NSF Science and Technology Center (STC) for Environmentally Responsible Solvents and Processes
Ruben G. Carbonell and Joseph M. DeSimone;
collaboration among NC State University, UNC-CH,
NCA&TSU, and U. Texas-Austin
National Science Foundation
$18 million ($5M to $6M to NCSU)
February 2000 - February 2005
The NSF Science and Technology Center (STC) for Environmentally Responsible Solvents and Processes is a collaboration among North Carolina State University, UNC-Chapel Hill, NC A&T State University, and the University of Texas - Austin. The STC will be the leading center in the world dedicated to discovering environmentally friendly processes using alternative solvents. The goal is to lead the "environmental revolution" in significantly reducing the amount of aqueous and organic wastes generated in the manufacture of polymers and chemicals, in painting, cleaning and coating operations, and in the production of textiles, paper, and microelectronic products.
Kenan Center for the Utilization of Carbon Dioxide in Manufacturing
Ruben G. Carbonell and Joseph M. DeSimone
16 corporate sponsors + Kenan Institute
$560,000 plus $70,000 (Kenan Institute)
July 1, 1997 - June 30, 2000
This is an industry-university research consortium with over 16 partners from industry and the national laboratories. Research is supported by the membership, as well as through federal and industrial grants to the Center. Projects are a collaborative effort with investigators from the physical sciences at UNC-Chapel Hill and engineering from North Carolina State University. There are four thrust areas for the research: catalysis and reaction engineering, cleaning and extraction technologies, chemical processing and coatings, and computational and analytical technologies.
Investigations and Development of CO2-Based Polymer Delivery Technologies
Ruben G. Carbonell and Joseph M. DeSimone, R.Gould, Saad A. Khan, and J. Edwards
Office of Naval Research
$190,000/year
December 15, 1997 - December 14, 2000
Our goal is to develop CO2-based coatings technologies that will allow the replacement of some of the hundreds of millions of pounds of solvents that are manufactured each year for use in coatings applications. CO2-based delivery systems are possible for binary systems containing either fluoro-polymers or silicones dissolved in CO2, or for ternary systems comprised of CO2-insoluble polymers and CO2-soluble surfactants that help to solubilize the polymer in the CO2 solvent. The chemical and physical properties of these systems are being investigated and delivery nozzles are being designed.
Delivery of Polymeric Coatings for the Protection of Monumental and Civil Infrastructure from Homogeneous Solutions of CO2
Ruben G. Carbonell, Joseph M. DeSimone, and Harold B. Hopfenberg
Dupont
$50,000/year
May 1, 1998 - April 30, 2001
Novel polymeric materials are being developed for the prevention of the deterioration of stone monuments and other civil infrastructure. The objective is to make the surface of the material hydrophobic to prevent the penetration of acid rain. These polymers will be delivered from high pressure solution in carbon dioxide, an environmentally-benign solvent.
Kenan-Italo Consortium for the Preservation of Monumental Works of Art
Ruben G. Carbonell, Joseph M. DeSimone and F. Piacenti
Kenan Institute for Engineering, Technology and Science
$50,000/year
April 13, 1994 - April 12, 2001
Polymeric materials used for the protection of monumental works of art must satisfy stringent requirements. This project characterizes the transport properties of natural stones that have been coated with fluoropolymers to prevent liquid water penetration. In particular, the transport of liquid water and water vapor through the stone samples are being evaluated. The relationship between polymer delivery rates to the surface and polymer penetration and pore blockage are being investigated.
Ligands from Combinatorial Libraries for Virus Detection and Removal
Ruben G. Carbonell and D. Brown
VITEX Technologies, Inc.
$115,000
June 1, 2000 - May 31, 2001
Solid phase combinatorial peptide libraries will be used to identify ligands that bind specifically to the surface of viral particles. Such ligands can be used to develop novel detection technologies as well as in the separation and isolation of viruses from plasma products. The technique might also lead to novel anti-viral therapeutic agents.
Affinity Purification of Proteins Using Ligands Derived from Peptide Libraries
Ruben G. Carbonell
Sandia National Laboratories
$145,000
October 1, 1997 - December 31, 1999
This project involves the screening of solid phase combinatorial peptide libraries to identify ligands for the affinity purification of proteins from complex mixtures. The effects of peptide density and the absorption and elution conditions on the yields of proteins are being investigated. Small peptides offer several advantages as ligands for the large-scale purification and detection of proteins and other biological molecules by affinity chromatography. These include low cost relative to antibodies, easy coupling chemistry, and stability during sterilization and elution steps.
Composite Polymer Electrolytes Using Fumed Silica Fillers: Synthesis, Rheology, and Electrochemistry
Saad A. Khan, Peter Fedkiw, and Gregory L. Baker
Department of Energy
$660,000
September 1997 - August 2000
This project involves developing novel composite polymer electrolytes possessing high conductivity, electrochemical stability, mechanical stability, and easy processability. These mutually exclusive properties will be arrived at by a new approach using surface-modified fumed silica fillers. By appropriate choice of these surface groups and the polymeric media, the rheological behavior of these systems can be tailored independently of the electrochemical characteristics, a feat that has eluded researchers to date. These advanced electrolytes will be used as new generation materials for secondary lithium batteries.
Novel Electrodeposited Nanocrystalline Metals and Composites
Carl Koch, Peter Fedkiw, and Jagdish Narayan
National Science Foundation
$540,000
August 1998 - July 2001
The focus of this project is to develop artifact-free nanocrystalline (nc) materials by electrodeposition. A study of the electrochemical parameters that control the grain size and chemistry of the nc films are a central focus of the research. Both Cu and Zn deposits will be prepared. In addition, nano-sized dispersoids will be co-deposited during the deposition, such as "soft" polystyrene and "hard" diamond, as a means to effect the properties of the deposit.
