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At least 19 records

High Resolution Imaging and Analysis of Terrestrial Impact Glass: Amorphous Materials, Phyllosilicates and Everything in Between

Introduction: Impact cratering is one of the most ubiquitous geologic processes shaping the surface of all solid bodies in our solar system. Impacts are also a major source of clay minerals, poorly crystalline clay-like phases and amorphous (i.e., lacking long-range atomic order) materials on Earth and Mars. Phyllosilicates and amorphous materials have consistently formed a major component (~20-70 wt%) of every single drilled rock and soil sample in Gale Crater on Mars, as determined by the CheMin instrument on Curiosity. The origin of the amorphous component is speculative, but could be primary impact or volcanic-produced glass(es) deposited via aeolian or fluvial processes, secondary aqueous alteration products or chemical precipitates; it is likely to be a combination of all three possibilities. Efforts to determine the composition of these materials across the rover’s traverse through Gale Crater are ongoing. Naturally occurring amorphous phases are found in a variety of environments on Earth, and terrestrial analogue studies may help shed light on how they may have formed on Mars. Primary and altered impact glass are likely widespread on Mars and may have contributed to the amorphous component found throughout Gale Crater. In its pristine, unaltered state, impact glass (i.e., melt glass) is considered amorphous. However, truly unaltered glass is rarely preserved in crater fill impactites as it quickly alters in the post-impact environ-ment, commonly forming a mixture of hydrated aluminosilicate phases whose structures are not always discernable at the microscale (i.e., they may be amorphous or contain short-range order). These phases are part of an incredibly complex group of materials; differences in their composition and crystalline structure (or lack thereof) and genetic relationship to the more well-crystalline clay minerals are often only discernable at the nanoscale, beyond the resolution of traditional X-ray diffractometers (XRD) and scanning electron microscopes/microprobes (SEM/EPMA) alone. In this contribution, we summarize recent results from ongoing characterization of clay minerals, poorly crystalline clay-like phases, and amorphous materials preserved in altered terrestrial impact glass from the Chicxulub (~66 Ma) and Ries (~15 Ma) impact structures. This work has been performed using a combination of high-resolution transmission electron microscopy (HR-TEM), SEM, microprobe/EPMA, Raman spectroscopy and XRD.

Impact crater↗

Potential Challenges in Near-Field Scanning Optical Microscopy for Space Applications

Near-field scanning optical microscopy (NSOM) also called scanning near-field optical microscopy (SNOM) is now well accepted as a powerful tool for sub-wavelength (nanoscale in the optical region) spatial resolution microscopy and a large number of related tasks. The importance lies in the fact of strategic advantages of standard microscopy but with significantly enhanced resolution. Since many modern optical diagnostic techniques have found useful applications in space, it is logical to consider the future role of NSOM in such situations. For example, protein crystal growth study under microgravity conditions is a valid candidate. If applied successfully, processes at molecular level can be studied during the growth. NSOM has already been demonstrated to be useful for the study of such crystals here on earth. The basic principle of NSOM can be illustrated. The illumination-collection mode is shown although several other possible approaches exist. In this, the sample is illuminated and the light from the sample is collected through the same tiny aperture opening. A tapered optical fiber is scanned near the sample surface. The tip is coated generally with a metal with a sub-wavelength aperture opening. The tip-sample distance is maintained constant while scanning. Thus, the optical signal available for collection is generally a function of the optical properties of the sample surface. Since the aperture is sub-wavelength in diameter and the tip is held very close (again in the sub-wavelength domain) to the surface, the lateral resolution in the sub-wavelength domain is obtained. Thus, the typical wavelength- order resolution of ordinary microscopy can be significantly enhanced while maintaining the strategic advantages (no need of sample in vacuum chamber, electron beams, etc). Commercial NSOM systems play a key role in the success and widespread acceptance of the tool. These commercial systems work fairly well in laboratory conditions on earth. However, they may not be deployed on a space mission as such with comparable outcome. In this communication we discuss several potential problems and some possible solutions.

