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At least 757 records · Page 42

Ultrashort Pulsed Laser Treatment: A Novel Sterilization Method for Planetary Protection

Introduction: On missions seeking signs of potential life elsewhere in the solar system, we have an obligation not to bring our own Earthly life with us. Reducing the bioburden (number of living microbes) on spacecraft is therefore required by the COSPAR Policy on Planetary Protection to target bodies that are of interest for understanding the origins of life (such as Mars). The method of spacecraft sterilization predominantly used by NASA is Heat Microbial Reduction, which is typically incompatible with heat-sensitive components such as optics and electronics, and is expensive and time-consuming. Here, we present preliminary results on a novel method for spacecraft hardware sterilization: high-intensity ultrashort (femtosecond) pulsed laser illumination. Femtosecond lasers use extremely high photon fluxes (10^29 photons/sec*cm^2, ~0.03 J/cm^2) in extremely short pulses, which can inactivate even stress-tolerant microbial spores with minimal damage to the spacecraft surface. This rapid sterilization technique could be carried out in situ in a spacecraft assembly clean room using high-speed surface scanning, saving critical time and resources. It also can potentially remove or reduce debris from inactivated cells and spores. Methods: To develop optimal laser processing parameters for inactivating planetary protection-relevant organisms on metal surfaces, we inoculated 1-cm^2 mirror-polished aluminum coupons with Bacillus subtilis spores (2x10^5 spores/coupon) and tested the effect of several parameters, including pulse count and fluence. Sterilization effectiveness was measured by recovering spores using a PVA (polyvinyl acetate) peel and conducting serial dilution and plating for colony-forming units (CFUs). Results: Our results show that pulse count and fluence both affect sterilization effectiveness and that within a certain pulse count range, increasing fluence increases effectiveness. We have demonstrated the ability to reduce viable microbial counts by at least 10^-4. Future work will include testing higher abundances and different species of microorganisms, effectiveness on complex surfaces, compatibility with sensitive surfaces, and quantification of cell debris removal. Femtosecond pulsed laser illumination has the potential to provide dramatic savings in both cost and schedule over current methods of bioburden reduction to prevent forward contamination. It may also have the potential for use in surface sterilization of returned samples to prevent back contamination.

Planetary Protection; Lasers; Sterilization; Bacil↗

The Air Quality Monitor “Benzene” Anomaly: Ground Testing and On-going Effects

The International Space Station (ISS) Air Quality Monitors (AQMs) have provided targeted in-flight analysis of volatile organic compounds (VOCs) in the ISS atmosphere since early 2013. During their initial half decade of use covering multiple sets of units, the AQMs performed well, meeting their validation criteria and showing excellent accuracy compared to archival samples. In addition to routine environmental monitoring, the AQMs have also been used during a number of contingency situations and investigations related to Environmental Control and Life Support Systems (ECLSS). These include a potential ammonia leak, increases in atmospheric ethanol, and efforts to locate potential sources of polydimethylsiloxanes that lead to the production of dimethylsilanediol (DMSD) in the US Water Processor Assembly (WPA). As the fleet of AQMs has aged, several issues have arisen. These have ranged from pervasive problems on electronics boards to loss of sensitivity due to operating in an elevated CO2 environment. The most notable issue encountered during on-orbit operations was incorrect identification of compounds. This initially occurred in mid-2020, when AQM1 reported the presence of benzene. While the AQM team questioned the validity of these results, the concentration of the “benzene” continued to increase and eventually exceeded the 30- and 180-day Spacecraft Maximum Allowable Concentration (SMAC). This led to wide-ranging efforts by a number of groups aimed at understanding the situation and identifying the source of the “benzene.” AQM1 failed after being relocated to the Russian Segment as part of the investigation, and the unit was returned for evaluation. When archive samples collected while the AQM was measuring elevated benzene showed no detectable benzene, the focus of the investigation shifted to determining the cause of the false positive readings. Here, we will discuss the results of this investigation by the AQM team, potential causes of the interference, and subsequent reporting of AQM1 results.

