finding: A new catalytic procedure has potential to provide a much improved general reduction process of C-X bonds avoiding use of toxic reagents and simplifying separations. Reduction of C-X (X = halogen) bonds is a frequently practiced reduction in organic synthesis. The most common method employed is the use of trialkyltin hydrides in a radical chain process. While an efficient process, several aspects of this method are unattractive. Tin compounds, especially the hydrides, are toxic and separating the tin halide by-products from the desired organic products can be difficult. Although thermodynamically feasible, the use of trialkyl silanes in place of trialkyl stananes for reduction is not effective due to the high bond energy of the Si-H bond. This problem can be circumvented by using [(CH3)3Si]3SiH with a lower Si-H bond energy. But this compound is quite expensive. In the course of our investigations on late metal catalyzed dehydropolymerizations of silanes we discovered an Ir(III) complex which efficiently catalyzes the reduction of alkyl halides by triethylsilane. For example, methylene chloride is reduced to methane, benzyl bromide and benzyl chloride are reduced to toluene and secondary alkyl chlorides are reduced to alkanes. This project has just been initiated and goals currently focus on: 1) exploration of the scope of the reduction in terms of both the organic substrates and the silanes and 2) investigation of the mechanism of the reduction. This new catalytic procedure has the potential to provide a much improved general CERSP, Page 21 of 230 reduction process of C-X bonds in which use of toxic reagents are avoided and separation of products from by-products will be simplified. Kinetics of Polymerization and Precipitation Principal Investigator: Michael Rubinstein with Post-doctoral fellow Zuowei Wang and under-graduate students: Emily Anderson and Carrie A. Betts Key finding: Kinetics of polymerization is reaction-controlled in dilute regime, and is diffusion-controlled in semi-dilute regime. The research objective is to study the competition between reactioncontrolled and diffusion-controlled polymerization and precipitation. Often monomers are soluble in a particular solvent, while high polymers are not. As polymerization process proceeds and polymers grow, they develop tendency to collapse into globules, coalesce with each other and precipitate from solution. While particles of coalesced polymers can be stabilized by block copolymers, polymerization process will proceed both inside these particles and for isolated chains in solution. We have developed computer code and have performed extensive simulations to investigate the initiation, propagation, and termination reaction for free radical polymerization in solvents of different quality at various concentrations of monomers and free radicals. Our simulations have demonstrated that in dilute regime the kinetics of polymerization is reaction-controlled and thus only depends on the monomer concentration, but in semi-dilute regime it is controlled by diffusion. These results are in agreement with theoretical predictions. We have also performed simulations on the network-like polymerization where the propagation species are chains with free radicals at both ends. Results of our simulations could be used to design the optimal mechanism for synthesizing novel elastomers. This project will be completed by November 2005. Continuous Homogeneous Solution Polymerization in Supercritical CO2 Principal Investigator: George W. Roberts and Joseph M. DeSimone with Tamer S. Ahmed (PhD student) Key finding: For hexafluoropropylene/vinylidene fluoride copolymers, those with high HFP content can be polymerized in scCO2 solution, while those with low HFP must use precipitation methods. Intermediate compositions can use either technique depending upon conditions. CERSP, Page 22 of 230 The objective of this project is to study the continuous solution copolymerization of various monomers in supercritical (sc) CO2. It will lead to the first in-depth understanding of monomer reactivity ratios in scCO2. Of particular interest are: a) copolymers of vinylidene fluoride (VF2) and hexafluoropropylene (HFP), one of the most common fluoroelastomers; b) copolymers of tetrafluoroethylene and 2,2bistrifluoromethyl-4,5-difluoro-1,3-dioxole monomers (Teflon AF®), which retains the outstanding chemical and thermal properties associated with perfluorinated polymers while having unique electrical, optical, and solubility properties; c) copolymers of fluoroalkyl methacrylates and related materials used as CO2-processable photoresists in 193 nm and 157 nm lithography. Any of these copolymers that are produced using a continuous polymerization process in a continuous stirred tank reactor (CSTR) should have a much narrower chemical composition distribution that copolymers of the same overall composition produced in batch processes. In the current stage, the main focus of the project is to study the copolymerization of VF2 with HFP in scCO2. According to the preliminary results, the cloud-point pressures of these copolymers (above a certain VF2 content) are accessible and decrease with copolymer fraction in CO2. Therefore, depending on the initial monomer ratio and reaction pressure, the reaction can proceed either heterogeneously or homogenously. This will provide the opportunity to understand precipitation polymerization and compare it to the well-known solution polymerization. Moreover, this will throw light on the effect of precipitation on the reaction kinetics, on the molecular weight, on the sequence-length distribution of the comonomers, as well as on the morphology and properties of the synthesized copolymers. In addition, one of the objectives of this project is to understand the origin behind the formation of poly(vinylidene fluoride) (PVDF) having a bimodal molecular weight distribution (MWD) during the course of precipitation polymerization of PVDF in scCO2. Accomplishments - Series of quantitative copolymerizations of VF2/HFP were done in a batch reactor using Perfluoro butyryl peroxide initiator for three different monomer ratios. - The CSTR system has been modified and refurbished to increase its useful life and its capabilities especially its pressure rating. The refurbished system will be received by mid of July 2005. - An improved version of the homogenous model that can account for the bimodal MWD of PVDF is in the phase of completion. The old model took into account only the decrease in the mobility of polymeric chains as they grow in CERSP, Page 23 of 230 size, which in turn impacts the termination of live radicals. The new version of the model added a chain transfer to polymer step. This improved the model prediction such that it can account now for both the bimodality and the broadness of the MWDs of PVDF. Continuous Catalytic Hydrogenation of Polystyrene in CO2-Expanded Decahydronapthalene Principal Investigator: George W. Roberts (lead) and Ruben G. Carbonell with Nathaniel Cain and Dawei Xu (PhD Students) We are investigating the continuous, heterogeneous catalytic hydrogenation of polystyrene in CO2-expanded decahydronapthalene (DHN). Hydrogenated polystyrene, polyvinylcyclohexane, has improved thermal and oxidative stability, and exhibits attractive optical properties, relative to polystyrene. Post-polymerization hydrogenation of polystyrene is being explored rather than direct polymerization of vinylcyclohexane. Polymerization of vinylcyclohexane is not successful because of the lack of stability of the growing intermediate chain. Polystyrene is a cheap commodity polymer and hydrogenation as a post-polymerization modification can provide the foundation to post-polymerization hydrogenations of other unsaturated polymers, such as styrene-butadiene-styrene copolymer. The development of a continuous process for hydrogenation of unsaturated polymers dissolved in expanded organic solvents is being investigated. Heterogeneous catalytic hydrogenation of polystyrene is being used as the model to investigate fixed bed technology applied to post-polymerization modification, hydrogenation in particular. Accomplishments: The viscosity of the dense CO2/DHN phase has been measured on a SPL 440 viscometer at 120oC and 90oC in the pressure ranges from 2100-5000 psig. Some preliminary measurements were also carried out on pure DHN at atmospheric pressure to test the ability of the viscometer to reproduce previously-reported values. The cis/tran-DHN mixture viscosity was between the values for pure cis-DHN and trans-DHN. Throughout the measurement process various modifications have been made to improve the operation of the viscometer. Some more important modifications include designing a piston-cylinder device to separate the pressurizing fluid from the measurement fluid. Also, a circulation pump has been installed to promote homogeneity within each phase before the data collection process is started. CERSP, Page 24 of 230 Some initial studies have been done using the dynamic light scattering (DLS) apparatus. Latex standards in water have been tested. A correlation program has been written to process the data from the DLS. The program calculates the diffusion coefficient and hydrodynamic radius of polymer coils in solution. Latex® standards were initially used to test the apparatus and the calculation of the hydrodynamic radius with known values. Two sizes of latex® standards were used and experiments were carried out over a range of solids concentrations. Scanning electron microscopy was also done on a set of 1 m latex® standards used in the DLS experiments. The SEM images verified the size of the latex® standards. The viscosity data being taken will be used to evaluate the advantages of using CO2 expanded DHN. The viscosity data will also be used with part of the calculation on the data taken from the dynamic light scattering experiments carried out on polystyrene dissolved in CO2 expanded DHN. Rheological Study of Commercial and scCO2-synthesized Polyvinylidene Fluoride (PVDF) Principal Investigators: Saad Khan, George Roberts, and Joseph DeSimone with Lauriane Scanu (Postdoc) Key finding: We have identified the presence and diagnosed the effects of long chain branching in polyvinylidene fluoride (PVDF). Direct synthesis of PVDF in CO2 may have advantages. The research objectives are to identify possible property differences between commercial and scCO2-synthesized PVDF, examine ways to identify branching in PVDF; demonstrate the advantages of bimodal molecular weight distribution vs. blends of PVDF, and determine the source of the bimodal molecular weight distribution of scCO2-synthesized PVDF. Techniques such as melt rheology, intrinsic viscosity and differential scanning calorimetry were used to characterize respectively the rheological, solution and thermal properties of commercial and scCO2-synthesized PVDFs. Five commercial PVDF samples generously provided by Arkema, Inc. were initially studied. The complex viscosity vs. frequency curve exhibits a typical pseudoplastic behavior for all PVDF samples but an unexpected behavior (no Newtonian plateau at low frequency and much higher viscosity) for one of them. Empirical correlations based on rheological parameters were used to identify the presence of a high level of long chain branching (LCB) in the latter PVDF sample, as well as a low level of LCB in two other samples. Study of the solution properties revealed that a high level of LCB CERSP, Page 25 of 230 leads to the formation of microgel, and hence partial solubility of the polymer in solution. On-going research is aimed at characterizing the polymer’s soluble and microgel fractions. Study of thermal properties showed that the melting point is 170°C for linear PVDFs, and decreases with increasing level of LCB. Crystallization temperature of PVDF is 135°C characteristic of an alpha-phase crystallization as expected for PVDF previously heated above the melting point. An additional small exothermic peak is registered between 50 to 70°C and seems to be linked to a conformational disorder of the chain in the PVDF crystals. Thermal study of scCO2synthesized PVDFs reveals the same properties as the commercial samples. Preliminary results of the rheological study showed that monomodal scCO2synthesized sample behave as linear PVDFs. Blends of linear and linear with LCB commercial PVDFs have been prepared using a minimelter. As expected, the rheology of linear polymer blends is the same as a linear polymer with rheological parameters which follow a log additive mixing rule while the rheology of linear and LCB polymer blends depends on the linear/LCB ratio. This research is aimed at determining the advantages of synthesizing fluoropolymers in supercritical CO2. At this point, several advantages have been identified: the feasibility of the synthesis in a cleaner solvent, at least the same rheological properties as suspension- or emulsion-polymerized PVDFs, and the preparation of blends (bimodal molecular weight distribution) with unique properties directly from the synthesis. This work will be completed by November 2005. Continuous Polymerization of Acrylic Acid in Supercritical Carbon Dioxide Principal Investigator: George W. Roberts and Joseph M. DeSimone with Tao Liu (PhD student) Key finding: Novel methods to make superabsorbent polymers with supercritical CO2 technology have been developed using post-polymerization neutralization of the cross-linked polymer. The overall objective of this project is to understand the behavior of continuous processes for polymerization of various monomers in supercritical carbon dioxide (scCO2). For the past several years, emphasis has been placed on the precipitation polymerization of acrylic acid. The major specific objectives for report period included: (1) Evaluate the effect of the major chemical and operating variables on the precipitation polymerization of acrylic acid in supercritical carbon dioxide (scCO2). The major variables are: residence time, reaction temperature, oxygen concentration and inhibitor concentration. The dependent variables of major concern are monomer CERSP, Page 26 of 230 conversion (polymerization rate) and polymer molecular weight. (2) Determine and model the kinetics of precipitation polymerization of acrylic acid in scCO2. Accomplishments include: (1) Polymer spheres of 10-100 micrometers in diameter were prepared by continuous precipitation polymerization of acrylic acid in supercritical CO2. (2) Cross-linking polymerization of acrylic acid in supercritical CO2 was studied in a 20-ml view cell. Both water-soluble and water-insoluble polymers were prepared. (3) Novel methods to make superabsorbent polymers with supercritical CO2 technology have been developed using post-polymerization neutralization of the cross-linked polymer. (4) CO2 absorption into poly(acrylic acid) was measured with a quartz crystal microbalance. The plasticization effect of CO2 on poly(acrylic acid) was evaluated using Chow’s equation. This project was completed in June 2005. H+ Super-conductive Materials Principal Investigator: Joseph DeSimone and Raymond Dominey, with Jennifer Kelly and Zhilian Zhou (PhD students) Key finding: Membranes have been developed that have ultra high-conductivity, surpassing commercially available membranes, as well as good mechanical stability. The present focus of this project is to develop new materials for proton exchange membranes used in fuel cells. There is growing interest to develop fuel cells for portable electrical devices, transportation and distributed power. The next generation of fuel cell membranes must outperform today’s most widely used material, Nafion®. Key challenges include: fuel crossover, low glass transition temperature, limited mechanical integrity at elevated temperatures, limited proton conductivity at low relative humidity, high conversion, and processing cost. Furthermore, the flat two-dimensional geometry of current PEM materials severely limits the power generation potential of fuel cells derived from these materials. Our research focuses on functional, liquid precursors synthesized in super critical CO2 or conventional solvents, which are crosslinked in neat liquid to form flat or patterned membranes. This research contributes to achieving the Center goals by employing CO2 as a reaction medium and using crosslinking chemistry in neat liquid, eliminating the use of additional solvents. Furthermore, fuel cells are environmentally friendly power supplies. For applications of portable devices, fuel cells eliminate the waste of batteries once fully used. Fuel cells used in transportation instead of combustion engines, eliminate any exhaust and produces clean byproducts, in some cases strictly water and heat. Developing new materials for fuel cells used in cars will also CERSP, Page 27 of 230 reduce dependence on crude oil and fossil fuels, potentially limiting coal burning sites that cause heavy pollution and radiation. The expected outcome of this research is development of new proton exchange membranes for hydrogen and methanol fuel cells for commercial and military use. Solution Properties of Polymers in CO2: Theory Principal Investigator: Michael Rubinstein with David Shirvanyants (Ph.D. student) and Erik Andersen (undergraduate) Key finding: We discovered unconventional effects of monomer-monomer interactions in intermediate solvents, leading to significant deviation from the classical models. The objective of the project is to understand how the effective interaction parameters of CO2-philic and CO2-phobic blocks change with pressure, temperature or density. We have constructed a scaling theory of polymers in solutions with different solvent quality paying particular attention to the universality of interaction parameters as well as to the effect of chain ends for low molecular weight polymers. We have developed a computer simulation code and conducted extensive computer simulations to test theoretical predictions and to construct the universal description of polymer chain swelling and collapse. We used molecular dynamics simulation of a coarse-grained polymer in an implicit solvent. We demonstrated that with increasing degree of polymerization polymers better follow the universal collapse/swelling transition line. We have discovered a new type of interactions distinct from excluded volume interactions that dominate polymer properties. We also show that the commonly used persistent or worm-like polymer models may be inapplicable to the chains with excluded volume interactions. Our studies on stiff polymer chains indicate the presence of different morphologies of collapsed macromolecules, which agrees with earlier works. This project will be completed by November 2005. Solution Properties of Polymers in CO2: SALLS, DLS Principal Investigator: Michael Rubinstein and J. M. DeSimone with Ji Guo (PhD student) Key finding: Very CO2-soluble homopolymers and copolymers were made to explore CO2 solubility successfully. CERSP, Page 28 of 230 Solubility plays a very important role in the synthesis, separation and process of polymers in CO2 systems. There are some important factors which affect the solubility of polymers such as temperature, CO2 density, polymer molecular weight and composition etc. The ability to dissolve polymers in scCO2 enables new opportunities in chemical manufacturing such as spin coating from liquid CO2, spray coating operations, separations, complexation of organic acids and heavy metals. In order to realize these options, it is necessary that to understand the solvent properties of CO2 for the future applications. Besides better understanding of the solubilization physical processes will also help to test the thermodynamic theories and fine-tuning numerical models. The light scattering techniques are powerful tools to quantitatively and systematically study the solution properties of various homopolymers and copolymers in CO2. Poly(1,1,2,2-tetrahydro perfluoro-octyl methacrylate) (PFOMA) has been synthesized and fractionated using CO2 as the solvent. There are two fractions, Mw~ 900kg/mol and 300kg/mol, has been studied. The refractive index increments of the polymer solution decrease from 0.12 mL/g to 0.10 mL/g with increasing CO2 density at 25oC. The hydrodynamic radius Rh of the polymer increases with the carbon dioxide density and temperature. The solvent quality of CO2 was shown to quantitatively improve with increasing temperature and CO2 density. This trend was confirmed by evaluation of both the second virial coefficient A2 and the diffusion second virial coefficient kD measured by static and dynamic light scattering. The • temperature is 27 • 1 oC at CO2 density 0.86g/mL and the • density is 0.88 •0.02 g/ml at 25 oC. The second virial coefficient, A2 is verified to be a universal function of the interaction parameter z, which z is a function of the reduced temperatures. We have in the first time demonstrated that the second virial coefficient A2 is a universal function of interaction parameter z based on reduced the solvent density. Furthermore, the relationship between two directly measured parameters, the second virial coefficient A2 and hydrodynamic radius expansion factor •H, follows a universal behavior without any additional assumptions of z. These results confirmed the solvent quality can be tuned by not only the solvent temperature but also the solvent density. This project will be completed by November 2005. Plasticization of Fluoropolymers in CO2: NMR at High Temperatures and Pressures Principal Investigators: E. T. Samulski with Lou Madsen (post doc) and Qian Zhao (PhD student) CERSP, Page 29 of 230 Key finding: 19F NMR has revealed morphological and glass transition information in TEFLON AF polymers, and a test polymer system (polyethylene oxide--PEO) has shown a crystallization temperature drop of 15•C upon immersion in CO2 at < 1000 psi, quantifying the plasticization effect of CO2. Study of solid polymers using NMR presents challenges, but can yield detailed information about polymer morphology, dynamics, and chemistry. Our near term goals include study of a family of fluoropolymers based on Teflon AF, which are being synthesized and processed using sc-CO2 in the DeSimone lab. These polymers show great promise as advanced lithographic photoresist materials due to their CO2 processabilty, thermal stability, and UV transparency. We are undertaking spectroscopy and relaxation time (T1 and T2) studies on 19F nuclei to provide motional and phase transition information. We are also in the process of pursuing experimentally challenging high pressure and high temperature studies. By immersing these polymers in fluid CO2 in the NMR spectrometer, we will have access to polymerization and plasticization dynamics in these materials. Our device currently has a temperature capability of at least 400•C, and we are designing for CO2 pressures above the critical pressure. Using a simple apparatus with a quartz NMR tube, we have been studying the CO2-plasticization of PEO using NMR relaxation studies at < 1200 psi and < 120•C. By observing 1H T1 relaxation versus temperature, we have observed a clear drop in the crystallization temperature of PEO by 15•C when immersed in CO2 at 800 psi. Thus, this test system shows a distinct plasticization effect, even at modest CO2 pressures and explains our successful CO2-mediated intercalation of clay {“Supercritical CO2-mediated intercalation of PEO in clay,” Q. Zhao and E. T. Samulski, Macromolecules, 36, 6967 - 6969 (2003)}. We have also quantified the amorphous/ crystalline fraction in PEO versus T and CO2 pressure, and are pursuing related studies. Further plasticization investigations on fluoropolymers, such as norbornene-based photolithography materials, with Tg and/or Tm < 120•C are ongoing. Kinetics of Polymerization and Motional Studies on “Liquid TEFLON” Fluoropolymers via H-1 and F-19 NMR Principal Investigator: E. T. Samulski and J. M. DeSimone with Lou Madsen (post doc) CERSP, Page 30 of 230 Key finding: We have obtained partially resolved 19F and 1H spectra of the crosslinked networks in “liquid TEFLON”, and are preparing to monitor polymerization kinetics in situ. Liquid TEFLON networks show unique processability and properties, and promise to revolutionize fields such as micro- and nanofluidics, fuel cell membranes, and low surface energy coatings. We are beginning 19F and 1H NMR studies on these materials to probe the kinetics of polymerization. So far, we have obtained partially resolved 19F and 1H spectra of the cross-linked networks, and are preparing to bring UV light into the NMR spectrometer in order to monitor polymerization kinetics in situ. Variable temperature studies using our existing NMR apparatus will also lend insight into morphology and thermal stability. Magic-Angle Spinning NMR experiments on these networks will also reveal highly resolved spectra, and we are investigating in situ photopolymerization under these conditions as well. Swelling and Crystallization of Homopolymer and Diblock Copolymer Thin Films is sc CO2 Principal Investigator: P.F. Green and K.P. Johnston with Yuan Li Key finding: PEO-b-PFOMA block copolymer thin films in CO2 are disordered at high temperatures, but as the temperature is reduced, the copolymer film exhibits order, and at still lower temperatures, it exhibits disorder again. Interfacial constraints have a profound impact on the properties of thin polymer films. Constraints on the translational and configurational entropy of the chains as well as enthalpic effects associated with chain-interface (free surface and substrate) interactions profoundly affect different properties in different ways. Of interest in this project is the development of a fundamental understanding of the properties of unstable thin films and of A-b-B diblock copolymers of various architectures in CO2. This past year we examined a series of diblock copolymers of different characteristics: PS-b-PFOMA, PEO-b-PFOMA, PS-b-PMMA, where PS is polystyrene, PFOMA is polyperfluoroctylmethacrylate, PEO is polyethylene oxide, and PMMA is polymethylmethacrylate. The thickness dimensions of the film, h, compared to the microphase separated dimensions determine the topography of the film. In a case where the same component of the diblock copolymer wets the free surface and the substrate, the film is uniform in thickness when the film thickness h is an integral multiple of the natural phase separation length scale; otherwise it forms relief structures. If the CERSP, Page 31 of 230 copolymer is disordered then the film is typically smooth. The PS-b-PFOMA system formed spherical micelles when cast on a substrate from a FREON-toluene solvent mixture in which it is compatible. Interestingly, the micelles are not present in the solvent but rapidly develop during the spin-coating process due to the rapid evaporation of one component of the mixture compared to the other. When annealed in vacuum or in CO2, the structure, while slightly swollen, remained in tact. This behavior contrasts a range of other diblock copolymers, PS-b-PMMA and PS-bPVP (PVP is polyvinylpyridine) which formed ordered films with the usual relief structures on a substrate. When annealed in toluene, the relief structures appear with dimensions reflecting the natural phase separation length scales! These findings reveal a new way to control the topography of the films. Secondly, these foregoing results also indicate that relative interactions between the polymer segments, the chemistry of the environment (vacuum, CO2, organic solvent) determines the structure of the film. In fact, PS-b-PMMA thin films, which are disordered in vacuum (air), can be induced to exhibit order in CO2 for the same reasons! The PEO-b-PFOMA block was also examined and in CO2 the behavior is remarkable. The system is disordered at high temperatures, but as the temperature is reduced, the copolymer film exhibits order, and at lower temperatures, it exhibits order again. This rather remarkable behavior has never been observed (to our knowledge) before in thin films and is the due to the influence of the relative interactions between the constituents in the system, and their dependence on temperature. One additional feature worth mentioning is that this diblock copolymer system differs from the others in that PEO crystallizes. However, in CO2, the crystallization is suppressed. Our future studies will involve quantification of the relevant parameters that characterize the structure in these systems in CO2. The related effects in the bulk will be examined using scattering techniques. Polymer Welding with CO2 Principal Investigator: Isaac C. Sanchez with Howard Abramowitz (MS student) Key finding: For the first time ever, we have been able to compute accurately by simulation the diffusion and solubility of CO2 in a glassy polymer. Our goal was to model this process by computer simulation. To this end it is important to determine the solubility and diffusion of CO2 in glassy polymers. We have demonstrated this for two very permeable polymers, poly (1-trimethylsilyl-1CERSP, Page 32 of 230 propane) (PTMSP) and a random copolymer of tetrafluoroethylene and 2,2bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole (TFE/BDD). These polymers have very similar and large fractional free volumes, but very different permeabilities. Using atomistic models, cavity size (free volume) distributions determined by a combination of molecular dynamic and Monte Carlo methods are consistent with the observation that PTMSP is more permeable than TFE/BDD. The average spherical cavity size in PTMSP is 11.2 Å whereas it is only 8.2 Å in TFE/BDD. These cavity size distributions determined by simulation are also consistent with free volume distributions determined by positron annihilation lifetime spectroscopy. In addition, we have calculated the solubilities and diffusion coefficients of CO2 in these polymers. The calculated solubility and diffusion coefficient are larger in PTMSP in agreement with experiment. On the experimental side, our collaborators in Mexico have shown that immiscible blends of polystyrene and polyisoprene can be compatibilized using a supercritical anti-solvent process in which CO2 is used as the anti-solvent. This project has ended. Thermodynamic Measurements for CO2 Containing Systems Principal Investigator: Vinayak N. Kabadi with S. Gutti and Connerly Stewart (MS students) Key finding: With this project, a thermodynamics laboratory has been developed that provides the Center with a facility for data measurements for CO2 systems. The objective of this project is to develop a laboratory at A&T for thermodynamic measurements for systems containing carbon dioxide. Properties to be measured include vapor-liquid equilibria (VLE), heats of mixing, volumes of mixing, and gas solubility. The VLE measurements are conducted by a continuous flow apparatus that has a temperature range –40oC to +100oC, and a pressure range from atmospheric to 5000 psia. Experiments were carried out for the carbon dioxidedifluoromethane and CO2 – fluorobenzene binary systems. Currently, data are being measured for the CO2 –ethyl lactate system. A new static VLE apparatus has been designed and is currently being built. The apparatus consists of a VLE cell fitted with a magnadrive stirring system. Sampling is carried out by multiple dip tubes introduced in the vapor and liquid phases, and samples are analyzed by an on-line GC. The apparatus can be used CERSP, Page 33 of 230 for VLE, LLE, VLLE and solid-vapor equilibrium measurements. The apparatus will be tested this summer and will then be ready for measurements for systems of interest to the research groups in the Center. Enthalpies and densities are measured using two calorimeters, an isothermal micro-calorimeter (temperature range –40oC to +80oC) attached to coils of tubing for dilatometric density measurements, and a differential scanning calorimeter (temperature range –40oC to +110oC). The apparatuses have been tested by data measurements for CO2 – CH2F2 system. Measurements are in progress for mixtures of CO2 and aqueous alkanolamines. In the future, data will be measured for systems of interest to the Center investigators. II.2a.2 Project Team II. Functional Materials and Devices PERSONNEL Institution NC State 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 NC A&T 1 Researcher's Name Nick Ashley Dipak Barua Candis Collins Kirill Efimenko Theodosia Gougousi Yasan Hussein Jae Hoon Kim Oscar Mvula Ke Wang Jeff Woodhead Amy Geissler Zweber Ruben Carbonell Jan Genzer Christine Grant Carl Osburn Gregory Parsons Leonitia Broadney Classification Graduate student (PhD) Graduate student (MS) Undergraduate Post doctoral associate Post-doctoral associate Graduate student (PhD) Graduate student (PhD) Undergraduate Post-doctoral associate Graduate student (PhD) Graduate student (PhD) Faculty Faculty Faculty Faculty Faculty Undergraduate CERSP, Page 34 of 230 2 3 4 5 6 7 8 9 10 UNC-Chapel Hill 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 UT-Austin 1 Leroy Covington Pam Garner Todd Levy Kimberly Moore Deardre Pullins Frederick Smith Benjamin Wilson Ken Roberts Leonard Uitenham Mary Kate Boggiano Thomas Chen Ginger Denison Kevin Herlihy Yuxiang Li Lanyuan Lu Ryan MacArthur Benjamin Maynor Evan Paul Lauren Portnow Renee Smith Pamela Visintin Dongxing Yang Max Berkowitz Joe DeSimone Malcolm Forbes Gene Irene Isaac Sanchez Graduate student (MS) Graduate student (MS) Undergraduate Graduate student (MS) Undergraduate Undergraduate Graduate (MS) Faculty Faculty Graduate student (PhD) Graduate student (MS) Graduate student (PhD) Graduate student (PhD) Graduate student (PhD) Graduate student (PhD) Post doctoral associate Post doctoral associate Undergraduate Undergraduate Undergraduate Graduate student (PhD) Graduate student (PhD) Faculty Faculty Faculty Faculty Faculty Affiliates Institution Texas A&M University Villanova University Name Perla Balbuena Carol Bessel CERSP, Page 35 of 230 Some faculty and students listed above participate in more than project area. Funding (reporting year) NSF Genzer $300,630 (2/04 – 1/07)* Genzer $270,038 (3/04 – 2/07)* Genzer $100.000 (6/04 – 5/05) Genzer $1,700.000 (4/04 – 3/08)* Parsons $158,836 (8/03-7/07)* Grant $640,000 (2000-05)* Grant $350,000 (2003-06)* Parsons (DMR) $158,836 (8/03-7/07)* K. Roberts $3,000,000 (11/03-10/08)* K. Roberts (NSF-NSEC nano-CEMMS $13,000,000, 10/03-10/08)* Center) Carbonell $201,000 (2001-04) Carbonell $374,378 (2002-05)* Forbes $465,000 (8/02-07/05)* Other K. Roberts (NIH) $946,039 (8/02–7/05) K. Roberts (DoD-UNCF) $560,000, 6/1/2004 – 5/31/2007)# K. Roberts (Futures Program) $14,500 (4/2004 – 12/2005)# Parsons (SEMATECH) $100,000 (4/04-3/05) Parsons – SolarAmp Inc. $100,000 (7/04–8/05) Genzer (Dreyfus Foundation) $60,000 (6/01-5/06)# Genzer (ONR) $150,000 (6/04-7/05) Genzer (ONR) $460,000 (4/05-3/08)# Genzer (Dreyfus Foundation) $41,386 (4/04-5/07)# Grant (National Textile Center) $600,000 (2001-2004) K. Roberts (DoE) $250,000 (9/03-8/06)# K. Roberts (NCA&T FUTURES Program) $15,000 (4/04 - 3/05) Carbonell (Am. Red Cross) $1,350,000 (2002-04) Funding (anticipated for next year) NSF See funding marked with * above CERSP, Page 36 of 230 Samulski Forbes (NSF) pending Other Forbes (PRF) pending See funding marked with # above Funding of Affiliates (reporting year) NSF Balbuena Other than NSF Balbuena (Dept. of Energy) $330,000 (7/04 - 6/08) $793,315 (6/05-7/08) $120,000 (11/05-10/08) $240,000 (4/01-3/05) $540,000 (9/01-8/04) Some funding listed under Project areas I and III also supplements work done here. Objective To develop fundamental understanding of phenomena involved in dissolution and removal of materials, formation of thin films and coatings, dimensional control of structures, and photochemical conversions So that feasibility of dry processes, materials and devices for cleaning, etching, lithography, organic and metal film deposition and chemical mechanical planarization can be demonstrated. Supercritical CO2 Annealing of Selected Organic Materials Principal investigator: E.A. Irene with PhD Student Yuxiang Li Key finding: We have spun-cast 5nm thick and thicker films of PVDF-TrFE and have characterized optical properties and static dielectric constants both for asprepared and for vacuum-annealed films up to 150oC. The present research is aimed at organic films that have known electronic applications (semiconductors and dielectrics) and the possible changes in electrical properties that occur as a result of treatment with supercritical (sc) CO2. Specifically the first organic film to be studied has been selected to be a co-polymer polyvinylidene fluoride-trifluoroethylene (PVDF-TrFE). PVDF-TrFE is a multifunctional electronic material that has a high static dielectric constant, and is both a piezoelectric and a ferroelectric. CERSP, Page 37 of 230 We have found a suitable solvent for spin casting films of PVDF-TrFE and have made and characterized films 5nm thick and thicker. We have determined the optical properties of the films and the static dielectric constant both for as-prepared films and for films annealed in vacuum up to 150oC. The impact of this research is twofold. Scientifically the effect of scCO2 infusion on materials properties and structure will lead to a greater understanding of interaction of scCO2 with the materials. Secondly, it is anticipated that several properties will be altered in a technologically significant manner such as surface smoothing, doping and solvent removal. Thus the findings could lead to improved materials and processes. It is also possible that there will be unanticipated changes in properties that may be technologically good or bad but will nevertheless need to be known and understood. Processing Photoresists in Carbon Dioxide Principal Investigators: R. G. Carbonell and J. M. DeSimone, with Amy Zweber (PhD student) and Ke Wang (Postdoc) Highlight: A process using CO2 has been demonstrated that results in rapid development rates while maintaining critical dimension control and potentially improving line edge roughness control. This project is aimed at studies on the processing of photoresist materials with carbon dioxide for enhanced lithographic performance. It has three major thrusts. The first is the use of carbon dioxide/surfactant mixtures to dry photoresist films that have been developed in aqueous solution. The second is the removal of excess solvent from thick photoresist films using carbon dioxide as an alternative to a post apply bake (PAB) after spin coating. The third involves the use of carbon dioxide with special additives to develop EUV photoresists. This third aspect is being done in collaboration with Micell Technologies, Inc., using their proprietary carbon dioxide compatible salts (CCS) process. An earlier component of this work, involving the spin coating of novel photoresists using liquid carbon dioxide as a solvent has been terminated due to the lack of availability of liquid carbon dioxide soluble photoresists. The current work has both experimental and theoretical components. Highpressure ellipsometry measurements and quartz crystal microbalance measurements are being used to track the swelling and mass transport characteristics of thin films in all these applications. The non-equilibrium thermodynamics of glassy polymers (NET-GP) theory has been used to describe CERSP, Page 38 of 230 both the equilibrium properties and the transport rates in the rubbery and glassy polymer regions in the presence of high-pressure carbon dioxide. This aspect of the work is being done in collaboration with researchers at the University of Bologna. It has been shown that the CCS process results in rapid development rates that can maintain critical dimension control. In addition, preliminary results indicate that the use of carbon dioxide for development may help improve line edge roughness (LER) control. Enhancement of Lithography Processes Development and Post Applied Bake Using CO2: CO2-Modified Principal Investigators: R. G. Carbonell and J. M. DeSimone with Amy E. Zweber (PhD student) Key finding: CO2 has been found to be useful in improving the drying process in several steps of the lithographic process used to manufacture computer chips. Lithography is an integral part in the production of integrated circuits. This work investigates the use of supercritical carbon dioxide (scCO2) to modify the development and post applied bake (PAB) steps in lithography to potentially enhance production and performance. Problems arise as smaller integrated circuit features are produced to reduce the overall size of the integrated circuit. During development, water between highaspect ratio features is dried. The high surface tension of water pulls features together and causes image collapse. The result is reduced yield and performance. In the literature, scCO2 has been utilized as a zero surface tension solvent to replace rinse solutions and dry photoresist features without image collapse. The shortest time reported to perform scCO2 drying for this application is 12 minutes. The goal of this research is to reduce the total development time to less than 3 minutes to be competitive with standard industry development times. After investigating the rates of the major mechanisms of drying including mass transfer removal and mechanical removal, we suggest potential short time approaches to carry out high pressure drying. Simple models have been used to provide approaches to the reduction of scCO2 drying time and experiments are being carried out to confirm reduction of image collapse. Drying thick films (30-100 microns) after spin coating is another promising area to apply scCO2 modifications in lithography. Thick films, used for packaging and wafer bumping applications, are currently dried in a convective oven for typically 30 minutes at 95oC to remove residual spin coating solvent. Using scCO2 drying, the drying time is reduced by at least a factor of two. We will investigate CO2/photoresist CERSP, Page 39 of 230 solvent phase behavior, residual solvent concentration profiles within the film after drying, film hydration after drying, and helium displacement of scCO2 after drying. Deposition of Thin Films from Liquid and Supercritical Carbon Dioxide Principal Investigators: R. G. Carbonell and J. M. DeSimone with Jaehoon Kim (PhD student) Highlight: Films deposited from liquid CO2 were much thinner, more uniform, and exhibited much fewer drying defects and better surface roughness than films from typical organic solvents. This project investigated the use of liquid carbon dioxide (l-CO2) and supercritical carbon dioxide (scCO2) as coating solvents to deposit small organic molecules, polymers and metal films. Two novel pieces of equipment, a highpressure free meniscus coating (hFMC) apparatus and an apparatus for film deposition by displacement from two immiscible supercritical phases (DISP), were designed and constructed to produce thin films from CO2 media. It was demonstrated that highly uniform and ultrathin films of sucrose octaacetate (SOA) and poly[2-(perfluorooctyl)ethyl acrylate] (PFOEA) can be formed on substrates consisting of native oxide of silicon (SiOx) using l-CO2 hFMC. The films deposited from l-CO2 were much thinner, more uniform, and exhibited much fewer drying defects and lower surface roughness compared to films from typical organic solvents. The unique surface properties of the PFOEA films from l-CO2 hFMC were also investigated. The lack of an interfacial boundary associated with the supercritical state of CO2 does not allow its use in traditional liquid-based coating processes. This drawback was overcome by introducing a fluid such as supercritical He that is not readily miscible with scCO2 to create an interfacial boundary. It was demonstrated that particles and films of SOA and PFOEA could be deposited on SiOx from the interfacial boundary between a scCO2 phase and a scHe phase using a solvent displacement (DISP) technique. The films deposited from DISP exhibit unique surface morphologies when compared with the films from l-CO2 hFMC and the films from normal dip coating with organic solvents. Even though l-CO2 and scCO2 have valuable properties as coating media, the poor solvent power of CO2 for most of polymeric materials is a major limitation. This limitation can be overcome by depositing polymeric precursors that are soluble in CO2 followed by subsequent polymerization directly on the surface. Ultrathin fluorinated films with optically clear and chemically resistant characteristics were produced by first depositing photocurable perfluoropolyether (•-,•-methacryloxy CERSP, Page 40 of 230 terminated perfluoropolyether) from l-CO2 hFMC and subsequently curing the deposited films. This deposition/reaction technique can be also utilized in metal film deposition. Nanosize copper particles and copper films were deposited on SiOx or titanium nitride substrates by first producing Cu (II) hexafluoroacetylacetonate hydrate films from DISP and subsequently reducing them in a hydrogen environment. It was also demonstrated that palladium catalyzed copper deposition using DISP and subsequent reduction can produce highly uniform and ultrathin Cu films. Drug Impregnation in Polymers Principal Investigators: R. G. Carbonell and J. McClain, with Nick Ashley (PhD) and Dawei Xu (Postdoc) This project is aimed at understanding the thermodynamic and transport processes that govern the incorporation of drugs into thin polymer films for drug delivery. There are three major approaches that will be pursued. The first involves the incorporation of drugs into the polymer from supercritical carbon dioxide and cosolvent. The second involves the incorporation of drug from a liquid solution into the polymer in the presence of high- pressure carbon dioxide. The third involves the coating of polymer/drug mixtures onto a surface using high-pressure free meniscus coating (hFMC) or displacement of immiscible supercritical phases (DISP) processes. Drugs and polymers of current interest in drug delivery will be used in these studies. High-pressure spectroscopy and quartz crystal microbalance (QCM) measurement will be used to analyze the partitioning and rate of transport of the drug into the polymer thin films. A high pressure IR cell for surface analysis of thin films is being designed. It is also of interest to study the effect of operating conditions on the morphology of the drug particles being incorporated. Other analytical methods such as AFM and SEM will be utilized to study film morphology and uniformity. This work is in collaboration with Genzer’s and Grant’s group on spectroscopy and QCM. In addition, theoretical models for drug partitioning based on the nonequilibrium thermodynamics of glassy polymers theory (NET-GP) developed at the University of Bologna will be used to underpin the experimental work. Anomalous Swelling of Thin Films by CO2 Principal Investigator: Isaac C. Sanchez Key finding: This is a new project so we have no results to report as yet. CERSP, Page 41 of 230 The objective of this project is to provide a definitive theoretical answer as to why swelling occurs in the vicinity of the “compressibility ridge” of a supercritical fluid such as CO2. To address the problem, we are using a combination of theory and Monte Carlo/molecular dynamic simulations. The primary hypothesis that we are testing is that CO2 is not uniformly absorbed into a thin film, but is surfaced adsorbed (critical wetting) or is preferentially absorbed in a thin surface zone. The accretion of relative low density CO2 in a surface zone would represent a significant increase in the overall thickness of a thin film, but not in a thick film. Photochemical Darkening of 193 nm Immersion Lithography Materials Principal Investigator: Malcolm D. E. Forbes with Thomas K. Chen, PhD student Key finding: Using 193 nm radiation we observed time–resolved electron paramagnetic resonance spectra in aqueous solution involving both sulfate radicals and hydroxyl radicals. Both redox and H–atom abstraction chemistry were observed. Our objectives have been modified somewhat since we started this project in late 2003. Originally we began to investigate 157 nm lithographic materials; however, when the industry changed to focus on 193 nm immersion, we refocused to study 193 nm degradation processes. During the course of 193 nm photochemistry experiments we observed time–resolved electron paramagnetic resonance spectra in aqueous solution involving both sulfate radicals and hydroxyl radicals. Both redox and H–atom abstraction chemistry were observed. This discovery is the subject of a manuscript in progress and has led to several major advances in our research program on amino acid oxidation processes (not STC funded). Molecular Dynamics Simulations of Water/CO2 Microemulsions. Principal Investigator: Max L. Berkowitz with Lanyuan Lu (PhD student) Key finding: We performed a series of molecular dynamics simulations to compare monolayers of perfluoropolyether