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116 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Preparation of Proton Exchange Membranes and Lithium Batteries from Melamine-containing Ormosils

Our laboratory has recently reported a series of rodcoil polymers for lithium batteries that display dimensionally stable films with good ionic conductivity. The rod segments consist of rigid linear and branched polyimides and the coil segments are polyethylene oxides (PEO). It has been proposed that good mechanical and transport properties are due to phase separation between the rod and coil segments. It was also observed that increased branching and molecular weight lead to increased conductivity. The following study was undertaken to assess the effects of phase separation in polyalkylene oxides connected by melamine linkages. Melamine was chosen as the linking unit because it provides a branching site, cation binding sites to help ionic transport between polymer chains, and the opportunity for self assembly through hydrogen bonding. Polymers were made by the reaction of cyanuric chloride with a series of amine-terminated alkylene oxides. A linear polymer was first made, followed by reaction of the third site on cyanuric chloride with varying ratios of monofunctional Jeffamine and (3-aminopropyl)triethoxysilane. The lithium trifluoromethane sulfonamide-doped polymers are then crosslinked through a sol-gel process to form free-standing films. Initial results have shown mechanically strong films with lithium conductivities on the order of 2 x 10(exp -5) S/cm at ambient temperature. In a separate study, organically modified silanes (Ormosils) that contain sulfonic acid derivatized melamines have been incorporated into proton exchange membranes. The membranes are made by reaction of the primary amine groups of various ratios of melamine derivative and difunctional Jeffamine (MW = 2000) with the epoxide group of (3-Glycidyloxypropyl)trimethoxysilane. The films were then cross-linked through a sol-gel process. Resulting sulfuric acid doped films are strong, flexible, and have proton conductivities on the order of 2 x l0(exp -2) S/cm (120 C, 25% relative humidity). Our best results have been observed when films contain 60% PEO and 40% sulfonated melamine.

Tigelaar, Dean M.↗
NASA NTRS2007

Use of Ionic Liquids in Rod-Coil Block Copolyimides for Improved Lithium Ion Conduction

Solvent-free, solid polymer electrolytes (SPE) have the potential to improve safety, increase design flexibility and enhance performance of rechargeable lithium batteries. Solution based electrolytes are flammable and typically incompatible with lithium metal anodes, limiting energy density. We have previously demonstrated use of polyimide rod coil block copolymers doped with lithium salts as electrolytes for lithium polymer batteries. The polyimide rod blocks provide dimensional stability while the polyethylene oxide (PEO) coil portions conduct ions. Phase separation of the rods and coils in these highly branched polymers provide channels with an order of magnitude improvement in lithium conduction over polyethylene oxide itself at room temperature. In addition, the polymers have been demonstrated in coin cells to be compatible with lithium metal. For practical use at room temperature and below, however, at least an order of magnitude improvement in ion conduction is still required. The addition of nonvolatile, room temperature ionic liquids has been shown to improve the ionic conductivity of high molecular weight PEO. Herein we describe use of these molten salts to improve ionic conductivity in the rod-coil block copolymers.

Meador, Mary Ann B.↗
NASA NTRS2006

2.4 Micrometer Cutoff Wavelength AlGaAsSb/InGaAsSb Phototransistors

We report the first AlGaAsSb/InGaAsSb phototransistors with a cutoff wavelength (50% of peak responsivity) of 2.4 micrometers operating in a broad range of temperatures. These devices are also the first AlGaAsSb/InGaAsSb heterojunction phototransistors (HPT) grown by molecular beam epitaxy (MBE). This work is a continuation of a preceding study, which was carried out using LPE (liquid phase epitaxy)-grown AlGaAsSb/InGaAsSb/GaSb heterostructures. Although the LPE-related work resulted in the fabrication of an HPT with excellent parameters [1-4], the room temperature cutoff wavelength of these devices (approximately 2.15 micrometers) was determined by fundamental limitations implied by the close-to-equilibrium growth from Al-In-Ga-As-Sb melts. As the MBE technique is free from the above limitations, AlGaAsSb/InGaAsSb/GaSb heterostructures for HPT with a narrower bandgap of the InGaAsSb base and collector - and hence sensitivity at longer wavelengths (lambda) - were grown in this work. Moreover, MBE - compared to LPE - provides better control over doping levels, composition and width of the AlGaAsSb and InGaAsSb layers, compositional and doping profiles, especially with regard to abrupt heterojunctions. The new MBE-grown HPT exhibited both high responsivity R (up to 2334 A/W for lambda=2.05 micrometers at -20 deg C.) and specific detectivity D* (up to 2.1 x 10(exp 11) cmHz(exp 1/2)/W for lambda=2.05 micrometers at -20 deg C).

Sulima, O. V.↗
NASA NTRS1977

A high pressure modulated molecular beam mass spectrometric sampling system

The current state of understanding of free-jet high pressure sampling is critically reviewed and modifications of certain theoretical and empirical considerations are presented. A high pressure, free-jet expansion, modulated molecular beam, mass spectrometric sampling apparatus was constructed and this apparatus is described in detail. Experimental studies have demonstrated that the apparatus can be used to sample high temperature systems at pressures up to one atmosphere. Condensible high temperature gaseous species have been routinely sampled and the mass spectrometric detector has provided direct identification of sampled species. System sensitivity is better than one tenth of a part per million. Experimental results obtained with argon and nitrogen beams are presented and compared to theoretical predictions. These results and the respective comparison are taken to indicate acceptable performance of the sampling apparatus. Results are also given for two groups of experiments related to hot corrosion studies. The formation of gaseous sodium sulfate in doped methane-oxygen flames was characterized and the oxidative vaporization of metals was studied in an atmospheric pressure flowing gas system to which gaseous salt partial pressures were added.

