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One dimensional model for analytical solution to problem of impulsive heat release by chemically generated waves in dilute, isothermal atmosphere
Plots of oxygen chemical potential against composition of lithium-oxygen solutions and sodium-oxygen solutions for a range of temperature were constructed. For each liquid metal two such plots were prepared. For one plot ideal solution behavior was assumed. For the other plot, existing solubility limit data for oxygen in the liquid metal were used to determine a first-order term for departure from ideality. The use of the plots in evaluating the oxygen gettering capability of refractory metals in liquid metal cooling systems is illustrated by a simple example involving lithium, oxygen, and hafnium.
A formula is obtained for the solubility of oxygen in solid Mo, determined in the range from 1400 to 1900 C by equilibrating rods of zone-refined Mo with mixtures of Mo and MoO2 powders. Using the known value of the free energy of formation of MoO2, a formula is obtained for the chemical potential of oxygen in the dilute solid solution. The heat of solution of oxygen in solid Mo and the excess entropy for the interstitial solid solution are also determined, assuming that the oxygen atoms reside in the octahedral interstices of bcc Mo.
The possible role of comets as sites for chemical and/or biological evolution is considered from both the positive and the negative viewpoints. On the negative side, it is pointed out that direct evidence for the chemical composition and size of cometary nuclei is lacking and the thermal history of comets is unknown, so that the length of time that liquid water could have been available ranges from zero to over a billion years. On the positive side, there remains the possibility that there may have been comets which retained liquid water in their interior for a sufficient time and that have more complex molecules than the amino acids and nucleic acid bases found in carbonaceous chondrities, and that the cometary environment may have been more favorable to the origin of life than the terrestrial. It has also been demonstrated that cometary material falls to earth at a significant rate. Problems in understanding the course of chemical evolution on earth may thus have a solution in cometary processes.
Weathering produces undesirable physical, chemical, and isotopic changes that might disturb the records of cosmochemical evolution that are sought in meteorites. Meteorites are physically disintegrated by crack propagation phenomena, including ice riving and secondary mineral riving, and are probably abraded by wind that is laden with ice crystals or dust particles. Chemical weathering proceeds by oxidation, hydration, carbonation, and solution and produces a variety of secondary minerals and mineraloids. Differential weathering under freezing conditions is discussed, as well as, the mineralogy of weathering products. Furthermore, the use of Antarctic alteration of meteorites could be used as an excellent analog for weathering on Mars or on cometary bodies.
A flash-evaporation technique is used to obtain vapor deposition characteristics for the binary alkali sulfates K2SO4 + Na2SO4 at 1 atm above 1100 K. The experimental equipment and techniques are described, and preliminary results are reported which indicate that this experimental technique meets most of the research requirements for studying multicomponent systems of current interest. The various deposition rate effects of introducing additives and the relevant inferences of condensate composition are presented, and the theoretical implications are discussed. It is concluded that alkali sulfate deposition and vaporization in combustion environments are inevitably influenced by chemical reactions such as hydroxide formation, and that solution nonideality is important even for homologous alkali-salt mixtures.
Current theoretical models of nucleosynthesis (N) in stars are reviewed, with an emphasis on their implications for Galactic chemical evolution. Topics addressed include the Galactic population II red giants and early N; N in the big bang; star formation, stellar evolution, and the ejection of thermonuclearly evolved debris; the chemical evolution of an idealized disk galaxy; analytical solutions for a closed-box model with continuous infall; and nuclear burning processes and yields. Consideration is given to shell N in massive stars, N related to degenerate cores, and the types of observational data used to constrain N models. Extensive diagrams, graphs, and tables of numerical data are provided.
A formvar replicator for installation in an aircraft pod has been designed, built, and flight tested on the NASA DC-8. The system incorporates a deicing capability (which can be pressure activated) to enable climb out through icing situations prior to deployment. The system can be operated at preselected speeds such that data can be recorded over a period of one to ten hours on 200 ft of 16mm film. A x2 speed control can be used during flight. Capability exists for detection of chemical constituents by appropriate doping of the formvar solution. An article entitled 'Measurements of ice particles in tropical cirrus anvils: importance in radiation balance' is attached as appendix A.
The N oxidation ratio, (HNO3)/(NO(x)), in the free troposphere is measured at approx. 1 to 9 (averaging approx. 5), consistently lower than the values of 15-100 which known theory suggests to be reached rapidly. This discrepancy casts doubt on current models' abilities to predict effects of NO sources on remote (NO), and so also (O3) and (OH). HNO3-to-NO(x) recycling processes involving HCHO in solution are appealing explanations for the ratio. Known chemical theory are illustrated using a Lagrangian box model of the mid-troposphere which simulates characteristic episodes form NO(x) input to HNO3 washout. Ratio and budget constraint equations for No(y) can usefully restrict conceivable explanations of missing chemistry of fast nitrogen cycling; most explanations could be called 'fast-cycles' or 're-NO(x)-ification.' These equations also show how current global models may suggest spuriously good N oxidation ratios and errors in OH. Aerosol or cloud droplets reactions with HCHO may produce (a) formic acid (which needs an appropriate source) and NO(x), or alternatively, (b) hydroxymethyl nitrate (or methyl dinitrate), which might supply a large, variable amount of 'missing NO(y) not currently measurable except by NO(y) instruments.