surfactants and hydrated polyether analogues at the water/supercritical CO2 interface. Parameters which are related to chain rigidity determine whether the surfactant has "good" or "bad" properties needed to create the microemulsion. CERSP, Page 42 of 230 Overall objective: Perform theoretical studies in order to get a comprehensive under-standing of the structure and dynamics of microemulsions in water/supercritical CO2 mixtures. We performed molecular dynamics simulations on systems containing monolayers of perfluorinated polyether ammonium carboxylate surfactant (PFPE COO-NH4+, MW=695.13) and its hydrogenated analogue PE-COO-NH4+ situated at the water/scCO2 interface to study the difference between the fluorinated and hydrogenated surfactants in order to explain their different surface activity. By changing the force field parameters that are responsible for the relative strength of intra- and inter- molecular interactions, we studied the influence of these interactions on the value of the surface tension. We found that intra-molecular interactions and molecular geometry play an important role in the surface activity of a “good” surfactant. Our simulation results are consistent with the results from the previous simulations on the reverse micellar systems performed in our group. We observed that the difference in the values of the surface tension for the fluorinated and hydrogenated surfactants corresponds to different two-dimensional headgroup distributions for the PFPE and PE surfactants. These different distributions are seen in both micellar and monolayer simulations. While in the PFPE case the simulations show that surfactants are distributed uniformly, the PE surfactants are clustering. Various types of analyses were performed in order to reveal the difference in tail conformations of PFPE and PE molecules. We found that the more rigid PFPE tails can provide more space between the surfactant tails for CO2 molecules to occupy this space. Thus the PFPE tails can be well solvated in CO2 solvent and as a consequence we observed uniformly distributed PFPE surfactants and the interface had a low surface tension. The more flexible PE tails are more disordered; this leaves less space for the CO2 molecules to penetrate between the surfactant tails, thus explaining the low solubility of these surfactants in CO2. We also performed energy and entropy calculations for the PE molecules when their headgroups were restricted to a lattice configuration on the interface plane. The positive change in the tail conformational entropy for these molecules when going from a restricted to an unrestricted state of motion in the plane of the interface is, in our opinion, the driving force for the formation of cluster configuration in the PE system. This driving force is not available in the case of PFPE because these surfactants have a rigid tail. This project will be completed by November 2005. Soft Lithography Principal Investigator: J. M. DeSimone with Ben Maynor (post-doc) and Kevin Herlihy (PhD). CERSP, Page 43 of 230 Key finding: Soft lithography has potential to be a tool for environmentally friendly mass production of nanomaterials in the near future. Soft lithography techniques, such as micro contact printing and imprint lithography, hold promise as high throughput, inexpensive, and environmentallyfriendly methods to produce micro and nanometer scale features in the form of wires, isolated particles, and embossed surfaces. When compared with traditional lithographic approaches such as photolithography or electron-beam lithography, soft lithography offers potential improvements in flexibility and resolution. Significant reductions in organic solvent processing and waste by-products are also possible because of the solvent-free or solvent-reduced nature of inherent to soft lithography. Applications including microfluidics, drug delivery, and microelectronics are all potential targets of soft lithography. Currently the DeSimone Lab is focused on a new soft lithography process, Pattern Replication In Non-wetting Templates (PRINT, see Section II.2a.3), which utilizes patterned perfluorinated polyether (PFPE) elastomeric molds rather than the more traditional poly (dimethylsiloxane) (PDMS), silicon, or glass materials to duplicate nano and microscale structures. The PFPE molds used in PRINT offer many advantages over other soft lithography materials, including organic compatibility, high gas permeability, easily tuned modulus, and low surface energy. PFPEs afford extremely high resolution reproductions of master templates at the nanometer scale. Current research topics include replication of patterned silicon wafers and “soft” nanometer scale objects such as self-assembled micelles and brush polymers. Molds of these master templates are used to reproduce nanometer scale structures of polymeric, organic, and inorganic materials. Fabrication and characterization of these nanostructured materials is our primary focus. Dielectric Deposition Principal investigator: Gregory Parsons with Qing Peng, PhD student This project, which started this year builds on the other STC project in our group, and will advance our understanding of film deposition from supercritical fluids to the area of deposition onto polymeric materials. The use of organic materials in electronic applications is growing substantially in areas including organic light emitting diodes, organic photovoltaic devices, and organic thin film transistors. For many of these applications, new materials are needed for flexible substrates and as coatings to encapsulate and protect the active electronic elements. The goal of this project will be to understand mechanisms associated with formation of thin inorganic CERSP, Page 44 of 230 coatings onto polymeric and molecular layers, and to assess potential applications and limitations of the materials developed. During the past months, a new student has begun to examine processes associated with aluminum oxide deposition using Al(acac)3 and H2O2 as an initial material of interest. For this activity, we have developed a cold-wall reactor design to better isolate deposition onto the substrate surface of interest, and initial runs are underway. We believe that the unique transport properties of sc-CO2 may give rise to unique inorganic structures and networks that penetrate into polymeric substrates to enhance density, as well as mechanical and barrier properties of the materials. We are also interested in examining low temperature film deposition onto molecular monolayers for advanced electronic and other applications. Metal Film Deposition Principal investigator: Gregory Parsons with Dipak Barua, MS student The objective is to define materials and processes of interest for advanced electronic applications that could be deposited from precursors dissolved in supercritical solvents. The goal is to define processes that could proceed at lower temperatures that current chemical vapor deposition processes, and/or result in materials with better uniformity, conformality, etc., than available with common techniques. We are also focused on exploring sc-CO2 systems in atomic layer deposition (ALD) processes for metals and dielectric thin films and nanostructures. This work supports the Center’s effort to expand the applications of sc-CO2 processing into new technology directions. During the past year, we have examined several material systems of interest in advanced electronic applications. Materials studied include: 1) Aluminum oxide (using Al(acac)3 and H2O2); 2) Palladium (from Pd hexafluoroacetylacetonate [Pd(hfac)2], and H2); 3) Ruthenium (from ruthenocene, [Ru(Cp)2] with H2O2, dry air or O2, and from Ru(tmhd)3, and H2O2); 4) Tungsten (from W carbonyl [W(CO)6] and H2); and 5) Rhodium (from Rh acetylacetonate, and dry air). Both continuous and alternating reactant exposure (ALD) processes were explored, predominantly for the Ruthenium and Al2O3 processes using a hot-wall reactor configuration. A cold-wall reactor design has been developed to enable better control of deposition temperature, and to better isolate deposition onto the substrate surface of interest. We believe that a better understanding of the deposition mechanisms is needed, including: 1) characterization of precursor concentrations dissolved in sc-CO2; and 2) characterization of reaction rates to evaluate kinetics of surface reactions. The student on this project has completed an MS degree, and will move off this project as of August 2005. We anticipate work will continue under a new post-doc in Fall 2005. CERSP, Page 45 of 230 Reactive Deposition of Metal- and Ceramic-Based Thin Films from Supercritical CO2 Principal Investigator: Ken Roberts, R. Carbonell and J. M. DeSimone with students: Pamela L. Garner, Kimberly A. Moore, Leroy Covington, and Benjamin Wilson (MS students) plus Todd F. Levy, Deardra M. Pullins, and Frederick J. Smith (undergraduates) Key finding: We have produced titania sol-gel thin films via spin coat deposition as measured by XRD and SEM. This project seeks to development unique methods for producing metal- and ceramic-based thin films from supercritical CO2 by means of reactive deposition techniques. We seek to develop novel alloys and surface morphologies for various metal and ceramic systems using sub-critical thin film deposition chemistries. The determination of the effects of process variables such as temperature, pressure, solution composition, reaction chemistry and mixing profile will be a key objective for the project. The films produced will be characterized using XRD, SEM, TEM, AFM, surface profilometry, and elemental analysis. Recent work by CERSP-supported student Ben Wilson resulted in the preparation of titania sol-gel films by means of spin coating methods. Titania sol-gels were prepared using the hydrolysis of Titanium (IV) isopropoxide (TTIP). XRD results of the sol-gel films indicate the presence of crystalline phases anatase TiO2. Future work will determine the effects of preparation variables on film thickness by means of surface profilimetry. Other work by Ben Wilson in collaboration with Prof. Dhananjay Kumar utilized pulsed laser deposition (PLD) under various oxygen pressures to deposit TiO2, thin films on glass and silicon substrates. Preliminary results indicate significant effects of oxygen pressure and substrate type on the morphology of the titania films. Titania films deposited on glass show the formation of oxide nanospheres and nanoclusters. At moderate oxygen pressure (50 Torr), TiO2 nanospheres with diameters between 35 to 60 nm were produced on glass as shown in Figure 1. At higher oxygen pressure (100 Torr), TiO2 nanoclusters with average sizes between 60 to 180 nm were produced on glass as shown in Figure 2. Future work will determine the effects of PLD preparation variables (i.e., film composition, substrate type, gas pressure, gas composition) on morphology. CERSP, Page 46 of 230 Fig. 1: PLD of TiO2 on Glass at 50 Torr Fig. 2: PLD of TiO2 on Glass at 100 Torr HF-Supercritical CO2 Etching of Dielectric Films Principal Investigator: E.A. Irene with PhD Students Dongxing Yang and Yuxiang Li Key finding: We have shown that HF-scCO2 etching of SiO2 films on single crystal Si does not affect the electronic integrity of the Si for slow and moderate etch rates. Previous STC research in this area has been directed at “proof of principle” whether SiO2 films grown on Si substrates can be etched using scCO2 with a F etchant instead of water. The present project objectives are: 1. to determine whether the electric integrity of the Si-SiO2 interface is altered by this new etching process; 2. CERSP, Page 47 of 230 to perform rapid SiO2 film etching in higher etchant concentrations so as to render the removal process more useful in microelectronics manufacturing; 3. to extend the research to include the HF-scCO2 etching of HfO2. This latter dielectric is a high K dielectric under consideration by the microelectronics community. We have now substantially confirmed previous preliminary results that HFscCO2 etching of SiO2 films on single crystal Si (using pyridine-HF complex in scCO2) does not affect the electronic integrity of the Si for slow and moderate etch rates. The viability of scCO2 etching processes for dielectrics hinge on two factors: the etch rates and the electrical quality after etching. We will address both issues and therefore yield information that can lead to a judgment about the viability of the scCO2 film etching process for microelectronics applications. Precision Rate Sensors for CO2 Based Microelectronic Dissolution/Deposition Processes Principal Investigator: Christine S. Grant with Yazan Hussain (Ph.D. student) The objective of this project is to implement the Quartz Crystal Microbalance (QCM) technique for studying different phenomena associated with thin films and to extend its application to high pressure systems. During the previous year, our research was focused on two points: 1. A comprehensive characterization of CO2 soluble polymer, poly(FOMA-rTHPMA), by means of measuring different variables with the QCM. 2. Characterization of PMMA/CO2 sorption/desorption 0.8 behavior to obtain experimental data that was Di used in developing a kinetic 0.6 ss ol ut io and thermodynamic model. n 35 C o m/mo [g/g] Experiments were planned accordingly. These include: 1. Measuring CO2 uptake into polymer films. 0.4 45 C o o 55 C 0.2 o 65 C 0.0 0 200 400 600 800 1000 1200 1400 1600 1800 Pressure [psi] Figure 3 Dissolution rate for poly(FOMA-rTHPMA) polymer in CO2 at different temperatures asCERSP, Page 48 of 230 a function of pressure. 2. Measuring dissolution rates and extent of polymer films in CO2. 3. Separating CO2 adsorption on the surface from the overall mass uptake. 4. Examining changes in surface morphologies before and after CO2 exposure using AFM and SEM. This research has demonstrated the wide applicability of the QCM as an analytical tool for high pressure systems. Besides being able to operate at high pressures, the QCM has proven to be a very versatile tool that can address several aspects of the process simultaneously and in-situ. For example, in Figure 3 the sorption of CO2 in poly(FOMA-r-THPMA) is shown. While obtaining such measurements, it is also possible, using the QCM, to measure the kinetics of the processes involved (i.e. sorption of CO2 and dissolution of polymer), to obtain the CO2-polymer phase diagram, to study the effect of film thickness, and to detect any changes in the physical properties of the film and/or its interaction with the surface, and to estimate the surface adsorption contribution to the total mass change. Optical Methods to Monitor Dissolution Principal Investigator: Jan Genzer with Post-doc Kirill Efimenko The overall research objective is to provide expertise in optical ellipsometry and apply the capabilities to investigating the interfacial performance of materials in CO2 as a function of temperature and pressure. The projects in which the instrument was used include: • Structure and chemistry of photoresist films spin coated • In-situ polymerization from supercritical CO2 • Structure of polymer films in CO2 • Structure of metallic films deposited from CO2 The VASE spectroscopic ellipsometer/high pressure cell & heating set up provides a unique instrument for studying the structure (thickness and concentration profiles) of thin polymer films. Our system allows for “real time” measurements of the kinetics of film development as a function of the CO2 pressure and temperature. Toward a “Dry” Chemical Mechanical Planarization (CMP) Process in CO2: Copper Etching and Steric Stabilization of Abrasive Particles Principal Investigator: Joseph DeSimone and Ruben Carbonell with Renee Smith (undergraduate) and Ginger Denison (PhD student) CERSP, Page 49 of 230 Key finding: We have successfully demonstrated the oxidation, chelation, and solvation of copper metal in a homogenous CO2 solution and a water-in-CO2 microemulsion system. The present focuses of the microelectronics industry include: increasing chip complexity, improving the density of electron carriers, and decreasing the dimensions of the interconnects into the sub-0.25 •m regime while maintaining high aspect ratios. Water-based chemical mechanical planarization or polishing (CMP) faces several technical challenges, as the industry implements porous low κ inorganic and organic interlayer dielectrics, and environmental challenges, due to the vast amounts of ultrapure water necessary for slurries and the large volume of toxic effluent produced. Thus, there exists a great demand for new CMP technologies which circumvent the technical and environmental drawbacks of the current aqueous and chlorinated organic solvents. Condensed CO2 has significant potential for replacing current CMP solvents as the reaction media because of its superior wetting properties, low toxicity, and recyclability, providing for both technical and environmental benefits. In working towards a condensed CO2-based CMP process, we have successfully investigated the oxidation and chelation of solid copper in liquid and supercritical CO2 using CO2 soluble peroxides and •-diketone chelating agents. We have also demonstrated significant copper etching using water-in-CO2 microemulsions using water-soluble chelating agents. Chemical Mechanical Planarization (CMP) Process Studies Principal Investigators: R. G. Carbonell and J. M. DeSimone with Jeff Woodhead (PhD student) This project was aimed at the characterization of performance of CMP slurries in high- pressure carbon dioxide. The role of applied pressure, solution viscosity, pad rotational speed, particle concentration, etchant concentration and operating pressure and temperature on the rate of removal and resulting uniformity of planarized copper surface was to be investigated. A small-scale CMP device for use with supercritical carbon dioxide slurries consisting of surface-modified particles and etchants was designed. Preliminary studies were carried out on the stability of particle suspensions in carbon dioxide, and an estimate was made of the costs associated with the largescale application of high-pressure carbon dioxide based CMP processes. The costs and time lines associated with the development of this process were compared to new CMP processes that are making significant inroads in the industry, including CERSP, Page 50 of 230 electrochemical mechanical planarization. Based on these preliminary considerations, it was decided that the time line and costs associated with the development of this process were so long that center resources were better utilized on projects supporting other aspects of functional materials. The student involved in this project, Jeff Woodhead, decided to change research areas, and this project has been terminated. Degradation Processes in Fuel Cells Principal Investigator: Malcolm D. E. Forbes with Ryan L. MacArthur, postdoc Key finding: We are applying technology (especially time-resolved EPR) developed in earlier studies to understand radical-based decomposition of fuel cell membranes. In the spring of 2005, with Tom Chen’s departure, we again realigned our objectives, this time toward NAFION degradation as applied to fuel cell technology. We have been attempting to reproduce this degradation in real time with pulsed production of hydroxyl radicals. To date the signals have been weak or traceable to solvent participation in the photochemistry, but we have yet to perform these experiments at higher temperatures, closer to the actual conditions of fuel cell operation. Also during the past year we have caught up with writing on older experiments related to STC activities, and our first publication acknowledging STC support will appear shortly in J. Poly. Sci. B. It involves an EPR spin probe study of CO2-induced plasticization of vinyl acetate and methyl methacrylate. We have also recently submitted a paper on TREPR studies of flexible polymethylene chain biradicals in CO2, where we observed the first major solvent effect on spin exchange couplings in such systems. This was sent to J. Phys. Chem. B. Currently, we are writing a third paper on free radical addition reactions of photo-initiators with methyl methacrylate in CO2, where we find very similar rate constants to those measured in conventional solvents, under either liquid or supercritical conditions for CO2. Calorimetric Measurement of the Thermophysical Properties of Biomaterials in Supercritical CO2 Principal Investigator: V. K. Kabadi. G. Bothun and Ken Roberts Key finding: Preliminary calorimetric data has been obtained for lipase in supercritical CO2. A new PC-based high pressure calorimetric system has been installed for this project. CERSP, Page 51 of 230 This project seeks to measure by means of high pressure calorimetry the interactions between biomaterials such as bioenzymes with supercritical CO2. This project seeks to develop preliminary data for the subsequent kinetic characterization of high pressure enzymatic reaction in supercritical CO2. II.2a.3 Project Team III. Nanostructures PERSONNEL Institution NC State 1 2 3 4 NC A&T UNC-Chapel Hill 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 UT-Austin Researcher's Name David Frankowski Brian Prevo Saad Khan Orlin Velev None Jai-Pil Choi Ginger Denison Elizabeth Enlow Larken Euliss Stephanie Gratton Sarah Kiehna Benjamin Maynor Ashish Pandya Yi-Young Park Evan Paul Jason Rolland Chris Welch Joseph DeSimone Royce Murray Marcie Waters Post doctoral associate Graduate student (PhD) Graduate student (PhD) Post doctoral associate Graduate student (PhD) Graduate student (PhD) Post doctoral associate Post doctoral associate Post doctoral associate Undergraduate Graduate student (PhD) Graduate student (MD/PhD) Faculty Faculty Faculty Classification Graduate student (PhD) Graduate student (PhD) Faculty Faculty CERSP, Page 52 of 230 1 Stephanie Adkins Graduate student (PhD) 2 Howard Abramowitz Graduate student (MS) 3 Ti Cao Undergraduate 4 Jasper Dickson Graduate student (PhD) 5 Josh Engstrom Graduate student (PhD) 6 Gaurav Gupta Graduate student (PhD) 7 Margaret Hotze Undergraduate 8 Aimee Iberg Undergraduate 9 Yuan Li Graduate student (PhD) 10 Luciana Meli Graduate student (PhD) 11 Carrie Amber Obenland Undergraduate 12 Mehul Patel Graduate student (PhD) 13 Joseph Pham Graduate student (PhD) 14 Matthew Poplawski Undergraduate 15 Won Ryoo Graduate student (PhD) 16 Aaron Saunders Graduate student (PhD) 17 Parag Shah Post doctoral associate 18 Griffin Smith Graduate student (PhD) 19 Peter Green Faculty 20 Keith Johnston Faculty 21 Brain Korgel Faculty 22 Lynn Loo Faculty 23 Peter Rossky Faculty 24 Stephen Webber Faculty Some faculty and students listed above may participate in more than project area. Funding (reporting year) NSF Murray (Chemistry Division) Rossky Velev Velev Waters (NSF Career Award) Other CERSP, Page 53 of 230 $1,016,000 (03/04-02/07)* $424,199 (1/02-12/05)* $ 430,800 (03/03 - 02/08)* $ 90,000 (09/02-08/04) $498,500 (2/01-1/06) Murray (Office of Naval Research) Murray (Dept. of Energy) Murray (Office of Naval Research) Rossky (Welch Foundation) Rossky (Texas Advanced Research Program) Velev (Camille and Henry Dreyfus) Velev (NER) Velev (DARPA) Velev (ARO) Velev Velev (NIH) Waters (Alfred P. Sloan Fellowship) Waters (NIH) Waters (NIH) $367,441 (10/01-9/04) $486,610 (7/02-6/05) $407,110 (10/04 - 9/07) $270,000 (9/03-8/06)# $98,000 (1/02-8/04) $ 275,000 (07/02-04/06)# $360,000 (9/04-8/07)# $ 40,0000 (09/01-09/05) # $ 112,000 (08/04-07/05) $ 84,000 (06/05 – 02/06)# $ 176,000 (07/04-06/06)# $40,000 (5/04-4/06)# $857,000 (8/04 – 7/08)# $1,034,400 (2/05 – 1/09)# NSF Funding (anticipated for next year) See funding marked with * above Other See funding marked with # above DeSimone (NIH) pending $249,729 (8/05-8/06) Murray (Dept. of Energy) $450,000 (8/05-8/08) Some funding listed under Project areas I and II also supplements work done here. Objective To develop fundamental understanding of beneficial properties of supercritical CO2 that enable control of synthesis, stabilization, deposition and self-assembly of nanoscale structures So that new sustainable processes for unique structures can be developed for commercialization. Diffusion and Electron Transfer Reactions of Metal-Based Nanoparticles in CO2 Media Principle Investigator: Royce W. Murray and J. M. DeSimone with Dr Jai-Pil Choi (post-doc) and Wei Wang (Ph.D. student supported by complementary funding) CERSP, Page 54 of 230 Key finding: Activation barrier energies decrease and electron hopping rates increase in films of 1.1 nm diameter, monolayer-protected Au38 nanoparticles that are contacted by a high pressure CO2 gas phase. We are using the plasticization and solvation effects of CO2 to probe the dynamics of electron transfers between molecule-like Au38 nanoparticles, which were synthesized and preliminarily characterized in the previous year. Electron transfer (ET) kinetics of nanoparticles is a relatively unexplored area. These nanoparticles exhibit relatively well-defined molecular orbitals, judging from their electrochemistry. How fast can a metal or metalloid object transfer electrons with its oxidized or reduced counterparts? The nanoparticles bear an organic capping layer to stabilize them, which also presents a barrier to ET. Is the barrier one simply of tunneling distance, or associated with local motions of reactants, or one involving carrier populations, or density of electronic state overlap, or coulombic effects of charge separation, or some other factor? These are questions central to electrical properties of nanoscale materials. CO2 plasticization—by sorption—allows for the systematic variation of local mobility properties. Electron transfers between molecule-like Au38 nanoparticles in films are being explored with several structural variants. In one, carrier holes are chemically generated in a Au38(SC2H4Ph)24 film: the electronic conductivity of the mixed valent film increases in a manner quantitatively consistent with a bimolecular hopping rate law. Subjecting Au38(SC2H4Ph)24 films to CO2 pressure (to 900 atm) also systematically increases electronic conductivity; this is interpreted as an increase in local mobility of reacting sites. In another setting, Au38(SC2H4Ph)24 nanoparticles that have been ligand-exchanged with thiolated poly(ethyleneglycol) (PEG) chains, such as Au38(SC2H4Ph)10(SC2H4(OC2H4)nOCH3)14, also exhibit increased electronic conductivity, consistent with a local mobility model. In yet another experiment, Au38(SC2H4Ph)10(SC2H4(OC2H4)nOCH3)14 nanoparticles are further plasticized by added PEG and CO2 pressure, such that electrochemical voltammetry can be employed to probe the electron hopping rate. Hopping rates are again increased by CO2 plasticization, activation energy barriers are depressed. The rates change in a manner exactly parallel to mobility of added electrolyte ions, which is interpreted as an effect of ion atmosphere relaxation kinetics. In summary, results are pointing to importance of local mobility and coulombic effects. Our future studies will involve quantifying these results to gain a better understanding of the thermodynamics. We also plan to examine bulk systems using SAXS and possibly tomography. CERSP, Page 55 of 230 Peptide Folding in Supercritical CO2 Principle Investigator: Marcey L. Waters with Sarah E. Kiehna (PhD student) Key finding: We have designed a helical peptide which is CO2-soluble due to its secondary structure, which is in turn induced by the nonpolar nature of the CO2 solvent. We have investigated methods for solubilizing peptides in CO2 and the impact of CO2 on peptide secondary structure. We have found that an acylated glucose can solublize an unstructured dipeptide, but in the case of an oligoalanine peptide, which takes on an helical structure, up to 5 residue peptides are soluble in CO2 at room temperature and 1100 psi. This same peptide is also water soluble. Incorporation of a d-alanine sidechain in the middle of the sequence destabilizes a helix by about 1 kcal/mol, and results in significantly decreased CO2 solubility. Thus, burial of the amide groups appears to be important for solubility. These peptides appear to be unstructured in other organic solvents, suggesting that CO2 induces secondary structure, resulting in enhanced solubility of the peptide. Polymer Filled Nanocomposites Principal investigator: Saad Khan with David Frankowski (Ph.D. student) Key finding: Organically-modified clays are amenable to melt intercalation in polydisperse polymer matrices containing short chains that effectively serve as dispersants. Extended annealing of these nanocomposites at elevated temperatures where polymer degradation takes place can affect clay microstructure and increase nanocomposite modulus substantially. The goal of this project is to develop polymer nanocomposites with tunable microstructures, rheology and processability using scCO2. In this regard we will exploit the plasticizing effect of scCO2 as well as its ability to modulate the dispersion and degree of aggregation/exfoliation in the nanocomposites. Specific fillers of interest include montmorillonite (clay), surface-functionalized fumed silica, and polymeric star micro-gels. The effects of organic/inorganic and soft/hard fillers with varying size, shape, and surface functionality are under study. Fumed silica and clay nanocomposites in polystyrene, polyethylene oxide, or polypropylene matrices have been prepared by extrusion and further annealed in air, vacuum, or CO2. No discerning effect of CO2 during extrusion was noted via rheology and x-ray diffraction. Annealing at high temperatures, whereby polymer degradation occurs, results in an order of magnitude increase in the dynamic moduli. CERSP, Page 56 of 230 The initial intercalation rate discerned from the time evolution of the elastic modulus is more than an order of magnitude faster in air than in nitrogen. Complementary results from gel-permeation chromatography confirm that clay intercalation is related to chain scission in an oxygen-rich environment. The practical implication of this observation is that organically-modified clays may be amenable to melt intercalation in polydisperse polymer matrices containing short chains that effectively serve as dispersants. While enhancing chain diffusivity, extended annealing of the nanocomposites in different inert environments (including vacuum and supercritical carbon dioxide) appears to have little effect on rheology and microstructure development. An important highlight is the dramatic effect of the intercalation environment (e.g. CO2 versus air) on the rheology, dispersion, and x-ray diffraction patterns of the polymer nanocomposites. Extended annealing of these nanocomposites at elevated temperatures where polymer degradation takes place can affect clay microstructure and increase nanocomposite modulus substantially. Intercalation of Polymers in CO2: Pseudodispersion Polymerization Principal Investigator: E. T. Samulski with Qian Zhao (PhD student) Key finding: CO2-mediated dispersion polymerizations produce nanocomposites at high yields without the need for extra surfactant to stabilize the system. Poly(methylmethacrylate) (PMMA)/clay nanocomposites have been prepared using a pseudo-dispersion polymerization of MMA monomer in the presence of fluorinated surfactant-modified clay (10F-clay) in supercritical carbon dioxide. The nanocomposites are characterized by Scanning electron Microscopy (SEM), Transmission Electron Microscopy (TEM), X-ray Diffraction (XRD), Thermal Gravimetric Analysis (TGA), and Dynamic Mechanical Analysis (DMA), and show partially exfoliated/intercalated structures as well as enhanced thermal stabilities, glass transition temperatures, and mechanical properties. It is also found that 10Fclay served not only as an inorganic filler, but also as an effective stabilizer for PMMA polymerization in CO2. The nature of the stabilizing mechanisms is inferred from FTIR studies. This CO2-mediated route allows for a clean synthesis of nanocomposites with high yields without the need for extra surfactant to stabilize the system. Synthesis, Stabilization and Separation of Nanocrystals CERSP, Page 57 of 230 Principal Investigator: Brian Korgel, Keith Johnston, K. T. Lim, and Peter Rossky with Ti Cao (undergraduate) Key finding: Sterically-stabilized organic monolayer coated metal nanocrystals can be dispersed in CO2 at low solvent densities. We developing new ligand chemistry to enable liquid CO2 dispersibility for nanocrystal deposition and processing. Nanocrystals, 20–100 Å in diameter, exhibit unique size-dependent optical, catalytic, magnetic, and electronic properties compared to their bulk counterparts. These properties could enhance a variety of technologies—such as coatings, environmental, chemical processing, medical, electronics, and sensing applications. By taking advantage of the unique solvation characteristics of supercritical fluids (SCF), specifically the ability to alter density through changes in pressure and temperature, investigators have shown that it is possible to improve many aspects of nanocrystal processing— such as separations, synthesis and self-assembly. The critical aspect to nanocrystal processing in CO2 has been the identification of suitable capping ligands that provide dispersibility. One major advance has been made in this direction with the synthesis and use of three different fluorinated capping ligands that have enabled nanocrystal dispersibility in CO2: perfluroalkanethiols, thiolated perfluoropolyether (PFPE) and thiolated fluorooctylmethacrylate (FOMA). The FOMA ligand actually enabled dispersibilty of small Au nanocrystals (<4 nm in diameter) in liquid CO2. This has been a major breakthrough, as many of the unique nanocrystal deposition strategies that we would like to employ require the use of liquid CO2 at its vapor pressure. To gain a more fundamental understanding of nanocrystal dispersibility and the role of the capping ligands in CO2, we have embarked on a combined experimental and theoretical program looking at nanocrystal steric stabilization. On the experimental side, we have been using small angle X-ray scattering (SAXS) from CO2-dispersed metal nanocrystals to study interparticle interactions as a function of solvent density. As expected, the nanocrystal dispersibility decreases with decreasing solvent density, and the larger nanocrystals precipitate at higher solvent density than smaller nanocrystals. But surprisingly, we found that for PFPE-coated nanocrystals that even at relatively high solvent density, where the nanocrystals appear to be well stabilized and dispersed, there is a significant amount of interparticle interaction and reversible clustering in solution. We have begun to employ theory and simulations to the steric stabilization problem to try to quantitatively understand the role of the ligands in CO2 dispersions of nanocrystals. This quantitative knowledge of steric stabilization in supercritical CO2 will be used to guide the design of ligands synthesized by our international collaborator, Kwon-Taek Lim, Korea National University, Pusan, Korea. CERSP, Page 58 of 230 Surfactants for Nanoparticle Synthesis and Assembly Principal Investigators: P. J. Rossky, B. Korgel, and K. P. Johnston Key finding: The analysis of the molecular interactions underlying the interactions between modified surfaces at nanoscale geometries will provide the basis for rational surfactant design for future technology development. The stabilization of dispersions of surfactant-capped nanoparticles and the controlled solubilization of nanoparticles in supercritical CO2 represent critical elements in nanoparticle synthesis, size selective separation, and controlled assembly into functional organized arrays. We are directly addressing the issues of nanoparticle solvation and interparticle interactions between nanoparticles in solution via molecular simulation. Direct simulations of net interparticle forces in CO2 via simulation of the free energy as a function of interparticle separation, and as a function of solvent thermodynamic state, are being carried out. We use a grand canonical hybrid Monte Carlo algorithm that allows efficient sampling of surfactant chains using Molecular Dynamics simulation while maintaining CO2 solvent at constant chemical potential. The method has been shown to give expected results manifesting strong attraction in a CO2 environment between gold nanoparticles that are not passivated. Surfactant modified surfaces show increasing stabilization with increasing CO2.pressure. Further, fluorocarbon surfactants manifest far better stabilization then hydrocarbon surfactant, in accord with experiment. The corresponding molecular level results for structure and interactions are being analyzed to provide the underlying explanation for these phenomena. The derived force curves can also be compared directly to those inferred from SAXS experiments. The analysis of the molecular interactions underlying the interactions between modified surfaces at nanoscale geometries will provide the basis for rational surfactant design for future technology development. Thin Films of Polymer-Nanoparticle Nanocomposites in CO2 Principal Investigator: P.F. Green and K.P. Johnston with Luciana Meli and Joseph Pham (PhD students) Key finding: Carbon dioxide may be used to control the morphology of dodecanethiol capped gold nanoparticles in polystyrene and polymethylmethacrylate CERSP, Page 59 of 230 thin films cast on SiOx substrates. CO2 may be utilized to anneal diblock copolymers to form templates to order nanocrystals selectively in one of the two phases. The primary goal of this project is to understand how to control the composition and spatial distribution of nanoparticles in polymer thin film matrices. Accomplishing this goal will eventually enable one to develop rules to process and to fabricate the materials with properties that are “tailored” for specific applications. Potential uses of polymer-based nanocomposites are varied, from structural applications, where the nanocomposites exhibit mechanical and thermal properties that are superior to those of the pure polymer, to device and sensor applications, where the nanocomposite exhibits functionality not achievable by the polymer nor by any other type of materials. Nano-particle organization and interactions in homopolymer thin films: In our most recent report, we mentioned that high resolution transmission electron microscopy shows evidence of hexagonal order of dodecanethiol capped gold nanoparticles in polystyrene thin films cast on SiOx substrates. We have made similar observations in PMMA (polymethylmethacrylate) thin films as well. The order is evident when the particles are of monodisperse dimensions. Secondary ion mass spectrometry measurements indicate that the dodecanethiol capped gold particles (4.5±0.5 nm) particles form layers at the free surface, not at the polymer/substrate interface, because the dodecanethiol possesses a lower surface tension than either PS (polystyrene) or PMMA. In PMMA, at 150°C, in vacuum, the gold particles coarsen via a coalescence mechanism to form larger particles. The data can be described by a time-invariant cluster size distribution, the Smoluchowski distribution. In CO2, at 50°C, on the other hand, the particles aggregate, abut remain stabilized by the ligands. They show a tendency to form islands of two layers in some cases. In PS at 150°C, coarsening, via coalescence, occurs; though it is less significant than in PMMA. However, in contrast to PMMA, some degree of particle coarsening occurs in PS at 50°C in CO2. The influence of CO2 is evident in that despite the driving force for aggregation, the particles remain ordered, at least locally whereas in air they coalesce at temperatures below which the ligands should be unstable. Secondly, the fact that the layer of high surface energy metal (gold) particles segregate to the surface, indicates that the chemistry of the ligands plays the dominant role in determining the interfacial properties. This will have important implications on fabrication processes. CERSP, Page 60 of 230 Nanoparticles in diblock copolymers: Most of our work has focused on the PS-b-PVP system. The PS-PVP system is highly segregated. Based on our experience with the influence of the ligands on the thermodynamics, we examined the effects of two different types of ligands, SH-PS ligands (mwt. of PS in 1000 g/mol) and of SH-C12H25 ligands on gold nanoparticles. We studied an asymmetric PS-b-PVP system, with PVP as the minor component, which should form a cylindrical morphology. At 10% nanoparticles, the nanoparticles aggregate but maintain local packing order (hexagonal symmetry). The order of the nanoparticles and aggregation is more significant with the SH-C12H25 ligands. Coalescence is evident in vacuum, as was the case in the homopolymers. At lower concentrations, particularly with the SH-PS ligands the coarsening was not significant. The rationale is that the nanoparticles are largely incorporated within the PS hosts at low concentrations. The interactions of the SH-PS ligands would be more apparent due to the enhanced compatibility with PS. At higher concentrations, the entropy is such that excess particles will macrophase separate to form separate phases. This is more pronounced with the more incompatible SH-C12H25 ligand system. Deposition of Functional Micro- and Nanoparticle Coatings Principal Investigator: Orlin D. Velev and Ruben G. Carbonell with Brian G. Prevo PhD student Key finding: We developed a method for rapid scalable deposition of antireflective and superhydrophobic coatings from silica nanoparticles that have potential for improving the performance of solar cells and windows. We have developed a robust technique for rapid assembly of colloid nanoparticle coatings from microliter droplets. The coatings were deposited by dragging with constant velocity a small volume of suspension confined in a meniscus between two plates. The governing mechanism of deposition is convective assembly at high volume fractions. Operational ‘phase’ diagrams were constructed, relating the 2D crystal layer thickness and packing symmetry to the process parameters. This technique works well for coatings from particles of sizes spanning the whole colloidal range, from nanocrystals to micrometer sized spheres. We achieved controlled deposition of conductive metal nanoparticle films and antireflective (AR) silica nanoparticle coatings. The electronic, optical and structural properties of the metal nanocoatings could be tuned through the deposition parameters. By varying the deposition speed of the AR silica coatings, the band of optimal transmission could be tuned across the breadth of the visible spectrum (from 450 to 650 nm). The AR coatings were further optimized by the use of particle mixtures, which reduced the reflectance loss on glass by up to 89%. We are pursuing an ongoing study on the CERSP, Page 61 of 230 deposition of antireflective and superhydrophobic coatings using liquid carbon dioxide as media. The nanocoatings developed could be used in applications ranging from nanoelectronics to energy efficient windows and solar cells. Nanoparticle Self-Assemblies on Patterned Surfaces Principal Investigator: Keith P. Johnston, Lynn Loo, Peter Green, Joe DeSimone, Peter Rossky, and Steve Webber with Griffin Smith (PhD student) Key finding: We report electrostatic stabilization of micrometer-sized inorganic particles at long range (several micrometers) in liquid and supercritical CO2 despite the ultra-low dielectric constant, as low as 1.5. The first phase of this project is to charge particles to facilitate interactions of particles with patterned surfaces. We report electrostatic stabilization of micrometersized inorganic particles at long range (several micrometers) in liquid and supercritical CO2 despite the ultra-low dielectric constant, as low as 1.5. Dynamic light scattering and settling velocities indicate a particle diameter of 620-740 nm. The electrophoretic mobility of -2.3 x 10-8 m2/V·s indicated a particle charge on the order of -1.1 x 10-17 C, or 70 elementary negative charges per particle. The balance of particle compression by an electric field versus electrostatic repulsion generated an amorphous arrangement of particles with 5 to 9 micrometer spacing, indicating Debye lengths greater than one micrometer. Scattering patterns also indicate that chains of particles may be achieved in CO2 by dielectrophoresis with alternating fields. The electrostatic stabilization has been achieved by preventing the counterions from ion pairing. Electrostatic stabilization has the potential to expand markedly the domain of colloid science in apolar supercritical fluids. Nanoparticle Self-assembly on Solid Surfaces Principal Investigator: Brian Korgel, Keith Johnston, Steve Webber, Peter Green, Ruben Carbonell, Orlin Velev, and K. T. Lim Key finding: Ordered monolayers of metal nanocrystals can be deposited from CO2 with better surface coverage than when using conventional solvents. Nanocrystals, 20–100 Å in diameter, exhibit unique size-dependent optical, catalytic, magnetic, and electronic properties compared to their bulk counterparts. These properties could enhance a variety of technologies—such as coatings, environmental, chemical processing, medical, electronics, and sensing applications. CERSP, Page 62 of 230 By taking advantage of the unique solvation characteristics of supercritical fluids (SCF), specifically the ability to alter density through changes in pressure and temperature, investigators have shown that it is possible to improve many aspects of nanocrystal processing— such as separations, synthesis and self-assembly. By developing a fluorinated capping ligand for nanocrystals that enabled dispersibility in liquid CO2—a thiolated fluorooctyl methacrylate (FOMA)—we were able to examine particle deposition from CO2 onto solid substrates. The CO2 system provides a unique deposition environment relative to conventional solvents, because dewetting instabilities that generally lead to solvent hole formation and inhomogeneous nanocrystal deposition can be avoided by using CO2. By controlling the CO2 deposition rate, the kinetics of the nanocrystal self-assembly process could be varied and studied. For the first time, the self-assembly kinetics could be probed with evaporation rate to estimate the effects of solvent evaporation. We found that the slowest evaporation rates led to hexatic monolayers, whereas the fastest deposition led to spatially disordered films of particles. One of the limiting factors to these studies was still the limited nanocrystal dispersibility in CO2 at low solvent density. We are still searching for a better capping ligand and with our international collaborator, Kwon-Taek Lim, Korea National University, Pusan, Korea, we will be synthesizing and exploring a library of ligands. Particle PRINTing Principal Investigator: J. M. DeSimone with Benjamin Maynor (post-doc), Larken Euliss (post-doc), Ashish Pandya (post-doc), Ji-Young Park (post-doc), Ginger Denison (PhD student), Jason Rolland (PhD student), Stephanie Gratton (PhD student), Elizabeth Enlow (PhD student), Chris Welch (MD/PhD student), Evan Paul (undergraduate) Key finding: PRINT (particle replication in non-wetting templates) can create monodisperse, completely isolatable nanoparticles of arbitrary shape and size as well as replicate self-assembled or biological molecules. PRINT (Particle Replication In Non-wetting Templates) is an imprint lithographic technique that we have pioneered. It creates completely isolatable objects of a wide variety of sizes and shapes. The objective of PRINT is to create polymeric drug delivery systems in which the delivery vehicles are completely monodisperse and selectively target the desired cells (e.g. cancer cells). It is important that the particles be monodisperse for dosing as well as for shape and size specific cellular uptake. These particles can be functionalized for cell targeting and can encapsulate cargos for delivery to the cell. CERSP, Page 63 of 230 Through PRINT, the ability to replicate a wide variety of shapes and sizes has been achieved. AFM calibration grids, self-assembled polymer molecules, and biological molecules have been successively replicated using PRINT. In some cases features as small as 1-2 nm have been seen. PRINT has the ability to replicate biological and self-assembled molecules which under other replicating conditions may become deformed or disassemble. The ability to collect completely isolatable particles in a usable form has been accomplished using various harvesting methods. It has also been shown that these particles can be functionalized with avidin and subsequently bind biotin. This research contributes to the Centers goals of environmentally friendly processes. The PRINT process requires no solvent usage as it is based on curing polymer liquids into solids. Harvesting the particles requires water or a