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A diethyl phosphonate containing oxazoline: Synthesis and characterization of monomer and homopolymer

Description: A diethyl phosphonate oxazoline monomer and its polymer have been synthesized. The monomer appears to polymerize via a ring-opening mechanism giving the expected polyethyleneimine backbone with pendant carbonyl groups. Two distinct molecular weights were produced during polymerization suggesting two mechanisms of chain growth. Studies are underway to elucidate the reasons for this. This polymer has potential as a metal-chelating agent.
Date: May 1, 1995
Creator: Hermes, R.E.; Thompson, R.D. & Valdez, L.S.
Partner: UNT Libraries Government Documents Department

Vacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters

Description: In this work we report on thevacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters. Clusters of methanol with water are generated via co-expansion of the gas phase constituents in a continuous supersonic jet expansion of methanol and water seeded in Ar. The resulting clusters are investigated by single photon ionization with tunable vacuumultraviolet synchrotron radiation and mass analyzed using reflectron mass spectrometry. Protonated methanol clusters of the form (CH3OH)nH + (n=1-12) dominate the mass spectrum below the ionization energy of the methanol monomer. With an increase in water concentration, small amounts of mixed clusters of the form (CH3OH)n(H2O)H + (n=2-11) are detected. The only unprotonated species observed in this work are the methanol monomer and dimer. Appearance energies are obtained from the photoionization efficiency (PIE) curves for CH3OH +, (CH 3OH)2 +, (CH3OH)nH + (n=1-9), and (CH 3OH)n(H2O)H + (n=2-9 ) as a function of photon energy. With an increase in the water content in the molecular beam, there is an enhancement of photoionization intensity for methanol dimer and protonated methanol monomer at threshold. These results are compared and contrasted to previous experimental observations.
Date: May 12, 2008
Creator: Ahmed, Musahid; Ahmed, Musahid; Wilson, Kevin R.; Belau, Leonid & Kostko, Oleg
Partner: UNT Libraries Government Documents Department

Structure and Evolution of Ordered Domains in Deeply Quenched Polyrthelene Melt

Description: Solidification of polymeric materials, a complex process in which the entangled polymer melt becomes a composite of amorphous and crystalline domains, strongly depends on how the melt is cooled below its crystallization temperature. If cooling is at moderate rates, the most common and well. understood mechanism is via nucleation and growth of spherulites, but special cases exist where crystallization is preceded by a pre pre-transition state induced by density fluctuations. Such multi-step crystallization scenarios are suggested by many experiments, and recent theoretical and simulation work. Via energetic and geometric analyses, we have examined the structure of mesomorphic domains and the dynamics of their formation and evolution, including atomic scale details of molecular addition to ordered domains, as well as particle dynamics in the system, including high mobility jumps in the ordered domains at wavelengths matching the monomer spacing.
Date: April 25, 2007
Creator: Lacevic, N; Fried, L & Gee, R
Partner: UNT Libraries Government Documents Department

Development of porous polymer monoliths for reverse-phase chromatography of proteins.

Description: The polymers developed in this project are intended for use as a stationary phase in reverse-phase chromatography of proteins, where the mobile phase is a solution of acetonitrile and a phosphate buffer, 6.6 pH. A full library of pore sizes have been developed ranging from 0.41{micro}m to 4.09 {micro}m; these pore sizes can be determined by the solvent ratio of tetrahydrofuran:methoxyethanol during polymerization. A column that can separate proteins in an isocratic mode would be a vast improvement from the common method of separating proteins through gradient chromatography using multiple solvents. In the stationary phase, the main monomers have hydrophobic tails, lauryl acrylate and steryl acrylate. Separations of small hydrophobic molecules and peptides (trial molecules) have efficiencies of 24,000-33,000 theoretical plates m{sup -1}. The combination of a highly non-polar stationary phase and a mobile phase where the polarity can be controlled provide for excellent separation.
Date: September 1, 2003
Creator: Shepodd, Timothy J. (Sandia National Laboratories, Albuquerque, NM) & Stephens, Christopher P. (Sandia National Laboratories, Albuquerque, NM)
Partner: UNT Libraries Government Documents Department

Intramolecular condensation reactions of {alpha}, {omega}- bis(triethoxy-silyl)alkanes. Formation of cyclic disilsesquioxanes