W T Wallace↗

The Air Quality Monitor “Benzene” Anomaly: Ground Testing and On-going Effects

The International Space Station (ISS) Air Quality Monitors (AQMs) have provided targeted in-flight analysis of volatile organic compounds (VOCs) in the ISS atmosphere since early 2013. During their initial half decade of use covering multiple sets of units, the AQMs performed well, meeting their validation criteria and showing excellent accuracy compared to archival samples. In addition to routine environmental monitoring, the AQMs have also been used during a number of contingency situations and investigations related to Environmental Control and Life Support Systems (ECLSS). These include a potential ammonia leak, increases in atmospheric ethanol, and efforts to locate potential sources of polydimethylsiloxanes that lead to the production of dimethylsilanediol (DMSD) in the US Water Processor Assembly (WPA). As the fleet of AQMs has aged, several issues have arisen. These have ranged from pervasive problems on electronics boards to loss of sensitivity due to operating in an elevated CO2 environment. The most notable issue encountered during on-orbit operations was incorrect identification of compounds. This initially occurred in mid-2020, when AQM1 reported the presence of benzene. While the AQM team questioned the validity of these results, the concentration of the “benzene” continued to increase and eventually exceeded the 30- and 180-day Spacecraft Maximum Allowable Concentration (SMAC). This led to wide-ranging efforts by a number of groups aimed at understanding the situation and identifying the source of the “benzene.” AQM1 failed after being relocated to the Russian Segment as part of the investigation, and the unit was returned for evaluation. When archive samples collected while the AQM was measuring elevated benzene showed no detectable benzene, the focus of the investigation shifted to determining the cause of the false positive readings. Here, we will discuss the results of this investigation by the AQM team, potential causes of the interference, and subsequent reporting of AQM1 results.

W T Wallace↗

The Air Quality Monitor “Benzene” Anomaly: Ground Testing and On-going Effects

The International Space Station (ISS) Air Quality Monitors (AQMs) have provided targeted in-flight analysis of volatile organic compounds (VOCs) in the ISS atmosphere since early 2013. During their initial half decade of use covering multiple sets of units, the AQMs performed well, meeting their validation criteria and showing excellent accuracy compared to archival samples. In addition to routine environmental monitoring, the AQMs have also been used during a number of contingency situations and investigations related to Environmental Control and Life Support Systems (ECLSS). These include a potential ammonia leak, increases in atmospheric ethanol, and efforts to locate potential sources of polydimethylsiloxanes that lead to the production of dimethylsilanediol (DMSD) in the US Water Processor Assembly (WPA). As the fleet of AQMs has aged, several issues have arisen. These have ranged from pervasive problems on electronics boards to loss of sensitivity due to operating in an elevated CO2 environment. The most notable issue encountered during on-orbit operations was incorrect identification of compounds. This initially occurred in mid-2020, when AQM1 reported the presence of benzene. While the AQM team questioned the validity of these results, the concentration of the “benzene” continued to increase and eventually exceeded the 30- and 180-day Spacecraft Maximum Allowable Concentration (SMAC). This led to wide-ranging efforts by a number of groups aimed at understanding the situation and identifying the source of the “benzene.” AQM1 failed after being relocated to the Russian Segment as part of the investigation, and the unit was returned for evaluation. When archive samples collected while the AQM was measuring elevated benzene showed no detectable benzene, the focus of the investigation shifted to determining the cause of the false positive readings. Here, we will discuss the results of this investigation by the AQM team, potential causes of the interference, and subsequent reporting of AQM1 results.

