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At least 271 records · Page 15

Thermal and Chemical Characterization of Composite Materials. MSFC Center Director's Discretionary Fund Final Report, Project No. ED36-18

The purpose of this research effort was to: (1) provide a concise and well-defined property profile of current and developing composite materials using thermal and chemical characterization techniques and (2) optimize analytical testing requirements of materials. This effort applied a diverse array of methodologies to ascertain composite material properties. Often, a single method of technique will provide useful, but nonetheless incomplete, information on material composition and/or behavior. To more completely understand and predict material properties, a broad-based analytical approach is required. By developing a database of information comprised of both thermal and chemical properties, material behavior under varying conditions may be better understood. THis is even more important in the aerospace community, where new composite materials and those in the development stage have little reference data. For example, Fourier transform infrared (FTIR) spectroscopy spectral databases available for identification of vapor phase spectra, such as those generated during experiments, generally refer to well-defined chemical compounds. Because this method renders a unique thermal decomposition spectral pattern, even larger, more diverse databases, such as those found in solid and liquid phase FTIR spectroscopy libraries, cannot be used. By combining this and other available methodologies, a database specifically for new materials and materials being developed at Marshall Space Flight Center can be generated . In addition, characterizing materials using this approach will be extremely useful in the verification of materials and identification of anomalies in NASA-wide investigations.

Stanley, D. C.↗

Ferritin-Templated Quantum-Dots for Quantum Logic Gates

Quantum logic gates (QLGs) or other logic systems are based on quantum-dots (QD) with a stringent requirement of size uniformity. The QD are widely known building units for QLGs. The size control of QD is a critical issue in quantum-dot fabrication. The work presented here offers a new method to develop quantum-dots using a bio-template, called ferritin, that ensures QD production in uniform size of nano-scale proportion. The bio-template for uniform yield of QD is based on a ferritin protein that allows reconstitution of core material through the reduction and chelation processes. One of the biggest challenges for developing QLG is the requirement of ordered and uniform size of QD for arrays on a substrate with nanometer precision. The QD development by bio-template includes the electrochemical/chemical reconsitution of ferritins with different core materials, such as iron, cobalt, manganese, platinum, and nickel. The other bio-template method used in our laboratory is dendrimers, precisely defined chemical structures. With ferritin-templated QD, we fabricated the heptagonshaped patterned array via direct nano manipulation of the ferritin molecules with a tip of atomic force microscope (AFM). We also designed various nanofabrication methods of QD arrays using a wide range manipulation techniques. The precise control of the ferritin-templated QD for a patterned arrangement are offered by various methods, such as a site-specific immobilization of thiolated ferritins through local oxidation using the AFM tip, ferritin arrays induced by gold nanoparticle manipulation, thiolated ferritin positioning by shaving method, etc. In the signal measurements, the current-voltage curve is obtained by measuring the current through the ferritin, between the tip and the substrate for potential sweeping or at constant potential. The measured resistance near zero bias was 1.8 teraohm for single holoferritin and 5.7 teraohm for single apoferritin, respectively.

Choi, Sang H.↗

Fast Electromechanical Switches Based on Carbon Nanotubes

Electrostatically actuated nanoelectromechanical switches based on carbon nanotubes have been fabricated and tested in a continuing effort to develop high-speed switches for a variety of stationary and portable electronic equipment. As explained below, these devices offer advantages over electrostatically actuated microelectromechanical switches, which, heretofore, have represented the state of the art of rapid, highly miniaturized electromechanical switches. Potential applications for these devices include computer memories, cellular telephones, communication networks, scientific instrumentation, and general radiation-hard electronic equipment. A representative device of the present type includes a single-wall carbon nanotube suspended over a trench about 130 nm wide and 20 nm deep in an electrically insulating material. The ends of the carbon nanotube are connected to metal electrodes, denoted the source and drain electrodes. At bottom of the trench is another metal electrode, denoted the pull electrode (see figure). In the off or open switch state, no voltage is applied, and the nanotube remains out of contact with the pull electrode. When a sufficiently large electric potential (switching potential) is applied between the pull electrode and either or both of the source and drain electrodes, the resulting electrostatic attraction bends and stretches the nanotube into contact with the pull electrode, thereby putting the switch into the "on" or "closed" state, in which substantial current (typically as much as hundreds of nanoamperes) is conducted. Devices of this type for use in initial experiments were fabricated on a thermally oxidized Si wafer, onto which Nb was sputter-deposited for use as the pull-electrode layer. Nb was chosen because its refractory nature would enable it to withstand the chemical and thermal conditions to be subsequently imposed for growing carbon nanotubes. A 200- nm-thick layer of SiO2 was formed on top of the Nb layer by plasma-enhanced chemical vapor deposition. In the device regions, the SiO2 layer was patterned to thin it to the 20-nm trench depth. The trenches were then patterned by electron- beam lithography and formed by reactive- ion etching of the pattern through the 20-nm-thick SiO2 to the Nb layer.

