CS2 - Candidate for the 3150-A Venus band
The 3150-A absorption on Venus, found by Barker et al. (1975), may be due to carbon disulfide. The stability and thermodynamics of the carbon chalcogenides are briefly discussed.
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The 3150-A absorption on Venus, found by Barker et al. (1975), may be due to carbon disulfide. The stability and thermodynamics of the carbon chalcogenides are briefly discussed.
A large number of planetary missions under consideration for the next two decades will be using radioisotope thermoelectric generators to provide the necessary spacecraft electrical power. Performance, reliability, lifetime and cost of these RTGs are expected to be more demanding and will require the development of advanced thermoelectric materials. An advanced thermoelectric materials development program is being conducted by JPL and is the subject of this paper. Under this program, alloys of rare earth chalcogenides have been synthesized and their thermoelectric properties evaluated. The selection of specific compounds on which the program is currently concentrating is influenced by criteria such as low thermal conductivity, reasonably high operating temperatures (not less than 1000 C) and stability of the compounds. The paper discusses the rationale, approach and current status of the program. In addition, the thermoelectric and thermophysical property measurement used to evaluate the materials are described. The preliminary results and analysis of these experimental data are also given.
Progress and plans in various areas of the NASA Space Power Program are discussed. Solar cell research is narrowed to GaAs, multibandgap, and thin Si cells for arrays in planar and concentrator configurations, with further work to increase cell efficiency, radiation hardness, develop flexible encapsulants, and reduce cost. Electrochemical research is concentrating on increasing energy and power density, cycle and wet stand life, reliability and cost reduction of batteries. Further development of the Ni-H2 battery and O2-H2 fuel cell to multihundred kW with a 5 year life and 30,000 cycles is noted. Basic research is ongoing for alkali metal anodes for high energy density secondary cells. Nuclear thermoelectric propulsion is being developed for outer planets exploration propulsion systems, using Si-Ge generators, and studies with rare earth chalcogenides and sulfides are mentioned. Power Systems Management seeks to harmonize increasing power supply levels with inner and outer spacecraft environments, circuits, demands, and automatic monitoring. Concomitant development of bipolar transistors, an infrared rectenna, spacecraft charging measurement, and larger heat pipe transport capacity are noted.
Cells utilizing the organic electrolyte, NaI in triglyme, operated at approx. 130 C with Na(+) - intercalating cathodes. However, their rate and stability were inadequate. NaAlCl4 was found to be a highly useful electrolyte for cell operation at 165-190 C. Na(+) intercalating chalcogenides reacted with NaAlCl4 during cycling to form stable phases. Thus, VS2 became essentially VS2Cl, with reversible capacity of approx 2.8 e(-)/V, and a mid-discharge voltage of approx 2.5V and 100 deep discharge cycles were readily achieved. A positive electrode consisting of VCl3 and S plus NaAlCl4 was subjected to deep-discharge cycles 300 times and it demonstrated identity with the in-situ-formed BSxCly cathode. NiS2 and NiS which are not Na(+)-intercalating structures formed highly reversible electrodes in NaAlCl4. The indicated discharge mechanism implies a theoretical capacity 4e(-)/Ni for NiS2 and 2e(-)/Ni for NiS. The mid-discharge potentials are, respectively, 2.4V and 2.1V. A Na/NiS2 cell cycling at a C/5 rate has exceeded 500 deep discharge cycles with 2.5e(-)/Ni average utilization. A 4 A-hr nominal capacity prototype Na/NiS2 cell was tested at 190 C. It was voluntarily terminated after 80 cycles. Further development, particularly of cathode structure and hardware should produce a battery capable of at least 50-W-hr/lb and more than 1000 cycles.
Theoretical work of two decades ago adequately explained the transport behavior and effectively guided the development of thermoelectric materials of high conversion efficiencies of conventional semiconductors (e.g., SiGe alloys). The more significant contributions involved the estimation of optimum doping concentrations, the reduction of thermal conductivity by solid solution doping and the development of a variety of materials with ZT approx. 1 in the temperature range 300 K to 1200 K. ZT approx. 1 is not a theoretical limitation although, experimentally, values in excess of one were not achieved. Work has continued with emphasis on higher temperature energy conversion. A number of promising materials have been discovered in which it appears that ZT 1 is realizable. These materials are divided into two classes: (1) the rare-earth chalcogenides which behave as itinerant highly-degenerate n-type semiconductors at room-temperature, and (2) the boron-rich borides, which exhibit p-type small-polaronic hopping conductivity.