William T Wallace↗

Compendium of Directors Colloquia 1999-2012

The Director s colloquium series was established primarily to provide a mechanism to bring high profile individuals to the Center to present new and innovative ideas to the entire Ames staff. More focused lecture series are arranged by specific divisions or departments. Before the year 1999, there is only a fragmentary record of who spoke in this series. Announcements to the staff were sent via land mail, and tickets were required to attend the colloquium. In 1999, the notification to attend colloquia became electronic and the entire resident staff was invited to attend. The centerwide announcement archive established in this timeframe created a lasting record of the Director s colloquia. The "Office of the Chief Scientist" at Ames had the responsibility for administering the colloquium series. When I became Chief Scientist on June 29, 1998, the program was not being used extensively and this continued to be the case through the years 1999-2002 of Harry McDonald s tenure as Director (see graph below). During Scott Hubbard s tenure as Director (September 19, 2002- February 15, 2006), the Director's colloquium series was used exclusively for high profile speakers from outside Ames whom he selected, such as lab directors from other research organizations around the Bay Area. During Pete Worden s tenure as Ames Director (May 4, 2006 -present) the colloquium series gained far greater use. First, I had greater discretion to select speakers for the colloquium series. Secondly, beginning in 2007, we established a 10-week Director's Colloquium Summer Series focused on enriching the experience of our many summer interns, and giving our top researchers within Ames Research Center an opportunity to present their work to the Center. The summer program has received rave reviews. This compendium contains a compilation of one-page descriptions (title, abstract and speaker biographies) for all of the 171 colloquia presented from the beginning of 1999 to October of 2012. The list of speakers includes four Nobel Laureates, six astronauts, three current or former Ames Center Directors, as well as many CEOs and other lab directors. Other featured speakers include famous mountain climbers, historians, movie stars, and former FBI agents and directors. Finally, the list includes world-class scientists and engineers representing a wide range of disciplines. It has been my privilege to host almost all of the colloquia presented in this compendium.

Langhoff, Stephanie↗

Source indicators of humic substances and proto-kerogen - Stable isotope ratios, elemental compositions and electron spin resonance spectra

Stable isotope ratios of C, N and H, elemental compositions, and electron spin resonance (ESR) data of humic acids and proto-kerogens from twelve widely varying sampling locations are presented. Humic acids and proto-kerogens from algal sources are more aliphatic and higher in N than those from higher plant sources. Oxygen content appears to represent a measure of maturation, even in Recent sediments, and S content may reflect redox conditions in the environment of deposition. The ESR data indicate that the transformation of humic substances to proto-kerogens in Recent sediments is accompanied by an increase in aromatic character. A combination of stable carbon isotope ratio and H/C ratio may be a simple but reliable source indicator which allows differentiation of marine-derived from terrestrially-derived organic matter. The stable nitrogen isotope ratios are useful indicators of nitrogen nutrient source. Deuterium/hydrogen isotope ratios appear to reflect variations in meteoric waters and are not reliable source indicators.

Stuermer, D. H.↗

Applications of Quantum Chemistry to the Study of Carbon Nanotubes

For several years, scientists at NASA Ames have been studying the properties of carbon nanotubes using various experimental and computational methods. In this talk, I will compare different strategies for using quantum chemistry calculations to describe the electronic structure, deformation and chemical functionalization of single wall carbon nanotubes (SWNT) and the physisorption of small molecules on nanotube surfaces. The SWNT can be treated as an infinite (periodic) or finite length carbon cylinder or as a polycyclic aromatic hydrocarbon (PAH) molecule with an imposed curvature maintained by external constraints (as if it were cut out of the SWNT surface). Calculations are carried out using DFT and MP2 methods and a variety of atomic orbital basis sets from minimal (STO-3G) to valence triple zeta. The optimal approach is based on the particular SWNT property of interest. Examples to be discussed include: nanotube fluorination and other functionalization reactions; coating of nanotubes by water vapor and low-molecular weight organic molecules; and the nature of the interface between SWNT and liquids such as water and amines. In many cases, the quantum chemistry calculations are used to parameterize or validate force fields for molecular dynamics simulations. The results of these calculations have helped explain experimental data and contributed to the design of novel materials and sensors based on carbon nanotubes. Some of this research is described in the following papers:

