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Dust That's Worth Keeping

Images taken of interstellar space often display a colorful canvas of portions of the electromagnetic spectrum. Dispersed throughout the images are interstellar clouds of dust and gas--remnants ejected from stars and supernovae over billions and billions of years. For more than 40 years, astronomers have observed that interstellar dust exhibits a consistent effect at a spectral wavelength of 2,175 angstroms, the equivalent of 5.7 electronvolts in energy on the electromagnetic spectrum. At this wavelength, light from stars is absorbed by dust in the interstellar medium, blocking the stars light from reaching Earth. The 2,175-angstrom feature, which looks like a bump on spectra, is the strongest ultraviolet-visible light spectral signature of interstellar dust and is visible along nearly every observational line of sight. Scientists have sought to solve the mystery of what causes the 2,175-angstrom feature by reproducing the effect in the laboratory. They speculated a number of possibilities, including fullerenes (buckyballs), nanodiamonds, and even interstellar organisms. However, none of these materials fits the data for the unique spectral feature. Limitations in the energy and spatial resolution achievable with electron microscopes and ion microprobes--the two main instruments used to study samples of dust--have also prevented scientists from finding the answer. A collaborative effort led by Livermore physicist John Bradley and funded by the National Aeronautics and Space Administration (NASA) has used a new-generation transmission electron microscope (TEM) and nanoscale ion microprobe to unlock the mystery. The Livermore group includes physicists Zu Rong Dai, Ian Hutcheon, Peter Weber, and Sasa Bajt and postdoctoral researchers Hope Ishii, Giles Graham, and Julie Smith. They collaborated with the University of California at Davis (UCD), Lawrence Berkeley National Laboratory, Washington University's Laboratory for Space Sciences in St. Louis, and NASA's Ames Research Center for their discovery. The team analyzed micrometer-size interplanetary dust particles (IDPs), each about one-tenth the diameter of a human hair. Within the particles, they found carriers of the 2,175-angstrom feature: organic carbon mixed with amorphous silicates (glass with embedded metals and sulfides, GEMS), two of the most common materials in interstellar space. Ishii says, 'Organic carbon and amorphous silicates are abundant in interstellar dust clouds, and abundant carriers are needed to account for the frequent astronomical observation of the 2,175-angstrom feature. It makes sense that this ubiquitous feature would come from common materials in interstellar space'. The group's results increase scientific understanding of the starting materials for the formation of the Sun, solar system, and life on Earth.

Interstellar matter↗

Correlated Microanalysis of Cometary Organic Grains Returned by Stardust

Preliminary examination (PE) of samples returned from Comet 81P/Wild 2 by the NASA Stardust mission revealed a wide variety of carbonaceous samples [e.g. 1]. Carbonaceous matter is present as inclusions, rinds, and films in polyminerallic terminal particles [2-4], as carbon-rich particles along track walls [2, 5, 6], and as organic matter in aerogel around tracks [7, 8]. The organic chemistry of these samples ranges from purely aliphatic hydrocarbons to highly-aromatic material, often modified by various organic functional groups [2, 4, 5, 9-11]. Difficulty arises when interpreting the genesis of these carbonaceous samples, since contaminants could be introduced from the spacecraft [12], aerogel [1, 8], or during sample preparation. In addition, hypervelocity capture into aerogel may have heated cometary material in excess of 1000 C, which could have significantly altered the structure and chemistry of carbonaceous matter. Fortunately, much of this contamination or alteration can be identified through correlated microanalysis with transmission electron microscopy (TEM), scanning-transmission X-ray microscopy (STXM), and nanoscale secondary ion mass spectroscopy (SIMS).

DeGregorio, B. T.↗

Carbon Nanotubes Based Quantum Devices

This document represents the final report for the NASA cooperative agreement which studied the application of carbon nanotubes. The accomplishments are reviewed: (1) Wrote a review article on carbon nanotubes and its potentials for applications in nanoscale quantum devices. (2) Extensive studies on the effects of structure deformation on nanotube electronic structure and energy band gaps. (3) Calculated the vibrational spectrum of nanotube rope and the effect of pressure. and (4) Investigate the properties of Li intercalated nanotube ropes and explore their potential for energy storage materials and battery applications. These studies have lead to four publications and seven abstracts in international conferences.

