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At least 757 records · Page 42

Silicates and variability in comets Okazaki-Levy-Rudenko (1989r) and Austin (1989c1)

Comet Okazaki-Levy-Rudenko (1989r) was studied over a wide range of wavelengths from the UV to the submillimeter. Using visual magnitude estimates from the IAU Circulars and reported submillimeter fluxes in conjunction with the thermal infrared spectroscopy and filter photometry, the nature of the grains and the behavior of the comet can be assessed and compared to other comets studied under this program. In addition, preliminary results from a collaborative infrared study of Comet Austin are presented which address the nature of the dust in that comet. Progress on a model for cometary properties and brightness behavior is discussed.

Russell, Ray W.↗

Strategies to Support Exploration of Mars' Surface

Surface Visible infrared spectroscopy has a long history of providing fundamental compositional discoveries in the solar system. However, we are entering a new era of Mars exploration in which missions will take place nearly every 2 years.The visible infrared spectral community thus faces a more rapid influx in data volume and variety than it has previously handled.Visible- infrared instruments are on the 1996 Mars Global Surveyor, 2001 Mars Odyssey 2003 Mars Exploration Rovers, 2003 Mars Express, 2005 Mars Reconnaissance Orbiter; and likely on the 2007 and 2009 missions. Interpretations of those data sets provide a critical foundation for geologic and climatic interpretations as well as an opportunity to select landing sites.

Kirkland, L.↗

Study of thermal stability and degradation of fire resistant candidate polymers for aircraft interiors

The thermochemistry of bismaleimide resins and phenolphthalein polycarbonate was studied. Both materials are fire-resistant polymers and may be suitable for aircraft interiors. The chemical composition of the polymers has been determined by nuclear magnetic resonance and infrared spectroscopy and by elemental analysis. Thermal properties of these polymers have been characterized by thermogravimetric analyses. Qualitative evaluation of the volatile products formed in pyrolysis under oxidative and non-oxidative conditions has been made using infrared spectrometry. The residues after pyrolysis were analyzed by elemental analysis. The thermal stability of composite panel and thermoplastic materials for aircraft interiors was studied by thermogravimetric analyses.

Hsu, M. T. S.↗

In-situ IR Spectroscopy Study of Reactions of C3 Oxygenates on Heteroatom (Sn, Mo, and W) doped BEA Zeolites and the Effect of Co-adsorbed Water

The reactions of acetone and hydroxyacetone over heteroatom doped BEA zeolites (Sn, Mo, and W) in the presence and absence of H 2 O vapor are investigated using infrared spectroscopy. Acetone is converted to mesityl oxide over Sn-BEA exclusively. At higher temperatures, larger oxygenates such as phorones, aromatics, and coke form. The presence of co-adsorbed water in Sn-BEA suppresses tautomerization. H 2 O vapor is also beneficial for minimizing coke formation at high temperatures. Hydroxyacetone is converted into 2-hydroxypropanal over Sn-BEA, exhibiting high affinity to Sn sites up to 400 °C. Sn-BEA catalyzes conversion of hydroxyacetone into the enol in the absence of H 2 O, but exposure to H 2 O induces the formation of 2-hydroxypropanal and subsequent conversion to acrolein. Furthermore, the Lewis acid descriptors are used to rationalize the reaction pathways. For the isomerization of hydroxyacetone into 2-hydroxypropanal, the hardness of acid sites influences the reaction and correlates with the overall Lewis acidity of the catalysts, respectively. However, the size of the exchanged metal significantly affects aldol condensation, where keto and enol forms of acetone adsorb to active sites simultaneously.