Problems in the design of optical systems for use with mid-IR (MIR; 10.6-micron) lasers are reviewed. The cryogenically operated lead-chalcogenide tunable diode lasers currently used as sources emit complex far-field patterns and require sophisticated beam collection, shaping, and guide optics. Since conventional optics using large mirrors and Ge lenses are often awkward to use and sensitive to vibration, and since optical fibers for the MIR have not been perfected, current research concentrates on hollow flexible rectangular metallic pipes. These pipes are shown to provide transmission of 95 percent or better over a 1-m length, with beam shaping and polarization control. The low transmission losses and wideband IR transmission of single-crystal alkali halides suggest the feasibility of their use in MIR optical fibers and waveguides.
Theoretical work of two decades ago adequately explained the transport behavior and effectively guided the development of thermoelectric materials of high conversion efficiencies of conventional semiconductors (e.g., SiGe alloys). The more significant contributions involved the estimaiation of optimum doping concentrations, the reduction of thermal conductivity by solid solution doping and the development of a variety of materials with ZT approx. 1 in the temperature range 300 K to 1200 K. ZT approx. 1 is not a theoretical limitation although, experimentally, values in excess of one were not achieved. Work has continued with emphasis on higher temperature energy conversion. A number of promising materials have been discovered in which it appears that ZT 1 is realizable. These materials are divided into two classes: (1) the rare-earth chalcogenides which behave as itinerant highly-degenerate n-type semiconductors at room-temperature, and (2) the boron-rich borides, which exhibit p-type small-polaronic hopping conductivity.
The high-temperature thermoelectric energy-conversion theory is examined. It is shown that semiconductors are the logical choices for high-figure of merit-value materials, but the requirements for optimization differ depending on whether the material is classed as a broad-band or narrow-band semiconductor. Optimization is discussed as a function of temperature. Phonon scattering mechanisms are considered; and for the reduction of thermal conductivity, basic material guidelines are given. Although experimental results indicate that ZT (where Z is the figure of merit and T is the temperature) of about 1 represents an upper limit, there is in fact, no theoretical limitation. It is unlikely that the Z values will be significantly reduced by radiation transfer at temperatures lower than 2000 K. The current status of materials research is also considered. The rare-earth chalcogenides which behave as n-type semi-conductors and the boron-rich borides which exhibit hopping p-type conductivity behavior are the materials that show promise for high-temperature Z values. The reasons for low thermal conductivities in these materials is discussed.
Rare-earth chalcogenides and boron-rich borides show promise. Report discusses search for materials performing more efficiently in high-temperature thermoelectric conversion. Begins with summary of developments during past three decades. Followed by brief introduction to theory of thermoelectric energy conversion, then by experimental findings and by some additional theory on specific materials.
An infrared photoresponsive element (RD) is monolithically integrated into a source follower circuit of a metal oxide semiconductor device by depositing a layer of a lead chalcogenide as a photoresistive element forming an ohmic bridge between two metallization strips serving as electrodes of the circuit. Voltage from the circuit varies in response to illumination of the layer by infrared radiation.
Report reviews current research in thermoelectric materials with view towards development of materials of greater energy-conversion efficiency. Emphasis on effort to understand and manipulate microstructure to increase thermoelectric figure of merit, Z. Thermoelectric properties of three broad categories of materials discussed. First category includes alloys of group IV elements like silicon and germanium. Second category is rare-earth chalcogenides. Third category includes narrow-band semiconductors, especially boron carbides.
The development of infrared-transmitting optical fibers as sensors for monitoring the cure of advanced composite materials is reported. Fourier transform infrared spectra are presented which were remotely sensed during the cure of a high performance polyimide resin and a graphite/polyimide matrix prepreg using an 0.1 mm O.D. x 3 m chalcogenide optical fiber. A discussion of the fiber and sensor element, absorption mechanism and potential applications is presented.
Ternary chalcogenide Si-As-Te system is an interesting semiconductor from the aspect of both basic physics and technological applications. Since a Si-As-Te system consists of a IV-III-II hedral bonding network, it has a very large glass forming region with a wide physical constant controllability. For example, its energy gap can be controlled in a range from 0.6 eV to 2.5 eV, which corresponds to the classical semiconductor Ge (0.66 eV), Si (1.10 eV), GaAs (1.43 eV), and GaP (2.25 eV). This fact indicates that it would be a suitable system to investigate the compositional dependence of the atomic and electronic properties in the random network of solids. In spite of these significant advantages in the Si-As-Te amorphous system, a big barrier impending the wide utilization of this material is the huge difficulty encountered in the material preparation which results from large differences in the weight density, melting point, and vapor pressure of individual elements used for the alloying composition. The objective of the FMPT/M13 experiment is to fabricate homogeneous multi-component amorphous semiconductors in the microgravity environment of space, and to make a series of comparative characterizations of the amorphous structures and their basic physical constants on the materials prepared both in space and in normal terrestrial gravity.
