Absorption of ethylene oxide and vinyl chloride on an iron /011/ surface and effect of these films on adhesion
Ethylene oxide and vinyl chloride adsorption on iron /011/ surface, and surface film effect on adhesion
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Ethylene oxide and vinyl chloride adsorption on iron /011/ surface, and surface film effect on adhesion
The sliding of polyvinyl chloride on nickel, iron and S-Monel has been studied by Auger electron spectroscopy. Polymer was not transferred to the metals, rather shear appeared to take place at the interface. The metal was progressively chlorinated as the polymer made multiple passes on the surface. The thickness of this chlorine film was the order of one atomic layer. Electron-induced desorption studies indicate that the chlorine is chemisorbed to the metal. These results are interpreted as evidence for mechanically induced and/or thermal degradation of the polymer during sliding. Degradation products of HCl and Cl2 which chemisorb to the metal are evolved near the interface.
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Sliding friction studies were conducted on an iron surface with exposure of that surface to various hydrocarbons and organic chlorides. The hydrocarbons included ethane, ethylene, ethyl chloride, methyl chloride and vinyl chloride. Auger cylindrical-mirror analysis was used to follow interactions of the hydrocarbon and organic chlorides with the iron surface. Results with vinyl chloride indicate friction-induced surface reactivity, adsorption to surface oxides, friction sensitivity to concentration and polymerization. Variation in the loads employed influence adsorption and, accordingly, friction. Unlike results with ethyl and vinyl chloride, friction-induced surface reactivity was not observed with ethane and ethylene.
Sliding friction studies were conducted on a clean and oxide-covered iron surface with exposure of that surface to various hydrocarbons. The hydrocarbons included ethane, ethylene ethyl chloride, methyl chloride, and vinyl chloride. Auger cylindrical mirror analysis was used to follow interactions of the hydrocarbon with the iron surface. Results with vinyl chloride indicate friction induced surface reactivity, adsorption to surface oxides, friction sensitivity to concentration and polymerization. Variation in the loads employed influence adsorption and accordingly friction. In contrast with ethyl and vinyl chloride, friction induced surface reactivity was not observed with ethane and ethylene.
Polymer copper sulfide composite films were prepared by treatment of polymer poly(vinyl chloride), poly(acrylonitrile), copolymer of vinyl chloride and vinyl acetate (90:10), and ABS resin copper (2) acetate composites with hydrogen sulfide. The films showed electrical conductivity higher than 0.015 S/cm when they contained more than 20 wt percent of copper sulfide. A poly(acrylonitrile)-copper sulfide composite film containing 40 to 50 wt percent of copper sulfide showed electrical conductivity of 10 to 150.0 S/cm and had relatively high mechanical strength to be used in practical purposes.
This Annual Performance Monitoring Report (PMR) for the Dense Non-Aqueous Phase Liquid (DNAPL) Source Zone (DSZ), Site-Wide Long-Term Monitoring (LTM), and Hot Spot (HS) 6 Air Sparge (AS) System presents the results of Year 13 operation of the hydraulic containment (HC) Interim Measure (IM), the results of performance monitoring direct-push technology (DPT) sampling and monitoring well sampling conducted in the DSZ, results of the biennial site-wide LTM event, and the results of operations and performance sampling of the HS 6 AS IM at Launch Complex 34 (LC34), located at Cape Canaveral Space Force Station (CCSFS), Florida. This site has been designated Solid Waste Management Unit (SWMU) CC054 under the Kennedy Space Center (KSC) Resource Conservation and Recovery Act (RCRA) Corrective Action Program. For the site-wide biennial LTM event, a total of 55 monitoring wells were sampled for volatile organic compounds (VOCs) in February 2023 and one well was sampled for polychlorinated biphenyls (PCBs) in December 2022. One well planned for VOC sampling was found to be destroyed and could not be sampled (CW0002). The LTM wells are screened in two lithologic zones: Layer 1 (0 to 25 feet below land surface [bls]) and Layer 2 (25 to 30 ft bls), and are located in the outlying areas of LC34 to monitor groundwater conditions within the Low-Concentration Plume (LCP), defined as concentrations exceeding Groundwater Cleanup Target Levels (GCTLs), and the High-Concentration Plume (HCP), defined as concentrations exceeding Natural Attenuation Default Concentrations (NADCs). Results from the biennial sampling event indicated overall plume stability and delineation for the plume, which extends over 300 acres. The operational period for Year 13 of the HCS was from April 1, 2022 to March 31, 2023. Operational runtime for the system was 90 percent during Year 13, with downtime events attributed to planned maintenance, system repairs, and power outages. As of March 31, 2023, a total of 313,673,241 cumulative gallons of groundwater containing 88,337 pounds of VOCs have been removed by the HCS. Influent concentrations of trichloroethene (TCE) have decreased since startup from approximately 280,000 μg/L (January 2010) to 12,000 μg/L (March 2023). During the reporting period, all effluent concentrations