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At least 235 records · Page 13

Performance and Analysis of Perfluoropolyalkyl Ether Grease Used on Space Shuttle Actuators--A Case Study

Actuators used on the United States space shuttle fleet are lubricated with unspecified amounts of Braycote 601 (Castrol Braycote) grease consisting of a perfluoropolyalkyl ether (PFPAE) base oil thickened with a polytetrafluoroethylene (PTFE) filler. Each shuttle has four body flap actuators (BFAs) (two on each wing) on a common segmented shaft and four rudder speed brake (RSB) actuators. The actuators were designed to operate for 10 years and 100 flights without periodic relubrication. Visible inspection of two partially disassembled RSB actuators in continuous use for 19 years raised concerns over possible grease degradation due to discoloration of the grease on several places on the surfaces of the gears. Inspection revealed fretting, micropitting, wear and corrosion of the bearings and gears. A small amount of oil dripped from the disassembled actuators. Whereas new grease is beige in appearance, the discolored grease consisted of both grey and reddish colors. Grease samples taken from the actuators together with representative off-the-shelf new and unused grease samples were analyzed by gravimetry for oil content; by inductively coupled plasma spectroscopy (ICP) for metals content; Fourier transform infrared (FTIR) spectroscopy for base oil decomposition; and by size exclusion chromatography (SEC) for determination of the molecular weight distributions of the grease oil. The Braycote 601 grease was stable after 19 years of continuous use in the sealed RSB actuators and was fit for its intended purpose. There were no significant chemical differences between the used grease samples and new and unused samples. Base oil separation was not significant within the sealed actuators. No corrosive effect in the form of iron fluoride was detected. The grey color of grease samples was due to metallic iron. The red color was due to oxidation of the metallic wear particles from the gears and the bearings comprising the actuators.

Morales, Wilfredo↗

Analysis of Black Bearing Balls from a Space Shuttle Body Flap Actuator

A significantly deteriorated ball bearing mechanism from a body flap actuator on Space Shuttle OV-103 was disassembled and the balls submitted for analysis in conjunction with Return to Flight activities. The OV-103 balls, referred to as the "black balls", were subjected to X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) and Raman micro spectroscopy, surface profilometry, and optical and electron microscopy. The spectroscopic results in combination with microscopy analysis allowed a determination of the lubricant degradation pathway. The chemical attack mechanism does not adequately explain the unique visual appearance of the black balls. Numerous efforts have unsuccessfully focused on duplication of the phenomena causing this unique surface structure and appearance of the black balls. Further detail will be presented supporting these conclusions along with plausible explanations of the unique black appearance to the balls.

Sovinski, Marjorie F.↗

Rotational spectroscopy at the Jet Propulsion Laboratory

Environmental monitoring, atmospheric remote sensing and astrophysical studies promoted by NASA require a strong basis of spectroscopic information. The rotational spectroscopy capabilities at NASAs Jet Propulsion Laboratory (JPL) are currently maintained for the measurement of key mission priorities that enable modeling and retrieval of geophysical data from the atmosphere as well as validation of the space-borne instruments in the Earth Observing System, particularly the Microwave Limb Sounder. Rotational spectra are measured using a variety of spectroscopic techniques including pulsed-beam Fourier transform microwave spectroscopy (at CalTech); millimeter wavelength Stark spectroscopy; millimeter, submillimeter and THz FM spectroscopy; laser sideband spectroscopy and Fourier Transform far-infrared spectroscopy. Remote measurements of atmospheric rotational spectra are made using two limb-sounder instruments in the submillimeter and THz. Recent advances in the direct synthesis of THz radiation that enable more efficient laboratory science will be presented. Software for comprehensive and systematic study of different molecular systems is maintained at JPL, the software is freely available via http://spec.jpl.nasa.gov and is used by our group to create and sustain the JPL spectral line catalog also available online.

molecular spectroscopy↗

Thermal and Chemical Characterization of Non-metallic Materials Using Coupled Thermogravimetric Analysis and Infrared Spectroscopy