Kaul, Anupama↗

Characterization of latent image of electron beam resist via critical-dimension resonant soft X-ray scattering

Metrology plays a crucial role in semiconductor manufacturing by providing accurate and precise measurement and characterization of critical parameters. With the development of high-resolution extreme ultraviolet lithography (EUVL) processes, critical dimensions are shrinking to sub-10 nm. Resist materials encounter the challenge of providing heightened sensitivity and a handle on exacerbating stochastic variations. A comprehensive understanding of the chemical profile of the latent image is pivotal for mitigating stochastic effects and optimizing pattern quality. However, the subtle differences in chemistry between the exposed and unexposed regions of the resists make it extremely challenging to characterize the latent images with sub-nanometer precision. Here, we develop the metrology with critical-dimension resonant soft X-ray scattering (CD-RSoXS) to probe the chemical profiles of latent images stored in resist after exposure. The combination of absorption spectroscopy and enhanced scattering contrast makes it possible to characterize the subtle structural and chemical variations in the latent image. Moreover, the results of the measurements are compared with the simulations with a finite element method–based Maxwell solver to extract a detailed profile of the latent and developed images. We demonstrate that the CD-RSoXS technique can provide valuable insights into the high spatial resolution and local chemical sensitivity simultaneously, which is crucial to understanding the resolution limits and stochastic effects in EUVL processes.

36 MATERIALS SCIENCE↗

Bulk Major and Trace Elemental Composition of an Aggregate Sample From Asteroid Bennu

On September 24, 2023, NASA’s OSIRIS-REx mission returned a capsule to Earth carrying material from asteroid Bennu. This event was the first time a U.S. mission delivered pristine samples from an asteroid and is the largest asteroid sample return to date. As these samples represent some of the oldest, most primitive, and pristine materials available to us, and which originate from a known and well-studied asteroid, they allow us a rare opportunity to gain a better understanding of the formation and evolution of our solar system. Key to understanding the material returned from asteroid Bennu is establishing its bulk chemical composition. Previous studies have shown that each chondrite group has a distinct elemental composition. For the carbonaceous chondrites specifically, each group exhibits a distinct pattern of moderately and highly volatile elemental depletions, relative to CI chondrites. CI chondrites are considered the most primitive chondrite group and broadly represent the solar photosphere composition. The two most striking features of these depletion patterns is that the moderately volatile element depletions increase with decreasing 50% condensation temperature and then plateau out at abundances that roughly correlate with matrix abundance. Due to these distinctive patterns, bulk elemental composition has become an important classification tool for establishing the different chondrite groups and the connections between them. As such, determining the bulk chemical composition of the Bennu aggregates will help to test two mission hypothesis: “Bennu’s bulk elemental composition reflects that of its main parent asteroid and is similar to the composition of the Sun, with depletions in moderately to highly volatile elements” and “Bennu’s dominant lithologies are comparable in bulk mineralogy, petrology, and composition to the most aqueously altered carbonaceous chondrites” . Furthermore as the carbonaceous and non-carbonaceous chondrites are thought to have likely formed in the inner and outer protoplanetary disk, respectively (e.g., [8]), determining the bulk chemical compositions of the Bennu aggregates will also help test the major mission hypothesis that “Bennu's parent body formed beyond the snow line by accretion of material in the pro-toplanetary disk” . Regarding chondrite formation, observed elemental patterns have been successfully used to model how the mixing of volatile-rich and volatile-poor chondritic components can produce the observed carbonaceous chondrites groups. They have also been significant in investigating how volatilization processes influenced chondrite formation. As such, establishing bulk chemical compositions of the pristine Bennu samples is vital for understanding the asteroid, and solar system formation. To begin this processes, we analyzed the bulk major and trace elemental compositions of Bennu aggregates.

