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Fire Safety in Extraterrestrial Environments

Despite rigorous fire-safety policies and practices, fire incidents are possible during lunar and Martian missions. Fire behavior and hence preventive and responsive safety actions in the missions are strongly influenced by the low-gravity environments in flight and on the planetary surfaces. This paper reviews the understanding and key issues of fire safety in the missions, stressing flame spread, fire detection, suppression, and combustion performance of propellants produced from Martian resources.

Friedman, Robert↗

Combustion of Metals in Reduced-Gravity and Extraterrestrial Environment

As a result of the ongoing exploration of Mars and the several unmanned and manned missions planned for the future, increased attention has been given to the use of the natural resources of the planet for rocket propellant production and energy generation. Since the atmosphere of Mars consists of approximately 95% carbon dioxide (CO2), this gas is the resource of choice to be employed for these purposes. Unfortunately, CO2 is also a final product in most combustion reactions, requiring further processing to extract useful reactants such as carbon monoxide (CO), oxygen (O2), and hydrocarbons. An exception is the use Of CO2 as an oxidizer reacting directly with metal fuel. Since many metals burn vigorously with CO2, these may be used as an energy source and as propellants for an ascent/descent vehicle in sample-collection missions on Mars. In response to NASA's Human Exploration and Development of Space (HEDS) Enterprise to search for appropriate in-situ resource utilization techniques, this investigation will study the burning characteristics of promising metal/CO2 combinations. The use of reduced gravity is essential to eliminate the intrusive buoyant flows that plague the high-temperature metal reactions, to remove the destructive effect of gravity on the shape of molten metal samples, and to study the influence of radiative heat transfer from solid oxides undisturbed by natural convection. In studies with large metal specimens, the burning process is invariably influenced by strong convective currents that accelerate the reaction and shorten the burning times. Although these currents are nearly absent from small burning particles, the high emissivity of the flames, rapid reaction, small length scales, and intermittent explosions make the gathering of any useful information on burning rates and flame structure very difficult. This investigation has the ultimate goal of providing a careful probing of flame structure and dynamics by taking advantage of large, free-floating spherical metal samples and their corresponding long burning times available in reduced gravity. The first set of experiments has been conducted with magnesium (Mg) samples burning in the low-gravity environment generated by an aircraft flying parabolic trajectories. Owing to its high adiabatic flame temperature, oxidizer/fuel ratio, and heat per unit mass of fuel, as well as its low toxicity and low ignition temperature, Mg has been identified as a promising metal fuel with CO2 as oxidizer. The experimental effort is complemented by the development of a numerical model combining gas-phase chemical kinetics and transport mechanisms.

Abbud-Madrid, A.↗

Combustion of Metals in Reduced-Gravity and Extraterrestrial Environments

As a result of the ongoing exploration of Mars and the several unmanned and possibly manned missions planned for the near future, increased attention has been given to the use of the natural resources of the planet for rocket propellant production and energy generation. Since the atmosphere of Mars consists of approximately 95% carbon dioxide (CO2), this gas is the resource of choice to be employed for these purposes. Since many metals burn vigorously with CO2, these may be used as an energy source or as propellants for a research vehicle on the surface of Mars. Shafirovich and Goldshleger conducted experiments with spherical particles up to 2.5 mm in diameter and found that the burning process was controlled by diffusion and that the particles exhibited pulsating combustion due to superheating of the Mg vapor trapped inside a protective oxide shell. They also proposed a reaction mechanism based on the gas-phase reaction, Mg + CO2 yields MgO + CO and the heterogeneous reaction Mg + CO yields MgO + C occurring on the sample surface. In all the above studies with large Mg particles, the burning process is invariably influenced by strong convective currents that accelerate the combustion reaction and shorten the burning times. Although these currents are nearly absent in the burning of small particles, the high emissivity of the flames, rapid reaction, and small length scales make the gathering of any useful information on burning rates and flame structure very difficult. The goal of this investigation is to provide a detailed study of flame structure by taking advantage of large, free-floating spherical metal samples and their corresponding long burning times available in a weightless environment. The use of reduced gravity is essential to eliminate the intrusive buoyant flows that plague high temperature metal reactions, to remove the destructive effect of gravity on the shape of molten metal samples, and to study the combustion behavior of metals in the presence of solid oxides undisturbed by natural convection. This work presents the most complete modeling of metal particle burning to date for Mg with CO2 and O2.