Vikram, Chandra S.↗

4.46 Ga Zircons Anchor Chronology of Lunar Magma Ocean

The crystallisation ages of lunar samples provide critical constraints on the minimum formation age of the Moon and its early evolution. Zircon crystals from Apollo 17 lunar impact melt breccia 72255 preserve ancient domains with a concordant average uranium-lead radiometric date of 4460 ± 31 Ma (Zhang et al., 2021), the oldest lunar zircon yet reported. To assess the possible mobility of radiogenic lead in zircon, which may lead to redistribution and clustering of Pb atoms that may cause a U-Pb age bias (Valley et al., 2014), we investigated a zircon grain from Zhang et al. (2021) by atom probe tomography (APT). The atomic spatial resolution analysis of individual mineral grains demonstrates the absence of nanoscale clustering of lead, which supports a 4.46 Ga ancient formation age for lunar zircon in sample 72255. This age pushes back the age of the first preserved lunar crust by ∼40 Myr and provides a minimum formation age for the Moon within 110 Myr after the formation of the solar system.

atom probe tomography↗

A 3D Printable Alloy Designed for Extreme Environments

Multiprincipal-element alloys are an enabling class of materials owing to their impressive mechanical and oxidation-resistant properties, especially in extreme environments. Here we develop a new oxide-dispersion-strengthened NiCoCr-based alloy using a model-driven alloy design approach and laser-based additive manufacturing. This oxide-dispersion-strengthened alloy, called GRX-810, uses laser powder bed fusion to disperse nanoscale Y 2 O 3 particles throughout the microstructure without the use of resource-intensive processing steps such as mechanical or in situ alloying. We show the successful incorporation and dispersion of nanoscale oxides throughout the GRX-810 build volume via high-resolution characterization of its microstructure. The mechanical results of GRX-810 show a twofold improvement in strength, over 1,000-fold better creep performance and twofold improvement in oxidation resistance compared with the traditional polycrystalline wrought Ni-based alloys used extensively in additive manufacturing at 1,093 °C. The success of this alloy highlights how model-driven alloy designs can provide superior compositions using far fewer resources compared with the ‘trial-and-error’ methods of the past. These results showcase how future alloy development that leverages dispersion strengthening combined with additive manufacturing processing can accelerate the discovery of revolutionary materials.

Timothy M. Smith↗

Flight Readiness of Mochii ISS-NL Portable Spectroscopic Electron Microscope

Electron microscopes (EM’s), are workhorse tools serving diverse fields such as materials science, biological science, and engineering. Scanning EM’s (SEM’s) in particular enable high magnification study and pinpoint chemical analyses of structures down to the nanoscale by providing a powerful blend of strong optical scattering, high native resolution, large depth of focus, and energy-dispersive X-ray spectroscopy (EDS). Mochii is the world’s smallest production electron microscope, scheduled to travel to the International Space Station (ISS) this spring where it will serve as an ISS National Laboratory (ISSNL) microgravity facility on successful demonstration. We previously reported on progress preparing Mochii for space flight, in particular flight integration verifications and science application testing. These included standard integration testing such as electromagnetic interference and flight vibration, and extend to unique functional testing such as magnetic susceptibility and extreme analog environment testing under the sea. Presently, Mochii payload flight hardware has completed testing and was handed over to NASA’s ISS payload processing facility in Houston. It will make its way to the the east coast for launch currently scheduled on Space-X CRS-20 for Mission increment 62 in March 2020.

Own, C. S.↗

Fabrication of Single, Vertically Aligned Carbon Nanotubes in 3D Nanoscale Architectures