36 MATERIALS SCIENCE↗

Carboxylic and dicarboxylic acids extracted from crushed magnesium oxide single crystals

Carboxylic and dicarboxylic acids (glycolic, oxalic, malonic and succinic) have been extracted with tetrahydrofuran (THF) and H2O from large synthetic MgO crystals, crushed to a medium fine powder. The extracts were characterized by infrared spectroscopy and 1H-NMR. The THF extracts were derivatized with tert-butyldimethylsilyl (t-BDMS) for GC-MS analysis. A single crystal separated from the extract was used for an x-ray structure analysis, giving the monoclinic unit cell, space group P21/c with ao = 5.543 A, bo = 8.845 A, co = 5.086 A, and beta = 91.9 degrees, consistent with beta-succinic acid, HOOC(CH2)COOH. The amount of extracted acids is estimated to be of the order of 0.1 to 0.5 mg g-1 MgO. The MgO crystals from which these organic acids were extracted grew from the 2860 degrees C hot melt, saturated with CO/CO2 and H2O, thereby incorporating small amounts of the gaseous components to form a solid solution (ss) with MgO. Upon cooling, the ss becomes supersaturated, causing solute carbon and other solute species to segregate not only to the surface but also internally, to dislocations and subgrain boundaries. The organic acids extracted from the MgO crystals after crushing appear to derive from these segregated solutes that formed C-C, C-H and C-O bonds along dislocations and other defects in the MgO structure, leading to entities that can generically be described as (HxCyOz)n-. The processes underlying the formation of these precursors are fundamental in nature and expected to be operational in any minerals, preferentially those with dense structures, that crystallized in H2O-CO2-laden environments. This opens the possibility that common magmatic and metamorphic rocks when weathering at the surface of a tectonically active planet like Earth may be an important source of abiogenically formed complex organic compounds.

NASA Discipline Exobiology↗

Surface intermediates identified using IR spectroscopy during the catalytic oxidation of C 2 H 6 on IrO 2 (1 1 0) at near-ambient pressures

Characterizing surface intermediates during catalysis is essential for developing mechanistic models of catalytic reactions and for identifying rate-controlling steps. Here, in this work, we used polarization-dependent reflection absorption infrared spectroscopy (PD-RAIRS) to investigate surface intermediates that form on IrO 2 (1 1 0) during the catalytic oxidation of C 2 H 6 at pressures near 0.5 Torr. Our results show that adsorbed CO and HCO 2 are the only intermediates detectable with PD-RAIRS across a wide range of temperatures and reactant compositions during complete C 2 H 6 oxidation, giving rise to dominant peaks at about 2093 and 1310 cm −1 , respectively. These assignments were corroborated by RAIRS measurements following CO and HCOOH adsorption in ultrahigh vacuum, RAIRS with C 2 H 6 – 18 O 2 mixtures during catalysis and vibrational frequencies and IR intensities computed using density functional theory. We find that increasing the C 2 H 6 mole fraction in the reaction mixture raises the CO surface coverage relative to HCO 2 , correlating with increasing catalytic oxidation rates. The formation of CO and HCO 2 surface species at temperatures well below catalytic ignition indicates that the overall rate of C 2 H 6 oxidation on IrO 2 (1 1 0) is governed by steps late in the reaction sequence, such as H 2 O formation, CO oxidation and HCO 2 dehydrogenation. These findings provide key insight into the mechanism of alkane oxidation on IrO 2 (1 1 0) and valuable input for first-principles microkinetic modeling.

Pope, Connor [Univ. of Florida, Gainesville, FL (U↗

Laboratory Spectra of Mixtures of CH4, C2H6, and CH3OH

Infrared spectroscopy is commonly used as a tool for identifying the composition of objects in the Solar System and beyond. Using laboratory spectra, optical constants can be calculated and used to create model spectra for comparison to spectra obtained from infrared telescopes. In this study, the optical constants of mixtures of simple organics, including CH4, C2H6, and CH3OH were calculated from 15 to 70 K, in the frequency range of 9000-500 cm(sup -1) (1.1-20 micrometers), at a spectral resolution of 1 cm(sup -1).