Jaffe, Richard L.↗

NASA Tech Briefs, July 2012

Topics covered include: Instrument Suite for Vertical Characterization of the Ionosphere-Thermosphere System; Terahertz Radiation Heterodyne Detector Using Two-Dimensional Electron Gas in a GaN Heterostructure; Pattern Recognition Algorithm for High-Sensitivity Odorant Detection in Unknown Environments; Determining Performance Acceptability of Electrochemical Oxygen Sensors; Versatile Controller for Infrared Lamp and Heater Arrays; High-Speed Scanning Interferometer Using CMOS Image Sensor and FPGA Based on Multifrequency Phase-Tracking Detection; Ultra-Low-Power MEMS Selective Gas Sensors; Compact Receiver Front Ends for Submillimeter-Wave Applications; Dynamically Reconfigurable Systolic Array Accelerator; Blocking Losses With a Photon Counter; Motion-Capture-Enabled Software for Gestural Control of 3D Mod; Orbit Software Suite; CoNNeCT Baseband Processor Module Boot Code SoftWare (BCSW); Trajectory Software With Upper Atmosphere Model; ALSSAT Version 6.0; Employing a Grinding Technology to Assess the Microbial Density for Encapsulated Organisms; Demonstration of Minimally Machined Honeycomb Silicon Carbide Mirrors; Polyimide Aerogel Thin Films; Nanoengineered Thermal Materials Based on Carbon Nanotube Array Composites; Composite Laminate With Coefficient of Thermal Expansion Matching D263 Glass; Robust Tensioned Kevlar Suspension Design; Focal Plane Alignment Utilizing Optical CMM; Purifying, Separating, and Concentrating Cells From a Sample Low in Biomass; Virtual Ultrasound Guidance for Inexperienced Operators; Beat-to-Beat Blood Pressure Monitor; Non-Contact Conductivity Measurement for Automated Sample Processing Systems; An MSK Radar Waveform; Telescope Alignment From Sparsely Sampled Wavefront Measurements Over Pupil Subapertures; Method to Remove Particulate Matter from Dusty Gases at Low Pressures; Terahertz Quantum Cascade Laser With Efficient Coupling and Beam Profile; Measurement Via Optical Near-Nulling and Subaperture Stitching; 885-nm Pumped Ceramic Nd:YAG Master Oscillator Power Amplifier Laser System; Airborne Hyperspectral Imaging System; Heat Shield Employing Cured Thermal Protection Material Blocks Bonded in a Large-Cell Honeycomb Matrix; and Asymmetric Supercapacitor for Long-Duration Power Storage.

Source record↗

Polyvinyl Alcohol and Medium Density Polyethylene Composite Materials for Neutron Radiation Shielding

Manned spacecraft venturing beyond the Earth’s Van Allen Belts will be subjected to high levels of radiation from both energetic particles emanating from the sun and from galactic atomic events, such as supernovae. The metal shell of a spacecraft offers some protection from gamma radiation and high energy particles originating from both the sun and cosmic sources. The interaction of these high energy particles and radiation with the spacecraft hull create secondary radiation and neutrons, additional hazards for astronauts and electronic systems. Shielding of neutrons is the most challenging of the high energy radiation, since neutrons have zero charge and are least affected by electrical fields, magnetic fields, and atomic forces. Previous studies showed that polyethylene is an effective neutron shielding material, due to its high hydrogen content. High energy neutrons are slowed to thermal neutrons through multiple collisions with the hydrogen atoms, increasing the effectiveness of neutron capture by boron-10 atoms. This study discusses the fabrication and testing of polyvinyl alcohol (PVOH) samples as a neutron shielding material, with comparison to medium density polyethylene (MDPE) composite samples to be used for neutron shielding for spacecraft. PVOH, an aqueous polymer, was chosen for hydrogen content and for enabling the use of organic reinforcement such as cellulose for secondary structural composites. OLTARIS (On-Line Tool for the Assessment of Radiation in Space) was used for radiation shielding simulation and compared with experimental data. Modeling indicates that the most effective shielding from radiation was in an aluminum layer backed by a polymer layer, either MDPE or PVOH. Cross-linked PVOH was also included in the OLTARIS modeling. All 3 polymer cases showed shielding improvement over aluminum alone, with similar dose equivalent reduction for galactic cosmic radiation(GCR)and for radiation from a solar particle event (SPE). Fourier Transform Infrared (FTIR) Spectroscopy was used to confirm the cross-linking in the PVOH sample and to determine the uniformity through the thickness. PVOH, cross-linked PVOH, and MDPE samples were tested for neutron shielding effectiveness using a 1 curie Americium-Beryllium neutron source. Test results indicated the most shielding in the cross-linked PVOH, followed by the pristine PVOH, and MDPE. Neutron testing suggests that polyvinyl alcohol is a good alternative to polyethylene for neutron shielding. The neutron shielding materials, PVOH and cross-linked PVOH developed under this research will enable the safe operation of spacecraft beyond the Earth’s protective Van Allen Radiation Belts. It will be crucial for NASA’s manned missions to the Moon or Mars to protect the health of astronauts and equipment from the harmful effects of excessive radiation.

