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At least 37 records · Page 2

FTIR Study of Vapor Offgassing from Orbiter Tile Re-Waterproofing Materials

The work presented in this paper was performed to identify and quantify the offgassing behavior of alternative re-waterproofmg materials under investigation for application to Shuttle Orbiter Thermal Protection System (TPS) tile and blanket materials. The purpose was to determine whether the new materials would cause a problem with the operational analysis of residual vapors using the current portable vapor analyzer, a Miran 203. The materials investigated were limited to dimethylethoxysilane (DMES) and proposed solvent selected as suitable for use in re-waterproofing Orbiter TPS. The solvent was selected in another phase of the overall project. Obiter TPS tiles were injected with the re-waterproofing materials under constant conditions of temperature, relative humidity and air flow. The vapor concentrations of offgassing materials were monitored using Fourier Transform Infrared (FTIR) multi-component analysis, and with the Miran 203 instruments. The procedure was to record the time dependent concentrations of offgassing materials as analyzed by the FTIR, and the time response of the Miran 203 to the materials under consideration. The FTIR was calibrated for vapor phase DMES, tetramethyldisiloxane (TMDS), ethanol and the hydrocarbon solvents to be used to dilute the DMES for application to the TPS tile. The Miran 203 was calibrated for the operational measurement of DMES airborne vapors. The FTIR data, shows for the first time that the principal product which offgases from the tile after the first hour is not DMES, but TMDS and ethanol. The Miran 203 response to TMDS is the primary reading after the re-waterproofing operation is completed. The operational use of the Miran 203 to measure DMES vapors after re-waterproofmg operations has been responding to TMDS. The results of this study suggest that the historical complaints that have contributed to the low threshold limit value (TLV) for DMES concentrations, as read with the Miran 203, are actually based on instrumental responses to TMDS, for which no other toxicology information is available at this time. While there is some interference, the use of the tested hydrocarbon solvents does not adversely affect the response of the Miran 203.

Mattson, C. B.↗

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↗

FTIR instrumentation to monitor vapors from Shuttle tile waterproofing materials

The Space Shuttle Thermal Protection System (TPS) tiles and blankets are waterproofed using DimethylEthoxySilane (DMEX) in the Orbiter Processing Facilities (OPF). DMES has a Threshold Limit Value (TLV) for exposure of personnel to vapor concentration in air of 0.5 ppm. The OPF high bay cannot be opened for normal work after a waterproofing operation until the DMES concentration is verified by measurement to be below the TLV. On several occasions the high bay has been kept closed for up to 8 hours following waterproofing operations due to high DMES measurements. In addition, the Miran 203 and Miran 1 BX infrared analyzers calibrated at different wavelengths gave different readings under the same conditions. There was reason to believe that some of the high DMES concentration readings were caused by interference form water and ethanol vapors. The Toxic Vapor Detection Laboratory (TVDL) was asked to test the existing DMES instruments and identify the best qualified instrument. In addition the TVDL was requested to develop instrumentation to ensure the OPF high bay could be opened safely as soon as possible after a waterproofing operation. A Fourier Transform Infrared (FTIR) spectrophotometer instrument developed for an earlier project was reprogrammed to measure DMES vapor along with ethanol, water, and several common solvent vapors. The FTIR was then used to perform a series of laboratory and field tests to evaluate the performance of the single wavelength IR instruments in use. The results demonstrated that the single wavelength IR instruments did respond to ethanol and water vapors, more or less depending on the analytical IR wavelength selected. The FTIR was able to separate the responses to DMES, water and ethanol, and give consistent readings for the DMES vapor concentration. The FTIR was then deployed to the OPF to monitor real waterproofing operations. The FTIR was also used to measure the time for DMES to evaporate from TPS tile under a range of humidity conditions in controlled laboratory tests. The combination of laboratory and field tests with the FTIR instrument demonstrated superior sensitivity, ability to reject interference from water and ethanol vapors, ruggedness to be transported from the lab to the OPF and set up without special procedures or degradation of performance. The multiple component vapor analysis algorithm was developed at KSC and incorporates automatic baseline correction and shape fitting of the spectra. The analysis for DMES, TetraMethylDiSiloxane (TMDS), ethanol, methanol, isopropanol, and baseline parameters uses 161 points per sample at 4 cm(exp -1) resolution, and processes an eight scan sample every ten seconds. The standard deviation of the measurements is 0.013 ppm and the upper linear limit is 125 ppm DMES. Based on successful demonstration of capabilities we produced three mobile instrument carts to be used in each OPF to support future waterproofing operations. The design and building of the 'DMES Carts' were accomplished in Fiscal year 1995.