Production and Characterization of Electrogalvanized Nanocomposites
Carl Koch, Peter Fedkiw, and Jagdish Narayan
International Lead Zinc Research Organization
$144,000
January 1999 - December 2001
The main objectives of the research are: (a) the determination and understanding of electrochemical parameters that control grain size, chemistry, and dispersoid morphology and distribution in zinc-based nanocrystalline coatings; and (b) characterization of the structure/property relationships of such coatings, with particular emphasis on coating adherence, hardness, and appearance, all of which are pertinent to automotive applications.
Electrooxidative Destruction of Organic Wastes Using Supercritical CO2 as a Reaction Media
Peter Fedkiw
Kenan Center for the Utilization of Carbon Dioxide in Manufacturing
$25,000
July 1998 - December 2000
This project will explore the use of near-critical and supercritical (SC) carbon dioxide as a solvent for the electrochemical destruction of organic wastes. The unique solvating advantages of SC carbon dioxide will be coupled with the tuneability and specificity of electrochemistry to oxidatively destroy organics to carbon dioxide, water, and minerals, with an initial focus on chlorinated hydrocarbons.
Gas Transport and Barrier Properties of Novel Aromatic Polyamides
Benny D. Freeman and J. Preston
National Science Foundation
$306,518
July 1, 1998 - June 30, 2001
Proprietary amorphous polyamides are used commercially in gas separation applications; liquid crystalline (LC) aromatic polyamides are among the most impermeable barrier polymers available. However, wholly aromatic polyamides in general and LC ones in particular are typically difficult to dissolve and have melting points near or above their decomposition temperatures, which makes processing quite difficult. This research program explores synthesis and gas sorption, transport, and permeation properties of novel, highly soluble aromatic polyamides, having either rigid rod backbones or semi-rodlike backbones and structural elements which could be precursors for further reactions such as crosslinking.
Novel Nonporous Fouling-Resistant Composite Nanofiltration Membranes and Membrane Separation Systems for Wastewater Treatment Important for CPSON5/PPSON1: Minimization of Oily and Non-Oily Waste
Benny D. Freeman
Department of Defense - Strategic Environmental Research and Development (SERDP) Program
$1,402,106
June 4, 1998 - June 3, 2001
This research program will be a collaborative project between North Carolina State University [NCSU] and Membrane Technology and Research, Inc. [MTR], Menlo Park, CA. This academic/industrial partnership is directed towards removing fundamental wastewater processing limitations related to membrane fouling by developing advanced high flux, low fouling membrane materials and reducing these advances to practice by preparing spiral wound membrane units suitable for field testing.
The Influence of Backpulsing on Fouling Properties of Novel Nanofiltration Membranes for Wastewater Remediation
Benny D. Freeman
Office of Naval Research
$80,000
November 15, 1997 - October 30, 1999
The use of backpulsing (or reverse filtration) has been shown to markedly enhance average permeate flux (by providing in situ membrane cleaning to remove foulants) in conventional ultrafiltration and microfiltration membranes, separations that are commonly carried out at 10-40 psi transmembrane pressure difference. Thus, in this program, we will construct a novel apparatus to evaluate the effect of backpulsing on fouling resistance of both novel materials being produced and characterized as part of our ongoing ONR program and commercial nanofiltration and ultrafiltration membranes, which will serve as standards. We will perform a variety of backpulsing experiments to explore the efficacy of this technique to enhance average permeate flux.
Development and Testing of New Nanofiltration Membranes for Application to Water Treatment
Benny D. Freeman, F. DiGiano, and Joseph M. DeSimone
American Water Works Association
$149,447
October 1997 - October 1999
Minimizing the frequency with which membranes must be rinsed and/or cleaned to remove foulant material is key to the success of membrane technology in water treatment. In this research program, we are synthesizing new heterophase polymers that have high water productivity and excellent selectivity, and are more fouling-resistant than conventional drinking water treatment membranes.
Very Low Surface Energy (<11 dynes cm-1) Heterophase Polymeric Materials for Membrane Separations: An Integrated Polymer Chemistry/Engineering Approach
Benny D. Freeman and Joseph M. DeSimone
Office of Naval Research
$1,080,101
April 1, 1994 - September 31, 1999
The composite experimental research effort includes materials synthesis, ultrafiltration characterization, biological foulant adhesion characterization, and oversight involving membrane module fabrication companies. This research program is among the first to combine a materials synthesis effort with bio-foulant adhesion and membrane separation performance characterization. Composite transport data and transmission electron microscopy results on a series of new materials is providing fundamental insight into the effect of morphology on transport properties.
Sorption and Transport of Organic Molecules in Polyethylene Terephthalate
Benny D. Freeman
$177,262
Eastman Chemical Company
January 1, 1996 - December 31, 1999
The migration of flavor molecules in poly(ethylene terephthalate) (PET) packaging can limit business opportunities by deleteriously affecting food and beverage package performance through flavor adulteration, scalping and, in refill applications, flavor carryover. Fundamental permeant partitioning and diffusion properties are critically important in understanding and controlling flavor adulteration, scalping, and flavor carryover. However, little information regarding flavor molecule partitioning and transport in PET is available. These composite considerations have stimulated the proposed cooperative research program. The primary objective of the research program is to determine equilibrium partitioning and sorption transport kinetics of model organic penetrant molecules in poly(ethylene terephthalate).
NSF CAREER Award: Fabrication of Nanoparticle Assemblies in Ordered Polymeric Matrices
Jan Genzer
National Science Foundation
$359,992
January 15, 1999 - December 31, 2003
In this project I propose to investigate experimentally
the formation, organization, and physical properties
of nanocomposites made of periodically modulated arrays
of
nanoparticles embedded in self-organized
two-component polymer matrices deposited onto solid substrates. The
organization and spatial distribution of the nanoparticles
will be adjusted by tailoring the structural properties of the
host polymer material. In particular, by using mixtures of
diblock copolymers or by using laterally phase-separated
polymer blends, the dimensions of the structural features in the
polymer matrix, and thus the distribution of the
embedded nanoparticles, will range from several nanometers to
several micrometers, respectively.