neutron, shielding, radiation, polyvinyl alcohol, ↗

2019 ARIA Proposal Final Report Public Abstract: What Happens to Life in an Ocean World Plume?

The NASA Cassini mission to Saturn discovered persistent jets of water being ejected into space from a subsurface ocean on the small moon Enceladus and evidence that this ocean is habitable for life. The ice resulting from these plumes forms the E Ring of Saturn. Missions are under study to fly through these plumes and collect and analyze samples to look for evidence of life. To support design and instrument selection for these missions, there is a critical need to understand what happens to microbial life adapted to a liquid environment when suddenly ejected into the vacuum of space. We experimentally determined the structural changes in microbial cells in liquid medium when ejected into vacuum. We first developed a vacuum chamber fitted with a feedthrough and nozzle allowing fluid to be injected into vacuum. The nozzle dispersed the fluid into micron-sized droplets. Fluid containing a population of E. Coli microbes was injected into the chamber and droplets were collected on microscope slides and small cups for imaging with a Scanning Electron Microscope (SEM). Epifluorescence microscopy, using a lipid stain, and SEM imaging were used to evaluate the cellular integrity of E. coli after injection through the pressurized nozzle into vacuum. The experimental samples showed a 94% decrease in visible intact E. coli cells as compared with control samples but showed a fluorescent residue in the shape of the sublimated droplets that indicated the presence of lipids. E. coli was selected for testing although other cell types could vary physiologically which could affect their response to a vacuum environment. More testing is needed to determine whether other types of microbial cells can survive the plume environment. However, these results suggest that lipids may be directly detectable evidence of life in icy world plumes, but organisms are unlikely to survive due to disruption of their cell walls.

C. R. Stoker↗

Test Facilities for SHERLOC Laser Development

The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument is a deep UV laser based spectrometer that is part of NASA’s Mars Perseverance rover. The laser is a pulsed 248.6 nm NeCu hollow cathode gas discharge laser. The design, development, and testing of lasers and laser power supplies (LPS) were performed by scientists and engineers at the Jet Propulsion Laboratory (JPL) and Photon Systems Inc. (PSI). While these lasers had been used previously in extreme terrestrial environments, before they had to be qualified for operation and functionality over the expected range of environmental situations (temperature cycling, vibration, mechanical shock, low pressure corona emission testing) over the course of mission life time. The SHERLOC laser/LPS testing facilities consisted of custom-tailored environmental test chambers with metrology/control electronics. A custom LabVIEW software package was developed to autonomously operate all test facilities using a multi-threaded, object-oriented programming architecture, tasked with interfacing with many instruments simultaneously for operation and data acquisition.

Houck, Andrew↗

Determining the Biogenicity of Microfossils in the Apex Chert, Western Australia, Using Transmission Electron Microscopy

For over a decade, the oldest evidence for life on this planet has been microfossils in the 3.5 Ga Apex Chert in Western Australia. Recently, the biogenicity of these carbon-rich structures has been called into question through reanalysis of the local geology and reinterpretation of the original thin sections. Although initially described as a stratiform, bedded chert of siliceous clasts, the unit is now thought to be a brecciated hydrothermal vein chert. The high temperatures of a hydrothermal environment would probably have detrimental effects to early non-hyperthermophilic life, compared to that of a shallow sea. Conversely, a hydrothermal origin would suggest that if the microfossils were valid, they might have been hyperthermophilic. Apex Chert controversy. The Apex Chert microfossils were originally described as septate filaments composed of kerogen similar in morphology to Proterozoic and modern cyanobacteria. However new thin section analysis shows that these carbonaceous structures are not simple filaments. Many of the original microfossils are branched and have variable thickness when the plane of focus is changed. Hydrothermal alteration of organic remains has also been suggested for the creation of these strange morphologies. Another point of contention lies with the nature of the carbon material in these proposed microfossils. Kerogen is structurally amorphous, but transforms into well-ordered graphite under high pressures and temperatures. Raman spectrometry of the carbonaceous material in the proposed microfossils has been interpreted both as partially graphitized kerogen and amorphous graphite. However, these results are inconclusive, since Raman spectrometry cannot adequately discriminate between kerogen and disordered graphite. There are also opposing views for the origin of the carbon in the Apex Chert. The carbon would be biogenic if the proposed microfossils are indeed the remains of former living organisms. However, an inorganic Fischer- Tropsch-type synthesis is also a possible explanation for the formation of large-aggregate carbonaceous particles and could also account for the depletion of (13)C observed.