buffer solution, but it is in this solution that the particles will be used. The expected outcome of this research is to develop a polymeric drug delivery system which will make current medicines more effective and possibly open the door to new treatments that could not be realized before. PRINTing Electroluminescent Polymers Principal Investigator: E. T. Samulski and J. M. DeSimone with Walter Schenck (PhD student) “Liquid TEFLON” molds appear to be suitable for PRINTing nanoparticles. Our goal is to determine if solutions of electroluminescent polymers will yield nanometer scale organic Quantum Dots and to explore optical aspects such as quantum confinement in these novel materials. (This project is collaborative but is not directly funded by the STC.) Colloidal Crystals and Porous Templates Principal Investigator: Keith Johnston, Peter Green, Brian Korgel, and Orlin Velev with Parag Shah (post-doc), Jasper Dickson (PhD student) and Howard Abramowitz (MS student) Key finding: We have demonstrated experimentally that CO2 facilitates the dispersion of metal nanocrystals into porous materials, especially in pore sizes <5 nm. The simplicity of the method allows for the facile production of nanocrystal/silica composites for applications such as catalysis CERSP, Page 64 of 230 and optoelectronics. The lack of a surface tension for supercritical CO2 and its low viscosity provide an opportunity to deposit nanocrystals into extremely small pores that are not accessible to liquid solvents due to wetting limitations. For conventional liquid solvents, the pore structure of the crystal will only be accessible to wetting solvents, limiting the nanocrystal ligands that can be implemented based on the hydrophilicity of the substrate. Supercritical CO2 without a surface tension will wet all types of pores thereby making the complete pore structure accessible. Additionally, the solvent removal step for wetting solvents, which can lead to the collapse of pores, is also eliminated. Gold nanocrystal dispersions in toluene-CO2 mixtures were infused into cylindrical pores in mesoporous silica to achieve high loadings over 2 wt% in 24 hours. The nanocrystals were highly dispersed according to transmission electron microscopy and the loadings approached equilibrium. In contrast, the loadings were small for infusion with pure toluene or toluene mixed with an antisolvent, methanol. The differences in loading were correlated with the long-ranged van der Waals forces between the gold and silica through the intervening solvent. These van der Waals forces became stronger as CO2 was added to toluene, as a consequence of a reduction in the Hamaker constant of the mixed intervening solvent, resulting in stronger nanocrystal adsorption. The decoupling of the nanocrystal synthesis step and the infusion step, leads to exquisite control of the nanocrystal size, morphology and dispersibility within the pores. Nanoparticles for High Bioavailability Principal investigator: Keith Johnston with Josh Engstrom (PhD student) Key finding: Protein activities comparable to conventional lyophilization are achieved with surface areas greater than 35m2/gm with the spray freezing into liquid process. Our objective is to produce nanostructured protein particles by using a small scale (≤1ml) spray freezing into liquid (SFL) process and to demonstrate better preservation of protein physical stability compared to the spray freeze drying (SFD) process. Various liquid cryogens may be utilized including CO2 and N2. The proteins lysozyme and lactate dehydrogenase (LDH) prepared by the SFL process had activity recoveries near 100% which matched samples prepared by conventional lyophilization. Activity recoveries for the same samples processed by SFD using a two fluid nozzle were between 80 and 85%. Specific surface areas (SSA’s) of dried CERSP, Page 65 of 230 powders produced by SFL ranged between 35 and 75m2/gm compared to 1m2/gm for powders prepared by lyophilization. Higher protein stabilities are achieved with SFL relative to SFD by minimizing the exposure of the protein solution to the air/liquid interface during freezing. Ultra rapid freezing of the protein solution in the SFL process produces high surface area powder on drying. SFL into a cryogen reduces exposure of proteins to the air/liquid interface during freezing helping to reduce protein denaturation and aggregation relative to SFD. Protein activities comparable to conventional lyophilization are achieved with surface areas greater than 35m2/gm with the SFL process. The ability to produce stable high surface area protein particles is useful for a wide variety of drug delivery formulations. Interfacial Properties of Surfactants for Microemulsions Principal Investigator(s): Keith P. Johnston, Joe DeSimone, Peter Rossky, and Steve Webber and Jasper Dickson (PhD student) Key finding: We have formed CO2-in-water (C/W) emulsions using hydrocarbon tertiary amines, a new class of surfactants for CO2-based dispersions A fundamental understanding of the relationship between interfacial properties and surfactant molecular architecture is being developed for the design of ligands and surfactants for the formation of stable microemulsions. The interfacial tension and surfactant adsorption at the planar water/CO2 interface have been measured for multiple classes of surfactants. The hydrophilic-CO2-philic balance (HCB) of these surfactants and the adsorption at the interface was varied by controlling tail branching, the headgroup, and the counterion (when applicable). Experimental results are compared with molecular dynamics computer simulations from Rossky’s group. This study has also focused on the ability of highly branched hydrocarbon non-ionic and ionic surfactants, including hydrocarbon dichain phosphates synthesized by the DeSimone group, to lower the interfacial tension at the water/CO2 interface. We have formed CO2-in-water (C/W) emulsions using hydrocarbon tertiary amines, a new class of surfactants for CO2-based dispersions. These nonfluorinated, low-MW surfactants were designed for an effective hydrophilic-CO2-philic balance (HCB) by using a weak hydrophile (tertiary amine) and applying the free fractional volume (FFV) and branching concepts to the tails. The benefits of increased methyl groups are seen in increased emulsion stability and lower CO2water interfacial tension (IFT). These relatively inexpensive non-fluorinated, nonpolymeric surfactants can make applications of CO2 more viable, and their structure CERSP, Page 66 of 230 and synthesis are easily adaptable for future study of further changes in surfactant architecture. II.2a.4 Project Team IV: Membrane Separations Institution Georgia Tech 1 2 3 4 NCA&T 1 2 3 4 5 6 UNC-CH 1 PERSONNEL Researcher's Name Classification Ryan Adams Madhava Kosuri John Perry William Koros Kingsley Nelson Katif Peay Willie Arnold Vincent Morehead Geoffrey Bothun Shamsuddin Ilias Valerie Ashby Graduate Student (PhD) Graduate Student (PhD) Graduate Student (PhD) Faculty Graduate Student (MS) Graduate Student (MS) Undergraduate Undergraduate Post doctoral associate Faculty Faculty Funding (reporting year) NSF Koros (NIRT-NSF) joint with S. Nair Bothun (NSF-DCF) Other than NSF Koros (Chevron) Koros (Medal) Koros (DOE-Basic Energy Science) Koros (Coca Cola) Koros (BP) Koros (Georgia Research Alliance) Ilias (US DOE - NETL) $120,000 (9/04-8/05) $200,000 (8/04-8/06)* $110,000 (10/04-9/05)* $40,000 (10/04-9/05)* $80,000 (11/04-10/05)* $61,500 (11/04-10/05)* $240,000 (11/04- 10/05)* $40,000 (7/04- 7/05) $199,981 (9/01-9/04) CERSP, Page 67 of 230 Ilias (US DOE - NETL) Ilias (US DOE - NETL) $199,996(10/02-9/05)* $192,509 (9/00-12/04) Funding (anticipated for next year) NSF See funding marked with * above Other than NSF See funding marked with # above Objective To develop fundamental understanding of phenomena specific to separation science and technology needed for cost-effective CO2 recovery and recycle So that new sustainable processes can be developed for commercialization. Polymer Hybrid Membranes Principal Investigator: William Koros Three projects are being pursued with an overall objective to develop continuous selective removal of CO2 from larger microsolutes (e.g., monomers such as tetrafluoroethylene and vinylidene fluoride) without the need for depressurization of the majority of the feed stream containing CO2 and the monomers. This goal is key to the continuous operation of processes in which CO2 is used as a reaction medium to stabilize tetrafluoroethylene in homo- and co-polymer polymerizations. Achieving this goal is the first step toward energy-efficient recycle of the CO2 to a wide variety of processes. Currently, there is no conventional technology known to achieve the above objective. All three of the following projects address this challenge in differing ways. These three projects are: (i) Zeolite-Polymer Hybrid Materials & Membranes with High Zeolite Content (with Ryan Adams, PhD student) (ii) Zeolite-Polymer Hybrid Materials & Membranes Based on Solvent Resistant Polymers (with Mudhava Kosuri, PhD student) (iii) Carbon-Polymer Hybrid Materials & Membranes (with John Perry, PhD student) CERSP, Page 68 of 230 Zeolite-Polymer Hybrid Materials and Membranes with High Zeolite Content Key finding: Zeolite-polyvinyl acetate composites were prepared and are being evaluated as membranes for high-pressure separation of CO2 from monomers. We have demonstrated levels previously unachieved (50%) and are attempting to reach levels up to 80%. This work seeks to leverage successes we have had in past involving the formation of hybrid materials comprised of blends of molecular sieve zeolites and flexible polymers at low (<20 wt%) loadings of zeolites in polyvinyl acetate. We discovered that the zeolites tend to rigidify the polymer directly adsorbed on the sieve surface and near to the surface. For instance, we have seen increases in Tg as high as 15-20 •C in some cases. We reasoned that at even higher sieve loading above 20%, the zones of influence due to the effects of the solid sieve surfaces on the interstitial polymer will overlap. This overlap will lead to stabilization of the membrane material, and should create membranes with size and shape discriminating abilities that approach those of the zeolite itself. We are exploring the maximum zeolite loadings that can be reached using protocols that can be extended to create useful separation membranes. Since the zeolites are able to easily pass CO2 while rejecting larger penetrants such as tetrafluorethylene, ethylene and vinylidene fluoride, the resulting membrane should be ideal for selective partial removal of CO2 to enable monomer recycle without energy-intensive depressurization. Ryan Adams has formulated his first set of samples with zeolite loadings as high as 50%. The mechanical properties are adequate for testing, and he is in the process of learning how to make sorption and transport measurements to characterize these samples. The most significant achievement of the project is the successful proof that much higher zeolite solids loadings can be achieved compared to what we prepared in the past. We hope to achieve ultimate loadings as high as 80 wt%. Zeolite-Polymer Hybrid Materials & Membranes Based on Solvent Resistant Polymers Key finding: A defect-free asymmetric hollow fiber membrane can be made using Torlon® polyimide polymer. This achievement encourages us that formation of an asymmetric membrane based on a hybrid zeolite-Torlon® blend is likely to be ultimately feasible. CERSP, Page 69 of 230 This work is motivated by our discovery that a family of commercially available polyimide-amide materials (Torlon®) has unusually good organic solvent resistance but can be formed into membranes with high selectivity for O2/N2 and He/N2 separation. If such a commercially available material can be used for CO2 removal from CO2/monomer mixtures, this would enable rapid implementation in practical processes. Despite the organic solvent resistance of the Torlon® family of polymers, the CO2/monomer selectivity may be inadequate for the demanding supercritical CO2/monomer mixtures we seek to separate. Our work at lower pressures with less robust polymers has shown that even incorporation of low levels (<20 wt%) of zeolite sieves stabilzes them against swelling by feed stream. We plan to incorporate such zeolites into Torlon® to further stabilize it and boost it selectivity to enable performing our targeted separations under supercritical conditions. Madhava Kosuri has demonstrated integrally skinned Torlon® asymmetric hollow fibers that are useful at low pressures to separate simple gases. The morphology of the fibers contains macrovoids, so they will not yet sustain the high transmembrane pressures required for the ultimate application. Madhava is working to improve the membrane morphology and has also begun to explore the issues involved in forming a nonasymmetric dense film zeolite loaded Torlon® film. The dense film samples enable testing model predictions of the performance enhancements achievable for the hybrid materials. The most significant achievement of the project is the successful demonstration that a true defect free asymmetric hollow fiber membrane can be made using Torlon® polymer. This achievement provides us with confidence that formation of an asymmetric membrane based on a hybrid zeolite-Torlon® blend is likely to be ultimately feasible. Carbon-Polymer Hybrid Materials and Membranes Key finding: It is necessary to “titrate” the tethering agent on the sieve surface to balance desirable adhesion vs. transport properties. The work on this project involves a PhD student, John Perry, an NSF Fellow. John’s work, which began in 2002, and it has been focused on developing higher selectivity membrane materials for natural gas purification applications. Completion of the third year of John’s NSF fellowship this summer provides a natural transition to expand the focus of his work to create materials for the supercritical CO2/monomer mixtures we seek to separate. This strategy gives our work on carbon-polymer hybrids a “jump start”, since John is already experienced in membrane formation and characterization. Our previous work has already shown that carbon molecular sieve particles, when adequately stabilized and dispersed in a suitable polymer matrix, can provide selectivity enhancements above that of the neat polymer. The previously CERSP, Page 70 of 230 used polymer, however, was not well matched in permeability to the available carbon molecular sieves, so we have identified a polyimide with higher permeability that is better suited for this application. The new polyimide is rich in rich in fluorine atoms in the dianhydride and diamine monomers and has a very high permeability. While well-matched to the carbons in terms of transport properties the new polyimide requires chemical compatibilization to achieve adequate adhesion to the carbon surface. Unlike zeolites, which can use simple silanes as tethering agents, applications involving carbons require novel tethers. John has been pursuing compatibilzation techniques starting with the attachment of primary aromatic amine to the surface of the molecular sieve carbon particles. These amines serve as tethering points that open the imide ring to produce an amide bond, thereby tethering a “priming layer” of polyimide to the surface of the molecular sieve carbon particles. Although this approach stabilizes the carbon particles from agglomerating, excessive opening of the imide ring on the priming polymer layer undermines the transport properties of the polyimide. Optimization of the tethering process is underway currently. The most significant achievement of the project is discovery of the need to “titrate” the extent of tethering agent on the sieve surface to balance desirable adhesion vs. transport properties. Ceramic Membranes Principal Investigators: Shamsuddin Ilias and Geoff Bothun, Discovery Corps Postdoctoral Fellow The two projects we are pursuing involve the transport properties of liquid and supercritical CO2, and comparative non-aqueous solvents, through mesoporous (250 nm pore diameters) ceramic membranes. Ceramic membranes are more robust and chemically stable than polymeric membranes, which is advantageous for rigorous high-pressure and solvent-based separations. However, little is currently known regarding non-aqueous solvent permeation through ceramic membranes, which are inherently hydrophilic. In addition to the objectives listed above by Dr. Koros (i.e. minimizing depressurization and facilitating continuous CO2 processing), the objectives of these projects are to (i) improve knowledge of non-aqueous solvent and condensed CO2 transport through ceramic membranes and (ii) provide reliable separation processes for selective microparticle and nanoparticle recovery from CO2. Such processes could be critical in the commercialization of emerging CO2 technologies such as semiconductor fabrication, nanoparticle formation, and polymerization, which are key research foci in CERSP. CERSP, Page 71 of 230 (i) Liquid and supercritical CO2 permeation in mesoporous ceramic membranes (with Kingsley Nelson and Katif Peay, MS students) (ii) Non-aqueous solvent transport in ceramic membranes (with Vincent Morehead and Willie Arnold, undergraduates) Liquid and Supercritical CO2 Permeation in Mesoporous Ceramic Membranes Key finding: Unique transport behavior has been observed for pure and multicomponent liquid and supercritical CO2 in mesoporous ceramic membranes that will facilitate the development of selective macromolecule and particle recovery. This project began 6/04 as collaboration between Dr. Geoff Bothun and Dr. Shamsuddin Ilias. Two MS graduate students worked on this project, Kingsley Nelson (graduated 5/05) and Katif Peay. Mr. Peay is continuing, and expanding on, Mr. Nelson’s work. This work examines the permeation behavior of liquid and supercritical CO2 through mesoporous ceramic membranes, as a “first step” to investigating selective particle and macromolecule recovery from CO2. Knowledge is also gained regarding non-aqueous solvent transport in ceramics, as CO2 acts as an organic solvent in condensed states. While this project is a new collaboration with novel goals, we are building on the previous success of Dr. Shamsuddin Ilias and his graduate students at NC A&T who have investigated continuous reverse microemulsion recovery from liquid CO2. Liquid and supercritical CO2 permeation is examined in a series of mesoporous ceramic membranes with varying pore size and different selective layer materials. Viscosity-corrected liquid flux values were used to test the applicability of Darcy’s law and to calculate/compare membrane permeability coefficients to other conditions (e.g. organic solvents, water, CO2+contaminants). Unique permeation behavior has been observed in dry and wet (120 ppm water) liquid CO2, consistent with CO2-membrane repulsion, CO2 and/or water adsorption, and water condensation in mesopores. We are currently examining the effect of CO2+cosolvents and different levels of CO2 hydration on permeation behavior. Multicomponent feed streams are frequently encountered CO2 technologies, and characterizing the effect of such feeds is needed for separation, recycle, and reuse. Non-aqueous Solvent Transport in Ceramic Membranes Key finding: Examining non-aqueous solvent permeation in mesoporous ceramic membranes has revealed the significance of molecular ordering and surfaceadsorption on permeation behavior, and will provide a link between the transport of liquid CO2 and conventional organic solvents. CERSP, Page 72 of 230 This project began 1/05 with two undergraduate researchers, Vincent Morehead and Willie Arnold, as part of the EXPERT program at NC A&T. The objective of this project is to examine the permeation behavior of non-aqueous solvents with different physical properties (e.g. density and viscosity) through ceramic membranes. Comparisons will be made to liquid and supercritical CO2 permeation to examine critical solvent properties in membrane transport. Comparing organic solvents to CO2 provides information on the role of surface tension in solvent transport; liquid CO2 has comparable solvent density and viscosity, but very low surface tension that allows high surface wetting. The permeation behavior of hydrophilic (e.g. alcohols) and hydrophobic (e.g. alkanes) organic solvents through mesoporous ceramic membranes is examined. Recent results for hydrophilic solvents – ethanol, butanol, and acetone – indicate a transient permeation profile for all solvents, possibly due to solvent physisorption or chemisorption at the surface hydroxyl site and a reduction in the effective membrane pore size. Pre- and post-water permeation experiments indicate that adsorption of these solvents was reversed with drying/regeneration. We are currently concluding our investigation of hydrophilic solvents and will examine hydrophobic solvents, the effect of multicomponent feed streams, and comparisons to CO2. Mr. Arnold is working with us this summer on this project. II.2a.5 Project Team V: Collaboration and Innovation Institution NC State 1 2 3 4 5 6 7 8 9 UNC-CH 1 Personnel Researcher's Name Ally Baker Felysha Jenkins Jennifer Lindberg Drew Rivers Jennifer Schneider Stephanie Tarant Bart Craig Denis Gray Pamela Martin Nancy Baker Classification Graduate student (MS) Graduate student (PhD) Graduate student (MS) Graduate student (PhD) Graduate student (PhD) Graduate student (PhD) Faculty Faculty Faculty Graduate student (PhD) CERSP, Page 73 of 230 2 Leo Cao 3 Christopher Maier 4 Qi Zhang 5 Marcus Donie 6 Catherine Blake Affiliate Southeastern Russ Osmond Polytechnic State University Graduate student (PhD) Graduate student (MS) Graduate student (PhD) Staff Faculty Faculty Funding (reporting year) NSF 1 NSF STC funding (Gray) 2 IUCRC Program (Gray) $394,177 $70,000 $3,000 (2004-2005) 1 Other Kenan Institute (Gray) Funding (anticipated for next year) NSF NSF STC funding (Gray) Other Kenan Institute (Gray) Objectives To develop and apply a fundamental understanding of social processes that foster collaboration and innovation In a way that • identifies factors that impact innovation and collaboration • identifies social and technical strategies to enhance collaboration and innovation • adds to the general knowledge base of innovation and collaboration So that CERSP and similar organizations are empowered to reach their scientific, technological and educational goals. $394,177 $3,000 (2005-2006) CERSP, Page 74 of 230 Overview During 2004-5 CERSP’s Innovation Research program completed the transition that it began during 2003-4. Previously, our social science research and education initiatives were carried out by two PIs, Dr. Sonnenwald from UNC CH and Dr. Gray from NCSU. Since our decision to broaden and diversify the social science research program coincided with Dr. Sonnenwald’s decision to move to another university, we were able to accelerate this process. Dr. Gray has assumed leadership for the research program that now supports four PIs, Drs. Gray, Craig, Martin (NCSU) and Blake (UNC-CH) and an education project headed by a consultant, Dr. Osmond. Projects summarized in this report include a previously funded project that was completed in December (Gray; Industry BoundarySpanners), a continuing seed project (Martin; SRMSI), and four new projects that were a by-product of a revision in our strategic plan and a RFP disseminated to a target departments within the participating universities. Each of these projects address issues that are of direct and immediate relevance to our center but are also of great relevance to centers nationally. Recently Completed and Continuing Projects Role of Organizational Boundary Spanners in Industry/University Collaborative Centers. Principal Investigator: Denis Gray with Stephanie Tarant (PhD, Psychology) Key finding: For the first time we can demonstrate that industrial boundary spanners (IBS) who proactively engage in suggesting, starting and steering cooperative research projects they are sponsoring at universities will realize greater R&D, commercialization and recruiting benefits for their firm. Objectives: To increase our understanding of the roles and behaviors industrial “boundary spanners” (IBS) play in cooperative research centers; To identify boundary spanner roles that quantitatively predict positive firm outcomes. Approach: Previous research has demonstrated that some firms report more benefits from participating in cooperative research centers than other firms. This project attempted to examine the extent to which the roles and behaviors engaged in by the IBS affect the benefits the firm realizes. This project involved collecting questionnaire data from 220 firm representatives from 35 centers. Descriptive analyses, factor analyses and multiple regression (logistic and OLS) were used to address project objectives. CERSP, Page 75 of 230 Accomplishments: This is the first empirical examination of IBS involved in IU Centers. Results demonstrated that IBS spend a significant amount of time each year on cooperative research center activities but receive little or no training and guidance on how to extract benefits from their partnership. We demonstrated that IBS engage in four roles: basic IBS; internal boundary spanner, external boundary spanner, and technology champion. While the latter three roles are significant predictors of R&D, commercialization and networking (recruiting) benefits, being an active external boundary spanner (being proactive in suggesting, starting and steering cooperative projects) had the largest and most consistent effect across all outcomes. Southeast Raleigh Mathematics and Science Initiative (SRMSI) (co-funded by NSF Post Doctoral Start up Award and Kenan Institute) Principal Investigator: Pamela P. Martin with Ally Baker (MS, Psychology); Felysha Jenkins (PhD, Psychology) Key finding: Fourteen of fifteen at-risk students involved in the after school project were promoted to the next grade. Objective: To design, implement and evaluate a community-based after school program in partnership with schools and faith communities targeted at under represented K-4 students. Approach: The Southeast Raleigh Mathematics and Science Initiative (SRMSI) is an innovative collaborative partnership between CERSP/NCSU, Wake County Public School System (WCPSS), Strengthening the Black Family, the Science House, and faith communities. The SRMSI innovation utilizes ecological and family-focused approaches to examine how the informal and formal social support networks help assist in promoting achievement among elementary students. Currently, the SRMRI is a pilot study located at Strengthening the Black Family. Accomplishments: Fifteen African American elementary students enrolled in the after-school math and science enrichment program. Eighty percent (n =12) of the students were male and twenty percent (n=3) were female. These participants were recruited from three magnet schools and one traditional school from WCPPS. The students represented kindergarten through fourth grade. Using the interim academic reports as the baseline assessment, fourteen out of the fifteen students under performed in all subject areas. At the end of the third quarter marking period, teachers reported better social skills plus homework completion for the majority students. Some modest improvement was noted in student grade level performance scores. In addition, the SRMRI (PSY 499-034) service learning course provided 15 CERSP, Page 76 of 230 undergraduate students the opportunity to gain applied learning experiences through mentoring and tutoring students in the community. The undergraduate students represented a variety of majors such as Biology, Psychology, Spanish, Textiles, and Engineering. The learning objectives for this course require mentors to reflect, challenge and deepen their understanding of the psychosocial and physical environments of individuals from diverse backgrounds. This has been funded as a seed project and applications for continuing funding of this project are being pursued. New and Continuing Projects An Analysis of Factors That Predict a Firm’s Decision to Join a Universitybased Industrial Consortia. Principal Investigator: Denis Gray with Drew Rivers (PhD; Psychology) Key finding: According to director ratings, trade shows and ads in trade magazines are relatively effective but underutilized mechanisms for developing leads for new member firms; over half of the firms recruited fail to make a decision to join or not join the center. Objectives: To identify center, organizational, and individual factors that affect a firm’s decision to join or not join an IU Center; To develop and test a multi-level predictive model of the factors that affect the decision to join an IU Center. Approach: This project is in the first year of a two-year effort. During Phase 1 of the project, qualitative and quantitative methods will be used to identify various methods centers use to recruit new members and the factors (e.g., needs, perceptions, decision making methods) that differentiate firms that join from firms that do not join centers. During Phase 2 of the project a model of firm decision making about center membership will be tested by collecting questionnaire data from a sample of firms that have recently made the decision to join or not join a center. Multivariate analyses will be used to identify the key organizational, personal and perceptual factors in the decision. Accomplishments: Web-based questionnaire data was recently collected from a sample of IU Center directors detailing their recruitment practices and the perceived effectiveness of those practices. Based on preliminary analyses we have identified materials and recruitment strategies directors think are most effective in recruiting members and which issues constitute the biggest acceptance and rejection factors for the membership decision. An interview guide has been developed to use CERSP, Page 77 of 230 with firm representatives and qualitative data collection will commence during the summer. Phase 2 will commence this fall. Leadership in Cooperative Research Centers (CRCs) Principal Investigator: S. Bart Craig with Jennifer T. Lindberg (MS, psychology) Key Finding: By identifying the personal characteristics that enable leaders to adapt to the unique demands of the cooperative R&D setting and developing a yardstick that leaders can use to measure themselves against that standard, this project will facilitate ongoing improvement in the leadership of R&D endeavors. Objectives: This research constitutes a step toward enhancing the effectiveness of CRC directors by (1) identifying the unique demands placed on individuals in director roles, (2) identifying personality and behavioral characteristics of individuals that are associated with effectiveness in director roles, (3) creating a standardized feedback tool that directors can use for their own ongoing performance improvement, and (4) pilot testing the new tool by providing developmental feedback to directors participating in this research. Approach: This project is in the first year of a two year effort. Steps 1 and 2 involve qualitative data collection and analysis and constitute Phase 1. Steps 3 and 4 are quantitative in nature and constitute Phase 2. When complete, the feedback tool will be made freely available to CRC directors and other leaders in research and development (R&D) settings. Although the stated focus of this project is on leadership in CRCs, by identifying the features of the CRC setting that are shared and unshared with other leadership settings, this research will also contribute to our understanding of leadership more generally. Accomplishments: Currently this project is approximately 40% through Phase 1. Interview protocols for CRC constituents have been developed, along with an empirically derived short form of a commercial creativity climate scale (KEYS®), and data collection is currently in progress. Text Mining Chemistry Literature Principal Investigator: Catherine Blake with Nancy Baker, (PhD, School of Information and Library Science), Leo Cao, (PhD, SILS); Christopher Maier (MS, SILS), and Qi Zhang, (PhD, Computer Science) Key finding: The underlying infrastructure is on track to enable text mining in chemistry literature over the summer 2005. CERSP, Page 78 of 230 Research objectives: Enable scientists to incorporate useful but difficult to access published literature seamlessly into their discovery processes. Approach: This project is in the first year of a two year effort. Phase 1 (Year 1) – Conduct a user study to understand the existing discovery behaviors of CERSP scientists and the role that scientific literature plays during the innovation process. Identify gaps between existing text mining technologies and the needs of chemists and chemical engineers within the CERSP. Phase 2 (Year 2) – Explore the application of existing text mining technologies that were developed with medical literature to chemistry literature. Design and develop new text mining technologies, such as information extraction and synthesis such that they are consistent with existing CERSP discovery behaviors. Demonstrate approach by identifying connections between chemistry and medical literatures. Accomplishments: Contract signed with the American Chemistry Society to obtain access to full text journal articles. We met with the Center management team and refocused our study from barriers to adoption to the intersection between medical and chemistry literature, framed by nanotechnology. Instructional Review Board approves interview questions and methodology. American Chemistry Society articles (more than 100,000) loaded on disk. Pre-processing is underway. Analysis is on track to begin over summer. A Multivariate Analysis of Factors that Predict Graduate Student Satisfaction and Performance in Cooperative Research Centers Principal Investigators: Denis Gray with Jennifer Schneider (PhD, Psychology) Key finding: Since previous researchers have not examined the impact of center structure, mechanisms and procedures on outcomes reported by current graduate students, there is a huge need to examine these issues in a methodologically sound multivariate study. Research objectives: To identify center characteristics and training mechanisms that might explain positive graduate student outcomes; To develop and test a multivariate model that explains the impact of university, center, and individual factors on subjective and objective outcomes of graduate students involved in cooperative research centers. Approach: Providing an enhanced educational experience is one of the major rationales for developing and supporting cooperative research centers. However, the available literature has failed to examine graduate students while they are involved in a center. This study will use multivariate regression (logistic and OLS) to examine the extent to which university, center mechanisms (e.g., team-based; multidisciplinary) and personal characteristics CERSP, Page 79 of 230 predict graduate student subjective (e.g., satisfaction), and objective (e.g., career goals, scholarly productivity) outcomes. Accomplishments: A comprehensive review of the literature has been conducted that demonstrates that we know very little about the impact of various center characteristics on center students and that no multivariate studies of students have been done. Access to a sample of >800 graduate students involved in centers has been negotiated and email addresses have been provided on a significant number. Focus groups were conducted with some current students to identify key center characteristics. A draft web-based questionnaire instrument has been developed and will be administered late summer or early fall. This project is partially funded with NSF IUCRC Program funding. 2b. Plans for FY2006 Our current programs in the area of simulations and modeling will be concluded by the end of FY2005 as we have reached the point of diminishing returns in those areas. New areas of focus will include advanced proton exchange membrane fuel cells and particle printing. We also plan to continue our gravitation towards medicinal delivery systems. These new focus areas are related and take advantage of recent breakthroughs in Functional Materials and Devices and Nanostructures research. We continue to pursue our strategy of identifying areas where we can have greatest impact while maintaining focus on sustainability. Our social science research program will research the four social dimensions of the innovation process: knowledge exchange, leadership, education and diversity. These research projects will support our on-going programs in these same four areas. Learning how to improve in these four areas can contribute as much to advancing sustainable technology as the technical research itself. Projects for 2005-2006 are given in Table II below. Projects which have been or will be completed by November 2005 are shown in italics in the lower right quadrant of the table. Table II 2005-6 Technical Research Projects Macromolecular Synthesis and Engineering Nanostructures CERSP, Page 80 of 230 Leader: Roberts NCSU Polymerization in CO2 Metal catalyzed reduction of C-H Brookhart ^ Continuous homogenous polymerization Roberts Post-polymerization hydrogenation Roberts Thermodynamic measurements Kabadi Calorimetry of macromolecules in CO2 Kabadi H+ super-conductive materials DeSimone# Polymer processing Plasticization of FP at hi temp and press: NMR Samulski Swelling & crystallization of DB thin films Green Leader: Johnston UT-A Synthesis and stabilization Diffusion & electron transport Murray Polypeptide microemulsions Waters^ Polymer filled nanocomposites Khan Intercalation of polymers Samulski # Synthesis, stabiliz’n, and separation of nanocrystals Korgel Surfactants for nanoparticle assembly Rossky Thin film nano-crystal composites Green Self-Assembly Controlled self-assembly Velev Nano self-assembly patterned surfaces Johnston Nano self-assembly solid substrates Korgel Applications Particle PRINTing DeSimone # Colloidal crystals & porous templates Johnston Nanoparticles for high bioavailability Johnston Interfacial properties Johnston Separations Leader: Koros Georgia Tech Polymer synthesis for separations Ashby# High zeolite-polymer hybrid Koros# Zeolite-solvent-resistant poly hybrid Koros# Carbon-polymer Koros# Mesoporous ceramic membranes Ilias# CERSP, Page 81 of 230 Functional Materials and Devices Leader: Parsons NCSU Dry film processes Annealing of organic films Irene# Deposition of thin films Carbonell FMC in drug delivery Carbonell Anomalous swelling of thin films Sanchez Lithography New materials for imprint lithography^ Photochemical darkening at 193 nm Forbes^ Soft lithography DeSimone# Deposition Welding of polymers using CO2 Sanchez* Rheological studies of PVDF Khan* Kinetics of polymerization & precip. Rubinstein* CO2 treatments of organic films Irene Solution properties: SALLS, DLS QCM: deposition/dissolution rates Grant DeSimone* Optical methods to monitor dissolution Genzer Solution properties: Theory Rubinstein* Fuel Cells Processing photoresists Carbonell* Degradation processes Forbes# Molecular dynamics Berkowitz* CMP process studies Carbonell* Continuous polymerization of acrylic acid # New projects started in FY2005 Roberts* ^Projects redirected during FY2005 Colors indicate schools: UNC-CH, NCSU, UT-A, GaTech and NCA&T * Projects completed during FY2005 2005-6 Social Science Research Projects Leader Denis Gray Leadership Successful leadership qualities in NSF Centers—Craig # Leadership workshop^—Osmond Knowledge Exchange Factors affecting success or failure of industrial consortia--Gray Development of cross-disciplinary text mining tools—Blake # Colors indicate schools: UNC-CH, NCSU, and NCA&T Diversity HCBU/Research I cooperative research— Gray # Studies of African-American churches in outreach—Martin # EXPERT mentoring program—Bothun # Education Factors affecting student satisfaction in Centers--Gray # New projects started in FY2005 ^ Projects redirected during FY2005 Dielectric deposition Parsons Metal film deposition Parsons Reactive deposition of metal and ceramic K. Roberts Etching/dissolution Projects completed in 2005 CERSP, Page 82 of 230 CERSP, Page 83 of 230 III. EDUCATION Education at all levels is important to achieving our Center’s long-term vision. We extensively leverage existing programs and resources to increase impact, including K-12 programs at Science House and various outreach programs at all universities. We demonstrate to large numbers of K-12 students that hands-on science is fun. In addition we teach that sustainability is a serious issue that they can do something about. Societal “buy-in” is required for innovation, especially in generating the “pull” for green technology. Our intent is not only to recruit a new generation of scientists but to help educate a new generation of citizens regarding the environmental impact of modern society and the necessity of sustainability. And by participating in these “outreach” activities our students hone their own understanding and communication skills. There have been no significant changes to the educational objectives since the last report. 1a. Objectives Education Objectives • Improve the educational process at all levels to provide a new generation of students with technical and leadership tools to support and implement “green chemistry”. • Enhance K-12 students’ and teachers’ knowledge of science and engineering, the importance of collaboration and how these fields contribute to a cleaner environment, through curriculum development and teachers’ workshops. in order to build broad societal support needed for implementing sustainable processes Our goals fit into two categories: internal and external. We have three internal educational goals: 1. Prepare students broadly for successful careers in industry, academia and government. 2. Use outreach to K-12 students as a means to improve communication skills of our students. 3. Help students, faculty and scientists contribute to the Center’s immediate success by providing them opportunities to learn and practice a variety of strategies and skills. We have broadened focus of our personal development program from collaboration and innovation to leadership workshop. Leadership is a key factor in CERSP, Page 84 of 230 implementation. Understanding the innovation process and the social processes of research collaboration are key components of leadership. Improving leadership skills among students facilitates our current research, as well as providing long-term benefits. Further, to effect a “revolution in sustainable technology” will require a new generation of students. To overcome the “forces of status quo” our students will need not only the technological skills but the leadership skills (with the resultant courage, self-confidence and political sensitivity) to lead this revolution. Our external educational goals are to: • Help K-12 students and teachers learn about science and engineering, the importance of collaboration and how these fields contribute to a cleaner environment, mainly through curriculum development, student presentations, and teacher workshops. • Involve the faculty and students of the Center in K-12 education to recruit future scientists and engineers, and to enhance K-12 education. • Develop and disseminate curriculum materials related to Center research. • Plan and implement teacher workshops and student programs. 1b. Performance and Management Indicators Quantitative metrics include: • The number (and percentage) participation in our Personal Development Program • The numbers of undergraduate, graduate and post-doctoral associates advised • Number of student awards and presenting external papers • Number of students giving external papers and publishing in professional journals • Undergraduate internships and percentage of students attending graduate school • The number of training modules produced and disseminated • A database documenting impacted teachers and number of students • Written evaluations by teachers of curriculum materials and teacher workshops • Telephone interviews with teachers using curriculum materials • The number of CERSP students and faculty members involved in outreach • Documented performance improvements in Center students vs. non-Center peer group CERSP, Page 85 of 230 Progress toward our external educational objectives is being assessed by a systematic evaluation conducted by Dr. Sharon Schulze, Associate Director of The Science House. She is employing for evaluation a metrics table that includes work products, measurement questions, measurement indicators, work product verification, and a timeline. 1c. Problems There were no significant problems during this period. 