The Role of Substrate Chemical Roughness and Chain Microstructure on Polymer Adsorption at Planar Interfaces
Jan Genzer
American Chemical Society - Petroleum Research Fund
$25,000
July 1, 1999 - June 30, 2001
The purpose of the proposed program is to initiate experimental and modeling studies, which aim at studying the adsorption of heteropolymers with defined microstructures (e.g., copolymers) on substrates with predefined chemical heterogeneity. During the course of the research we plan to investigate: (i) the role of the copolymer microstructure (block vs. random vs. alternating) and the copolymer molecular weight on adsorption, and (ii) the effect of size and spatial distribution of the substrate chemical heterogeneities on the amount of adsorbed copolymer. The experimental part of the project will be complemented with calculations using a 2- and 3-dimensional self-consistent field model and Monte Carlo simulations.
Acquisition of Equipment for Molecular Interfacial Research and Education
Jan Genzer, Christine S. Grant, Peter K. Kilpatrick, Gregory N. Parsons, Richard J. Spontak
National Science Foundation, Instrumentation for Materials Research
$142,204 plus $94,400 cost sharing (College of Engineering, NCSU)
August 15, 1999 - July 1, 2000
The Department of Chemical Engineering at North Carolina State University requests support to purchase (i) a variable angle spectroscopic ellipsometer (VASE), (ii) a dynamic contact angle (DCA) system, and (iii) an interfacial rheometer (IFR). The acquisition of these new instruments will provide important new capabilities for investigating adsorption of self-assembling organic molecules at solid/liquid and liquid/liquid interfaces and their organization in thin film geometries. The acquired equipment would also play a major role in training both undergraduate and graduate students at the Department of Chemical Engineering at North Carolina State University in new hands-on laboratory courses in interfacial science.
Development of Novel Anticorrosive Coatings with Tunable Wetting Properties
Jan Genzer
NACE International
$10,000
July 1, 2000 - June 30, 2001
We propose a novel method of tailoring the surface properties of poly(dimethyl siloxane) (PDMS) networks. The technique is based on the combination of (i) mechanical manipulation of the grafted PDMS substrate and (ii) the well known grafting reaction between w(CH2)xSiCl3 molecules and OH functionalities present on PDMS surfaces. We believe this relatively simple procedure can have a tremendous impact on producing coatings and other surface active layers with tunable properties.
POWRE: Interfacial Analysis of the Deposition and Removal of Organic Films from Solid Surfaces
Christine S. Grant
National Science Foundation Professional Opportunities for Women in Research and Education (POWRE) Program
$65,000
June 1998 - May 2000
The POWRE grant will enable our group to access highly specialized analytical equipment at the University of Minnesota's Center for Interfacial Engineering to study the interfacial properties of films during decontamination and fouling processes. The following systems will be studied: the hydration and swelling of supported phospholipid films in aqueous surfactant solutions and the high temperature degradation and deposition of lubricant films on metal surfaces. The proposed research represents a departure from our earlier work by focusing on a closer evaluation of the changes in the chemical and physical properties of the contaminant film using interfacial characterization techniques.
Development of International Environmental/Chemical Engineering Computer Educational Aids: A Partnership Between NCSU and the University of Science and Technology (UST) in Ghana, West Africa
Christine S. Grant
Engineering Information Foundation
$75,000
1998 - 1999
The major goal of this project is the compilation of environmental/ChE computer based problems with an international perspective. The key stages of the project include: (1) acquisition of environmental data by ChE students at UST by either chemical sampling, or from industrial/municipal waste information, (2) utilization of software programs to analyze and model the Ghana environmental data, and (3) development of a textbook of problems and case studies that can be incorporated into the undergraduate chemical engineering curriculum. This project represents the first joint research/educational program between the NCSU's COE and UST.
The Use of Sequestrants for the Removal of Calcium Salt Deposits from Stainless Steel Surfaces
Christine S. Grant
National Science Foundation
$160,000
September 1999 - August 2001
This research investigates the role of mass transfer and
surface reactions on the removal of calcium mineral films
(i.e., calcium phosphate, calcium oxalate and calcium
carbonate) from stainless steel using sequestrant solutions in
alkaline environments. Fundamental interfacial
mechanisms describing the interaction of the sequestrant ligand with
calcium phosphate are key to understanding the surface
and bulk solution reactions. Research on the use of
polyaspartic acid as an environmentally benign cleaning agent for
calcium salts has led to interactions with a new set of
compa
nies (Bayer, Merck and Donlar Corporations); providing
an important link of our research to chemical and
pharmaceutical industries.
National Science Foundation (NSF) Green Processing Undergraduate Research Program
Christine S. Grant and Steven W. Peretti
National Science Foundation
$640,000
2000 - 2005
This program provides educational research experiences for students in Green (environmentally friendly) Processing (over 100 in next 5 years). In this 10 week summer program in the NCSU CHE department students will interact with the Kenan CO2 Center and the NSF STC for Environmentally Responsible Solvents and Processes. In addition to research programs directed by faculty mentors, professors in the NSF Research Ethics Initiative at NCSU will conduct an ethics symposium series focused on topics in engineering and environmental ethics. National and targeted recruiting at a group of predominantly undergraduate institutions and HBCU,s and Research One universities will ensure a diverse student population.
Environmentally Benign CO2-Based Surfactant Decontamination Processes
Christine S. Grant (Ruben G. Carbonell and Joseph M. DeSimone)
National Science Foundation Science and Technology Center for Environmentally Responsible Solvents and Processes
Approximately $300,000 over 5 years
1999 - 2004
The overall research objective is to develop the ability to visualize and quantify the removal of contaminants from a solid substrate in both liquid and supercritical CO2 based surfactant cleaning. The project takes a systematic approach to collect, interpret and classify image data collected during decontamination operations. The study will investigate the fundamental transport and interfacial phenomena associated with the removal of thin films and eventually particulate matter from solid surfaces. Particular attention will be paid to the diffusion and mass transfer in CO2 surfactant systems and mechanisms associated with cleaning.
