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At least 559 records · Page 31

Synthesis of temperature and solvent-resistant polymers

Development of silicone polymers, polyimides, and polyisocyanurates for use as insulation, coatings, or adhesives under adverse environmental conditions is discussed. Chemical structure of the organic compounds is presented. Physical and mechanical properties of the compounds are analyzed.

Webster, J. A.↗

Recent advances in chemical evolution and the origins of life

Consideration is given to the ideas of Oparin and Haldane who independently suggested more than 60 years ago that the first forms of life were anaerobic, heterotrophic bacteria that emerged as the result of a long period of chemical abiotic synthesis of organic compounds. It is suggested that at least some requirements for life are met in the Galaxy due to the cosmic abundance of carbon, nitrogen, oxygen, and other biogenic elements; the existence of extraterrestrial organic compounds; and the processes of stellar and interstellar planetary formation.

Oro, John↗

Survey of less-inflammable hydraulic fluids for aircraft

A survey of current information on civil and military development of less-inflammable hydraulic fluids for aircraft is presented. Types of less-inflammable fluid reported include: glycol derivative, water base, silicone, ester, and halogenated compound. Specification requirements, physical and chemical properties, hydraulic-system test results, and advantages and disadvantages of various hydraulic fluids are discussed. For completely satisfactory service, some modification of currently available fluids or of present hydraulic-system parts still appears necessary.

FRICTION AND LUBRICATION↗

National Emission Standards for Hazardous Air Pollutants (NESHAP) Memorandum of Agreement (MOA) Between NASA Headquarters and MSFC (Marshall Space Flight Center) for NASA Principal Center for Review of Clean Air Regulations

This paper presents a memorandum of agreement on Clean Air Regulations. NASA headquarters (code JE and code M) has asked MSFC to serve as principle center for review of Clean Air Act (CAA) regulations. The purpose of the principle center is to provide centralized support to NASA headquarters for the management and leadership of NASA's CAA regulation review process and to identify the potential impact of proposed CAA reguations on NASA program hardware and supporting facilities. The materials and processes utilized in the manufacture of NASA's programmatic hardware contain HAPs (Hazardous Air Pollutants), VOCs (Volatile Organic Compounds), and ODC (Ozone Depleting Chemicals). This paper is presented in viewgraph form.

Caruso, Salvadore V.↗

Exploration Challenges: Transferring Ground Repair Techniques to Space Flight Application

Fulfilling NASA's Vision for Space Exploration will demand an extended presence in space at distances from our home planet that exceed our current experience in space logistics and maintenance. The ability to perform repairs in lieu of the customary Orbital Replacement Unit (ORU) process where a faulty part is replaced will be elevated from contingency to routine to sustain operations. The use and cost effectiveness of field repairs for ground based operations in industry and the military have advanced with the development of technology in new materials, new repair techniques and new equipment. The unique environments, accessibility constraints and Extra Vehicular Activity (EVA) issues of space operations will require extensive assessment and evolution of these technologies to provide an equivalent and expected level of assurance to mission success. Challenges include the necessity of changes in design philosophy and policy, extremes in thermal cycling, disruptive forces (such as static charge and wind entrainment) on developed methods for control of materials, dramatically increased volatility of chemicals for cleaning and other compounds due to extremely low pressures, the limits imposed on dexterity and maneuverability by current EVA equipment and practices, and the necessity of unique verification methodology. This paper describes these challenges in and discusses the effects on the established ground techniques for repair. The paper also describes the leading repair methodology candidates and their beneficial attributes for resolving these issues with the evolution of technology.