DeGregorio, B. T.↗

Preparation and Characterization of Polyimide/Organoclay Nanocomposites

Organically modified montmorrrillonite clay, containing a long chain aliphatic quarternary ammonium cation, was used to prepare polyimide/organoclay hybrids. Several approaches were examined in an attempt to achieve fully exfoliated nanocomposites. These included simple mixing of the clay in a pre-made high molecular weight poly(amide acid) solution; simple mixing followed by sonication of the organoclay/poly(amide acid) solutions; and the preparation of high molecular weight poly(amide acid)s in the presence of the organoclay dispersed in N-methyl-2-pyrrolidinone (NMP). The best results were obtained using the in-situ polymerization approach. The resulting nanocomposite films (both amide acid and imide), containing 3-8% by weight of organoclay, were characterized by differential scanning calorimetry (DSC), dynamic thermogravimetric analysis (TGA), transmission electron microscopy (TEM), X-ray diffraction (XRD), and thin film tensile properties. A significant degree of dispersion was observed in the nanocomposite films of the amide acid and the imide. After thermal treatment of amide acid films to effect imidization, in both air and nitrogen, the films were visually darker than control films without clay and the level of clay dispersion appeared to have decreased. In the latter case, the separation between the layers of the clay decreased to a spacing less than that present in the original organoclay. These observations suggest that thermal degradation of the aliphatic quarternary ammonium cation occurred likely during thermal treatment to effect imidization and solvent removal. These thermal degradation effects were less pronounced when thermal treatment was performed under nitrogen. The polyimide/organoclay hybrid films exhibited higher room temperature tensile moduli and lower strength and elongation to break than the control films.

Delozier, D. M.↗

Characterization of Individual Aerosol Particles Associated with Clouds (CRYSTAL-FACE)

The aim of our research was to obtain data on the chemical and physical properties of individual aerosol particles from near the bottoms and tops of the deep convective systems that lead to the generation of tropical cirrus clouds and to provide insights into the particles that serve as CCN or IN. We used analytical transmission electron microscopy (ATEM), including energy-dispersive X-ray spectrometry (EDS) and electron energy-loss spectroscopy (EELS), and field-emission electron microscopy (FESEM) to compare the compositions, concentrations, size distributions, shapes, surface coatings, and degrees of aggregation of individual particles from cloud bases and the anvils near the tropopause. Aggregates of sea salt and mineral dust, ammonium sulfate, and soot particles are abundant in in-cloud samples. Cirrus samples contain many H2SO4 droplets, but acidic sulfate particles are rare at the cloud bases. H2SO4 probably formed at higher altitudes through oxidation of SO2 in cloud droplets. The relatively high extent of ammoniation in the upper troposphere in-cloud samples appears to have resulted from vertical transport by strong convection. The morphology of H2SO4 droplets indicates that they had been at least yartiy ammoniated at the time of collection. They are internally mixed with organic materials, metal sulfates, and solid particles of various compositions. Ammoniation and internal mixing of result in freezing at higher temperature than in pure H2SO4 aerosols. K- and S-bearing organic particles and Si-Al-rich particles are common throughout. Sea salt and mineral dust were incorporated into the convective systems from the cloud bases and worked as ice nuclei while being vertically transported. The nonsulfate particles originated from the lower troposphere and were transported to the upper troposphere and lower stratosphere.