Mattson, C. B.↗

Resin Characterization in Cured Composite Materials

Molecular-level characterization of polymeric matrix resin in cured graphite-reinforced composite materials now determined through analysis of diffuse reflectance (DR) with Fourier Transform Infrared (FTIR) spectroscopy. Improved analytical method based on diffuse reflectance. DR/ FTIR technique successfully applied to analysis of several different composites and adhesives impossible to analyze by conventional methods.

Young, P. R.↗

Photovoltaics module interface: General purpose primers

The interfacial chemistry established between ethylene vinyl acetate (EVA) and the aluminized back surface of commercial solar cells was observed experimentally. The technique employed is called Fourier Transform Infrared (FTIR) spectroscopy, with the infrared signal being reflected back from the aluminum surface through the EVA film. Reflection infrared (IR) spectra are given and attention is drawn to the specific IR peak at 1080/cm which forms on hydrolytic aging of the EVA/aluminum system. With this fundamental finding, and the workable experimental techniques, candidate silane coupling agents are employed at the interface, and their effects on eliminating or slowing hydrolytic aging of the EVA/aluminum interface are monitored.

Boerio, J.↗

Study of balloon and thermal control material degradation aboard LDEF

The initial results of analysis performed on a number of polymeric materials which were exposed aboard the Long Duration Exposure Facility (LDEF) are discussed. These materials include two typical high altitude balloon films (a polyester and a polyethylene) and silver-backed Teflon from thermal control blanket samples. The techniques used for characterizing changes in mechanical properties, chemical structure and surface morphology include Fourier Transform Infrared (FTIR) spectroscopy, scanning electron microscopy, and dynamic mechanical analysis.

Letton, Alan↗

The influence of flowing afterglow exposure on the degradation of various polymeric materials

Changes in polymer properties which result after exposure to an atomic oxygen-rich environment of a flowing afterglow are presented. Dynamic mechanical and Fourier Transform Infrared (FTIR) spectra as well as scanning electron microscopy micrographs were employed to monitor variations in mechanical properties and chemical and physical structure. Polymers analyzed include polystyrene, PEKK, and a polyester.

Letton, Alan↗

Fourier transform infrared and Raman spectroscopic characterization of homogeneous solution concentration gradients near a container wall at different temperatures

Fourier transform infrared (FTIR) and Raman spectroscopic techniques were used to study the solution concentration gradient in succino nitrile-rich and water-rich homogeneous solutions. The spectroscopic data shows significant concentration dependency. Although FTIR-attenuated total reflectance could not yield surface spectra since the evanescent infrared wave penetrated deep into the bulk solution, it showed that water-rich clusters were decreased at higher temperatures. This result is consistent with the calorimetric results reported earlier.

Loo, B. H.↗

Mapping compositional and particle size variations across Silver Lake Playa: Relevance to analyses of Mars TIR data

The high spectral and spatial resolution thermal infrared (TIR) data to be acquired from the upcoming Mars Observer-Thermal Emission Spectra (TES) mission will map the composition and texture of the Martian sediments. To prepare for these data, portions of two remote sensing experiments were conducted to test procedures for extracting surface property information from TIR data. Reported here is the continuing analysis of Thermal Infrared Multispectral Scanner (TIMS) data, field emission spectra, laboratory Fourier Transform Infrared (FTIR) reflectance spectra, and field observations with respect to the physical characteristics (composition, emissivity, etc.) of Silver Lake playa in southern California.