P Koefoed↗

Computer program to solve two-dimensional shock-wave interference problems with an equilibrium chemically reacting air model

The computer program EASI, an acronym for Equilibrium Air Shock Interference, was developed to calculate the inviscid flowfield, the maximum surface pressure, and the maximum heat flux produced by six shock wave interference patterns on a 2-D, cylindrical configuration. Thermodynamic properties of the inviscid flowfield are determined using either an 11-specie, 7-reaction equilibrium chemically reacting air model or a calorically perfect air model. The inviscid flowfield is solved using the integral form of the conservation equations. Surface heating calculations at the impingement point for the equilibrium chemically reacting air model use variable transport properties and specific heat. However, for the calorically perfect air model, heating rate calculations use a constant Prandtl number. Sample calculations of the six shock wave interference patterns, a listing of the computer program, and flowcharts of the programming logic are included.

Glass, Christopher E.↗

Enhancement of chemical oscillations by self-generated convective flows

Chemical feedback loops in fluids can produce not only chemical oscillations, but also density variations that generate solutal buoyancy forces, which in turn initiate fluid flow. Using analytical and computational models, we herein examine how the reaction-induced flows alter the chemical oscillations in a fluid-filled chamber whose top and bottom walls are coated with different enzymes. Due to this chemo-fluidic coupling, the systems form oscillating flow patterns, which combine the characteristic size of the buoyancy-driven convection rolls with the frequency of the chemical oscillations. With changes in the distance between the enzyme-coated walls, the convective flows not only enhance or suppress the chemical oscillations, but also substantially increase the amplitude and frequency of the oscillations and extend the regime of the oscillatory behavior. These design principles can facilitate the development of artificial biochemical networks that act as chemical clocks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid Patterning and Advanced Device Structures for Low Cost Manufacturable Crystalline Si IBC Cells

Recent record efficiency Si cells have had an interdigitated back contact (IBC) design where both positive and negative contacts are fabricated on the back side of the Si wafer. Many industry groups have investigated IBC cells but used photolithography to pattern the rear contacts although it is considered impractical for low cost, high volume manufacturing. Alternative patterning methods using lasers and mechanical masking have been utilized in fabrication of patterned regions in IBC Si solar cells to replace photolithography. Another exciting advance in Si solar cell technology has been replacing the high temperature diffusion of doped regions inside the crystalline Si wafer with low temperature deposition of very thin layers of doped amorphous hydrogenated Si (a-Si:H) on the Si wafer. This is called a Si heterojunction (HJ) device. The a-Si:H provides excellent passivation of surface defects and has produced the highest open circuit voltages (VOC) of any Si solar cell device structure. The Institute of Energy Conversion (IEC) demonstrated the first IBC-HJ solar cell combining these two strategies in 2007 and has fabricated IBC-HJ cells with 20% efficiency using three photolithography steps. Despite the demonstrated efficiency potential of this device by industry groups (>26%) there is no commercial production because of the challenges of patterning and processing the structure in an industrial environment. Our work sought to address that challenge. The objective of this 3 year project was to develop the processing for the IBC-HJ Si solar cell using lasers for patterning and contact formation instead of photolithography. Laser patterning enables rapid, contactless manufacturing of patterned regions. We intensively studied laser fired contacts, laser patterning of the a-Si multi-layer stacks and metal layers and the use of plasma shadow masks. After an exhaustive focus in the first year on the laser fired emitter (LFE) and contact (LFC), we were unable to achieve VOC greater than 660 mV, compared to the 720 mV required to meet our milestones. We discovered that an additional issue with our original IBC structure was the presence of an inversion layer at the back surface connecting the p and n regions which reduced the VOC and fill factor (FF). We developed innovative methods for characterizing the inversion layer. These two limitations in the original design lead to development of a new IBC-HJ process sequence and device structure which we called Plasma Masked Laser Processed (PMLP). It retained the original high efficiency features including manufacturability. The LFC was replaced with a standard n-type a-Si HJ contact. The inversion layer was eliminated by replacing the previous p-type stack in the gap with an n-type or SiN stack. The PMLP used laser ablation of a multi-layer a-Si stack followed by chemical etching to open the n-contact. It required deposition of a patterned stack through a mask in the plasma deposition chamber. This turned out to be a source of significant problems due to inevitable unwanted deposition ‘leakage’ under the mask. This formed a blocking contact on the emitter which significantly reduced Voc and FF. Several iterations in PMLP device structure and chemical etching steps resulted in a large improvements, e.g. the efficiency increasing from 3 to 15% and Voc from 450 to 660 mV but they were unable to completely eliminate it. The best IBC-HJ device we fabricated had only 15% efficiency. For perspective, our standard FHJ devices had 20% efficiency.