Lu, Jian-Ping↗

In-situ Nanoscale Ablation

An understanding of the ablation of carbon-based materials is crucial to modeling the behavior of atmospheric entry spacecrafts equipped with thermal protection systems (TPS).Carbon is the backbone of TPS systems such as PICA (phenolic-impregnated carbon ablator).Therefore in the present work we study ablation of highly oriented pyrolytic graphite (HOPG)in oxygen at temperatures up to 1000°C done within a gas reaction cell housed in a scanning transmission electron microscope (STEM). Observation of the HOPG oxidation on specimens sectioned parallel and normal to the carbon basal planes in the presence of oxygen are reported.Pitting caused by residual oxygen and/or platinum particles from the sectioning process was observed before oxygen gas flow was established at 750°C in the specimen sectioned with the carbon basal planes parallel to the beam direction. Introduction of oxygen flow caused rapid oxidation moving in a uniform front that completely consumed the HOPG in approximately 1.5minutes. The specimen sectioned with the carbon basal planes normal to the beam direction did not show the same pitting phenomenon but exhibited rapid oxidation at 1000°C that proceeded in a uniform front and completed in approximately 1 minute. All specimens tested had a husk resembling the original specimen shape left over after oxidation. It is concluded that this husk is most likely ash impurity from the HOPG or impurities from the sectioning process or E-chip. A residual gas analyszer (RGA) was successfully used to monitor gas flows during the experiments but was yet unsuccessful in monitoring oxidation gas products produced during the experiment.Future studies will optimize the RGA setup in order to maximize the potential for detecting these species. These in-situ studies successfully show how this highly ordered carbon ablates on a nano- and micro-scopic length scale and can be used to provide fundamental understanding of carbon ablation that can be used to design the next-generation of TPS systems.

Nanoscale Ablation↗

Computer Code for Nanostructure Simulation

Due to their small size, nanostructures can have stress and thermal gradients that are larger than any macroscopic analogue. These gradients can lead to specific regions that are susceptible to failure via processes such as plastic deformation by dislocation emission, chemical debonding, and interfacial alloying. A program has been developed that rigorously simulates and predicts optoelectronic properties of nanostructures of virtually any geometrical complexity and material composition. It can be used in simulations of energy level structure, wave functions, density of states of spatially configured phonon-coupled electrons, excitons in quantum dots, quantum rings, quantum ring complexes, and more. The code can be used to calculate stress distributions and thermal transport properties for a variety of nanostructures and interfaces, transport and scattering at nanoscale interfaces and surfaces under various stress states, and alloy compositional gradients. The code allows users to perform modeling of charge transport processes through quantum-dot (QD) arrays as functions of inter-dot distance, array order versus disorder, QD orientation, shape, size, and chemical composition for applications in photovoltaics and physical properties of QD-based biochemical sensors. The code can be used to study the hot exciton formation/relation dynamics in arrays of QDs of different shapes and sizes at different temperatures. It also can be used to understand the relation among the deposition parameters and inherent stresses, strain deformation, heat flow, and failure of nanostructures.