Branch, M. C.↗

Combustion Of Metals In Reduced Gravity And Extraterrestrial Environments

The recent focus of this research project has been to model the combustion of isolated metal droplets and, in particular, to couple the existing theories and formulations of phenomena such as condensation, reaction kinetics, radiation, and surface reactions to formulate a more complete combustion model. A fully transient, one-dimensional (spherical symmetry) numerical model that uses detailed chemical kinetics, multi-component molecular transport mechanisms, condensation kinetics, and gas phase radiation heat transfer was developed. A coagulation model was used to simulate the particulate formation of MgO. The model was used to simulate the combustion of an Mg droplet in pure O2 and CO2. Methanol droplet combustion is considered as a test case for the solution method for both quasi-steady and fully transient simulations. Although some important processes unique to methanol combustion, such as water absorption at the surface, are not included in the model, the results are in sufficient agreement with the published data. Since the major part of the heat released in combustion of Mg, and in combustion of metals in general, is due to the condensation of the metal oxide, it is very important to capture the condensation processes correctly. Using the modified nucleation theory, an Arrhenius type rate expression is derived to calculate the condensation rate of MgO. This expression can be easily included in the CHEMKIN reaction mechanism format. Although very little property data is available for MgO, the condensation rate expression derived using the existing data is able to capture the condensation of MgO. An appropriate choice of the reference temperature to calculate the rate coefficients allows the model to correctly predict the subsequent heat release and hence the flame temperature.

Abbud-Madrid, A.↗

Miniature Gas Chromatograph (GC): Penning Ionization Electron Spectroscopy (PIES) Instrument for the Trace Analyses of Extraterrestrial Environments

In situ exploration of the solar system to identify its early chemistry as preserved in icy bodies and to look for compelling evidence of astrobiology will require new technology for chemical analysis. Chemical measurements in space flight environments highlight the need for a high level of positive identification of chemical compounds, since re-measurement by alternative techniques for confirmation will not be feasible. It also may not be possible to anticipate all chemical species that are observed, and important species may be present only at trace levels where they can be masked by complex chemical backgrounds. Up to now, the only techniques providing independent sample identification of GC separated components across a wide range of chemical species have been Mass Spectrometry (MS) and Ion Mobility Spectrometry (IMS). We describe here the development of a versatile and robust miniature GC detector based on Penning Ionization Electron Spectroscopy (PIES), for use with miniature GC systems being developed for planetary missions. PIES identifies the sample molecule through spectra related to its ionization potential. The combination of miniature GC technology with the primary identification capabilities of PIES provides an analytical approach ideal for planetary analyses.

Kojiro, Daniel R.↗

The Health Risks of Extraterrestrial Environments (THREE) 2019 Annual Report

THREE is an encyclopedic website (http://three.jsc.nasa.gov) about the space radiation environment and its health risks to humans. The goal for the site is threefold: 1. to serve as a starting point for researchers new to either space, radiation, or both; 2. to serve as a source of useful information for established investigators; 3. to serve as a teaching tool for students; and, 4. to serve as a NASA reference source on all scientific aspects of space radiation and health. THREE is funded by the Space Radiation (SR) Element within NASA’s Human Research Program (HRP). The THREE Editorial Board is responsible for oversight of the content and policies for the website. The website is hosted by the NASA Johnson Space Center.

