Results for “Microwave chemistry” — Page 15

DOE OSTI2019

Enhanced yield-mobility products in hybrid halide Ruddlesden–Popper compounds with aromatic ammonium spacers

We show hybrid halide Ruddlesden–Popper compounds are related to three-dimensional hybrid AMX 3 perovskites (e.g. where A is a monovalent cation, M is a divalent metal cation, and X is a halogen) with the general formula L 2 A n–1 M n X 3n+1 where L is a monovalent spacer cation. The crystal structure comprises perovskite-like layers separated by organic cation spacers. Here two Ruddlesden–Popper compounds with a conjugated cation, 2-(4-biphenyl)ethylammonium (BPEA) prepared by solvothermal and solvent evaporation techniques are reported. The structures of the two compounds: (BPEA) 2 PbI 4 and (BPEA) 2 (CH 3 NH 3 )Pb 2 I 7 , were solved by X-ray crystallography. The aromatic rings of the BPEA groups are well-separated in the organic layers leading to optical properties comparable to n = 1 and 2 hybrid halide Ruddlesden–Popper compounds with simpler alkyl ammonium cations. The ambient stability of both compounds over time was also confirmed by powder X-ray diffraction. Finally, the transient photoconductance, measured by time-resolved microwave conductivity, show that the compounds have maximum yield-mobility products respectively of 0.07 cm 2 V –1 s –1 and 1.11 cm 2 V –1 s –1 for (BPEA) 2 PbI 4 and (BPEA) 2 (CH 3 NH 3 )Pb 2 I 7 , both slightly enhanced over what has been measured for compounds with simpler ( n -butylammonium) spacer cations.

36 MATERIALS SCIENCE↗

NASA NTRS1990

Submillimeter and millimeter observations of solar system objects

Microwave spectroscopy of solar system objects was supported. It necessarily involves millimeter and submillimeter wavelengths where rotational transitions reside. The existing national facilities are at OVRO, the 12-meter at Kitt Peak, UC array at Hat Creek, the Caltech CSO on Mauna Kea, and the 14-meter at the Univ. of Massachusetts, near Amherst. The group used all of these instruments in the last year except the Univ. of Massachusetts 14-meter. This wavelength range (0.3 to 3 mm) is about to enjoy an explosion of interest as submillimeter receivers become better and easier to use. This region of the spectrum is rich in transitions of molecules that exist in the planetary atmospheres which can be studied for temperature-pressure profiles, wind tracers, and atmospheric chemistry. The list of solar system objects that have been recently addressed with these techniques include: (1) Venus: CO studies of T-P profiles, winds, and photochemistry; SO2 detections; Continuum mapping remains to be done at 1 mm; (2) Earth H2O, CO, NO, NO2, O(18)O, etc. as a test bed for other atmospheres; (3) Mars: H2O, CO, O(18)O studies of T-P profiles, winds (fall of 1990), and photochemistry; (4) Saturn: Same as Jupiter plus submillimeter and millimeter mapping of the ring system; (5) Uranus and Neptune: Continuum thermal mapping; and (6) Titan: CO, HCN, and HC3NT-P information and photochemistry. Recent results are given.

Muhleman, Duane O.↗

NASA NTRS1996

On the Capabilities of Using AIRSAR Data in Surface Energy/Water Balance Studies

The capabilities of using remote sensing data, and in particular multifrequency/multipolarization SAR data, like AIRSAR, for the retrieval of surface parameters, depend considerably on the specificity of each application. The potentials, and limitations, of SAR data in ecological investigations are well known. Because the chemistry is a major component in such studies and because of the almost lacking chemical information at the wavelengths of SAR data, the capabilities of using SAR-derived information in such studies are considerably limited. However, in the case of surface energy/water balance studies, the determination of the amount of water content, both in the soil and in the plants, is a major component in all modeling approaches. As the information about water content is present in the SAR signal, then the role of SAR data in studies where water content is to be determined becomes clearly predominant. Another situation where the role of SAR data becomes dominant over other remote sensing systems is the case of dense canopies. Because of the penetration capabilities of microwave data, which is especially superior as compared to optical data, information about the canopy as a whole and even the underlying soil is contained in the SAR data, while only the top canopy provides the information content in the case of optical data. In the case of relatively dense canopies, as has been demonstrated in this study, such different penetration capabilities provide very different results in terms of the derived total canopy water content, for instance. However, although all such capabilities are well known, unfortunately there are also well known limitations. Apart from calibration-related aspects (that we will not consider in this study), and apart from other intrinsic problems (like image noise, topographic corrections, etc.) which also significantly affect the derived results, we will concentrate on the problem of extracting information from the data. Even at this level, methods are still not fully well established, especially over vegetation-covered areas. In this paper, an algorithm is described which allows derivation of three fundamental parameters from SAR data: soil moisture, soil roughness and canopy water content, accounting for the effects of vegetation cover by using optical (Landsat) data as auxiliary. Capabilities and limitations of the data and algorithms are discussed, as well as possibilities to use these data in energy/water balance modeling studies. All the data used in this study were acquired as part of the Intensive Observation Period in June-July 1991 (European Multisensor Aircraft Campaign-91), as part of the European Field Experiment in a Desertification- threatened Area (EFEDA), a European contribution to the global-change research sponsored by the IGBP program (Bolle et al., 1993).