Filikhin, Igor↗

Flame Synthesis Used to Create Metal-Catalyzed Carbon Nanotubes

Metal-catalyzed carbon nanotubes are highly ordered carbon structures of nanoscale dimensions. They may be thought of as hollow cylinders whose walls are formed by single atomic layers of graphite. Such cylinders may be composed of many nested, concentric atomic layers of carbon or only a single layer, the latter forming a single-walled carbon nanotube. This article reports unique results using a flame for their synthesis. Only recently were carbon nanotubes discovered within an arc discharge and recognized as fullerene derivatives. Today metal-catalyzed carbon nanotubes are of great interest for many reasons. They can be used as supports for the metal catalysts like those found in catalytic converters. Open-ended nanotubes are highly desirable because they can be filled by other elements, metals or gases, for battery and fuel cell applications. Because of their highly crystalline structure, they are significantly stronger than the commercial carbon fibers that are currently available (10 times as strong as steel but possessing one-sixth of the weight). This property makes them highly desirable for strengthening polymer and ceramic composite materials. Current methods of synthesizing carbon nanotubes include thermal pyrolysis of organometallics, laser ablation of metal targets within hydrocarbon atmospheres at high temperatures, and arc discharges. Each of these methods is costly, and it is unclear if they can be scaled for the commercial synthesis of carbon nanotubes. In contrast, flame synthesis is an economical means of bulk synthesis of a variety of aerosol materials such as carbon black. Flame synthesis of carbon nanotubes could potentially realize an economy of scale that would enable their use in common structural materials such as car-body panels. The top figure is a transmission electron micrograph of a multiwalled carbon nanotube. The image shows a cross section of the atomic structure of the nanotube. The dark lines are individual atomic layer planes of carbon, seen here in cross section. They form a nested series of concentric cylinders, much like the growth rings on a tree. This sample was obtained by the supported catalyst method, whereby the nanoscale catalysts are dispersed on a substrate providing their support. The substrate with catalyst particles was immersed within an acetylene diffusion flame to which nitrogen had been added to eliminate soot formation. Upon removal from the flame, the nanotubes were dispersed on a holder suitable for electron microscopy. Although not seen in the figure, the tube diameter reflects that of the catalyst particle.

VanderWal, Randy L.↗

Ferroelectric Material Application: Modeling Ferroelectric Field Effect Transistor Characteristics from Micro to Nano

All present ferroelectric transistors have been made on the micrometer scale. Existing models of these devices do not take into account effects of nanoscale ferroelectric transistors. Understanding the characteristics of these nanoscale devices is important in developing a strategy for building and using future devices. This paper takes an existing microscale ferroelectric field effect transistor (FFET) model and adds effects that become important at a nanoscale level, including electron velocity saturation and direct tunneling. The new model analyzed FFETs ranging in length from 40,000 nanometers to 4 nanometers and ferroelectric thickness form 200 nanometers to 1 nanometer. The results show that FFETs can operate on the nanoscale but have some undesirable characteristics at very small dimensions.

MacLeod, Todd, C.↗

Nano-Magnets and Additive Manufacturing for Electric Motors

High power density is required for application of electric motors in hybrid electric propulsion. Potential path to achieve high power density in electric motors include advanced materials, lightweight thermal management, lightweight structural concepts, high power density power electronics, and advanced manufacturing. This presentation will focus on two key technologies for achieving high power density, advanced magnets and additive manufacturing. The maximum energy product in current magnets is reaching their theoretical limits as a result of material and process improvements. Future improvements in the maximum energy product for magnets can be achieved through development of nanocomposite magnets combining the hard magnetic phase and soft magnetic phase at the nanoscale level. The presentation will provide an overview of the current state of development for nanocomposite magnets and the future path for doubling the maximum energy product. The other part of the presentation will focus on the role of additive manufacturing in fabrication of high power density electric motors. The presentation will highlight the potential opportunities for applying additive manufacturing to fabricate electric motors.

materials↗

High-Resolution and Analytical TEM Investigation of Space Radiation Processing Effects in Primitive Solar System Materials and Airless Planetary Surface Environments

Energetic ions present in the diverse plasma conditions in space play a significant role in the formation and modification of solid phases found in environments ranging from the interstellar medium (ISM) to the surfaces of airless bodies such as asteroids and the Moon. These effects are often referred to as space radiation processing, a term that encompasses changes induced in natural space-exposed materials that may be only structural, such as in radiation-induced amorphization, or may involve ion-induced nanoscale to microscale chemical changes, as occurs in preferential sputtering and ion-beam mixing. Ion sputtering in general may also be responsible for partial or complete erosion of space exposed materials, in some instances possibly bringing about the complete destruction of free-floating solid grains in the ISM or in circumstellar nebular dust clouds. We report here on two examples of the application of high-resolution and analytical transmission electron microscopy (TEM) to problems in space radiation processing. The first problem concerns the role of space radiation processing in controlling the overall fate of Fe sulfides as hosts for sulfur in the ISM. The second problem concerns the known, but as yet poorly quantified, role of space radiation processing in lunar space weathering.