Description: Under acidic sol-gel polymerization conditions, 1,3-bis(triethoxysilyl)-propane (1) and 1,4-bis(triethoxysilyl)butane (2) were shown to preferentially form cyclic disilsesquioxanes 3 and 4 rather than the expected 1,3-propylene- and 1,4-butylene-bridged polysilsesquioxane gels. Formation of 3 and 4 is driven by a combination of an intramolecular cyclization to six and seven membered rings, and a pronounced reduction in reactivity under acidic conditions as a function of increasing degree of condensation. The ease with which these relatively unreactive cyclic monomers and dimers are formed (under acidic conditions) helps to explain the difficulties in forming gels from 1 and 2. The stability of cyclic disilsesquioxanes was confirmed withe the synthesis of 3 and 4 in gram quantities; the cyclic disilsesquioxanes react slowly to give tricyclic dimers containing a thermodynamically stable eight membered siloxane ring. Continued reactions were shown to perserve the cyclic structure, opening up the possibility of utilizing cyclic disilsesquioxanes as sol-gel monomers. Preliminary polymerization studies with these new, carbohydrate-like monomers revealed the formation of network poly(cyclic disilsesquioxanes) under acidic conditions and polymerization with ring-opening under basic conditions.
Date: August 1, 1996
Creator: Loy, D.A.; Carpenter, J.P.; Myers, S.A.; Assink, R.A.; Small, J.H.; Greaves, J. et al.
Partner: UNT Libraries Government Documents Department

Engineered monodisperse mesoporous materials

Description: Porous materials technology has developed products with a wide variety of pore sizes ranging from 1 angstrom to 100`s of microns and beyond. Beyond 15{angstrom} it becomes difficult to obtain well ordered, monodisperse pores. In this report the authors describe efforts in making novel porous material having monodisperse, controllable pore sizes spanning the mesoporous range (20--500 {angstrom}). They set forth to achieve this by using unique properties associated with block copolymers--two linear homopolymers attached at their ends. Block copolymers phase separate into monodisperse mesophases. They desired to selectively remove one of the phases and leave the other behind, giving the uniform monodisperse pores. To try to achieve this the authors used ring-opening metathesis polymerization to make the block copolymers. They synthesized a wide variety of monomers and surveyed their polymers by TGA, with the idea that one phase could be made thermally labile while the other phase would be thermally stable. In the precipitated and sol-gel processed materials, they determined by porosimetry measurements that micropores, mesopores, and macropores were created. In the film processed sample there was not much porosity present. They moved to a new system that required much lower thermal treatments to thermally remove over 90% of the labile phase. Film casting followed by thermal treatment and solvent extraction produced the desired monodisperse materials (based solely on SEM results). Modeling using Density Functional Theory was also incorporated into this project. The modeling was able to predict accurately the domain size and spacing vs. molecular weight for a model system, as well as accurate interfacial thicknesses.
Date: August 1, 1997
Creator: Saunders, R.S.; Small, J.H.; Lagasse, R.R.; Schroeder, J.L. & Jamison, G.M.
Partner: UNT Libraries Government Documents Department

Sol-gel chemistry by ring-opening polymerization

Description: Sol-gel processing of materials is plagued by shrinkage during polymerization of the alkoxide monomers and processing (aging and drying) of the resulting gels. The authors have developed a new class of hybrid organic-inorganic materials based on the solventless ring-opening polymerization (ROP) of monomers bearing the 2,2,5,5-tetramethyl-2,5-disilaoxacyclopentyl group, which permits them to drastically reduce shrinkage in sol-gel processed materials. Because the monomers are polymerized through a chain growth mechanism catalyzed by base rather than the step growth mechanism normally used in sol-gel systems, hydrolysis and condensation products are entirely eliminated. Furthermore, since water is not required for hydrolysis, an alcohol solvent is not necessary. Monomers with two disilaoxacyclopentyl groups, separated by a rigid phenylene group or a more flexible alkylene group, were prepared through disilylation of the corresponding diacetylenes, followed by ring closure and hydrogenation. Anionic polymerization of these materials, either neat or with 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane as a copolymer, affords thermally stable transparent gels with no visible shrinkage. These materials provide an easy route to the introduction of sol-gel type materials in encapsulation of microelectronics, which they have successfully demonstrated.
Date: February 7, 2000
Creator: Rahimian, Kamyar & Loy, Douglas A.
Partner: UNT Libraries Government Documents Department