Moreno, Jose F.↗

NASA NTRS1986

The organic aerosols of Titan

A dark reddish organic solid, called tholin, is synthesized from simulated Titanian atmospheres by irradiation with high energy electrons in a plasma discharge. The visible reflection spectrum of this tholin is found to be similar to that of high altitude aerosols responsible for the albedo and reddish color of Titan. The real (n) and imaginary (k) parts of the complex refractive index of thin films of Titan prepared by continuous dc discharge through a 0.9 N2/0.1 CH4 gas mixture at 0.2 mb is determined from X-ray to microwave frequencies. Values of n (approx. 1.65) and k (approx. 0.004 to 0.08) in the visible are consistent with deductions made by groundbased and spaceborne observations of Titan. Many infrared absorption features are present in k(lambda), including the 4.6 micrometer nitrile band. Molecular analysis of the volatile components of this tholin was performed by sequential and nonsequential pyrolytic gas chromatography/mass spectrometry. More than one hundred organic compounds are released; tentative identifications include saturated and unsaturated aliphatic hydrocarbons, substituted polycylic aromatics, nitriles, amines, pyrroles, pyrazines, pyridines, pyrimidines, and the purine, adenine. In addition,acid hydrolysis produces a racemic mixture of biological and nonbiological amino acids. Many of these molecules are implicated in the origin of life on Earth, suggesting Titan as a contemporary laboratory environment for prebiological organic chemistry on a planetary scale.

Khare, B. N.↗

NASA NTRSDate not supplied

GEOS Constituent Data Assimilation beyond Aura MLS: Assimilating NASA SAGE III/ISS profiles of stratospheric water vapor

Water vapor in the lower stratosphere is an important trace gas for atmospheric chemistry and radiative budget with direct impact on climate. During the last quarter of the 20th century, the Stratospheric Aerosol and Gas Experiment (SAGE) missions were crucial in monitoring the stratospheric ozone loss and the subsequent recovery as well as trends in water vapor linked to surface temperature trends. The SAGE III instrument aboard the International Space Station (ISS) continues the SAGE mission record, with high vertical resolution profiles of water vapor (and other constituents) since mid-2017. The NASA GEOS Earth system model has the capability to assimilate multi-constituents from ground and space-based instruments using the GEOS Constituent Data Assimilation System (CoDAS). Reanalysis products of stratospheric water vapor without data constraints are historically poor, and two recent reanalyses which assimilated stratospheric constituents observed by the Microwave Limb Sounder (MLS) improve the representation of stratospheric composition, including water vapor, when compared against independent observations. The MLS instrument is on NASA's Aura satellite which is expected to be decommissioned in the coming years. Here we demonstrate that while the number of solar occultation observations a day from SAGE III/ISS is about 1 % of the total number of profiles observed globally by MLS, the chemical timescales of water vapor in the lower stratosphere are long enough that the SAGE III/ISS data can provide a useful constraint on the assimilated product. Analyzed water vapor fields from assimilating only SAGE III/ISS water vapor profiles agree well with independent stratospheric observations, including when compared against the frost-point hygrometers at the three NOAA stations. Over the five-year period from 2017 through 2022, the analyzed water vapor using SAGE III/ISS captures many of the features seen with the assimilation of MLS observations. Note, this ability is reduced over regions where the SAGE III/ISS instrument provides infrequent or no observations (associated with the orbit of the ISS), as highlighted in the case study period following the eruption of the tropical underwater volcano Hunga Tonga in early 2022. Nevertheless, there is a clear benefit to the assimilation of stratospheric water vapor from SAGE III/ISS observations, allowing us to continue to monitor stratospheric composition for climate assessments following the impending loss of Aura.