Thermogravimetric analysis (TGA) is widely employed in the thermal characterization of non-metallic materials, yielding valuable information on decomposition characteristics of a sample over a wide temperature range. However, a potential wealth of chemical information is lost during the process, with the evolving gases generated during thermal decomposition escaping through the exhaust line. Fourier Transform-Infrared spectroscopy (FT-IR) is a powerful analytical technique for determining many chemical constituents while in any material state, in this application, the gas phase. By linking these two techniques, evolving gases generated during the TGA process are directed into an appropriately equipped infrared spectrometer for chemical speciation. Consequently, both thermal decomposition and chemical characterization of a material may be obtained in a single sample run. In practice, a heated transfer line is employed to connect the two instruments while a purge gas stream directs the evolving gases into the FT-IR, The purge gas can be either high purity air or an inert gas such as nitrogen to allow oxidative and pyrolytic processes to be examined, respectively. The FT-IR data is collected real-time, allowing continuous monitoring of chemical compositional changes over the course of thermal decomposition. Using this coupled technique, an array of diverse materials has been examined, including composites, plastics, rubber, fiberglass epoxy resins, polycarbonates, silicones, lubricants and fluorocarbon materials. The benefit of combining these two methodologies is of particular importance in the aerospace community, where newly developing materials have little available data with which to refer. By providing both thermal and chemical data simultaneously, a more definitive and comprehensive characterization of the material is possible. Additionally, this procedure has been found to be a viable screening technique for certain materials, with the generated data useful in the selection of other appropriate analytical procedures for further material characterization.

Huff, Timothy L.↗

Thermal and Chemical Characterization of Non-Metallic Materials Using Coupled Thermogravimetric Analysis and Infrared Spectroscopy

Thermogravimetric analysis (TGA) is widely employed in the thermal characterization of non-metallic materials, yielding valuable information on decomposition characteristics of a sample over a wide temperature range. However, a potential wealth of chemical information is lost during the process, with the evolving gases generated during thermal decomposition escaping through the exhaust line. Fourier Transform-Infrared spectroscopy (FT-IR) is a powerful analytical technique for determining many chemical constituents while in any material state, in this application, the gas phase. By linking these two techniques, evolving gases generated during the TGA process are directed into an appropriately equipped infrared spectrometer for chemical speciation. Consequently, both thermal decomposition and chemical characterization of a material may be obtained in a single sample run. In practice, a heated transfer line is employed to connect the two instruments while a purge gas stream directs the evolving gases into the FT-IR. The purge gas can be either high purity air or an inert gas such as nitrogen to allow oxidative and pyrolytic processes to be examined, respectively. The FT-IR data is collected realtime, allowing continuous monitoring of chemical compositional changes over the course of thermal decomposition. Using this coupled technique, an array of diverse materials has been examined, including composites, plastics, rubber, fiberglass epoxy resins, polycarbonates, silicones, lubricants and fluorocarbon materials. The benefit of combining these two methodologies is of particular importance in the aerospace community, where newly developing materials have little available data with which to refer. By providing both thermal and chemical data simultaneously, a more definitive and comprehensive characterization of the material is possible. Additionally, this procedure has been found to be a viable screening technique for certain materials, with the generated data useful in the selection of other appropriate analytical procedures for further material characterization.

Huff, Timothy L.↗

Absolute band intensities in the nu19/nu23 (530 cm(-1)) and nu7 (777 cm(-1)) bands of acetone ((CH3)2CO) from 232 to 295 K

Absolute band intensities of acetone ((CH3)2CO) in the nu19/nu23 and nu7 band systems near 530 and 777 cm(-1), respectively, were measured at temperatures of 232, 262 and 295 K, using a Fourier transform infrared (FTIR) spectrometer. No evident temperature dependence for the band intensities was observed. The dipole moments and the fundamental band intensities were derived in the harmonic oscillator approximation. The results are useful for the spectroscopic retrieval of acetone concentrations in the upper atmosphere.

Acetone/chemistry↗

Sublimation of Laboratory Ices Millimeter/Submillimeter Experiment (SubLIME): Structure-Specific Identifications of Products from UV-photolyzed Methanol Ice