Schimmerling, Walter↗

Analysis of Electrical Characteristics of Thin Film Photovoltaic Cells

Solar energy is the most abundant form of energy in many terrestrial and extraterrestrial environments. Often in extraterrestrial environments sunlight is the only readily available form of energy. Thus the ability to efficiently harness solar energy is one of the ultimate goals in the design of space power systems. The essential component that converts solar energy into electrical energy in a solar energy based power system is the photovoltaic cell. Traditionally, photovoltaic cells are based on a single crystal silicon absorber. While silicon is a well understood technology and yields high efficiency, there are inherent disadvantages to using single crystal materials. The requirements of weight, large planar surfaces, and high manufacturing costs make large silicon cells prohibitively expensive for use in certain applications. Because of silicon s disadvantages, there is considerable ongoing research into alternative photovoltaic technologies. In particular, thin film photovoltaic technologies exhibit a promising future in space power systems. While they are less mature than silicon, the better radiation hardness, reduced weight, ease of manufacturing, low material cost, and the ability to use virtually any exposed surface as a substrate makes thin film technologies very attractive for space applications. The research group lead by Dr. Hepp has spent several years researching copper indium disulfide as an absorber material for use in thin film photovoltaic cells. While the group has succeeded in developing a single source precursor for CuInS2 as well as a unique method of aerosol assisted chemical vapor deposition, the resulting cells have not achieved adequate efficiencies. While efficiencies of 11 % have been demonstrated with CuInS2 based cells, the cells produced by this group have shown efficiencies of approximately 1 %. Thus, current research efforts are turning towards the analysis of the individual layers of these cells, as well as the junctions between them, to determine the cause of the poor yields. As a student of electrical engineering with some material science background, my role in this research is to develop techniques for analyzing the electrical characteristics of the CuInS2 cells. My first task was to design a shadow mask to be used to place molybdenum contacts under a layer of CuInS;! in order to analyze the contact resistance between the materials. In addition, I have also analyzed evaporated aluminum top contacts and have tested various methods of increasing their thicknesses in order to decrease series resistance. More recently I have worked with other members of the research group in reviving a vertical cold-wall reactor for experimentation with CuInS2 quantum dots. As part of that project, I have improved the design for a variable frequency and pulse width square wave generator to be used in driving the precursor injection process. My task throughout the remainder of my tenure is to continue to analyze and develop tools for the analysis of electrical properties of the CuInS2 cells with the ultimate goal of discovering ways to improve the efficiency of our photovoltaic cells. Traditionally, photovoltaic cells are based on a single crystal silicon absorber. While The research group lead by Dr. Hepp has spent several years researching copper indium