LDRD final report on nano-scale engineering of smart membranes

Description: A new approach to the fabrication of porous, amorphous inorganic membranes using organic pore templates was investigated. The pore templates were a new family of hybrid organic-inorganic monomers. As background for membrane work, the monomers were polymerized by sol-gel techniques to make crosslinked polymers. Molecular modeling was used to create computer simulations of the materials and provide insight into their composites, were then converted into porous silicas using low temperature oxygen plasma techniques. A select few of the monomers were copolymerized with silica monomers to form non-porous thin films on mesoporous substrates. The films were converted into porous silica thin films with thermal oxidations and the resulting membranes were tested for gas selectivities and flux.
Date: September 1, 1997
Creator: Loy, D.A.; Jamison, G.M. & Assink, R.A.
Partner: UNT Libraries Government Documents Department

Non-Shrinking Sol-Gel Type Polymers by Ring Opening Polymerizations

Description: We have designed a new class of cyclic siloxane compounds that behave as sol-gel systems when ring open polymerized using a hydroxide base. These monomers polymerize through chain growth polymerization. unlike conventional alkoxysilane sol-gel precursors, to form sol-gel polymers. They do not require solvent or water for polymerization, show no visible shrinkage or cracking during polymerization and are thermally stable. We have successfully utilized these materials in encapsulation of microelectronics. Current efforts are focused toward expanding this family of ROP monomers and optimization of their mechanical properties.
Date: April 5, 1999
Creator: Loy, D.A. & Rahimian, K.
Partner: UNT Libraries Government Documents Department

Ethylene oxidation in a well-stirred reactor

Description: The detailed ethylene oxidation data set of Thornton, obtained for a well-stirred reactor operated fuel-lean at atmospheric pressure and for temperatures of 1003K to 1253K, is used as a basis for the comparison of chemical kinetic mechanisms reported in the literature and for the development of a new ethylene oxidation mechanism. The mechanisms examined are those of Westbrook and Pitz and Dagaut et al. These mechanisms indicated that unusually large rates for the vinyl decomposition reaction are required to obtain agreement with the Thornton data set. A new ethylene oxidation mechanism is developed in order to overcome some of the drawbacks of the previous mechanisms. The new mechanism closely simulates the overall rate of loss of ethylene, and the concentation of CO, CO{sub 2}, H{sub 2}, CH{sub 2}O, C{sub 2}H{sub 2}, CH{sub 3}OH, CH{sub 4}, and C{sub 2}H{sub 6} measured for the stirred reactor. Predictions by this mechanism are dependent on a new high temperature vinyl oxidation route, C{sub 2}H{sub 3} + O{sub 2} = CH{sub 2}CHO + O with a k{sub C2H3+O2=CH2CHO+O}/k{sub C2H3+O2=CH2O+HCO} branching ratio of 1.20 at 1053K to 2.05 at 1253K. The branching ratio values were dependent upon the extent of fall-off for the C{sub 2}H{sub 3} + O{sub 2} = CH{sub 2}O + HCO reaction.
Date: October 1, 1994
Creator: Marinov, N.M. & Malte, P.C.
Partner: UNT Libraries Government Documents Department


Description: The authors have mapped the physics of a system of random copolymers onto a time-dependent density functional-type field theory using techniques of functional integration. Time in the theory is merely a label for the location of a given monomer along the extent of a flexible chain. We derive heuristically within this approach a non-local constraint which prevents segments on chains in the system from straying too far from each other, and leads to self-assembly. The structure factor is then computed in a straightforward fashion. The long wave-length limit of the structure factor is used to obtain the elastic modulus of the network. It is shown that there is a surprising competition between the degree of micro-phase separation and the elastic moduli of the system.
Date: October 1, 2000
Creator: CHITANVIS, S. M.
Partner: UNT Libraries Government Documents Department


Description: The objective of this research was the design, synthesis and evaluation of inexpensive, nonfluorous carbon dioxide thickening agents. We followed the same strategy employed in the design of fluorinated CO{sub 2} polymeric thickeners. First, a highly CO{sub 2}-philic, hydrocarbon-based monomer was to be identified. Polymers or oligomers of this monomer were then synthesized. The second step was to be completed only when a CO{sub 2}-soluble polymer that was soluble in CO{sub 2} at pressures comparable to the MMP was identified. In the second step, viscosity-enhancing associating groups were to be incorporated into the polymer to make it a viable thickener that exhibited high CO{sub 2} solubility at EOR MMP conditions. This final report documents the CO{sub 2} solubility of a series of commercial and novel polymers composed of carbon, hydrogen, oxygen and, in some cases, nitrogen.
Date: October 1, 2004
Creator: Enick, Robert M.; Beckman, Eric J. & Hamilton, Andrew
Partner: UNT Libraries Government Documents Department

