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At least 235 records · Page 13

Formation of Residual Gases from Source Materials in Closed Crystal Growth Systems

Different, non-constituent cases are present in crystal growth systems and may affect processes like growth rate in PVT or voids formation and detached solidification in melt growth systems. The presence of the gas may be detrimental or advantageous depending on its amount and composition, and on the process in question. The presence of the cases, their amount and composition, can be caused and changed by diffusion through and desorption from the growth container material. We have investigated these phenomena for silica glass ampoules. We also found, that residual cases can be generated by the source materials: even very high purity commercial elements and compounds may contain trace amounts of impurities, particularly oxides. The oxides may have low volatilities themselves but their reaction with other species, particularly carbon and hydrogen, may produce volatile compounds like water or carbon oxides. The amount of the gas and its composition is dependent on the original purity of the material (oxide contaminants) and the heat treatment of the source prior to sealing. In many cases. particularly at temperatures below about 900 C and in well-outgassed ampoules, this mechanism dominates. The problem is of a particular importance in sealed systems where the amount and composition of the gas cannot be directly controlled. Therefore, a reasonable knowledge and understanding of the origin, composition, magnitude, and change with time of gases present in sealed ampoules may be important for a meaningful control and interpretation of crystal growth processes. We have investigated this phenomenon in more details for a number of elements and compounds, primarily for II-VI and IV-VI materials. Different source pre-treatment and annealing procedures were applied, and subsequent consecutive annealings and measurements were done to determine the origin and development of the gas in the systems.

Palosz, W.↗

The Origin and Time Dependence of the Amount and Composition of Non-Constituent Gases Present in Crystal Growth Systems

Presence of different, non-constituent gases may be a critical factor in crystal growth systems. In Physical Vapor Transport processes the cras(es) can be used intentionally (to prevent excessively high, unstable growth conditions), or can evolve unintentionally during the course of the process (which may lead to undesired reduction in the -rowth rate). In melt growth, particularly under low gravity conditions (reduced hydrostatic pressure) the gas present in the system may contribute to formation of voids in the growing crystals and even to a separation of the crystal and the liquid phase [1]. On the other hand, some amount of gas may facilitate 'contactless' crystal growth particularly under reduced gravity conditions [2 - 6]. Different non-constituent gases may be present in growth ampoules, and their amount and composition may change during the crystallization process. Some gases can appear even in empty ampoules sealed originally under high vacuum: they may diffuse in from the outside, and/or desorb from the ampoule walls. Residual gases can also be generated by the source materials: even very high purity commercial elements and compounds may contain trace amounts of impurities, particularly oxides. The oxides may have low volatilities themselves but their reaction with other species, particularly carbon and hydrogen, may produce volatile compounds like water or carbon oxides. The non-constituent gases, either added initially to the system or evolved during the material processing, may diffuse out of the ampoule during the course of the experiment. Gases present outside (e.g. as a protective atmosphere or thermal conductor) may diffuse into the ampoule. In either case the growth conditions and the quality of the crystals may be affected. The problem is of a particular importance in sealed systems where the amount of the gases cannot be directly controlled. Therefore a reasonable knowledge and understanding of the origin, composition, magnitude, and change with time of gases present in sealed ampoules may be important for a meaningful control and interpretation of crystal growth processes. This problem is of a particular importance for processing of electronic materials in space because (i) safety considerations require using sealed systems only, and (ii) high cost of crystal growth experiments in microgravity calls for a throughout, accurate description of the processing conditions necessary for a meaningful, efficient, and conclusive interpretation of the space results. In this paper we present the results of our extensive studies on gases in closed crystal growth systems which include: (a) Degassing properties of fused silica; (b) Generation of inert gases by source materials (CdTe, ZnTe, CdZnTe, ZnSe, PbTe, PbSe, PbSeTe); (c) Diffusive cas losses from silica glass ampoules.