K. Emma Knowland↗

NASA NTRSDate not supplied

GEOS Constituent Data Assimilation Beyond Aura MLS: Assimilating NASA SAGE III/ISS Profiles of Stratospheric Water Vapor

Water vapor in the lower stratosphere is an important trace gas for atmospheric chemistry and radiative budget with direct impact on climate. During the last quarter of the 20th century, the Stratospheric Aerosol and Gas Experiment (SAGE) missions were crucial in monitoring the stratospheric ozone loss and the subsequent recovery as well as trends in water vapor linked to surface temperature trends. The SAGE III instrument aboard the International Space Station (ISS) continues the SAGE mission record, with high vertical resolution profiles of water vapor (and other constituents) since mid-2017. The NASA GEOS Earth system model has the capability to assimilate multi-constituents from ground and space-based instruments using the GEOS Constituent Data Assimilation System (CoDAS). Reanalysis products of stratospheric water vapor without data constraints are historically poor, and two recent reanalyses which assimilated stratospheric constituents observed by the Microwave Limb Sounder (MLS) improve the representation of stratospheric composition, including water vapor, when compared against independent observations. The MLS instrument is on NASA's Aura satellite which is expected to be decommissioned in the coming years. Here we demonstrate that while the number of solar occultation observations a day from SAGE III/ISS is about 1 % of the total number of profiles observed globally by MLS, the chemical timescales of water vapor in the lower stratosphere are long enough that the SAGE III/ISS data can provide a useful constraint on the assimilated product. Analyzed water vapor fields from assimilating only SAGE III/ISS water vapor profiles agree well with independent stratospheric observations, including when compared against the frost-point hygrometers at the three NOAA stations. Over the five-year period from 2017 through 2022, the analyzed water vapor using SAGE III/ISS captures many of the features seen with the assimilation of MLS observations. Note, this ability is reduced over regions where the SAGE III/ISS instrument provides infrequent or no observations (associated with the orbit of the ISS), as highlighted in the case study period following the eruption of the tropical underwater volcano Hunga Tonga in early 2022. Nevertheless, there is a clear benefit to the assimilation of stratospheric water vapor from SAGE III/ISS observations, allowing us to continue to monitor stratospheric composition for climate assessments following the impending loss of Aura.

K. Emma Knowland↗

NASA NTRSDate not supplied

GEOS Constituent Data Assimilation Beyond Aura MLS: Assimilating NASA SAGE III/ISS Profiles of Stratospheric Water Vapor

Water vapor in the lower stratosphere is an important trace gas for atmospheric chemistry and radiative budget with direct impact on climate. During the last quarter of the 20th century, the Stratospheric Aerosol and Gas Experiment (SAGE) missions were crucial in monitoring the stratospheric ozone loss and the subsequent recovery as well as trends in water vapor linked to surface temperature trends. The SAGE III instrument aboard the International Space Station (ISS) continues the SAGE mission record, with high vertical resolution profiles of water vapor (and other constituents) since mid-2017. The NASA GEOS Earth system model has the capability to assimilate multi-constituents from ground and space-based instruments using the GEOS Constituent Data Assimilation System (CoDAS). Reanalysis products of stratospheric water vapor without data constraints are historically poor, and two recent reanalyses which assimilated stratospheric constituents observed by the Microwave Limb Sounder (MLS) improve the representation of stratospheric composition, including water vapor, when compared against independent observations. The MLS instrument is on NASA's Aura satellite which is expected to be decommissioned in the coming years. Here we demonstrate that while the number of solar occultation observations a day from SAGE III/ISS is about 1 % of the total number of profiles observed globally by MLS, the chemical timescales of water vapor in the lower stratosphere are long enough that the SAGE III/ISS data can provide a useful constraint on the assimilated product. Analyzed water vapor fields from assimilating only SAGE III/ISS water vapor profiles agree well with independent stratospheric observations, including when compared against the frost-point hygrometers at the three NOAA stations. Over the five-year period from 2017 through 2022, the analyzed water vapor using SAGE III/ISS captures many of the features seen with the assimilation of MLS observations. Note, this ability is reduced over regions where the SAGE III/ISS instrument provides infrequent or no observations (associated with the orbit of the ISS), as highlighted in the case study period following the eruption of the tropical underwater volcano Hunga Tonga in early 2022. Nevertheless, there is a clear benefit to the assimilation of stratospheric water vapor from SAGE III/ISS observations, allowing us to continue to monitor stratospheric composition for climate assessments following the impending loss of Aura.