Christoffersen, R.↗

Ceramic Aerogel Composite Materials and Characterization

Aerogels a.k.a "Solid Smoke" are gels with the liquid phase replaced by gas, leaving behind a highly porous material with a nanoscale framework. Due to the porous, nanoscale structure, aerogels have the lowest known density and conductivity of solids. Aerogels have the potential for being a breakthrough material because of their extremely light weight and unique properties. In this paper, we address overcoming their most profound weaknesses: mechanical fragility and very high surface activity, which leads to a lowered sintering temperature. A matrix of ceramic aerogel composite materials was produced to investigate their properties and functionality. Mechanical property measurements and Scanning Electron Micrographs are used to identify trends and structure of these ceramic composite materials. Thermal cycling was used to identify the sintering points of the materials.

White, Susan↗

Nanoscale Materials Make for Large-Scale Applications

Since its dawning days, NASA has been at the forefront of developing and improving materials for aerospace applications. In particular, NASA requires dramatic advancements in material properties to enhance the performance, robustness, and reliability of its launch vehicles, spacecraft, and the International Space Station. Such advancements over the years include noise-abatement materials, fire-resistant fibers, heat-absorbing insulation, and light-but-strong moldable composites. In 1991, a new carbon fiber called a carbon nanotube was discovered and fully substantiated by a Japanese electron microscopist. Its dramatic strength and low density (20 times the tensile strength and one-sixth the density of steel) were turning the heads of materials scientists and engineers all around the world, including those who developed equipment for NASA. While NASA did not invent the carbon nanotube, it is working to advance the fibrous material for widespread, low-cost application in sending humans beyond low-Earth orbit, well into the outer reaches of the universe. Carbon nanotubes have the potential to reduce spacecraft weight by 50 percent or more, by replacing the heavier copper wires currently used, according to NASA scientists. Furthermore, NASA researchers have reported a new method for producing integrated circuits using carbon nanotubes instead of copper for interconnects. This technology has the capability to extend the life of the silicon chip industry by 10 years. Because of this growing interest in carbon nanotubes and their perpetual possibilities, NASA has funded both internal and external research in this field.

Source record↗

Bench-scale synthesis of nanoscale materials

A novel flow-through hydrothermal method used to synthesize nanoscale powders is introduced by Pacific Northwest Laboratory. The process, Rapid Thermal Decomposition of precursors in Solution (RTDS), uniquely combines high-pressure and high-temperature conditions to rapidly form nanoscale particles. The RTDS process was initially demonstrated on a laboratory scale and was subsequently scaled up to accommodate production rates attractive to industry. The process is able to produce a wide variety of metal oxides and oxyhydroxides. The powders are characterized by scanning and transmission electron microscopic methods, surface-area measurements, and x-ray diffraction. Typical crystallite sizes are less than 20 nanometers, with BET surface areas ranging from 100 to 400 sq m/g. A description of the RTDS process is presented along with powder characterization results. In addition, data on the sintering of nanoscale ZrO2 produced by RTDS are included.