McLemore, Carole A.↗

Nanoparticle/Polymer Nanocomposite Bond Coat or Coating

This innovation addresses the problem of coatings (meant to reduce gas permeation) applied to polymer matrix composites spalling off in service due to incompatibility with the polymer matrix. A bond coat/coating has been created that uses chemically functionalized nanoparticles (either clay or graphene) to create a barrier film that bonds well to the matrix resin, and provides an outstanding barrier to gas permeation. There is interest in applying clay nanoparticles as a coating/bond coat to a polymer matrix composite. Often, nanoclays are chemically functionalized with an organic compound intended to facilitate dispersion of the clay in a matrix. That organic modifier generally degrades at the processing temperature of many high-temperature polymers, rendering the clay useless as a nano-additive to high-temperature polymers. However, this innovation includes the use of organic compounds compatible with hightemperature polymer matrix, and is suitable for nanoclay functionalization, the preparation of that clay into a coating/bondcoat for high-temperature polymers, the use of the clay as a coating for composites that do not have a hightemperature requirement, and a comparable approach to the preparation of graphene coatings/bond coats for polymer matrix composites.

Miller, Sandi G.↗

Feasibility Study of Venus Surface Cooling Using Chemical Reactions with the Atmosphere

A literature search and theoretical analysis were conducted to investigate the feasibility of cooling a craft on Venus through chemical reformation of materials from the atmosphere. The core concept was to take carbon dioxide (CO2) from the Venus atmosphere and chemically reform it into simpler compounds such as carbon, oxygen, and carbon monoxide. This process is endothermic, taking energy from the surroundings to produce a cooling effect. A literature search was performed to document possible routes for achieving the desired reactions. Analyses indicated that on Venus, this concept could theoretically be used to produce cooling, but would not perform as well as a conventional heat pump. For environments other than Venus, the low theoretical performance limits general applicability of this concept, however this approach to cooling may be useful in niche applications. Analysis indicated that environments with particular atmospheric compositions and temperatures could allow a similar cooling system to operate with very good performance. This approach to cooling may also be useful where the products of reaction are also desirable, or for missions where design simplicity is valued. Conceptual designs for Venus cooling systems were developed using a modified concept, in which an expendable reactant supply would be used to promote more energetically favorable reactions with the ambient CO2, providing cooling for a more limited duration. This approach does not have the same performance issues, but the use of expendable supplies increases the mass requirements and limits the operating lifetime. This paper summarizes the findings of the literature search and corresponding analyses of the various cooling options.

Evans, Christopher↗

Feasibility Study of Venus Surfuce Cooling Using Chemical Reactions with the Atmosphere

A literature search and theoretical analysis were conducted to investigate the feasibility of cooling a craft on Venus through chemical reformation of materials from the atmosphere. The core concept was to take carbon dioxide (CO2) from the Venus atmosphere and chemically reform it into simpler compounds such as carbon, oxygen, and carbon monoxide. This process is endothermic, taking energy from the surroundings to produce a cooling effect. A literature search was performed to document possible routes for achieving the desired reactions. Analyses indicated that on Venus, this concept could theoretically be used to produce cooling, but would not perform as well as a conventional heat pump. For environments other than Venus, the low theoretical performance limits general applicability of this concept, however this approach to cooling may be useful in niche applications. Analysis indicated that environments with particular atmospheric compositions and temperatures could allow a similar cooling system to operate with very good performance. This approach to cooling may also be useful where the products of reaction are also desirable, or for missions where design simplicity is valued. Conceptual designs for Venus cooling systems were developed using a modified concept, in which an expendable reactant supply would be used to promote more energetically favorable reactions with the ambient CO2, providing cooling for a more limited duration. This approach does not have the same performance issues, but the use of expendable supplies increases the mass requirements and limits the operating lifetime. This paper summarizes the findings of the literature search and corresponding analyses of the various cooling options

Evans, Christopher↗

Beginning of Viniculture in France

Chemical analyses of ancient organic compounds absorbed into the pottery fabrics of imported Etruscan amphoras (ca. 500-475 B.C.) and into a limestone pressing platform (ca. 425-400 B.C.) at the ancient coastal port site of Lattara in southern France provide the earliest biomolecular archaeological evidence for grape wine and viniculture from this country, which is crucial to the later history of wine in Europe and the rest of the world. The data support the hypothesis that export of wine by ship from Etruria in central Italy to southern Mediterranean France fueled an ever-growing market and interest in wine there, which, in turn, as evidenced by the winepress, led to transplantation of the Eurasian grapevine and the beginning of a Celtic industry in France. Herbal and pine resin additives to the Etruscan wine point to the medicinal role of wine in antiquity, as well as a means of preserving it during marine transport.

