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Characterization of polyxylylenes with solid state {sup 13}C nuclear magnetic resonance spectroscopy

Description: Polyxylylenes are thermoplastics used as encapsulants for electronic devices. Five polyxylylenes were prepared by pyrolysis of [2.2]paracyclophanes and characterized by solid state {sup 13}C NMR spectroscopy. The chemical shift data, in combination with interrupted decoupling experiments, allowed assignment of resonances to their carbon sources in the polymers. This confirmed the integrity of the xylylene building block in the polymers and is consistent with linear polymers. No crosslinking could be detected within the NMR sensitivity limits. Residual paracyclophane was detected by {sup 13}C CP MAS NMR spectroscopy in the polyxylylene samples prepared at room temperature; however discrete {sup 13}C resonances due to amorphous and crystalline phases in the polymers were not resolved.
Date: February 1, 1996
Creator: Loy, D.A.; Assink, R.A.; Jamison, G.M.; McNamara, W.F.; Schneider, D.A. & Prabakar, S.
Partner: UNT Libraries Government Documents Department

Densities of Sodium Tetrafluoroborate Aqueous Solutions at 20 Degrees C

Description: Analytical data and plant solution compositions are often reported in molarity units. Densities of salt solutions are needed to convert the concentrations to molal basis in order to utilize physical property data that have been established on a molal basis, for example, solution reaction equilibrium constants or activity coefficients. We report here the densities at 20.0 Degrees C of sodium tetrafluoroborate (NaBF4) solutions from 0.05 molal to 9.0 molal, near saturation of 9.2 molal.
Date: July 9, 2002
Creator: Crooks, W.J. III
Partner: UNT Libraries Government Documents Department

Trifluoromethylmetallate anions as components of molecular charge transfer salts and superconductors.

Description: Whereas polymeric and common inorganic anions frequently deprive the synthetic chemist of a chance to modify a charge transfer salt's structure through anion alterations, discrete organometallic anions provide a vast opportunity to probe the structure/property correlations of a material through rational synthetic methods. We have recently undertaken a research effort aimed at the crystallization of conducting charge transfer salts which possess modifiable, organometallic anions as the charge compensating entities. This research has been richly rewarded with the discovery of a new family of bis(ethylenedithio) tetrathiafulvalene (BEDT-TTF or ET) based molecular superconductors. Herein is presented a summary of over twenty {kappa}(ET){sub 2}M(CF{sub 3}){sub 4}(1,1,2-trihaloethane) (M = Cu, Ag, Au) superconducting salts. Three new related salts are also reported: (ET){sub 2} [trans-Ag(CF{sub 3}),(CN){sub 2}], {kappa}{sub L}(BEDT-TSF){sub 2}Ag(CF{sub 3}){sub 4}(TCE), and {kappa}{sub L}(ET){sub 2}Ag(CF{sub 3}){sub 3}Cl(TCE).
Date: October 14, 1998
Creator: Schlueter, J. A.
Partner: UNT Libraries Government Documents Department


Description: The annular slug flow regime has been investigated in vertical upflow without heating through the use of an electrical conductivity probe. The Teflon cladding and seals of the probe were found to work to at least 488 deg F. When the inlet velocity was sufficientiy high, the quality at transition was found to be a constant for each pressure going from 8.6% at215 psia to 17.6% at 615 psia. No fully developed bubbly flow was observed. (auth)
Date: November 1, 1963
Creator: Griffith, P.
Partner: UNT Libraries Government Documents Department

Thermophysical properties of HFC-143a and HFC-152a. Final report, April 1, 1993--June 30, 1994

Description: Numerous fluids have been identified as promising alternative refrigerants, but much of the information needed to predict their behavior as pure fluids and as components in mixtures does not exist. In particular, reliable thermophysical properties data and models are needed to predict the performance of the new refrigerants in heating and cooling equipment and to design and optimize equipment to be reliable and energy efficient. The objective of this fifteen-month project has been to provide highly accurate, selected thermophysical properties data for refrigerants HFC-143a (CH{sub 3}CF{sub 3}) and HFC-152a (CH{sub 3}CHF{sub 2}) and to use these data to fit complex equations of state and detailed transport property models. The new data have filled gaps in the existing data sets and resolved problems and uncertainties that existed in and between the data sets.
Date: July 1, 1994
Creator: Haynes, W. M.
Partner: UNT Libraries Government Documents Department

Synthesis and self-assembly of fluorocarbon- and hydrocarbon-modified hydrophilic polymers. Final report