K. Emma Knowland↗

DOE OSTI2021

Optoelectronic property comparison for isostructural Cu 2 BaGeSe 4 and Cu 2 BaSnS 4 solar absorbers

To target mitigation of anti-site defect formation in Cu 2 ZnSnS 4–x Se x , a new class of chalcogenides, for which Ba or Sr (group 2) replace Zn (group 12), has recently been introduced for prospective solar absorber application. Cu 2 BaGeSe 4 (CBGSe) and Cu 2 BaSnS 4 (CBTS) are two such compounds, which share a common trigonal crystal structure (P3 1 space group) and similar quasi-direct band gap (~2 eV). While CBTS-based films have already been studied, there are no reports yet on films and solar cells based on related CBGSe. To identify key differences and similarities in the electronic properties between these two materials, electronic characteristics (e.g., carrier concentration, mobility, electron affinity, defect levels, recombination, and charge carrier kinetics) of vacuum-deposited CBGSe and CBTS films are compared using a variety of characterization methods. Hall effect measurements reveal that CBGSe films have relatively higher hole carrier concentration and lower mobility (3 × 10 15 cm –3 , 0.6 cm 2 V –1 s –1 ) compared to CBTS (5 × 10 12 cm –3 , 3.5 cm 2 V –1 s –1 ). Photoelectron spectroscopy yields low electron affinity values for both CBGSe (3.7 eV) and CBTS (3.3 eV), pointing to the necessity of pursuing low electron affinity buffer materials for both types of absorbers. At low temperatures, CBGSe films show free-exciton photoluminescence, as well as pronounced deep-level emission at ~1.4 eV, while CBTS films exhibit a strong bound-exciton signal with noticeably less intense deep-level emission than for CBGSe. Charge carrier kinetics, transport, and recombination properties of both types of films are also analyzed using optical-pump terahertz-probe spectroscopy and time-resolved microwave conductivity. The first CBGSe prototype solar cells (using chemical bath deposited CdS as a buffer layer) show a maximum of 1.5% efficiency with ~0.62 V open-circuit voltage. Furthermore, the measured properties point to possible limiting factors for CBGSe and related films for PV and optoelectronics and provide insights on possible approaches for improvement within this multinary chalcogenide family.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1984

Laboratory degradation of Kapton in a low energy oxygen ion beam

An atomic oxygen ion beam, accelerated from a tunable microwave resonant cavity, was used at Lewis Research Center to bombard samples of the widely used polyimide Kapton. The Kapton experienced degradation and mass loss at high rates, which may be comparable to those found in Space Shuttle operations if the activation energy supplied by the beam enabled surface reactions with the ambient oxygen. The simulation reproduced the directionality (ram-wake dependence) of the degradation, the change in optical properties of the degraded materials, and the structure seen in scanning electron micrographs of samples returned on the Shuttle Trails with a substituted argon ion beam produced no rapid degradation. Energy Dispersive X-ray Analysis (EDAX) showed significant surface composition changes in all bombarded samples. Mass loss rates and surface composition changes are discussed in terms of the possible oxidation chemistry of the interaction. Finally, the question of how the harmful degradation of materials in low Earth orbit can be minimized is addressed.

Ferguson, D. C.↗

NASA NTRS1983

Laboratory degradation of Kapton in a low energy oxygen ion beam

An atomic oxygen ion beam, accelerated from a tunable microwave resonant cavity, was used at Lewis Research Center to bombard samples of the widely used polyimide Kapton. The Kapton experienced degradation and mass loss at high rates, which may be comparable to those found in Space Shuttle operations if the activation energy supplied by the beam enabled surface reactions with the ambient oxygen. The simulation reproduced the directionality (ram-wake dependence) of the degradiation, the change in optical properties of the degraded materials, and the structure seen in scanning electron micrographs of samples returned on the Shuttle Trails with a substituted argon ion beam produced no rapid degradation. Energy Dispersive X-ray Analysis (EDAX) showed significant surface composition changes in all bombarded samples. Mass loss rates and surface composition changes are discussed in terms of the possible oxidation chemistry of the interaction. Finally, the question of how the harmful degradation of materials in low earth orbit can be minimized is addressed.