14 SOLAR ENERGY↗

One Structure, Two Elements—LuGe 2 Superconductor vs Ordinary Metallic Conductor LuSn 2 . A Case Study on How Site-Selective Germanium for Tin Atom Substitution Leads to Modulating of the Charge Distribution

The substitution of chemically similar elements in a given crystal structure is an effective way to enhance physical properties, but the understanding on such improvements is usually impeded because the substitutions are random, and the roles of the different atoms cannot be distinguished by crystallographic symmetry. Herein, we provide a detailed crystallographic analysis and property measurements for the continuous solid solutions LuGe x Sn 2–x (0 < x < 2). The results show that there is no apparent change of the global symmetry, with the end-members LuGe 2 and LuSn 2 , as well as the intermediate LuGe x Sn 2–x compositions adopting the ZrSi 2 type structure (space group Cmcm, Pearson index oC12). Yet, the refinements of the crystal structures from single-crystal X-ray diffraction data show that Ge–Sn atom substitutions are not random, but occur preferentially at the zig-zag chain. The patterned distribution of two group 14 elements leads to a significant variation in chemical bonding and charge ordering within the other structural fragment, the 2D square nets, thereby resulting in tuned electron transport. The enhancement is greater than the typical Bloch-Gruneisen model, and more akin to the parallel-resistor model. Magnetization measurements on single crystals show bulk superconductivity in all LuGe x Sn 2–x samples with shielding fractions as high as 90%. Specific heat data confirm the effect to originate from residual metallic tin in the material, indicating that Sn atom substitutions in the 2D square nets cause disruptions of the hypervalent bonding and local anisotropy, which ultimately leads to vanishing of the superconducting state in the end-member LuGe 2 . This work sheds light on how the complexity in chemical interactions by two different carbon congeners leads to changes in the physical properties and how they can be correlated with the induced charge distribution. Furthermore, these studies also provide a general approach to modulation of charge density, and thus, of emerging physical properties in other classes of intermetallic systems based on the main-group elements of groups 13 to 15.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Artificial Intelligence Guided Studies of van der Waals Magnets

A materials informatics framework to explore a large number of candidate van der Waals (vdW) materials is developed. In particular, in this study a large space of monolayer transition metal halides is investigated by combining high-throughput density functional theory calculations and artificial intelligence (AI) to accelerate the discovery of stable materials and the prediction of their magnetic properties. Here, the formation energy is used as a proxy for chemical stability. Semi-supervised learning is harnessed to mitigate the challenges of sparsely labeled materials data in order to improve the performance of AI models. This approach creates avenues for the rapid discovery of chemically stable vdW magnets by leveraging the ability of AI to recognize patterns in data, to learn mathematical representations of materials from data and to predict materials properties. Using this approach, previously unexplored vdW magnetic materials with potential applications in data storage and spintronics are identified.