Molecular Simulation of Fluid Behavior in Narrow Pores and Pore Networks
Keith E. Gubbins
National Science Foundation, National Resource Allocations Committee (NRAC)
$110,000/year
May 1, 2000 - April 20, 2002
The work under this project is aimed at understanding the behavior of simple fluids in porous media, in particular the effects of such confinement on phase transitions, chemical equilibria and transport properties. Current projects being pursued are studies of shifts in the freezing transition in porous carbons, improved molecular models of activated carbons, effect of confinement on diffusion rates in carbons, and the influence of pore size, material and state conditions on chemical reaction equilibria. These large simulations are carried out on supercomputers at several NSF national centers (San Diego, Illinois and University of Texas) under a large NRAC grant.
Adsorption and Diffusion in Well-Characterized Adsorbent Materials
Keith E. Gubbins
Department of Energy
$230,000/year
August 1, 1998 - October 31, 2001
A wide-ranging study, using molecular simulation and experimental methods, of adsorption, separation and diffusion of gases and liquids in nanoporous materials is supported under this project. The main emphases are on (a) studies of water and gas hydrates in activated carbons and large pore aluminosilicate materials, (b) the development of improved and realistic models of porous glasses, sol-gel materials and polymers, and (c) the design of highly selective adsorbent systems for removal of trace components.
CISE Postdoctoral Research Associate: Molecular Simulation of Phase Transitions
Keith E. Gubbins
National Science Foundation
$46,174
July 1, 1997 - June 30, 2000
This grant supports a postdoctoral research associate to develop advanced molecular simulation methods for the study of phase transitions in realistic models of mesoporous glasses and activated carbons. Both equilibrium and kinetic aspects of capillary condensation (gas-liquid transitions) and liquid-liquid separation are being investigated.
Effect of Confinement on Reaction Equilibrium in Porous Materials
Keith E. Gubbins
$44,670
National Science Foundation
August 1, 1999 - July 31, 2000
In this project advanced Monte Carlo simulation methods are being used to determine the effect of material, pore size, surface properties, and other variables on chemical reaction equilibria and heats of reaction. Materials under study include activated carbons, carbon nanotubes, porous silica glasses and aerogels.
US-Venezuela Cooperative Research Project: Modeling Adsorption and Dynamics of Water and Aqueous Solutions on Activated Carbons
Keith E. Gubbins and E. Muller
National Science Foundation
$38,256
March 1, 1997 - February 29, 2000
This project involves a cooperative research program between the PI at NC State University and Prof. E. Muller at Simon Bolivar University in Caracas, Venezuela. The behavior of water and aqueous solutions adsorbed in activated carbons is under investigation, with particular interest in selective adsorption and the formation of gas hydrates in carbons.
Phase Separation and Molecular Dynamics of Fluids and Solids in Porous Media
Keith E. Gubbins and M. Sliwinska-Bartkowiak
US-Poland Maria Sklodowska Curie Foundation
$38,000
December 1, 1997 - November 30, 2000
This project is a joint molecular simulation/experimental effort to investigate the freezing and liquid-liquid separation of fluid mixtures adsorbed in well-characterized porous media. The experimental work is carried out by a team of professors at the Institute of Physics, Adam Mickiewicz University, Poznan, Poland. The complementary theoretical and molecular simulation program is carried out at NC State University.
Computer Simulation Studies of the Thermodynamics of Protein Folding and Aggregation
Carol K. Hall
National Science Foundation
$200,500
December 1, 1997 - November 30, 2000
This research program is aimed at understanding the mechanisms by which solutes prevent protein aggregation. By simulating the properties of model proteins and solutes on the computer, we explore how protein folding and kinetics are influenced by protein type and concentration, denaturant concentration, solute type and concentration, and temperature. Our theoretical work should assist scientists in (1) choosing and/or designing solutes to suppress unwanted aggregation, (2) optimizing the in vitro refolding of recombinant proteins by manipulation of process variables, and (3) providing a future basis for the modeling of medically-important proteins such as b-amyloid, the protein whose aggregation is associated with Alzheimer's disease.
Theoretical Treatment of the Thermophysical Properties of Fluids Containing Chain-Like Molecules
Carol K. Hall
Department of Energy
$300,000
June 1, 1997 - May 31, 2000
This research program has three main objectives: (1) to further develop and refine the Generalized Flory theory for mixtures, particularly those of practical interest to the polymer industry, e.g. polymer solutions, polymer blends, and copolymer-containing blends, (2) to enhance our understanding of the static and dynamic properties of polymer networks and gels, with special focus on network deformation and gel swelling, and (3) to develop a detailed molecular level understanding of the role played by entanglements in the dynamics of polymer melts.
Theories for Fluid Mixtures Containing Chain-Like Molecules
Carol K. Hall
American Chemical Society-Petroleum Research Fund
$60,000
July 1, 1998 - August 31, 2000
This research program is aimed at developing an equation of state that is capable of predicting the experimentally observed thermodynamic properties, including phase equilibria, of fluids and fluid mixtures containing chain-like molecules ranging in length from alkanes to polymers. The Generalized Flory Dimer theory is being extended to mixtures of practical interest to the petroleum, chemical and polymer industries, i.e. mixtures with asymmetries in segment site, chain length, and attractions, either between species or along the chain.
Computer Simulation Studies of Protein Aggregation
Carol K. Hall
National Institutes of Health
$493,839
May 1, 1999 - April 30, 2003
This research program is aimed at understanding the basic principles underlying protein aggregation. The goal is to develop molecular-level models that capture the essential features that govern the competition between protein folding and aggregation. Our primary tool in this project is discontinuous molecular dynamics computer simulation, an extremely fast technique that allows us to follow the motion of model biological molecules in detail over biologically-relevant time scales. These simulations are expected to serve as a future basis for modelling the aggregation of medically important proteins such as those implicated in Alzheimer's disease, prion ("mad cow") disease and cataracts.
Theoretical Treatment of the Thermophysical Properties of Fluids Containing Chain-Like Molecules
Carol K. Hall
Department of Energy
$415,000
July 1, 2000 - May 31, 2003
This research program is aimed at enhancing our understanding of the behavior of fluids and fluid mixtures containing long flexible, chain-like molecules ranging in length from alkanes to polymers. The project is divided into three parts: (1) exploring and classifying phase diagrams for binary mixtures of chain-like molecules, (2) predicting complete phase diagrams (including solid, liquid and vapor) for binary mixtures of Lennard Jones molecules, and (3) simulating the dynamic properties of entangled polymer melts. The theories resulting from this work could eventually serve as the foundation upon which to build thermophysical property correlations for petroleum, natural gas, and polymers.