Palosz, Witold↗

Volatile compounds in shergottite and nakhlite meteorites

Since discovery of apparent carbonate carbon in Nakhla, significant evidence has accumulated for occurrence of volatile compounds in shergotties and nakhlites. Results are presented from a study of volatile compounds in three shergottites, one nakhlite, and three eucrite control samples. Shergotties ALHA77005, EETA79001, and Shergotty, and the nakhlite Nakhla, all contain oxidized sulfur (sulfate) of preterrestrial origin; sulfur oxidation is most complete in EETA79001/Lith-C. Significant bulk carbonate was confirmed in Nakhla and trace carbonate was substantiated for EETA79001, all of which appears to be preterrestrial in origin. Chlorine covaries with oxidized sulfur, whereas carbonate and sulfate are inversely related. These volatile compounds were probably formed in a highly oxidizing, aqueous environment sometime in the late stage histories of the rocks that are now represented as meteorites. They are consistent with the hypothesis that shergottite and nakhlite meteorites originated on Mars and that Mars has supported aqueous geochemistry during its history.

Gooding, James L.↗

Detoxification of Halon Fire-Extinguishant Products

Ammonia compounds absorb toxic hydrogen halides as they are produced. Toxic acid vapors resulting from use of Halon (or equivalent) fire extinguishers immediately changed into nontoxic ammonium compounds when extinguishers contain some ammonia or ammonium carbonate. If ammonium carbonate used, particle size of resulting neutral compounds controlled to eliminate virtually any absorption into the lungs.

Miller, E. L.↗

The Search for Water and Other Volatiles in Martian Surface Materials: The Thermal Evolved Gas Analyzer (TEGA)

Volatile-bearing minerals and phases (e.g., Fe-oxyhydroxides, phyllosilicates, carbonates, sulfates, palagonites, glasses) may be important components of the Martian regolith. However, essentially no information exists on the mineralogical composition of volatile-bearing phases in the regolith. The Thermal Evolved Gas Analyzer (TEGA), which was part of the Mars Polar Lander payload, was to determine the abundances of two of the most important volatile compounds (i.e., water and carbon dioxide) in the martian soil and to identify the minerals or phases that harbor these volatiles. The TEGA instrument was composed of a differential scanning calorimeter (DSC) interfaced with evolved gas analysis (EGA). The EGA consisted of a Herriott cell of a tunable-diode laser (TDL) spectrometer that determines CO2 and H2O abundances. The sample chamber was to operate at about 100 mbar (-76 torr) with a N2 carrier gas flow of 0.4 sccm. Specifications of TEGA are described in detail elsewhere in this volume.

Ming, D. W.↗

Molecular and Enantiomeric Analysis of Organic Compounds in Carbonaceous Meteorites

Carbonaceous meteorites are relatively enriched in carbon. Much of this carbon is in the form of soluble organic compounds. The Murchison and Murray meteorites are the best-characterized carbonaceous meteorites with respect to organic chemistry. Their content of organic compounds has led to an initial understanding of early solar system organic chemistry as well as what compounds may have played a role in the origin of life (Cronin and Chang, 1993). Reported compounds include: amino acids, amides, carboxylic acids, sulfonic acids, and polyols. This talk will focus on the molecular and enantiomeric analysis of individual meteoritic compounds: polyol acids; and a newly identified class of meteorite compounds, keto acids, i.e., acetoacetic acid, levulinic acid, etc. Keto acids (including pyruvic) are critically important in all contemporary organisms. They are key intermediates in metabolism and processes such as the citric acid cycle. Using gas chromatography-mass spectrometry we identified individual meteoritic keto acids after derivatization to one or more of the following forms: isopropyl ester (ISP), trimethyIsiIy1 (TMS), tert-butyldimethylsilyl (BDMS). Ongoing analyses will determine if, in addition to certain amino acids from Murchison (Cronin and Pizzarello, 1997), other potentially important prebiotic compounds also contain enantiomeric excesses, i.e., excesses that could have contributed to the current homochirality of life.

Cooper, George↗

Enantiomer Excesses in Meteoritic Organic Compounds: a Role for Radiation-Magnetism?