Petroy, S. B.↗

Analysis of pressure-broadened ozone spectra in the 3 micron region

This work involves the analysis of a series of McMath Fourier Transform Infrared (FTIR) spectra of ozone broadened by mixing with air (four different pressures), nitrogen (three pressures), or oxygen (three pressures). Each spectrum covers the region from 2396 to 4057 cm(-1). This study focused on the 3 sub nu sub 3 band in t 3000 to 3060 cm(-1). The band is analyzed by first dividing its region into small intervals containing a few well isolated absorption lines of reasonable intensity. Each of these small intervals is fit by multiple iterations of the nonlinear least squares program until residuals (the difference between calculated and observed spectrum, as a percent of the strongest intensity in the interval) are minimized to a reasonable value which corresponds to the noise level of the measured spectrum. Position, intensity, and half-width are recorded for later analysis. From the measured half-widths, a pressure broadening coefficient was determined for each absorption line. Pressure shifts were determined by comparing observed line positions in the spectra of the diluted ozone samples to tabulated line positions determined from spectra of pure gas samples. Comparisons to other work on ozone indicate that the broadening and shift coefficients determined in this study are consistent with those determined in other spectral regions.

Prochaska, Eleanor S.↗

Airborne lidar mapping of vertical ozone distributions in support of the 1990 Clean Air Act Amendments

The 1990 Clean Air Act Amendments mandated attainment of the ozone standard established by the U.S. Environmental Protection Agency. Improved photochemical models validated by experimental data are needed to develop strategies for reducing near surface ozone concentrations downwind of urban and industrial centers. For more than 10 years, lidar has been used on large aircraft to provide unique information on ozone distributions in the atmosphere. However, compact airborne lidar systems are needed for operation on small aircraft of the type typically used on regional air quality investigations to collect data with which to develop and validate air quality models. Data presented in this paper will consist of a comparison between airborne differential absorption lidar (DIAL) and airborne in-situ ozone measurements. Also discussed are future plans to improve the airborne ultraviolet-DIAL for ozone and other gas observations and addition of a Fourier Transform Infrared (FTIR) emission spectrometer to investigate the effects of other gas species on vertical ozone distribution.

Uthe, Edward E.↗

Spectroscopic inferences from HIS measurements of atmospheric thermal emission

Radiometrically accurate observations of the earth's emission spectrum from 3.8 to 16.6 microns have been made using the High-resolution Interferometer Sounder (HIS) to look downward from the NASA U2/ER2 aircraft or upward from the ground. These observations have been used to demonstrate the substantially improved vertical resolution of temperature and water vapor soundings derived from high resolution spectra (resolving power from 1800 to 3800), as compared to soundings from the low resolution filter radiometer observations used in current satellite sounders. The HIS observations have also demonstrated that Fourier Transform Infrared (FTIR) instruments are especially well suited to absolute emission measurements of broad spectral bands at high resolution. A fundamental advantage of FTIR instruments for accurate calibration is wavelength integrity, the same property which has made FTIR the standard for very high resolution absorption measurements. The long wavelength part of a HIS downwelling radiance spectrum is compared to a calculated spectrum. The calculation uses the AFGL HITRAN/86 line file and FASCOD2 line-by-line program with atmospheric state data from in situ measurements. In general, agreement between HIS and FASCOD2 spectra is remarkably good, a tribute to the current state of spectral line files and line-by-line codes. Reproducible differences between HIS observations and FASCOD2 line-by-line calculations lead to the following conclusions: (1) The FASCOD2 water vapor continuum in the longwave window region from 10 to 13 microns (750 to 1000 cm(exp -1)) gives reasonable agreement with radiance observations; (2) The model H2O continuum from 7 to 8 microns (1250 to 1425 cm(exp -2)) needs adjustment to reduce its contribution by about 60 percent; (3) CO2 absorption in the region from 13.1 to 14.3 microns (700 to 760 cm(exp -1)) is too small in the model; and (4) Water vapor line strengths in the region from 8.1 to 9.1 microns (1100 to 1230 cm(exp -1)) need to be increased about 30 percent.