Plasma energy recycle and conversion of polymeric (MSW) waste. Final report

Description: Final report summarizing research project results of studies of the thermal plasma recycling of polymers, including polyethylene and polypropylene. High levels of recovery of monomers were obtained from the process developed under this study.
Date: December 5, 2000
Creator: Knight, Richard & Grossman, Elihu D.
Partner: UNT Libraries Government Documents Department

Production of high-energy chemicals using solar energy heat. Project 8999, final report for the period September 1, 1977--May 31, 1978

Description: The first phase of a study to identify candidate processes and products suitable for future exploitation using high-temperature solar energy is presented. This phase has been principally analytical, consisting of techno-economic studies, thermodynamic assessments of chemical reactions and processes, and the determination of market potentials for major chemical commodities that use significant amounts of fossil resources today. The objective was to identify energy-intensive processes that would be suitable for the production of chemicals and fuels using solar energy process heat. Of particular importance was the comparison of relative costs and energy requirements for the selected solar product versus costs for the product derived from conventional processing. The assessment methodology used a systems analytical approach to identify processes and products having the greatest potential for solar energy-thermal processing. This approach was used to establish the basis for work to be carried out in subsequent phases of development. It has been the intent of the program to divide the analysis and process identification into the following three distinct areas: (1) process selection, (2) process evaluation, and (3) ranking of processes. Four conventional processes were selected for assessment namely, methanol synthesis, styrene monomer production, vinyl chloride monomer production, and terephthalic acid production.
Date: December 1, 1978
Creator: Dafler, J.R.; Sinnott, J.; Novil, M.; Yudow, B.D. & Rackoff, M.G.
Partner: UNT Libraries Government Documents Department


Description: Photochemical conversion of CO{sub 2} to fuels or useful chemicals using renewable solar energy is an attractive solution to both the world's need for fuels and the reduction of greenhouse gases. Rhenium(I) and ruthenium(II) diimine complexes have been shown to act as photocatalysts and/or electrocatalysts for CO{sub 2} reduction to CO. We have studied these photochemical systems focusing on the identification of intermediates and the bond formation/cleavage reactions between the metal center and CO{sub 2}. For example, we have produced the one-electron-reduced monomer (i.e. Re(dmb)(CO){sub 3}S where dmb = 4,4'-dimethy-2,2'-bipyridine and S = solvent) either by reductive quenching of the excited states of fac-[Re(dmb)(CO){sub 3}(CH{sub 3}CN)]PF{sub 6} or by photo-induced homolysis of [Re(dmb)(CO){sub 3}]{sub 2}. We previously found that: (1) the remarkably slow dimerization of Re(dmb)(CO){sub 3}S is due to the absence of a vacant coordination site for Re-Re bond formation, and the extra electron is located on the dmb ligand; (2) the reaction of Re(dmb)(CO){sub 3}S with CO{sub 2} forms a CO{sub 2}-bridged binuclear species (CO){sub 3}(dmb)Re-CO(O)-Re(dmb)(CO){sub 3} as an intermediate in CO formation; and (3) the kinetics and mechanism of reactions are consistent with the interaction of the CO{sub 2}-bridged binuclear species with CO{sub 2} to form CO and CO{sub 3}{sup 2-}.
Date: November 30, 2007
Partner: UNT Libraries Government Documents Department