from the HCS (aqueous and vapor) were below regulatory reporting limits, indicating the system continues to operate as intended. Performance monitoring was conducted in December 2022 within the DSZ to evaluate TCE contamination. Groundwater samples were collected via DPT at nine locations, consistent with previous events between 2017 and 2021. Full vertical profile sampling was completed at each DPT from 8 to 98 feet bls, at 5-foot intervals. The DPT performance monitoring results are summarized in this PMR. The results revealed TCE remains at concentrations greater than 11,000 μg/L in the DSZ (1-percent solubility, indicative of DNAPL) at eight of the nine DPT locations and at depths ranging from 8 to 98 feet bls. In addition to DPT sampling, groundwater samples were collected from deep monitoring wells in the DSZ area (Layers 7 and 8) in December 2022 to verify vertical delineation. Layer 7/8 monitoring well results were non-detect in December 2022, with exception of three wells (IW0162, IW043D2, and IW044D2), where TCE, cis-1,2-dichloroethene (cDCE), and/or vinyl chloride (VC) were detected above GCTLs. These wells are screened 105 to 115 feet bls, which is below the existing recovery well capture zone. TCE was first detected in IW0162 in December 2021 and has since been sampled at least monthly to monitor TCE concentrations. The maximum TCE concentration during this operational period was 15,000 μg/L at IW0162 in March 2023. Because of the increased TCE concentrations in this well, a new recovery well (RW21D), screened 86 to 106 feet bls, was installed in January 2023 and incorporated into existing HCS operations. The HS 6 AS IM was initiated in 2018 with 160 AS wells, and expanded in 2019 with an additional 140 AS wells. Quarterly performance monitoring was reduced to semi-annual in 2020. The HS 6 AS system remained operational during the reporting period covered under this report. The results of the HS 6 system operation and semi-annual performance monitoring are summarized in this report. Semi-annual monitoring results collected in April and October 2022 show concentrations of contaminants of concern (cDCE, trans-1,2-dichloroethene, and vinyl chloride) are generally decreasing and not impacting the surface water drainage canal, indicating the HS 6 IM is meeting objectives. A Phase Two Expansion of the HS 6 AS IM was recently completed. As of the date of this report, the expansion became operational in August 2023 and the first quarter of monitoring was conducted in November 2023. Details of the construction, start-up, and performance monitoring will be included in a future Annual PMR. Overall, the tasks associated with Year 13 operation of the HC IM, operation of the HS 6 AS IM, and biennial site-wide sampling were performed in accordance with recommendations included in the previous 2021 LC34 (Year 12) annual report. Evaluation of results from the HC IM and HS 6 IM show that these systems are operating as designed and meeting performance objectives. Results from the site-wide biennial LTM program also show that the overall network of monitoring wells is adequate to continue monitoring plume-wide conditions.
This Air Sparge (AS) System Construction Completion, Performance Monitoring, and Long-Term Monitoring (LTM) Report presents activities conducted at the Paint and Oil Locker (POL) (Solid Waste Management Unit [SWMU] 067) and Supply Warehouse #3 (SW3) (SWMU 088) sites located at the Kennedy Space Center (KSC), Florida. Activities include implementation and Year 1 (Quarters [Q] 1 through 4) and Q5 operation, maintenance, and monitoring (OM&M) activities and performance monitoring results for the AS Interim Measure (IM) in the POL Southern Treatment Area, LTM results for the POL Northern Area and SW3, and supplemental direct push technology (DPT) sampling at both sites to support the LTM and performance monitoring programs. The timeframe for activities included in this report extends from August 2019 to August 2022. The scope for these sites currently includes two main components, which are documented within this report: (1) LTM at SW3 and POL Northern Area where an AS system began operation at these sites in May 2009 and June 2013, respectively, and subsequently turned off for both sites in March 2018 (during the previous reporting period); and (2) Active AS operations and performance monitoring in the POL Southern Treatment Area where an AS system was installed and began operation in 2021. The AS IM in the POL Southern Treatment Area was implemented between 2019 and 2021 to treat a chlorinated solvent groundwater plume that resulted from historic operations supporting the National Aeronautics and Space Administration’s (NASA) Space Program. The objective of the AS IM is to remediate groundwater within the treatment zone to support transition to monitored natural attenuation (MNA). The overall Corrective Action objective is to reduce concentrations of trichloroethene (TCE), cis-1,2-dichloroethene (cDCE), trans-1,2- dichloroethene (tDCE), and vinyl chloride (VC) present in groundwater to levels below their respective State of Florida Groundwater Cleanup Target Levels (GCTLs). The AS IM was installed in the POL Southern Treatment Area to target the high concentration plume (HCP), which includes a source zone (SZ) area where TCE was found to exceed 11,000 micrograms per liter (µg/L), and extend to a depth of 30 feet below land surface (bls).