Plasma-enhanced chemical vapor deposition (PECVD) and high-throughput manufacturing techniques for integrating single, aligned carbon nanotubes (CNTs) into novel 3D nanoscale architectures have been developed. First, the PECVD growth technique ensures excellent alignment of the tubes, since the tubes align in the direction of the electric field in the plasma as they are growing. Second, the tubes generated with this technique are all metallic, so their chirality is predetermined, which is important for electronic applications. Third, a wafer-scale manufacturing process was developed that is high-throughput and low-cost, and yet enables the integration of just single, aligned tubes with nanoscale 3D architectures with unprecedented placement accuracy and does not rely on e-beam lithography. Such techniques should lend themselves to the integration of PECVD grown tubes for applications ranging from interconnects, nanoelectromechanical systems (NEMS), sensors, bioprobes, or other 3D electronic devices. Chemically amplified polyhydroxystyrene-resin-based deep UV resists were used in conjunction with excimer laser-based (lambda = 248 nm) step-and-repeat lithography to form Ni catalyst dots = 300 nm in diameter that nucleated single, vertically aligned tubes with high yield using dc PECVD growth. This is the first time such chemically amplified resists have been used, resulting in the nucleation of single, vertically aligned tubes. In addition, novel 3D nanoscale architectures have been created using topdown techniques that integrate single, vertically aligned tubes. These were enabled by implementing techniques that use deep-UV chemically amplified resists for small-feature-size resolution; optical lithography units that allow unprecedented control over layer-to-layer registration; and ICP (inductively coupled plasma) etching techniques that result in near-vertical, high-aspect-ratio, 3D nanoscale architectures, in conjunction with the use of materials that are structurally and chemically compatible with the high-temperature synthesis of the PECVD-grown tubes. The techniques offer a wafer-scale process solution for integrating single PECVD-grown nanotubes into novel architectures that should accelerate their integration in 3D electronics in general. NASA can directly benefit from this technology for its extreme-environment planetary missions. Current Si transistors are inherently more susceptible to high radiation, and do not tolerate extremes in temperature. These novel 3D nanoscale architectures can form the basis for NEMS switches that are inherently less susceptible to radiation or to thermal extremes.

Kaul, Anupama B.↗

Phase-Imaging with a Sharpened Multi-Walled Carbon Nanotube AFM Tip: Investigation of Low-k Dielectric Polymer Hybrids

Phase shift tapping mode scanning force microscopy (TMSFM) has evolved into a very powerful technique for the nanoscale surface characterization of compositional variations in heterogeneous samples. Phase shift signal measures the difference between the phase angle of the excitation signal and the phase angle of the cantilever response. The signal correlates to the tip-sample inelastic interactions, identifying the different chemical and/or physical property of surfaces. In general, the resolution and quality of scanning probe microscopic images are highly dependent on the size of the scanning probe tip. In improving AFM tip technology, we recently developed a technique for sharpening the tip of a multi-walled carbon nanotube (CNT) AFM tip, reducing the radius of curvature of the CNT tip to less than 5 nm while still maintaining the inherent stability of multi-walled CNT tips. Herein we report the use of sharpened (CNT) AFM tips for phase-imaging of polymer hybrids, a precursor for generating nanoporous low-k dielectrics for on-chip interconnect applications. Using sharpened CNT tips, we obtained phase-contrast images having domains less than 10 nm. In contrast, conventional Si tips and unsharpened CNT tips (radius greater than 15 nm) were not able to resolve the nanoscale domains in the polymer hybrid films. C1early, the size of the CNT tip contributes significantly to the resolution of phase-contrast imaging. In addition, a study on the nonlinear tapping dynamics of the multi-walled CNT tip indicates that the multi-walled CNT tip is immune to conventional imaging instabilities related to the coexistence of attractive and repulsive tapping regimes. This factor may also contribute to the phase-contrast image quality of multi-walled CNT AFM tips. This presentation will also offer data in support of the stability of the CNT tip for phase shift TMSFM.