Buseck, Peter R.↗

Microbial Pigments and Their Degradation Products as Biosignatures

Carotenoids are a class of vibrant biological pigments that have a characteristic chemical structure centered around a polyene core (Lu et al. 2018). Carotenoids and their derivatives are candidate biosignatures because they can persist in the terrestrial geologic record for up to 1.73 billion years (Vinnichenko et al. 2020), have specific structures that are likely the result of complex pathways, mediate the survival of many microorganisms in Mars and Ocean Worlds analog environments, and are detectable with multiple techniques, including Raman spectroscopy. In this project, we aim to investigate the detectability of carotenoid pigments with different spectroscopic methods to inform future instrument selection. We compare the spectra of five unaltered carotenoids, two model compounds, and carotenoid-forming archaeon with visible and deep UV Raman spectroscopy and UVVis absorption spectrophotometry. We then use one model pigment, beta-carotene, to evaluate the likelihood that unique spectral properties of carotenoids, or their refractory byproducts, would be preserved and detectable on a remote planetary surface by exposing it to simulated conditions for Mars. Sample Acquisition. Pigments betacarotene, lutein, zeaxanthin, astaxanthin, and lycopene were purchased from Sigma Aldrich. Halobacterium salinarum NRC-1 was acquired from Carlina Biological and grown in Halobacterium media. Mineral salts including sodium sulfate, sodium carbonate, and halite were used to form matrices in which the beta-carotene was embedded before exposure. Pigment-mineral mixes were at a 1:10 ratio in water. Analytical Techniques. Deep UV Raman data were collected on a custom laboratory mapping spectrometer called MOBIUS (Mineral and Organic Based Investigations using Ultraviolet Spectroscopy), which is an analog to the SHERLOC instrument on the Mars 2020 Perseverance rover (Bhartia et al. 2021). It features a 248.56 nm NeCu pulsed laser, liquid nitrogen-cooled detector, and tunable optical setup. Visible Raman data were collected using a Horiba Jobin Yvon LabRam HR spectrometer with a frequencydoubled Nd:YAG laser (532 nm) and a HeNe laser (633 nm). A VWR 6300 PC UV/Visible Spectrophotometer was used to collect absorption data for carotenoid solutions, model compounds, and solvents in UVpermissible capped cuvettes. Data were collected from 190-1100 nm at 1 nm increments. All spectral data were analyzed using Igor Pro 9 (Wavemetrics). Irradiation. We used a vacuum chamber equipped with a cryostat and a flood electron gun to simulate Martian surface temperatures, low pressures, and ionizing radiation (10keV, 10μA for 6h at 200K for our initial tests). The samples were prepared by drying the pigment-mineral mix onto polished metal tabs, then mounted on the cryostat for processing. Samples were then analyzed directly on the tabs after exposure. Results: In comparing the visible and deep UV Raman spectra of unaltered pigments, we found that they differed drastically. Carotenoids are often studied with visible Raman and typically have peaks at 1525 cm-1 and 1157 cm-1, due to the stretching of the C=C and C-C bonds in the polyene structure. However, in deep UV, the strongest feature is at ~1630 cm-1 and is broad, possibly indicating that multiple peaks are forming this feature. This stark difference is likely due to different preresonant enhancement effects. The UV-Vis results show that there is an absorption band in the deep UV <300 nm, which supports the hypothesis that the 248.6 nm excitation is interrogating another aspect of carotenoids than visible Raman. Our preliminary exposure tests indicated that pigments – even without minerals present - were largely unaltered in the applied conditions, with only a slight broadening in the primary polyene peaks apparent in the visible Raman data. Figure 1. A) Visible vs. deep UV Raman spectra of unaltered beta carotene. B) Schematic of exposure. Conclusions: Our results to date indicate that deep UV and visible Raman spectroscopy, both techniques with planetary mission heritage from Mars 2020 (Wiens et al. 2021, Bhartia et al. 2021), may be used in a complementary manner to observe carotenoids. In addition, we find that beta-carotene is largely resistant to our current exposure conditions, though there may be some amount of amorphization of the material which could cause the broadening of the peaks at 1525 and 1157 cm-1. As a next step, we aim to increase the dosage and duration of exposure to observe degradation of the parent pigment, possibly add UV as a factor via an Ar mini-arc UV lamp and use GC-MS to characterize possible degradation products.