Biocatalysis Near and Above 100°C: Physiological, Enzymological and Engineering Studies
Michael W. Adams (Univ. of Georgia), John A. Baross (Univ. of Washington), and Robert M. Kelly (NCSU)
National Science Foundation
$285,000
September 1996 - August 1999
This project examines both basic and applied issues of enzymes from two model hyperthermophiles, the archaeon Pyrococcus furiosus (Tmax 105°C) and the bacterium Thermotoga maritima (Tmax 90°C). This will done in light of sequence information on the entire genomes of both organisms which will be available during the course of the project. We will also continue to explore the diversity of hyperthermophiles in both deep sea and continental geothermal sites, and the types of enzymes they contain will be examined for their physiological significance, thermostability/thermoactivity and/or biotechnological potential.
Bioenergetic and Physiological Studies of Hyperthermophilic Archaea
Robert M. Kelly
Department of Energy
$285,000
August 1996 - July 1999
The physiological and bioenergetic characteristics of the hyperthermophilic archaea must be better understood, if this novel group of organisms is be used to the best scientific and technological advantage. This project addresses these issues from the perspectives of intracellular proteolysis and bioenergetics for members of the order Thermococcales.
Biological and Chemical Energetics of Deep Sea Subsurface Life
Michael W. Adams (University of Georgia), John A. Baross (University of Washington), and Robert M. Kelly
National Science Foundation
$225,000
August 1998 - July 2001
The isolation of hyperthermophiles (microorganisms that grow at 90°C and above) from both deep sea (< 2 km) subfloor fluids immediately following a volcanic eruption and from diffuse flow vent fluids associated with stable hydrothermal vents indicates the existence of a deep sea, subsurface microbial biosphere. The overall objective of this project is to examine the specific nature of the microbial population within deep sea subsurface environments, such that the results will serve as a paradigm for the characterization of extraterrestrial environments and potential life forms therein.
Thermophilic Enzyme Hydrolysis of Water-Soluble Polymers: Interrelationship Between Biocatalysis and Rheology
Saad A. Khan, Robert M. Kelly, and Robert K. Prud'homme (Princeton University)
National Science Foundation
$226,051
August 1997 - August 2000
Novel approaches to extend the useful temperature range for enzymes used for hydraulic fracturing of oil and gas wells have been identified that rely upon newly discovered hyperthermophilic enzymes and new concepts in copolymer blends for galactomannan polymers. Preliminary research has resulted in the identification of several hyperthermophilic microorganisms capable of producing hemicellulosic enzymes active in galactomannan hydrolysis. As such, the objectives of this collaborative study are to understand the physical chemistry and rheology of existing and proposed polymeric fracturing solutions during enzymatic hydrolysis at high temperatures.
Biomolecular and Engineering Studies of Extremely Thermophilic Xylose (Glucose) Isomerases
J. Gregory Zeikus (Michigan State University) and
Robert M. Kelly
National Science Foundation
$244,915
November 1998 - October 2001
Enzymes from thermophiles and hyperthermophiles
represent attractive candidate biocatalysts when applications
require high-temperature operations. One such operation
is glucose conversion to fructose by xylose
(glucose)
Chemical Engineering
isomerases (XIs) in the production of high fructose corn syrup. This study, containing both biochemical engineering and biomolecular aspects, focuses on the XIs from the thermophilic and the hyperthermophilic eubacterial genera Thermoanaerobacterium and Thermotoga.
Rheological Studies on Blends of Dendritic and Linear Polymers
Saad A. Khan
Research Triangle Institute/Environmental Protection Agency
$110,000
August 1998 - October 2001
Dendrimers and hyperbranched polymers offer tremendous potential for use as coating systems because of their uniqueness in displaying low viscosities even at high molecular weights. The proposed research will focus on obtaining a fundamental understanding of the rheology of dendritic polymers and their blends in terms of the micro-/molecular-structure of the system so as to facilitate development of systems that show low viscosity at high solids level.
Predictive Modeling of Flow Properties in Food Systems Containing Dairy-Based Ingredients
Brian Farkas, Christopher Daubert, and Saad A. Khan
Dairy Management Inc. (DMI)/Southeast Dairy Foods Research Center (SDFRC)
$175,025
January 1997 - December 1999
This project focuses on investigating the rheological behavior of milk and hydrocolloid mixtures under aseptic processing conditions and developing empirical models to predict the viscosity of these systems under these conditions. Results from the research could be used by the dairy industry to improve products and manufacturing processes.
Rheological Characterization of Enzymatically Modified Galactomannans
Saad A. Khan and Robert M. Kelly
Department of Agriculture
$194,612
September 1996 - August 1999
In this project, newly discovered hemicellulases from high temperature microorganisms are being used to modify galactomannans to achieve favorable thickening properties. These enzymes are functional and stable at temperatures approaching and exceeding 100°C. As such, the galactomannan solutions that are treated have significantly less viscosity and are more amenable to enzymatic processing. The ability to use enzymes in this way and at these high temperatures has not yet been available but could expand the applications for thickening agents. Fundamental insights into the relationship between biochemical modifications and thickening properties of the resulting galactomannan solution will be sought in this investigation.
Composite Polymer Electrolytes Using Surface-Functionalized Fumed Silica: Synthesis, Rheology, and Electrochemistry
Saad A. Khan, Peter S. Fedkiw, and Gregory L. Baker
Department of Energy
$660,359
October 1997 - September 2000
This project involves developing novel composite polymer electrolytes with high conductivity, electrochemical stability, mechanical stability and easy processability. These mutually exclusive properties will be arrived at using a new approach utilizing surface modified fumed silica fillers. By appropriate choice of these surface groups and the polymeric media, the rheological behavior of these systems can be tailored independently of the electrochemical characteristics, a feat that has eluded researchers to date. These advanced electrolytes will be used as new generation materials for secondary lithium polymer batteries.