This Annual Performance Monitoring Report (PMR) for the Dense Non-Aqueous Phase Liquid (DNAPL) Source Zone (DSZ) and Hot Spot 6 (HS 6) Air Sparge (AS) System presents the results of Year 12 operation of the hydraulic containment (HC) Interim Measure (IM), the results of performance monitoring direct-push technology (DPT) sampling and monitoring well sampling conducted in the DSZ, and the results of operations and performance sampling of the HS 6 AS IM at Launch Complex 34 (LC34), located at Cape Canaveral Space Force Station (CCSFS), Florida. Site-wide biennial LTM sampling was not conducted during this reporting period and is scheduled to be conducted in December 2022. The timeframe for activities documented in this PMR extends from April 1, 2021 to March 31, 2022. LC34 has been designated Solid Waste Management Unit CC054 under the Kennedy Space Center (KSC) Resource Conservation and Recovery Act Corrective Action Program. The objective of the HC IM at LC34 is to contain the DSZ and deep dissolved-phase trichloroethene (TCE) high concentration plume via operation of a hydraulic containment system (HCS). The pre-IM design 300 micrograms per liter (μg/L) TCE groundwater contour was used to establish the deep zone capture area for deep recovery wells, and the shallow zone capture area was defined by the DSZ. The system began operating in 2010, and in 2015, the system was expanded to provide HC for areas within the 300 μg/L TCE groundwater isocontours of HS 3 and 4. In 2018 and 2019, an investigation was conducted to re-characterize the DSZ, which included investigating TCE mass in Layer 7. This data was subsequently used to optimize the pumping rates of the HCS to more adequately capture residual contaminant mass. The operational period for Year 12 of the HCS was from April 1, 2021 to March 31, 2022. Operational runtime for the system was 94 percent during Year 12, with downtime events attributed to planned maintenance, system repairs, and power outages. As of March 31, 2022, a total of 285,712,801 gallons of groundwater containing 84,933 pounds of VOCs have been removed by the HCS. Influent concentrations of TCE have decreased since startup from approximately 280,000 µg/L (January 2010) to 12,000 µg/L (March 2022). During the reporting period, all effluent concentrations from the HCS (aqueous and vapor) were below regulatory reporting limits, indicating the system continues to operate as intended. Performance monitoring was conducted in December 2021 within the DSZ to evaluate TCE contamination. Groundwater samples were collected via DPT at nine locations, consistent with previous events in 2017, 2018, 2019, and 2020. Full vertical profile sampling was completed at each DPT from 8 to 98 ft bls, at 5 foot intervals. The DPT performance monitoring results are summarized in this PMR. The results revealed TCE remains at concentrations greater than 11,000 µg/L in the DSZ (1-percent solubility, indicative of DNAPL) at eight of the nine DPT locations at depths ranging from 8 to 98 ft bls. An overall increasing trend of TCE concentrations was observed in DPT samples during this reporting period, which may be due to several recovery wells that were turned off during the AS Pilot Study in the DSZ that operated from July 2021 to February 2022 (documented separately from this report). The maximum TCE concentration in 2021 was 15,400,000 µg/L in the 58 ft bls depth interval at DPT597 (previous maximum result in 2020 was 1,690,000 at 48 ft bls at DPT596). During the 2021 DPT event, the overall majority of TCE contamination was identified in the 58 ft bls interval (below Layer 4), where in the previous year the majority of mass was observed in Layer 4. This trend appears to indicate continued mass discharge from Layer 4 (fine-grained unit). In addition to DPT sampling, monitoring well samples were collected from deep wells in the DSZ area (Layers 7 and 8) to verify vertical delineation. All monitoring well results were non-detect or below cleanup levels, with exception of one well (IW0162, screened 105 to 115 ft bls, which is below the existing recovery well capture zone) where TCE was identified above cleanup target levels. The HS 6 AS system remained operational during the reporting period covered under this report. The HS 6 AS IM was initiated in 2018 with 160 AS wells, and expanded in 2019 with an additional 140 AS wells. Quarterly performance monitoring was reduced to semi-annual prior to this operational period. The results of the HS 6 system operation and semi-annual performance monitoring are summarized in this report. Semi-annual monitoring results collected in April and October 2021 show concentrations of contaminants of concern (cis-1,2-dichloroethene, trans-1,2- dichloroethene, and vinyl chloride) are generally decreasing and not impacting the surface water drainage canal, indicating the HS 6 IM is meeting objectives. Overall, the tasks associated with Year 12 operation of the HC IM and operation of the HS 6 AS IM were performed in accordance with the recommendations of the 2020 LC34 (Year 11) Operations, Maintenance, and Monitoring Report for DNAPL Source Zone, Site Wide LongTerm Monitoring, and Hot Spot 6 Air Sparging System PMR (NASA, 2021c). Evaluation of results from the HC IM and HS 6 IM show that these systems are operating as designed and meeting performance objectives.