Characterization of nanoparticle formation and aggregation on mineral surfaces

Description: The research effort in the Waychunas group is focused on the characterization and measurement of processes at the mineral-water interfaces specifically related to the onset of precipitation. This effort maps into one of the main project groups with the Penn State University EMSI (CEKA) known as PIG (Precipitation Interest Group), and involves collaborations with several members of that group. Both synchrotron experimentation and technique development are objectives, with the goals of allowing precipitation from single molecule attachment to sub-monolayer coverage to be detected and analyzed. The problem being addressed is the change in reactivity of mineral interfaces due to passivation or activation by precipitates or sorbates. In the case of passivation, fewer active sites may be involved in reactions with environmental fluids, while in the activated case the precipitate may be much more reactive than the substrate, or result in the creation of a higher density of active sites. We approach this problem by making direct measurements of several types of precipitation reactions: iron-aluminum oxide formation on quartz and other substrates from both homogeneous (in solution) nucleation, and heterogeneous (on the surface) nucleation; precipitation and sorption of silicate monomers and polymers on Fe oxide surfaces; and development of grazing-incidence small angle x-ray scattering (GISAXS) as a tool for in-situ measurement of precipitate growth, morphology and aggregation. We expect that these projects will produce new fundamental information on reactive interface growth, passivation and activation, and be applicable to a wide range of environmental interfaces.
Date: April 19, 2007
Creator: Waychunas, Glenn & Jun, Young-Shin
Partner: UNT Libraries Government Documents Department

Kinetics of helium bubble formation in nuclear materials

Description: The formation and growth of helium bubbles due to self-irradiation in plutonium has been modeled by a discrete kinetic equations for the number densities of bubbles having k atoms. Analysis of these equations shows that the bubble size distribution function can be approximated by a composite of: (1) the solution of partial differential equations describing the continuum limit of the theory but corrected to take into account the effects of discreteness, and (2) a local expansion about the advancing leading edge of the distribution function in size space. Both approximations contribute to the memory term in a close integrodifferential equation for the monomer concentration of single helium atoms. The present theory is compared to the numerical solution of the full kinetic model and to previous approximation of Schaldach and Wolfer involving a truncated system of moment equations.
Date: October 13, 2005
Creator: Bonilla, L L; Carpio, A; Neu, J C & Wolfer, W G
Partner: UNT Libraries Government Documents Department

Top Value-Added Chemicals from Biomass - Volume II—Results of Screening for Potential Candidates from Biorefinery Lignin

Description: This report evaluates lignin’s role as a renewable raw material resource. Opportunities that arise from utilizing lignin fit into one of three categories: 1)power, fuel and syngas (generally near-term opportunities) 2) macromolecules (generally medium-term opportunities) 3) aromatics and miscellaneous monomers (long-term opportunities). Biorefineries will receive and process massive amounts of lignin. For this reason, how lignin can be best used to support the economic health of the biorefinery must be defined. An approach that only considers process heat would be shortsighted. Higher value products present economic opportunities and the potential to significantly increase the amount of liquid transportation fuel available from biomass. In this analysis a list of potential uses of lignin was compiled and sorted into “product types” which are broad classifications (listed above as power—fuel—syngas; macromolecules; and aromatics). In the first “product type” (power—fuel—gasification) lignin is used purely as a carbon source and aggressive means are employed to break down its polymeric structure. In the second “product type” (macromolecules) the opposite extreme is considered and advantage of the macromolecular structure imparted by nature is retained in high-molecular weight applications. The third “product type” (aromatics) lies somewhere between the two extremes and employs technologies that would break up lignin’s macromolecular structure but maintain the aromatic nature of the building block molecules. The individual opportunities were evaluated based on their technical difficulty, market, market risk, building block utility, and whether a pure material or a mixture would be produced. Unlike the “Sugars Top 10” report it was difficult to identify the ten best opportunities, however, the potential opportunities fell nicely into near-, medium- and long-term opportunities. Furthermore, the near-, medium- and long-term opportunities roughly align with the three “product types.” From this analysis a list of technical barriers was developed which can be used to identify research needs. Lignin presents ...
Date: October 1, 2007
Creator: Holladay, John E.; White, James F.; Bozell, Joseph J. & Johnson, David
Partner: UNT Libraries Government Documents Department


Description: Dynamic mechanical analysis has been used to characterize the effects of tritium gas (initially 1 atm. pressure, ambient temperature) exposure over times up to 2.3 years on several thermoplastics-ultrahigh molecular weight polyethylene (UHMW-PE), polytetrafluoroethylene (PTFE), and Vespel{reg_sign} polyimide, and on several formulations of elastomers based on ethylene propylene diene monomer (EPDM). Tritium exposure stiffened the elastic modulus of UHMW-PE up to about 1 year and then softened it, and reduced the viscous response monotonically with time. PTFE initially stiffened, however the samples became too weak to handle after nine months exposure. The dynamic properties of Vespel{reg_sign} were not affected. The glass transition temperature of the EPDM formulations increased approximately 4 C. following three months tritium exposure.
Date: November 12, 2008
Creator: Clark, E
Partner: UNT Libraries Government Documents Department