Description: Over the past 3 years, work was done in several areas: effect of spacer lengths on degree of association of hydrophobically modified polyacrylamides; fluorocarbon mediated association of R{sub F}- substituted polyacrylamide-2-(acrylamido)-2-methyl-propane sodium sulfonate copolymers; hydrophobic association in R{sub F}(R{sub H})-modified poly(N,N-dimethylacrylamide)(PDMA) and polyvinylpyrrolidone; synthesis of R{sub F}-containing poly(N- isopropyl acrylamide)`s; synthesis of HM narrow MWD telechelics PDMA and PDMA block copolymers; and studies of telechelic R{sub F}(R{sub H}) derivatives of polyethyleneglycols. 15 refs, 7 figs, 2 tabs.
Date: November 1, 1996
Creator: Hogen-Esch, T.E.
Partner: UNT Libraries Government Documents Department

Perfluoro(Methylcyclohexane) Tracer Tagging Test and Demonstration

Description: On February 14 and 15, 2000, a demonstration of current perfluorocarbon tagging technology and the future potential of these methods was held at Oak Ridge National Laboratory (ORNL). The demonstration consisted of a brief technical discussion followed by a laboratory demonstration. The laboratory demonstrations included the detection of letters, parcels, briefcases and lockers containing perfluorocarbon-tagged papers. Discrimination between tagged and non-tagged items and between three perfluorocarbon tags was demonstrated along with the detection of perfluorocarbon in a background of non-fluorinated volatile organic solvent. All demonstrations involved real-time detection using a direct sampling ion trap mass spectrometer. The technical results obtained at ORNL during and in preparation for the demonstration are presented in Appendix 1 to assist Tracer Detection Technology Corp. in further evaluating their position on development and marketing of perfluorocarbon tracer technology.
Date: September 26, 2000
Creator: Sigman, M.E.
Partner: UNT Libraries Government Documents Department

Subsurface barrier integrity verification using perfluorocarbon tracers

Description: Subsurface barriers are an extremely promising remediation option to many waste management problems. Gas phase tracers include perfluorocarbon tracers (PFT`s) and chlorofluorocarbon tracers (CFC`s). Both have been applied for leak detection in subsurface systems. The focus of this report is to describe the barrier verification tests conducted using PFT`s and analysis of the data from the tests. PFT verification tests have been performed on a simulated waste pit at the Hanford Geotechnical facility and on an actual waste pit at Brookhaven National Laboratory (BNL). The objective of these tests were to demonstrate the proof-of-concept that PFT technology can be used to determine if small breaches form in the barrier and for estimating the effectiveness of the barrier in preventing migration of the gas tracer to the monitoring wells. The subsurface barrier systems created at Hanford and BNL are described. The experimental results and the analysis of the data follow. Based on the findings of this study, conclusions are offered and suggestions for future work are presented.
Date: December 1, 1996
Creator: Sullivan, T.M.; Heiser, J.; Milian, L. & Senum, G.
Partner: UNT Libraries Government Documents Department

Effect of a fluorinated nickel surface on the decomposition of perfluorodiethoxymethane

Description: Perfluoropolyethers (PFPEs) are a commercial class of lubricants widely used in computer and aerospace industries. This is a study of the degradation of a perfluorinated ether in the presence of a metal fluoride. Perfluorodiethoxymethane (PFDEM) is a PFPE analog. Temperature programmed desorption shows no contribution of PFDEM toward nickel fluoride on an NiF{sub 2} surface obtained by CF{sub 3}I adsorption. Higher coverages of nickel fluoride do not show any evidence of NiF{sub 2} contribution from PFDEM. The results do not agree with the idea that a fluorinated surface might induce decomposition of PFPEs, leading to addition fluoride formation on the surface. The metal fluoride bond strength is not a legitimate concern for decomposition of PFE lubricants. Impurity in PFPEs might be the cause of initial surface fluoridation leading to breakdown of PFPEs which could cause additional metal fluoride formation. It is clear that the reaction of PFPEs with metals does not involve a direct formation of a simple M-F bond; results do not show any C-F bond cleavage of the fluorinated ether and do not support a proposed autocatalytic mechanism.
Date: November 9, 1995
Creator: Sreevidya, S.
Partner: UNT Libraries Government Documents Department

Novel Sorption/Desorption Process for Carbon Dioxide Capture (Feasibility Study)

Description: Western Research Institute and the University of Wyoming Enhanced Oil Recovery Institute have tested a novel approach to carbon dioxide capture in power plants and industrial operations. This approach is expected to provide considerable cost savings, in terms of regeneration of the sorbent. It is proposed that low molecular weight, low volatility liquid fluorocarbons be utilized to absorb CO{sub 2} due to their unusual affinity for the gas. The energy savings would be realized by cooling the fluorocarbon liquids below their melting point where the CO{sub 2} would be released even at elevated pressure. Thus, the expense of heating currently used sorbents, saturated with CO{sub 2}, under low pressure conditions and then having to compress the released gas would not be realized. However, these fluorinated materials have been shown to be poor carbon dioxide absorbers under conditions currently required for carbon capture. The project was terminated.
Date: November 1, 2008
Creator: Tuminello, William; Radosz, Maciej & Shen, Youqing
Partner: UNT Libraries Government Documents Department