36 MATERIALS SCIENCE↗

Plasmon-Mediated Intramolecular Methyl Migration with Nanoscale Spatial Control

Plasmonic materials interact strongly with light to focus and enhance electromagnetic radiation down to nanoscale volumes. Due to this localized confinement, materials that support localized surface plasmon resonances are capable of driving energetically unfavorable chemical reactions. In certain cases, the plasmonic nanostructures are able to preferentially catalyze the formation of specific photoproducts, which offers an opportunity for the development of solar-driven chemical synthesis. Here, using plasmonic environments, we report inducing an intramolecular methyl migration reaction, forming 4-methylpyridine from N-methylpyridinium. Using both experimental and computational methods, we were able to confirm the identity of the N-methylpyridinium by making spectral comparisons against possible photoproducts. This reaction involves breaking a C–N bond and forming a new C–C bond, highlighting the ability of plasmonic materials to drive complex and selective reactions. Additionally, we observe that the product yield depends strongly on optical illumination conditions. This is likely due to steric hindrance in specific regions on the nanostructured plasmonic substrate, providing an optical handle for driving plasmonic catalysis with spatial specificity. Furthermore, this work adds yet another class of reactions accessible by surface plasmon excitation to the ever-growing library of plasmon-mediated chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

North China Plain as a hot spot of ozone pollution exacerbated by extreme high temperatures

Abstract. A large population in China has been exposed to both severe ozone (O3) pollution and extreme heat under global warming. Here, the spatiotemporal characteristics of coupled extremes in surface O3 and heat (OPCs) over China are investigated using surface observations, a process-based chemical transport model (GEOS-Chem), and multi-model simulations from Phase 6 of the Coupled Model Intercomparison Project (CMIP6). North China Plain (NCP; 37–41∘ N; 114–120∘ E) is identified as a hot spot of OPCs, where more than half of the O3 pollution days are accompanied by high temperature extremes. OPCs over NCP exceeded 40 d during 2014–2019, exhibiting an increasing trend. Both O3 concentrations and temperatures are elevated during OPCs compared with O3 pollution days occurring individually (OPIs). Therefore, OPCs impose more severe health impacts to humans than OPIs, but the stronger health effects are mainly driven by the higher temperatures. GEOS-Chem simulations further reveal that enhanced chemical production resulting from hot and stable atmospheric conditions under anomalous weather patterns primarily contributes to the exacerbated O3 levels during OPCs. In the future, CMIP6 projections suggest increased occurrences of OPCs over NCP in the middle of this century, but by the end of this century, OPCs may decrease or increase depending on the pollutant emission scenarios. However, for all future scenarios, extreme high temperatures will play an increasingly important role in modulating O3 pollution in a warming climate.

Wang, Pinya (ORCID:0000000170347868)↗

Production of large-area single-crystal wafers of cubic SiC for semiconductor devices

A reproducible process is described for growing a thick single-crystal layer of cubic SiC on a single-crystal Si wafer by chemical vapor deposition. A buffer layer, grown in situ, is used between the cubic SiC and the Si substrate to minimize the effect of lattice mismatch. Layers of up to 34 microns thick and several sq cm in area have been grown. Wafers are obtained by chemically removing the Si substrates from the grown layers. Excellent electron channeling patterns produced by these wafers indicate very good crystal quality. Preliminary electrical measurements have yielded electron mobilities up to 380 sq cm/Vs.

Nishino, S.↗

How do the Properties of Allan Hills 84001 Compare With Accepted Criteria for Evidence of Ancient Life?

Criteria for Past Life: To be confident that any sample contains evidence of past life or biogenic activity, one must determine beyond a shadow of a doubt that certain well-established features or biomarker signatures are present in the sample. In the case of martian samples, the criteria for past life have not been established because if life existed on the planet, we have no way of knowing its detailed characteristics. Lacking independent evidence about the nature of possible past life on Mars, the scientific community must use, for the time being, the criteria established for ancient samples from the Earth: (1) Do we know the geologic context of the sample? Is it compatible with past life? (2) Do we know the age of the sample and its stratigraphic location? Are they understood enough to relate possible life to geologic history? (3) Does the sample contain evidence of cellular morphology? (4) What structural remains of colonies or communities exist within the samples? (5) Is there any evidence of biominerals showing chemical or mineral disequilibria? (6) Is there any evidence of stable isotope patterns unique to biology? (7) Are there any organic biomarkers present? (8) Are the features indigenous to the sample? For acceptance of past life in a geologic sample, essentially all of these criteria must he met.