Nguyen, Cattien V.↗

Defect Clustering and Nano-phase Structure Characterization of Multicomponent Rare Earth-Oxide-Doped Zirconia-Yttria Thermal Barrier Coatings

Advanced thermal barrier coatings (TBCs) have been developed by incorporating multicomponent rare earth oxide dopants into zirconia-based thermal barrier coatings to promote the creation of the thermodynamically stable, immobile oxide defect clusters and/or nanophases within the coating systems. In this paper, the defect clusters, induced by Nd, Gd, and Yb rare earth dopants in the zirconia-yttria thermal barrier coatings, were characterized by high-resolution transmission electron microscopy (TEM). The TEM lattice imaging, selected area diffraction (SAD), and electron energy-loss spectroscopy (EELS) analyses demonstrated that the extensive nanoscale rare earth dopant segregation exists in the plasma-sprayed and electron-physical-vapor-deposited (EB PVD) thermal barrier coatings. The nanoscale concentration heterogeneity and the resulting large lattice distortion promoted the formation of parallel and rotational defective lattice clusters in the coating systems. The presence of the 5-to 100-nm-sized defect clusters and nanophases is believed to be responsible for the significant reduction of thermal conductivity, improved sintering resistance, and long-term high temperature stability of the advanced thermal barrier coating systems.

Zhu, Dongming↗

Nanoscale Hot-Wire Probes for Boundary-Layer Flows

Hot-wire probes having dimensions of the order of nanometers have been proposed for measuring temperatures (and possibly velocities) in boundary-layer flows at spatial resolutions much finer and distances from walls much smaller than have been possible heretofore. The achievable resolutions and minimum distances are expected to be of the order of tens of nanometers much less than a typical mean free path of a molecule and much less than the thickness of a typical flow boundary layer in air at standard temperature and pressure. An additional benefit of the small scale of these probes is that they would perturb the measured flows less than do larger probes. The hot-wire components of the probes would likely be made from semiconducting carbon nanotubes or ropes of such nanotubes. According to one design concept, a probe would comprise a single nanotube or rope of nanotubes laid out on the surface of an insulating substrate between two metallic wires. According to another design concept, a nanotube or rope of nanotubes would be electrically connected and held a short distance away from the substrate surface by stringing it between two metal electrodes. According to a third concept, a semiconducting nanotube or rope of nanotubes would be strung between the tips of two protruding electrodes made of fully conducting nanotubes or ropes of nanotubes. The figure depicts an array of such probes that could be used to gather data at several distances from a wall. It will be necessary to develop techniques for fabricating the probes. It will also be necessary to determine whether the probes will be strong enough to withstand the aerodynamic forces and impacts of micron-sized particles entrained in typical flows of interest.

Tedjojuwono, Ken T.↗

High Resolution Transmission Electron Microscopy (HRTEM) of nanophase ferric oxides

Iron oxide minerals are the prime candidates for Fe(III) signatures in remotely sensed Martian surface spectra. Magnetic, Mossbauer, and reflectance spectroscopy have been carried out in the laboratory in order to understand the mineralogical nature of Martian analog ferric oxide minerals of submicron or nanometer size range. Out of the iron oxide minerals studied, nanometer sized ferric oxides are promising candidates for possible Martian spectral analogs. 'Nanophase ferric oxide (np-Ox)' is a generic term for ferric oxide/oxihydroxide particles having nanoscale (less than 10 nm) particle dimensions. Ferrihydrite, superparamagnetic particles of hematite, maghemite and goethite, and nanometer sized particles of inherently paramagnetic lepidocrocite are all examples of nanophase ferric oxides. np-Ox particles in general do not give X-ray diffraction (XRD) patterns with well defined peaks and would often be classified as X-ray amorphous. Therefore, different np-Oxs preparations should be characterized using a more sensitive technique e.g., high resolution transmission electron microscopy (HRTEM). The purpose of this study is to report the particle size, morphology and crystalline order, of five np-Ox samples by HRTEM imaging and electron diffraction (ED).

Golden, D. C.↗

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.↗

Monolithically Integrated, Mechanically Resilient Carbon-Based Probes for Scanning Probe Microscopy

Scanning probe microscopy (SPM) is an important tool for performing measurements at the nanoscale in imaging bacteria or proteins in biology, as well as in the electronics industry. An essential element of SPM is a sharp, stable tip that possesses a small radius of curvature to enhance spatial resolution. Existing techniques for forming such tips are not ideal. High-aspect-ratio, monolithically integrated, as-grown carbon nanofibers (CNFs) have been formed that show promise for SPM applications by overcoming the limitations present in wet chemical and separate substrate etching processes.