Mastrapa, Rachel↗

Ultrathin Free-Standing Oxide Membranes for Electron and Photon Spectroscopy Studies of Solid–Gas and Solid–Liquid Interfaces

Free-standing ultrathin (~2 nm) films of several oxides (Al 2 O 3 ,TiO 2 , and others) have been developed, which are mechanically robust and transparent to electrons with E kin ≥ 200 eV and to photons. We demonstrate their applicability in environmental X-ray photoelectron and infrared spectroscopy for molecular level studies of solid-gas (≥1 bar) and solid-liquid interfaces. These films act as membranes closing a reaction cell and as substrates and electrodes for electrochemical reactions. The remarkable properties of such ultrathin oxides membranes enable atomic/molecular level studies of interfacial phenomena, such as corrosion, catalysis, electrochemical reactions, energy storage, geochemistry, and biology, in a broad range of environmental conditions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Mechanisms of Polyethylene Terephthalate Pellet Fragmentation into Nanoplastics and Assimilable Carbons by Wastewater Comamonas

Comamonadaceae bacteria are enriched on poly(ethylene terephthalate) (PET) microplastics in wastewaters and urban rivers, but the PET-degrading mechanisms remain unclear. Here, we investigated these mechanisms with Comamonas testosteroniKF-1, a wastewater isolate, by combining microscopy, spectroscopy, proteomics, protein modeling, and genetic engineering. Compared to minor dents on PET films, scanning electron microscopy revealed significant fragmentation of PET pellets, resulting in a 3.5-fold increase in the abundance of small nanoparticles (<100 nm) during 30-day cultivation. Infrared spectroscopy captured primarily hydrolytic cleavage in the fragmented pellet particles. Solution analysis further demonstrated double hydrolysis of a PET oligomer, bis(2-hydroxyethyl) terephthalate, to the bioavailable monomer terephthalate. Supplementation with acetate, a common wastewater co-substrate, promoted cell growth and PET fragmentation. Of the multiple hydrolases encoded in the genome, intracellular proteomics detected only one, which was found in both acetate-only and PET-only conditions. Homology modeling of this hydrolase structure illustrated substrate binding analogous to reported PET hydrolases, despite dissimilar sequences. Mutants lacking this hydrolase gene were incapable of PET oligomer hydrolysis and had a 21% decrease in PET fragmentation; re-insertion of the gene restored both functions. Thus, we have identified constitutive production of a key PET-degrading hydrolase in wastewater Comamonas, which could be exploited for plastic bioconversion.

54 ENVIRONMENTAL SCIENCES↗

Contaminant Investigation and Pre‐Processing Opportunities for Textile‐To‐Textile Recycling

Millions of metric tons of textiles are landfilled or incinerated each year in the United States, with less than 1% of textiles recycled into new clothing or fabrics. To counter this trend, a growing number of companies and researchers are exploring how a circular economy can be applied to support textile‐to‐textile recycling. A significant barrier they face comes down to quickly and efficiently extracting pure feedstock material from post‐consumer garments that feature a mix of natural and synthetic fibers. Textile recyclers prefer pure feedstocks, as working with mixed sources typically means lower throughput, higher risk of equipment failure, and diminished business margins. To facilitate a circular economy for textiles, methods, and technologies are needed that can efficiently separate out materials and contaminants from end‐of‐life textiles to increase the flow of pure feedstocks to recyclers. This paper summarizes findings from interviews with a cross section of textile recyclers and from a review of literature to define basic feedstock requirements. In addition to our qualitative research, we deconstruct a bale of post‐consumer textiles and analyze them using computer‐vision imaging, Fourier transform infrared spectroscopy (FTIR), and machine learning. The resulting data are used to set system‐level design inputs for an automated contaminant removal system to process post‐consumer clothing into appropriate feedstocks for recycling. To set the system's levels for automated real‐time near‐infrared analysis, we identify the minimum percentage of primary material that any single garment in a load of used clothing must contain for the average of the full output stream to meet the target purity levels of recyclers. Here, the envisioned automated system can also address undesirable trace materials that might contaminate the processed stream by using imaging cameras coupled with artificial intelligence to identify sections of clothing for de‐trimming. Proof‐of‐concept machine learning algorithms are evaluated to locate and identify trims or garment areas with hidden contaminant materials. Integrating these methods into automated textile cutting systems can provide a cost‐effective means for increasing feedstock purity from used clothing, which can advance circularity for textiles by helping recyclers to reach production volumes and quality targets that were not possible solely with manual dismantling operations.