Carbonaceous chondrites contain an insoluble “macromolecular” carbon phase as well as discrete soluble organic compounds including amino acids and sugar derivatives. Both the macromolecular carbon and the sugar derivatives are thought to have formed through aqueous formaldehyde chemistry. Formaldehyde is a ubiquitous molecule in interstellar space environments and therefore its chemistry was likely important during the formation of the Earth and other planets. It was also likely delivered throughout Earth's history: it is found in comets and (asteroidal) meteorites. Among the reactions of formaldehyde, those in water are thought to be an important part of the primordial route to today’s nucleic acids, DNA and RNA. A plausible pre-biotic path to these biopolymers would begin with the "formose" reaction, the self-reaction of formaldehyde in an alkaline aqueous medium. Formaldehyde's inclusion in the young solar system’s planets would have provided a relatively fast route to a variety of hydroxylated compounds related to nucleic acids and metabolism, including sugars, sugar acids, sugar alcohols, and formaldehyde polymers.

Cooper, G.↗

Prebiotic materials from on and off the early Earth

One of the great puzzles of all time is how did life arise? It has been universally presumed that life arose in a soup rich in compounds made mostly of carbon, the kind of which we are currently composed. Where did these organic molecules come from? In this talk I will review proposed contributions to pre-biotic organic chemistry from both terrestrial processes (i.e., hydrothermal vents, Miller-Urey syntheses) and also from space. While the former is perhaps better known and more commonly taught in school, we now know that comet and asteroid dust deliver tons of organics to the Earth every day, and there is a growing consensus among scientists that molecules from space played an important role in making the Earth habitable, and perhaps even provided specific compounds that were directly related to the origin of life.

Bernstein, Max↗

Carborane Dopant Strengthens Pitch Char

Addition of small amount of soluble, organic boron compound to matrix precursor of carbon-fiber/carbon-matrix (carbon/carbon) composite increases strength and toughness of composite. Compound catalyzes graphitization of matrix, giving rise to greater degree of graphitization at lower processing temperature. Technique used to advantage in carbon/carbon materials requiring lower temperature processing, such as those with inhibited matrices or materials sensitive to changes in fiber properties.

D Kyle Brown↗

Total hydrocarbon analysis by ion mobility spectrometry

Astronauts must be alerted quickly to chemical leaks that compromise their health and the success of their missions. An ideal leak detector would be equally sensitive to all compounds that might constitute a hazard and insensitive to nontoxic compounds. No ideal sensor exists; thus, selection of a methodology is a series of compromises. The commonly used methods are either insensitive at the low exposure levels set by OSHA, NASA, and other organizations or are selectively insensitive to important classes of chemicals such as Freons. After extensive study and experience, the Toxicology Group at JSC has selected ion mobility spectrometry (IMS) for development into a broad range, sensitive detector. In addition to the sensing method, signal processing is important leak detection because a background signal can be expected at all times. The leak-detecting instrument must be programmed to discriminate between authentic leaks and background fluctuations caused by routine operations. The results of an evaluation of the prototype THA is presented in terms related to spacecraft operations. The evaluation included determination of instrumental parameters such as stability and response times. We also included responses to some common components of spacecraft atmospheres in pure form and in binary and ternary mixtures. The output of the four algorithms to the mixtures was found to be noticeably different. These responses are compared on the basis of their utility for signaling a chemical leak. As a means of evaluating its resistance to a falsely positive response, the THA was challenged with carbon dioxide and methane, compounds whose concentrations normally increase in spacecraft air during human habitation. The instrument showed virtually no response to these interferences. Although the prototype THA is designed for space flight, this detector is expected to be useful for field screening at chemical waste dumps and other environmentally sensitive locations.

Cross, John H.↗

Biological cycling of atmospheric trace gases

A detailed critical review was conducted of present knowledge of the influence of biological processes on the cycling of selected atmospheric gas constituents--methane, carbon monoxide, and gaseous compounds of nitrogen (nitrous oxide, ammonia, nitric oxide, and nitrogen dioxide) and sulfur (hydrogen sulfide and sulfur dioxide). The identification was included of biological and other sources of each gas, a survey of abundance measurements reported in the literature, and a review of the atmospheric fate of each contituent. Information is provided on which to base conclusions regarding the importance of biological processes on the atmospheric distribution and surface-atmosphere exchange of each constituent, and a basis for estimating the adequacy of present knowledge of these factors. A preliminary analysis was conducted of the feasibility of monitoring the biologically influenced temporal and spatial variations in abundance of these gases in the atmosphere from satellites.