Characterize and Modify Microstructure in Water-Borne Inks
Maury Balik, Richard Spontak, and Saad A. Khan
Environmental Protection Agency
$245,000
October 1996 - October 1999
Polystyrene latexes with chemically or physically grafted polyethylene oxide chains are being synthesized for use as zero VOC water-borne inks and coatings. This multidisciplinary effort combines synthesis, materials characterization and an understanding of the colloidal interactions among the latex particles, that is needed to develop this into a viable technology.
On the Origins of Petroleum-Water Emulsions: The Role of Asphaltene, Resins, and Colloidal Aggregation
Peter Kilpatrick
Shell Oil Company
$372,000
July 1, 1997 - December 30, 1999
The central role of polar resins and asphaltenes in fossil fuels in stabilizing water-in-oil and oil-in-water emulsions has been elucidated with 19 different crudes. The asphaltenes aggregate through discotic -bond or electron-transfer interactions to form primary agglomerates which subsequently crosslink at the oil-water interface to stabilize these emulsions. Our laboratory has developed mechanistic understanding of this phenomenon and how it is related to and governed by asphaltene composition and chemistry, resin-to-asphaltene ratio, aromatic solvency, and aromatic hydrocarbon type.
Structural Analysis of Heavy Crudes: Role of Acid-Base Imbalance in Surface Activity and Emulsion Stabilization
Peter K. Kilpatrick
Exxon Production Research Company
$25,000
January 1, 1998 - December 31, 1999
Asphaltenes from differing crudes can have dramatically differing effects in their ability to stabilize water-in-oil emulsions. It is believed that the origin of these differences lies in the cohesive energy density of asphaltene-asphaltene interactions. Specifically, -bonding and H-bonding both contribute to asphaltene aggregation and the complementarity between acidic and basic sites is believed to be essential for film stability. In this study, the detailed chemistry and structure of asphaltene aggregates from four heavy crudes are studied.
Towards a Greening of the Petroleum Industry: Minimizing Emulsion and Foam Formation
Peter K. Kilpatrick and Richard J. Spontak
National Science Foundation
$200,001
July 1, 1998 - June 30, 2001
Asphaltenes play the central role in the stabilization of emulsions and foams, serious production and refining issues for the petroleum industry. The relationships among asphaltene chemistry; aggregation; film strength, rheology, and microstructure; and emulsion stability will be explored. Chemistry will be probed by a variety of spectroscopies and chromatographies, aggregation by small angle neutron scattering, film strength and rheology by microscopy and interfacial stress rheometry, and emulsion strength by critical voltage. This is the first molecular chemical study of asphaltene film-forming mechanisms.
Mechanisms of Foam Formation in Petroleum-Gas Mixtures
Peter K. Kilpatrick
Nalco-Exxon Energy Chemicals
$35,000
February 1, 1999 - December 31, 1999
One of the major challenges associated with deep-sea production of petroleum is the creation of large foam heads due to expansion and decompression of dissolved gases in the crude (methane, ethane, etc.). Due to the limited space offshore, foam must be rapidly broken. In this mechanistic study, we apply our knowledge of emulsion stabilization to study the basic causes of foam stability: asphaltenes, waxes, and asphaltene aggregation.
Engineered Alpha Helices for Pore Transport Regulation
Peter K. Kilpatrick and Jan Genzer
National Science Foundation
$100,001
March 1, 2000 - February 29, 2002
A dominant folding motif of many peptides is the a-helix. Using the Schiffer-Edmundson a-helical wheel representation, amino acids in specific sequences can be designed to yield a-helices which are amphiphilic and can organize into supramolecular aggregates capable of spanning biological and synthetic membranes and capable of mediating solute transport. We propose to explore their potential use as synthetic, tunable a-helix formers to be used as regulators of transport through synthetic and biological membranes.
Isolation and Characterization of Asphaltenes and Waxes from Organic Deposits: Relationship to Parent Crude Petroleum
Peter K. Kilpatrick
Shell Exploration and Production
$71,300
April 1, 2000 - December 31, 2000
Precipitation and deposition of organic solids from
crude oil during production, transportation, and production of
pe
troleum is a ubiquitous challenge in the industry. Little
is understood about the thermodynamic character and
chemical identity of the solids which precipitate and deposit.
Much of this is attributable to the complex character
chemically and physically of the asphaltenes and waxes in crude,
the likeliest candidates for precipitation and deposition.
The goal of the proposed project is to study, in a detailed
chemical and physical fashion, the asphaltene and wax
fractions of both (1) parent crude oils and (2) organic deposits
from these parent crude oils. Detailed analytical techniques
will be exploited for characterizing the chemistry of these
fractions.
The Role of Naphthenates and Crude Blends in Water-in-Crude Oil Emulsion Stabilization
Peter K. Kilpatrick
Industrial Consortium (Nalco-Exxon, ExxonMobil, Shell/Equilon, Texaco, Statoil, Norsk-Hydro, ABB)
$125,000
December 31, 1999 - December 31, 2000
Asphaltenes, resins, and the solvency of the crude are known to play significant roles in the stabilization of water-in-crude oil emulsions. What is considerably less well understood are the roles of naphthenic acids (or naphthenates) and of asphaltene incompatibility due to blending on emulsion stability. In this industrially sponsored consortium project, we are studying model and whole petroleum naphthenates and blends utilizing the methods of critical electric field, interface rheology, and the centrifugation technique.
Selected Energy Epitaxial Deposition (SEED) and Low-Energy Electron Microscopy (LEEM) of AlN, GaN and SiC Thin Films
Robert F. Davis and Henry H. Lamb
Office of Naval Research
$700,000
November 1, 1997 - October 31, 1999
Wide bandgap (WBG) semiconductors (e.g., SiC and III-V nitrides) have a variety of realized and potential commercial applications in optoelectronics and in high-power, high-frequency microelectronic devices. The quality of heteroepitaxial GaN thin films remains a significant hindrance to further commercial development. The objectives of this research are to improve heteroepitaxial growth of III-V nitrides and SiC by performing (a) epitaxial growth using supersonic molecular beams, (b) in-situ real-time characterization of growth processes using LEEM and other techniques, (c) Monte Carlo simulations of nucleation and growth processes.