ancient medicine↗

Beginning of Viniculture in France

Chemical analyses of ancient organic compounds absorbed into the pottery fabrics of imported Etruscan amphoras (ca. 500-475 B.C.) and into a limestone pressing platform (ca. 425-400 B.C.) at the ancient coastal port site of Lattara in southern France provide the earliest biomolecular archaeological evidence for grape wine and viniculture from this country, which is crucial to the later history of wine in Europe and the rest of the world. The data support the hypothesis that export of wine by ship from Etruria in central Italy to southern Mediterranean France fueled an ever-growing market and interest in wine there, which, in turn, as evidenced by the winepress, led to transplantation of the Eurasian grapevine and the beginning of a Celtic industry in France. Herbal and pine resin additives to the Etruscan wine point to the medicinal role of wine in antiquity, as well as a means of preserving it during marine transport.

biomolecular archaeology↗

Conversion and Extraction of Insoluble Organic Materials in Meteorites

We endeavor to develop and implement methods in our laboratory to convert and extract insoluble organic materials (IOM) from low car-bon bearing meteorites (such as ordinary chondrites) and Precambrian terrestrial rocks for the purpose of determining IOM structure and prebiotic chemistries preserved in these types of samples. The general scheme of converting and extracting IOM in samples is summarized in Figure 1. First, powdered samples are solvent extracted in a micro-Soxhlet apparatus multiple times using solvents ranging from non-polar to polar (hexane - non-polar, dichloromethane - non-polar to polar, methanol - polar protic, and acetonitrile - polar aprotic). Second, solid residue from solvent extractions is processed using strong acids, hydrochloric and hydrofluoric, to dissolve minerals and isolate IOM. Third, the isolated IOM is subjected to both thermal (pyrolysis) and chemical (oxidation) degradation to release compounds from the macromolecular material. Finally, products from oxidation and pyrolysis are analyzed by gas chromatography - mass spectrometry (GCMS). We are working toward an integrated method and analysis scheme that will allow us to determine prebiotic chemistries in ordinary chondrites and Precambrian terrestrial rocks. Powerful techniques that we are including are stepwise, flash, and gradual pyrolysis and ruthenium tetroxide oxidation. More details of the integrated scheme will be presented.

Locke, Darren R.↗

Triton Hopper: Exploring Neptune's Captured Kuiper Belt Object

Neptune's moon Triton is a fascinating object, a dynamic moon with an atmosphere, and geysers. Triton is unique in the outer solar system in that it is most likely a captured Kuiper belt object (KBO), a leftover building block of the solar system. When Voyager flew by it was the coldest body yet found in our solar system (33 degrees Kelvin) and had volcanic activity, geysers, and a thin atmosphere. It is covered in ices made from nitrogen, water, and carbon-dioxide, and shows surface deposits of tholins, organic compounds that may be precursor chemicals to the origin of life. Exploring Triton will be a challenge well beyond anything done in previous missions; but the unique environment of Triton also allows some new possibilities for mobility. We developed a conceptual design of a Triton Hopping probe that both analyzes the surface and collects it for use to propel its hops. The Hopper would land near the South Pole in 2040 where geysers have been detected. Depending the details of propulsion chosen the Hopper should be able to jump over 300 kilometers in 60 hops or less, exploring the surface and thin atmosphere on its way. This craft will autonomously carry out detailed scientific investigations on the surface, below the surface (drilling) and in the upper atmosphere to provide unprecedented knowledge of a KBO-turned moon and expanding NASA's existing capabilities in deep space planetary exploration to include Hoppers using different ices for propellant. Triton is roughly 2700 kilometers in diameter with a surface of mostly frozen nitrogen, mostly water ice crust and core of metal and rock. Its gravity is half that of Earth's Moon and its atmosphere is 170,000th of Earth's or 0.3 of Mars.The mission concept studied investigated the full surface and atmospheric phenomenon: chemical composition of surface and near subsurface materials, the thin atmosphere, volcanic and geyser activity. Measurements of all these aspects of Triton's unique environment can only be made through focused in-situ exploration with a well-instrumented craft. And this craft will be provided revolutionary mobility, nearly global, using in-situ ices as propellants. While other concepts have looked at gathering gases at Mars to propel a hopper, long periods of time are needed to gather the thin CO2 atmosphere. Several gases, mainly nitrogen are on the surface in a readily dense ice form and just need to be picked up, vaporized and used for propellant.