Submillimeter/far-IR spectroscopy was used to detect and quantify organic molecules sublimated after the ultraviolet photolysis (at 12 K) and warm-up (up to 300 K) of a methanol (CH3OH) ice sample. Eleven sublimated photoproducts were uniquely identified: carbon monoxide (CO), formaldehyde (H2CO), ketene (C2H2O), acetaldehyde (CH3CHO), ethylene oxide (CH2OCH2), vinyl alcohol (CH2CHOH), ethanol (CH3CH2OH), dimethyl ether (CH3OCH3), methyl formate (HCOOCH3), glycolaldehyde (HOCH2CHO), and acetone ((CH3)2CO). Two additional products were detected in the photolyzed ice by Fourier-transform infrared (FTIR) spectroscopy: carbon dioxide (CO2) and methane (CH4). The rotational temperatures and gas densities were calculated for the organics containing two or more C atoms via a rotation diagram analysis, and the gas-phase submillimeter/far-IR technique was used in tandem with mass spectrometry and FTIR spectroscopy of the ice during photolysis. The abundance ratios of the sublimated species (normalized to methanol) were compared to those observed in hot cores (Orion-KL, Sagittarius B2(N), and IRAS 16293-2422(B)) and in comets C/2014 Q2 (Lovejoy) and 67P/Churyumov–Gerasimenko.

K M Yocum↗

Sublimation of Laboratory Ices Millimeter/Submillimeter Experiment (SubLIME): Structure-Specific Identifications of Products from UV-photolyzed Methanol Ice

Submillimeter/far-IR spectroscopy was used to detect and quantify organic molecules sublimated after the ultraviolet photolysis (at 12 K) and warm-up (up to 300 K) of a methanol (CH3OH) ice sample. Eleven sublimated photoproducts were uniquely identified: carbon monoxide (CO), formaldehyde (H2CO), ketene (C2H2O), acetaldehyde (CH3CHO), ethylene oxide (CH2OCH2), vinyl alcohol (CH2CHOH), ethanol (CH3CH2OH), dimethyl ether (CH3OCH3), methyl formate (HCOOCH3), glycolaldehyde (HOCH2CHO), and acetone ((CH3)2CO). Two additional products were detected in the photolyzed ice by Fourier-transform infrared (FTIR) spectroscopy: carbon dioxide (CO2) and methane (CH4). The rotational temperatures and gas densities were calculated for the organics containing two or more C atoms via a rotation diagram analysis, and the gas-phase submillimeter/far-IR technique was used in tandem with mass spectrometry and FTIR spectroscopy of the ice during photolysis. The abundance ratios of the sublimated species (normalized to methanol) were compared to those observed in hot cores (Orion-KL, Sagittarius B2(N), and IRAS 16293-2422(B)) and in comets C/2014 Q2 (Lovejoy) and 67P/Churyumov–Gerasimenko.

K. M. Yocum↗

A laboratory analog for the carrier of the 3 micron emission of the protoplanetary nebula IRAS 05341+0852

A mixture of the polycyclic aromatic hydrocarbons (PAHs), acenaphthylene and acenaphthene, when subjected to the energetic environment of a hydrogen plasma, is transformed into a material that exhibits an infrared absorption profile in the 3 micron region that is an excellent match of the protoplanetary nebula IRAS 05341+0852 emission profile in the same wavelength region. Acenaphthylene and acenaphthene were chosen as precursors in the experiment because these molecules have a structure that can be described as a keystone in a process in which carbon atoms in a stellar wind condense into PAH species. The spectral match between experiment and observations appears to validate that scenario.

Non-NASA Center↗

Spectroscopic characterization of collagen cross-links in bone

Collagen is the most abundant protein of the organic matrix in mineralizing tissues. One of its most critical properties is its cross-linking pattern. The intermolecular cross-linking provides the fibrillar matrices with mechanical properties such as tensile strength and viscoelasticity. In this study, Fourier transform infrared (FTIR) spectroscopy and FTIR imaging (FTIRI) analyses were performed in a series of biochemically characterized samples including purified collagen cross-linked peptides, demineralized bovine bone collagen from animals of different ages, collagen from vitamin B6-deficient chick homogenized bone and their age- and sex-matched controls, and histologically stained thin sections from normal human iliac crest biopsy specimens. One region of the FTIR spectrum of particular interest (the amide I spectral region) was resolved into its underlying components. Of these components, the relative percent area ratio of two subbands at approximately 1660 cm(-1) and approximately 1690 cm(-1) was related to collagen cross-links that are abundant in mineralized tissues (i.e., pyridinoline [Pyr] and dehydrodihydroxylysinonorleucine [deH-DHLNL]). This study shows that it is feasible to monitor Pyr and DHLNL collagen cross-links spatial distribution in mineralized tissues. The spectroscopic parameter established in this study may be used in FTIRI analyses, thus enabling the calculation of relative Pyr/DHLNL amounts in thin (approximately 5 microm) calcified tissue sections with a spatial resolution of approximately 7 microm.