2a. Internal Educational Activities Activity Name Led by Intended Audience Weekly Videoconference Seminars Marcus Donie, student leaders, and Tom Cox Students and faculty of the CERSP Approx Number of 40 per week (approximately 1500 total contacts) Attendees (if appl.) Highlight Details: Our weekly interactive videoconference sessions have continued as described previously. The number of student seminars remained at two seminars per session this year. Student and faculty participation has fallen about 20% this year. We will seek to restructure the seminar series next year as a means to reinvigorate it in 2006. Our original model (i.e., to use the series to facilitate collaboration) may be outdated as collaboration continues to flourish even as attendance declines. CERSP, Page 86 of 230 Activity Name Led by Intended Audience Innovation Seminar Prof. Denis Gray Students and faculty of the CERSP Approx Number ~50 persons per seminar (total of 200 reached including remote of Attendees viewers) Highlight: Details: Three nationally renowned speakers conducted seminars during FY2005. Our new “Entrepreneur” seminar was highly successful. Based upon informal feedback sought from students we changed the focus of the Innovation Seminar. Though past speakers were highly regarded in their fields, the vast majority of our technical students requested a more practical focus. A webbased seminar feedback questionnaire was implemented which indicated a very positive evaluation of this new focus. This focus and feedback mechanism is continuing to be used for all seminars. In response to feedback, the intended audience of our innovation seminar series has changed to focus more strongly on students. Goals of the seminar remain: to provide students and faculty involved in the center with an understanding of how the innovation process works, highlighting aspects of the process that are relevant to their experience; and stimulating interest in and discussion about innovation and its management. During FY2005 the Innovation Seminar Series included three nationally recognized speakers. The following presenters have presented during the current fiscal year: (1) Dr. Walt Plosila, Senior Researcher, Battelle, “Fueling Innovation: The Role of State S&T Initiatives”; (2) Dr. E.J. Woodhouse, Associate Professor RPI, “Political Barriers to the Greening of Chemistry” and (3) Dr. Mary Wyer, Psychology in the Public Interest, NC State U, “Myths and Realities of Women’s Participation in Science and Engineering: Is There a Problem and Why?” In addition a panel of three Center faculty members (Profs. DeSimone, Johnston, and Carbonell) discussed their CERSP, Page 87 of 230 entrepreneurial experiences in 10 widely differing types of innovations, from licensing technology to start ups. Based upon attendance and audience participation, this was the most popular seminar in the five-year history of the series. The seminar series is jointly sponsored and coordinated by CERSP, Center for Innovation Management Studies (CIMS) and the Kenan Institute for Engineering and Science. A steering committee of representatives from these organizations led by Denis Gray has been formed to plan and implement the series. Activity Name Led by Intended Audience Approx Number of Attendees (if appl.) Highlight: Collaboration Workshop Dr. Russ Osmond Students of the CERSP ~50 persons from NC State, UNC-CH, and NC A&T State University Dr. Russ Osmond presented four seminars on improving leadership skills, primarily through improved communications. CERSP, Page 88 of 230 Details: This workshop has evolved from a “one-time experience” to an ongoing learning experience, and from one focused entirely on communication to one focused on leadership. Leadership is a key factor in implementation. Understanding the innovation process and the social processes of research collaboration are key components of leadership. Improving leadership skills from students to the Director facilitates our current research, as well as providing long-term benefits. Further, to effect a “revolution in sustainable technology” will require a new generation of students. To overcome the “forces of status quo” our students will need not only the technological skills but the leadership skills (with the resultant courage, self-confidence and political sensitivity) to lead this revolution. This year we focused strongly on students enrolled in the EXPERT program at NC A&T. Two sessions were conducted there and A&T students were transported to participate directly in a third session. We continue to give students questionnaires to complete prior to the workshop in order to provide guidance as to their “thinking styles”. In addition to the main workshop session, follow-up sessions are conducted periodically. Moreover, we are working to get all of the course material onto our website, as was started last year. Surveys of students continue to indicate that they enjoy the workshop and thought it was valuable. We anticipate continuing the transition from (only) to leadership as the workshop focus, expand participation, and to make as much of possible available in a “self-teaching” format utility. communication to continue to the material as to increase its CERSP, Page 89 of 230 Workshop Leadership Schedule Level of abstraction Theory Phase l (Fall) Content Introduction to model (focus on individual) All new students Implementation Application Phase III (Spring) Scientific leadership (getting things done) Phase II (Winter) Making the connection (meetings) (focus on teams) Targets Research groups (practice skills) Prospective graduates CERSP Summer Interns at UNC-CH and NC State *EXPERT Student from NCA&T (see below for description of EXPERT program). Interns participated in the following supplementary program activities: 1. Orientation 2. Welcoming Luncheon 3. Laboratory Safety 4. Entrepreneurs’ Round Table 5. Collaboration Workshop 6. Graduate School Seminar 7. Weekly Videoconference Group Meetings 8. Tour of DuPont Fayetteville Works Plant 9. Exit Interviews 10. Oral presentations CERSP, Page 90 of 230 Our summer program continues to expand in program activities as well as diversity of students. The class of 2004 attracted 6 interns from underrepresented groups (URG) while the current class attracted 8 URG interns. CERSP utilizes two main mechanisms to attract interns: • Solicit interns from EXPERT program (a pilot program developed by CERSP for underrepresented undergraduates in mechanical and chemical engineering department of NC A&T) • Leverage existing programs in order to nationally reach high school and undergraduate students: o SPGRE program sponsored by Prof. Henry Frierson at UNC-CH No. Last First Faculty Mentor Student Mentor Locatio n Class (http://www.unc.edu/depts/res/spgre.htm) and the related Research Education Support (RES) Program (http://www.ibiblio.org/res/); o Project SEED (http://www.projectseed.org/) at UNC-CH (focusing on African-American high school students); o NSF STC Undergraduate Research Coordination program (http://www.cens.ucla.edu/stcure/index.html). Approximately half of the students supported this summer were EXPERT students (six of the eleven interns). In addition, one SPGRE student, two UNC undergraduate, and two high school students were supported. This narrow program selection criterion afforded us the largest pool of competitive underrepresented students while allowing us to maintain a high quality research and career development program for the interns. Activities were similar those offered in 2004 with the addition of DuPont tour, collaboration workshop, and expanded versions of Entrepreneurship and Graduate School seminars.Below is a table that indicates the names of the summer interns, faculty mentor, student mentor, location within CERSP partner sites, and classification of intern (funding source/status). CERSP, Page 91 of 230 1 2 3 4 5 6 7 8 9 10 11 *Alford, *Collins, DeLeon, Jonathan Candis David DeSimone Philip , *Morehea d, *Mvula, Jones *Paul, Portnow, Redden, West, Vincent Oscar Derek. Evan M. Lauren Jacina Kyle Sergei Sheiko Christine Grant Joseph DeSimone Joseph DeSimone George Roberts Ruben Carbonell John van Zanten Joseph DeSimone Joseph DeSimone Joseph DeSimone Joseph DeSimone Jamie Boyce Yazan Hussain Junhoe Cha Ben Maynor Nathaniel Cain & Laura Beth Dong Alan Chang UNC NCSU UNC UNC NCSU NCSU CERSP/Undergr ad. CERSP/Undergr ad. CERSP/Undergr ad. Other/High School CERSP/Undergr ad. CERSP/Undergr ad. CERSP/Undergr ad. CERSP/Undergr ad. ONR/Undergrad. SPGRE/Undergr ad. DuPont/High School Shaun Tanner NCSU and Chris Kloxin Larken Euliss Jason Yarbrough Jennifer Kelly Zhilian Zhou UNC UNC UNC UNC Exit interviews were held with nine of the eleven summer interns at UNC-CH and NCState. A summary of comments is given in the following table. Ninety percent of the students said that the experience interested them in graduate school for the first time or reinforced their interest. CERSP, Page 92 of 230 Table IIIA Exit Interview Summary Summer 2005 Administrative issues o Salary and related issues not explained adequately o No food in dorms the first week or on weekends, an unanticipated expense o Parking is expensive; can we provide or recommend options? o They claim they did not receive abstracts of videoconferences beforehand; are they on our normal distribution list? Orientation Good. Might include more about the STC and website Lab and safety video Very good. Having mentors (in most cases more than one) very useful Entrepreneurship o Excellent. Even those not interested in doing it themselves were interested to see how things work o Having it early was good as it put into context a lot of what was going on. Collaboration workshop Excellent. This was the highest rated part of the program. Everyone liked it. Graduate school seminar Mixed. Some, mostly A&T and similar, found it very useful. Others felt like they knew most of what was covered; e.g., “life as a grad student” was redundant as they were living with grad students all summer. Some felt it was too specific to NCSU; others, that it was too long and detailed. DuPont tour Mixed. Most felt that it was interesting but too short for the time required to get there. Would like to have seen more of the plant, less on safety. Periodic group meetings o Very good. Those who had these felt they were more worthwhile for them than Thursday videoconferences. o Enjoyed seeing how Joe “operates” Thursday CERSP o Poor. Most felt they were a waste of time. Would rather spend the time in the lab. They did not have the background to understand content. o Perhaps should make these optional, perhaps requiring only when someone from intern’s lab is speaking. General comments o Probably not appropriate for high school (at least at rising junior level) • Starts too early (they’re still in school) • Don’t have the background o Interest in graduate school increased for undergrads • Confirmed interest for those unsure • Initiated interest for some who had not considered it o Should consider extending to ten weeks as eight weeks is too little time to complete lab project with all of the external activities o Mentors were excellent! CERSP, Page 93 of 230 A summer intern from the class of 2004, Desmond Harvey, presented his CERSP funded research at the Historically Black Colleges and Universities Undergraduate Program's (HBCU-UP) 2005 National Research Conference in New Orleans, Louisiana February 10-13, 2005. The conference was sponsored by Southern University at New Orleans Program for Excellence in Science, Mathematics, and Computer Technology and the National Science Foundation. Desmond placed third overall in the Chemistry category. A new REU proposal was submitted by CERSP partner, NC State University, but the proposal was not awarded. The Environmental Chemistry Laboratory Manual for Undergraduates has been put on hold for a while since our lead partner at Villanova University has recently accepted a temporary position as Program Officer of Inorganics, Bioinorganics and Organo-metallics (IBO) at the National Science Foundation. EXPERT Program The EXperimental Program for Education through Research & Training (EXPERT) is a multiyear, multidisciplinary undergraduate research and development program offered by CERSP through the Mechanical & Chemical Engineering Department at NCA&T. EXPERT is directed by Dr. Geoff Bothun (an NSF Discovery Corp Postdoctoral Fellow); in addition, the CERSP manage-ment team and NC A&T faculty also provide input and guidance. Focusing on green chemistry and engineering, EXPERT aims to (i) improve the research experience for undergraduates, (ii) enhance the skills of future scientists and engineers, and (iii) promote diversity in science and technology. A primary goal is to increase the number of students from underrepresented groups seeking graduate education in science and engineering. EXPERT began Fall 04 and recently completed its first academic year. Twenty-two students were provided scholarships through CERSP: 8 freshman ($1000/yr), 9 sophomores ($1000/yr), 3 juniors ($3600/yr), and 2 seniors ($4000/yr) of which 8 are female and 20 are African American. The success of EXPERT has been utilized by the College of Engineering and Chemical Engineering program at NC A&T as a recruiting tool for Fall 05. 1. Coordinating EXPERT (04-05): a. Students met on a biweekly basis to take part in development workshops and seminars. i. Guide to acing chemistry ii. Graduate school workshop (partnered with NC-LSAMP) iii. Online lab training and research ethics (NCSU) CERSP, Page 94 of 230 iv. Internship/job searching seminar (NC A&T Career Services) v. Entrepreneurial seminar (Prof. Joseph DeSimone) vi. K-12 CERSP outreach training (Dr. Mary Louise Bellamy, NCSU) vii. Two CERSP collaboration workshops viii. Technical communication seminar b. Identified summer research and internship programs – all 18 eligible EXPERT students are participating in rewarding research or internship programs, with 6 students awarded CERSP summer internships. c. EDSTAR (Raleigh, NC) was selected to evaluate EXPERT and the DCF postdoctoral position. Funding provided by DCF grant. i. Analyst attended EXPERT meetings and interviewed Bothun ii. Student evaluations given 12/04 and 4/05 1. High student satisfaction as of 12/04 with suggestions for more community outreach and research seminars iii. Formal analysis for 04-05 academic year currently being prepared 2. Mentoring (04-05): a. Upperclassmen research projects i. 5 juniors and seniors (2-Bothun/Ilias; 2-Kabadi; 1-Lou) ii. 2 juniors mentored by Bothun/Ilias were co-supervised by a graduate student b. Recruiting i. 6 offer letters sent to incoming freshman for Fall 05. All 6 accepted the offer and plan to attend NC A&T ii. An outstanding incoming sophomore was added for Fall 05 c. Cascading mentoring program implemented Spring 05 i. NC A&T faculty ® graduate students ® juniors and senior research assistants ® freshman and sophomores (high school to be added for 06) ii. EXPERT director serves as “overall mentor” iii. Additional advisor/student meetings to expose juniors and seniors to a collaborative research group atmosphere and to discuss and share results iv. Students were informed of what mentoring involves, how a mentoring relationship should be perceived, and how to mentor v. Significant focus will be given Fall 05 to better facilitate this program CERSP, Page 95 of 230 3. Research involving EXPERT students (04-05): a. Membrane research projects (Bothun/Ilias in collaboration with Koros) i. Organic solvent permeation through ceramic membranes ii. Liquid and supercritical CO2 transport through ceramic membranes: Hydration and co-solvent effects iii. Selective particle removal from liquid and supercritical CO2 b. Thermodynamic research projects i. Phase equilibria in CO2-alkanol amine systems (Kabadi) ii. Phase equilibria for semiconductor dehydration with CO2 and co-solvents (Kabadi/Bothun in collaboration with Carbonell) iii. Thermophysical enzyme properties in supercritical CO2 (Bothun/Kabadi/Roberts) c. Polymer degradation project (Lou) The one area in which we are not pleased is retention of freshmen. Of the 22 students for the 04-05 academic year, 4 freshman failed to meet academic standards and were removed from EXPERT; and 1 senior graduated (17 continuing in Fall 05). On the other hand, 100% of qualifying EXPERT students had summer research or other professional preparatory experiences. Four have industrial internships and the rest are doing research at Harvard, Virginia Tech, UNC-CH, NC State and NC A&T. Production of Students A primary output of the Center is its students. The following table summarizes placement of students who graduated during FY2005. Details are provided in Section VIII.3. Six MS degrees were completed; average time to completion was between two and three years. Three of the six MS graduates have entered PhD programs; one, to industry; one, to the US Patent Office; and one, to high school teaching. There were 14 PhD degrees granted. Average time to completion was less than five years. Seven PhD graduates entered industrial research; one, a research institute; one, a government position; and five post-docs (all foreign students). Of eight post doctoral associates completing their tenures, five went on become university professors; and three, to industrial positions. Thirty-eight percent of students—including BS, MS and PhD—were seeking additional training (72% of those seeking additional training are foreign students). Of PhDs recipients, 57% were US citizens, while 67% of MS and 38% of post docs were US citizens. Overall 59% of all those leaving were US citizens. Center Graduate Placement CERSP, Page 96 of 230 Category Unknown Industry Gov't Undergrad MS PhD Post-Doc Totals 2 2 1 1 7 3 12 1 1 2 Res. Inst. 1 1 Add'l Deg. 1 3* 5* 9 Academia Total %US 1# 5 6 4 6 14 8 32 100 67 57 38 59 * 7 of 8 foreign MS and PhD graduates went on to higher education in the US # hi school 2b. Professional Development Activities Examples of professional development activities include: • All graduate students third-year and above and post-doctoral associates gave • • • • • presentations at Center-wide videoconference seminars, nominally once per nine months. There were a total of 71 student presentations. Six different students served to organize, coordinate and conduct the abovementioned videoconference seminars. Students and post-doctoral associates participated in the Innovation Seminar Series and in safety training and seminar delivery skills conducted by the CERSP Fifty-two students and five faculty members at UNC-CH, NCA&T and NC State U participated in Collaboration Workshops.Thirty-two students and postdoctoral associates gave 52 presentations at 19 different professional conferences. Nine students presented talks at our annual NSF site visit October 5, 2004 and 36 presented posters. Sixty-one students co-authored 76 peer-reviewed papers or book chapters.Four students presented at the Separations Research Program at UT-Austin. CERSP, Page 97 of 230 • Most of our graduate students assisted in mentoring our 43 undergraduate interns Students are encouraged to participate in professional conferences, but are required to present papers or posters if travel to the conference is involved. All of these activities serve to advance the objectives of the Center. As students improve their communication skills, weekly seminars become more productive. As they develop organizational skills, as through leading the seminars, they relieve administrative burden on the faculty. Most importantly, the quality of students produced by the Center is improved as their skill set is developed. Students are strongly encouraged to participate in K-12 outreach our program either via classroom demonstrations, speaking at existing venues or mentoring teachers in Environmental Science workshops. This experience has been shown to be beneficial professionally. Not all participate, but those who do generally find it to be rewarding on several levels. 2c. External Educational Activities In the past year the Center carried out a coordinated K-12 education outreach program. Through teacher workshops and student presentations and demonstrations, this program directly reached 533 teachers and ~1700 students in North Carolina and Texas. Our second Environmental Science laboratory manual was developed initially to focus on middle school teachers and students. Many of the labs in the manual, however, are also appropriate for elementary school teachers and students. Consequently, this past year our workshops in North Carolina and Texas targeted both middle school and elementary school science teachers. Through distribution of exemplary learning materials, this program continues to reach indirectly an estimated 1,000 teachers and 160,000 students per year in these states. Among the exemplary learning materials being distributed are Environmental Science laboratory books for both high school and middle school grades, aligned with the North Carolina and Texas state science curricula. Over 4500 of these lab manuals have been distributed to date. The Science House continued to provide training to CERSP scientists to use and conduct classroom visits with its kits for hands-on science demonstrations, “Fun with Polymers!” and “Fun with Carbon Dioxide!” Center faculty and staff participated in numerous teacher and student programs. CERSP, Page 98 of 230 Through the distribution of educational materials, teacher training programs, an updated educational web site, and a new electronic newsletter for teachers and students, the Center K-12 outreach is achieving national visibility. The Center has partnered with several other education and service organizations to increase its reach and, especially, to increase access to students from underrepresented groups. The CERSP K-12 outreach program extends far beyond the bounds of the CERSP faculty, staff, and students. Numerous teachers from other states attend our presentations at educational meetings and use our web site. We collaborated with five non-CERSP education organizations, including two non-CERSP HBCU’s. Our efforts supported several other programs such as the NCSU SATELLITE camp for high school students from rural schools. We have conducted teacher workshops from Edenton, North Carolina, to El Paso, Texas. Progress on New K-12 Education Initiatives From July 1, 2004 through June 30, 2005, the K-12 Program has made significant progress on its new educational initiatives, some of which were described briefly in the 2004 annual report to NSF. Each of these initiatives is listed below, and progress that has been made is detailed. We plan to continue all of these new initiatives during 2005-2006, as well as continue our ongoing education work, described elsewhere in this report. Make significant progress toward the development of Volume II of the high school lab manual: Ten laboratory activities have been chosen for the new high school lab manual from several different sources, including Project WET, Bottle Biology/Wisconsin FAST Plants, The National Association of Biology Teachers (NABT), and SEPUP (Lab-Aids, Inc.). Formal permission to reprint these activities has already been obtained from three of our sources. The targeted publication date is December 2005. Work has begun on correlating these labs with the revised 2004 North Carolina Science Standard Course of Study (SCOS). A new feature of Volume II of the high school manual is the correlation of these labs with the state math curricula for North Carolina and Texas, as well as the state science curricula. An example of how one of these new activities will be correlated with the North Carolina Mathematics Standard Course of Study (SCOS) is described in Table IIIB. CERSP, Page 99 of 230 Table IIIB. So Much Depends On So Little Math Extensions - Possible Answers Feeding the World We cut the apple down to 1/32 of its volume. Assuming the apple is a sphere, is the surface area we peeled 1/32 of the surface area of the apple? Justify your answer. Yes. Justification can be provided by a logical argument or by use of the equations for surface area of a sphere and surface area of a spherical lune. Look up the volume of the Earth. Assume the Earth is a perfect sphere. Following our model, calculate how many square meters of the Earth's soil can be used to produce food. Approximations will vary. o Earth Volume: 1,086,230,340,743,040,000,000 cubic meters o Earth Radius: 6,378,000 meters o Usable soil: 15,966,461,970,000 square meters Research how much land is required to raise food for one person for a year. Also research the current population and population predictions. Research will vary. It is recommended that population statistics be gained from the Census Bureau (Currently approximately 6,486,882,948 people). An article which would also be interesting for students to read with respect to this issue is "The shrinking salad bowl: Houses and malls becoming the fastest-growing crop in California" by Debora K. Rich. This article can be found online at http://www.energybulletin.net. The following conversion may be helpful: 1 acre = 4,047 square meters. Draw conclusions about feeding the Earth's population based on your answers in problem 2 and 3. Answers will vary. If everyone ate as Americans did then the Earth would already have trouble sustaining the population. The predicted growth in population will require more land for growing crops. Resource Reliability Read "Timely Topics: Our Food is Grown on How Much Soil". This activity is the same as the one done in class. However, this particular write up has two mistakes. The first mistake occurred only once but the second mistake occurred more than once in this paper. What mistakes did Ms. Harper make? What changes should she make to her paper? People often misinterpret information. Facts must be correctly used to remain facts. You should always read with your brain, especially when the reliability of the resource is unknown. Ms. Harper made a mistake when listing her current world population. The population is off by a factor of 10. In other words, she has the population listed as being in the ten billions rather than the billions. Ms. Harper forgets that only one quarter of the original orange represents land. The rest is water. Thus instead of 1/8 the land being deserts, swamps, mountains, the Antarctic and Arctic, she should say that 1/2 of the land makes up deserts, swamps, mountains, and the Antarctic and Arctic. Additionally it should say that the other 1/2 of land represents where people live. The other time she makes this mistake is in the last bullet. She says that 3% of this land is able to grow food. Rather it should say 12.5% (1/8) of the land is able to grow food. It must be noted that Ms. Harper could be using "land" to mean "the Earth's surface". If so, perhaps she should reevaluate her word choice. CERSP, Page 100 of 230 Upgrade website: A web site has been developed that is devoted exclusively to the Center’s K-12 outreach activities. All Center-related teacher workshops, educational publications, and other educational initiatives are being advertised on this web page. This page includes links to various carbon dioxide related educational materials. Teachers can easily access activities that use CO2 in the classroom. Correlations have been made between these CO2 activities and National Science Education Standards, and the state science curricula for North Carolina and Texas. These correlations have been placed on the web site; they make the activities more useful for teachers across the country, as well as those in North Carolina and Texas. Julie Beier, a Center graduate student, has worked this past year with The Science House staff members to expand the web site and make it more user friendly for K-12 teachers across the country. Our new CERSP K-12 initiative, “Focus on A Scientist” electronic newsletter was placed on the new web site in January of 2005. Ms. Beier has completed most of the pages for the revised CERSP K-12 web site, which can be viewed at [http://www.science-house.org/CO2]. The following statistics have been gathered on the use of the new web site from an online web site data summary: The total number of “hits” per month to the CERSP K-12 web site has increased remarkably as shown in the following figure. 100,000 80,000 60,000 40,000 20,000 0 Dec Feb Apr The increase in use from December 2004 through May 2005 is most likely attributable to several factors: (1) The updated website went “online” at the end of January 2005. (2) Also at the end of January 2005, the first issue of the “Focus on A Scientist” Newsletter was mailed electronically to teachers in North Carolina and Texas. The newsletter refers them to the CERSP K-12 web site, where they can learn more information about Sustainable Technology, CERSP scientists, and CERSP, Page 101 of 230 classroom activities. (3) This website is more “user friendly” for teachers, and is being advertised well. (4) The CERSP summer 2005 workshop registration forms went online at the end of January, and more teachers registered electronically on our website this year than last year. (Note: Even after all of the summer workshops were listed on the web site as “full” in April 2005, and online registration decreased dramatically, the number of hits per month continued to increase. The increase in hits from January through May 2005 cannot, therefore, be attributed solely to online workshop registration.) Continue the development of an original book of inquiry based K-12 activities to be published initially in serial form as an electronic newsletter and placed on the web site: The new CERSP “Focus on A Scientist” project was initiated by e-mailing two electronic to K-12 teachers in North Carolina and Texas. More newsletters are being developed. The two newsletters that have been e-mailed include interviews with two CERSP scientists, a hands-on activity helping students understand concepts related to the research of these scientists, and information about careers in chemistry and chemical education. The newsletters can be viewed at [http://www.science-house.org/CO2/meetsci/focus/], and brief descriptions are as follows: Meet A Chemist: Dr. Devin Flowers: Football Player Becomes A Chemist! Activity: Fun with Polymers! Meet A Chemical Engineer: Ms. Joan Patterson: She’s Making Recycling Better for the Environment! Activity: Recycling by the Numbers! Educators from all over the country have begun subscribing to the newsletters, giving the CERSP K-12 program even more national visibility. These newsletters, which include pictures of CERSP scientists and information about salaries for chemists and engineers, have apparently met an important need among educators accessing the web site. For example, during March, April, and May 2005, the search string “scientist pictures” has been the most frequently listed search string, based on our online web site data summary. The search string “salaries of chemists” is frequently listed, also. Conduct distance-learning workshops for K-12 teachers: So far, our attempts since May 2002 to conduct a distance learning workshop have been unsuccessful. We have worked with the North Carolina School of Science and Mathematics (NCSSM) in Durham, NC, to set up workshops that would be broadcast from that site. One was scheduled for early 2004 with teachers in Cape Hatteras, North Carolina, and was canceled because of an ice storm. Advertising of other workshops from the NCSSM site have been unsuccessful, with very low registration. CERSP, Page 102 of 230 Next school year, we will consider the feasibility of conducting distance learning workshops in conjunction with The Science House Satellite Office in Asheville, North Carolina. Lindsay Moody is Outreach Coordinator for that site, has a strong background in environmental science, and is in close contact with science teachers in that vicinity. Since we have had requests on some of our written teacher evaluation forms from summer workshops to conduct teacher workshops in the Western region of the state, this plan may very well satisfy an important need for teachers in Western North Carolina. Expand plans to conduct workshops for K-12 teachers in conjunction with Historically Black Colleges and Universities in North Carolina: In December 2003, CERSP partnered with the Environmental Resource Program (ERP) of the University of North Carolina at Chapel Hill and the NC Math Science Education Network (NC-MSEN) Pre-College Program at Elizabeth City State University (ECSU) to write a grant proposal to the Z. Smith Reynolds Foundation. The proposal, “Partnering to Bring Environmental Science Education Resources to Teachers in Low-Wealth Eastern NC Communities”, was funded and work began in early 2004 to implement the proposal. Hands-on environmental science workshops were conducted for teachers at ECSU and The Science House Eastern Satellite Office on the following dates: July 6-8, 2004 September 25, 2004 January 3, 2005 March 12, 2005 One of the summer 2005 CERSP teacher workshops is being hosted by Fayetteville State University (FSU) on June 28-30, 2005. Ms. Clararene Glover, Acting Director of the FSU Math/Science Education Center, has worked closely with Mary Louise Bellamy to arrange details. Dennis Johnson, Outreach Coordinator for The Science House Satellite Office in Fayetteville, has helped advertise the workshop among teachers with whom he works. One of the advantages of a partnership with FSU is that DuPont, located in Fayetteville, is using CERSP technology to manufacture Teflon• in a more environmentally friendly way than it has been made traditionally. Workshop participants will learn about this technology, as well as how to arrange field trips for students to DuPont during the school year. Guest university teaching to pre-service K-12 science teachers: Mary Louise Bellamy, Jamila Simpson, and Julie Beier guest taught two classes in the UNC Chapel Hill Department of Education on October 21 and 22, 2004. Pre-service CERSP, Page 103 of 230 K-5 teachers – undergraduates preparing to teach elementary students – in these classes participated in several CERSP labs, including one from each of the demonstration kits. CERSP chemistry graduate students from UNC Chapel Hill, Jennifer Kelly, and Ji Guo, were also involved in this effort. They observed and assisted in order to learn to conduct the classroom kit activities. Professional Involvement and Recognition Members of the CERSP K-12 program are very concerned with state and national issues in science education. Through the professional involvement listed below, we are working at a level on which we are able to have a positive impact on K-12 education at the state and national levels. Jamila Simpson, CERSP K-12 Graduate Research Assistant, won a nationally competitive scholarship, “The National Association for Research in Science Teaching (NARST) Equity and Ethics Committee Scholarship,” to attend the annual meeting of the National Association for Research in Science Teaching, held in Dallas, Texas in April 2005. Jamila Simpson is a member of NARST and a member of the North Carolina Science Teachers Association (NCSTA). Julie Beier, CERSP K-12 Graduate Research Assistant, won a scholarship and attended the American Chemical Society (ACS) Petroleum Research Fund Summer School on Green Chemistry on July 31 – August 7, 2004, in Philadelphia, Pennsylvania. She presented a poster on CERSP K-12 work. Julie Beier co-authored a paper, along with some of the other participants in the ACS 2004 Summer School in Green Chemistry. This paper, “Green Challenges: Student Perspectives from the 2004 ACS-PRF Summer School on Green Chemistry”, was accepted for publication by the journal Green Chemistry in April 2004. Mary Louise Bellamy serves as a board member of the National Science Education Leadership Association (NSELA), serving as Director of Region C. Through her connections with other national leaders in science education who serve on this board, she has successfully advertised the CERSP “Focus on A Scientist” newsletter in several states. Mary Louise Bellamy is a board member of the North Carolina Science Leadership Association (NCSLA). Since 2003, she has served as a District Director, and she was recently elected President-Elect of the organization. In the spring of 2005, Mary Louise Bellamy was named an Outstanding Extension Service Award Recipient for the College of Physical and Mathematical Sciences (PAMS) at NC State University. CERSP, Page 104 of 230 In the spring of 2005, Mary Louise Bellamy was inducted into the Academy of Outstanding Faculty Engaged in Extension (AOFEE) at NC State University. Mary Louise Bellamy served on an NSF GK-12 proposal review panel at NSF in Arlington, VA on August 5-6, 2004. Mary Louise Bellamy attended the Fourth NSF Research Centers Educators Network (NRCEN) conference in Pasadena, California on April 6-9, 2005. The conference theme was Broadening the Impact of NRCEN/ Internal Collaboration to Enhance External Engagement. An important outcome of the meeting was a plan to set up a web site for interaction among NRCEN members throughout the year. David Haase was elected Vice-Chair of the Executive Committee of the Forum on Education of the American Physical Society. Progress on Ongoing K-12 Education Activities Members of the CERSP K-12 program continue the work that was initiated during the previous years of the grant. Some highlights of this ongoing work are listed below and detailed in the charts that follow. Presentations at National and State Science Teacher Conferences: Mary Louise Bellamy presented a teacher workshop at the 2005 National Science Teachers Association (NSTA) annual conference in Dallas, Texas based on labs in the CERSP middle school lab manual. Even though the workshop was at 5:00 p.m. on Thursday afternoon, over 100 teachers from many regions of the country attended, many having to sit on the floor! CERSP again co-sponsored the 2005 Expanding Your Horizons (EYH) Conference, along with the Howard Hughes Medical Institute. The conference is hosted each year by North Carolina State University (NCSU), and is designed to encourage seventh grade girls in North Carolina to pursue mathematics, science, and engineering as careers. Approximately 439 students, teachers, and chaperones from across the state attended EYH this year. Teacher workshops are held at the state and national levels. Three-day, hands-on workshops are held each summer at three different sites in North Carolina so as to reach as many teachers in the state as possible. CERSP scientists and K-12 staff members continue to visit schools and host field trips for K-12 teachers and students in North Carolina and Texas. These events usually include hands-on activities and demonstrations from the two CERSP Demonstration Kits, “CO2 in the Classroom!” and “Fun with Polymers!” CERSP, Page 105 of 230 Activity Name Led by Intended Audience Teacher Workshops Based on the Middle School Environmental Science Manual Mary Louise Bellamy Middle school, elementary school, and high school science teachers (Note: Those workshops that are starred (*) were for preservice elementary teachers. They represent CERSP guest teaching for the UNC Chapel Hill Department of Education.) 402 teachers (directly) Train teachers in the basics of environmental science and prepare them to teach middle, elementary, and high school science using the Middle School Environmental Science Laboratory Manual developed by The Science House, and the CERSP Polymer and Carbon Dioxide Demonstration Kits A series of workshops and presentations based on the middle school lab manual, published during a previous reporting period, and CERSP demonstration kits, is being implemented for middle, elementary, and high school science teachers in North Carolina and Texas. Each workshop participant receives a free copy of the lab manual. Workshops conducted during this reporting period are as follows: Approx Number reached Objective Details Activity Name Z. Smith Reynolds Led By Intended Audience Location Date( s) Numbe r of Teache rs Attendi ng Mary Louise High school Elizabeth City Bellamy, Michele science State University 7/6/04 throug 20 CERSP, Page 106 of 230 Environment al Science Workshop Hands-On Environment al Science Z. Smith Reynolds Environment al Science Follow-Up Workshop Kloda, Robin Joyner, Julie Beier, Jamila Simpson, Colleen Karl, Judy Day Mary Louise Bellamy, Jamila Simpson, Julie Beier, Ken Roberts, Geoff Bothun, Michele Kloda Mary Louise Bellamy, Jamila Simpson, Michele Kloda, Robin Joyner, Colleen Karl teachers (ECSU); Elizabeth City, NC; The Science House Eastern Satellite Office; Edenton, NC h 7/8/04 Middle and Elementary school teachers Hairston Middle School; Greensboro, NC 7/20/0 4 throug h 7/22/0 4 12 Hands-On Environment al Science Emily BuchHague, Mary Louise Bellamy Fun with CO2 Mary Louise and Polymers! Bellamy Mary Louise Bellamy, Jamila * Hands-On Environment Simpson, Jennifer Kelly al Science * Hands-On Environment al Science Hands-On Mary Louise Bellamy, Julie Beier, Ji Guo Mary Louise Elizabeth City High school State University science (ECSU); Elizabeth teachers City, NC El Paso Middle and Independent Elementary School District, Isleta Independent school School District, science Texas teachers Elementary Delta Kappa , Middle, and High Gamma Meeting; NC School of school Science & Math; science Durham, NC teachers Elementary UNC Chapel Hill pre-service Department of Education; Chapel science Hill, NC teachers Elementary UNC Chapel Hill pre-service Department of Education; Chapel science Hill, NC teachers Middle and Science Teachers 9/25/0 4 24 10/9/0 4 60 10/23/ 04 10 10/21/ 04 19 10/22/ 04 23 11/04/ 32 CERSP, Page 107 of 230 Environment al Science Bellamy Elementary school science teachers Hands-On Environment al Science Z. Smith Reynolds Environment al Science Follow-Up Workshop Z. Smith Reynolds Environment al Science Follow-Up Workshop Mary Louise Bellamy Middle and Elementary school science teachers Association of Texas (STAT) annual CAST convention; Corpus Christi, Texas North Carolina Science Teachers Association (NCSTA) annual convention; Greensboro, NC 04 11/11/ 04 34 Hands-On Environment al Science Hands-On Environment al Science Hands-On Environment al Science Michele Kloda, Colleen Karl Mary Louise Bellamy, Michele Kloda, Julie Beier, Jamila High school Simpson, science Colleen Karl teachers Elementary , Middle, and High school Mary Louise Bellamy, Colleen science teachers Karl Middle and Mary Louise Bellamy, Jamila Elementary school Simpson, Julie science Beier, Michele teachers Kloda Middle and Mary Louise Bellamy, Jamila Elementary school Simpson, Julie science Beier, Michele teachers Kloda, Joe High school Bertie County High science School; Bertie teachers County, NC 1/3/05 10 Elizabeth City State University (ECSU); Elizabeth City, NC National Science Teachers Association (NSTA) annual convention; Dallas, Texas The Science House, NCSU; Raleigh, NC Fayetteville State University (FSU); Fayetteville, NC 3/12/0 5 10 3/31/0 5 100 6/7/05 throug h 6/9/05 24 6/28/0 5 throug h 6/30/0 24 CERSP, Page 108 of 230 DeSimone, Ev Baucom 5 Activity Name Carbon Dioxide Demonstration Kit, Polymer Demonstration Kit, CERSP lab manual activity presentations, and other science demonstrations Mary Louise Bellamy K-12 students and teachers 1211 students, 46 teachers Develop educational materials to be used to help teachers (1) explain and demonstrate the relevance of carbon dioxide and polymers to students, and (2) understand environmental problems and possible solutions to these problems. A Carbon Dioxide (CO2) Demonstration Kit, produced by The Science House staff, has been available on four* CERSP campuses since early 2002. The kit includes demonstrations that make CO2 interesting and relevant to the lives of K-12 students. A Polymer Demonstration Kit was also developed and produced by The Science House staff and distributed to four* of the CERSP campuses. The kit includes demonstrations that make polymers interesting and relevant to the lives of K-12 students. Center students and staff have taken the CO2 Kit and the Polymer Kit to the following locations and presented them before the numbers of students and teachers listed in the table below.** In addition, some activities from the CERSP high school and middle school lab manuals are now being done by CERSP K-12 staff members with K-12 students. These numbers are also included in the table below. * In 2004, electronic copies of the activities in the two demonstration kits were also distributed to the fifth and newest CERSP campus, The Georgia Institute of Technology. ** Brief descriptions of some of the science presentations Led by Intended Audience Approx Number of Attendees Objective Details CERSP, Page 109 of 230 conducted by Texas CERSP scientists can be found after this table. Some of these include excellent science activities not found in the CERSP Demonstration Kits. Activity Name Led By Mary Louise Bellamy, Jamila Simpson, Julie Beier Jamila Simpson Julie Beier, Sharon Schulze Ken Roberts, Leo Broadney Ken Roberts Ken Roberts Mary Louise Bellamy, Julie Beier, Jamila Simpson Intended Audience Location Frankin Elementar Elementary School visited The y school Science House; students NCSU; Raleigh, and teachers NC Method Elementar Community Church; Raleigh, y school NC students Elementar y school students Middle school students Middle school students Middle school students Middle school students St. Timothy’s School; Raleigh, NC Jackson Middle School; Greensboro, NC Guilford Middle School; Greensboro, NC Aycock Middle School; Greensboro, NC Centennial Middle School visited The Science House; NCSU; Raleigh, Date Numbe r of Studen ts Attendi ng Number of Teacher s Attendin g Fun with CO2 and Polymers! Fun with CO2 and Polymers! Elementary Science Fair Projects A&T SOS Engineering Program A&T SOS Engineering Program A&T SOS Engineering Program Fun with CO2 and Polymers! 9/22/0 4 25 10/23/ 04 20 11/17/ 04 25 11/17/ 04 14 11/22/ 04 14 11/23/ 04 14 1/23/0 5 10 2 0 0 0 0 0 3 CERSP, Page 110 of 230 Fun with CO2 and Polymers! Fun with CO2 and Polymers! Fun with CO2 and Polymers! Fun with CO2! Fun with CO2 and Polymers! Fun with CO2 and Polymers!, Physics on the Road Fun with CO2 and Polymers! Fun with CO2 and NC NC School of Science & Math Mary Louise visited The Bellamy, Julie Science House; Beier, Jamila High NCSU; Raleigh, Simpson, Brian school NC Prevo students Garner YMCA Elementar after school y, middle, program visited Mary Louise and high The Science Bellamy, House; NCSU; school Jamila Raleigh, NC students Simpson Ponderosa Jamila Elementar Elementary School; Simpson, Julie y school Fayetteville, NC Beier students Brian Prevo, Julie Beier, Elementar Fuller Elementary Jamila y school School; Raleigh, Simpson students NC Lauriane Scanu, Joan Patterson, Dillard Drive Jamila Elementar Elementary Simpson, Julie y school School; Raleigh, Beier NC students The NCSU SATELLITE Mary Louise program visited Bellamy, The Science Jamila High House; NCSU; Simpson, Mike school Raleigh, NC Smith students Middle and Jennifer Kelly, elementar St. Thomas More y school School; Chapel Ginger students Hill, NC Denison Geoff Bothun, Elementar Cone Elementary Pam Garner y school School; 2/17/0 5 14 1 3/2/05 30 5 3/3/05 80 4/29/0 5 40 4 2 4/14/0 5 60 3 5/12/0 5 36 12 2/10/0 50 5 3/15/0 5 29 1 3 CERSP, Page 111 of 230 Polymers! WE@UT Jasper Dickson Fun with CO2 ! Aaron Saunders Crazy Science Extravagan za Mehul Patel Encounter with Engineering (EWE) Introduce a Girl to Engineering Day Griffin Smith Luciana Meli, Yuan Li, Stephanie Adkins, Vibha students High school girls, including 5 African American and 5 Hispanic students Elementar y school students, including 4 females, 4 African American, and 10 Hispanic K-12 students, including 50 females, 15 African American, and 50 Hispanic students K-12 girls, including 8 African American, and 7 Hispanic students Elementar y and middle school Greensboro, NC UT-Austin 7/15/0 50 4 4 Brentwood Elementary 10/22/ 20 School; Austin, TX 04 1 University Baptist 11/8/0 Church; UT-Austin 4 100 5 UT-Austin 2/12/0 5 40 2/26/0 5 400 0 UT-Austin 0 CERSP, Page 112 of 230 Srinivasan Explore UT Aaron Saunders, Luciana Meli, Mehul Patel Careers in Engineering for Women Stephanie Summer Adkins, Vibha Camp Srinivasan girls, including 80 African American and 30 Hispanic students K-12 students, including 50 females, 40 African American, and 10 Hispanic students UT-Austin Middle school girls, including 6 African American and 8 Hispanic students UT-Austin 3/5/05 100 0 6/7/05 40 0 Brief descriptions of some of the Texas K-12 activities listed above are as follows: • WE@UT: Women in Engineering at UT is sponsored by the Society of Women Engineers at UT-Austin. Scientists gave demonstrations from the CO2 demonstration kit, including dancing pasta and floating soap bubbles. • Encounter with Engineering (EWE) is sponsored by the Society of Women Engineers at UT-Austin. • Introduce a Girl to Engineering Day is sponsored by the Women in Engineering Program at UT-Austin. CERSP, Page 113 of 230 • Explore UT is sponsored by UT-Austin. The university is open to the public every year and several departments participate in this campus-wide event. Interactive demos were set up using the CO2 demonstration kit provided by the NSF-STC. Students and their families learned about the phase behavior of CO2, physical properties (density in comparison to air, etc.), chemical reactions, etc., as well as the use of CO2 as an environmentally friendly solvent in industry, commercial applications, and research within the STC. The experiments included dancing pasta, floating bubbles and candles extinguisher. • Careers in Engineering for Women Summer Camp is a weeklong summer camp for middle school girls designed to increase the representation of women in engineering and technical fields. It is held at the Chemical Engineering Building at UT-Austin. Eighty 6th and 7th grade girls participated, 10% of whom were African American and 4% were Hispanic. CEW is an outreach program currently organized and directed by the Society of Women Engineers (SWE) at the University of Texas at Austin. The purpose of CEW is to encourage middle school girls to develop an interest in math, science and engineering through hands-on experiences, to introduce middle school girls to engineering career options, and to promote an ongoing support and learning network for middle school girls to pursue their interest in math, science and engineering Involvement of Center Members in K-12 Outreach: Since inception of CERSP over 100 Center graduate students, staff members, post-doctoral students, and faculty members have been involved in K-12 outreach. During the past year ~50 students, post docs, staff and faculty are documented to have participated in many types of K-12 outreach activities. Some of their names and activities are listed in the tables elsewhere in this report. A more comprehensive list of all Center members and their K-12 Outreach activities can be found by visiting the Center web site, and accessing the K-12 Outreach page. Many students participated in multiple activities, including Ginger Denison, Brian Prevo, Jennifer Kelly, and Joan Patterson. Some highlights of contributions of Center faculty members, students, and administrators include: • participation in teacher workshops; • presentations in K-12 schools using the CO2 and Polymer Demonstration Kits; • participation in the annual Expanding Your Horizons (EYH) Conference, which encourages seventh grade girls to pursue mathematics, science, and engineering as careers. In 2005, 354 seventh grade girls and 85 teachers CERSP, Page 114 of 230 from 50 schools in 20 North Carolina counties participated in EYH. Over 40 percent of the seventh grade girls were African American. Over 58 women scientists, mathematicians, and engineers presented hands-on sessions to the girls and their teachers. David Haase, CERSP K-12 Outreach Director, and Mary Louise Bellamy, CERSP K-12 Outreach Coordinator, both served on the Steering Committee for EYH and participated in the event. CERSP cosponsored EHY with the Howard Hughes Medical Institute, and paid for the work of the program coordinator. The CERSP K-12 program also became involved in the new CERSP EXPERT program based at A&T University. On February 28, 2005, Mary Louise Bellamy traveled to A&T University and met with Geoff Bothun, Ken Roberts, and 11 students in the CERSP EXPERT program. All participants received training in some of the hands-on activities from the CERSP CO2 and Polymer Demonstration Kits. On March 15, 2005, Geoff visited Cone Elementary School in Greensboro, NC, and led 29 fifth grade students and four teachers through hands-on activities using the kits. He plans to have EXPERT students accompany him on school visits in the future. Bill Koros, CERSP PI at the Georgia Institute of Technology, worked with Mary Louise Bellamy this year to expand K-12 outreach to Georgia. He now has electronic copies of the activities in the CERSP CO2 and Polymer Demonstration Kits. Bill plans to meet with a principal and some teachers in Georgia during the summer of 2005 to share these activities with them, and plan school visits for the 2005-2006 school year. The teachers and students with whom Bill will be working are part of “The North Metro Program” in Atlanta, whose mission is “to provide research-based, high quality, systemic, results-driven, job embedded, and standards-based professional learning opportunities for the P-12 educators of the Metro Atlanta area in order to support the highest level of student learning for every P-12 child.” Bill also has electronic information about the new “Focus on A Scientist” project, and will begin advertising this program to science educators in Georgia soon. Activity Name Led by Intended Audience Approx Number reached Objective Math and Physical Sciences-Internship in Public Science Education Dr. Darlene K. Taylor with $374K grant from NSF Directly, Science Teaching Fellows Directly, four; indirectly, thousands of pre-K through-12 and their teachers through Museum of Natural Life exhibits Promote teacher leadership, address teacher retention and advance CERSP, Page 115 of 230 Highlight Details K-12 science, technology and mathematics education through training and enrichment activities for teachers. Four Fellows selected for the 2002 Summer Internship are now in their fourth summer. Visit http://www2.ncsu.edu/kiets/index.html for details about interns and their projects. The grant was extended until the end of this year due to the fact that the 4 Kenan Fellows do not complete their fellowship until June and for now their projects are in the final stages. Impact Statement: Over the past five years, the CERSP K-12 outreach program has increased the capacity of The Science House to serve education in North Carolina and other states. The connection to CERSP has also enhanced the involvement of The Science House in national science education circles. Through CERSP, The Science House has acquired experience in leading teacher training at other universities and in other states. This capability was applied in the NSF Rice Blast Laboratory teacher training programs in Texas, Kentucky, and Arizona. Several other multi-campus research programs have solicited the aid of The Science House in designing K-12 outreach components. The recent elections of Mary Louise Bellamy and David Haase to leadership positions in state and national science education organizations show the broader national science education involvement enhanced by the CERSP collaboration. The CERSP K-12 program has collaborated over the previous year with the institutions and individuals listed below. 