Parsons, Ryan [Rochester Institute of Technology, ↗

Geophysical Impacts and Spectroscopic Identification of a Hydrous Iron Sulfate on Icy Worlds

Over geologic time-scales, large volumes of exogenic sulfur ions from Io's plasma torus have been supplied to the surface of Europa and Ganymede, which, combined with recent interpretations of orbiter images, dynamical modeling, and surface-subsurface exchange, suggests further sulfur transport into the interior of the icy worlds. These observations motivate mixed-phase spectral modeling for interpreting orbiter spectroscopy data and determination of hydration states of candidate surface materials including hydrous sulfates. In this work, we present a combined experimental and theoretical study of the low temperature and high pressure vibrational spectral signature of the iron-sulfate monohydrate endmember, szomolnokite (FeSO 4 ·H 2 O). By employing synchrotron Fourier-transform infrared spectroscopy (FTIR) in the diamond anvil cell up to 23 GPa and down to 20 K, we explore the extreme range of pressure-temperature domains relevant to icy environments throughout our solar system and beyond. Combined with our density-functional theory quantum-mechanics molecular dynamics results, we demonstrate that experimentally observed infrared features in the O-H stretching region commonly associated with nH 2 O (n > 1) hydration states can be attributed to a pure monohydrate without the need for pressure-induced exsolved ice, other coexisting hydrous iron sulfates, or strong overtone and combination modes. We further discuss the possibility of lateral variations in density and shear properties on icy worlds associated with temperature variations and the high-pressure phases of kieserite group monohydrated sulfates.

Geosciences↗

Aged and unaged pine wood pyrogenic organic matter: mineralization, elemental analysis and spectroscopy data (February 2020)

In this study, we used a pyrogenic organic matter (PyOM) degrading Streptomyces isolate – a globally common soil bacterium – to investigate the effects of physical (freeze-thaw and wet-dry), chemical (oxidation), and biological (microbial community incubation) ageing on the chemical properties and mineralizability of 350°C and 550°C pine wood PyOM. We used Fourier Transform Infrared spectroscopy (FTIR) and elemental analysis to characterize the aged and unaged PyOM, and cavity ring-down spectroscopy to trace CO2 emissions. The carbon (C) mineralization data from incubation of aged and unaged PyOM with the isolate are provided in co2cmg_picarro_022020.csv. This dataset contains raw carbon dioxide (CO2) data measured on the cavity ring-down spectroscopy over 1 month of incubation. The dataset also includes processed data such as cumulative CO2 emitted over multiple cycles of measurement and CO2 values normalized by the total carbon content in each PyOM treatment. The carbon, hydrogen and nitrogen elemental content of aged and unaged 350°C and 550°C pine wood PyOM are provided in CHN_pyom.csv. The relative peak heights measured during the FTIR analysis of aged and unaged PyOM are provided in ftir_peaks_rel.csv.

54 ENVIRONMENTAL SCIENCES↗

Infrared nanoimaging and nanospectroscopy of electrochemical energy storage materials and interfaces

Electrochemical interfaces are central to the function and performance of energy storage devices. Thus, the development of new methods to characterize these interfaces, in conjunction with electrochemical performance, is essential for bridging the existing knowledge gaps and accelerating the development of energy storage technologies. Of particular need is the ability to characterize surfaces or interfaces in a non-destructive way with adequate resolution to discern individual structural and chemical building blocks. To this end, sub-diffraction-limit low-energy infrared optical probes that exploit near-field interactions within atomic force microscopy platforms, such as pseudoheterodyne nanoimaging, photothermal nanoimaging and nanospectroscopy, and nanoscale Fourier transform infrared spectroscopy, are all powerful emerging techniques. These are capable of non-destructive surface probing and imaging at nanometer resolution. This review outlines recent efforts to characterize ex situ, in situ, and operando electrode materials and electrochemical interfaces in rechargeable batteries with these advanced infrared near-field probes.