Description: Charge transfer associations are a well-established phenomena and a rather extensively investigated one also. Since the acceptor component of such complexes normally does not exist as a liquid under standard conditions, they wish to report on two organic liquids which function as acceptor components with suitable complimentary molecules. As indicated in Figure 1 (the presence of an extended shoulder in the spectra of the mixture), pentafluorobenzonitrile (PFBN) complexes with N,N,N{prime},N{prime}-tetramethyl-p-phenylenediamine (TMPD), with N,N-dimethylaniline (DMA), and with phenothiazine in cyclohexane. In addition, crystalline complexes of TMPN-PFBN and DMA-PFBN are obtained when the pure materials are mixed. These two organic bases also form solid complexes with hexafluorobenzene (HFB) when the materials are mixed in the pure state in a ratio of 1:1. However, new absorption bands are not detected in the spectra (in cyclohexane solutions) of mixtures of TMPD or DMA with HFB. When HFB is used as a solvent for TMPD or DMA, the solutions are visibly yellow. However, with time a reaction occurs as evident by the formation of a black precipitate. The solid complex formed between TMPD-PFBN, which is orange, was analyzed by a combination extraction and spectroscopic method and by vapor phase chromatography and found to contain a ratio of the two components of 1:1 which agrees with an elemental analysis of this complex. Analysis of DMA-PFBN or DMA-HFB complexes were complicated by the presence of excesses of the liquid components on the crystalline complexes. When attempts are made to dry the crystals, the crystals dissociate as the excesses evaporate until the crystals and the two components totally disappear. The TMPD-HFB complex was not analyzed. The complex between phenothiazine and PFBN as not isolated as a crystalline material. The association constants for the TMPD-PFBN and MDA-PFBN complexes were determined according to the method of Hildebrand and Benesi. The ...
Date: October 31, 1967
Creator: Corker, Gerald A. & Calvin, Melvin
Partner: UNT Libraries Government Documents Department


Description: A nozzle plate cartridge for the extraction section and a mixed plate cartridge containing both stainless steel and fluorothene sieve plates for the scrub section were developed. In 3- and 4-in.-diameter glass columns, these cartridges have a urnnium-extraction efficiency as good as, or better than, the present cartridge; they have a scrubbing efficiency, based on the transfer of chloride ion, which is about the same as the present cartridge. (auth)
Date: August 16, 1956
Creator: Hesson, G.M.
Partner: UNT Libraries Government Documents Department

Perfluorodiethoxymethane on nickel and nickel oxide surfaces

Description: The interaction of perfluorodiethoxymethane with a nickel single crystal, Ni(100); a nickel crystal with chemisorbed oxygen, Ni(100)-c(2x2)O; and a nickel crystal with nickel oxide crystallites, NiO(100) is investigated in an ultra high vacuum environment using thermal desorption spectroscopy and high resolution electron energy loss spectroscopy. Nickel, a component of hard disk drives and stainless steel, is used to represent metal surfaces in these {open_quotes}real{close_quotes} systems. Perfluorodiethoxymethane is used in this study as a model compound of industrial perfluoropolyether lubricants. These lubricants are known for their exceptional stability, except in the presence of metals. Perfluorodiethoxymethane contains the acetal group (-OCF{sub 2}O-), believed to be particularly vulnerable to attack in the presence of Lewis acids. Since the surfaces studied show increasing Lewis acidity at the nickel atom sites, one might expect to see increasing decomposition of perfluorodiethoxymethane due to acidic attack of the acetal group. No decomposition of perfluorodiethoxymethane is observed on the clean Ni(100) surface, while more research is needed to determine whether a small decomposition pathway is observed on the oxygenated surfaces, or whether sample impurities are interfering with results. The strength of the bonding of perfluorodiethoxymethane to the surface is found to increase as the nickel atoms sites become more acidic in moving from Ni(100) to Ni (100)-c(2x2)O to NiO (100).
Date: March 3, 1994
Creator: Jacobson, J.
Partner: UNT Libraries Government Documents Department

Mild acidic pretreatment to enhance low severity coal liquefaction promoted by cyclic olefins. Quarterly report, July 1995--September 1995

Description: Research continued on low severity coal liquefaction. Research using high temperature infrared of cyclic olefins progressed well during this quarter. Several fluorinated solvents were found that provide a high temperature medium for isotetralin and its aromatic and aliphatic analogues.
Date: March 1, 1996
Creator: Curtis, C.W.
Partner: UNT Libraries Government Documents Department

Electrophoretic NMR measurements of lithium transference numbers in polymer gel electrolytes