1) The Carolina Environmental Program of The University of North Carolina at Chapel Hill (CEP) received funding for a grant from the Z. Smith Reynolds Foundation, Partnering to Bring Environmental Science Education Resources to Teachers in Low-Wealth Eastern NC Communities. Michele Kloda at CEP was our contact for this grant. More details about this grant are provided elsewhere in this report. The CERSP K-12 Education program participated in the implementation of this grant, as did The Science House Eastern Satellite Office in Edenton, NC; and the NC Math Science Education Network (NC-MSEN) PreCollege Program at Elizabeth City State University (ECSU), listed below. 2) Howard Hughes Medical Institute (HHMI) (1) cosponsored the Expanding Your Horizons (EYH) Conference with CERSP, which was hosted by North Carolina CERSP, Page 116 of 230 State University (NCSU) on March 8, 2005. (2) HHMI also funds The Science House Eastern Satellite Office in Edenton, NC, which participated in the Z. Smith Reynolds Foundation grant, described above. Judy Day, HHMI Biology Outreach Coordinator, was our contact for HHMI. 3) NC Math Science Education Network (NC-MSEN) Pre-College Program at Elizabeth City State University (ECSU) helped write and implement the Z. Smith Reynolds Foundation grant, described elsewhere. Robin Joyner, Director of the Pre-College Program at ECSU, was our contact for this grant, and our host for the teacher workshops held in conjunction with this grant. 4) Guilford County Public Schools hosted the CERSP K-12 summer workshop in 2004 at Hairston Middle School. Dr. Patricia LeGrand, Curriculum Specialist for Guilford County Public Schools, was our contact for that workshop. 5) Fayetteville State University hosted the CERSP K-12 summer workshop in 2005 at the Lyons Science Center. Ms. Clararene Glover, Acting Director of the Math/Science Education Center, was our contact for that workshop. 2d. Integration of Research and Education No significant changes from last report. 2e. Plans Internal • Expand the Collaboration Workshop into an ongoing Leadership Series • Continue Innovation Seminar Series utilizing surveys to maintain student interest • Develop plan to improve retention of freshmen EXPERT students • Develop a proposal for a Discovery Corps Fellowship to “institutionalize” the gains being made in EXPERT • Improve management practices to coordinate Educational Program External • Continue development of an original book of inquiry based K-12 activities to be published initially in serial form as an electronic newsletter and placed on the web site • Continue writing profiles of Center scientists as part of the original book, and begin placing these profiles on the web site • Continue to conduct teacher workshops based on the middle school lab manual and Center CO2 and Polymer Demonstration Kit activities CERSP, Page 117 of 230 • Expand use of satellite offices of Science House (particularly Fayetteville and Asheville) in CERSP K-12 programs • Continue to give demonstrations in K-12 classrooms using the CO2 and Polymer Demonstration Kits. • Complete development of Volume II of the high school lab manual. • Conduct distance-learning workshops for K-12 teachers as interest is expressed by them • Continue plans to conduct workshops for K-12 teachers in conjunction with Historically Black Colleges and Universities in North Carolina. • Make provisions to respond to technical questions received via the internet • Seek ways to extend NCA&T undergraduate education program into K-12; e.g., include NCA&T student(s) in “Meet a Student”; explore on-line mentoring opportunity • Expand website to include information on EXPERT program • Document final results of our collaboration with the MPS Fellows and the NC Museum of Natural Science As many of our diversity goals depend upon educational processes, several of the above plans are also mentioned in Section VI of this report. CERSP, Page 118 of 230 IV. KNOWLEDGE TRANSFER 1a. Objectives A “revolution in sustainable technology” can occur only if we focus on the right technology and others are confident enough in that technology to implement it. We consider Knowledge Transfer and Collaboration/ Partnerships to be closely linked, and so we define objectives jointly. Also, we prefer the term “knowledge exchange” to cover the entire process. These objectives are to • Establish multi-dimensional communication pathways by which o knowledge developed in the CERSP can be efficiently transferred to those who will implement it and/or benefit from it o information regarding views and needs outside the CERSP are factored into our plans o governmental agencies are apprised of our accomplishments, plans and needs o the public is informed regarding the benefits of sustainability • Leverage resources of the Center to establish individual and organizational partnerships by establishing collaborative links, both internal and external in order to convert technical knowledge into successful, sustainable processes Establishing multi-dimensional communication pathways is a key element of the innovation process. It is important that the industrial sector be aware of our capabilities and have input to our research program. Through public outreach initiatives we hope to improve understanding of how technology contributes to quality of life and how sustainability issues are part of the “life-style equation”. We help empower people to make informed decisions that will affect their quality of life. CERSP knowledge exchange objectives are achieved through outreach activities to industry, communities and governmental officials. Industrial outreach programs provide vital technological assistance for today's economy while laying the groundwork for future growth and knowledge. Knowledge transfer is further achieved through publications, the media, demonstrations, presentations, tours, partnerships, public forums, the Internet, and workshops. This section highlights knowledge transfer accomplishments of the CERSP. 1b. Performance and Management Indicators Knowledge Transfer and Collaboration Performance Measures CERSP, Page 119 of 230 • Exchanges with industrial and entrepreneurial affiliates and government officials, Center-sponsored symposia, workshops, and use of facilities for knowledge exchange • Personnel exchanges, number of visiting scientists and number of joint papers • Number of papers published and presented at professional meetings • Number of invited presentations • Dissemination of information via CERSP Newsletter and website • Patent donations, filings, acquisitions and other intellectual property management • Support NSF and our Center in public forums as opportunities arise Descriptions of the types of exchanges sought and documented are given in the previous annual report. 1c. Problems and Issues The primary issue this year has been reconstituting the Kenan Center, described below. The transition has gone through two iterations since 2003. While this is not yet a “problem” we do need to have our affiliates program firmly established and operational within the next year. 2a. Knowledge Transfer Activities Knowledge Transfer Activity Led by Highlights: Industrial Consortium Prof. Ruben G. Carbonell Per our plan outlined in last year’s annual report, Kenan Center for Utilization of Carbon Dioxide in Manufacturing was dissolved this year. Our attempt to form a new Consortium for Integrated Carbon Dioxide Technology for Microelectronics (CICTM) was unsuccessful, but we are re-establishing our industrial affiliates program along a broad technological front. CERSP, Page 120 of 230 Details: Last year we identified “Microelectronics” as a major new implementation domain, anticipating transition of the industry to 157nm irradiation technology. When the industry leader, Intel, dropped 157 nm programs so did many other companies who had invested hundreds of millions of dollars in 157nm lithography. Several months down this path we revised our strategic plan (to the one described herein) reflecting this reality. Microelectronics was broadened to become “Functional Materials and Devices.” We decided to change strategy for our industrial affiliates program. A frontal assault across the entire range of process steps to “revolutionize” the industry is too expensive and not supported by industry. Rather than trying to displace incumbent technology broadly, we have now decided to focus on a few steps with higher probability of success. Meanwhile, we will seek other applications for emerging studies in our laboratories. Rather than closing this domain entirely, we have widened its view to related topics applying similar technology not directly associated with microelectronics. For example, studies in photolithography have lead to discovery of “soft lithography” capable of replicating nanostructures and to technology that might be applicable to fuel cells. Both of these areas fall within our vision and mission. Our industrial affiliates program was modified to require minimal contribution by participants. We will use this funding to improve information dissemination by frequent direct exchange with industrial scientists rather than using it, as we did in the past, to fund supplemental research. We anticipate that improved dissemination will result in more meaningful collaborations, with fewer but larger research contracts. These contracts will aim at strengthening specific technology of commercial interest by focusing on thematic, one-on-one projects between Center researchers and individual companies. This approach has been accepted by our proposed industrial affiliates. Industrial Separations Technology Consortium Prof. Keith P. Johnston CERSP, Page 121 of 230 Knowledge Transfer Activity Led by Separations Research Program Highlights Details http://uts.cc.utexas.edu/~utsrp/SRP/index.htm SRP involves 30 industrial firms which are listed on the above website An excellent conference was hosted by SRP on April 4-5, 2005. Presentations, models, and databases are available at the above website by filling out the online form. The Separations Research Program is a cooperative industry/university program that performs fundamental research of interest to chemical, biotechnological, petroleum refining, gas processing, pharmaceutical and food companies. CERSP participates by having Keith Johnson, who is also a project team leader, leading nanoparticle research efforts in SRP. Four students and Prof. Keith Johnston spoke at the meeting. One CERSP Newsletter was issued (November/December 2004) and a second will be issued around July/August 2005. The November/December 2004 issue highlighted the accomplishments of students associated with CERSP. Six hundred newsletters were printed and approximately 400 have been distributed to date. 2b. Other Knowledge Transfer Activities Knowledg e Transfer Activity Led by Support of NSF Activities Prof. Joe DeSimone, Prof. Denis Gray, and Dr. Everett Baucom CERSP, Page 122 of 230 Details: We provided the following support of NSF activities and policies: (1) Denis Gray served as invited panelist at Center Meeting on behalf of NSF, Belfast, Northern Ireland, Spring 2005 (2) Denis Gray served as invited panelist international conference panel, Turin, Italy, Spring 2005 (3) Denis Gray spoke to Irish equivalent of NSF, Dublin, Ireland, Spring 2005 (4) Denis Gray spoke by invitation in panel discussion at NSFsponsored EPSCoR Leadership Retreat in Washington, DC on Feb 22-23, 2005 (5) Denis Gray served as Invited panelist as part of the Carolina Seminar on Economic Development: “After the Factories: What the economic model of North Carolina in the 21st Century” series. Panel: Deploying the assets of post-secondary education for the economic development of North Carolina. Other panelists included Dr. John Bardo, Chancellor Western Carolina University and Dr. J.B. Milliken, President, University of Nebraska. (6) E. I. Baucom participated in panel discussion commercialization of green chemistry involving members of the government of Victoria, Australia (7) E. I. Baucom spoke by invitation at Green Chemistry: An Australian Imperative. Talk entitled “CERSP: Involving Academia, Industry and Government” in Canberra, Australia, on April 23, 2005. (8) E. I. Baucom spoke by invitation in panel discussion at NSFsponsored EPSCoR Leadership Retreat. Talk entitled “Involving Industry and State Governments” in Washington, DC on Feb 22-23, 2005 A total of 88 publications receiving full or partial CERSP support were issued or in press as of mid-June. This includes 72 papers (70 peer-reviewed) and five book chapters issued through June 2005 plus an additional 11 papers in press. Of these 88 publications, 59% involve collaboration outside the PI’s research group—27 collaborations within the Center; and 25, outside the Center. A total of 110 external papers or posters were presented, including 68 presentations at conferences (4 abroad) and 42 invited lectures (11 abroad). Prof. Ruben Carbonell and Prof. Keith Johnston were two of three organizers of the 7th International Symposium on Supercritical Fluids, held in Orlando, Florida, May 1-4, 2005. This is the most important international conference on this topic, CERSP, Page 123 of 230 held biennially. This year it was very well attended, with 400 scientists and engineers, including 250 from overseas. CERSP faculty and students played a major role, presenting 18 papers at the ISSF symposium. Liquidia Technologies is a UNC-CH/NC State spinout company that was founded in November 2004. Liquidia has licensed technology from the University that was partially supported by CERSP funds as well as ONR funds. The technology licensed includes the imprint lithographic and PRINT technologies described in Sections II.2a.2 and II.2a.3 of this report, respectively. Two CERSP-supported PhD students, Ginger Denison and Jason Rolland, completed their PhDs in March 2005 and are scientific co-founders of the company. Liquidia has raised $2.5 million of private equity in February 2005. It is now also sponsoring research in Prof. DeSimone’s laboratory. 2c. Plans We have consistently demonstrated a track record in citations per publication that far exceeds the national average during the last two reporting periods and decided not to report this topic for the current reporting year. However, as this is a key indicator of scientific merit, we will resume reporting next year. Media reports will continue to be documented, and we will continue to publish annual newsletters. We will continue to emphasize activities with the international scientific community. In addition, significant effort will be dedicated to restructuring the Kenan Center for Utilization of Carbon Dioxide in Manufacturing as a means to improve knowledge transfer within the context of our new research organization. (See Section VII.4.) We have begun discussions with the Friday Center for Life-long Learning at UNC-CH to develop a continuing education series beginning in Spring 2006. This series is a very popular program in continuing education, but historically has covered mostly topics in the humanities, history (especially historical background of current events), the arts, etc. There have been few if any sessions on the sciences, least of all current research. Typical attendees are teachers, retirees, alumni, local business leaders and others interested in expanding their education. We believe this forum could be an important new mechanism for us to reach community leaders. Our initial working concept for the series is “What’s the Big Idea?” We envision this as an ongoing annual series of four two-hour seminars as part of the Friday Center program. CERSP will lead the inaugural sessions. Elements of the program will include descriptions of the cutting-edge science going on in the Center; how an NSF Center integrates social science, education, and diversity to enrich a CERSP, Page 124 of 230 research program focusing on sustainability; how the innovation process works local entrepreneurial activity; and some recent commercial activity based upon CERSP work. In following years CERSP would still lead the series but would bring in speakers from other scientific and medical areas to keep the subject matter fresh and “cutting edge”. The program will be coordinated with Endeavors magazine, a University publication that highlights faculty research and its impact on North Carolina. CERSP, Page 125 of 230 V. PARTNERSHIPS 1a. Objectives CERSP is committed to identifying and establishing partnerships to explore the study and development of energy-efficient and environmentally-friendly processes to replace water and organic solvents in selected applications. A “revolution in sustainable technology” can occur only if we focus on the right technology and others are confident enough of that technology to implement it. We consider Knowledge Transfer and Collaboration/Partnerships to be closely linked, and so the technical objectives are coincident. These objectives are to • Establish multi-dimensional communication pathways by which o knowledge developed in the CERSP can be efficiently transferred to those who will implement it and/or benefit from it and o information regarding views and needs outside the CERSP are factored into our plans o governmental agencies are apprised of our accomplishments, plans and needs o the public is informed regarding the benefits of sustainability • Leverage resources of the Center to establish individual and organizational partnerships by establishing collaborative links, both internal and external in order to convert technical knowledge into successful, sustainable processes Establishing multi-dimensional communication pathways is a key element of the innovation process. It is important that the industrial sector be aware of our capabilities and have input to our research program. Through public outreach initiatives we hope to improve understanding of how technology contributes to quality of life and how sustainability issues are part of the “life-style equation”. We help empower people to make informed decisions that will affect their quality of life. CERSP knowledge exchange objectives are achieved through outreach activities to industry, communities and governmental officials. Industrial outreach programs provide vital technological assistance for today's economy while laying the groundwork for future growth and knowledge. Knowledge transfer is further achieved through publications, the media, demonstrations, presentations, tours, partnerships, public forums, the Internet, and workshops. This section highlights partnerships of the CERSP. In addition, we have the added objective of establishing educational partnerships, especially with HMUs and other minority-serving organizations, to help achieve our educational and diversity objectives. These partnerships are described in Sections III and VI, respectively. CERSP, Page 126 of 230 Our goals are to find creative ways to • draw upon the expertise of and stimulate interest within the broader community (including academia, government, and industry and social as well as technical sciences) • encourage and facilitate technical collaboration both within and outside the Center, especially with foreign institutions and US government laboratories • establish links with HMU to facilitate recruiting and to encourage scientific careers among their graduates • utilize our facilities effectively by publicizing their availability and sharing • utilize resources of National Laboratories as appropriate • provide a mechanism for focusing our work in those areas of greatest impact These objectives and goals have not changed since the last reporting cycle. 1b. Performance and Management Indicators • Exchanges with supporting industrial consortia, Center-sponsored symposia, workshops, and laboratory tours for knowledge transfer • Personnel exchanges and number of visiting scientists sharing facilities • Number of joint papers • Patent donations, filings, acquisitions and other intellectual property management 1c. Problems There have been no significant problems. 2a. Activities Listed in the following table are collaborations between CERSP personnel and external researchers. Total documented external partnerships have increased from 123 to 126 during the year, including 16 new partnerships. Thirteen previous partnerships have become inactive. Of these 126, fourteen are national or other government labs, 48 are from foreign institutions (from 23 different countries on six continents), 45 are with US universities, and 19 are from industrial concerns. If five Center scientists are collaborating with an individual outside the Center, that is counted as one partnership. These include collaboration on intellectual issues as well as equipment sharing and often lead to joint papers. CERSP, Page 127 of 230 Partnerships Led by Organization Name No First Name Last Name 1 2 3 4 5 6 7 8 9 Dr. M. Prof. G. Prof. A. Adam Afrane Albini Collaborations with Outside Scientists Principal Investigators see below for details. Institution and Locale Area of Collaboration CNRS Solution properties with Grenoble, France DeSimone U. of Science and Carbonell: CO2 extraction Technology Kamusi, of medicinal plants for pharmaceuticals Ghana Photoinitiated organic University of Venice synthesis in CO2 with DeSimone Venice, Italy Instituto Technological de Celaya Celaya, Theoretical/experimental Mexico with I. Sanchez University of Minnesota Fuel cell with DeSimone Center for Innovation Management Studies Gray: PDP development NCSU Department of Study of miniemulsions Chemistry, Univ. of with Keith P. Johnston, et Hull, Hull, UK al Rohm and Haas Reactions in CO2 with DeSimone Philadelphia, PA Georgia Institute of Technology Separations with Koros ScCO2 polymerization with University of Salerno, It DeSimone Seoul National ScCO2 polymerization with DeSimone University Prof. Javier Alvarado Prof. Frank Bates Dr. Al Bean Prof. Bernie Binks Dr. Robert Blankenship Bush Caputo Char Dr. David Prof. 10 Giuseppe Prof. 11 Kookheon CERSP, Page 128 of 230 Prof. Piero 12 Tundo 13 Dr. Henry 14 Dr. Will 15 Luke Ciao Cochran Conley Connal 16 Prof. Andrew Cooper 17 Prof. Sandro da Rocha 18 Dr. Ralph 19 Judy Dammel Day 20 Prof. Andrey Dobrynin 21 Prof. J. Donlagic 22 Prof. Julian Eastoe 23 Prof. Charles Eckert 24 Dr. B. Farago 25 Dr. Stephen Feldberg 26 Dr. D. A. Fischer Study phase-transfer UNC-CH Chapel Hill, catalysts reactions with DeSimone; NC Polymer structure with Spontak and DeSimone ORNL Oak Ridge, TN (SANS and SAXS) DeSimone: Optical density International Sematech measurement at 157 nm University of Melbourne Synthesis of polymer star Melbourne, Australia micro-gels via ATRP DeSimone student University of Liverpool exchange Dept of Chemical Engg. Wayne State University Rossky: Simulations of Detroit, MI water/CO2 DeSimone: Photoresist Clariant Corporation formulation Expanding Your Horizons Howard Hughes project w/ Mary Louise Bellamy Medical Institute University of Monte Carlo Simulation of Connecticut Polymeric Surfactants with Storrs, CT Rubenstein Coatings from CO2 with U. of Maribor Slovenia Carbonell University of Bristol Bristol, UK Surfactants with Johnston Georgia Institute of Technology Bill Koros DeSimone and Adam: ILL Structural studies using SANS Grenoble, France Brookhaven National Lab Royce Murray NIST Genzer NEXAFS analysis CERSP, Page 129 of 230 27 Prof. Neil 28 Robert Foster Franich 29 Prof. Benny Freeman 30 Prof. Henrich Frielinghaus 31 Prof. Luis H. Garcia-Rubio 32 Dr. E. 33 Dr. Sylvan Geissler Gerard 34 Clararene Glover Prof. Jose35 Marie Griffiths 36 Prof. B. Gunnoe 37 Prof. Afife 38 Dr. Jason 39 Dr. Buxing 40 Dr. Carol 41 Prof. Marc 42 Dr. Max Guvenc Hallett Han Haney Hillmyer Hiramatsu University of New South Wales Forest Research New York Dept of Chem Engineering UT-A Institut für Festkörperforschung, D-52425 Jülich, Germany University of South Florida Tampa, Florida ILL Grenoble, France Atofina Corporation, King of Prussia, PA Acting Director of the Math/Science Education University of North Carolina-CH NCSU Dept of Chemistry Ankara (Turkey) University, Chemical Engineering Department Georgia Institute of Technology Chinese Academy of Sciences Agilent Technologies ScCO2 polymerization with DeSimone Adhesives for wood with Carbonell I. Sanchez Simulations with Berkowitz Nanoparticles with Johnston Structural studies using SANS PVDF with Roberts and DeSimone Environmental Science Workshops w/Bellamy Gray: Training evaluation Green chemistry for pharmaceuticals Dispersion polymerization in scCO2 with DeSimone Separations with Koros ScCO2 polymerization with DeSimone 43 Prof. Justin Holmes G. Roberts DeSimone: Fuel cell University of Minnesota membrane Wako Chemicals DeSimone: Photoacid Richmond, VA generator samples University College Cork, Ireland Johnston: microemulsions CERSP, Page 130 of 230 44 Dr. Michael Hu Prof. 45 Michelle Janowiak 46 Dr. Stein T. Johansen 47 Robin 48 Prof. J. Prof. 49 Hwayong Prof. Soo 50 Hyun 51 Dr. Brian Joyner Kadla Kim Kim Kipp 52 Dr. Douglas Kiserow 53 Michele Prof. 54 Barbara Prof. 55 Jacqueline 56 Takanori Kloda Knudson Krim Kudo ORNL Oak Ridge, TN Catalysis with K. Roberts University of South Nanoparticles with Florida Tampa, Florida Johnston Materials Technology Division, SINTEF, Spontak: Polymer Norway processing Director of the PreCollege Program, Z. Smith Reynolds Elizabeth City State Foundation grant proposal University w/ Mary Louise Bellamy NCSU School of Extraction of wax from Forestry cardboard with Carbonell Seoul National ScCO2 polymerization with DeSimone University Seoul National ScCO2 polymerization with DeSimone University E. I. du Pont Fluoropolymers with Fayetteville, NC DeSimone U. S. Army Research Polymers with Carbonell Office Research, RTP and G. Roberts Carolina Environmental Bring Environmental Program University of Education Resources to North Carolina-Chapel Teachers in Low-Wealth Eastern North Carolina Hill Advanced materials University of Kentucky synthesis in scCO2 Dept. of Physics NCSU Grant: QCM technology Spontak: twin-screw Clariant Corporation extruder Department of Mechanical Engineering, NCA&T K. Roberts CNRS Ecole de Chemie de Montpellier Dispersion polymerization France with DeSimone; Seoul National ScCO2 polymerization with DeSimone University CERSP, Page 131 of 230 57 Dr. Dhanajay Kumar 58 Prof. P. Prof. Youn59 Woo Lee LacroixDesmazes 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 Curriculum Specialist Environmental Science Dr. Patricia LeGrand for Guilford County, NC Workshops w/Bellamy U. of Ljubljana High pressure trickle bed Prof. J. Levec Slovenia reactor with Carbonell Korea National University Pusan, Prof. KwonSurface studies with Taek Lim Korea Johnston Polymer structure with Spontak and DeSimone ORNL Dr. J.S. Lin Oak Ridge, TN (SANS and SAXS) North Carolina A&T State University Dr.Jianzhong Lou K. Roberts University of Celaya Theoretical/exper'tal with Prof. Gabriel Luna-Barcenas Mexico Webber Polymerization in SCCO2 Dr. Ali Mahadavian Iran Polymer Institute with DeSimone University of Toronto Khan and Spontak: Toronto, Canada Foaming of polysiloxanes Prof. Ian Manners Exxon Polymer Research Center Dr. Eric J Markel Baytown, TX Catalysis with K. Roberts Center for Innovation Management Studies Prof. Steven Markham Gray: PDP development NCSU Rossky: Intermolecular Dept of Chemistry potentials involving Prof. Mark Maroncelli Penn State University fluorocarbon Atofina Polymer processing with Dr. Jerome Martinache Brussels, Belgium Khan Sematech Green and Johnston: Dr. Hunter Martinez Austin, Tx Microelectronics cleaning Air Force Research Foaming mesophases with Samulski and G. Roberts Dr. Benji Marujama Lab WPAFB, Ohio Carnegie Mellon Prof. University, Pittsburgh, Matyjaszewski PA Sergei Sheiko Krzysztof Virginia Modeling the CO2/PVDF phase equilibria with G. Commonwealth Prof. Mark McHugh University, Richmond, Roberts CERSP, Page 132 of 230 VA Polymer structure with ORNL Spontak and DeSimone (SANS and SAXS) Oak Ridge, TN SABANCI University Submicron imaging with Istanbul, Turkey DeSimone Simulations of chain Georgia Tech structure for steric Atlanta, GA stabilization with Webber Chevron Research Co Zeolites with Ilias and Richmond, CA Koros University of Ulm Ulm, Germany Sergei Sheiko City University of NY, Murray: Au nanoparticles Queens College electrochemistry North Carolina A&T State University K. Roberts U. of Southern Mississippi and Argon DeSimone: Fuel cell National Lab membrane Seoul National ScCO2 polymerization with DeSimone University Russian Academy of Sciences Rubinstein: simulations Synthesis of anisotropic University of Hull particles (Velev) University of Texas- Koros: high pressure Austin separations Non-wovens Cooperative Research Center at the College Extrusion equipment with of Textiles, NCSU Khan University of Melbourne Synthesis of polymer star Melbourne, Australia micro-gels via ATRP Instituto de Fisica, Computer simulations of Universidad Nacional CO2 in glassy and liquid Autonoma de Mexico polymers with Sanchez CERSP, Page 133 of 230 76 Dr. Yuri Melnichenko 77 Prof. Yusuf Menceloglu 78 Prof. Carson Meredith 79 Dr. Stephen Miller 80 Prof. Martin Moeller 81 Prof. Michael Mirkin 82 Dr. Abdul Mohammed 83 Prof. Robert Moore 84 Prof. Ji Won Pak 85 Dr. Sergei Prof. 86 Vesselin 87 Prof. Don Panyukov Paunov Paul 88 Dr. Behnam Pourdeyhimi 89 Prof. Greg Qiao Ramirez90 Dr. Guillermo Santiago 91 Dr. Paul Prof. 92 Timothy 93 Prof. Tom Resnick Romack Russell 94 Prof. J. Sankar 95 Prof. Henry Sanoff 96 Prof. Giulio Sarti Prof. 97 Maurizio Selva 98 Dr. Shumei Shi 99 Dr. Richard Smith 100 Prof. James Spivey 101 Prof. C. Prof. 102 Masataka Staudt-Bickle Sugimoto Consultant East Carolina University Greenville, DeSimone: CO2 cleaning NC Green and Johnston: Univ. of Massachusetts Neutron reflectivity Director of NSF Center for Smart Materials, K. Roberts: Use of NCA&T, Greensboro, equipment to characterize NC films School of Design NCSU Gray: Space for innovation University of Bologna University of Foscaria, Italy North Carolina State University Tohoku University Louisiana State U. Baton Rouge, LA University of Heidelberg, Germany Yamagata University Yamagata, Japan University of Puerto Rico Mayaquez University of Venice Venice, Italy Rovirai Virgili University Tarragona, Spain NCSU School of Forestry Sandia Corp. Livermore, CA Bill Koros Phase transfer catalysis with DeSimone G. Roberts ScCO2 polymerization with DeSimone G. Roberts: Direct conversion of CO2 to acetate derivatives Membranes with W. Koros Polypropylene-clay nanocomposites Phase transfer catalysis in CO2 with DeSimone SAFT calculations with Hall and Gubbins Extraction of wax from cardboard with Carbonell DeSimone CERSP, Page 134 of 230 Fluoropolymers with DeSimone 103 Prof. David Suleiman 104 Prof. P. Prof. 105 Lourdes 106 Prof. R. 107 Dr. J. Tundo Vega Venditti Wang 108 Dr. Z Wang DeSimone: Fuel cell University of Minnesota membrane Green and Johnston: Univ. of Massachusetts Neutron reflectivity Polymer structure with Spontak and DeSimone ORNL Oak Ridge, TN (SANS and SAXS) Univ. of Nottingham Nottingham, UK Rubinstein: simulations Green and Johnston: Sematech Austin, Tx Microelectronics cleaning Multidisciplinary Recruitment of women in Studies NCSU sciences with Gray ScCO2 polymerization with DeSimone Sogang University DeSimone and Carbonell: Dept of Electrical Engg Training with clean room and tools NCSU Calculations with St. Petersburg, Russia Rubinstein Kenan Center Solvay, S. A., Brussels, G. Roberts: analyses of Belgium the PVDF Atofina Chemicals, Inc., King of Prussia, G. Roberts: analyses of PA the PVDF G. Roberts: initiators for Wako Chemicals, Inc., acrylates and safety information Richmond, VA Stockhausen, Inc G. Roberts: Greensboro, NC superabsorbant polymers Air Products Allentown, G. Roberts: MW PA measurements NCSU College of Spontak: twin-screw Textiles extruder 109 Dr. Michale Ward 110 Prof. Jim Watkins 111 Dr. George Wignall 112 Prof. Ian 113 Dr. Josh 114 Dr. Mary Prof. Ki115 Pung 116 Ginger Withers Wolf Wyer Yoo Yu 117 Prof. E. Zhulina Numerous 118 researchers Various 119 researchers Various 120 researchers Various 121 researchers Various 122 researchers Various 123 researchers Research 124 staff CERSP, Page 135 of 230 Various 125 researchers Various 126 researchers G. Roberts and J. M. E. I. du Pont DeSimone fluoropolymers Size exclusion Viscotek Corporation, chromatography on PVDF Houston, TX with Saad Khan 2b. Other Outcomes or Impacts of Partnership Activities Our partnership with the Triangle National Lithography Center is developing as planned, with changes that reflect “mid-course corrections” in our lithography programs. (See Sections II.1c and II.2a.2 for a description of those changes.) The TNLC facility has been crucial to developments in lithography, both classical and soft lithography. Rather than fabricating masters remotely we can now do that work “inhouse”. This not only saves valuable time but, because samples rapidly degrade after exposure, enables us to improve definition greatly. Most recently the stepper is being used to develop solvent-free lithography and cleaning processes for future device generations. Systems to coat and develop resists using liquid and supercritical CO2 are an integral part of the TNLC. Moreover, CERSP industrial affiliates are beginning to use these facilities. We expect the TNLC to be a powerful drawing point as we continue to focus on lithographic processes. The TNLC is an Affiliate of the National Nanotechnology Infrastructure Network (NNIN), a partnership of thirteen user facilities, supported by NSF, providing unparalleled opportunities for nanoscience and nanotechnology research. Though we have not made substantial use of these other facilities to date it is important for use to maintain contact with the scientists in this network, both to remain at the forefront of research and to benchmark ourselves and our work. With our continuing high level of internal collaboration, we have decided to discontinue documenting these. With the advent of the EXPERT program, we are now beginning to see effective partnerships between NCA&T and Georgia Tech, UNC-CH and NC State, catalyzed by our Discovery Corps Fellow, Dr. Geoff Bothun. 2c. Plans The CERSP is about collaboration and therefore we will endeavor to maintain useful partnerships listed above and engage in new ones as important opportunities CERSP, Page 136 of 230 present themselves. We do not anticipate any major changes in direction. We expect to add (and discontinue) external partnerships selectively. We anticipate developing some sort of educational/research partnership with NC Central University under the auspices of Prof. Darlene Taylor. The Industrial Affiliates program will remain a key mechanism for maintaining industrial partnerships. We will continue to encourage prospective partners to tour our facilities if our on-line and video tours do not suffice. CERSP, Page 137 of 230 VI. DIVERSITY "There is no better fertile ground for innovation than a diversity of experience. And that diversity of experience arises from a difference of cultures, ethnicities, and life backgrounds. A successful scientific endeavor is one that attracts a diversity of experience, draws upon the breadth and depth of that experience, and cultivates those differences, acknowledging the creativity they spark." - Prof. Joseph M. DeSimone on his website 1a. Objectives Our overall objective in this area is to encourage students from underrepresented groups to seek and succeed in careers in science and mathematics. We intend to do that by • providing support to K-12 outreach programs targeting underrepresented groups • actively recruiting from those groups to fill CERSP positions • providing research linkages between Georgia Tech, NCSU and UNC-CH with NCA&T to encourage students to seek PhDs in engineering and science • providing support for NCA&T to strengthen its graduate programs through facilities upgrades and other means as appropriate • providing research experiences and mentoring to undergraduate students through REU (Research Experiences for Undergraduates), SPGRE (Summer Pre-Graduate Research Experiences), EXPERT (EXperimental Program in Education and Research Training) at NC A&T and similar outreach programs • seeking partnerships and lecturing relationships with HMUs other than NCA&T in order to strengthen our recruiting base for REU and SPGRE programs and graduate schools There have been no changes in our objectives though we have set some very aggressive goals as outlined in the following section. We have also changed the way in which we describe the role that diversity plays in meeting Center goals. Joe DeSimone’s quote at the beginning of this section reflects our beliefs: Innovation is a social process and diversity plays a key role in that process. Diversity means more than “throwing together” a diverse group. To harness the power of diversity we need contributions from everyone. Our leadership workshop (described under Section III) aims to provide students with the confidence to participate fully and the tools to CERSP, Page 138 of 230 recognize our differences and to build upon those differences to improve output of collaborative efforts. 1b. Performance and Management Indicators • Number of students contacted • Internship participation • Number of under-represented minorities entering graduate programs, employed as scientists and engineers • Number and percentage of URG students and PIs participating in CERSP • Number of CERSP participants involved in diversity-enhancing activities Our performance versus these indicators is described below. CERSP has adopted a “continuous improvement mindset” since the early days of our center. While we are proud of our accomplishments in the diversity area we feel there is room for significant improvement. To that end we have established additional “stretch” goals to challenge ourselves in the second phase of our center. Stretch Goals • Demonstrate significant commitment to and success in exceeding national averages in education/training diverse pool of science and engineering students • Add goals, milestones, and actions to our existing diversity strategic plan • Develop outreach connections with predominantly female and underrepresented minority institutions (including deans and department chairs of those institutions) • Strengthen connections with at Louis Stokes Alliance for Minority Participation (LSAMP) and add one or more of the following - Alliances for Graduate Education in the Professoriate (AGEP) - Tribal Colleges and Universities Program (TCUP) - Centers for Research Excellence in Science & Technology (CREST) • Operate a diversity-oriented REU program • As a priority, support NC A&T EXperimental Program for Education in Research and Training (EXPERT, discussed in detail below.) 1c. Problems There were no significant problems during this year. 2a. Center Contributions to Development of Human Resources CERSP, Page 139 of 230 Our primary strategy to contribute to the scientific and engineering resources of the United States is a long-term one. We're focusing on getting U.S. kids excited about science via our K-12 outreach programs and our website. We especially seek to point out to young people the applicability of our activities to improve the health and well-being of society in general. And we’re supporting internships to encourage undergraduates and high school students to choose scientific careers. These programs are significantly weighted towards historically underrepresented segments of society. All else being equal we recruit US citizens. But the pool of qualified post-docs applying to US universities is composed largely of non-U.S. citizens (especially Asians) and our Center is no different, though the numbers are considerably less skewed than in the past. Post-docs comprise 44% US citizens plus 5% permanent residents; 38% are Asian; 17%, European; and 5%, Latin-American. Of PhD students, 66% are US citizens, about the same as last year. However, 72% of MS students are US citizens, well up from only 29% last year. This change is largely due to our concerted effort to recruit African-American graduate students at NCA&T into CERSP programs. Among undergraduates, 98% are US citizens. K-12 outreach focused on diversity. Many of the outreach activities detailed under Education (Section III.2b) focus on underrepresented groups. We will not repeat them here. Suffice to say that, due to the demographics of North Carolina and Texas K-12 programs are potentially diversity enhancing by definition. As a weighted average, over 2/3 of the public school populations of these states are from underrepresented groups (URG). By this logic (and including the fact that many programs targeted URG students), we directly reached more than 1300 URG students and indirectly reached over 100,000 URG students this year. In so doing, ~50 CERSP students, faculty and staff participated in diversity-enhancing activities. CERSP recruiting CERSP actively recruits from underrepresented segments of society. Thirty-nine faculty, 18 post-docs, 75 graduate students, 41 undergraduates, two high school, eight staff and two visiting scientists received support from the Center this year. Thirty-eight percent of faculty (including one visually impaired Caucasian male), 68% of post-docs, and 54% of graduate students and 83% of undergraduates—60% of all CERSP personnel—are from historically underrepresented groups (URG). Of all students and post-docs, 65% are from URGs, and 81% of this group is minority or female. Details are given in the following tables. CERSP, Page 140 of 230 Demographics of Center Personnel Class Hi school Undgrad Graduate Post-doc Faculty Vis Sci Staff Total Caucasian M F* 1 6 17 2 24 1 51 7 20 3 6 1 5 42 African-American M* F* 1 15 8 3 2 1 30 0 12 5 2 3 1 23 Asian M F* 1 17 3 3 1 25 0 7 3 1 11 H/L* 1 1 1 3 6 % Total URG* 2 41 76# 18# 39 2 8 50 83 54 68 38+ 100 75 186# 60+ * Underrepresented groups # Totals include dnwtp (do not wish to participate) but % & individual categories do not + Includes 1 visually impaired Summary Demographics of Students and Post-doctoral Associates Percentage of 2004 Category 2005 Numbers Percentage of 2005 total total Females 66 45% 45% African-American 48 37% 20% Asian 32 24% 32% Hispanic/Latino 2 2% 4% Minority + female 106 81% 77% These numbers are significantly changed from last year in three categories. Total number of undergraduates increased 50%, but number of URG students is up CERSP, Page 141 of 230 113%. This is mainly due to the increased number of African-American undergraduates, males (up 400% from 3 to 15) and females (up 100% from 6 to 12). Total number of African-American undergraduates has tripled overall in 2005. African-Americans comprise 36% of CERSP students and post-doctoral associates. This mainly reflects the great success we have had in recruiting into our EXPERT program, which comprises 91% African-American undergraduates. The number of post-docs from URGs increased 8 to 11 and the percentage increased from 44 to 68% in this relatively small group. This is viewed as a statistical aberration rather than deriving from concerted action on our part. The total number of graduate students is up by nine, mainly due to the fact that we were in transition this year with an abnormally large number of projects starting up and shutting down. The following figure graphically shows distribution for the entire CERSP (n=182, excluding four who did not participate in demographics analysis). Starting upper right and proceeding clockwise, solid blue is Caucasian male (25%), light blue cross-hatched is combined Hispanic, Latino, and American Indian of both genders (3%), Caucasian female (23%), African-American male (16%), African-American female (13%), Asian female (6%) and green is Asian male (14%). Underrepresented groups are represented by cross-hatch and historically, numerically dominant groups by solid colors. Undergraduate research experiences We continue to reach high school and undergraduate students from under-represented groups through the SPGRE program sponsored by Prof. Henry Frierson at UNC-CH (http://www.unc.edu/depts/res/spgre.htm) and the related Research Education Support (RES) Program (http://www.ibiblio.org/res/), Project SEED (http://www.projectseed.org/) at UNC-CH (focusing on African-American high school students), and programs at NCA&T led by Dr. Geoff Bothun (EXPERT) and Prof. Kenneth Roberts. During this year 41 undergraduate and two high school students received research experiences with guidance from CERSP graduate students, post-doctoral CERSP, Page 142 of 230 associates and professors. URG students constituted 81% of this group. Details are given in Section III.2.d. In addition to our own summer research experiences, we aid students in finding other positions. While six EXPERT students were supported by CERSP this summer, an additional 12 had research experiences elsewhere. In total, 100% of qualified EXPERT students had summer research experiences. Dr. Darlene Taylor served on the 2004 Abstract Selection Committee for the National Convention of Society for the Advancement of Chicanos and Native Americans in Science (SACNAS). In that capacity she reviewed for submitted chemistry abstracts authored by student presenters. She also participated in the SACNAS E-Mentoring Program through periodic contacts with Karen Watts, a 2nd grade elementary teacher Preliminary plans to establish joint K-12 programs on military bases in the area have been cancelled. Troop deployments to Afghanistan and Iraq have been too disruptive to the local community. Remaining families and teachers are challenged to maintain even existing programs let alone starting a new one. However, we are working through Science House to identify a significant opportunity to contribute in the Fayetteville, NC area, where Fort Bragg is located. 2b. Impact on Enhancing Diversity at the Center Overall the CERSP has been very successful in recruiting from underrepresented groups. The table under Section VI.2a summarizes results. Last year we reported plans to develop a cascaded mentoring program (EXPERT) at NCA&T. That program has been started under the leadership of an NSF Discovery Corps Fellow, Dr. Geoff Bothun. We anticipate getting some 40 African-American students onto a graduate school track in chemistry or engineering. The program is off to a great start. Details of this program are given in Section III.2.a. One of our concerns regarding recruitment of African-American students is that we not simply out-compete others for these students, but that we increase the size of the talent pool. As we evolve our mentoring program at NCA&T we will make sure that our scholarship students are involved themselves in K-12 outreach to increase recruitment into college. 