SUCCEED Student Transitions Focus Team
David F. Ollis
National Science Foundation/Univ. Florida
$49,000/yr
September 1997 - August 1999
Chair eight campus teams to identify best practices and hold workshops on transitions "in" and "out" of university, including (i) summer bridge programs, (ii) women and minority peer mentoring, (iii) multidisciplinary capstone design, and (iv) practice experiences (co-op, international).
E123 Scale-up
David F. Ollis, Sarah Rajala
National Science Foundation/Univ. Florida
$20,000/yr (partial)
September 1997 - August 1999
Prepare a "take-apart" laboratory to handle much/all of entering first-year engineering class.
Photocatalytic Air Purification
David F. Ollis
National Science Foundation
$15,000 (3-year travel grant)
May 1998 - April 2000
Travel allowance for research collaboration with Dr. Pierre Pichat, Director, French lab studying photocatalysis.
Investigation of Pollution Prevention Alternative Technologies in the Garment and Textile Care Industries
Perry Grady, Gary Mock, Robert McCall, Michael Overcash
US Environmental Protection Agency
$450,000
May 1998 - April 2001
Concern over perchloroethylene has led to development and testing of alternative technologies for cleaning clothes labeled "dry clean only." The dry cleaning community has asked for help in the identification of potentially promising technologies and information on making decisions. This works to provide guidance for the evaluation of the cleaning systems, to identify a feasible technology, and to provide the required support to make it successful.
High-K Dielectrics by Remote PECVD
Gregory N. Parsons
SRC/SEMATECH Center for Front End Processing
$250,000
April 1, 1998 - March 31, 2001
High dielectric-constant (high-k) insulating layers are critical for advanced sub 100nm CMOS IC devices. In collaboration with researchers in Physics, Materials Science, and Electrical Engineering, our group is developing plasma deposition approaches for ultra-thin high-k metal oxide dielectric layers (including Al2O3 and Y2O3). Auger Electron Spectroscopy is used to characterize the thermodynamic and kinetic stability of these layers in contact with silicon, and materials are characterized using IV and CV analysis. The goal is to achieve < 1A/cm2 when the equivalent oxide thickness is less than 1 nm, and demonstrate good n- and p- channel transconductance in CMOS devices.
NSF CAREER Award: Plasma Chemical Vapor Deposition of Amorphous Silicon Thin Films Near Room Temperature Using Inert Ion Enhanced Processes
Gregory N. Parsons
National Science Foundation
$310,000
June 1996 - November 2000
Novel approaches for film synthesis have been
identified that result in dense, non-porous materials near room
temperature. Preliminary results indicate that an
ion-enhanced hydrogen desorption process in plasma activated
chemical
vapor deposition, which has previously not been
documented, may be critical for achieving high film density.
The objective of this study includes the desorption and
analysis of these plasma activated deposition processes. The
results will lead to new low temperature capabilities in silicon
thin film materials, and devices, and extend our
understanding of low temperature surface chemistry in plasma
activated materials synthesis and plasma/surface interactions.
Kinetics of Ultra-Thin Metal Oxide and Silicate Film Deposition on Silicon
Gregory N. Parsons
National Science Foundation
$240,000
July 2000 - June 2003
As electronic device processing moves towards the nanometer-scale, the ability to predict and control sub-nm composition and structure at material interfaces is becoming more critical. Continued scaling of transistors to sub-100 nm gate lengths will require new metal oxide gate insulators with higher dielectric constant to maintain large capacitances (i.e. equivalent to <1nm of SiO2) and minimize gate tunneling current. Through studies of Al2O3 deposition on Si, we find that the interface structure is determined by the kinetics of individual deposition reaction steps that favor consumption of the silicon substrate, even when the deposited bulk oxide is thermodyanamically stable on silicon. For this project, we will study kinetics of interface layer formation during deposition of metal oxides on silicon. This will include studies of surface treatment on substrate consumption and interface oxide formation, and electrical performance of silicon/metal oxide and silicate interfaces.
Plasma Sensing and Analysis
Gregory N. Parsons
National Science Foundation Engineering Research Center for Advanced Electronic Materials Processing
$60,000/year
August 1992 - September 30, 1999
This project is aimed at demonstrating mass spectroscopic techniques for real-time sensing of gas phase chemical species during plasma processing, and the description of physical and chemical processes occurring in thin film deposition. Our goal is to demonstrate a process sensing and simulation tool that is capable of detecting and characterizing process fluctuations and faults, as well as, supplying information from each run (i.e. film thickness) that could be carried forward in the process stream. Real time integrated sensing and modeling can minimize the impact of statistical process fluctuations to improve product yield and throughput.
Membrane-Based Biological Destruction of Toxic Organics
Steven W. Peretti
Strategic Environmental Research and Development Program (SERDP) /Arcadis, Geraghty, & Miller
$67,000
April 2, 2000 - October 1, 2000
Microporous coated and uncoated hollow fibers are used to support extraction of VOCs from a gas into a liquid and to support a biofilm capable of completely degrading the VOCs. Small pilot-scale units will be constructed and operated. This work will establish the potential for this technology to be applied in a full-scale demonstration at other USAF aircraft painting sites. Currently, we are evaluating the performance of the biomembrane reactor under multi-species, multi-substrate conditions.
Chemical Engineering
Promoted Zinc Chromite Catalysts for Higher Alcohol Synthesis in a Slurry Reactor
George W. Roberts
Department of Energy
$199,811
October 1, 1997 - September 30, 2000
Higher alcohols, specifically 2-methyl-1-alcohols, are being synthesized from hydrogen and carbon monoxide in a slurry reactor. A novel family of slurry liquids, consisting of fused-ring cyclic compounds, is being used which permits the reactor to be operated at temperatures of approximately 375°C. The research is based on zinc chromite catalysts promoted with potassium and cesium.