Kaul, Anupama B.↗

Apatite Nanoresponse to Acidic Dissolution

Phosphorus uptake by plants and organisms is one of the most important life-sustaining processes occurring in the critical zone (CZ). Because 95% of Earth’s reserves is relatively immobile in the form of apatite, plants and organisms rely on molecular scale solubilization process to extract available P. As the world experiences a global P shortage, influencing food production, it becomes increasingly important to understand apatite dissolution. The detailed study of chemically weathered apatite surfaces at the μm to nm-scale is key to understanding P solubilization and uptake in the CZ, allowing for better crop management and efficient fertilization. Apatite weathering is generally viewed in terms of a pH-dependent process where protons weaken atomic bonds, this leading to the disintegration of the apatite structure. A general feature of apatite weathering in acid and near neutral pH conditions is an apparent non-stoichiometric dissolution characterized by [Ca/P]aq > 1.66 in both fluorapatites (FAP) and hydroxyapatites (HAP). This process leads to the formation of a surface altered layer (SAL) with a different composition from the bulk, which many have argued is a Ca-depleted “leached layer.” We investigated apatite weathering at the nanoscale using FIB-prepared TEM-foils. Our preliminary results based on laboratory-altered FAP at ambient T and pH 3 show the formation of amorphous SALs with a maximum thickness of ~10 nm. High resolution chemical mapping and profiling using STEM-EELS and STEM-EDXS indicate that the SALs are generally, but not always, depleted in Ca and enriched in P. These results provide an alternate view of the mechanism of apatite dissolution with stoichiometric breakdown of the apatite structure, followed by the reprecipitation of an amorphous surface layer depleted in Ca. This mechanism can be described in terms of coupled interfacial dissolution-reprecipitation (CIDR), which is increasingly viewed as a universal mechanism of silicate mineral and glass dissolution. Our observation that apatite may dissolve similarly to silicates implies not only that apatite weathering may be more complex than originally thought, but also that the CIDR mechanism may extend beyond silicates.

mineralogy↗

Nanoscale Deformable Optics

Several missions and instruments in the conceptual design phase rely on the technique of interferometry to create detectable fringe patterns. The intimate emplacement of reflective material upon electron device cells based upon chalcogenide material technology permits high-speed, predictable deformation of the reflective surface to a subnanometer or finer resolution with a very high degree of accuracy. In this innovation, a layer of reflective material is deposited upon a wafer containing (perhaps in the millions) chalcogenic memory cells with the reflective material becoming the front surface of a mirror and the chalcogenic material becoming a means of selectively deforming the mirror by the application of heat to the chalcogenic material. By doing so, the mirror surface can deform anywhere from nil to nanometers in spots the size of a modern day memory cell, thereby permitting realtime tuning of mirror focus and reflectivity to mitigate aberrations caused elsewhere in the optical system. Modern foundry methods permit the design and manufacture of individual memory cells having an area of or equal to the Feature (F) size of the design (assume 65 nm). Fabrication rules and restraints generally require the instantiation of one memory cell to another no closer than 1.5 F, or, for this innovation, 90 nm from its neighbor in any direction. Chalcogenide is a semiconducting glass compound consisting of a combination of chalcogen ions, the ratios of which vary according to properties desired. It has been shown that the application of heat to cells of chalcogenic material cause a large alteration in resistance to the range of 4 orders of magnitude. It is this effect upon which chalcogenidebased commercial memories rely. Upon removal of the heat source, the chalcogenide rapidly cools and remains frozen in the excited state. It has also been shown that the chalcogenide expands in volume because of the applied heat, meaning that the coefficient of expansion of chalcogenic materials is larger than 1. In this innovation, chalcogenidebased cells are addressed (as though they are a memory), and heated and cooled according to well-established criteria. In doing so, the exact size of chalcogenide cell deformation is known and predictable; therefore, the deformation of the reflective surface is, likewise, known and predictable. Control electronics can also be implemented so that a closed-loop feedback can be maintained. Changing the contents of the chalcogenide memory cells can compensate for any change in environmental effects that might cause a change in optical path. This real-time control provides significant control and stability in use conditions.