Non-NASA Center↗

Characterization of the degradation of gamma-irradiated elastomers using Raman spectroscopy

This report presents key findings from Raman spectroscopic analysis of gamma-irradiated rubber samples extracted from a laminated lead-damped rubber (LDR) seismic isolation device. The samples were exposed to gamma radiation from a 60Co source in a Foss Therapy Services gamma irradiator, reaching absorbed doses up to 1600 kGy. A distinct threshold near 400 kGy was identified, beyond which significant spectral changes were observed. Two Raman peaks - at approximately 425 cm-1 and 2440 cm-1 - were tracked as a function of dose using Gaussian fitting. The 425 cm-1 peak, attributed to sulfur–sulfur (S–S) bond stretching (resulting from vulcanization of the rubber), exhibited a dose-dependent upshift, indicating radiation-induced crosslinking within the sulfur-based polymer network. Conversely, the 2440 cm-1 peak, likely associated with vibrational modes of additives or impurities, showed a downward shift with increasing dose, suggesting chain scission and degradation of non-rubber constituents. These results provide first-of-a-kind insights into the microstructural evolution of elastomers under high-dose gamma irradiation and establish a preliminary dose threshold for significant degradation. Future work will incorporate multi-modal characterization—including Fourier Transform Infrared (FTIR) spectroscopy, scanning electrom microscopy (SEM) of the rubber surface morphology, thermogravimetric analysis (TGA) to determine changes in thermal stability, and mechanical testing—to correlate molecular-level changes with macroscopic performance of these elastomers as damping media in seismic isolation devices. These findings are expected to provide regulatory guidance and design criteria for qualifying low-damping rubber seismic isolators in advanced nuclear reactor applications.

36 - MATERIALS SCIENCE↗

Infrared spectroscopic studies of the effect of elevated temperature on the association of pyroglutamic acid with clay and other minerals

Fourier transform i.r. measurements of L-pyroglutamic acid dispersed in a matrix of a clay, silica or alumina have been obtained at various temperatures between 25 and 220 degrees C. The i.r. spectrum of L-pyroglutamic acid varies in a manner dependent upon the matrix material and shows considerable change as the temperature of the mixtures is increased. The differences in the spectrum at elevated temperatures are explained in terms of a chemical reaction between hydroxyl groups in the matrix and the carboxylic acid. The i.r. spectra of trimethylsilyl derivatives of L-pyroglutamic acid and aluminum pyroglutamate were also measured to assist the understanding of spectra and interpretation of the spectral changes dependent upon increasing temperature.

Aluminum Oxide/analysis/chemistry↗

Uncovering the binding nature of thiocyanate in contact ion pairs with lithium ions

Ion pair formation is a fundamental molecular process that occurs in a wide variety of systems, including electrolytes, biological systems, and materials. In solution, the thiocyanate (SCN–) anion interacts with cations to form contact ion pairs (CIPs). Due to its ambidentate nature, thiocyanate can bind through either its sulfur or nitrogen atoms, depending on the solvent. This study focuses on the binding nature of thiocyanate with lithium ions as a function of the solvents using FTIR, 2D infrared spectroscopy (2DIR) spectroscopies, and theoretical calculations. The study reveals that the SCN– binding mode (S or N end) in CIPs can be identified through 2DIR spectroscopy but not by linear IR spectroscopy. Linear IR spectroscopy shows that the CN stretch frequencies are too close to one another to separate N- and S-bound CIPs. Moreover, the IR spectrum shows that the S–C stretch presents different frequencies for the salt in different solvents, but it is related to the anion speciation rather than to its binding mode. A similar trend is observed for the anion bend. 2DIR spectra show different dynamics for N-bound and S-bound thiocyanate. In particular, the frequency–frequency correlation function (FFCF) dynamics extracted from the 2DIR spectra have a single picosecond exponential decay for N-bound thiocyanate and a biexponential decay for S-bound thiocyanate, consistent with the binding mode of the anion. Lastly, it is also observed that the binding mode also affects the line shape parameters, probably due to the different molecular mechanisms of the FFCF for N- and S-bound CIPs.