This Hot Spot (HS) Area 6 Air Sparge Expansion – Phase Three Implementation Work Plan (IWP) was prepared by Tetra Tech, Inc., for the National Aeronautics and Space Administration (NASA) under the Indefinite Delivery Indefinite Quantity Contract 80KSC019D0011-80KSC019F0067, for the implementation of an Air Sparging (AS) Interim Measure (IM) at Launch Complex 34 (LC34), located at Cape Canaveral Space Force Station (CCSFS), Florida. LC34 has been designated as Solid Waste Management Unit (SWMU) CC054 under the Kennedy Space Center (KSC) Resource Conservation and Recovery Act (RCRA) operating permit. Expansion of the HS 6 IM will include installation of an additional 192 AS wells to depths of approximately 40 feet below land surface (bls) to remediate contaminated groundwater within two areas located west and northeast of the existing HS 6 AS treatment area. These areas were delineated via direct push technology investigations in September and October 2023. The expansion will target “hot spot” concentrations of cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC), which are the contaminants of concern in these areas with concentrations greater than 10-times Florida Department of Environmental Protection Natural Attenuation Default Concentrations. The highest cDCE and VC concentrations detected in the proposed phase three expansion area were 58,000 micrograms per liter (μg/L) (32 to 36 feet bls) and 12,000 μg/L (23 to 27 feet bls), respectively. The objective for this expansion is to remediate contaminated groundwater within the treatment zone to support transition to long-term monitoring. This phase three expansion will add an additional 9.4 acres of treatment area to the HS 6 IM, which currently covers approximately 26.9 acres.
This Year 2 Air Sparge (AS) System Performance Monitoring (PM) Report for Paint and Oil Locker (POL) Solid Waste Management Unit (SWMU) 067 Southern Treatment Area and Long- Term Monitoring (LTM) Report for POL Northern Area (SWMU 067) and Supply Warehouse #3 (SW3) SWMU 088 documents ongoing remedial efforts at the POL and SW3 sites at Kennedy Space Center (KSC), Florida. The overall goal for these sites is to reduce concentrations of groundwater contaminants of concern (COCs), specifically trichloroethene (TCE), cis-1,2-dichloroethene (cDCE), trans-1,2-dichloroethene (tDCE) and vinyl chloride (VC), to below the State of Florida Groundwater Cleanup Target Levels (GCTLs). Remediation and reporting of POL and SW3 have been streamlined over the years due to the proximity of the two sites. The scope for these sites currently includes two main components: (1) LTM at SW3 and the POL Northern Area, where an AS system began operation in May 2009 (with expansion in December 2012) and June 2013, respectively, and subsequently turned off for both sites in March 2018 (NASA, 2019a); and (2) Active AS operations and PM in the POL Southern Treatment Area where an AS system was installed and began operation in 2021. The timeframe for activities covered under this report is from September 2022 to July 2023. Based on Year 2 system operation and PM results, the AS system at POL operated as designed and successfully met the performance objective of reducing VOCs to concentrations that support transition of the site from active remediation to long-term monitoring. The results from the samples collected from performance monitoring wells within the AS system ROI showed a significant decrease in COC concentrations since the baseline sampling event conducted in April 2020. Based on the Year 2 OM&M and monitoring results obtained from the POL Southern Treatment Area, the IM objective to reduce concentrations to below the LTM transition target concentrations for TCE, cDCE, tDCE, and VC has been achieved. LTM sampling events at SW3 were conducted in October 2022 and July 2023. LTM sampling was conducted at the POL Northern Area in October 2022, December 2022, March 2023, and July 2023. Analytical results from October 2022 and July 2023 generally indicate that concentrations of COCs have been stable or decreasing compared to the previous year. TCE remains greater than the NADC in one monitoring well (POL-MW0034S) and greater than the GCTL in one monitoring well (POL-MW0009S). Concentrations of cDCE were greater than the GCTL in one monitoring well (POL-MW0026S), and tDCE was non-detect or less than the GCTL in all monitoring wells sampled. VC was greater than the GCTL in four monitoring wells (MW0024, MW0025, MW0027, and MW0028) at SW3 and one monitoring well (MW0026S) at the POL Northern Area.