Kasick, Michael P.↗

A Structural and Molecular Approach for the Study Biomarkers

Investigation of the nucleation and growth of crystals in both abiotic and biotic systems is critical to seemingly diverse disciplines of geology, biology, environmental science, and astrobiology. While there are abundant studies devoted to the determination of the structure and composition of inorganic crystals, as well as to the development of thermodynamic and kinetic models, it is only recently that research efforts have been directed towards understanding mineralization in biological systems (i.e., biomineralization). Biomineralization refers to the processes by which living organisms form inorganic solids. Studies of the processes of biomineralization under low temperature aqueous conditions have focused primarily on magnetite forming bacteria and shell forming marine organisms. Many of the biological building materials consist of inorganic minerals (calcium carbonate, calcium phosphate, silica or iron oxide) intricately combined with organic polymers (like proteins). More recently, efforts have been undertaken to explore the nature of biological activities in ancient rocks. In the absence of well-preserved microorganisms or genetic material required for the polmerase chain reaction (PCR) method in molecular phylogenetic studies, using biominerals as biomarkers offers an alternative approach for the recognition of biogenic activity in both terrestrial and extraterrestrial environments. The primary driving force in biomineralization is the interaction between organic and inorganic phases. Thus, the investigation of the ultrastructure and the nature of reactions at the molecular level occurring at the interface between inorganic and organic phases is essential to understanding the processes leading to the nucleation and growth of crystals. It is recognized that crystal surfaces can serve as the substrate for the organization of organic molecules that lead to the formation of polymers and other complex organic molecules, and in discussions of the origins of life, is referred to as organic synthesis on mineral surfaces. Furthermore, it is suggested that the interaction between mineral surfaces and simple organic molecules resulted in the formation of amino acids, RNA, and perhaps other more complex molecules such as proteins. On the other hand, in natural systems, it is recognized that functional groups on cell walls or membranes of microorganisms serve as sites of nucleation and crystallization. The precise replication of biominerals with controlled structure, morphology, size and texture is not confined to higher organisms as it also occurs in primitive prokaryotic cells such as magnetotactic bacteria and cyanobacteria. This suggests that the principal strategies of biomineralization were established early on in the evolutionary history of organisms. It is critical, therefore, to search for common mechanisms within diverse biological systems. One such common factor is the capability for organization and self-assembly. Organic macromolecules such as proteins and lipids can aggregate and polymerize forming membranes or extracellular matrix. At the organic-inorganic interface, several factors such as lattice geometry, polarity, stereochemistry and topography may act in concert to control nucleation and growth of crystals. Although several models have been proposed that discuss the significance of these factors for biomineralization, no comprehensive experimental data are available. In contrast to crystallization in exclusively inorganic systems, the kinetics of reaction and structural relationships between organic and inorganic phases in biominerals or biomimetic material is poorly understood. For example, it is not clear if the concept of epitactic growth (geometrical matching of unit cells at the interface of a secondary crystal growing on a primary crystal) applies to organic-inorganic systems. In contrast to inorganic templates that often have a smooth and rigid surface that promotes epitactic growth, biological substrates are usually rough and result in a large degree of mismatch. It is apparent that factors controlling the reaction at the crystal-matrix interface are strongly dependent upon the nature of the substrate. Therefore, characterization of the assembled organic surface and surface structure of the inorganic phase is crucial to understanding the processes of biomineralization. The focus of our research is the investigation of the processes leading to the nucleation and growth of crystals on both natural and synthetic systems through an interdisciplinary approach that integrates molecular biology, morphology and mineralogy using advanced preparation and analytical techniques. We have studied run-products, particularly magnetite, siderite and other carbonates, that resulted from extracellular biomineralization by extremophiles isolated from a variety of extreme environments ranging from permafrost to hydrothermal vent systems. The results of this study are critical to recognizing biomarkers in terrestrial and extraterrestrial environments.

Thomas-Keprta, Kathie↗

Rockballer Sample Acquisition Tool

It would be desirable to acquire rock and/or ice samples that extend below the surface of the parent rock or ice in extraterrestrial environments such as the Moon, Mars, comets, and asteroids. Such samples would allow measurements to be made further back into the geologic history of the rock, providing critical insight into the history of the local environment and the solar system. Such samples could also be necessary for sample return mission architectures that would acquire samples from extraterrestrial environments for return to Earth for more detailed scientific investigation.

Giersch, Louis R.↗

Exploring the chemical dynamics of phenanthrene (C 14 H 10 ) formation via the bimolecular gas-phase reaction of the phenylethynyl radical (C 6 H 5 CC) with benzene (C 6 H 6 )

The exploration of the fundamental formation mechanisms of polycyclic aromatic hydrocarbons (PAHs) is crucial for the understanding of molecular mass growth processes leading to two- and three-dimensional carbonaceous nanostructures (nanosheets, graphenes, nanotubes, buckyballs) in extraterrestrial environments (circumstellar envelopes, planetary nebulae, molecular clouds) and combustion systems. While key studies have been conducted exploiting traditional, high-temperature mechanisms such as the hydrogen abstraction–acetylene addition (HACA) and phenyl addition–dehydrocyclization (PAC) pathways, the complexity of extreme environments highlights the necessity of investigating chemically diverse mass growth reaction mechanisms leading to PAHs. Employing the crossed molecular beams technique coupled with electronic structure calculations, we report on the gas-phase synthesis of phenanthrene (C 14 H 10 )—a three-ring, 14π benzenoid PAH—via a phenylethynyl addition–cyclization–aromatization mechanism, featuring bimolecular reactions of the phenylethynyl radical (C 6 H 5 CC, X 2 A 1 ) with benzene (C 6 H 6 ) under single collision conditions. The dynamics involve a phenylethynyl radical addition to benzene without entrance barrier leading eventually to phenanthrene via indirect scattering dynamics through C 14 H 11 intermediates. The barrierless nature of reaction allows rapid access to phenanthrene in low-temperature environments such as cold molecular clouds which can reach temperatures as low as 10 K. Furthermore, this mechanism constitutes a unique, low-temperature framework for the formation of PAHs as building blocks in molecular mass growth processes to carbonaceous nanostructures in extraterrestrial environments thus affording critical insight into the low-temperature hydrocarbon chemistry in our universe.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laboratory Studies of Astronomical Ices: Reaction Chemistry and Spectroscopy