2c. Plans In general, our plans are to continue to use the excellent systems already in place. However, we plan to increase the attention we are giving the AfricanAmerican, native-American and Hispanic/Latino populations in North Carolina: CERSP, Page 143 of 230 • Identifying and coordinating our K-12 outreach with existing H/L-serving organizations • Coordinate with 2006 Summer Undergraduate Research Experience (SURE) program at Georgia Tech to get an appointment for an NCA&T student • Continue to encourage faculty participation in diversity programs • Develop outreach connections with predominantly female and underrepresented minority institutions (including deans and department chairs of those institutions) • Lead effort to establish a NOBCChE chapter at UNC-CH • As a priority, support and strengthen NCA&T EXperimental Program for Education in Research and Training (EXPERT). Per plan, recruit 24 students. An additional dimension to our diversity efforts is expected in the future as one of our CERSP research associates and outreach leaders, Dr. Darlene Taylor, has recently accepted a tenure track faculty position in the Chemistry Department at NC Central University, an HMU located in Durham, NC. Since Taylor will continue to work in the capacity of RICHES outreach leader while she begins her new position at NCCU, we anticipate strong collaborations that should impact our summer programs, our pool of PhD trainees, and the legacy of CERSP overall. CERSP, Page 144 of 230 VII. MANAGEMENT 1a. Organizational Strategy There have been no major changes in overall organizational strategy or rationale. The organization chart of the CERSP for FY2005, illustrated in Appendix B, shows the affect of starting the EXPERT program at NCA&T and shutting down the REU program at NC State. 1b. Performance and Management Indicators The role of management is to provide leadership, install systems and set and oversee performance measures to achieve results. Management implementation mechanisms have not changed. Goals, objectives and performance measures are summarized in the strategic plan. These have been slightly modified from last year to clarify our focus. 1c. Problems and Issues Prof. Leonard Uitenham of NCA&T, a member of our management team, was called to active duty in the US Marines and has not been available this year. Prof. Vinayak Kabadi has ably filled in for him. Dr. Darlene Taylor has accepted a tenuretrack faculty position at North Carolina Central University in Durham. She will continue to serve as RICHES outreach leader for the next reporting year. We have been able to manage without major disruptions. We have adopted a different way of presenting Center activities. This is described in our revised Strategic Plan, given at the end of this section. We felt that we have not been adequately communicating how our social science, education and diversity programs were integrated fully into Center activities and how all the pieces fit. We believe our new description with accompanying icon more accurately and thoroughly describes the vital roles these programs play in our Center. 2. Management and Communications Systems There have been no changes to management and communications systems. 3. External Advisory Board CERSP, Page 145 of 230 Two new members were appointed to our External Advisory Board this year. Dr. Parry Norling is a visiting fellow at the Chemical Heritage Foundation in Philadelphia and visiting adjunct professor in the physics department at Georgetown University (Washington, DC) where he teaches a course “Industrial Problems in Physics”. Dr. William Holton, visiting research professor at NC State University (Raleigh), is former Vice President for Research Operations with the Semiconductor Research Corporation (SRC). Biographical sketches of new EAB members are given it Appendix A2. Current members and affiliations are summarized in Table VIIA. Nine of the sixteen members (57%) are from underrepresented groups. Four of our original board members are still active. We plan to continue to renew our board at an average rate of two or three members per year. Three members are leaving for 2006. Prof. Jose-Marie Griffiths, former Director of the Sara Fine Institute for Interpersonal Behavior & Technology, Information Technology Division at the University of Pittsburgh, PA, has been appointed Chair, School of Information and Library Science at UNC-CH. In order to maintain our board as “external” she has opted to resign and will be replaced shortly. Bill Tucci has accepted a position with the Kenan Foundation. We have contacted another person from the NC Department of Public Instruction await administrative approval. Finally, Dr. Carol Bessel, Associate Professor of Chemistry at Villanova University, has accepted a one-year assignment at NSF and so will go on leave of absence while she is in that position. She will not be replaced as her absence is temporary. Table VIIA. 2004-5 External Advisory Board Members Dr. Paul Anastas Professor Yolanda Banks Anderson White House Office of Science & Director, Environmental Science Technology Policy Program Executive Office of the President NC Central University Washington, DC Durham, NC Ernest R. Bibby Professor Carol Bessel Assistant Superintendent for School Associate Professor Improvement Planning and Technology, Department of Chemistry Granville County Schools Oxford, NC Villanova University Villanova, PA Dr. Ken Carter Prof. Jose-Marie Griffiths Assoc. Professor of Chemistry Chair University of Massachusetts School of Information and Library Amhearst, MA Science University of North Carolina-Chapel Hill CERSP, Page 146 of 230 Prof. Bala Subramaniam Chemical and Petroleum Engineering Director, NSF ERC for Environmentally Beneficial Catalysis University of Kansas, Lawrence, KS Dr. Miriam John Ms. Laura McClain Vice President, California Laboratory Sandia Research & Operations Manager Graduate Studies Office National Laboratory Meredith College, Raleigh, NC Livermore, CA Dr. Lloyd Robeson Dr. David Roessner Principal Research Associate Associate Director Science and Technology Center S&T Policy Program Air Products & Chemicals, Inc. SRI International Allentown, PA Center for Science, Technology & Educational Development, Flagstaff, AZ Dr. Ralph Taylor-Smith Mr. William J. Tucci Associate, Battelle Ventures Section Chief Princeton, NJ N. C. Dept. of Public Instruction Raleigh, NC Dr. Diane J. Hymes Director of Technology, New Product Development Lam Research Corporation Fremont, CA Dr. William Holton Research Professor of Electrical Engineering North Carolina State University Raleigh, North Carolina Dr. Parry Norling Visiting Fellow Chemical Heritage Foundation Philadelphia, Pennsylvania The External Advisory Board met on May 9 and May 27, 2005. The meetings comprised a review of our status, focusing on comments made by the NSF Site Review Team. A total of ten EAB members participated in this videoconference. This was our first attempt to conduct an EAB meeting by videoconference, and it proved to be an effective medium. A great many helpful comments were made, especially regarding our Strategic Plan. Plans to revamp our industrial affiliates program were endorsed. The meeting agenda and minutes are given in Appendix C. CERSP, Page 147 of 230 4. Strategic Plan Our revised Strategic Plan is documented below. The icon referenced in the text is shown in Figure VIIA at the end of this Section. Introduction and Background The purpose of the strategic plan is to focus all Center programs around key technical and social domains which support our vision: sustainable technology. Every activity within our Center should support our vision in a clear, unique way while being fully integrated with other Center activities. Our multi-disciplinary organization leverages diversity and understanding of social dynamics to realize the vision of the Center. These interactions are illustrated by our icon below. Technical domains (Macromolecular Synthesis and Engineering; Functional Materials and Devices; Nanostructures, and Separations) are represented in the icon by interlinked circles, indicating that technologies of each area are interdependent. Technical thrusts and conducted against a background of inter-related social programs that seek to further long-term technical goals. Four social domains (Leadership, Knowledge Exchange, Diversity and Education) represented by the square background, address the “social dimensions” of innovation. Our Innovation Process Research Program, represented by the circumscribed circle, supports these social domains. By understanding fundamentally what drives successful behavior in these key areas we hope to facilitate interdisciplinary research and the innovation process. The strategic plan is intended to establish direction and provide alignment, not to provide a roadmap set in concrete. It is updated annually and allows for flexibility, within limits. Both the product and the process are important. The direction that the Center takes over time results from hundreds of individual decisions. Thus, it is important not only to establish the right direction with our strategic plan but also to get everyone’s understanding, input and commitment. We develop our strategic plan as a cascade process. As the plan is being developed or revised, draft versions are “cascaded” throughout the Center to assure that everyone understands and has opportunity to input to the plan. Having agreed to the final plan everyone is expected to make decisions and take action aligned with it. Strategic planning is a cascade process on a second level as well: each step is linked to the preceding one with shorter range, narrower focus and greater detail. The process proceeds through vision mission goals objectives (VMGO). Performance measures are developed in each of the five areas shown on our icon CERSP, Page 148 of 230 (all research thrusts are taken together for reporting purposes). Planning began in 1999 with analysis of needs that supercritical fluids technology might address. We identified the barriers which separate us from the future to which we aspire. The need for sustainable “green” chemical processes was identified, leading to a vision reflecting the difference we hope to make. Current Strategic Plan Our vision is to enable a revolution in sustainable technology through cuttingedge, integrated physical science/engineering; social science; and educational programs. A “revolution in sustainable technology” captures the visionary part of this statement. Revolution implies risk. We purposefully undertake the type of highrisk/high-reward (high impact) research that industry increasingly avoids. Our vision and mission are meant to endure the life of the Center and beyond. Our statement of mission describes, at a high level of abstraction, the means we use to overcome barriers and achieve our vision. By including social processes, education and diversity in our mission statement, we mean to state unequivocally that these are as important to the ultimate success of our Center as technology; they are not “add-on” elements. Our mission is to: Support multi-disciplinary, fundamental research to identify and enable sustainable processes and products using CO2-related technologies Enable our science and technology to have broad societal benefit by understanding and applying social processes that foster collaboration, innovation and action; by attracting and educating diverse students at all levels; and by promoting the benefits of sustainability. "Identify and enable sustainable processes and products” means that we plan for and target our fundamental, cutting-edge science to have practical applications. “Sustainable” implies environmentally benign, energy efficient and economically competitive. “CO2-related technology” describes the focus of our cutting edge science and engineering. Technical Domains While our research focuses on fundamental understanding, our overarching technical goal is to identify and demonstrate feasibility of sustainable processes, materials, and devices as candidates for further development. Domains are selected by our Technical Coordinating Committee (TCC) based upon TCC assessment (with input from our industrial affiliates) of (1) where our technology can have maximum impact and (2) where potential exists for strong market growth for applications of our “green” technology. Our strategy is CERSP, Page 149 of 230 based upon the assumption that new technology is more readily accepted in emerging, high-value areas. Here rapid development and growth with changing technology are the norm. Acceptance of new technology in these areas is more likely than in commodity areas where investment is imbedded and growth slow. Details of the current plan are given in Table VIIB and specific projects listed in Table VIIC. The interlinked circles on our icon represent current technical domains and indicate that each area supports all of the others. For example, projects in Macromolecular Synthesis and Engineering provide polymers for those in Functional Materials and Devices. Meniscus coating studies in Functional Materials and Devices supports self-assembly studies in Nanostructures. Understanding of surfactant properties in Nanostructures supports developments in Macromolecular Synthesis and Engineering. Technology developed in Separations supports all other technical domains as economical recovery and recycle is a key to commercial success. In general we employ a strategy of time-sequencing: “open, narrow, close”. There is no specific period for these stages, but each is generally about two years (corresponding to the usual funding period). And most projects will go through them. At any given time projects in the Center may be in any of the three stages. (See Table VIIC as an example.) This is one mechanism that we use to keep the Center dynamic, constantly seeking renewal in order to remain at the frontier. During the “open” phase thinking is divergent as we seek to build broad fundamental understanding and develop necessary tools and facilities in a given field. We try to avoid pre-conceived notions of what is or is not important. Later, with input from various “knowledge exchanges” and our own scouting activities, we narrow our focus to specific areas that appear promising. In the “close” phase we prepare for transition. Projects may be closed if no additional fundamental studies are required. If the work has identified a potential commercial target(s) “close” may mean terminating STC-funded fundamental work in favor of sponsored research. If no sponsor is found “close” may mean literally shutting down the project or modifying the focus based on external factors. Projects may be closed due to a change of strategic plan. They may also be closed if annual review by the TCC decides that we aren’t leaders in the area as in the case of small molecule catalysis and biotech projects, where we lacked critical mass to lead. Social Science Domains The second part of our mission “enable our science to have broad societal benefit by understanding social processes that foster collaboration, innovation, and action” reflects our belief that technology alone is insufficient to achieve a revolution. CERSP, Page 150 of 230 People, not just technology, effect change; thus our social programs are keys to the long-term success of our Center. These programs include exchanges, workshops and scholarly studies that are also of immediate value within the Center. They encompass all four social domains shown on our icon. The Innovation Process Research Program contributes to • leadership: study of successful leadership qualities among directors of NSFsponsored centers and tools to improve such qualities; and a leadership workshop for students • “knowledge exchange”: study of factors contributing to success or failure of industrial consortia, development of cross-disciplinary text-mining tools, and an innovation workshop • diversity: study of factors contributing or hindering HCBU/Research I cooperative research, a pilot program regarding possible role of AfricanAmerican churches in outreach, and a multi-dimensional mentoring/scholarship program aimed at recruiting African-American students into STEM graduate programs • education: study of factors contributing to student success within NSFsponsored centers Leadership is a key factor in “action” or implementation. Understanding the innovation process, including social processes of research collaboration, are key components of leadership. Improving the leadership skills of Center participants, from students to the Director, facilitates our current research, as well as providing long-term benefits. Further, to effect a “revolution in sustainable technology” will require a new generation of students. Our students will need not only the technological skills but the leadership skills (with the resultant courage, selfconfidence and political sensitivity) to lead this revolution. Our academic study of successful leadership qualities and feedback mechanisms for complex, multidimensional research should improve operations in current and future NSF centers, including our own. Within the Center our leadership plan is to employ a few key operational structures to implement our strategic plan. The management team has made clear the need for integration of all aspects of the Center. We employ Center-level, sitelevel and thrust area-level leadership teams to coordinate all Center activities. Our vision requires that our work have great impact. We choose our projects carefully to have that impact. Projects must provide technical leadership or they will not be funded. If we cannot be among the leaders in a particular area, we will redeploy resources to areas in which we can. CERSP, Page 151 of 230 Effective “knowledge exchange” is required for successful implementation of our technology. We prefer that term rather than more commonly used terms “technology transfer” or “knowledge transfer”. “Exchange” implies continual communication on multiple fronts. It involves all of our constituencies: scientists, students, industry and society—directly and via our External Advisory Board, which we use extensively. Most technical exchange is among academic and industrial researchers, but as appropriate we also involve development boards, legislative and regulatory bodies, venture capitalists, etc. We need their input and seek to make them allies in our “revolution”. “Exchange” implies on-going co-operation, not “fait accompli” communication of plans. Exchange with industry remains critical, including constructive criticism of our research, market information, and supply of materials and research technology not generally available. Our industrial affiliates program requires minimal contribution by participants. We use this funding to improve information dissemination by frequent direct exchange with industrial scientists rather than using it to fund supplemental research. We anticipate that improved dissemination will result in more meaningful collaborations, with fewer but larger research contracts. These contracts will aim at strengthening specific technology of commercial interest by focusing on thematic, one-on-one projects between Center researchers and individual companies. Large chemical companies are becoming increasingly dependent upon investing in startups as a way to acquire new technology. Thus, we will involve more entrepreneurial and venture capital organizations in knowledge exchange activities. While our target audience may be broadening somewhat, our role in the innovation process is unchanged. We seek to advance the frontiers of science, to enable, and to catalyze change. We “develop” only to the extent necessary to advance science; e.g., by developing tools for specific experimentation. Exchange has been and will continue to be accomplished by many means: shared facilities, papers (especially joint), industrial affiliations and “sabbaticals”, licensing of IP, symposia, surveys, presentations in a wide range of conferences and forums (technical and non-technical), newsletters, articles in the public press, museum exhibits, continuing education courses, etc. Diversity is an integral dimension of our Center—not only diversity in race and gender but diversity of thought, skills, and discipline—and is necessary to successful innovation. While brilliant ideas come from individuals, innovation requires diversity. We seek to elicit the benefits of diversity by recognizing differences and providing communication skills to bridge and capitalize on differences. We study past HBCU/Research I collaborations in order to identify factors for success or failure. We seek and support diverse populations at all levels—from K-12 students to faculty CERSP, Page 152 of 230 to members of our External Advisory Board. While we “count” extensively, more importantly we seek ways to increase diversity in the pool of scientists and engineers entering graduate schools. Education at all levels is important to achieving our Center’s long-term vision. We extensively leverage existing programs and resources to increase impact, including K-12 programs at Science House and various outreach programs at all universities. We demonstrate to large numbers of K-12 students that hands-on science is fun. In addition we teach that sustainability is a serious issue that they can do something about. Societal “buy-in” is required for innovation, especially in generating the “pull” for green technology. Our intent is not only to recruit a new generation of scientists but to help educate a new generation of citizens regarding the environmental impact of modern society and the necessity of sustainability. And by participating in these “outreach” activities our students hone their own understanding and communication skills. Research Program Evolution Having identified barriers and established a vision and mission, we initially defined “thrust areas” with shorter term goals supporting our vision. Thrust areas were defined so as to have greatest impact in overcoming key barriers. Specific projects were developed to achieve these shorter term goals. We update our plan annually, consistent with our initial vision and mission. While our vision and mission have changed little, objectives, goals, domains and/or performance measures change periodically. This evolution is driven both by our discoveries—growing recognition of the capabilities of our technology—and external factors. We are currently on our fourth set of “thrust areas” or “domains”. We now use the term “implementation domain” to remind ourselves that the eventual goal is commercialization of technology that we develop. While the three-phase approach described above under Technical Domains is the norm, we are flexible. For example, in our Renewal Proposal we identified “Microelectronics” as a major new implementation domain, anticipating transition of the industry to 157nm irradiation technology. When the industry leader, Intel, dropped 157 nm programs so did many other companies who had invested hundreds of millions of dollars in 157nm lithography. Several months down this path we revised our strategic plan (to the one described herein) reflecting this reality. Microelectronics was broadened to become “Functional Materials and Devices.” Several projects were redirected within months of their start, but without significant loss of momentum or student research time. CERSP, Page 153 of 230 This recent foray into and out of microelectronics is consistent with our strategy outlined above. The strategy was appropriate, but our understanding of industry structure was flawed. While processes evolve rapidly (fitting our strategy), the underlying technology is firmly embedded. A frontal assault across the entire range of process steps to “revolutionize” the industry is too expensive and not supported by industry. Rather than trying to displace incumbent technology broadly, we have now decided to focus on a few steps with higher probability of success. Meanwhile, we will seek other applications for emerging studies in our laboratories. Rather than closing this domain entirely, we have widened its view to related topics applying similar technology not directly associated with microelectronics. For example, studies in photolithography have lead to discovery of “soft lithography” capable of replicating nanostructures and to technology that might be applicable to fuel cells. Both of these areas fall within our vision and mission. Social science programs have gone through one cycle of evolution. Our early focus on collaboration was appropriate initially as we needed to develop tools and skills for remote collaboration. We have reconstituted our social science research as the Innovation Process Research Program. It encompasses all aspects of “Social Domains”—leadership, “knowledge exchange”, education and diversity—in an effort to understand how these factors can facilitate the Center’s multi-disciplinary research and the innovation process: e.g., in taking technology to commercialization. These projects are selected not only to be excellent stand-alone academic work but to provide real time information useful for ongoing Center operations. Strategic Synopsis The following “strategic synopsis” summarizes our current strategic plan, including vision, mission, goals, objectives, performance measures and research program plan for 2005-2006. Table VIIB. Vision, Mission, Goals, Objectives and Performance Measures Vision and Mission Our vision is to enable a revolution in sustainable technology through cuttingedge, integrated physical science/engineering; social science; and educational programs. Our mission is to Support multi-disciplinary, fundamental research to identify and enable sustainable processes and products using CO2-related technology CERSP, Page 154 of 230 Enable our science and technology to have broad societal benefit by understanding and applying social processes that foster collaboration and innovation; by attracting and educating diverse students at all levels; and by promoting the benefits of sustainability. Goals, Objectives and Performance Measures Research Objectives • Develop fundamental understanding of o Macromolecular synthesis and engineering: kinetic and transport mechanisms, thermodynamics, phase equilibria; factors affecting polymeric structure of materials and function in CO2-related systems, including catalytic and post-polymerization processes o Nanostructures: beneficial properties of supercritical CO2 that enable control of synthesis, stabilization, deposition and self-assembly of nano-scale structures o Functional materials and devices: phenomena involved in dissolution and removal of materials, formation of thin films and coatings, dimensional control of structures, and photochemical conversions o Separations: phenomena specific to separation science and technology needed for CO2 processing • Integrate fundamental understanding in these areas to demonstrate processes for functional materials; e.g., for electronic, optical, energy and therapeutic applications in order to identify and demonstrate feasibility of sustainable processes, materials, and devices as candidates for further development. • Explore new frontiers in relevant basic science in order to identify new areas for application of sustainable technology • Develop fundamental understanding of key factors impacting leadership, knowledge exchange, education and diversity in order to facilitate the innovation process Research Performance Measures • Number of peer-reviewed publications in professional journals • Reference citations • Presentations at major professional meetings, invited lectures and seminars, etc. • Number and quality of external collaborative interactions • Matching funds attracted CERSP, Page 155 of 230 • Effective utilization (and sharing) of facilities • Number of effective tools to facilitate cross-disciplinary research, such as those for full-text data mining Education Objectives • Improve the educational process at all levels to provide a new generation of students with technical and leadership tools to support and implement “green chemistry”. • Enhance K-12 students’ and teachers’ knowledge of science and engineering, the importance of collaboration and how these fields contribute to a cleaner environment, through curriculum development, classroom visits, and teacher workshops. in order to build broad societal support needed for implementing sustainable processes Education Performance Measures • The numbers of undergraduate, graduate and post-doctoral associates advised • Undergraduate internships and percentage of students attending graduate school • Number of students receiving awards and presenting external papers • Written evaluations by teachers of curriculum materials and teacher workshops • The number of training modules produced and disseminated • A database documenting impacted teachers and number of students • The number of CERSP students and faculty members involved in outreach • Documented performance improvements in Center students vs. non-Center peer group Knowledge Exchange Objectives • Establish multi-dimensional communication pathways by which o knowledge developed in the CERSP can be efficiently transferred to those who will implement it and/or benefit from it and o the views and needs outside the CERSP are factored into our plans o governmental agencies are apprised of our accomplishments, plans and needs • Leverage resources of the Center to establish individual and organizational partnerships in order to convert technical knowledge into successful, sustainable processes CERSP, Page 156 of 230 Knowledge Exchange Performance Measures • Exchanges with industrial and entrepreneurial affiliates and government officials, Center-sponsored symposia, workshops, and use of facilities for knowledge exchange • Personnel exchanges, number of visiting scientists and number of joint papers • Dissemination of information via CERSP Newsletter and website • Patent donations, filings, acquisitions and other intellectual property management Diversity Objective Encourage members of underrepresented groups (URG) to seek and succeed in careers in science and engineering by focusing on them K-20 outreach, mentoring and recruiting efforts in order to help build a diverse workforce and reap the benefits of diversity Diversity Performance Measures • Social science studies completed documenting effective programs to accomplish objective • Tools to improve URG participation in research, resulting from social science studies • Number of URG students participating in STC-sponsored events • Number and %age of CERSP-affiliated URG students who enter graduate programs • Number and %age of URG faculty and support provided • Number and percentage of STC participants involved in diversity-enhancing activities • Number of strategic alliances with national networking organizations devoted to URGs • Number of connections with HBCUs as measured by lectures and exchanges Leadership Objectives • Develop and apply fundamental understanding of social processes fostering collaboration, innovation, and action in the CERSP in order to empower individuals to reach career goals while furthering the organization’s scientific, technological and educational goals • Study, develop, improve and apply leadership skills of STC participants at all levels in order to enhance effectiveness of Center operations CERSP, Page 157 of 230 Leadership Performance Measures • The number (and percentage) participating in our Personal Development Program • The number and effectiveness of leadership tools developed and implemented • Annual review and revision of strategic plan Table VIIC 2005-6 Technical Research Projects Macromolecular Synthesis and Engineering Nanostructures Leader: Roberts NCSU Polymerization in CO2 Metal catalyzed reduction of C-H Brookhart ^ Continuous homogenous polymerization Roberts Post-polymerization hydrogenation Roberts Thermodynamic measurements Kabadi Calorimetry of macromolecules in CO2 Kabadi H+ super-conductive materials DeSimone# Polymer processing Plasticization of FP at hi temp and press: NMR Samulski Swelling & crystallization of DB thin films Green Leader: Johnston UT-A Synthesis and stabilization Diffusion & electron transport Murray Polypeptide microemulsions Waters^ Polymer filled nanocomposites Khan Intercalation of polymers Samulski # Synthesis, stabiliz’n, and separation of nanocrystals Korgel Surfactants for nanoparticle assembly Rossky Thin film nano-crystal composites Green Self-Assembly Controlled self-assembly Velev Nano self-assembly patterned surfaces Johnston Nano self-assembly solid substrates Korgel CERSP, Page 158 of 230 Functional Materials and Devices Leader: Parsons NCSU Dry film processes Annealing of organic films Irene# Deposition of thin films Carbonell FMC in drug delivery Carbonell Anomalous swelling of thin films Sanchez Lithography New materials for imprint lithography^ Photochemical darkening at 193 nm Forbes^ Soft lithography DeSimone# Deposition Dielectric deposition Parsons Metal film deposition Parsons Reactive deposition of metal and ceramic K. Roberts Etching/dissolution Applications Particle PRINTing DeSimone # Colloidal crystals & porous templates Johnston Nanoparticles for high bioavailability Johnston Interfacial properties Johnston Separations Leader: Koros Georgia Tech Polymer synthesis for separations Ashby# High zeolite-polymer hybrid Koros# Zeolite-solvent-resistant poly hybrid Koros# Carbon-polymer Koros# Mesoporous ceramic membranes Ilias# Projects completed in 2005 Welding of polymers using CO2 Sanchez* Rheological studies of PVDF Khan* Kinetics of polymerization & precip. Rubinstein* CO2 treatments of organic films Irene Solution properties: SALLS, DLS QCM: deposition/dissolution rates Grant DeSimone* Optical methods to monitor dissolution Genzer Solution properties: Theory Rubinstein* Fuel Cells Processing photoresists Carbonell* Degradation processes Forbes# Molecular dynamics Berkowitz* CMP process studies Carbonell* # New projects started in Continuous polymerization of acrylic acid FY2005 Roberts* ^Projects redirected during FY2005 Colors indicate schools: UNC-CH, NCSU, * Projects completed during FY2005 UT-A, GaTech and NCA&T 2005-6 Social Science Research Projects Leader Denis Gray CERSP, Page 159 of 230 Leadership Successful leadership qualities in NSF Centers—Craig # Leadership workshop^—Osmond Knowledge Exchange Factors affecting success or failure of industrial consortia--Gray Development of cross-disciplinary text mining tools—Blake # Colors indicate schools: UNC-CH, NCSU, and NCA&T Diversity HCBU/Research I cooperative research— Gray # Studies of African-American churches in outreach—Martin # EXPERT mentoring program—Bothun # Education Factors affecting student satisfaction in Centers--Gray # New projects started in ^ Projects redirected during FY2005 FY2005 CERSP, Page 160 of 230 Figure VII A. New Icon for CERSP CERSP, Page 161 of 230 VIII. Center-Wide Outputs and Issues 1a. Center Publications Peer-Reviewed Publications (August 2004- June 2005) 1. Anderson, Darren; Anthony, Jennifer; Chanda, Arani; Denison, Ginger*; Drolet, Melissa; Fort, Diego; Joselevich, Maria; Whitfield, Justin (2004). “Green approaches: a new horizon for future scientists.” Green Chemistry 1, G5-G9. 2. Andre, P.; S. L. Folk, M. Adam, M. Rubinstein, and J. M. DeSimone (2004). “Light Scattering Study of Polydimethyl Siloxane in Liquid and Supercritical Carbon Dioxide,” J. Phys. Chem. A 108, 9901-9907. 3. Bessel, Carol A.; Denison, Ginger M.; DeSimone, Joseph M.; DeYoung, James; Gross, Stephen; Schauer, Cynthia K.; Visintin, Pamela “Etchant Solutions for the Removal of Cu(0) in a Supercritical CO2-Based ‘Dry’ Chemical Mechanical Planarization Process for Device Fabrication,” J. Am. Chem. Soc. 2003, 125(17), 4980-4981. (not previously reported). 4. Blatchford, Marc A.; Raveendran, Poovathinthodiyil; Wallen, Scott L. (2003) “Spectroscopic Studies of Model Carbonyl Compounds in CO2: Evidence for Cooperative C-H O Interactions,” Journal of Physical Chemistry A, 107(48), 10311-10323 (not reported as published in 2004 report) 5. Burns, R. L.; K. M. Steel, S. D. Burns and W. J. Koros (2004). “Explanation of a selectivity maximum as a function of the material structure for organic gas separation membranes”, Industrial & Engineering Chemistry Research, 43(18), 5942-5949. 6. Cao, T.; K. P. Johnston and S. E. Webber (2005). “CO2-Enhanced Transport of Small Molecules in Thin PMMA Films,” Macromolecules, 38, 1335-1340. 7. Carruthers, S. B.; G. Ramos and W. J. Koros (2004). ”Morphology of integral-skin layers in hollow fiber gas separation membranes”, Journal of Applied Polymer Science, 90(2), 399-411. 8. Chennamsetty, Naresh; Bock, Henry; Scanu, Lauriane F.; Siperstein, Flor R.; Gubbins, Keith E.. (2005). “Cosurfactant and cosolvent effects on surfactant selfassembly in supercritical carbon dioxide,” Journal of Chemical Physics, 122(9), 094710/1-094710/11. CERSP, Page 162 of 230 9. Colina, C. M.; Galindo, A.; Blas, F. J.; Gubbins, K. E. (2004) “Phase behavior of carbon dioxide mixtures with n-alkanes and n-perfluoroalkanes,” Fluid Phase Equilibria 222-223, 77-85. 10. Colina, Coray M.; Gubbins, Keith E. (2005). “Vapor-Liquid and Vapor-LiquidLiquid Equilibria of Carbon Dioxide/n-Perfluoroalkane/n-Alkane Ternary Mixtures,” J. Phys. Chem. B 109(7), 2899-2910. 11. Cotugno, S.; E. DiMaio, G. Mensitieri, S. Iannace, G.W. Roberts, R.G. Carbonell and H.B.Hopfenberg, (2005). “Characterization of Microcellular Biodegradable Polymeric Foams Produced from Supercritical Carbon Dioxide Solutions,” I&EC Research 44(6), 1795-1803. 12. Damle, S. and W. J. Koros (2005). “Sorp-Vection: An Unusual MembraneBased Separation”, AIChE Journal 51, 1396-1405. 13. Dickson, Jasper L.; Ortiz-Estrada, Ciro; Alvarado, Juan F. J.; Hwang, Ha Soo; Sanchez, Isaac C.; Luna-Barcenas, Gabriel; Lim, Kwon Taek; Johnston, Keith P. (2004) “Critical flocculation density of dilute water-in-CO2 emulsions stabilized with block copolymers,” Journal of Colloid and Interface Science 272(2), 444456. 14. Dickson, J. L.; P. G. Smith, V. V. Dhanuka, V. Srinivasan, M. T. Stone, P. J. Rossky, J. A. Behles, J. S. Keiper, B. Xu, C. S. Johnson, J. M. DeSimone and K. P. Johnston (2005). “Interfacial Properties of Fluorocarbon and Hydrocarbon Phosphate Surfactants at the Water - CO2 Interface,” Industrial & Engineering Chemistry Research, 44, 1370-1380. 15. Dickson, J. L.; P. S. Shah, B. P. Binks and K. P. Johnston (2004). “Steric Stabilization of Core-Shell Nanoparticles in Liquid Carbon Dioxide at the Vapor Pressure,” Langmuir, 20, 9380-9387. 16. Dobrynin, A. V.; R. H. Colby, and M. Rubinstein (2004). “Polyampholytes,” J. Pol. Sci.: Polym. Phys. B42, 3513-3538. 17. Frankowski, D.J.; Fournier-Bidoz, S.; Manners, I.; Ozin, G.A.; Khan, S.A.; Spontak, R.J. (2004). Tunable Microcellular Morphologies from Poly(ferrocenylsilane) Ceramic Precursors Foamed in Supercritical CO2. Macromolecular Chemistry and Physics 2004, 2398-2408. 18. Frankowski, D.J.; Raez, J.; Manners, I.; Winnik, M.A.; Khan, S.A.; Spontak, R.J. (2004). “Formation of Dispersed Nanostructures from CERSP, Page 163 of 230 Poly(ferrocenyldimethylsilane-b-dimethylsiloxane) Nanotubes Upon Exposure to Supercritical Carbon Dioxide,” Langmuir 20, (21), 9304-9314. 19. Guo, Rui; Dimitra Georganopoulou, Stephen W. Feldberg, Robert Donkers, Royce W. Murray (2005). “Supporting Electrolyte and Solvent Effects On Single Electron Double Layer Capacitance Charging of Hexanethiolate-Coated Au140 Nanoparticles,” Anal. Chem. 77, 2662-2669. Partially funded. 20. Hall, Carol K. (2005) Preface. Fluid Phase Equilibria 228-229, 2. 21. Hoggan, E. N.; Flowers, D.; Wang, Ke.; DeSimone, J. M.; Carbonell, R. G. (2004). “Dry Lithography Using Liquid and Supercritical Carbon Dioxide-based Chemistries and Processes”; IEEE Transactions 17(4), 510-516. 22. Hussain, Yazan; Krim, Jacqueline; Grant, Christine. (2005) “OTS adsorption: A dynamic QCM study,” Colloids and Surfaces, A: Physicochemical and Engineering Aspects 262(1-3), 81-86. 23. Jimenez, Victoria L.; Dimitra G. Georganopoulou, Ryan J. White, Amanda S. Harper, Allan J. Mills, Dongil Lee and Royce W. Murray (2004). A Hexanethiolate Monolayer-Protected 38 Gold Atom Cluster, Langmuir, 20, 6864-6870. Partially funded 24. Johnston, K. P.; S. R. P. Da Rocha, C. T. Lee, G. Li and M. Z. Yates (2004). “Colloid and interface science for CO2-based pharmaceutical processes,” Drugs and the Pharmaceutical Sciences, 138, 213-245. 25. Jones, C. A.; Geissler, A.; DeYoung, J. P.; McClain, J. B.; Carbonell, R.; *DeSimone, J. M. (2004). “Applications of “Dry” Processing in the Microelectronics Industry Using Carbon Dioxide”; Critical Reviews in Solid State and Materials Sciences 29, 97-109. 26. Jones, Charles A.; Yang, Dongxing; Irene, Eugene A.; Gross, Stephen M.; Wagner, Mark; DeYoung, James; DeSimone, Joseph M. (2003) “HF Etchant Solutions in Supercritical Carbon Dioxide for ‘Dry’ Etch Processing of Microelectronic Devices,” Chemistry of Materials 15(15), 2867-2869. (not previously reported) 27. Koros, W. J. (2004). “Evolving beyond the thermal age of separation processes: membranes can lead the way”, AIChE Journal., 50(10), 2326-2334. 28. LaRue, I.; M. Adam, M. da Silva, S. Sheiko and M. Rubinstein (2004). “Wormlike CERSP, Page 164 of 230 Micelles of Block Copolymers: Measuring the Linear Density by AFM and Light Scattering”, Macromolecules 37, 5002-5005. 29. Li, Zhengmin; Hall, Carol K. (2004), “Phase Behavior in Model Homopolymer/CO2 and Surfactant/CO2 Systems: Discontinuous Molecular Dynamics Simulations,” Langmuir 20(20), 8559-8568. 30. Liu, B.; Rolland, J. P.; DeSimone, J. M.; Bard*, A. J. (2005). “Fabrication of Ultramicro-electrodes Using A ‘Teflon-like’ Coating Material”, Anal. Chem. 77, 3013-3017. 31. Liu T., DeSimone J. M. and Roberts G. W. (2005). “Continuous Precipitation Polymerization of Acrylic Acid in Supercritical Carbon Dioxide: The Polymerization Rate and the Molecular Weight”. Journal of Polymer Science Part A: Polymer Chemistry 43(12), 2546-2555. 32. Lu, L., and M. L. Berkowitz (2004). Molecular Dynamics Simulation of a Reverse Micelle Self Assembly in Supercritical CO2. J. Am. Chem. Soc. 126, 1025410255. 33. Lu, X.; B. A. Korgel, K. P. Johnston (2005). “Synthesis of Germanium Nanocrystals in High Temperature Supercritical CO2,” Nanotechnology 16, S389S394. 34. Lu, X.; K. J. Ziegler, A. Ghezelbash, K. P. Johnston, B. A. Korgel (2004). “Synthesis of Germanium Nanocrystals in High Temperature Supercritical Fluid Solvents,” NanoLetters, 4, 969-974. 35. Meli, L.; J. Q. Pham, K. P. Johnston and P. F. Green (2004). “Polystyrene thin films in CO2,” Physical Review E: Statistical, Nonlinear, and Soft Matter Physics, 69, 051601/1-051601/8. 36. Moore, T. T.; S. Damle, P. J. Williams and W. J. Koros (2004). “Characterization of low permeability gas separation membranes and barrier materials; design and operation considerations”, Journal of Membrane Science 245(1-2), 227-231. 37. Moore, T. T.; R. Mahajan, D. Q. Vu and W. J. Koros (2004). “Hybrid membrane materials comprising organic polymers with rigid dispersed phases”, AIChE Journal, 50(2), 311-321. 38. Panyukov, S. P., and M. Rubinstein (2005). “Explanation of Anomalous Scaling of Swollen Entangled Chains”, Macromolecules 38, 3511-3514. CERSP, Page 165 of 230 39. Prevo, B. G.; J. C. Fuller, III and O. D. Velev (2005). “Rapid deposition of gold nanoparticle films with controlled thickness and structure by convective assembly,” Chem. Mater., 17, 28. 40. Raveendran, Poovathinthodiyil; Blatchford, Marc A.; Hurrey, Michael L.; White, Peter S.; Wallen, Scott L.. (2005). “Crystallization and processing of carbohydrates using carbon dioxide,” Green Chemistry 7(3), 129-131. 41. Raveendran, Poovathinthodiyil; Fu, Jie; Wallen, Scott L. (2003) “Completely green synthesis and stabilization of metal nanoparticles,” Journal of the American Chemical Society 125(46), 13940-13941. (not reported in 2004 report) 42. Raveendran, Poovathinthodiyil; Ikushima, Yutaka; Wallen, Scott L. (2005), “Polar Attributes of Supercritical Carbon Dioxide,” Accounts of Chemical Research 38(6), 478-485. 43. Rolland, J. P.; Hagberg, E. C.; Carter,* K. R.; DeSimone, J. M. (2004). “High Resolution Soft Lithography: Enabling Materials for Nano-Technologies”, Angew. Chem. Int. Ed. 43, 5796-5799. 44. Saunders, A. E.; B. A. Korgel (2005). “Observation of an AB Phase in Bidisperse Nanocrystal Superlattices,” ChemPhysChem 6, 61-65. 45. Saunders, A. E.; B. A. Korgel (2004). “Second Virial Coefficient Measurements of Dilute Gold Nanocrystal Dispersions Using Small Angle X-ray Scattering,” Journal of Physical Chemistry B 108, 16732-16738. 46. Saunders, A. E.; P. S. Shah, E. J. Park, K. T. Lim, K. P. Johnston and B. A. Korgel (2004). “Solvent Density-Dependent Steric Stabilization of Perfluoropolyether-Coated Nanocrystals in Supercritical Carbon Dioxide,” Journal of Physical Chemistry B, 108, 15969-15975. 47. Saunders, A. E.; P. S. Shah, M. B. J. Sigman, T. Hanrath, H. S. Hwang, K. T., K. P. Johnston and B. A. Korgel (2004). “Inverse Opal Nanocrystal Superlattice Films,” Nano Letters, 4, 1943-1948. 48. Saunders, A.E.; M.B. Sigman, B.A. Korgel (2004). “Growth Kinetics and Metastability of Monodisperse Tetraoctylammonium Bromide-Capped Gold Nanocrystals,” Journal of Physical Chemistry B 108, 193-199. CERSP, Page 166 of 230 49. Sehgal, Amitabh C.; Kelly, Robert M. (2003) “Strategic Selection of Hyperthermophilic Esterases for Resolution of 2-Arylpropionic Esters,” Biotechnology Progress 19(5), 1410-1416. (not previously reported) 50. Senapati, S., and M. L. Berkowitz (2004). “Computer Simulation Studies of Water States in Perfluoro Polyether Reverse Micelles: Effects of Changing the Counterion,” J. Phys. Chem. A. 108, 9768-9776. 51. Shah, P. S.; T. Hanrath, K. P. Johnston, B. A. Korgel (2004). “Nanocrystal and Nanowire Synthesis and Dispersibility in Supercritical Fluids,” Journal of Physical Chemistry B 108, 9574-9587. 52. Shieh, F.; A. E. Saunders, B. A. Korgel (2005). “General Shape Control of Colloidal CdS, CdSe, CdTe Quantum Rods and Quantum Rod Heterostructures,” Journal of Physical Chemistry B 109, 8538-8542. 53. Sigman, M.B.; A.E. Saunders, B. A. Korgel (2004). “Metal Nanocrystal Superlattice Nucleation and Growth,” Langmuir 20, 978-983. 54. Sirard, S. M.; H. Castellanos, P. F. Green and K. P. Johnston (2004). “Spectroscopic Ellipsometry of Grafted Poly(dimethylsiloxane) Brushes in Carbon Dioxide,” J. Supercritical Fluids 32, 265-273. 55. Siripurapu, S.; J. M. DeSimone, S. A. Khan and R. J. Spontak (2004). “LowTemperature, Surface-Mediated Foaming of Polymer Films”, Advanced Materials 16, 989-994. 56. Siripurapu, S.; DeSimone, J. M.; Khan, S. A.; Spontak*, R. J. (2005). “Controlled Foaming of Polymer Films Through Restricted Surface Diffusion and the Addition of Nanosilica Particles or CO2-Philic Surfactants”; Macromolecules 38, 22712280. 57. Siripurapu, S.; R.J. Spontak and S.A. Khan (2004). “Surface-Constrained Foaming of Polymer Thin Films with Supercritical Carbon Dioxide”, Macromolecules 37, 9872-9879. 58. Steenhuis, H. and Gray, D.O. (2005). “Strategic decision making in public funded innovative organizations: An exploratory study,” International Journal of Technology Transfer and Commercialisation, pp. 127-147. CERSP, Page 167 of 230 59. Striolo, Alberto; Colina, Coray M.; Gubbins, Keith E.; Elvassore, Nicola; Lue, Leo. (2004). “The Depletion Attraction between Pairs of Colloid Particles in Polymer Solution,” Molecular Simulation 30(7), 437-449. 60. Visintin, P. M.; Carbonell, R. G.; Schauer, C. K.; DeSimone*, J. M. (2005). “Chemical Functionalization of Silica and Alumina Particles for Dispersion in Carbon Dioxide”; Langmuir 21, 4816- 4823. 61. Visintin, Pamela M.; Bessel, Carol A.; White, Peter S.; Schauer, Cynthia K.; DeSimone, Joseph M. (2005). “Oxidative Dissolution of Copper and Zinc Metal in Carbon Dioxide with tert-Butyl Peracetate and a -Diketone Chelating Agent,” Inorganic Chemistry 44(2), 316-324. 62. Wang, Xiao-Yan; Lee, Kenneth M.; Lu, Ying; Stone, Matthew T.; Sanchez, I. C.; Freeman, B. D. (2004) “Cavity size distributions in high free volume glassy polymers by molecular simulation,” Polymer 45(11), 3907-3912. 63. Wind, J. D.; D. R. Paul and W. J. Koros (2004). “Natural gas permeation in polyimide membranes”, Journal of Membrane Science 228(2), 227-236. 64. Wu, You-Ting; P.J. Akoto-Ampaw , M. Elbaccouch , M. L. Hurrey , S. L. Wallen, and Christine S. Grant (2004). “Quartz crystal microbalance (QCM) in highpressure carbon dioxide: Experimental aspects of QCM theory and CO2 adsorption”, Langmuir 20 (9): 3665-3673. 