25 ENERGY STORAGE↗

Complex Refractive Index of Ammonium Nitrate in the 2-20 micron Spectral Range

Using high resolution Fourier Transform Infrared Spectroscopy (FTIR) absorbance/transmittance spectral data for ammonium sulfate (AMS), calcium carbonate (CAC) and ammonium nitrate (AMN), comparisons were made with previously published complex refractive indices data for AMS and CAC to infer experimental parameters to determine the imaginary refractive index for AMN in the infrared wavelength range from 2 to 20 microns. Kramers-Kronig mathematical relations were applied to calculate the real refractive index for the three compositions. Excellent agreement for AMS and CAC with the published values was found, validating the complex refractive indices obtained for AMN. Backscatter calculations using a lognormal size distribution for AMS, AMN, and CAC aerosols were performed to show differences in their backscattered spectra.

Jarzembski, Maurice A.↗

Observation of Quadratic (Charge-2) Weyl Point Splitting in Near-Infrared Photonic Crystals

Weyl points are point degeneracies that occur in momentum space of 3D periodic materials and are associated with a quantized topological charge. Here, the splitting of a quadratic (charge-2) Weyl point into two linear (charge-1) Weyl points in a 3D micro-printed photonic crystal is observed experimentally via Fourier-transform infrared spectroscopy. Using a theoretical analysis rooted in symmetry arguments, it is shown that this splitting occurs along high-symmetry directions in the Brillouin zone. This micro-scale observation and control of Weyl points is important for realizing robust topological devices in the near-infrared.

47 OTHER INSTRUMENTATION↗

Enabling quantitative analysis of complex polymer blends by infrared nanospectroscopy and isotopic deuteration

Atomic-force microscopy coupled with infrared spectroscopy (AFM-IR) deciphers surface morphology of thin-film polymer blends and composites by simultaneously mapping physical topography and chemical composition. However, acquiring quantitative phase and composition information from multi-component blends can be challenging using AFM-IR due to the possible overlapping infrared absorption bands between different species. Isotope labeling one of the blend components introduces a new type of bond (carbon-deuterium vibration) that can be targeted using AFM-IR and responds at wavelengths sufficiently shifted toward unoccupied regions (around 2200 cm –1 ). In this project, AFM-IR was used to probe the surface morphology and chemical composition of three polymer blends containing deuterated polystyrene; each blend is expected to exhibit various degrees of miscibility. AFM-IR results successfully demonstrated that deuterium labeling prevents infrared spectral overlap and enables the visualization of blend phases that could not normally be distinguished by other scanning probe techniques. The nanoscale domain composition was resolved by fast infrared spectrum analysis. Overall, we presented isotope labeling as a robust approach for circumventing obstacles preventing the quantitative analysis of multiphase systems by AFM-IR.

36 MATERIALS SCIENCE↗

Network structure in alteration layer of boroaluminosilicate glass formed by aqueous corrosion

Exogenously-added LiCl has been shown to slightly accelerate the corrosion rate of a boroaluminosilicate glass called International Simple Glass (ISG) in aqueous solutions over forward- and residual-rate regimes, while KCl and CsCl impede. To understand the effect of exogenously added electrolytes on resulting hydrous species and the network structure of alteration layers, infrared spectroscopy was implemented. It was found that the fraction of molecular water relative to the surface-bound hydroxyl species is lower in the KCl and CsCl conditions compared to the LiCl and pure water conditions. An approximation for the spectral features of the thin surface films from an experimentally-obtained specular-reflectance infrared (SR-IR) spectrum was proposed; results indicate no significant difference in the Si-O bonding network of the alteration layers formed in the presence of exogenously added LiCl, KCl and CsCl. Furthermore, the observed change in corrosion rates might be linked to the relative abundance of molecular water species in the porous network, rather than the silicate bonding structure.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