Hitchcock, D. R.↗

The ablation of graphitic materials in the sublimation regime.

A large variety of graphitic materials have been tested in an arc heated air stream at a surface pressure of 4.3 atm and a nominal surface temperature of 3925 K. Included were commercial and developmental grades of artificial graphites, both two and three dimensional carbon-carbon composites, composites seeded with refractory compounds, and several special materials such as pyrolytic graphite, mesophase graphite, glassy carbon, and natural graphite. ATJ graphite was used as a control material. Except for the seeded materials which had poor performance, the mass loss rate for all the man-made graphitic materials fell within the range of 17 per cent less to 30 per cent more than the rate for ATJ. Thus it is concluded that wide variations in constituents, processing, fabrication and structure have relatively little effect on the ablation performance of graphitic materials, at least under the conditions of the present tests. Particulate mass loss was observed for all the materials tested and is the dominant mechanism for mass removal at the present test conditions. It is suggested that this mechanism results from physical failure, primarily by compressive thermal stress.

Lundell, J. H.↗

The Viking mission search for life on Mars

The scientific payload on the Viking Mars landers is described. Shortly after landing, two facsimile cameras capable of stereoscopic imaging will scan the landing site area in black and white, color, and infrared to reveal gross evidence of past or present living systems. A wide range mass spectrometer will record a complete mass spectrum for soil samples from mass 12 to mass 200 every 10.3 sec. Three experiments based on different assumptions on the nature of life on Mars, if it exists, will be carried out by the bio-lab. A pyrolytic release experiment is designed to measure photosynthetic or dark fixation of carbon dioxide or carbon monoxide into organic compounds. A labelled release experiment will test for metabolic activity during incubation of a surface sample moistened with a solution of radioactively labelled simple organic compounds. A gas exchange experiment will detect changes in the gaseous medium surrounding a soil sample as the result of metabolic activity. The hardware, function, and terrestrial test results of the bio-lab experiments are discussed.

Klein, H. P.↗

Gas and aerosol fluxes

The development of remote sensing techniques to address the global need for accurate distribution and flux determinations of both man made and natural materials which affect the chemical composition of the atmosphere, the heat budget of the Earth, and the depletion, of stratospheric ozone is considered. Specifically, trace gas fluxes, sea salt aerosol production, and the effect of sea surface microlayer on gas and aerosol fluxes are examined. Volatile sulfur, carbon, nitrogen, and halocarbon compounds are discussed including a statement of the problem associated with each compound or group of compounds, a brief summary of current understanding, and suggestions for needed research.

Martens, C. S.↗

Interiors of the giant planets

Unlike the terrestrial planets, the giant planets - Jupiter, Saturn, Uranus, and Neptune - have retained large amounts of the carbon, nitrogen, and oxygen compounds that were present in their zone of formation. A smaller fraction of the available hydrogen and helium was retained. The distribution and relative amounts of these components in the interiors of the Jovian planets can be inferred from theoretical and experimental data on equations of state and from the planets' hydrostatic equilibrium response to rotation.

Hubbard, W. B.↗

Application of the Parker flash method to high temperature thermoelectrics

Mathematical aspects of thermal diffusivity measurements are reviewed and applied to develop an experimental setup at JPL. Certain approximations commonly appearing in the literature are examined in some detail and rejected based upon sensitive slope variations having significant impact on the results. The final mathematical formulation used was one developed by Parker et al. (1961), which evaluated the diffusivity in a way that could be simply evaluated by examining an oscilloscope trace. A computer algorithm was written to examine solution sensitivity to the number of terms taken in the infinite series. The mathematical technique is being used at JPL to evaluate diffusivities of graphite, Boron Carbon and Lanthanum Sulphur compounds in the temperature range of 300 K to 1200 K.

Noon, E. L.↗