The Liquid Propellant Program (LPP) computer code is a super-set of the industry standard Two Dimensional Kinetics (TDK) computer code. The TDK code uses a two dimensional method of characteristics solution with fully coupled finite rate kinetics for axially symmetric nozzles. The chemical reactions are modeled with a generalized reaction package that include three dimensional body efficiencies and four reaction rate forms. The code performs optional solutions for frozen or equilibrium flow. TDK evaluates discrete shocks, both attached or induced. The Transonic module models variable mixture ratio profiles from the combustion chamber injector. The Mass Addition Boundary Layer module (MABL) calculates the boundary parameters with the same chemistry options, and includes transpiration or tangential slot injection of gas at the wall. The LPP upgrades include: planar nozzle, scarfed nozzles, plug nozzles, and scramjet nozzle configurations. The code evaluates both upper and lower wall flow simulation, and includes the interaction with the external flow. The MABL module evaluates equilibrium radiation heat transfer for both upper and lower walls. In addition, LPP code models combustion effects due to injector inefficiencies with the Spray Combustion Analysis Program (SCAP) module. The LPP package provides extensive post plotting capabilities for flow visualization. The LPP is sufficiently fast and robust to provide performance predictions for extensive parametric studies and sufficiently accurate to provide flow field and performance solutions for detailed studies.
The existing gasket seals used in electroplating of the Constellation-X mirrors are difficult to assemble, and the current seal material is hydrophobic and too thick. The combination of the above problems result in: 1) non-uniform plating; 2) defect sites such as pits on the mirror edges; 3) "bear claws" on the edges of the mandrels and mirrors causing difficulties in shell-mirror separations; and 4) leakage of the plating solution past the seals into the mandrel causing chemical etching of the mandrel interior. This paper reports the results of this summer study in searching for alternate seal materials chemically compatible with the electroplating solvent. Fifteen common elastomeric rubber seal materials made-by Parker Seals were investigated including butyl, ethylene propylene, fluorosilicone, nitrile, Viton fluorocarbon, and silicone. Test results showed that Viton fluorocarbon compounds as a group were superior to the other tested compounds for chemical compatibility with the plating bath.
MscL, a 15 kDa transmembrane protein, is the only component involved in the formation of a 3 nS channel in the inner membrane of Escherichia coli that opens in response to mechanical or osmotic stress. While previous data had suggested that the functional MscL complex might be a hexamer, a recent crystallographic study of the MscL homologue from M. tuberculosis reveals a pentameric structure. The present work further examines the stoichiometry of the E. coli MscL using a variety of biochemical approaches. Detergent-purified 6His-MscL in solution and MscL in the membrane could be chemically crosslinked with the products displaying ladderlike patterns on SDS gels. Three crosslinking agents (EDC, DMS, and DMA) used at saturating concentrations invariably generated pentamers as the largest product. DSS produced additional bands corresponding to larger complexes although the pentamer band appeared to be the predominant product at high levels of crosslinker. It is not clear whether these extra bands reflect a difference in the crosslinking chemistry of DSS or whether its spacer arm is the longest of those used, or a combination of both facts. For the detergent-solubilized 6His-MscL both sedimentation equilibrium and gel chromatography showed the presence of multiple species. Thus the longer spacer arm could permit both intra- and intercomplex linkages. Nonetheless, the patterns obtained with all agents are consistent with and strongly suggest a pentameric organization for the MscL channel. Expression of MscL as genetically engineered double or triple subunit tandems yields low numbers of functional channels as compared to expressed monomers. The double-tandem assemblies must have an even number of subunits and crosslinking in the membrane confirmed hexamerization. Gel chromatography clearly demonstrated that the channels formed from the double tandems were larger than those formed from WT MscL, consistent with the native channel being pentameric. The observation that both double and triple tandems form channels of normal conductance implies that the pentameric assembly is to some degree independent of the number of subunit repeats in the polypeptide precursor. The channel is thus a pentameric core with the 'extra' subunits left out of the functional complex. From sedimentation equilibrium and size-exclusion chromatography, we also conclude that MscL complexes are not in a dynamic equilibrium with monomers, but are pre-assembled; and thus, their gating properties must result from changes in the conformation of the entire complex induced by the mechanical stress.