Ferguson, D. C.↗

DOE OSTI2023

Next Generation Fiber-Encapsulated Nanoscale Hybrid Materials for Direct Air Capture with Selective Water Rejection

Recently, NOHMs sorbents have been demonstrated to be highly stable and tunable for CO2 capture and have negligible vapor pressure, but their main drawbacks are high viscosity and high gas transfer limitation in their neat bulk phase. This project explored gas-assisted electrospinning processing coupled with promising encapsulation matrices such as Polymers with Intrinsic Microporosity (PIM-1) and polyacrylonitrile (PAN)/organopolysilizane (OPSZ) polymer/ceramic hybrid materials, which were demonstrated to be effective novel carriers for the active NOHMs sorbents. These encapsulation materials were evaluated by their thermal stability, hydrophobicity, permeability, and CO2 selectivity. The manufacturing parameters such as component composition and processing solvent were linked to bulk sorbent properties, e.g., surface area, pore volume, fiber thickness, capture capacity, capture kinetics, etc. These investigations resulted in fundamental knowledge and technical know-how that will be useful for scaling up the nanofiber mat contactor design. The encapsulation materials and design has been shown to not only increase the thermal oxidative stability of the NOHMs, but also yield significantly reduced pressure drop and increased performance of large modular air filters. 70 PAN: 30 OPSZ/NIPEI fibers exhibited the highest capture performance with 1.5 mmol CO2/g∙h kinetics the first hour under 100% CO2 condition, followed by 80 PAN: 20 OPSZ/NIPEI and 90 PAN: 10 OPSZ/NIPEI, while 90 PAN: 10 OPSZ/NIPEI fibers performed the best with 0.25 mmol CO2/g∙h of the initial kinetics under 400 ppm CO2 concentration. All the fabricated fibers demonstrated stable capture performances up to 15 cycles of adsorption and desorption. Using encapsulated NOHMs, the study found that the microwave could help regenerate the capture materials within 20 minutes without chemically degrading the materials. A high-level TEA/LCA study was performed to evaluate the feasibility of this technology at scale. These estimates show that the sorbent cost and environmental impact levels are comparable to other existing technologies. Overall, these findings increase the technological feasibility of using liquid-like, low vapor pressure NOHMs as a next generation sorbent for the direct air capture of CO2.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Structure and composition of blueberry fiber pectin and xyloglucan that bind anthocyanins during fruit puree processing

Blueberry is a well-known source of antioxidants and prebiotic dietary fiber yet the fate of these health-beneficial ingredients during fruit processing it is not understood. Detailed composition and structure of blueberry pomace (PF) remaining after commercial blueberry fruit puree processing, as well as the water soluble and water insoluble fractions, were determined. The PF was comprised of dietary fiber (60.8%) that was largely insoluble (46.2% vs. 14.6% soluble dietary fiber) pectin, xyloglucan, arabinoxylan and mannan polysaccharides, fructose (11.22%) and glucose (10.37%) free sugars, protein (9%), fat (5%), and anthocyanins (6444.5 μg/g). The most abundant anthocyanins detected in PF were malvidin 3-arabinoside and peonidin 3-glucoside and the pectin was determined to be methyl-esterified and acetylated rhamnogalacturonan I with a 4,5-unsaturated function at the non-reducing end based on oligosaccharide structural analysis. Blueberry PF xyloglucan oligosaccharide side chain structures included xylose, arabinose and galactose consistent with arabino-xyloglucan structure. Additionally, microwave-assisted extraction of blueberry PF (pH 2 for 10 min at 80 °C) was performed to more clearly elucidate pectin structure, and revealed a pectin polymer with high molar mass (1072 kDa) and viscosity that was dependent upon the molar mass. A random coil shape was confirmed for both the blueberry PF and microwave extracted blueberry pectin, which agreed with previous reports that flexible blueberry pectin contributes to strong anthocyanin binding. In summary, the blueberry pomace anthocyanin content was slightly higher than that reported for fresh whole blueberry fruit, which suggests that most blueberry anthocyanins adhered to the pomace fiber, and most likely the insoluble pectin, during and after processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2011