Buehler, M. F.↗

Capillography of Mats of Nanofibers

Capillography (from the Latin capillus, 'hair', and the Greek graphein, to write ) is a recently conceived technique for forming mats of nanofibers into useful patterns. The concept was inspired by experiments on carpetlike mats of multiwalled carbon nanotubes. Capillography may have the potential to be a less-expensive, less-time-consuming alternative to electron-beam lithography as a means of nanoscale patterning for the fabrication of small devices and instruments. In capillography, one exploits the lateral capillary forces exerted on small objects that pierce the surface of a liquid. If the small objects are identical, then the forces are always attractive. Two examples of the effects of such forces are the agglomeration of small particles floating on the surface of a pond and the drawing together of hairs of a wet paintbrush upon removal of the brush from water. Because nanoscale objects brought into contact remain stuck together indefinitely due to Van der Waals forces, patterns formed by capillography remain even upon removal of the liquid. For the experiments on the mats of carbon nanotubes, a surfactant solution capable of wetting carbon nanotubes (which are ultra-hydrophobic) was prepared. The mats were wetted with the solution, then dried. Once the mats were dry, it was found that the nanotubes had become ordered into various patterns, including nestlike indentations, trenches, and various combinations thereof. It may be possible to exploit such ordering effects through controlled wetting and drying of designated portions of mats of carbon nanotubes (and, perhaps, mats of nanofibers of other materials) to obtain patterns similar to those heretofore formed by use of electron-beam lithography. For making patterns that include nestlike indentations, it has been conjectured that it could be possible to control the nesting processes by use of electrostatic fields. Further research is needed to understand the physics of the patterning processes in order to develop capabilities to control patterns formed in capillography.

Noca, Flavio↗

Space Plasma Ion Processing of the Lunar Soil: Modeling of Radiation-Damaged Rim Widths on Lunar Grains

Chemically and microstructurally complex altered rims around grains in the finest size fraction (<20 micron) of the lunar regolith are the result of multi-stage processes involving both solar ion radiation damage and nanoscale deposition of impact or sputter-derived vapors. The formation of the rims is an important part of the space weathering process, and is closely linked to key changes in optical reflectance and other bulk properties of the lunar surface. Recent application of field-emission scanning transmission electron microscope techniques, including energy dispersive X-ray spectral imaging, is making it easier to unravel the "nano-stratigraphy" of grain rims, and to delineate the portions of rims that represent Radiation-Amorphized (RA) host grain from overlying amorphous material that represents vapor/sputter deposits. For the portion of rims formed by host grain amorphization (henceforth called RA rims), we have been investigating the feasibility of using Monte Carlo-type ion-atom collision models, combined with experimental ion irradiation data, to derive predictive numerical models linking the width of RA rims to the grain s integrated solar ion radiation exposure time.

Chamberlin, S.↗

Novel Nanolaminates for Aerospace Applications

Nanolaminate manufacturing (NLM) is a new way of developing materials whose properties can far exceed those of homogeneous materials. Traditional alloys, composites and bulk laminates tend to average the properties of the materials from which they were made. With nanostructured materials, the high density of interfaces between dissimilar materials results in novel material properties. For example, materials made -from alternating nanoscale layers of metals and oxides have exhibited thermal conductivities far below those of the oxides themselves. Also, metallic nanolaminates can have peak strengths 100 times lager than the bulk constituent metals. Recent work at MSFC has focused on the development of nickel/aluminum oxide (Ni/Al2O3)) nanolaminates. Ni/Al2O3 nanolaminates are expected to have better strength, creep and fatigue resistance, oxygen compatibility, and corrosion resistance than the traditional metal-matrix composites of this material, which has been used in a variety of aerospace applications. A chemical vapor deposition (CW) system has been developed and optimized for the deposition of nanolaminates. Nanolaminates with layer thicknesses between 10 and 300 nm have been successfully grown and characterization has included scanning electron microscopy (SEM) and atomic force microscopy (AFM) Nanolaminates have a large variety of potential applications. They can be tailored to have both very small and anisotropic thermal conductivities and are promising as thermal coatings for both rock$ engine components and aerobraking structures. They also have the potential to be used in aerospace applications where strength at high temperatures, corrosion resistance or resistance to hydrogen embrittlement is important. Both CVD and magnetron sputtering facilities are available for the deposition of nanolayered materials. Characterization equipment includes SEM, AFM, X-ray diffraction, transmission electron microscopy, optical profilometry, and mechanical tensile pull testing.