Direct Synthesis of Acetic Acid via Carboxylation of Methane
George W. Roberts
Environmental Protection Agency
$369,623
December 11, 1998 - December 10, 2001
The direct synthesis of acetic acid by the reaction of two greenhouse gases, carbon dioxide and methane, is being explored. Transition metal catalysts on basic supports are being evaluated for their ability to catalyze this reaction. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) is being used to study the ability of these catalysts to activate carbon dioxide and methane.
Polymerization of VF2 in Carbon Dioxide/Solvay
George W. Roberts
Solvay Corporation (through University of North Carolina at Chapel Hill)
$124,513
April 1, 1999 - September 30, 2000
The kinetics of vinylidene fluoride polymerization in supercritical carbon dioxide are being investigated using different free radical initiators. The properties of the polymer are being determined as a function of operating conditions. The decomposition kinetics of the initiators are also being studied in supercritical carbon dioxide.
Phase Equilibrium for Polymer/Monomer/Initiator/Carbon Dioxide Systems
George W. Roberts (Joseph M. DeSimone)
National Science Foundation Science and Technology Center for Environmentally Responsible Solvents and Processes
Approximately $105,000
November 1, 1999 - October 31, 2000
The partitioning of various solutes between a supercritical phase and a polymer phase are being studied over a range of conditions (temperature, pressure, solute concentration) that are representative of continuous polymerization reactors with supercritical carbon dioxide as the reaction medium. Fundamental studies of phase equilibrium for each component will be constructed.
Continuous Step-Growth Polymerization in Supercritical Carbon Dioxide
George W. Roberts (Joseph M. DeSimone and Ruben G. Carbonell)
National Science Foundation Science and Technology Center for Environmentally Responsible Solvents and Processes
Approximately $125,000/year
October 1997 - September 2000
The effect of supercritical carbon dioxide on the solid-state polymerization of poly(bisphenol A carbonate) is being studied. In the process, three key parameters that affect the behavior of this reaction will be measured: (1) the diffusion coefficient of phenol in polycarbonate, (2) the equilibrium constant of the reaction, and (3) the forward transesterification rate constant. These quantities will be determined as a function of both temperature and carbon dioxide pressure.
Morphological and Property Studies of Dibenzylidene Sorbitol Gels
Richard J. Spontak
Milliken Chemicals
$80,000
January 1998 - December 2000
Addition of sugar acetals such as dibenzylidene sorbitol (DBS) to low-molar-mass organic solvents or high-molar-mass polymers often results in the formation of a recognition-driven fibrillar network. These "tectonic" additives afford the possibility of physical gelation, thixotropy and viscosity control. We are currently examining the morphological and rheological characteristics of several model systems, as well as using molecular mechanics and dynamics simulations, to investigate the mechanism and kinetics of DBS-induced gelation and, ultimately, network dynamics and structural reorganization upon deformation.
Modification of Polymer Blend Miscibility through the Use of Supercritical Carbon Dioxide
Richard J. Spontak and Saad A. Khan
Kenan Center for the Utilization of Carbon Dioxide in Manufacturing
$90,000
January 1998 - December 2000
Supercritical carbon dioxide is currently used to alter the viscosity and thermal properties of a polymer melt by plasticizing the polymer and increasing its free volume. This project aims to exploit this neutral solvation effect by controllably altering the miscibility of polymer blends, which in turn could lead to processing windows of homogeneous systems previously unavailable. Thus far, we have demonstrated that supercritical carbon dioxide lowers the cloud point of an upper critical solution temperature (UCST) polymer blend at moderate pressures. This reduction is countered at high pressures due to the effect of hydrostatic pressure on compressible polymers.
NSF CAREER Award: Complex Fluids Dynamics
- A Research and Teaching Program
John H. van Zanten
National Science Foundation
$75,000/year
May 1, 1997 - April 30, 2001
The factors controlling Brownian motion in viscoelastic media and the potential of using particle motion as a probe of soft material dynamics are being investigated. A diffusing wave spectrometer is used to measure particle mean square displacements and the resultant data are analyzed with the methods of statistical physics. Of particular interest are wormlike micelle systems and the role osmotic compressibility plays in modulating Brownian motion in soft materials.
Microscopic Basis of Polymer-Supercritical Fluid Phase Behavior: Effects of Polymer-Solvent Interactions and Chain Stiffness
John H. van Zanten and M.A. McHugh (Virginia Commonwealth University)
National Science Foundation GOALI Program
$115,380/year
April 1, 1998 - March 31, 2001
Our goal is to develop is to develop an understanding of the microscopic basis of polymer-supercritical fluid phase behavior. As such we have focused on polyolefin-compressed alkane systems in which the energetics are well matched in order to isolate the effects of chain architecture on chain properties. Small angle neutron scattering and dynamic light scattering are utilized to probe these solutions in the semidilute and dilute regimes respectively. This work is being extended to investigating fluoropolymer analogs and their behavior in fluorocarbon solvents and compressed carbon dioxide.
Characterization of Polymer-Inorganic Interfaces: from Basic Polymer Physics to Industrial Relevant Applications
John H. van Zanten
NIST Polymers Division
$37,910/year
September 1, 1996 - August 31, 2000
Methods are being developed to probe the interfacial region in glass fiber-filled polymer composite materials. Fluorescence spectroscopy is being used in conjunction with a novel fluorophore-silance coupling agent chemical sensor to develop a robust process control sensor as well as a noninvasive technique for probing the relevant physics occuring in the polymer-inorganic glass interfacial region.
DNA-Cationic Liposome Complexes: Size, Composition, and Formation Kinetics
John H. van Zanten
Valentis, Inc
$25,000/year
July 1, 1999 - June 30, 2001
Nonviral gene delivery vectors are being explored as a viable alternative to viral-based gene delivery systems in gene therapy applications. Our goal is to develop a robust method for characterizing the size and composition polydispersity which is inherenet to these complex systems, detailed kinetic models capable of predicting final gene delivery properties and composition/structure/processing/transfection relations.