low conductivity materials↗

Characterizing and Engineering Trehalose Biosynthesis Pathways to Improve Acetate Tolerance in Pseudomonas putida KT2440

Alkaline pretreatment can depolymerize lignin into a diverse mixture of monomers and smaller compounds, enabling bioconversion of these compounds to value-added chemicals in engineered bacterial hosts such as Pseudomonas putida KT2440. Acetate and salts comprise approximately 8% and 32% of the lignin stream, respectively. High concentrations of these components can cause cell death in P. putida, so lignin-derived streams must be fed in lower amounts to decrease stress. Investigation of the mechanisms of bacterial tolerance to chemicals in lignin-rich substrates is therefore required to overcome this obstacle in lignin bioconversion. Previous work has shown that trehalose, an endogenously produced disaccharide, is involved in tolerance to heat, cold, and osmotic stress, as well as implicated in acid stress in other bacteria. As such, trehalose biosynthesis presents a useful target to increase acetate and osmotic tolerance in P. putida. This work investigates the native TreSA, TreSB, and TreY/TreZ trehalose biosynthesis pathways in this bacterial strain as well as the OtsAB pathway of Sphingobium sp. SYK-6. Overexpression of the OtsAB pathway in P. putida increased tolerance to acetate relative to wild-type. Additionally, functional knockouts of treSA, treSB, treY, and treZ in P. putida showed that interruption of any trehalose biosynthesis pathway, and, in the case of TreY/TreZ, interruption of the pathway at any point, significantly hindered growth in acetate as well as on glucose and LB broth. Each trehalose biosynthesis pathway was then engineered for overexpression in P. putida to determine whether overexpression of these genes conferred additional tolerance to acetate. The TreSA, TreSB, OtsA, and OtsB enzymes were also expressed and purified to determine the reaction rates and kinetics of these pathways. The hypothetical glycoside hydrolase family 15 protein, encoded in the gene located in between otsB and otsA in the Sphingobium operon, was purified as well to investigate its potential involvement in the OtsAB pathway. The findings of this work illuminated the mechanisms of trehalose biosynthesis in P. putida and identified genetic targets to improve strain tolerance to common components of alkaline-pretreated lignin streams. These findings could ultimately improve yields of desired products from lignin in engineered strains of P. putida.

alkaline pretreatment↗

Facet Preferencing by Chemical Substitution Controls Semi-Hydrogenation Selectivity in Ternary Pyrite-Type Intermetallic Compounds

Intermetallic compounds serve as model catalysts for selective hydrogenation reactions, offering precise control over the active site composition(s), geometric and electronic structure. The addition of a third element to form a ternary intermetallic alters the exposed crystal facet(s), demonstrating a strategy to impart improved catalytic behavior in intermetallic catalysts. The site-specific substitution of a small fraction of Pd atoms with Au in pyrite-type PdSb 2 results in the preferential exposure of the (100) facet over the (111) facet. Electron back scattered diffraction and density functional theory calculations confirm the facet change upon the substitution of Pd with Au to form the ternary Pd 1−x Au x Sb 2 (0.075 ≤ x ≤ 0.25). The (100) facet demonstrates higher net alkene selectivity due to significantly weaker alkene binding compared to the (111) facet. Distinct from our prior work on chemical substitution to directly alter the active site composition, this work demonstrates the indirect modification of active sites via preferential facet exposure.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Local cation order and ferrimagnetism in compositionally complex spinel ferrites