Volz, Martin↗

Thermal Characterization of Fe3O4 Nanoparticles Formed from Poorly Crystalline Siderite

Increasing interest in environmental geochemistry has led to the recognition that crystals with sizes in the nanometer range (e.g., colloids and nanoscale precipitates) and poorly crystalline compounds (e.g., ferrihydrites) may comprise the majority of reactive mineral surface area near the Earth s surface. When the diameters of individual particles are in the range of 100 nm or less, the surface energy contribution to the free energy modifies phase stability. This results in stabilization of polymorphs not normally encountered in the macrocrystal domain. These phases potentially have very different surface-site geometries, adsorptive properties, and growth mechanisms, and exhibit size-dependent kinetic behavior. Thus nanophases dramatically modify the physical and chemical properties of soils and sediments. In a more general sense, the characteristics of nanocrystals are of intense technological interest because small particle size confers novel chemical, optical, and electronic properties. Thus, nanocrystalline materials are finding applications as catalytic substrates, gas phase separation materials, and even more importantly in the field of medicine. This is an opportune time for mineral physicists working on nanocrystalline materials to develop collaborative efforts with materials scientists, chemists, and others working on nanophase materials of technological interest (e.g., for magnetic memories). Our objective in this study was to synthesize submicron (<200 nm) magnetite and to study their thermal and particle size properties.

Lauer, H. V., Jr.↗

Portable Electron Microscopy for ISS and Beyond

Advances in space exploration have evolved in lockstep with key technology advances in diverse fields such as materials science, biological science, and engineering risk management. Research in these areas, where structure and physical processes come together, can proceed rapidly in part due to sophisticated ground-based analytical tools that help re-searchers develop technologies and engineering processes that push frontiers of human space exploration. Electron microscopes (EM) are an example of such a workhorse tool, lending a unique blend of strong optical scattering, high native resolution, large depth of focus, and spectroscopy via characteristic X-ray emission, providing exquisite high-magnification structural imaging and chemical analysis. Ground-based EM’s have been essential in NASA research for many years. In particular, in mineralogy and petrology, EM is used to understand the origin and evolution of the solar system, particularly rocky bodies. In microbiology, EM has helped visualize the architecture of tissues and cells. In engineering/materials science, EM has been used to characterize particulate debris in air and water samples, determine pore sizes in ceramics/catalysts, understand the nature of fibers, determine composition and morphology of new and existing materials, and characterize micro-textures of vapor deposited films. EM is highly effective at investigating a wide variety of nanoscale materials/biomaterials at the core of many of NASA’s inquiries. Despite exquisite optical performance and versatility, EM’s are traditionally large, heavy, and have high power consumption. They are also expensive so they tend to be housed at universities and large research institutions, or at major industrial laboratory sites with support staff, supplies, and skilled operators. Since most organizations cannot support their own EM, samples are often sent to these large institutions and service centers to be imaged, at great expense and of-ten with delay of weeks to months for complex analyses. Complexity, high cost, and maintenance associated with collecting EM image data has until now severely limited fields in which EM is used. Making EM accessible outside constrained terrestrial laboratory environments will bring EM’s performance and versatility to a much broader range of scientific and engineering endeavors, including in space.

Own, C. S.↗

Indigenous Carbonaceous Matter in the Nakhla Mars Meteorite

Detailed microanalysis of the Martian meteorite Nakhla has shown there are morphologically distinct carbonaceous features spatially associated with low-T aqueous alteration phases including salts and id-dingsite. A comprehensive suite of analytical instrumentation including optical microscopy, field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) spectroscopy, focused ion beam (FIB) microscopy, transmission electron microscopy (TEM), two-step laser mass spectrometry (mu-L(sup 2)MS), laser mu-Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and nanoscale secondary ion mass spectrometry (NanoSIMS) are being used to characterize the carbonaceous matter and host mineralogy. The search for carbonaceous matter on Mars has proved challenging. Viking Landers failed to unambiguously detect simple organics at either of the two landing sites although the Martian surface is estimated to have acquired at least 10(exp15) kg of C as a consequence of meteoritic accretion over the last several Ga. The dearth of organics at the Martian surface has been attributed to various oxidative processes including UV photolysis and peroxide activity. Consequently, investigations of Martian organics need to be focused on the sub-surface regolith where such surface processes are either severely attenuated or absent. Fortuitously since Martian meteorites are derived from buried regolith materials they provide a unique opportunity to study Martian organic geochemistry.

Clemett, S. J.↗