Thermochemical analyses of equilibrium partial pressures over oxides with and without the presence of the respective element condensed phase, and hydrogen, chalcogens, hydrogen chalcogenides, and graphite are presented. Theoretical calculations are supplemented with experimental results on the rate of decomposition and/or sublimation/vaporization of the oxides under dynamic vacuum, and on the rate of reaction with hydrogen, graphite, and chalcogens. Procedures of removal of a number of oxides under different conditions are discussed.
Sol-gel processing techniques have been used to apply thin porous films to the surfaces of planar infrared (IR) waveguides to produce widely useful chemical sensors. The thin- film coating serves to diminish the concentration of water and increase the concentration of the analyte in the region probed by the evanescent IR wave. These porous films are composed of silica, and therefore, conventional silica surface modification techniques can be used to give the surface a specific functional character. The sol-gel film was surface-modified to make the film highly hydrophobic. These sensors were shown to be capable of detecting non-polar organic analytes, such as benzonitrile, in aqueous solution with detection limits in the ppb range. Further, these porous sol-gel structures allow the analytes to diffuse into and out of the films rapidly, thus reaching equilibrium in less than ten seconds. These sensors are unique because of the fact that their operation is based on the measurement of an IR absorption spectrum. Thus, these sensors are able to identify the analytes as well as measure concentration with high sensitivity. These developments have been documented in previous reports and publications. Recently, we have also targeted detection of the polar organic molecules acetone and isopropanol in aqueous solution. Polar organics are widely used in industrial and chemical processes, hence it is of interest to monitor their presence in effluents or decontamination process flows. Although large improvements in detection limits were expected with non-polar organic molecules in aqueous solutions using very hydrophobic porous sol-gel films on silicon attenuated total reflectance (Si ATR) waveguides, it was not as clear what the detection enhancements might be for polar organic molecules. This report describes the use of modified sol-gel-coated Si ATR sensors for trace detection and quantitation of small polar organic molecules in aqueous solutions. The detection of both acetone and isopropanol molecules in aqueous solution has been previously reported for chalcogenide fiber optic sensors. The sol-gel film was produced using a mixture of ethyltriethoxysilane and tetraethoxysilane and the surface modification was carried out using trimethylchlorosilane. We have demonstrated that this film concentrates the target polar analytes from aqueous solution in the region probed by the evanescent wave to improve detection limits by as much as a factor of 450.
This flight definition project has the specific objective of investigating the kinetics of nucleation and crystal growth in high temperature inorganic oxide, glass forming melts in microgravity. It is related to one of our previous NASA projects that was concerned with glass formation for high temperature containerless melts in microgravity. The previous work culminated in two experiments which were conducted aboard the space shuttle in 1983 and 1985 and which consisted of melting (at 1500 C) and cooling levitated 6 to 8 mm diameter spherical samples in a Single Axis Acoustic Levitator (SAAL) furnace. Compared to other types of materials, there have been relatively few experiments, 6 to 8, conducted on inorganic glasses in space. These experiments have been concerned with mass transport (alkali diffusion), containerless melting, critical cooling rate for glass formation, chemical homogeneity, fiber pulling, and crystallization of glass forming melts. One of the most important and consistent findings in all of these experiments has been that the glasses prepared in microgravity are more resistant to crystallization (better glass former) and more chemically homogeneous than equivalent glasses made on Earth (1 g). The chemical composition of the melt appears relatively unimportant since the same general results have been reported for oxide, fluoride and chalcogenide melts. These results for space-processed glasses have important implications, since glasses with a higher resistance to crystallization or higher chemical homogeneity than those attainable on Earth can significantly advance applications in areas such as fiber optics communications, high power laser glasses, and other photonic devices where glasses are the key functional materials.
This publication contains the proceedings for the Non-Volatile Memory Technology Symposium 2001 that was held on November 7-8, 2001 in San Diego, CA. The proceedings contains a a wide range of papers that cover current and new memory technologies including Flash memories, Magnetic Random Access Memories (MRAM and GMRAM), Ferro-electric RAM (FeRAM), and Chalcogenide RAM (CRAM). The papers presented in the proceedings address the use of these technologies for space applications as well as radiation effects and packaging issues.
Memory technologies are divided into two categories. The first category, nonvolatile memories, are traditionally used in read-only or read-mostly applications because of limited write endurance and slow write speed. These memories are derivatives of read only memory (ROM) technology, which includes erasable programmable ROM (EPROM), electrically-erasable programmable ROM (EEPROM), Flash, and more recent ferroelectric non-volatile memory technology. Nonvolatile memories are able to retain data in the absence of power. The second category, volatile memories, are random access memory (RAM) devices including SRAM and DRAM. Writing to these memories is fast and write endurance is unlimited, so they are most often used to store data that change frequently, but they cannot store data in the absence of power. Nonvolatile memory technologies with better future potential are FRAM, Chalcogenide, GMRAM, Tunneling MRAM, and Silicon-Oxide-Nitride-Oxide-Silicon (SONOS) EEPROM.