We present an exploration of a family of compositionally complex cubic spinel ferrites featuring combinations of Mg, Fe, Co, Ni, Cu, Mn, and Zn cations, systematically investigating the average and local atomic structures, chemical short-range order, magnetic spin configurations, and magnetic properties. All compositions result in ferrimagnetic average structures with extremely similar local bonding environments; however, the samples display varying degrees of cation inversion and, therefore, differing apparent bulk magnetization. Additionally, first-order reversal curve analysis of the magnetic reversal behavior indicates varying degrees of magnetic ordering and interactions, including potentially local frustration. Finally, reverse Monte Carlo modeling of the spin orientation demonstrates a relationship between the degree of cation inversion and the spin collinearity. Collectively, these observations correlate with differences in synthesis procedures. This work provides a framework for understanding magnetic behavior reported for “high-entropy spinels,” revealing many are likely compositionally complex oxides with differing degrees of chemical short-range order—not meeting the community established criteria for high or medium entropy compounds. Moreover, this work highlights the importance of reporting complete sample processing histories and investigating local to long-range atomic arrangements when evaluating potential entropic mixing effects and assumed property correlations in high entropy materials.

36 MATERIALS SCIENCE↗

A Novel Surface Treatment for Titanium Alloys

High-speed commercial aircraft require a surface treatment for titanium (Ti) alloy that is both environmentally safe and durable under the conditions of supersonic flight. A number of pretreatment procedures for Ti alloy requiring multi-stages have been developed to produce a stable surface. Among the stages are, degreasing, mechanical abrasion, chemical etching, and electrochemical anodizing. These treatments exhibit significant variations in their long-term stability, and the benefits of each step in these processes still remain unclear. In addition, chromium compounds are often used in many chemical treatments and these materials are detrimental to the environment. Recently, a chromium-free surface treatment for Ti alloy has been reported, though not designed for high temperature applications. In the present study, a simple surface treatment process developed at NASA/LaRC is reported, offering a high performance surface for a variety of applications. This novel surface treatment for Ti alloy is conventionally achieved by forming oxides on the surface with a two-step chemical process without mechanical abrasion. This acid-followed-by-base treatment was designed to be cost effective and relatively safe to use in a commercial application. In addition, it is chromium-free, and has been successfully used with a sol-gel coating to afford a strong adhesive bond after exposure to hot-wet environments. Phenylethynyl containing adhesives were used to evaluate this surface treatment with sol-gel solutions made of novel imide silanes developed at NASA/LaRC. Oxide layers developed by this process were controlled by immersion time and temperature and solution concentration. The morphology and chemical composition of the oxide layers were investigated using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Auger electron spectroscopy (AES). Bond strengths made with this new treatment were evaluated using single lap shear tests.

Lowther, S. E.↗

Production of itaconic acid from alkali pretreated lignin by dynamic two stage bioconversion

Abstract Expanding the portfolio of products that can be made from lignin will be critical to enabling a viable bio-based economy. Here, we engineer Pseudomonas putida for high-yield production of the tricarboxylic acid cycle-derived building block chemical, itaconic acid, from model aromatic compounds and aromatics derived from lignin. We develop a nitrogen starvation-detecting biosensor for dynamic two-stage bioproduction in which itaconic acid is produced during a non-growth associated production phase. Through the use of two distinct itaconic acid production pathways, the tuning of TCA cycle gene expression, deletion of competing pathways, and dynamic regulation, we achieve an overall maximum yield of 56% (mol/mol) and titer of 1.3 g/L from p -coumarate, and 1.4 g/L titer from monomeric aromatic compounds produced from alkali-treated lignin. This work illustrates a proof-of-principle that using dynamic metabolic control to reroute carbon after it enters central metabolism enables production of valuable chemicals from lignin at high yields by relieving the burden of constitutively expressing toxic heterologous pathways.

59 BASIC BIOLOGICAL SCIENCES↗