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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.↗

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.↗