65. Xu, B.; Lynn, G. W.; Guo, J.; Melinchenko, Y. B.; Wignall, G. D.; McClain, J. B.; DeSimone, J. M.; Johnson, Jr., C. S. (2005). “NMR and SANS Studies of Aggregation and Microemulsion Formation by Phosphorous Fluorosurfactants in Liquid and Supercritical Carbon Dioxide”; C. S. J. Phys. Chem. 109, 10261-10269. 66. Xu, D.; R. G. Carbonell, G. W Roberts, and D. J. Kiserow (2005). “Phase Equilibrium for the Hydrogenation of Polystyrene in CO2-swollen Solvents”, J. Supercrit. Fluids, 34, 1. 67. Ye, W.; DeSimone (2005). J. M. “Emulsion Polymerization of N-Ethylacrylamide in Supercritical Carbon Dioxide”; Macromolecules 38, 2180-2190. 68. Young, J. L.; and DeSimone, J. M. (2005). “Advantages of Supercritical Carbon Dioxide for Composite Particle Synthesis Using Water-Soluble or Water-Reactive Monomers”; Macromolecules 38, 4542-4544. CERSP, Page 168 of 230 69. Zhao, Qian; Samulski, Edward T. (2003), “Supercritical CO2-Mediated Intercalation of PEO in Clay,” Macromolecules 36(19), 6967-6969. (not previously reported) 70. Zhulina, E. B.; M. Adam, I. LaRue, S. Sheiko, and M. Rubinstein (2005). “Diblock Copolymer Micelles in a Dilute Solution,” Macromolecules 38, 5330-5351. Papers shown in red above were reported as being in press in 2004 Annual Report. Papers shown in Times font were previously published but not previously reported. In Press as of July 2005 1. Harbron, Elizabeth J.; W. Clayton Bunyard and Malcolm D. E. Forbes (2005). “EPR Spin Probe Study of Carbon Dioxide Induced Polymer Plasticization”, J. Poly. Sci. B: Polym. Phys. 2. Leach, W. T.; D. T. Simpson, T. N. Val, Z. Yu, K. T. Lim, E. J. Park, R. O. Williams and K. P. Johnston (2005). “Encapsulation of Protein Nanoparticles into Uniform-Sized Microspheres Formed in a Spinning Oil Film.” J. Pharm. Sci. Tech.. 3. Li, Zhengmin; Hall, Carol K.. “Parametric Studies of Interaction Strengths in Polymer/CO2 Systems: Discontinuous Molecular Dynamics Simulations”. Langmuir ACS ASAP. 4. Liu, T.; DeSimone, J. M.; Roberts, G. (2005). “Continuous Precipitation Polymerization of Acrylic Acid in Supercritical Carbon Dioxide: Polymerization Rate and Polymer Molecular Weight”; J. Polym. Sci. Part A: Polymer Chemistry. 5. Lu, X.; B. Korgel and K. P. Johnston (2005). “Synthesis of germanium nanocrystals in high temperature supercritical CO2,” Nanotechnology. 6. Prevo, B. G.; Y. Hwang and O. D. Velev (2005). “Convective assembly of antireflective silica coatings with controlled thickness and refractive index,” Chem. Mater. 7. Rolland, J. P.; Maynor, B. W.; Euliss, L. E.; Exner, A. E.; Denison, G. M.; DeSimone*, J. M (2005). “Direct Fabrication and Harvesting of Monodisperse, CERSP, Page 169 of 230 Shape Specific Nano-Biomaterials”; J. Am. Chem. Soc. 8. Ryoo, W.; J. L. Dickson, V. V. Dhanuka, S. E. Webber, R. T. Bonnecaze and K. P. Johnston (2005). “Electrostatic Stabilization of Colloids in Carbon Dioxide: Electrophoresis and Dielectrophoresis,” Langmuir, ACS ASAP. 9. Steenhuis, H.J. and Gray, D.O. (2005). “A review of structure and research strategy development in NSF Science and Technology Centers: Heterogeneity as the norm,” International Journal of Technology Transfer and Commercialisation. 10. Whittier, R. E., Xu, D., van Zanten, J. H., Kiserow, D. J., and Roberts, G. W., “Viscosity of Polystyrene Solutions Expanded with Carbon Dioxide”, J. Appl. Poly. Sci. 11. Xu, D., Carbonell, R. G., Kiserow, D. J., and Roberts, G. W., “Hydrogenation of Polystyrene in CO2-Expanded Solvents: Catalyst Poisoning”, Ind. Eng. Chem. Res. Books and Book Chapters (August 2004-June 2005) 1. Kennedy, K. A.; Roberts, G. W.; and DeSimone, J. M. (2005). “Heterogeneous Polymerization of Fluoro-olefins in Supercritical Carbon Dioxide”; in Advances in Polymer Science 175, 329-346; Editor; Springer, Okubo, M. 2. Kiserow, D. J.; Shi, C.; Roberts*, G. W.; Gross, S. M.; DeSimone, J.M. (2005) “Solid-State Polymerization of Poly(bisphenol A carbonate) Facilitated by Supercritical Carbon Dioxide””; in Advances in Polycarbonates; Editors: Brunelle, D. J.; Korn, M. R.; ACS Symposium Series 898: 86-94. 3. Paisner, S. N.; and DeSimone, J.M. (2004) “Micro- and Nanoporous Materials Developed Using Supercritical Carbon Dioxide”; in Polymers for Microelectronics and Nanoelectronics; Editors: Lin, Q.; Pearson, R. A.; Hedrick, J. C.; ACS Symposium Series 874: 223-235. 4. Raveendran, Poovathinthodiyil; Wallen, Scott L. (2003) “Dissolving carbohydrates in CO2: Renewable materials as CO2-philes,” ACS CERSP, Page 170 of 230 Symposium Series 860 (Supercritical Carbon Dioxide) 270-284 (not previously reported). 5. Wang, Xiaoyan; K.M. Lee, Y. Lu, M. T. Stone, B. D. Freeman, and I. C. Sanchez (2005). “Modeling Transport Properties in High Free Volume Glassy Polymers,” ACS Symposium Series #916, New Polymeric Materials, Ljiljana S. KorugicKarasz, William J. MacKnight and Ezio Martuscelli, editors. Chapters shown in red above were reported as being in press in 2004 Annual Report. Chapters shown in Times font were previously published but not previously reported. Not peer reviewed (August 2004-June 2005) 1. Denison, Ginger M.; Jones, Charles, III; DeYoung, James; Gross, Steve; McClain, James; Zannoni, Luke; Hicks, Evan; Wood, Colin; Boggiano, Mary Kate; Visintin, Pamela; Bessel, Carol; Schauer, Cynthia; DeSimone, Joseph M. (2004). “The use of "dry" CO2-based technologies for the enhanced fabrication of microelectronic devices”, Polymeric Materials Science and Engineering, 90, 152153. 2. Denison, Ginger M.; Visintin, Pamela M.; DeSimone, Joseph M.; and Bessel, Carol (2003). “Copper chemical mechanical planarization processes in carbon dioxide”, Proceedings - Electrochemical Society, 2002-22 (Copper Interconnects, New Contact Metallurgies, Structures, and Low-k Interlevel Dielectrics), 254-259. 1b. Presentations Invited Lectures (All are partially or fully supported by NSF STC) 1. Baucom, E. I.; “CERSP: Involving Academia, Industry and Governments”, invited for Conference on Green Chemistry: An Australia Imperative, Canberra, Australia, April 20, 2005. 2. Baucom, E. I.; “CERSP: Involving Industry and State Governments”, invited for EPSCoR University Leadership Retreat, Washington, DC, February 22, 2005. CERSP, Page 171 of 230 3. Bothun, G.D.; “EXPERT program at NCA&TSU”, NSF Panelist for 2005 Discovery Corps Fellowship, Feb 2005. 4. Bothun, G.D.; “EXPERT program at NCA&TSU”, NSF “Workshop on the Postdoctorate” - Invited, Arlington, VA, Nov 2004 5. Carbonell, Ruben G. “Thin Film Coatings from Liquid and Supercritical Carbon Dioxide”, International Symposium on Supercritical Fluids, Orlando, FL, May 1-4, 2005 6. DeSimone, Joseph M.; “The Carbon Dioxide Technology Platform: From the Synthesis and Processing of Fluoropolymers to Totally “Dry” Microelectronics Processes and Dry Cleaning Garments”; “Fluoropolymers for use in Next Generation Microfluidic Devices, Micromolding/Soft Lithographic Techniques, and as Proton Exchange Membranes and Inks for use in Fuel Cells” Ralph Milkovich Lectures, University of Akron, OH, November 4-5, 2004. 7. DeSimone, Joseph M.; “Fluoropolymers for use in Next Generation Microfluidic Devices, Micromolding/Soft Lithographic Techniques, and as Proton Exchange Membranes”, Rauscher Memorial Lecture, Rensselaer Polytechnic Institute, NY, November 9, 2004. 8. DeSimone, Joseph M.; “Fluoropolymers for use in Next Generation Microfluidic Devices, Micromolding/Soft Lithographic Techniques, and as Proton Exchange Membranes”, Keynote Speaker, 4th Annual Intel Polymer Workshop, Intel, Portland, OR, November 11, 2004. 9. DeSimone, Joseph M.; “Fluoropolymers for use in Next Generation Photolithography, Soft Lithography, Microfluidics and Proton Exchange Membranes”, 2nd International Conference On Advanced Materials and Nanotechnology, MacDiarmid Institute, Wellington, New Zealand, February 6-11, 2005. 10. DeSimone, Joseph M.; “New PEM Materials for Fuel Cell Applications”, Advances in Materials for Proton Exchange Membrane Fuel Cell Systems 2005, Asilomar Conference Grounds, Pacific Grove, CA, February 21, 2005. 11. DeSimone, Joseph M.; “Carbon Dioxide Based Chemistries and Processes for Materials Sciences Applications”, 229th ACS National Meeting, San Diego, CA, March 13-17, 2005. CERSP, Page 172 of 230 12. DeSimone, Joseph M.; “New Materials for Advanced Technologies: From Labon-a-Chip Applications to the Fabrication of Harvestable, Monodisperse Shapespecific Particles”, Phi Lambda Upsilon Distinguished Lecturer Seminar, NC State University, Raleigh, NC, March 31, 2005. 13. DeSimone, Joseph M.; “Innovating in the Triangle”, Council for Entrepreneurial Development, Atherton, CA, April 13, 2005. 14. Gray, D. O., spoke at a Center Meeting on behalf of NSF, Belfast, Northern Ireland, Spring 2005 15. Gray, D. O., spoke to Irish equivilent of NSF, Dublin, Ireland, Spring 2005 16. Gray, D. O., spoke at Imperial College London, Spring 2005 17. Gray, D. O., participated in international conference panel, Turin, Italy, Spring 2005 18. Koros, W. J., “Large scale gas and vapor separations using membranes: The need for an integrated approach”, Invited Keynote Lecture, 1st Joint AIChE-IIChE Conference, Mumbai, India, December 2004. 19. Koros, W. J.; “Opportunities and challenges for practical inorganic-organic hybrid membrane materials, Invited Keynote Lecture, 3rd International Zeolite Membrane Meeting, Breckenridge, CO, July 2004. 20. Koros, W. J.; “The next generation of membrane materials and structures for separation of gas mixtures with the potential to minimize energy”, Workshop on Membrane Science Using X-Ray Techniques at Argonne National Laboratory, Argonne, IL, August 2004. 21. Koros, W. J.; “Membranes & membrane processes for the chemical processing industries”, Seminar and short course as part of the Visiting Professor Program at the Universidad Ibero Americana, Mexico, D. F., August 2004. 22. Koros, W. J.; “Advanced membranes for nonaqueous separations to minimize industrial energy use”, Lawrence Livermore National Labs, CA, September 2004. 23. Johnston, K. P.; “Chemical/Mechanical Process for Supercritical Carbon Dioxide Cleaning of Porous Methylsilsesquioxane (pMSQ) Dielectric Films with Surfactants”, University of Arizona, Tuscon, AZ, July 22, 2004. CERSP, Page 173 of 230 24. Johnston, K. P.; “Particle Engineering for Rapid Release of Nanostructured Poorly Water Soluble Drugs”, AAPS Meeting, Baltimore, MD, November 7, 2004 (with Jason McConville) 25. Johnston, K. P.; “Particle Engineering in Pharmaceutical Product Development”, Schering Plough, Kenilworth, NJ, December 10, 2004. 26. Johnston, K. P.; “Microelectronics Processing with CO2” Praxair, Buffalo, NY, January 14, 2005. 27. Johnston, K. P.; “Spray Freezing Proteins to Form Stable Particles” Praxair, Buffalo, NY, January 14, 2005. 28. Johnston, K. P.; “Novel Strategies for Stabilization and Assembly of Metal and Semiconductor Nanocrystals in Solution”, University North Texas, Dallas, TX, February, 8, 2005. 29. Johnston, K. P.; “CO2 Formulations for Cleaning, Drying, and Repairing Porous Low Dielectric Constant Materials” International Sematech, Austin, TX, February 23, 2005 30. Murray, R., "Metal Quantum Dots: Size Dependent Chemistry and Electrochemistry" Plenary Lecture at the meeting of the Electrochemistry Division of the Italian Chemical Society, September 2004. 31. Murray, R., The Lind Lectures at the Univ. of TN and ORNL, Golden Quantum Dots: Synthesis, Analysis, Electrochemistry, and Golden Quantum Dots: Luminescence, Ligand and Electron Transfer Chemistry, October, 2004. 32. Murray, R., ”Analytical and Separation Chemistry of Metal Quantum Dots” (Pittsburg Conference Award symposium for James Jorgenson) PITTCON, Orlando FL March 1, 2005 33. Murray, R., “Electron Transfer Chemistry Of Metal Quantum Dots” (Charles N. Reilley award symposium for Alan Bond) PITTCON, Orlando FL, March 2, 2005 34. Murray, R., “Publishing Chemistry Process, Ethics, Libraries and the Web” and “Chemistry and Electrochemistry of Metal Quantum Dots” Joel Broberg Lectures, University of North Dakota, April 18 – 20, 2005. 35. Murray, R., “Chemistry and Electrochemistry of Metal Quantum Dots”, Lipscomb Lecture at University of South Carolina, April 22, 2005. CERSP, Page 174 of 230 36. Velev, Orlin; Workshop on Field-Assisted Nanocolloid Self-Assembly (manipulation and assembly of nanoparticles, microparticles and live cells) University of Twente, Enschede, The Netherlands, November 2004. 37. Velev, Orlin; “Nanomaterial fabrication by self-assembly and electric fields”, Sandia National Laboratory, Albuquerque, NM, May 2005. 38. Velev, Orlin; Department of Chemical Engineering, University of Florida, FL, (onchip manipulation and assembly of nanoparticles, microparticles and droplets) December 2004. 39. Velev, Orlin; “On-chip manipulation and assembly of nanoparticles, microparticles and droplets”, Department of Polymer Science & Engineering, University of Massachusetts, Amherst, MA, October 2004. 40. Velev, Orlin; “Nanomaterial fabrication by self-assembly and electric fields”, General Electric Inc., Albany, NY, January 2005 41. Velev, Orlin; “Nanomaterial fabrication by self-assembly and electric fields”, Unilever Research and Development Center, Vlaardingen, Netherlands, November 2004. 42. Zhou, Zhilian; and Joseph M. DeSimone; "New Super Proton-conductive, High Acid-containing Fluoropolymer PEMs from Cured Liquid Precursors", 2nd international conference on green and sustainable chemistry and 9th annual green chemistry and engineering conference, Washington, DC, June 20-24, 2005. Conference Presentations (All are partially or fully supported by NSF STC) 1. Ahmed, T.S.; DeSimone, J.M; Roberts G.W., “Batch Copolymerization of Vinylidene Fluoride with Hexafluoropropylene in Supercritical Carbon Dioxide”, 7th International Symposium on Supercritical Fluids, Orlando, Fl, May 1-4, 2005. 2. Beier, Julie; “K-12 Program in the Center for Environmentally Responsible Solvents and Processes”, Petroleum Research Fund Summer School on Green Chemistry, Philadelphia, PA July 31-August 7, 2004. 3. Berkowitz, M “The structure and dynamics of reverse micelles”, ACS Spring Meeting, San Diego, CA (2005) CERSP, Page 175 of 230 4. Bothun, G.D., “Pressurized solvents in whole-cell bioprocessing”, NC A&T SU Chemical Engineering Seminar September 2004. 5. Bothun, G.D., “CO2-based membrane technology: Research, education, and outreach”, invited presentation, NC A&T SU Graduate School Symposium sponsored by NSF NC-LSAMP Oct 2004. 6. Coberly, B. & Gray, D.O., “Faculty satisfaction and organizational commitment with Industry-University Research Centers”, Triple Helix5, Capitalization of Knowledge: Cognitive, economic, social and cultural aspects, Turin, Italy, May 2005. 7. DeSimone, Joseph M.; Carol A. Bessel, Ginger M. Denison, Amber Evans, Dorothy Skaf and Royce Murray, “Copper Chemical Mechanical Planarization: Electrochemical Aspects”, SERMACS 2004, Research Triangle Park, NC, November 13, 2004. 8. DeSimone, Joseph M.; “Perfluoropolyether Fouling Release”, ONR Coatings and Biofouling Program Review, Sedona, AZ, January 21, 2005. 9. DeSimone, Joseph M.; “Perfluoropolyether Fouling Release”, ONR Coatings and Biofouling Program Review, Baltimore, MD, June 16, 2005. 10. Frankowski, D.J.; Fournier-Bidoz, S.; Manners, I.; Ozin, G.A.; Khan, S.A.; Spontak, R.J., "Tunable Micro- and Mesocellular Morphologies from Poly(ferrocenylsilane) Ceramic Precursors Foamed in Supercritical CO2." NC ACS Polymer Discussion Group-Richard D. Gilbert Award Symposium, Raleigh, Feb. 2005. 11. Frankowski, D.J.; Fournier-Bidoz, S.; Manners, I.; Ozin, G.A.; Khan, S.A.; Spontak, R.J., "Tunable Microcellular Morphologies from PFS Ceramic Precursors Foamed in scCO2." South Eastern Regional Meeting of the American Chemical Society, Durham, Oct. 2004. 12. Grant, Christine S.; Hussain, Yazan; Wu, You Ting. “Green Dissolution Processes” 56th Southeast Regional Meeting of the American Chemical Society, Research Triangle Park, NC, United States, November 10-13, 2004. 13. Gray, D.O., “Looking inside the research center “black box”: Research strategies for understanding why and how some center stakeholders perform better than others”. Panel on Centers evaluation: Challenges and methodological CERSP, Page 176 of 230 approaches, at American Evaluation Association Conference, Atlanta, GA., November 2004. 14. Gray, D.O.; Stewart, G. & Steenhuis, H., “Optimizing the payoff from patent donations: PAATI and a Research Agenda”. Technology Transfer Society (T2S) 26th Annual Conference Program, Albany, NY, September 2004. – Travel Supported by CERSP 15. Guo, Ji; DeSimone, Joseph M.; Rubinstein, Michael; Adam, Mireille. “Light Scattering Study of Fluroro-Homopolymer Poly(Zonyl-TM) in Carbon Dioxide.” 56th Southeast Regional Meeting of the American Chemical Society, Research Triangle Park, NC, United States, November 10-13, 2004 16. Guo, Ji; J. M. DeSimone, “Light Scattering Study of Fluorinated Alkyl Methacrylate polymer in Carbon Dioxide”, International Symposium on Supercritical Fluids, Orlando, FL, May 1, 2005. 17. Guo, Ji; and J. M. DeSimone, “Light Scattering Study of Fluorinated Alkyl Methacrylate polymer in Carbon Dioxide”, National Meeting of American Physical Society, Los Angles, CA, March 21-25, 2005. 18. Harvey, Desmond presented his CERSP funded research at the Historically Black Colleges and Universities -Undergraduate Program's (HBCU-UP) 2005 National Research Conference in New Orleans, Louisiana February 10-13, 2005. 19. Hussain, Yazan; and Christine Grant, "The Applications of Quartz Crystal Microbalance in High Pressure Carbon Dioxide," International Symposium on Supercritical Fluids, Orlando, FL, May 2005. 20. Johnston, K. P.; “Chemical/mechanical Process for Supercritical Carbon Dioxide Cleaning of Porous Methylsilsesquioxane (pMSQ) Dielectric Films with Surfactants”, AIChE Annual Meeting, Austin, TX, November 8-12, 2004 (with J. Keagy). 21. Johnston, K. P.; “Welding Colloidal Crystals with Carbon Dioxide”, AIChE Annual Meeting, Austin, TX, November 8-12, 2004 (with H. Abramowitz, P. Green and P. Shah). 22. Johnston, K. P.; “Controlled Precipitation of Naproxen Nanoparticles”, AIChE Annual Meeting, Austin, TX, November 8-12, 2004 (with M.E. Matteucci). CERSP, Page 177 of 230 23. Johnston, K. P.; “Steric Stablization of Nanoparticles in Liquid Carbon Dioxide at the Vapor Pressure”, AIChE Annual Meeting, Austin, TX, November 8-12, 2004 (with J.L. Dickson, B.P. Binks, and P.S. Shah). 24. Johnston, K. P.; “Tertiary Amines for CO2-Based Dispersions”, AIChE Annual Meeting, Austin, TX, November 8-12, 2004 (with G. Smith, K.T. Lim and H.S. Hwang). 25. Johnston, K. P.; “Stabilization of Carbon Dioxide-in-water Emulsions with Silica Nanoparticles”, AIChE Annual Meeting, Austin, TX, November 8-12, 2004 (with J.L. Dickson, and B.P. Binks). 26. Johnston, K. P.; “Spontaneous Ordering of Nanoparticles at the PolymerSubstrate Interface”, AIChE Annual Meeting, Austin, TX, November 8-12, 2004 (with L. Meli and P. Green). 27. Johnston, K. P.; “Synthesis of Ge Nanocrystals in a High Temperature Supercritical Solvent” AIChE Annual Meeting, Austin, TX, November 8-12, 2004 (with X. Lu and B.A. Korgel). 28. Johnston, K. P.; “Small-Angle X-ray Scattering Measurement of Nanocrystal Interactions in Supercritical Carbon Dioxide” AIChE Annual Meeting, Austin, TX, November 8-12, 2004 (with A.E. Saunders, K.T. Lim, B.A. Korgel and P.S. Shah). 29. Johnston, K. P.; “Self-assembly of Inverse Opal Nanocrystal Thin Films”, AIChE Annual Meeting, Austin, TX, November 8-12, 2004 (with A.E. Saunders, M.B. Sigman, K.T. Lim, B.A. Korgel, P.S. Shah, and T. Hanrath). 30. Johnston, K. P.; “Controlled Precipitation of Naproxen Nanoparticles”, AAPS Meeting, Baltimore, MD, November 7, 2004 (with Michal Matteucci, Todd Crisp, True Rogers, James Hitt and Robert O. Williams III). 31. Johnston, K. P.; “Morphology of Poorly Water Soluble Drug Nanoparticles by a Cryogenic SEM Technique”, AAPS Meeting, Baltimore, MD, November 7, 2004 (with Todd Crisp, Michal Matteucci and Robert O. Williams III). 32. Johnston, K. P.; “Wet Chemical Synthesis of Germanium Nanoparticles”, Mater. Res. Soc. Meeting, San Francisco, CA, March 31, 205 (with Xianmao Lu and Brian Korgel) 33. Johnston, K. P.; “Using Supercritical Carbon Dioxide for Cleaning and Repair of Porous Methylsilsesquioxane (pMSQ) Dielectric Films” Int. Symp. on CERSP, Page 178 of 230 Supercritical Fluids, Orlando, FL, May 1-4, 2005 (with John Keagy, Xiaogang Zhang, Yuan Li, Joseph Pham, Peter F. Green, Todd Rhoad, Frank Weber, Eric Busch, and Josh Wolf). 34. Johnston, K. P.; “Novel Concepts for Colloid Stabilization in Supercritical Fluid Carbon Dioxide with Hydrocarbon Surfactants” Int. Symp. on Supercritical Fluids, Orlando, FL, May 1-4, 2005 (with Won Ryoo, Griffin Smith, and Roger Bonnecaze) 35. Johnston, K. P.; “Nanoparticle Dispersions and Solid-Stabilzed Emulsions in Carbon Dioxide” Int. Symp. on Supercritical Fluids, Orlando, FL, May 1-4, 2005 (with Jasper L. Dickson, Bernard P. Binks, Ti Cao, and Stephen E. Webber) 36. Johnston, K. P.; “Small Angle X-Ray Scattering Measurements of Metal Nanocrystals Dispersed in Supercritical Carbon Dioxide” Int. Symp. on Supercritical Fluids, Orlando, FL, May 1-4, 2005 (with Aaron E. Saunders, Kwon T. Lim, and Brian A. Korgel) 37. Johnston, K. P.; “Interfacial Micellar Structures Formed by Block Copolymer in Thin Films” Int. Symp. on Supercritical Fluids, Orlando, FL, May 1-4, 2005 (with Yuan Li, and Peter F. Green) 38. Johnston, K. P.; “Ordering of Nanoparticles in Thin Film Homopolymer Matrices” Int. Symp. on Supercritical Fluids, Orlando, FL, May 1-4, 2005 (with Luciana Meli, and Peter F. Green) 39. Johnston, K. P.; “CO2-Enhanced Transport of Small Molecules in Polystyrene and PMMA Thin Films” Int. Symp. on Supercritical Fluids, Orlando, FL, May 1-4, 2005 (with Ti Cao, and S. E. Webber) 40. Johnston, K. P.; “Stabilization of Inorganic Nanoparticles in CO2 Using Surfactants” Int. Symp. on Supercritical Fluids, Orlando, FL, May 1-4, 2005 (with Griffin Smith and Won Ryoo) 41. Johnston, K. P.; “Synthesis of Ge Nanocrystals in a High Temperature Supercritical Solvent” Int. Symp. on Supercritical Fluids, Orlando, FL, May 1-4, 2005 (with Xianmao Lu, Yoonjung Bae, Allen Bard, and Brian Korgel) 42. Johnston, K. P.; “Infusion of Gold Nanoparticles in Mesoporous Silica using scCO2” Int. Symp. on Supercritical Fluids, Orlando, FL, May 1-4, 2005 (with Gaurav Gupta, Parag Shah, Xiaogang Zhang, Aaron Saunders, and Brian Korgel) CERSP, Page 179 of 230 43. Jones, Charles A., III; Yang, Dongxing; DeYoung, James; Irene, Eugene A.; DeSimone, Joseph M. “Etching of SiO2 Thin Films in Supercritical Carbon Dioxide”. Abstracts, 56th Southeast Regional Meeting of the American Chemical Society, Research Triangle Park, NC, United States, November 10-13, 2004. 44. Kelly, Jennifer Y.; and DeSimone, Joseph M.; “New Functionalized Liquids for Proton Exchange Membranes in Fuel Cells”, International Symposium on Supercritical Fluids, Orlando, FL, May 1, 2005. 45. Kelly, Jennifer Y.; and DeSimone, Joseph M.; “New Materials for Proton Exchange Membranes in Fuel Cells”, Advances in Materials for Proton Exchange Membrane Fuel Cell Systems 2005, Asilomar, CA, February 21, 2005. 46. Kelly, Jennifer Y.; and DeSimone, Joseph M.; “New Materials for Proton Exchange Membranes in Fuel Cells”, SERMACS 2004, Raleigh, NC, November 13, 2004. 47. Koros, W. J., “Inorganic membrane separations for emerging CO2 technologies”, 2nd Int'l Conference on Green and Sustainable Chemistry/9th Annual Green Chemistry and Engineering Conference, Washington DC, June 2005. 48. Koros, W. J., “Hydration and cosolvent effects on liquid and supercritical CO2 transport through a series of mesoporous ceramic membranes”, North American Membrane Society, Providence, RI, June 2005. 49. Koros, W. J., “Inorganic membrane separations for compressed CO2 technologies: Transport mechanisms, hydration, and co-solvent”, 7th Int’l Symposium on Supercritical Fluids, Orlando, FL May 2005. 50. Liu T., DeSimone J. M., and Roberts G. W., “Continuous Precipitation Polymerization of Acrylic Acid in Supercritical Carbon Dioxide: Experiments, Kinetics and Modeling”, 7th International Symposium on Supercritical Fluids, Orlando, FL., May 1 – 4, 2005. 51. Madsen, Louis A.; Chao, Alex; Samulski, Edward T. “Motion and phase behavior of CO2-processed Teflon AF and copolymers measured by high temperature NMR,” 227th ACS National Meeting, Anaheim, CA, United States, March 28-April 1, 2004 (not reported in 2004). 52. Roberts, G. W.; D. Xu, R. Whittier, R. G. Carbonell, and D. J. Kiserow, “Hydrogenation of Polystyrene in Solvents Expanded by Supercritical Carbon CERSP, Page 180 of 230 Dioxide” (Paper O-335), 19th North American Catalysis Society Meeting, Philadelphia, PA, May 22-27, 2005. 53. Roberts, G. W.; D. Xu, R.Whittier, D. J. Kiserow, and R. G. Carbonell, “Hydrogenation of Polystyrene in Solvents Expanded by Supercritical Carbon Dioxide” 5th International Symposium on Catalysis in Multiphase Reactors/4th International Symposium on Multifunctional Reactors, Portoroz-Portotose, Slovenia, June 15-18, 2005. 54. Scanu, L.F.; J.M. DeSimone, G.W. Roberts and S.A. Khan. “Is supercritical CO2polymerized polyvinylidene fluoride branched? A rheological view point.” American Chemical Society, San Diego, CA, 2005. 55. Scanu, L.F.; J.M. DeSimone, G.W. Roberts and S.A. Khan. “Melt rheology of poly(vinylidene fluoride): Evidence of long chain branching?” Society of Rheology, Lubbock, TX, 2005. 56. Scanu, L.F.; J.M. DeSimone, G.W. Roberts and S.A. Khan. “Is supercritical CO2polymerized polyvinylidene fluoride branched? A rheological view point.” Southeastern Regional Meeting of the American Chemical Society, Research Triangle Park, Durham, NC , 2004. 57. Tarant, S. & Gray, D.O., “The role of organizational boundary-spanners in industry/university cooperative relation: Descriptive findings”, Technology Transfer Society (T2S) 26th Annual Conference Program, Albany, NY. September 2004 – Travel supported by CERSP 58. Tarant, S. & Gray, D.O., “The role of organizational boundary spanners in industry/ university collaborative relationships: Predictive Findings”, Triple Helix5, Capitalization of Knowledge: Cognitive, economic, social and cultural aspects, Turin, Italy, May 2005 – Travel Supported by CERSP. 59. Toker, U. & Gray, D.O., “Spaces For Innovation: The influence of workspace on innovation processes in university research centers”. Triple Helix5, Capitalization of Knowledge: Cognitive, economic, social and cultural aspects, Turin, Italy, May 2005. 60. Velev, O., and Ketan Bhatt, 79th ACS Colloid and Surface Science Symposium, Potsdam, NY, June 2005. 61. Velev, O., and Suk Tai Chang, 79th ACS Colloid and Surface Science Symposium, Potsdam, NY, June 2005. CERSP, Page 181 of 230 62. Velev, O., and Vesselin Paunov, 79th ACS Colloid and Surface Science Symposium, Potsdam, NY, June 2005. 63. Velev, O., and Brian Prevo, MRS National Spring Meeting, San Francisco, CA, April 2005. 64. Velev, O., and Vesselin Paunov, MRS National Spring Meeting, San Francisco, CA, April 2005. 65. Xu, D.; R. G. Carbonell, D. J. Kiserow, and G. W. Roberts, “Hydrogenation of Polystyrene in CO2-Expanded Liquids”, International Symp. on Supercritical Fluids, Orlando, FL, May 1-4, 2005. 66. Zhao, Qian; Samulski, Edward T. CO2-mediated clay-polymer composites. 229th ACS National Meeting, San Diego, CA, United States, March 13-17, 2005. 67. Zhou, Zhilian; Raymond Dominey and Joseph M. DeSimone, "Liquid NAFION” Membranes for Fuel Cell Applications”, Advances in Materials for Proton Exchange Membrane Fuel Cell Systems 2005, Pacific Grove, CA, Feb 20-23, 2005. 68. Zweber, Amy; J. M. DeSimone, and R. Carbonell, “Enhancement of Lithography Processes Using CO2: CO2-Modified Development”, International Symposium on Supercritical Fluids, Orlando, FL, May 1, 2005. 1c. Other Dissemination Activities • • • • • • • • • One Center Newsletter CD-ROMs describing posters presented at affiliates meeting CD-ROM describing the facilities of the Center Significant reporting via our website (~15,000 hits on STC website during the year plus >300,000 hits on K-12 website) Weekly technical seminars offered via the internet (time delayed and password protected) Leadership workshops and innovation seminars offered via the internet Searchable database of carbon dioxide patents Videotapes of Innovation Seminar series; also streaming versions on the website Eight-page pamphlet describing the Center and its activities CERSP, Page 182 of 230 2. Awards and Honors Recipie nt 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3 1 4 1 5 1 6 Christine Grant Royce Murray Royce Murray Royce Murray Royce Murray Royce Murray Royce Murray Royce Murray Orlin Velev Kevin Herlihy W. J. Koros W. J. Koros W. J. Koros Jennifer Kelly Joseph DeSimon e Joseph DeSimon e Reason Award Career achievement Career achievement Career achievement Career achievement Career achievement Career achievement Career achievement Career achievement Career achievement for Award Name and Contributor American Institute of Chemical Engineers, Board of Directors Editor-in-Chief of the ACS research journal Analytical Chemistry Member of the Report Review Committee of the NRC Chair, Chemistry Section of the National Academy of Sciences. Luigi Galvani Medal award Lind Lectures at the Univ. of TN Broberg Lectures at North Dakota State University Lipscomb Lecture at South Carolina University. Sigma Xi research award (NCSU chapter) Founding president, Materials Research Society UNC-CH Georgia Tech Faculty Member of the Year, Graduate Student Award Universidad Ibero-Americana Visiting Professorship Chemcon 2004 Distinguished Speaker Award Date 20032006 continui ng continui ng 5/1/05 9/04 10/04 4/05 4/05 2004 5/05 2004 2004 12/04 2005 2005 2005 Leadership Career achievement Career achievement Career achievement Outstanding K12 outreach “Science Hall of Fame” UNC-CH Career achievement Career achievement Editorial Board, Journal of Supercritical Fluids Editorial Board, Journal of Polymer Science CERSP, Page 183 of 230 1 7 1 8 1 9 2 0 2 1 2 2 2 3 2 4 2 5 2 6 2 7 2 8 2 9 3 Joseph DeSimon e Joseph DeSimon e Joseph DeSimon e Joseph DeSimon e Joseph DeSimon e Joseph DeSimon e Joseph DeSimon e Joseph DeSimon e Joseph DeSimon e Joseph DeSimon e Joseph DeSimon e Joseph DeSimon e Geoff Bothun Desmon Career achievement Career achievement Career achievement Career achievement Career achievement Career achievement Career achievement Career achievement Career achievement Career achievement Career achievement Fellow, Defense Sciences Research Council (DSRC) of DARPA Strategic Planning Group on Materials, Duke University Scientific Advisory Committee, Center for Nanophase Mater. Sciences at ORNL Member, Board of Directors, Council for Entrepreneurial Development (CED) 2005 Entrepreneurial Excellence Award for Life Science Spin-out of the Year CEDNC Elected member of the National Academy of Engineering Member American Academy of Arts and Sciences 20042005 2005 2005 6/15/05 6/15/05 2/05 5/05 2005 American Chemical Society Awar Creative Invention 2005 2005 Phi Lamda Upsilon / Glaxo Smith Distinguished Lectureship at NC State 2005 2004 William H. Rauscher Lecture in Chemistry, Rensselaer Polytechnic Ins 2004 2004 Milkovich Memorial Lectures, De Polymer Science, University of Akron 11/04 Career 2004 North Carolina Distinguished Lec Award from the NC Section of the ACS 2004 achievement Achievement in Travel Award to speak at 230th ACS diversity meeting 2005 Excellent Undergraduate Program (HBCU-UP) 2/10- CERSP, Page 184 of 230 0 3 1 3 2 3 3 3 4 3 5 3 6 3 7 3 8 3 9 4 0 4 1 4 2 d Harvey presentation Excellent presentation Research Qian accomplishment Zhao s Aaron Research Saunder accomplishment s s Jan Career Genzer achievement Career Edward accomplishment Samulski s Career Carol accomplishment s Hall Verun Undergraduate Dhanuka research career Mary L. Career Bellamy achievement Mary L. Career Bellamy achievement Mary L. Bellamy Paul Kropp David Haase Career achievement Career teaching achievement Career achievement Xiaoyan Wang 2005 National Research Conference 13/05 in New Orleans, Louisiana (3rd place prize) Best Poster Award at National AIChE Fall meeting in Separations Division 2004 Richard D. Gilbert Award Symposium 2/10/05 2004 George Kozmetsky Award for Outstanding Graduate Research in Nanotechnology. 1/10/05 John H. Dillon medal of the American Physical Society Jefferson Science Fellow Elected member of National Academy of Engineering George H. Mitchell Award for ChE NC State University Outstanding Extension Service Award President-elect, North Carolina Science Leadership Association Academy of Outstanding Faculty NC State U, College of Physical Sciences and Math 2005 Johnston Award for Excellence in Teaching at UNC-CH Vice-chair Executive Committee, Forum on Education, American Physics Society 5/24/05 2/05 4/05 4/27/05 Spring 2005 Spring 2005 2/3/05 Spring 2005 3. M.S. and Ph.D. students who graduated during the reporting period, with placements. Including the number of years taken since entering graduate school CERSP, Page 185 of 230 to complete the Ph.D. & postdoctoral associates who left the STC during the reporting period, with placements. Student Name Zaneta L. Howard Leonitia Broadney Atasha Sutton Snead, David Ti Cao Connie Lo Howard Abramowitz Dipak Barua Thomas Chen Ansley Exener Kingsley Nelson Rameshwar Yadav Elizabeth Coberly Ginger Denison Jason Rolland Degree(s Years ) to Degree BS BS 12/05 Pre-BS BS BS BS MS MS MS MS MS MS PhD PhD PhD 5 4.7 2.3 2 Placement Dow Chemical, Midland, MI Internship at Kimberley Clark, Roswell, GA Returned to Spelman College Graduate school Unknown Unknown US Patent Washington, DC PhD at NCSU on unrelated topic Office, teaching high school in Raleigh PhD Program U of Georgia Caterpillar Tractor, Ohio Ph.D. Program NC State U Office of Planning and Evaluation, NC Dept. of Vocational Rehabilitation Liquidia, Inc., Chapel Hill, NC Liquidia, Inc., Chapel Hill, NC Exxon-Mobil, Houston, TX Air Products, Pennsylvania Jasper Dickson (finishing 8/05) PhD Karen Kennedy PhD CERSP, Page 186 of 230 Jae Hoon Kim Zhengmin Li Tao Liu Joseph Pham (finished 8/04) Won Ryoo Tarant, Stephanie Visintin, Pamela Bin Xu Dawei Xu Coray Colina PhD PhD PhD PhD PhD ^ PhD PhD PhD PhD Post-doc 4 5 4 4 4.7 4 4 ARO post-doc NC State Post-doc in Materials Science at NC State Post doc with Roberts NCSU Sematech International, Austin,Tx Samsung, Seoul, Korea Leadership Council, Corporate Executive Board CMP Company Post doc at UCLA Post doc w/Carbonell NCSU Post doc at UNC-CH 2004-5 and Assoc Prof. Penn State U. in 2006 in Materials Science Dept. Position in San Jose, California Queen Mary College, University of London 2004-5; Asst. Prof. Cal. Poly at San Luis Obispo Asst. Prof. U. of Sao Paulo, Brazil Pfizer Pharmaceutical, Groton, Ct Industrial position Austin, TX Asst professor, U. of Maryland, Baltimore County Asst. Prof. of Chemistry, North Carolina Central University Ke Wang Toker, Umut Post doc Post-doc 2 Luis Dias Parag Shah (finished fall 2004) Vibha Srinivasan Theodosia Gougousa Darlene Taylor Post-doc Post-doc Post-doc Post doc Post-doc 2 CERSP, Page 187 of 230 ^ Thesis defense planned for coming fiscal year. Currently employed at Samsung. Those shown in red were reported last year as being in temporary positions, perhaps a few months short of completing their degrees. CERSP, Page 188 of 230 4a. General outputs of knowledge transfer activities Patents: 1. PCT filed 1/8/04: Polyhedral Silsequioxane – Containing Polymers for Microelectronic Applications 2. PCT, filed 1/21/05: Liquid Materials for use in Electrochemical Cells 3. PCT, filed 12/2004: Methods for fabricating isolated micro-and nano-structures using soft or imprint lithography 4. PCT, filed 2/2005: Functional Materials and Novel Methods for the Fabrication of Microfluidic Devices 5. PCT, filed 12/04 Process for Preparing Superabsorbents in Polymers Supercritical Carbon Dioxide 1. US Patent 6,747,179; June 8, 2004; Carbon Dioxide Soluble Polymers and Swellable Polymers for Carbon Dioxide based Application; Inventors: J. M. DeSimone, Eva Birnbaum, Ruben Carbonell, Stephanie Crette, James B. McClain, T. Mark McClesky, Kimberly Powell, Timothy Romack, Willaim Tumas. 2. US Patent 6,764,809; July 20, 2004; “CO2-Processes, photoresists, polymers and photoactive compounds for Microlithography”; Inventors: J. M. DeSimone, Ruben Carbonell, Jonathan Kendall, Chris McAdams. 3. US Patent 6,765,030; July 20, 2004; “Methods of Forming Polymeric Structures Using Carbon Dioxide and Polymeric Structures Formed Thereby”; Inventors: J. M. DeSimone, Sarah Paisner. 4. US Patent 6,790,870; September 14, 2004; “Methods of Making Foamed Materials of Blended Thermoplastic Polymers Using Carbon Dioxide”; Inventors: J. M. DeSimone, S. A. Khan, J. R. Royer, R. J. Spontak, T. A. Walker, Y. Gay, S. Siripurapu. 5. US Patent 6,806,332; October 19, 2004; "Continuous Process for Making Polymers in Carbon Dioxide"; Inventors - J. M. DeSimone; George Roberts, Paul Charpentier. CERSP, Page 189 of 230 6. US Patent 6,900,267; May 31, 2005; “Methods of CO2-Assisted Reactive Extrusion”: Inventors: Royer, J.; DeSimone, J. M.; Roberts, G.; Kahn, S. 4b. Other outputs of knowledge transfer activities made during the reporting period not listed above 5. Participants in Center activities Per NSF guidelines, a person is considered a participant if he/she works 160 hours at the Center. We chose to define “works at the Center” broadly. Undergraduates funded by external funds (e.g., REU) are listed if Center personnel direct their projects and their work is directly applicable to the Center. A number of undergraduates fall into this category. The number of participants in the Center is up 13 from last year. Most of this increase is due to the fact that we had an unusually high number of changes in programs (i.e., startups and shut downs). Our reporting period spans parts of two summers. Our reporting year does not coincide with the academic year, so we often report two students or post docs filling one position; that is, one individual might finish and another begin in essentially the same position in the same reporting year. Both names would be included. THIS TABLE HAS BEEN MODIFIED TO DELETE CONFIDENTIAL INFORMATION Participant Name Abramowitz, Howard Adams, Ryan Adkins, Stephanie Ahmed, Tamer Instituti on* UT-A GaTech UT-A NCSU UNCCH UNCCH UNCCH NCA&T CERSP, Page 190 of 230 1 2 3 4 5 Alford, Jonathan 6 Andersen, Erik 7 Anderson, Emily Applewhite, 8 Monte 9 Arnold, Willie 10 Ashby, Valerie Ashley, Nick 11 Baker, Ally 12 Baker, Nancy 13 Balbuena, Perla 14 Barua, Dipak 15 Baucom, Everett 16 Beier, Julie Bellamy, Mary 17 Louise 18 Berkowitz, Max 19 Bessel, Carol 20 Betts, Carrie 21 Blake, Catherine Boggiano, Mary 22 Kate 23 Bothun, Geoffrey 24 Boulware, Sonya 25 Bratcher, Sandra Broadney, 26 Leonitia Brookhart, 27 Maurice 28 Brooks, Brandon 29 Cain, Nathaniel 30 Caldwell, Corey 31 Cao, Leo 32 Cao, Ti Carbonell, 33 Ruben NCA&T UNCCH NCSUb UNCCHs NCSUd NCSU UNCCH NCSUc NCSUc UNCCH UNCCH UNCCH UNCCHs UNCCH NCA&T NCA&T NCA&T NCA&T UNCCH NCA&T NCSU NCA&T UNCCHs UT-A NCSU CERSP, Page 191 of 230 Chapman,Johna 34 ustin 35 Chen, Thomas 36 Choi, Jai-Pil Clark, Joyce 37 Hilliard 38 Coberly, Beth 39 Colina, Coray 40 Collins, Candis 41 Cooke, Sharon 42 Covington, Leroy 43 Craig, Bart 44 Darkwa, James 45 DeLeon, David 46 Denison, Ginger DeSimone, 47 Joseph DeSimone, 48 Philip 49 Dhanuka, Varun 50 Dickson, Jasper 51 Donie, Marcus 52 Efimenko, Kirill 53 Engstrom, Josh 54 Enlow, Elizabeth 55 Euliss, Larken 56 Forbes, Malcolm Frankowski, 57 David 58 Garner, Pamela UNCCH UNCCH UNCCH NCSUc NCSUb NCSU NCA&T NCSUc NCA&T NCSUb UNCCH UNCCH UNCCH UNCCH UNCCH UT-A UT-A UNCCH NCSU UT-A UNCCH UNCCH UNCCH NCSU NCA&T CERSP, Page 192 of 230 59 Genzer, Jan Gougousi, 60 Theodosia 61 Green, Peter 62 Grant, Christine Gratton, 63 Stephanie 64 Gray, Denis 65 Guo, Ji 66 Gupta, Guarau Gutti, 67 Sareshkumar 68 Haase, David 69 Haithcock, Vicki Haithcock, 70 Rhonda 71 Hall, Carol 72 Horton, Dujuan 73 Hotze, Margaret 74 Hussain, Yazan 75 Iberg, Aimee Ilias, 76 Shamsuddin 77 Irene, Eugene 78 Ison, Forrest 79 Jenkins, Felysha Johnson, 80 Meegan 81 Johnston, Keith 82 Jones, Charles 83 Jones, Derek 84 Kabadi, Vinayak 85 Keagy, John 86 Kelly, Jennifer NCSU NCSU UT-A NCSU UNCCH NCSUb UNCCH UT-A NCA&T NCSUc UNCCH UNCCH NCSU NCA&T UT-A NCSU UT-A NCA&T UNCCH NCA&T NCSUb NCA&T UT-A UNCCH NCA&T NCA&T UT-A UNC- CERSP, Page 193 of 230 87 Khan, Saad 88 Kiehna, Sarah 89 Kim, Jae Hoon 90 Kingsley, Nelson 91 Kocz, SaRAH! 92 Korgel, Brian 93 Koros, William# 94 Kosuri, Madhava LeGrande, 95 Sharnee 96 Levy, Todd 97 Li, Yuan 98 Li, Yuxiang Lindberg, 99 Jennifer 10 0 Liu, Tao 10 1 Loo, Lynn 10 2 Lu, Lanyuan 10 3 Madsen, Lou 10 4 MacArthur, Ryan 10 Maier, 5 Christopher 10 6 Martin, Pamela 10 Mayfield, 7 Shatara 10 Maynor, 8 Benjamin 10 McNair, Desiree CH NCSU UNCCH NCSU NCA&T UNCCH UT-A GaTech Ga Tech NCA&T NCA&T UT-A UNCCH NCSUb NCSU UT-A UNCCH UNCCH UNCCH NCSUb NCSUb NCA&T UNCCH NCA&T CERSP, Page 194 of 230 9 11 0 Meli, Luciana 11 Millington, 1 Michael 11 2 Moore, Kimberly 11 Morehead, 3 Vincent 11 4 Murray, Royce 11 5 Mvula, Oscar 11 6 Nelson, Kingsley 11 7 Ntuen, Uduak 11 Obenland, 8 Carrie 11 9 Osburn, Carl 12 0 Pandya, Ashish 12 1 Park, Ji-Young 12 Parsons, 2 Gregory 12 3 Patel, Mehul 12 4 Patterson, Joan 12 5 Paul, Evan 12 6 Peay, Katif 12 7 Peng, Qing 12 8 Perry, John UT-A NCA&T NCA&T NCA&T UNCCH NCA&T NCA&T UT-A UT-A NCSUa UNCCH UNCCH NCSU UT-A NCSU NCA&T NCA&T NCSU Ga Tech CERSP, Page 195 of 230 12 9 Pham, Joseph 13 Poplawski, 0 Matthew 13 1 Portnow, Lauren 13 2 Prevo, Brian 13 3 Pullins, Deardre 13 4 Redden, Jacina 13 5 Rivers, Drew 13 6 Roberts, George 13 Roberts, 7 Kenneth 13 8 Rolland, Jason 13 Rosenberg, 9 Daniel 14 0 Rossky, Peter 14 Rubinstein, 1 Michael 14 Rutkoski, 2 Christopher 14 3 Ryoo, Won 14 Samulski, 4 Edward 14 5 Sanchez, Isaac 14 6 Saunders, Aaron 14 7 Scanu, Lauriane 14 Schauer, Cindy UT-A UT-A UNCCH NCSU NCA&T UNCCH NCSUb NCSU NCA&T UNCCH NCSU UT-Aa UNCCH NCA&T UT-A UNCCH UT-A UT-A NCSU UNCCERSP, Page 196 of 230 8 14 Schneider, 9 Jennifer 15 0 Schulze, Sharon 15 1 Shah, Parag 15 2 Shirvanyants, David 15 3 Simpson, Jamila 15 4 Smith, Frederick 15 5 Smith, Griffin 15 6 Smith, Renee 15 7 Snoke, Elizabeth 15 Stewart, 8 Connorly 15 9 Tanner, Shaun 16 Tarant, 0 Stephanie 16 1 Taylor, Darlene 16 2 Trembath, Dawn 16 Uitenham, 3 Leonard 16 4 Val, Naomi 16 5 Velev, Orlin 16 6 Visintin, Pamela 16 7 Wang, Ke CH NCSUb NCSUc UT-A UNCCH NCSUc NCA&T UT-A UNC NCSUc NCA&T NCSU NCSUb UNCCH NCSUb NCA&T UT-A NCSU UNCCH NCSU CERSP, Page 197 of 230 16 8 Wang, Xiaochu 16 9 Wang, Xiaoyan 17 0 Wang, Zuowei 17 Washington, 1 Rashawn 17 2 Waters, Marcy 17 Webber, 3 Stephen 17 4 Welch, Chris 17 5 West, Kyle 17 Wilson, 6 Benjamin 17 7 Woodhead, Jeff 17 8 Xu, Bin 17 9 Xu, Dawei 18 0 Yang, Dongxing 18 1 Yang, Jian 18 2 Zhang, Qi 18 3 Zhao, Qian 18 4 Zhou, Zhilian Amy 18 Zweber, 5 Geissler # No UT-A UT-A UNCCH NCA&T UNCCH UT-A UNCCH UNCCH NCA&T NCSU UNCCH NCSU UNCCH UNCCH UNCCHf UNCCH UNCCH NCSU disability except for this person, who is visually impaired. CERSP, Page 198 of 230 * All UNC-CH personnel are in the Chemistry Dept. except those marked as UNCCHs, who are in the School of Information and Library Science, and those marked as UNC-CHf, who are in the Department of Computer Science. All NCA&T are in the Dept. of Mechanical and Chemical Engineering; all Georgia Tech are in the Dept. of Chemical Engineering; all UT-Austin are in the Dept. of Chemical Engineering except those marked UT-Aa, who are in the Chemistry Dept; all NC State are in Dept of Chemical Engineering except those marked NCSUa, who are in the Electrical and Computer Engineering Dept.; NCSUb, who are in the Psychology Dept.; NCSUc, who are with the Science House; and NCSUd is an affiliate of NCSU located at Texas A&M. 6. Provide a summary listing of all of the Center’s research, education, knowledge transfer and other institutional partners (the total number of non-academic organizations, including industry, states, and other Federal agencies which work or share resources with the Center). Organization Name 1 2 3 4 5 6 7 University of North Carolina-CH North Carolina State University North Carolina A&T State Univ. University of Texas-Austin Georgia Institute of Technology Villanova University Texas A&M University Organization Address Type* University University University University Technical Institute University University Chapel Hill, NC Contact Name Type of Partner** 160 hrs or more? (indicate Y/N) Yes Joseph M. Research DeSimone Raleigh, NC Ruben Carbonell Greensboro, Leonard NC Uitenham Austin, TX Atlanta, GA Villanova, PA College Station, TX Keith Johnston William Koros Carol Bessel Perla Balbuena Research, K-12 Yes education Research, diversity Research Research Research Research Yes Yes Yes No No CERSP, Page 199 of 230 8 9 Southeastern Polytechnic State University CNRS University Atlanta, GA Russell Osmond Communication No workshop Research Research Research, equipment Research Knowledge transfer Research (facilities) Yes No No No No in general; yes, some individuals Yes 10 University of Venice, Italy 11 Oak Ridge National Lab 12 Sandia Livermore 13 Kenan Center for Utilization of CO2 in Manufacturing 14 Triangle National Lithography Lab Research institute University National Laboratory National Laboratory Industrial Consortium (a few CO2 companies) Laboratory Grenoble, Mirial France Adam Venice, Italy Pietro Tundo Oak Ridge, George TN Wignall Livermore, Miriam CA John Various Various Raleigh, NC Carl Osburn *For organization type, please indicate whether the partner organization is a company, national laboratory, Federal government, state/local government, NGO, or other **For type of partner, please indicate whether the partner organization is a research, education, knowledge transfer, diversity, or other partner. You may list more than one type, if applicable. 7. Summary Table for internal NSF reporting purposes Nine 1 the number of participating institutions (all academic institutions that participate Five full participants, three U.S. and one foreign affiliate (Texas A&M in activities at the Center) Univ., Villanova Univ., Southeastern Polytechnic State Univ. and University of Venice, Italy). 2 the number of institutional partners Six (total number of non-academic Oak Ridge NL and Sandia CERSP, Page 200 of 230 Livermore NL; CNRS, Grenoble, France; Kenan Center for Utilization of CO2 in Manufacturing; Consortium for Integrated CO2 Technology in Microelectronics; Triangle National Lithography Laboratory Universities $1,553,806 3 the total leveraged support (sum of $100,000 funding for the Center from all sources Kenan Institute In-kind $730,747 other than NSF) Total $2,284,553 November 1, 2004 to October 31, 2005 period 4 the number of participants (total number 186 CERSP personnel are “official of people who utilize center facilities; participants” in Center facilities. not just persons directly supported by Some of the 126 external NSF) collaborators listed in Section V and a few of those listed in Section IV used facilities to some degree, but no one outside the Center met the 160 hr/year criterion. participants, including industry, states, and other federal agencies, at the Center) 8. Summary of Media Reports for Reporting Year 2004-5 (June 30, 2004- May 28, 2005) Date 30-Jun-04 11-Sep04 12-Oct-04 Fall 2004 04-Nov04 05-Nov04 08-NovTitle Engineering a Better Economy CERSP Institutions Rated Among Top DeSimone Helps Lead Nanomedicine Initiative NCSU Scientists visit Blue Ridge Elementary DeSimone Receives Milkovich Award Johnston Receives Award UNC-CH Ranked First in Entrepreneurship Source NSF Directorate for Engineering US News and World Report UNC Gazette Ararat, VA News U. of Akron News UT-A press release Forbes.com CERSP, Page 201 of 230 04 10-Nov04 22-Nov04 14-Dec04 Winter 2005 14-Feb05 14-Feb05 21-Feb05 24-Feb05 11-Mar05 16-Mar05 24-May04 25-May05 Creating EXPERTs in Green Technology Green ChemistryTakes Root Nanoscale Soft Lithography Demonstrated The Entrepreneurial Balancing Act* UNC tops for science postdocs DeSimone elected to National Academy of Engineering Two NC State Faculty Named to National Academy of Engineering UNC researchers study fuel cells Fueled by UNC/NCSU technology, startup raises $2.2M Fuel cell research could transform power generation Science Next Wave USA Today Angewandte Chemie Chemical Pilot Magazine Science@Carolina Science@Carolina NC State Press Release UNC news release Triangle Business Online Science@Carolina DeSimone Elected to Academy of Arts and Sciences Sciences@Carolina UNC chemist named State Department Jefferson Science Fellow Science@Carolina * This is a web-based publication which we cannot reproduce. 