25 ENERGY STORAGE↗

Electronic Layer Decoupling Driven by Density-Wave Order in La 4⁢ Ni 3 ⁢O 10

We probe the density-wave transition of the trilayer nickelate La 4⁢ Ni 3 ⁢O 10 with polarization-resolved infrared spectroscopy. The low-energy electrodynamics is strongly anisotropic, with metallic in-plane and insulating out-of-plane character. In the ordered phase, the anisotropy grows more than an order of magnitude as the out-of-plane conductivity is sharply suppressed. We interpret this enhancement as an effective electronic decoupling of the Ni-O layers driven by a spin-density-wave-induced redistribution of Ni−𝑑 𝑧 2 occupation within the trilayers. This electronic response is accompanied by clearly shifting and splitting out-of-plane phonons, compatible with a density-wave instability of electronic origin.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Quantitative Infrared-to-Terahertz Nanospectroscopy of Semiconductors

Semiconductor technology now employs few-nanometer features, necessitating tools probing electronic properties on the same length scale. While the concentration of free charge carriers is routinely measured, the scattering rate remains challenging to access at the nanoscale. Here, we present ultrabroadband (5–50 THz) synchrotron infrared nanospectroscopy as a quantitative metrology tool for semiconductors. This technique can determine both the charge carrier concentration and scattering rate with percent-level accuracy, and it is inherently capable of ∼10 nm spatial resolution. We study silicon with different doping levels and confirm the method’s accuracy by statistical analysis and comparison with established far-field infrared spectroscopy. Near-field measurements systematically reveal charge-carrier concentrations ∼30% lower than far-field values, consistent with increased surface sensitivity and surface depletion. Our work establishes synchrotron infrared nanospectroscopy as a precise tool for quantitative nanoscale semiconductor characterization and paves the way toward all-optical characterization of surface depletion effects.

36 MATERIALS SCIENCE↗

Real-time measurements of endogenous CO production from vascular cells using an ultrasensitive laser sensor

Carbon monoxide (CO) has been implicated as a biological messenger molecule analogous to nitric oxide. A compact gas sensor based on a midinfrared laser absorption spectroscopy was developed for direct and real-time measurement of trace levels (in approximate pmol) of CO release by vascular cells. The midinfrared light is generated by difference frequency mixing of two nearinfrared lasers in a nonlinear optical crystal. A strong infrared absorption line of CO (4.61 microm) is chosen for convenient CO detection without interference from other gas species. The generation of CO from cultured vascular smooth muscle cells was detected every 20 s without any chemical modification to the CO. The sensitivity of the sensor reached 6.9 pmol CO. CO synthesis was measured from untreated control cells (0.25 nmol per 10(7) cells/h), sodium nitroprusside-treated cells (0.29 nmol per 10(7) cells/h), and hemin-treated cells (0.49 nmol per 10(7) cells/h). The sensor also detected decreases in CO production after the addition of the heme oxygenase (HO) inhibitor tin protoporphyrin-IX (from 0.49 to 0.02 nmol per 10(7) cells/h) and increases after the administration of the HO substrate hemin (from 0.27 to 0.64 nmol per 10(7) cells/h). These results demonstrate that midinfrared laser absorption spectroscopy is a useful technique for the noninvasive and real-time detection of trace levels of CO from biological tissues.

Non-NASA Center↗

The composition of gases from a diffusion flame above longleaf pine needle fuel beds

The gas and tar composition of a diffusion flame from longleaf pine needles is currently poorly understood and more data are needed to fill in the gap between pyrolysis data and smoke plume data, thus improving physical and chemical modeling of wildland smoke formation. A pilot experiment to measure light gas and tar composition of such a flame is described for three flame regions: persistent flame (flame base), intermittent flame, and smoke plume. Flame gases from 24 experimental fires were collected in canisters and analyzed using EPA method TO-14A for CO 2 , CO, H 2 , CH 4 , and C 2 to C 7 hydrocarbon gases. Condensed gas (tar) samples were collected and analyzed using GC/MS. Other light gases were measured using FTIR spectroscopy. Results from compositional data analysis suggest significant differences in (relative) concentration of compounds detected in the three regions of the flame. Statistical tests for differences in flame zones were performed using the canister data: Concentration of hydrocarbons relative to CO and CO 2 decreased from the persistent flame zone above the pyrolyzing needles through the intermittent flame region into the flame-free plume. This was likely due to both chemical reactions (oxidation) occurring in the flame as well as the introduction of air into the flame/plume by entrainment.

Biomass↗