pigments↗

Cathode Modeling of Solid-State Batteries

The search for safe, reliable, and compact high-capacity energy storage devices has led to increased interest in all-solid-state battery research. The use of solid electrolytes provides enhanced safety and durability due to their reduced flammability and increased mechanical strength compared to organic liquid electrolytes. Still, the use of solid electrolytes remains challenging. Computational modeling plays a substantial role in addressing these challenges. A particle dynamics electromechanical model for simulating electrochemical processes in a solid-state battery cathode will be presented. The model presents cathode microstructure at the particle level as a mixture of ionically conductive solid electrolyte particles, electrically conductive carbon additives, and cathodic reactant particles. After densification, the particle connectivity is analyzed to reconstruct the complex electric network connecting reactant particles with an anodic and cathodic current collectors through the electrolyte and carbon particles. The Kirchhoff’s matrix equation describing this electric network, is solved to obtain values of various critical parameters, such as the overall conductivity of the cathode for lithium ions and electrons, cathodic reactant material utilization, and the distribution of the electric current and voltages within the cathode. In addition, by representing the reactant particles as electrolyte or galvanic microcells governed by the Butler-Volmer electrochemical equation, the overall performance of battery cells during charge or discharge processes, respectively, can be predicted for a given cathodic powder composition. The presented model, executed on a high-performance computing architecture, essentially provides a valuable guidance in designing and developing future solid-state batteries.

solid-state battery↗

Particle size effects on viscosity of silver pastes: A manufacturer's view

Particles from a variety of silver powders were investigated by scanning electron microscopy and particle size analyses. Particle size distribution curves and volume population graphs were prepared for these silver powders and for glass powders with optimum, extra fine and coarse particle sizes. The viscosity at a given shear rate and slope of viscosity over a range of shear rates were determined for thick film pastes made with these powders. Because of particle anomalies and variations, the need for flexibility to achieve the best printing qualities for silver pastes was evident. It was established that print quality, dried and fired film density and optimum contact of silver particles with silicon, important for cell electrical output, could be achieved by adjusting the slope of viscosity that fell outside of the range, -0.550 to -0.650. This was accomplished through organic vehicle technology that permitted a change in the slope of viscosity, up or down, while maintaining a constant silver and total solids content.

Provance, J.↗

Genesis Concentrator Target Particle Contamination Mapping and Material Identification

The majority of surface particles were found to be < 5 microns in diameter with increasing numbers close to the optical resolution limit of 0.3 microns. Acceleration grid EDS results show that the majority of materials appear to be from the SRC shell and SLA materials which include carbon-carbon fibers and Si-rich microspheres in a possible silicone binder. Other major debris material from the SRC included white paint, kapton, collector array fragments, and Al. Image analysis also revealed that SRC materials were also found mixed with the Utah mud and salt deposits. The EDS analysis of the acceleration grid showed that particles < 1 m where generally carbon based particles. Chemical cleaning techniques with Xylene and HF in an ultrasonic bath are currently being investigated for removal of small particles by the Genesis science team as well as ultra-pure water megasonic cleaning by the JSC team [4]. Removal of organic contamination from target materials is also being investigated by the science team with the use of UV-ozone cleaning devices at JSC and Open University [5]. In preparation for solar wind oxygen analyses at UCLA and Open University [1, 2], surface particle contamination on three Genesis concentrator targets was closely examined to evaluate cleaning strategies. Two silicon carbide (Genesis sample # 60001 and 60003) and one chemical vapor deposited (CVD) 13C concentrator target (60002) were imaged and mosaic mapped with optical microscopes. The resulting full target mosaic images and particle feature maps were subsequently compared with non-flight, but flight-like, concentrator targets and sample return capsule (SRC) materials. Contamination found on the flown concentrator acceleration grid was further examined using a scanning electron microscope (SEM). Energy dispersive X-ray spectroscopy (EDS) for particle identification was subsequently compared with the optical images from the flown targets. Figure 1 show that all three targets imaged in this report are fully intact and do not show any signs of material fractures. However, previous ellipsometry results and overview imaging of both flown SiC targets show a solar wind irradiation gradient from the center focal point to the outer edge [3]. In addition, due to the hard landing, each target has experienced varying degrees of impacts, scratches, and particle debris from the spacecraft and Utah impact site.

Calaway, Michael J.↗