11 September 2004: CERSP Institutions Rated Among Top In its annual ranking, America’s Best Colleges 2005, U. S. News has rated three CERSP among its top educational values. Nationally UT-Austin, UNCChapel Hill and NC State University rank 1, 2 and 4, respectively, among public universities. The formula used to determine which schools offer the best value relates a school's academic quality, as indicated by its U.S. News ranking, to the net cost of attendance for a student who receives the average level of financial aid. The higher the quality of the program and the lower the cost, the better the deal. To view the ratings click here. http://www.usnews.com/usnews/edu/college/rankings/brief/bestvalues/bvnatudoc_br ief.php CERSP, Page 202 of 230 12 October 2004: DeSimone Nanomedicine Tuesday Dr. Tony Waldrop, chancellor for economic inaugurates the of interdisciplinary workshops, “Nanomedicine: Imaging, and part of UNC’s the National Health Roadmap initiative. Helps Lead Initiative October 12, vice research and development, first in a series research Materials, Modeling,” as response to Institutes of Profs. Joseph DeSimone, professor of chemistry; Richard Superfine and Jianping Lu, professors of physics and astronomy; and Greg Forest, professor of mathematics will present this workshop to principal investigators in all areas of science who are interested in enhancing their involvement in interdisciplinary research. The workshop, which is organized by the UNC Roadmap Executive Committee, takes place from 4 pm to 7 pm in the Bioinformatics Bldg. auditorium. Reception will follow. The NIH proposed its Roadmap initiative in 2003 as “an integrated vision to deepen our understanding of biology, stimulate interdisciplinary research teams, and reshape clinical research to accelerate medical discovery and improve people's health.” Researchers at UNC have responded enthusiastically to this initiative, winning five major interdisciplinary grants in September. The Carolina Roadmap team will continue to facilitate interdisciplinary collaboration in response to this initiative. CERSP, Page 203 of 230 In the Fall 2004 Jan Genzer and Kirill Efimenko, a research associate in the Genzer group, went to visit children in elementary school in Ararat, VA (one of the very rural areas in the US) to teach them about science. Attached is a press release from the local newspaper. Prof. J. M. DeSimone was recognized on November 4, 2004 by the University of Akron with an award presented annually commemorating Ralph Milkovich. The award recognizes an international figure who has made significant contributions to polymer science and engineering. DeSimone presented two lectures, one describing the CO2 technology platform and one describing use of fluoropolymers in replicating microand nanostructures. For details visit the website http://www2.uakron.edu/cpspe/seminar/milkovich.html. 05 November 2004:Johnston Receives Award Dr. Johnston is a leader in utilizing industrial gases in chemical processing and in drug delivery. He has made seminal contributions in drug delivery in the formation of nanoparticles of proteins and poorly water soluble drugs, in the use of compressed gases in inorganic nanoparticle synthesis and assembly, and in polymer processing. His group’s innovative discoveries have spawned research programs in CERSP, Page 204 of 230 numerous laboratories throughout the world and led to commercial processes including formation of pharmaceutical nanoparticles, synthesis of Si nanoparticles and nanowires, CO2 dry cleaning, CO2 processing of low k dielectric insulators in semiconductor manufacturing and supercritical water oxidation (EcoWaste systems). The work has been sponsored by the National Science Foundation, the Department of Energy, the Dow Chemical Company, the Welch Foundation, the Separations Research Program, Texas Materials Institute and Center for Nano- and Molecular Science at UT. He is the Vice-President of the Int. Soc. for the Advancement of Supercritical Fluids and directs UT’s efforts in a multi-university NSF Science and Technology Center on Environmentally Responsible Solvents and Processes. Research Innovation that has been Commercialized Group IV Semiconductor Nanocrystals In a collaboration with Brian Korgel, large quantities of robust, highly crystalline, organic-monolayer passivated silicon and germanium nanocrystals and nanowires were synthesized in compressed fluids above 400 oC. At the high temperatures needed for crystallization, these fluids provide solvation of a steric stabilizer to arrest particle growth. The smallest nanocrystals, 1.5 nm in diameter, exhibit discrete optical transitions and luminescence quantum yields up to 23%, far above earlier values. This discovery was a finalist in the Discover Magazine Awards for Technological Innovation in 2001. These Si nanoparticles and nanowires are being investigated in optoelectronic devices in a start-up company, Innovalight, which has licensed the technology. Protein drug delivery and rapidly dissolving poorly water soluble drugs Johnston’s group introduced in 1993 a new CO2-based process, precipitation with a compressed antisolvent, for the formation of submicron and micron sized materials of a wide variety of inorganic and organic materials including pharmaceuticals. This technology was further developed in England by Peter York and licensed to Inhale Therapeutics (now Nektar) for $250,000,000. Recently, Johnston’s group, in collaboration with Bill Williams in UT-Pharmacy, has invented a process, spray freezing into liquid (SFL), for producing high surface area drug nanoparticles for both stable proteins and poorly water soluble drugs. Dow has provided them $2,000,000 in research support, licensed the technology and used it to start a new business, Bioaqueous, to achieve high dissolution rates of poorly water soluble drugs. CERSP, Page 205 of 230 Surfactants for Reactions, Separations, and Materials Processing in CO2 CO2 with no surface tension is being exploited in microelectronics processing to prevent image collapse of photoresists due to capillary forces as features sizes shrink below 150 nm. Johnston has designed surfactants to make CO2 based processes viable for drying of photoresists without collapse, and cleaning and repairing porous low k dielectric insulators. He is collaborating with Peter Green in chemical engineering, Sematech, Motorola and Micell Technology. 08 November 2004: UNC-CH Ranked First in Entrepreneurship Lots of universities offer degrees in business, but a new initiative at UNC fosters entrepreneurial thinking and skills throughout the liberal arts and sciences, as well as the business curriculum. That's why The Princeton Review and Forbes.com rank Carolina the nation's top university for fostering entrepreneurship. Three factors were cited in the rankings: the launch of the Carolina Entrepreneurial Initiative (CEI) to promote entrepreneurship among faculty, staff and students across the university; a new minor in entrepreneurship in the College of Arts and Sciences; and Kenan-Flagler Business School’s undergraduate business degree with a concentration in entrepreneurship. “Students are encouraged to participate in a variety of extracurricular activities, including the Carolina Entrepreneurship Club and Students in Free Enterprise, and to exploit school-sponsored programs like the Carolina Launch Program, designed to guide students through the process of starting up their own venture,” Forbes.com wrote in The 25 Most Entrepreneurial Campuses. “The school also partners with a number of prominent companies, including Ernst & Young, which hosts the Master Panel of Entrepreneurs, during which award-winning entrepreneurs share their stories with students." The Carolina Launch Program is part of the CEI, an $11 million program funded in part by a grant from the Ewing Marion Kauffman Foundation to infuse entrepreneurial approaches to education campuswide and help faculty, staff and students at UNC launch ventures of all kinds – commercial, social and artistic. "This is an important honor acknowledging the university’s commitment to fostering the entrepreneurial spirit that fuels the economic engine of our country and drives social change," said John D. Kasarda, director of the CEI, which involves programs across the university. "We are fortunate to benefit from the curriculum and programs of the Center for Entrepreneurial Studies and the Carolina Entrepreneurial Initiative as we spur innovation and foster entrepreneurship at UNC." CERSP, Page 206 of 230 Forbes.com partnered with The Princeton Review, which compiled data from 357 top colleges and universities nationwide, asking a series of questions about how they encourage and train undergraduate students to become successful entrepreneurs. 10 November 2004: Bothun and EXPERT Noted in AAAS Publication The EXPERT program at NCA&T State University and its director, Dr. Geoff Bothun, are highlighted in a recent article in Science's Next Wave, a publication of the American Association for Advancement of Science. (The article was originally published on Science's Next Wave MiSciNet: See also the homepage at http://nextwave.sciencemag.org/. Thanks to AAAS for permission to reproduce this article on our website free of charge.) Creating EXPERTs in Green Technology It's a long trip from Bear River High School, in the small northern California town of Grass Valley, to North Carolina Agricultural and Technical State University (N.C. A&T) in Greensboro, North Carolina. The distance is both geographical and cultural. But, for Geoffrey Bothun (pictured left), 29, a Bear River graduate, it has been a pleasant trip so far. As a postdoctoral fellow, Bothun established, earlier this year, a new research and education program at N.C. A&T. This makes Bothun both a westerner come east and a white scientist at a predominantly AfricanAmerican university. He relishes both roles. Interest in Minority Education The southeast isn't completely new to Bothun, who was able to observe and acclimate to the region while doing his graduate work at the University of Kentucky, Lexington, where he received a Ph.D. in chemical engineering. He likes the people he has met in the southeast, finding them "easy to approach" and "open to close personal relationships." VICTOR D. CHASE UNITED STATES 20 OCTOBER 2004 RELATED ARTICLES As a postdoctoral fellow, Geoffrey Bothun established, earlier this year, a new research and education program at N.C. A&T. CERSP, Page 207 of 230 So far, his first, brief experience as a member of a minority group has been strongly positive. "I'm getting a little perspective on what it might be like for a minority person to be in a predominantly white community. I don't want to suggest that I am beginning to understand what it's like because I don't think I could, but I'm starting to get a little bit of a taste of what it's like to be in an area where you are in the minority." And, he adds, "I haven't had any negative experiences. The students we have in the program are welcoming." When he first applied for a postdoctoral position, Bothun's primary interests were in research and academia, and he did not have a strong inclination toward minority education. But being at a predominantly African-American university has made him acutely aware of the need for diversity in science and engineering education. "Now that I've gotten more involved, I realize more than ever that the process of innovation benefits greatly from diversity, in the sense that people with unique backgrounds bring unique solutions to problems. That's one of the real reasons it's so important, beside the social morality of science being representative of our society and not being an exclusive club. ... Diversity is really key to innovation," he says. Bothun is actively promoting diversity through the program he created at N.C. A&T to recruit incoming freshmen interested in chemical engineering, mechanical engineering, or chemistry. He hopes the program will guide them toward graduate school, research, and careers in academia. Dubbed EXPERT, for Experimental Program for Education in Research and Training, the program focuses on promoting diversity through recruiting and mentoring, and it offers special seminars, advanced research programs, and substantial stipends to participants. Community outreach is another key part of the program and involves EXPERT students in secondary-school classroom demonstrations. This volunteerism is designed to inspire underrepresented minority students to enter careers in the sciences. Keeping It Clean The research projects that EXPERT students are involved in focus on environmentally friendly technologies, a thrust that comes from Bothun's interest in environmental issues and the fact that the program was established in conjunction with the National Science Foundation's (NSF's) Science and CERSP, Page 208 of 230 Technology (S&T) Center for Environmentally Responsible Solvents and Processes, a consortium of five universities that includes N.C. A&T. Having respect for the environment and all living things is an intrinsic part of Bothun's outlook on life. It was also one of the driving forces behind his choice of an academic research career. "It seems like all the projects I'm involved with have some sort of element of improving a current process, making it safer, more responsible, more friendly to the environment," he says. Bothun's interest in education is also personal or arises from personal connections. He comes from a family of teachers. His father, formerly a college professor, now teaches high school, while his mother teaches kindergarten through fifth grade. He also has a younger sister who is a high school teacher. When he entered college, Bothun intended to major in secondary education, but he soon switched to chemistry to satisfy his love of math, analytical problem solving, and the environment. He received a bachelor's degree in chemical engineering and chemistry in 1998. At first blush, chemical engineering may not seem like the right field for someone whose focus is on improving the environment. But Bothun has a different take. "People need goods and services," he says. "Whether we need the amount we have or want is another question." Nonetheless, the use of oil, coal, electricity, and manufacturing is requisite to satisfy those needs. And, he adds, "chemical engineers and chemists who want to reduce emissions from plants can apply their skills toward making these processes more environmentally responsible." "Taking It Out" Bothun's Ph.D. research involved the development of technologies to allow supercritical fluids such as carbon dioxide (CO2) to be used as replacements for environmentally damaging liquid solvents in industrial processes. He is continuing this research as part of the postdoctoral fellowship that brought him to N.C. A&T. This work is based on the fact that every fluid has a temperature and pressure point at which it becomes supercritical, meaning it can no longer be distinguished as a gas or a liquid but has properties of both. Carbon dioxide goes supercritical at about 88 degrees F and 1070 psi, at which point it has CERSP, Page 209 of 230 liquid densities and low viscosity, making it a good solvent. Although CO2 has developed a bad name as a greenhouse gas, in its supercritical state it can be used as an environmentally benign solvent. Furthermore, as Bothun explains, when it is collected, whether as a byproduct of industrial processes or from the environment, for use in a closed-loop system, "you are taking it out of the environment." Knowing that he wanted to continue his research and teach following receipt of his doctorate, Bothun began a search for a university-based postdoctoral position. It didn't take him long to learn about the NSF-funded S&T center,' which was looking for postdocs interested in establishing undergraduate research programs. The fit with his interests made it a natural choice. Another Discovery Simultaneously, Bothun came across another compatible NSF program. Called the Discovery Corps Fellowship Program, it aims to combine research and educational expertise to address areas of national need, one of which is the need to increase minority representation in the halls of scientific academia. This fell right in line with one of the core goals of the S&T center, so Bothun teamed with people from the center to write an application for a Discovery Corps Fellowship. The application they filed had two aspects: establishment of the EXPERT program at N.C. A&T, and participation (by Bothun) in a collaborative research project. He won the fellowship --"CO2-Based Membrane Technology: Research, Education and Outreach"--and headed for North Carolina. Supercritical CO2 is used in a number of applications, such as the synthesis of polymers and particles in the pharmaceutical and nanotechnology industries, where CO2 must first be pressurized to reach the critical state, depressurized so the products can be recovered, then repressurized again to repeat the process. The idea is to use membranes in place of the depressurization step now necessary to collect the particles produced in the manufacturing process. This would negate the need to repressurize the CO2 in a closed-loop system and save energy. "It's a batch process that's energy intensive," says Bothun. "Our goal is to employ membranes to make these processes more continuous." "Pretty Neat" Projects The education part of Bothun's fellowship is based on the precept that "when CERSP, Page 210 of 230 you expose undergraduates to research, they generally get interested in graduate school because they see the research can be pretty neat, especially when they are contributing to significant and fundamental projects," said Bothun. Having just opened EXPERT to student participation during the fall 2004 semester, Bothun already has 21 students enrolled: eight freshmen, nine sophomores, two juniors, and two seniors. All but one are African-American students, with an almost equal division between men and women. EXPERT freshmen and sophomores attend about 20 meetings and seminars each academic year to discuss their concerns and progress, and to learn about topics such as technical communications--an area that Bothun feels needs special attention--and career opportunities, especially as they relate to graduate education. "Ph.D.s talk about their experiences and try to demystify the graduate process and let everybody know that, 'you can do it too. It is not unattainable,' " says Bothun. When the students reach their junior and senior years, they become deeply involved in specific research projects. Still in its infancy, EXPERT has already created considerable buzz within the N.C. A&T engineering department, and it is motivating at least some students to improve their grades. Having had to turn some students away for grade-point average issues, Bothun told them, "if you can bring your grades up, we'll see what we can do next year." It is a strong stimulus for students hoping to become EXPERTs. Victor D. Chase is a freelance writer and may be reached at 4vdc@optonline.net. 22 November 2004: USA Today Reports on Green Chemistry In November 22 on-line report, USA Today cites DeSimone's work on TEFLON in a report on "Green Chemistry". Visit the website http://www.usatoday.com/news/science/2004-11-21-green_x.htm for entire report. 14 December 2004: Nanoscale Soft Lithography Demonstrated Recent work of Prof. J. M. DeSimone and associates at the University of North Carolina –Chapel Hill was featured on the cover of the International Edition of CERSP, Page 211 of 230 Angewandte Chemie (2004-43/43). Photocurable, liquid perfluoropolyethers (PFPEs) have been shown to be ideal materials for nanoscale pattern transfer and imprint lithographic processes. Enabling Materials for Nanoscale Soft Lithography Recent work of Prof. J. M. DeSimone and associates at the University of North Carolina –Chapel Hill has been featured on the cover of the International Edition of Angewandte Chemie (2004-43/43). (See below.) Photocurable, liquid perfluoropolyethers (PFPEs) have been shown to be ideal materials for nanoscale pattern transfer and imprint lithographic processes. PFPEs exhibit the positive attributes of both elastomers (such as polydimethylsiloxane, PDMS) and rigid materials (such as glass) without the drawbacks of either. For example, PFPEs exhibit extremely low surface energy, resist chemical attack and swelling by organic solvents, and can mold extremely small features precisely in repeated molding procedures. A commercially available hydroxy-terminated PFPE (Solvay) treated with isocyanoato ethyl methacrylate produces a low viscosity liquid, PFPE-DMA. Incorporating a photoinitiator such as 1-hydroxy-cyclohexyl phenyl ketone produces a photocurable liquid resin. A silicone master (A) was used to produce a mold by filling with the liquid resin and curing with UV light. After curing, the PFPE mold was easily removed (B). The mold was then used to make replicates of the original silicon master. Liquid trimethylopropane triacrylate, a photopolymer resin, was poured onto a clean, smooth silicon wafer. The mold was pressed onto this liquid, which was cured by UV light. The replicate was virtually identical to the master, reproducing 140nm lines separated by 70nm (C). Performance of these materials suggests that much smaller features may be reproducible. PDMS does not reproduce similar results. The full article is published in Angew. Chem. Ind. Ed. 2004, 43, 5796-5799. Additional information is available at www.angewandte.org. This work was partially supported by the STC for Environmentally Responsible Solvents and Processes under NSF Agreement No. CHE-9876674. PFPE Mold CERSP, Page 212 of 230 Si Master Triacrylate Replicate 140 nm lines 70 nm spacing 70 nm lines 140 nm spacing 140 nm lines 70 nm spacing Figure A Figure B Figure C CERSP, Page 213 of 230 Winter 2005 Chemical Pilot Magazine “The Entrepreneurial Balancing Act” features Prof. Joe DeSimone. Characteristics of a successful entrepreneur are discussed in this article. Professor Joe DeSimone is featured as a prime example of an inventor/entrepreneur. He describes some of the factors required in a successful startup, primarily the willingness to take prudent risks. Visit the website http://www.nsfstc.unc.edu/newsticker/Entrepreneur.pdf to read the article. SCIENCES NEWS UNC tops for science postdocs 14-Feb-2005 UNC-Chapel Hill ranks first among U.S. academic institutions recognized as "best places to work for postdocs,” according to The Scientist magazine. Joining Carolina in the top three slots for U.S. academic institutions were Washington University in St. Louis and the Massachusetts Institute of Technology. The new ranking examines working conditions for postdoctoral fellows in the life sciences as part of the magazine’s third annual survey. Other U.S. academic institutions listed were Michigan State University, fourth; Medical College of Wisconsin, fifth; University of Michigan, sixth; Virginia Commonwealth University, seventh; University of Alabama at Birmingham, eighth; Emory University, ninth; and the University of Kansas, 10th. Carolina was listed sixth among all U.S. institutions, including government institutions and private research centers. The U.S. Environmental Protection Agency campus in Research Triangle Park topped that overall list, followed by the Fred Hutchinson Cancer Research Center in Seattle, National Cancer Institute in Maryland, and National Institute of Environmental Health Sciences in Research Triangle Park. More than 3,500 survey respondents rated a valuable training experience, access to research equipment and library resources and a good mentoring relationship as the factors contributing to a great workplace. The magazine invited more than 40,000 individuals who registered at its Web site and identified themselves as a non-tenured life scientist working at a noncommercial research institution in the United States, Canada, Western Europe or Israel. Overall, the magazine evaluated the 125 U.S. institutions and 66 non-U.S. institutions that had five or more responses. CERSP, Page 214 of 230 Sciences@Carolina SCIENCES NEWS DeSimone elected to National Academy of Engineering 14-Feb-2005 Joseph M. DeSimone, W.R. Kenan Jr. distinguished professor of chemistry and chemical engineering at the University of North Carolina at Chapel Hill and N.C. State University, has been elected to membership in the National Academy of Engineering. Election to the prestigious national organization is among the highest professional distinctions awarded in the field of engineering. The academy is a private, nonprofit institution that advises the federal government and conducts independent studies on important topics in engineering and technology. The organization announced the election of 74 new members and 10 foreign associates on Feb. 11. Including DeSimone, UNC has six faculty members who are academy members. DeSimone, who holds more than 70 U.S. patents, has been widely recognized for discovering a revolutionary way to use carbon dioxide in place of conventional organic solvents for environmentally responsible manufacturing, cleaning and processing. His method has already led to the development of a new kind of Teflon and a form of dry cleaning that produces no hazardous byproducts. DuPont built a $40 million plant in Fayetteville to produce the new Teflon, which has applications in data communications, semiconductors, automotive parts and other industrial markets. DeSimone directs UNC’s new Institute for Advanced Materials, Nanoscience and Technology, an interdisciplinary endeavor drawing on the university’s research strengths in polymer science, nanomaterials and nanobiosciences, and involving faculty from the curriculum in applied and materials sciences, and the departments of chemistry, computer science, mathematics, and physics and astronomy. DeSimone also is co-director of the Kenan Center for the Utilization of Carbon Dioxide in Manufacturing, a not-for-profit research organization sponsored by 16 corporations worldwide, and director of the National Science Foundation’s Science CERSP, Page 215 of 230 Technology Center for Environmentally Responsible Solvents and Processes, a collaborative endeavor with five universities. He was chairman and co-founder of Micell Technologies Inc. (1996-2003), the company that pioneered the carbon dioxide dry cleaning technology. 11 March: "Fueled by UNC/NCSU technology, startup raises $2.2M" article by Leo John from Triangle Business Online DURHAM – A startup armed with technology licensed from the University of North Carolina at Chapel Hill and North Carolina State University has raised $2.2 million in first round financing, money the company will use to move into new offices and hire seven employees. Liquidia Technologies was founded to commercialize a new type of material developed by Joe DeSimone, a chemistry and chemical engineering professor at both UNC and NCSU, and Edward T. Samulski, a chemistry professor at UNC. They hope to raise another $300,000 to close the round at $2.5 million. Investors funding the round include individual angles, CTI Molecular Imaging, a Knoxville, Tenn.-based medical device company, and Firelake Capital Management, a Palo Alto, Calif.-based investment firm. The capital should allow the company to sustain development for a year, says Bruce Boucher, Liquidia’s president. Boucher says a local venture fund – he declined to say which one – is considering topping off the round with $300,000. “We ended up turning other investors down,” says Boucher, a former finance chief of Magellan Laboratories, which was sold to Cardinal Health in 2002. Magellan cofounder Lowry Caudill has signed on as a member of Liquida’s board of directors. In an e-mail response, DeSimone wrote that he is not prepared to discuss the company’s financing. Liquidia plans to deploy the money to set up operations. The seven hires would bring the employee roster to 12 for the company, which plans to move into 4,400 square feet of office space at Keystone Park in May. CERSP, Page 216 of 230 Besides being an investor in the company, CTI Molecular Imaging could be a boost in another way. CTI, which sells medical equipment such as positron emission tomography, or PET, machines, in December licensed Liquidia’s material to develop its own devices. Liquidia will earn royalties from any product sales. Liquidia’s material – a liquid at room temperature – becomes a powerful solid when exposed to light for a few minutes. The resulting material combines properties of silicon and glass and makes new application possible, the company says. Possible uses for Liquidia’s technology are in microfluidics, a technology applied to create the flow of liquids in miniature applications – such as ink in a printer cartridge. It also might be used to create molds during the manufacture of microchips and to produce large quantities of nanotech particles. Boucher says Liquidia’s material can be used to improve existing products as well as to create new ones. For DeSimone, Liquidia Technologies is his third technology venture. In 1995, he launched Micell Technologies, a company that developed a novel technology to dry clean clothes. He also founded BioStent, which in 2003 was bought by Guidant Corp. in a two-phase deal worth $16 million. Article from Sciences@Carolina SCIENCES NEWS Fuel cell research could transform power generation 16-Mar-2005 By Mary Catherine Hendrix UNC researchers, led by distinguished chemist Joseph DeSimone, are among the newest participants in the N.C. Fuel Cell Alliance, formed last summer to explore renewable and efficient energy sources. Fuel cells directly produce power by converting chemical energy into electrical energy. UNC researchers are concerned with Proton Exchange Membrane (PEM) fuel cells; these use hydrogen or methanol as fuel. Unlike a battery that discharges, a fuel cell will continue to operate as long as it receives fuel. CERSP, Page 217 of 230 Researchers have installed a fuel cell test station in the department of chemistry. The station is allowing researchers to test the heart of the fuel cell, the "membraneelectrode assembly," and its components. Pending grants from the Defense Advanced Research Projects Agency ($2.2 million) and the U.S. Department of Energy ($2.3 million) will, if approved, complement existing support through the National Science Foundation (NSF) Science and Technology Center for Environmentally Responsible Solvents and Processes. These grants could provide $5 million for operating expenses over three years. "We think Carolina can have a big impact by making breakthroughs in basic science that can fundamentally transform the way power is harnessed from fuel cells," said DeSimone, the W.R. Kenan Jr. distinguished professor of chemistry and chemical engineering at UNC and N.C. State University. DeSimone also directs the National Science Foundation (NSF) Science and Technology Center for Environmentally Responsible Solvents and Processes and the new Institute for Advanced Materials, Nanoscience and Technology at UNC. First devised in 1839, fuel cells are not currently used in commercial industry. Researchers believe they have the potential to provide energy for a wide range of applications, such as powering laptops, providing light and heat to homes and running automobiles. Fuel cell markets are currently valued at nearly $1 billion and are expected to grow to more than $13 billion in the next decade, according to projections cited by the N.C. Fuel Cell Alliance. "You can use fuel cells anywhere you use batteries. For example, if you used a fuel cell in a laptop it could last about a week, instead of lasting three-to-four hours with batteries," said Everett Baucom, deputy director of the NSF Science and Technology Center and adjunct professor of chemistry at UNC. "Then, instead of recharging the cell you would simply replace the fuel cartridge." UNC’s fuel cell research will focus on portable uses for the technology, including laptops, cellular phones and U.S. departments of Defense and Homeland Security applications, DeSimone said. Fuel cells offer high automotive fuel efficiency, low emissions and silent operation. UNC researchers are taking this field in a new direction, said DeSimone. CERSP, Page 218 of 230 "Most of the PEMs used in fuel cell manufacture are solid materials. We are pioneering liquid precursors. Having a liquid precursor can open new ways of fabricating fuel cells." --Hendrix is a senior with a double major in psychology and journalism and mass communications. May 10, 2005 Reception Honors NC State Engineers Elected to National Academy of Engineering North Carolina State University and the College of Engineering hosted a reception May 9 in honor of two faculty members elected to the National Academy of Engineering (NAE) this spring.Dr. Carol K. Hall, Alcoa Professor of Chemical and Biomolecular Engineering at NC State, and Dr. Joseph M. DeSimone, the William R. Kenan, Jr. Distinguished Professor of Chemistry at the University of North Carolina at Chapel Hill and Chemical and Biomolecular Engineering at NC State, received the honor, which is one of the highest professional distinctions in engineering. In addition to the reception, the Memorial Bell Tower was illuminated with red light during the evening of May 9 in honor of the accomplishments of Hall and DeSimone. North Carolina State University currently has 11 National Academy of Engineering members on the faculty.Membership in the NAE recognizes those who have made outstanding contributions to “engineering research, practice, or education.” For more information about Hall and DeSimone’s election to the NAE, go to http://www.engr.ncsu.edu/news/awards/NAE2.html. May 16: DeSimone Elected to Academy of Arts and Sciences Prof. Joseph M. DeSimone has been elected Fellow of the American Academy of Arts and Sciences in recognition of "preeminent contributions" in his field. This brings the total number of UNC faculty members who have been elected to academy membership to 27. Among the 196 fellows and 17 foreign honorary members named to the academy this year are U.S. Supreme Court Chief Justice William Rehnquist, painter Jeff Koons, Nobel Prize-winning physicist Eric Cornell, journalist Tom Brokaw and Nobel Prize-winning Polish poet Wislawa Szymborska. CERSP, Page 219 of 230 DeSimone is Kenan distinguished professor of chemistry and chemical engineering in UNC's College of Arts and Sciences and at N.C. State University. He has been a member of the college's faculty since receiving his doctorate from Virginia Polytechnic Institute and State University in 1990. He received his bachelor's degree from Ursinus College in 1986. DeSimone, who holds more than 100 U.S. patents, has been widely recognized as an innovative polymer scientist and for discovering revolutionary ways to use carbon dioxide in place of conventional organic solvents for environmentally responsible manufacturing, cleaning and processing. Earlier this year, DeSimone was elected to membership in the National Academy of Engineering, one of the highest honors in the field. He is the youngest member of NAE. In addition, he directs the National Science Foundation's Science Technology Center for Environmentally Responsible Solvents and Processes, a collaborative endeavor with five universities. DeSimone also directs UNC's new Institute for Advanced Materials, Nanoscience and Technology, an interdisciplinary endeavor drawing on UNC research strengths in polymer science, nanomaterials and nanobiosciences, and involving faculty from the curriculum in applied and materials sciences, and the departments of chemistry, computer science, mathematics, and physics and astronomy. The American Academy of Arts and Sciences was founded in 1780 by our nation’s leaders to cultivate the arts and sciences. It is one of the oldest learned societies in the country and is unique in its breadth and scope. Throughout its history it has gathered individuals with diverse interests and perspectives to participate in studies and projects focusing on critical social and scholarly issues. Prof. DeSimone will be inducted in ceremonies to be held on October 8, 2005 in Cambridge, Massachusetts. Excerpted in part from May 2, 2005 General Alumni Association Newsletter SCIENCES NEWS DeSimone elected to American Academy 24-May-2005 Joseph M. DeSimone, the W.R. Kenan Jr. distinguished professor of chemistry and chemical engineering at UNC Chapel Hill and North Carolina State University, has CERSP, Page 220 of 230 been elected a Fellow of the American Academy of Arts and Sciences. He is one of 196 new Fellows and 17 new Foreign Honorary Members recognized by the Academy for leadership in scholarship, business, the arts or public affairs. Jack D. Griffith, Kenan distinguished professor of microbiology and immunology in UNC’s School of Medicine and member of the UNC Lineberger Comprehensive Cancer Center, was also elected to the Academy. DeSimone, who holds over 100 U.S. patents, has been widely recognized for being an innovative polymer scientist, and especially for discovering revolutionary ways to use carbon dioxide in place of conventional organic solvents for environmentally responsible manufacturing, cleaning and processing. “Fellows are selected through a highly competitive process that recognizes individuals who have made preeminent contributions to their disciplines and to society at large,” said Academy President Patricia Meyer Spacks. New Fellows include Nobel Prize-winning physicist Eric Cornell, Supreme Court Chief Justice William Rehnquist, and four Pulitzer Prize winners: dramatist Horton Foote, playwright Tony Kushner, novelist Alison Lurie and cartoonist Art Spiegelman. Earlier this year DeSimone was elected to membership in the National Academy of Engineering, one of the highest honors in the field. His environmentally responsible methods have already led to the development of a new kind of Teflon and a form of dry cleaning that produces no hazardous byproducts. DuPont built a $40 million plant in Fayetteville, N.C., to produce the new Teflon, which has applications in data communications, semiconductors, automotive parts and other industrial markets. He was chairman and co-founder of Micell Technologies, Inc. (1996-2003), the company that pioneered the carbon dioxide dry cleaning technology and the precision cleaning of electronic devices. DeSimone directs UNC’s new Institute for Advanced Materials, Nanoscience and Technology, an interdisciplinary endeavor drawing on the University’s research strengths in polymer science, nanomaterials, and nanobiosciences, and involving faculty from the curriculum in applied and materials sciences, and the departments of chemistry, computer science, mathematics, and physics and astronomy. DeSimone recently launched a new company, Liquidia Technologies,which exploits liquid fluoropolymers for uses in microfluidics, imprint lithography and nano-medicine. CERSP, Page 221 of 230 DeSimone is also director of the National Science Foundation’s Science Technology Center for Environmentally Responsible Solvents and Processes, a collaborative endeavor with five universities. SCIENCES NEWS UNC chemist named State Department Jefferson Science Fellow 26-May-2005 U.S. Secretary of State Condoleezza Rice introduced UNC distinguished chemist Edward T. Samulski as a new Jefferson Science Fellow, chosen to offer science counsel to the U.S. Department of State, at a Tuesday (May 24) afternoon ceremony held in the State Department’s Benjamin Franklin Room. Samulski, Cary C. Boshamer professor of chemistry in the University of North Carolina at Chapel Hill, is one of five tenured professors nationwide to receive the prestigious State Department honor. Former Secretary of State Colin L. Powell established the program in October 2003 to continue elevating the role of science and technology in U.S. foreign policy. The program brings renowned science professors from American universities to the State Department for one-year assignments, followed by a five-year consultancy after they return to their academic careers. The Jefferson Fellows are chosen through a competition administered by the National Academy of Sciences and the Office of the Science and Technology Adviser to the Secretary of State. They are selected for their scientific achievements, articulation and communication skills, abilities to accurately describe scientific topics for non-scientific audiences and their interest in science and engineering policy. “The Jefferson Fellowship honors one of our nation’s most brilliant and innovative presidents, and the fellowship program is designed to bring such people to help our government with the challenges of our society and our science,” said Bruce Carney, senior associate dean for the sciences and the Samuel Baron distinguished professor of physics and astronomy at UNC. “Ed Samulski is being honored above many other extremely talented faculty from across the nation. The honor is well-deserved, and I have no doubt that his service will be of great value to all of us,” he added. CERSP, Page 222 of 230 The salary and benefits of each Jefferson Fellow are being paid by the academic institution at which the tenured appointment is held. Each fellow also will receive a stipend of $50,000 from funding provided by the MacArthur Foundation and the Carnegie Corp. The Jefferson Fellows will travel occasionally as a part of their tenure, and stipends will be available for that purpose. “This new program is superbly designed to enable science and policy to interface,” said Samulski. “Its creators have done a brilliant job of ensuring that nonpartisan, objective information can be provided and integrated smoothly into policy decisions.” Samulski said he was looking forward to the challenge of working in areas with which he was not as familiar. “I think they are interested in having people who can look at a wide range of scientific subjects analytically and anticipate the implications for policy. This kind of problem solving is very appealing to me. “Science is a universal language, with the capacity to unite individuals and nations around the globe. Its importance can only increase over the coming decades as the world shrinks and the playing field levels. To be able to contribute to this future is an honor for me.” Samulski has been a member of the UNC faculty since January 1988 and was chairman of the chemistry department from 1995-2000. His major research interests are the structure and dynamics of soft materials such as liquid crystals and elastic polymers. In 2004, Samulski and his students announced that they had found unequivocal evidence of a biaxial nematic liquid crystal, a scientific achievement that had eluded researchers for more than 30 years. He is co-director of the multi-university NASA Institute on Biologically Inspired Materials, a NASA-funded consortium of research institutions that is working to create new materials that might revolutionize civil aviation and space travel. CERSP, Page 223 of 230 APPENDIX A1. Biographical Sketches of New Professors There have been no new professors added to the Center this past year. APPENDIX A2. Biographical Sketches of New Members of Exterior Advisory Board Professor William C. Holton Email Holton@eos.ncsu.edu Telephone (919) 5155246 Fax (919) 515-3027 Homepage http://www.ece.ncsu.edu/nano Professor William C. Holton (Department of Electrical and Computer Engineering, Box 7911, North Carolina State University, Raleigh, NC) has been a Visiting Research Professor at NCSU since January 1996. Since coming to NCSU he has been an active co-principal investigator and served as a Member of the National Academy of Sciences Panel to evaluate Air Force Nanotechnology (2001-2002). Before joining NCSU, Dr. Holton was Vice President for Research Operations with the Semiconductor Research Corporation (SRC). In this capacity he directed SRC’s university research program and participated in the guidance of the SRC as the semiconductor industry’s premier research sponsor of university research. As SRC VP he also served Advisory Boards for the Microelectronics Center of North Carolina (1990-95) and for DARPA on Advanced Lithography (1989-90). Prior to joining SRC in 1984, Dr. Holton was Director of Research, Development & Engineering and Chief Scientist for the Semiconductor Group of Texas Instruments Incorporated, responsible for the direction of the Semiconductor Process Development Laboratories, the CAD Circuit Design Division, design of all new semiconductor products, and production of semi-conductor custom products. The development of TI’s digital signal processor was initiated as his direction in 1979. As Chief Scientist, he was responsible for the Semiconductor Group strategic plan. Prior to this he was director of TI’s Advanced Components Laboratory, responsible for advanced VLSI silicon and GaAs technology. He received his Ph.D. at the U. of Illinois and his B.S. at U. of North Carolina at Chapel CERSP, Page 224 of 230 Hill. He has published extensively in fields pertaining to these responsibilities (120 publications). He is a Fellow of the IEEE and a Fellow of the APS. He also received the IEEE Frederick Philips Award (1998) “for outstanding contributions in the management of R&D resulting in effective innovation in the electrical & electronics industry.” His research interests include semiconductor physics and modeling of electronic devices, carrier transport in bulk and hetero-structures, low dimensional physics, quantum transport, quantum computing, nuclear magnetic resonance, electron spin resonance in solids. Dr. Parry Norling Dr. Parry Norling is a visiting fellow at the Chemical Heritage Foundation in Philadelphia where he writing a chapter for a book entitled “Innovation, Learning, and Institutional Change: Patterns of Knowledge Changes.” From 2001-2003 he was AAAS (American Association for the Advancement of Science) Technology Fellow at the Science and Technology Policy Institute at RAND in Washington DC; he retired December 1998, after 33 years from the DuPont Company where he held a number of R&D and production management positions plus two years as Corporate Director of Health and Safety. Following his retirement, in a part-time capacity, he was Corporate Technology Adviser at DuPont acting as an adviser to the Chief Technology Officer. A graduate of Harvard College and Princeton University with a BA in physical sciences and PhD in polymer chemistry, he is past-chairman of the International Union of Pure and Applied Chemistry’s (IUPAC) CHEMRAWN (CHEMical Research Applied to World Needs) committee, past-Chairman of the Industrial Research Institute (IRI) , member the Conservation Technical Advisory Committee of the CERSP, Page 225 of 230 Philadelphia Museum of Art, member of the Board of Limen House (a United Way agency), member of the Academy of Life Long Learning at the University of Delaware, and Fellow of the American Association for the Advancement of Science (class of 2000). He is currently a visiting adjunct professor in the physics department at Georgetown University where he teaches a course “Industrial Problems in Physics”. His interests include squash, tennis, paddle tennis, canoeing, skiing, hiking and reading. His email address is norling@rand.org CERSP, Page 226 of 230 Appendix B1 CERSP Organization Chart Administrative Oversight Board Provosts from UNC-CH NCSU, UT-A, NC A&T Kenan Center Director R. G. Carbonell Administrative Assistant II V.P.Haithcock Director J. M. DeSimone Co-Director R. G. Carbonell Deputy Director E. I. Baucom Site Coordinators* UNC-CH: J. M. DeSimone NCSU: R. G. Carbonell NCA&T: L. C. Uitenham # UT-Austin: K P Johnston Network Technician D. N. Donie Program Assistant IV S. C. Kocz External Advisory Board J. D. Roessner-Chair Social Sciences Coordinator D. O. Gray Leader K-12 Education D. G. Haase EXPERT Coord. G. D. Bothun RICHES Leader D. K. Taylor Accounting Technician III R. Haithcock K-12 Ed. Coord. M. L. Bellamy * Members of Technical Coordinating Committee with V. S. Ashby and W. C. Holton # V. N. Kabadi temporarily replaces L. C. Uitenham CERSP, Page 227 of 230 Appendix C1 Agenda for CERSP External Advisory Board Conference 1:00 – 4:00 PM May 9, 2005 Agenda review DeSimone Review 2004 NSF site visit comments DeSimone Revised Strategic Plan Baucom Management and Research Issues DeSimone Restructuring of Research Macromolecular synthesis and engineering Functional materials Nano-particles and -structures Separations Restructuring of Industrial Consortium Minimal investment Individual research contracts emphasized Change in IP strategy Similar to Kenan Center for UCDM otherwise Social Science Update on social science research projects Collaboration and innovation RICHES Update and plans Baucom Taylor Agenda for CERSP External Advisory Board Conference 10:00 AM – 12:00 PM May 27, 2005 Diversity EXPERT update Bothun CERSP, Page 228 of 230 K-12 update Bellamy EAB membership 2005 NSF site visit Baucom Baucom Formal minutes were not issued. Comments related almost exclusively to the strategic plan, and those comments were incorporated into an extensive re-write of that plan as well as development of a new “icon” illustrating the Center’s activities and how those inter-relate. CERSP, Page 229 of 230 CERSP, Page 230 of 230