In this article, we will describe the work of the Cosmic Ice Laboratory at NASA’s Goddard Space Flight Center to characterize the composition of and to understand the chemistry occurring in icy bodies in the Solar System and beyond. Our work has touched on a wide range of extraterrestrial environments including icy interstellar grains, small bodies such as comets and asteroids, and planets and moons. We are especially interested in the chemical and physical changes that occur in ices as a result of thermal changes or exposure to radiation. To this end, we conduct experiments designed to simulate cold extraterrestrial environments and measure physical properties of single- and multi-component ices. We expose ices to radiation (e.g., MeV protons or keV-MeV electrons) or high-energy photons (e.g., UV) to initiate physical and chemical changes. We conduct experiments using cryo-vacuum chambers equipped with analytical tools and radiation sources to make most of our measurements, including the collection of all spectroscopic data,in situ. When possible and appropriate, we also collect reaction products for further ex situ analysis. The work of the Cosmic Ice Lab provides critical data to astrochemists and others seeking to understand observations, make predictions, and plan future space missions.

Christopher K Materese↗

Autonomous Assembly of Modular Structures in Space and on Extraterrestrial Locations

The new U.S. National Vision for Space Exploration requires many new enabling technologies to accomplish the goals of space commercialization and returning humans to the moon and extraterrestrial environments. Traditionally, flight elements are complete subsystems requiring humans to complete the integration and assembly. These bulky structures also require the use of heavy launch vehicles to send the units to a desired location. This philosophy necessitates a high degree of safety, numerous space walks at a significant cost. Future space mission costs must be reduced and safety increased to reasonably achieve exploration goals. One proposed concept is the autonomous assembly of space structures. This concept is an affordable, reliable solution to in-space and extraterrestrial assembly. Assembly is autonomously performed when two components join after determining that specifications are correct. Local sensors continue monitor joint integrity post assembly, which is critical for safety and structural reliability. Achieving this concept requires a change in space structure design philosophy and the development of innovative technologies to perform autonomous assembly. Assembly of large space structures will require significant numbers of integrity sensors. Thus simple, low-cost sensors are integral to the success of this concept. This paper addresses these issues and proposes a novel concept for assembling space structures autonomously. Core technologies required to achieve in space assembly are presented. These core technologies are critical to the goal of utilizing space in a cost efficient and safe manner. Additionally, these novel technologies can be applied to other systems both on earth and extraterrestrial environments.

Alhorn, Dean C.↗

Low-temperature formation of pyridine and (iso)quinoline via neutral–neutral reactions

Aromatic molecules represent fundamental building blocks in prebiotic chemistry and are contemplated as vital precursors to DNA and RNA nitrogen bases. However, despite the identification of some 300 molecules in extraterrestrial environments, the pathways to pyridine (C 5 H 5 N), pyridinyl (C 5 H 4 N•), and (iso)quinoline (C 9 H 7 N) – the simplest represen-tative of mono and bicyclic aromatic molecule carrying nitrogen – are elusive. Here, we afford compelling evidence on the gas-phase formation of methylene amidogen (H 2 CN•) and cyanomethyl (H 2 CCN•) radicals via molecular beam studies and electronic structure calcula-tions. The modeling of the chemistries of Taurus Molecular Cloud (TMC-1) and Titan’s atmosphere contemplates a complex chain of reactions synthesizing pyridine, pyridinyl, and (iso)quinoline from H 2 CN• and H 2 CCN• at levels of up to 75%. Furthermore, this study affords unique entry points to precursors of DNA and RNA nitrogen bases in hydrocarbon-rich extraterrestrial environments thus changing the way we think about the origin of prebiotic molecules in our Galaxy.

79 ASTRONOMY AND ASTROPHYSICS↗