Revercomb, H. E.↗

Optical characterization of LDEF contaminant film

Dark brown molecular film deposits were found at numerous locations on the Long Duration Exposure Facility (LDEF) and have been documented in great detail by several investigators. The exact deposition mechanism for these deposits is as yet unknown, although direct and scattered atomic oxygen, and solar radiation interacting with materials outgassing products have all been implicated in the formation process. Specimens of the brown molecular film were taken from below the flange of the experimental tray located at position D10 on the LDEF. The tray was one of two, comprising the same experiment, the other being located on the wake facing side of the LDEF satellite at position B4. Having access to both trays, we were able to directly compare the effect that orientation with respect to the atomic oxygen flux vector had on the formation of the brown molecular film deposits. The film is thickest on surfaces facing toward the exterior, i.e. the tray corner, as can be seen by comparing the lee and wake aspects of the rivets. The patterns appear to be aligned not with the velocity vector but with the corner of the tray suggesting that flux to the surface is due to scattered atomic oxygen rather than direct ram impingement. The role of scattered flux is further supported by more faint plume patterns on the sides of the tray. The angle of these plumes is strongly aligned with the ram direction but the outline of the deposit implies that incident atoms are scattered by collisions with the edges of the opening resulting in a directed, but diffuse, flux of atomic oxygen to the surface. Spectral reflectance measurements in the 2 to 10 micron (4000 to 1000 wavenumbers) spectral range are presented for the film in the 'as deposited' condition and for the free standing film. The material was analyzed by FTIR (Fourier Transform Infrared) microspectroscopy using gold as the reference standard. The 'as deposited' specimen was on an aluminum rivet taken from beneath the tray flange while the free film was obtained by chipping some of the material from the rivet. The transmission spectrum over the 2 to 10 micron range for the free film is presented. This spectrum appears to be essentially the same as that presented by Crutcher et.al. for films formed at vent sites which faced into the ram direction and suggested to originate from urethanes and silicones used on the LDEF. Banks et. al. state that silicones, when exposed to atomic oxygen, release polymeric scission fragments which deposit on surfaces and form a glassy, dark contaminant layer upon further atomic oxygen exposure and solar irradiation.

Blakkolb, Brian K.↗

Spectroscopic studies of model polar stratospheric cloud films

Fourier transform infrared (FTIR) spectroscopy has been used to study nitric-acid/ice films representative of type I polar stratospheric clouds (PSCs). These studies reveal that in addition to amorphous nitric acid/ice mixtures, there are three stable stoichiometric hydrates of nitric acid: nitric-acid monohydrate (NAM), dihydrate (NAD), and trihydrate (NAT). We also observe two distinct crystalline forms of the trihydrate, which we denote alpha- and beta-NAT. These two forms appear to differ in their concentration of crystalline defects, but not in their chemical composition. In addition to probing the composition of type I PSCs, we have also used FTIR spectroscopy to study the interaction of HCl with model PSC films. In this work we find that for HCl pressures in the range 10 exp -5 to 10 exp -7 Torr, HCl is taken up by ice at 155 K to form a thin layer of HCl.6H2O. At 193 K, the uptake of HCl by ice was consistent with less than or equal to monolayer coverage. Uptake of HCl by alpha and beta-NAT at 175 K was also consistent with less than or equal to monolayer coverage.