Gibson, E. K., Jr.↗

Fuel cell crimp-resistant cooling device with internal coil

A cooling assembly for fuel cells having a simplified construction whereby coolant is efficiently circulated through a conduit arranged in serpentine fashion in a channel within a member of such assembly. The channel is adapted to cradle a flexible, chemically inert, conformable conduit capable of manipulation into a variety of cooling patterns without crimping or otherwise restricting of coolant flow. The conduit, when assembled with the member, conforms into intimate contact with the member for good thermal conductivity. The conduit is non-corrodible and can be constructed as a single, manifold-free, continuous coolant passage means having only one inlet and one outlet. The conduit has an internal coil means which enables it to be bent in small radii without crimping.

Wittel, deceased, Charles F.↗

Groundwater flowpath characteristics drive variability in per- and polyfluoroalkyl substances (PFAS) loading across a stream-wetland system

Groundwater dependent ecosystems in areas with industrial and military land use are at risk of direct exposure to a wide range of contaminants, including PFAS chemicals. Glaciated terrain often has mixed high and low permeability sediments coupled with groundwater flow-through lake features. These hydrogeologic attributes create highly complex ‘source to seep’ dynamics that make spatiotemporal contaminant transport patterns difficult to predict. We investigated one such system in detail using a suite of heat-tracing and chemical methods. Numerous (n=57) preferential groundwater discharge zones (vertical flux rates ranging 0.2 to 3.2 m/d) were identified across the upper Quashnet River stream-wetland system in Mashpee, MA, USA, adjacent to an Air Force Base with several known PFAS source areas. Surface-water and groundwater samples were collected and analyzed (n=145) for precursors and terminal PFAS compounds between March and September 2022. Samples were collected at identified seeps along the Quashnet River (n=59), from wells upgradient from the stream-wetland system (n= 44), from contributing flow-through kettle lakes (n=8), and at multiple locations along the Quashnet River (n=34). Samples from seeps and wells had measured PFAS concentrations ranging from non-detect to approximate 3,500 ng/L (mean= 1,650 ng/L), and a range of deuterium excess values (3.2 to 15.9 per mil) indicative of varying degrees of groundwater-lake interaction prior to emergence at the discharge zones. Groundwater-lake interaction along flowpaths that sourced the sampled seeps was farther supported by significant correlations (p < 0.01) between deuterium excess and %PFAS precursors, and between %PFAS precursors and multiple terminal PFAS compounds (e.g., PFPeS, PFBS, PFHxS). However, some sampled seeps contributing groundwater to the stream-wetland system had much higher total PFAS concentrations (>1000 ng/L) than the upgradient kettle lakes, despite showing lake (evaporative) isotopic signatures, indicating the potential for groundwater flowpath convergence at wetland discharge zones and the influence of lakebed PFAS precursor reactions. PFAS compounds and water isotopic composition at sampled multilevel groundwater wells, rivers, lakes, and seeps suggest that a complex mixture of source groundwater and flowpath characteristics are responsible for diverse observed PFAS mixtures at preferential discharge zones across the stream-wetland system. Further, total PFAS loading patterns to the Quashnet River via groundwater discharge remained remarkably similar from winter to summer to fall conditions, despite a regional dry period in late summer 2022 with the upper river channel completely drying. This work addresses gaps in the existing PFAS literature by demonstrating the importance of subsurface fate and transport on PFAS compound concentrations in controlling contaminant mass loading in preferential groundwater discharge zones and presents a transferrable field toolkit for efficient characterization of spatially preferential PFAS transport dynamics.

Contaminant transport↗

JPL Electronic Nose: From Sniffing Brain Cancer to Trouble in Space

What Is An Electronic Nose? An array of non-specific chemical sensors, controlled and analyzed electronically, which mimics the action of the mammalian nose by recognizing patterns of response. An Enose: (1.) ENose measures background resistance in each sensor and establishes a baseline. (2.) Contaminant comes in contact with sensors on the sensing head. (3.) The sensing films, change physical properties, such as thickness or color, as air composition changes. (4.) Sensor response is recorded by a computer, the change in resistance is computed, and the distributed response pattern of the sensor array is used to identify gases and mixtures of gases. (5. Responses of the sensor array are analyzed and quantified using software developed for the task.

chemical sensing↗