Stearns, C. A.↗
NASA NTRS2001

Quantum Mechanical Study of Nanoscale MOSFET

The steady state characteristics of MOSFETS that are of practical Interest are the drive current, off-current, dope of drain current versus drain voltage, and threshold voltage. In this section, we show that quantum mechanical simulations yield significantly different results from drift-diffusion based methods. These differences arise because of the following quantum mechanical features: (I) polysilicon gate depletion in a manner opposite to the classical case (II) dependence of the resonant levels in the channel on the gate voltage, (III) tunneling of charge across the gate oxide and from source to drain, (IV) quasi-ballistic flow of electrons. Conclusions dI/dV versus V does not increase in a manner commensurate with the increase in number of subbands. - The increase in dI/dV with bias is much smaller then the increase in the number of subbands - a consequence of bragg reflection. Our calculations show an increase in transmission with length of contact, as seen in experiments. It is desirable for molecular electronics applications to have a small contact area, yet large coupling. In this case, the circumferential dependence of the nanotube wave function dictates: - Transmission in armchair tubes saturates around unity - Transmission in zigzag tubes saturates at two.

Svizhenko, Alexei↗
NASA NTRS1987

DC electrical, thermal, and spectroscopic properties of various condensation polyimides containing surface cobalt oxide

Doping polyimides with cobalt ion causes the room temperature direct current electrical resistivity to decrease relative to the polymer alone, the reduction being most pronounced for the air-side of the cobalt modified polyimides. At a constant electrical field, resistivity for the volume, air-side and glass-side modes decreases yet further with an increase in temperature as expected for semiconductors and insulators. X-ray photoelectron spectroscopy indicates the air-side of the cobalt modified polyimides is predominantly Co3O4. The bulk resistivity of the air-side and activation energy of conduction for this surface are comparable to high purity sintered Co3O4. Charging characteristics at room temperature indicate a substantial polymer matrix contribution to both the glass-side and volume mode measurements but a negligible contribution to the air-side electrical properties. Volume electrical resistivity for similar additive levels is reduced by increasing the molecular flexibility of the host polymer.

Rancourt, J. D.↗
NASA NTRS2006

Experimental Partitioning of Cr(3+) and Sc(3+) into Olivine: Mechanisms and Implications

Olivine (Mg, Fe)Si2O4 does not, by stoichiometry, accept cations such as Sc(3+) or Cr(3+). However, the partition coefficients of Sc and Cr between olivine and liquid are significant 0.2-1.0. We have measured Cr(3+) partition coefficients of near unity and have grown olivines with nearly 3 wt.% Sc2O3. Therefore, there must be a simple means of charge balancing 3+ ions in a crystal structure that was obviously not designed to receive other than 2+ ions on the olivine M sites. The simplest explanation is that two 3+ ions enter the olivine structure by displacing three 2+ ions and creating an M site vacancy. Even this explanation has difficulties. For minor elements in our experiments (~1 wt.%) the odds of a minor element 3+ ion finding a second 3+ for charge balance are of the order of 100:1 against. Because of the reducing conditions of our experiments, Fe(3+) will not suffice; and Al(3+) is not in sufficient quantity in olivine for charge balance. Therefore, Cr or Sc must, in effect, charge balance itself. For true trace elements, the problem is compounded many times. For an ion at the 10 ppm level the chances of finding a second (for example) Sc ion is approx.10(exp 5):1 against. Of course, any other 3+ ion would suffice but comparisons between percent level doping experiments and trace level partitioning indicate that Henry s law is obeyed. This implies that the same substitution mechanism occurs at both the percent and tens of ppm levels. There are two simple solutions to this problem: (i) The electrical conductivity of olivine is such that charge balance need not be local. This requires substantial domains within the olivine crystal in electrical contact by migration of vacancies or electronic defects. (ii) The 3+ cation brings along its own charge-balancing ion because it existed as a dimer in the silicate liquid. Olivine is not a true insulator but is actually a p-type semiconductor. Even so, electrical communication by this means is unlikely over the tens or hundreds of unit cells that would be required for charge balance to be local. Therefore, we cautiously favor the idea that melt speciation is the means by which 3+ ions enter the olivine structure. Possibly this model might be tested by in situ XAFS measurements or by molecular dynamical calculations.

Jones, John↗
NASA NTRS1988

New MBE buffer for micron- and quarter-micron-gateGaAs MESFETs

A new buffer layer has been developed that eliminates backgating in GaAs MESFETs and substantially reduces short-channel effects in GaAs MESFETs with 0.27-micron-long gates. The new buffer is grown by molecular beam epitaxy (MBE) at a substrate temperature of 200 C using Ga and As sub 4 beam fluxes. The buffer is crystalline, highly resistive, optically inactive, and can be overgrown with high quality GaAs. GaAs MESFETs with a gate length of 0.27 microns that incorporate the new buffer show improved dc and RF properties in comparison with a similar MESFET with a thin undoped GaAs buffer. To demonstrate the backgating performance improvement afforded by the new buffer, MESFETs were fabricated using a number of different buffer layers and structures. A schematic cross section of the MESFET structure used in this study is shown. The measured gate length, gate width, and source-drain spacing of this device are 2,98, and 5.5 microns, respectively. An ohmic contact, isolated from the MESFET by mesa etching, served as the sidegate. The MESFETs were fabricated in MBE n-GaAs layers grown on the new buffer and also in MBE n-GaAs layers grown on buffer layers of undoped GaAs, AlGaAs, and GaAs/AlGaAs superlattices. All the buffer layers were grown by MBE and are 2 microns thick. The active layer is doped to approximately 2 x 10 to the 17th/cu cm with silicon and is 0.3 microns thick.

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