Molecular Anions in Protostars, Prestellar Cores and Dark Clouds

From our recent survey work using the Green Bank Telescope, microwave emission lines from the hydrocarbon anion C6H(-) and its parent neutral C6H have been detected in six new sources. Using HC3N = 10(exp -9) emission maps, we targeted the most carbon-chain-rich sources for our anion survey, which included the low-mass Class 0 protostar L1251A-IRS3, the prestellar cores L1389-SMM1 and L1512, and the interstellar clouds Ll172A, TMC-1C and L1495B. Derived [C6H(-)]/[C6H] anion-to-neutral ratios are approximately 1-10. The greatest C6H(-) column densities are found in the quiescent clouds TMC-1C and L1495B, but the anion-to-neutral ratios are greatest in the prestellar cores and protostars. These results are interpreted in terms of the physical and chemical properties of the sources, and the implications for molecular cloud chemistry are discussed.

Cordiner, Martin↗

NASA NTRS2022

SAGE III/ISS Ozone and NO2 Validation Using Diurnal Scaling Factors

We developed a set of solar zenith angle, latitude- and altitude-dependent scaling factors to account for the diurnal variability in ozone (O3) and nitrogen dioxide (NO2) when comparing Stratospheric Aerosol and Gas Experiment (SAGE) III/ISS observations to observations from other times of day. The scaling factors are calculated as a function of solar zenith angle from the four-dimensional output of a global atmospheric chemistry model simulation of 2017–2020 that shows good agreement with observed vertical profiles. Using a global atmospheric chemistry model allows us to account for both chemically and dynamically driven variability. Both year-specific scale factors and a multi-year monthly climatology are available to decrease the uncertainty in inter-instrument comparisons and allow consistent comparisons between observations from different times of day. We describe the variability in the diurnal scale factors as a function of space and time. The quasi-biennial oscillation (QBO) appears to be a contributing factor to interannual variability in the NO2 scaling factors, leading to differences between years that switch sign with altitude. We show that application of these scaling factors improves the comparison between SAGE III/ISS and OSIRIS NO2 and between SAGE III/ISS and OMPS LP, OSIRIS, and ACE-FTS O3 observations. The comparisons between SAGE III/ISS O3 for sunrise or sunset vs. Microwave Limb Sounder (MLS) daytime or nighttime observations are also more consistent when we apply the diurnal scaling factors. There is good agreement between SAGE III/ISS V5.2 ozone and correlative measurements, with differences within 5 % between 20 and 50 km when corrected for diurnal variability. Similarly, the SAGE III/ISS V5.2 NO2 agreement with correlative measurement is mostly within 10 %. While the scale factors were designed for use with SAGE III/ISS observations, they can easily be applied to other observation intercomparisons as well.

Sarah A. Strode↗

DOE OSTI2020

Automated Construction of Potential Energy Surfaces Suitable to Describe van der Waals Complexes with Highly Excited Nascent Molecules: The Rotational Spectra of Ar–CS( v ) and Ar–SiS( v )

Some reactions produce extremely hot nascent products which nevertheless can form sufficiently long-lived van der Waals (vdW) complexes—with atoms or molecules from a bath gas—as to be observed via microwave spectroscopy. Theoretical calculations of such unbound resonance states can be much more challenging than ordinary bound-state calculations depending on the approach employed. One encounters not just the floppy, and perhaps multiwelled potential energy surface (PES) characteristic of vdWs complexes, but in addition, one must contend with excitation of the intramolecular modes and its corresponding influence on the PES. Straightforward computation of the (resonance) rovibrational levels of interest, involves the added complication of the unbound nature of the wave function, often treated with techniques such as introducing a complex absorbing potential. Here, we have demonstrated that a simplified approach of making a series of vibrationally effective PESs for the intermolecular coordinates—one for each reaction product vibrational quantum number of interest—can produce vdW levels for the complex with spectroscopic accuracy. This requires constructing a series of appropriately weighted lower-dimensional PESs for which we use our freely available PES-fitting code AUTOSURF. The applications of this study are the Ar–CS and Ar–SiS complexes, which are isovalent to Ar–CO and Ar–SiO, the latter of which we considered in a previously reported study. Using a series of vibrationally effective PESs, rovibrational levels and predicted microwave transition frequencies for both complexes were computed variationally. A series of shifting rotational transition frequencies were also computed as a function of the diatom vibrational quantum number. The predicted transitions were used to guide and inform an experimental effort to make complementary observations. Comparisons are given for the transitions that are within the range of the spectrometer and were successfully recorded. Calculations of the rovibrational level pattern agree to within 0.2% with experimental measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1999