Description: Polymer gel electrolytes are of increasing interest for plastic lithium batteries largely because of their high room temperature conductivity. Several studies have probed their conductivity and electrochemical stability but very little work has been done related to lithium transference numbers. Lithium ion transference numbers, the net number of Faradays carried by lithium upon the passage of 1 Faraday of charge across a cell, are key figures of merit for any potential lithium battery electrolytes. The authors describe here their application of electrophoretic NMR (ENMR) to the determination of transference numbers of lithium ions in polymer gel electrolytes. Two types of polymer gel electrolytes were selected for this study: PAN/PC/EC/LiX and Kynar/PC/LiX. Results obtained for the two types of gels are compared and the effects of anion, polymer-ion interactions and ion-ion interactions on lithium transference numbers are discussed. Significant differences in the behavior of transference numbers with salt concentration are observed for the two types of gels. This may be due to the extent of interaction between the polymer and the ions. Implications for solid polymer electrolytes are discussed.
Date: May 1997
Creator: Dai, H.; Sanderson, S.; Davey, J.; Uribe, F. & Zawodzinski, T. A., Jr.
Partner: UNT Libraries Government Documents Department

Energy and global warming impacts of HFC refrigerants and emerging technologies: TEWI-III

Description: The use of hydrofluorocarbons (BFCs) which were developed as alternative refrigerants and insulating foam blowing agents to replace chlorofluorocarbons (CFCs) is now being affected by scientific investigations of greenhouse warming and questions about the effects of refrigerants and blowing agents on global warming. A Total Equivalent Warming Impact (TEWI) assessment analyzes the environmental affects of these halogenated working fluids in energy consuming applications by combining a direct effect resulting from the inadvertent release of HFCs to the atmosphere with an indirect effect resulting from the combustion of fossil fuels needed to provide the energy to operate equipment using these compounds as working fluids. TEWI is a more balanced measure of environmental impact because it is not based solely on the global warming potential (GWP) of the working fluid. It also shows the environmental benefit of efficient technologies that result in less CO{sub 2} generation and eventual emission to the earth`s atmosphere. The goal of TEWI is to assess total global warming impact of all the gases released to the atmosphere, including CO{sub 2} emissions from energy conversion. Alternative chemicals and technologies have been proposed as substitutes for HFCs in the vapor-compression cycle for refrigeration and air conditioning and for polymer foams in appliance and building insulations which claim substantial environmental benefits. Among these alternatives are: (1) Hydrocarbon (HC) refrigerants and blowing agents which have zero ozone depleting potential and a negligible global warming potential, (2) CO{sub 2} as a refrigerant and blowing agent, (3) Ammonia (NH{sub 3}) vapor compression systems, (4) Absorption chiller and heat pumping cycles using ammonia/water or lithium bromide/water, and (5) Evacuated panel insulations. This paper summarizes major results and conclusions of the detailed final report on the TEWI-111 study.
Date: June 1, 1997
Creator: Sand, J.R.; Fischer, S.K. & Baxter, V.D.
Partner: UNT Libraries Government Documents Department

Molecular modeling of the pendant chain in Nafion{reg_sign}

Description: Ion transport through perfluorosulfonic acid ionomers such as Nafion{reg_sign} is controlled by both the microstructure of the polymer and the charge and water distribution in the hydrated polymer. The authors present here the results of theoretical calculations on the side chain of Nafion{reg_sign}, establishing microscopic information for the modeling of water modeling of water modeling of water and proton transport in the membrane. Optimized geometries for the trifluoromethane sulfonic acid fragment (CF{sub 3}SO{sub 3}H), the di-trifluoromethane ether fragment (CF{sub 3}OCF{sub 3}), and the side chain (CF{sub 3}{single_bond}OCF{sub 2}CF(CF{sub 3})OCF{sub 2}CF{sub 2}SO{sub 3}H) were determined by means of both ab initio Hartree Fock theory with second order Moeller-Plesset electron correlation corrections, and density functional theory with Becke`s three parameter hybrid method. Several rotational potential energy surfaces were calculated to assess chain flexibility and proton accessibility. A probe water molecule was added to each of the fragments to characterize hydrophilic sites. These calculations confirmed that the sulfonic acid group is hydrophilic and the ethers are hydrophobic. Molecular dynamics simulations were then performed on the side chain to check the conditions required to stretch the pendant chain. Thermal averages of several structural parameters assessing the flexibility and stretch of the chain were computed from selected conformations produced in the simulation and these results indicate that although the sulfonate group is free to rotate, the chain stretches little. The construction of a potential energy surface for rotation about the second ether group suggests that the side chain exists in a folded or curled up conformation. A physical continuum dielectric solvent model was used to obtain free energies of electrostatic interaction of the fragments and the full chain with the solvent.
Date: March 1, 1998
Creator: Paddison, S.J. & Zawodzinski, T.A.
Partner: UNT Libraries Government Documents Department