Based in San Diego, KAIROS Scientific develops molecular biology methods, instrumentation, and computer algorithms to create solutions to challenging problems in the medical and chemical industries. company s pioneering efforts in digital imaging spectroscopy (DIS) enable researchers to obtain spectral and/or time-dependent information for each pixel or group of pixels in a two-dimensional scene. In addition to having Yang s NASA experience at its foundation, KAIROS Scientific was established with the support of many government grants and contracts. Its first was a NASA Small Business Innovation Research (SBIR) grant, from Ames Research Center, to develop HIRIM, a high-resolution imaging microscope embodying both novel hardware and software that can be used to simultaneously acquire hundreds of individual absorbance spectra from microscopic features. Using HIRIM s graphical user interface, MicroDIS, scientists and engineers are presented with a revolutionary new tool which enables them to point to a feature in an image and recall its associated spectrum in real time.
SiC SiC Ceramic Matrix Composites (CMCs) are a game changer for advanced power generation equipment because of their high temperature capability, oxidation resistance, and light weight that translate to significant reduction in fuel consumption and emission. Limitations of SiC SiC CMCs include surface recession and component cracking and associated chemical and physical degradation in the CMC. The solution pursued to mitigate surface recession of SiC SiC CMCs is the incorporation of coating systems that provide surface protection, which has become known as an Environmental Barrier Coating (EBC). The development of EBCs for the protection of SiC SiC CMCs was a continuation of coating development work for corrosion protection of silicon-based monolithics. The first and second generation EBCs developed in mid 1990s-early 2000s laid the foundation for current EBCs. Environmental degradation that limits EBC life includes surface recession by steam, oxidation in steam environments, and CMAS-EBC reactions. Many engine tests have been conducted since late 1990s and a first CMC component entered into service in 2016 in a commercial engine. The introduction of CMCs represents significant challenges as failure of the EBC means rapid reduction in component life. A reliable lifing method and engine-relevant testing methods to validate life need to be developed. This paper will current activities on EBC development and testing at NASA.
Supercritical Water Oxidation (SCWO) technology is under consideration by NASA for treatment of wastewater and other wet waste streams. The dramatic changes in water's thermophysical properties near its critical point (374◦C and 22 MPa) result in nearly complete solubility of organics and gases. The absence of inter–phase transport processes and phase separation results in dramatically reduced reaction timescales and the elimination of complications of two–phase transport and processing in reduced gravity. Other advantages are that the product streams are microbially inert,benign, amenable to resource recovery and organic waste. This paper first described the design and construction of tubular SCWO reactor built at NASA Glenn. It consists of separate wastewater and oxidizer inlets, which are independently heated and pressurized to conditions approaching the critical point of water. These flows enter a reactor chamber having a volume of 62 ml. The reactor section is heated to the desired temperature in the range of 450 ◦C – 650 ◦C. A pressure regulator maintains the operating pressure nominally between 27.6 MPa and 28.3 MPa. The reacted fluid is captured downstream of the pressure regulator during an experiment run. A separate vent line may also be used for collection of the effluent. Next, the results of SCWO experiments using both a representative organic (ethanol) as well as a wastewater simulant provided by NASA Ames are presented. Raman analysis of the pre–reacted and post–reacted solutions are presented. Finally, initial efforts on supplementary chemical kinetics modeling of ethanol oxidation with and without inclusion of a nitrogenous compounds (ammonia) are presented.
Kinetics of a reaction network that follows mass-action rate laws can be described with a system of ordinary differential equations (ODEs) with polynomial right-hand side. However, it is challenging to derive such kinetic differential equations from transient kinetic data without knowing the reaction network, especially when the data are incomplete due to experimental limitations. We introduce a program, PolyODENet, toward this goal. Based on the machine-learning method Neural ODE, PolyODENet defines a generative model and predicts concentrations at arbitrary time. As such, it is possible to include unmeasurable intermediate species in the kinetic equations. Importantly, we have implemented various measures to apply physical constraints and chemical knowledge in the training to regularize the solution space.
Here, the study of Eu intermetallic compounds has allowed the exploration of valence fluctuations and transitions in 4𝑓 electron systems. Recently, a Eu 2 Pt 6 Al 15 phase synthesized by arc-melting followed by a thermal treatment was reported M. Radzieowski et al. [J. Am. Chem. Soc. 140, 8950 (2018)], which undergoes a transition upon cooling below 45 K that was interpreted as a valence transition from Eu 2+ to Eu 3+ . In this paper, we present the discovery of another polymorph of Eu 2 Pt 6 Al 15 obtained by high temperature solution growth, which presents different physical properties than the arc-melted polycrystalline sample. Despite the similarities in crystal structure and chemical composition, the Eu valence transition is almost fully suppressed in the solution-grown crystals, allowing the moments associated with the Eu 2+ state to order antiferromagnetically at around 14 K. A detailed analysis of the crystal structure using single crystal x-ray diffraction reveals that, although the solution grown crystals are built from the same constituent layers as the arc-melted samples, these layers present a different stacking. The effect of different thermal treatments is also studied. Different anneal procedures did not result in significant changes in the intrinsic properties, and only by arc-melting and quenching the crystals we were able to convert them into the previously reported polymorph.
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