Strauss, Karl F.↗

Carbon Nanostructure Examined by Lattice Fringe Analysis of High Resolution Transmission Electron Microscopy Images

The dimensions of graphitic layer planes directly affect the reactivity of soot towards oxidation and growth. Quantification of graphitic structure could be used to develop and test correlations between the soot nanostructure and its reactivity. Based upon transmission electron microscopy images, this paper provides a demonstration of the robustness of a fringe image analysis code for determining the level of graphitic structure within nanoscale carbon, i.e. soot. Results, in the form of histograms of graphitic layer plane lengths, are compared to their determination through Raman analysis.

VanderWal, Randy L.↗

Carbon Nanostructure Examined by Lattice Fringe Analysis of High Resolution Transmission Electron Microscopy Images

The dimensions of graphitic layer planes directly affect the reactivity of soot towards oxidation and growth. Quantification of graphitic structure could be used to develop and test correlations between the soot nanostructure and its reactivity. Based upon transmission electron microscopy images, this paper provides a demonstration of the robustness of a fringe image analysis code for determining the level of graphitic structure within nanoscale carbon, i.e., soot. Results, in the form of histograms of graphitic layer plane lengths, are compared to their determination through Raman analysis.

VanderWal, Randy L.↗

Detection of Strand Cleavage And Oxidation Damage Using Model DNA Molecules Captured in a Nanoscale Pore

We use a biological nano-scale pore to distinguish among individual DNA hairpins that differ by a single site of oxidation or a nick in the sugar-phosphate backbone. In earlier work we showed that the protein ion channel alpha-hemolysin can be used as a detector to distinguish single-stranded from double-stranded DNA, single base pair and single nucleotide differences. This resolution is in part a result of sensitivity to structural changes that influence the molecular dynamics of nucleotides within DNA. The strand cleavage products we examined here included a 5-base-pair (5-bp) hairpin with a 5-prime five-nucleotide overhang, and a complementary five-nucleotide oligomer. These produced predictable shoulder-spike and rapid near-full blockade signatures, respectively. When combined, strand annealing was monitored in real time. The residual current level dropped to a lower discrete level in the shoulder-spike blockade signatures, and the duration lengthened. However, these blockade signatures had a shorter duration than the unmodified l0bp hairpin. To test the pore sensitivity to nucleotide oxidation, we examined a 9-bp hairpin with a terminal 8-oxo-deoxyguanosine (8-oxo-dG), or a penultimate 8-oxo-dG. Each produced blockade signatures that differed from the otherwise identical control 9bp hairpins. This study showed that DNA structure is modified sufficiently by strand cleavage or oxidation damage at a single site to alter in a predictable manner the ionic current blockade signatures produced. This technique improves the ability to assess damage to DNA, and can provide a simple means to help characterize the risks of radiation exposure. It may also provide a method to test radiation protection.

Vercoutere, W.↗

Segregation and Phase Transformations Along Superlattice Intrinsic Stacking Faults in Ni-Based Superalloys

In this study, local chemical and structural changes along superlattice intrinsic stacking faults combine to represent an atomic-scale phase transformation. In order to elicit stacking fault shear, creep tests of two different single crystal Ni-base superalloys, ME501 and CMSX-4, were performed near 750 degrees Centigrade using stresses of 552 megapascals and 750 megapascals, respectively. Through high resolution Scanning Transmission Electron Microscopy (STEM) and state-of-the-art energy dispersive x-ray spectroscopy, ordered compositional changes were measured along SISFs (Superlattice Intrinsic Stacking Faults) in both alloys. For both instances, the elemental segregation and local crystal structure present along the SISFs are consistent with a nanoscale to D019 (ordering of a hexagonal close-packed crystal) phase transformation. Another notable observation is prominent Cr- and Co-rich Cottrell atmospheres and new evidence of more complex reordering processes responsible for the formation of these faults. These findings are further supported using density functional theory calculations and High Angle Annular Dark Field (HAADF) STEM image simulations.

STEM-EDS↗