Tolbert, Margaret A.↗

Orbital processing of high-quality CdTe compound semiconductors

CdZnTe crystals were grown in one-g and in micro-g for comparative analysis. The two micro-g crystals were grown in the Crystal Growth Furnace during the First United States Microgravity Laboratory mission (USML-1). The samples were analyzed for chemical homogeneity, structural perfection, and optoelectronic performance (infrared transmission). Fourier Transform Infrared (FTIR) transmission of both ground and flight materials showed that the infrared transmission was close to theoretical, 63% versus 66%, suggesting that the material was close to the stochiometric composition during both the ground and flight experiments. Infrared microscopy confirmed that the principal precipitates were Te and their size (1-10 microns) and density suggested that the primary flight and ground base samples experienced similar cooling rates. Macrosegregation was predicted, using scaling analysis, to be low even in one-g crystals and this was confirmed experimentally, with nearly diffusion controlled growth achieved even in the partial mixing regime on the ground. Radial segregation was monitored in the flight samples and was found to vary with fraction solidified, but was disturbed due to the asymmetric grvitational and thermal fields experienced by the flight samples. The flight samples, however, were found to be much higher in structural perfection than the ground samples produced in the same furnace under identical growth conditions except for the gravitational level. Rocking curve widths were found to be substantially reduced, from 20/35 (one-g) to 9/20 (micro-g) for the best regions of the crystals. The full width at half maximum (FWHM) of 9 arc seconds is as good as the best reported terrestrially for this material. The ground samples were found to have a fully developed mosaic structure consisting of subgrains, whereas the flight sample dislocations were discrete and no mosaic substructure was evident. The defect density was reduced from 50-100,000 (one-g) to 500-25000 EPD (micro-g). These results were confirmed using rocking curve analysis, synchrotron topography, and etch pit analysis. The low dislocation density is thought to have resulted from the near-absence of hydrostatic pressure which allowed the melt to solidify with minimum or no wall contact, resulting in very low stress being exerted on the crystal during growth or during post-solidification cooling.

Larson, David J., Jr.↗

Surface contamination analysis technology team overview

A team was established which consisted of representatives from NASA (Marshall Space Flight Center and Langley Research Center), Thiokol Corporation, the University of Alabama in Huntsville, AC Engineering, SAIC, Martin Marietta, and Aerojet. The team's purpose was to bring together the appropriate personnel to determine what surface inspection techniques were applicable to multiprogram bonding surface cleanliness inspection. In order to identify appropriate techniques and their sensitivity to various contaminant families, calibration standards were developed. Producing standards included development of consistent low level contamination application techniques. Oxidation was also considered for effect on inspection equipment response. Ellipsometry was used for oxidation characterization. Verification testing was then accomplished to show that selected inspection techniques could detect subject contaminants at levels found to be detrimental to critical bond systems of interest. Once feasibility of identified techniques was shown, selected techniques and instrumentation could then be incorporated into a multipurpose inspection head and integrated with a robot for critical surface inspection. Inspection techniques currently being evaluated include optically stimulated electron emission (OSEE); near infrared (NIR) spectroscopy utilizing fiber optics; Fourier transform infrared (FTIR) spectroscopy; and ultraviolet (UV) fluorescence. Current plans are to demonstrate an integrated system in MSFC's Productivity Enhancement Complex within five years from initiation of this effort in 1992 assuming appropriate funding levels are maintained. This paper gives an overview of work accomplished by the team and future plans.

Burns, H. Dewitt↗

Growth of nitric acid hydrates on thin sulfuric acid films

Type I polar stratospheric clouds (PSCs) are thought to nucleate and grow on stratospheric sulfate aerosols (SSAs). To model this system, thin sulfuric acid films were exposed to water and nitric acid vapors (1-3 x 10(exp -4) Torr H2O and 1-2.5 x 10(exp -6) Torr HNO3) and subjected to cooling and heating cycles. Fourier Transform Infrared (FTIR) spectroscopy was used to probe the phase of the sulfuric acid and to identify the HNO3/H2O films that condensed. Nitric acid trihydrate (NAT) was observed to grow on crystalline sulfuric acid tetrahydrate (SAT) films. NAT also condensed in/on supercooled H2SO4 films without causing crystallization of the sulfuric acid. This growth is consistent with NAT nucleation from ternary solutions as the first step in PSC formation.

Iraci, Laura T.↗

Comparison of column abundances from three infrared spectrometers during AASE 2

Three Fourier transform infrared (FTIR) spectromenters were based on board the NASA DC-8 during the second Airborne Arctic Stratospheric Expedition (AASE II) in 1992. Two FTIRs used solar absorption and one used thermal emission. We compare over 2000 measurements from these 3 FTIRs, on 12 DC-8 flights, for closely coincident air masses and times, both inside and outside the polar vortex. In the majority of cases the offset biases are quite small, in the range 1-4%, and comparable to the absolute precisions expected. In most cases the rms scatter is in the range 4-11%; this scatter is unlikely to be geophysical, but rather is probably instrumental or analytical in origin.

Traub, W. A.↗