Diagnostic for Plasma Enhanced Chemical Vapor Deposition and Etch Systems

In order to meet NASA's requirements for the rapid development and validation of future generation electronic devices as well as associated materials and processes, enabling technologies ion the processing of semiconductor materials arising from understanding etch chemistries are being developed through a research collaboration between Stanford University and NASA-Ames Research Center, Although a great deal of laboratory-scale research has been performed on many of materials processing plasmas, little is known about the gas-phase and surface chemical reactions that are critical in many etch and deposition processes, and how these reactions are influenced by the variation in operating conditions. In addition, many plasma-based processes suffer from stability and reliability problems leading to a compromise in performance and a potentially increased cost for the semiconductor manufacturing industry. Such a lack of understanding has hindered the development of process models that can aid in the scaling and improvement of plasma etch and deposition systems. The research described involves the study of plasmas used in semiconductor processes. An inductively coupled plasma (ICP) source in place of the standard upper electrode assembly of the Gaseous Electronics Conference (GEC) radio-frequency (RF) Reference Cell is used to investigate the discharge characteristics and chemistries. This ICP source generates plasmas with higher electron densities (approximately 10(exp 12)/cu cm) and lower operating pressures (approximately 7 mTorr) than obtainable with the original parallel-plate version of the GEC Cell. This expanded operating regime is more relevant to new generations of industrial plasma systems being used by the microelectronics industry. The motivation for this study is to develop an understanding of the physical phenomena involved in plasma processing and to measure much needed fundamental parameters, such as gas-phase and surface reaction rates. species concentration, temperature, ion energy distribution, and electron number density. A wide variety of diagnostic techniques are under development through this consortium grant to measure these parameters. including molecular beam mass spectrometry (MBMS). Fourier transform infrared (FTIR) spectroscopy, broadband ultraviolet (UV) absorption spectroscopy, a compensated Langmuir probe. Additional diagnostics. Such as microwave interferometry and microwave absorption for measurements of plasma density and radical concentrations are also planned.

Cappelli, Mark A.↗

DOE OSTI2023

Temperature-dependent complex dielectric permittivity: a simple measurement strategy for liquid-phase samples

Abstract Microwaves (MWs) are an emerging technology for intensified and electrified chemical manufacturing. MW heating is intimately linked to a material’s dielectric permittivity. These properties are highly dependent on temperature and pressure, but such datasets are not readily available due to the limited accessibility of the current methodologies to process-oriented laboratories. We introduce a simple, benchtop approach for producing these datasets near the 2.45 GHz industrial, medical, and scientific (ISM) frequency for liquid samples. By building upon a previously-demonstrated bireentrant microwave measurement cavity, we introduce larger pressure- and temperature-capable vials to deduce temperature-dependent permittivity quickly and accurately for vapor pressures up to 7 bar. Our methodology is validated using literature data, demonstrating broad applicability for materials with dielectric constant ε' ranging from 1 to 100. We provide new permittivity data for water, organic solvents, and hydrochloric acid solutions. Finally, we provide simple fits to our data for easy use.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2005

The Effect of 17-4 PH Stainless Steel on the Lifetime of a Pennzane(Trademark) Lubricated Microwave Limb Sounder Antenna Actuator Assembly Ball Screw for the AURA Spacecraft

During ground based life testing of a Microwave Limb Sounder (MLS) Antenna Actuator Assembly (AAA) ball-screw assembly, lubricant darkening and loss were noted when approximately 10 percent of required lifetime was completed. The MLS-AAA ball screw and nut are made from 17-4 PH steel, the nut has 440C stainless steel balls, and the assembly is lubricated with a Pennzane formulation containing a three weight percent lead naphthenate additive. Life tests were done in dry nitrogen at 50 C. To investigate the MLS-AAA life test anomaly, Spiral Orbit Tribometer (SOT) accelerated tests were performed. SOT results indicated greatly reduced relative lifetimes of Pennzane formulations in contact with 17-4 PH steel compared to 440C stainless steel. Also, dry nitrogen tests yielded longer relative lifetimes than comparable ultrahigh vacuum tests. Generally, oxidized Pennzane formulations yielded shorter lifetimes than non-oxidized lubricant. This study emphasizes surface chemistry effects on the lubricated lifetime of moving mechanical assemblies.

Jones, William R., Jr.↗