Toxic gases produced by the combustion or thermo-oxidative degradation of materials such as wire insulation, foam, plastics, or electronic circuit boards in space shuttle or space station crew cabins may pose a significant hazard to the flight crew. Toxic gas sensors are routinely evaluated in pure gas standard mixtures, but the possible interferences from polymer combustion products are not routinely evaluated. The NASA White Sands Test Facility (WSTF) has developed a test system that provides atmospheres containing predetermined quantities of target gases combined with the coincidental combustion products of common spacecraft materials. The target gases are quantitated in real time by infrared (IR) spectroscopy and verified by grab samples. The sensor responses are recorded in real time and are compared to the IR and validation analyses. Target gases such as carbon monoxide, hydrogen cyanide, hydrogen chloride, and hydrogen fluoride can be generated by the combustion of poly(vinyl chloride), polyimide-fluoropolymer wire insulation, polyurethane foam, or electronic circuit board materials. The kinetics and product identifications for the combustion of the various materials were determined by thermogravimetric-IR spectroscopic studies. These data were then scaled to provide the required levels of target gases in the sensor evaluation system. Multisensor toxic gas monitors from two manufacturers were evaluated using this system. In general, the sensor responses satisfactorily tracked the real-time concentrations of toxic gases in a dynamic mixture. Interferences from a number of organic combustion products including acetaldehyde and bisphenol-A were minimal. Hydrogen bromide in the products of circuit board combustion registered as hydrogen chloride. The use of actual polymer combustion atmospheres for the evaluation of sensors can provide additional confidence in the reliability of the sensor response.
Stark effect saturable absorber modulation of passively Q switched carbon dioxide laser, using difluoroethane, difluoroethylene, methyl fluoroform, trichloroethylene and vinyl chloride
The adhesion and friction behavior of the platinum metals group was examined with clean surfaces and surfaces selectively contaminated with oxygen, vinyl chloride (C2H3Cl), and methyl mercaptan (CH3SH). A pin or disk specimen configuration was used with the pin being a single crystal of gold of the (111) orientation and with the platinum metal disks also being single crystals of the (111) or (0001) orientation. Loads applied ranged from 1 to 10 g and a sliding velocity of 0.7 mm/min was employed. Results indicate adhesion and transfer of gold to all of the platinum metals. Despite this observation friction differences existed among the metals in the group. These differences are related to surface chemical activity. Adsorption of various friction reducing species was selective. With some adsorbates present strong adhesive forces between metals were still observed.
Three lithium SO2 cells, two lithium CF cells, and a vinyl chloride cell, all with crimped seals, and all strictly experimental, were independently discharged on resistors. Three temperatures were used and several different storage temperatures. Discharge rate generally on the nominal discharges were 0.1 amp, 0.5 amp, and 1 amp. Tests results show that the crimp seals are inadequate, especially for the SO2 cells. Normal discharges present no hazards. All cells discharge to zero. The problem of lithium cell explosions, such as occurred during off-limits testing, is discussed.
Multiple infrared photon absorption is a quite general process which molecules can undergo when placed in a high flux of infrared energy, such as the focussed beam of a CO2 laser. In order to understand how this process works, one must be able to follow the evolution of the molecules through their internal states, populated by photon absorption. Double-resonance spectroscopy is the method of a choice for getting at this information. A system pumped by CO2 laser radiation can be examined with a tunable laser probe beam, such as that from a lead-salt diode laser. From such an experiment, one can directly observe Rabi modulation of the absorption lines, determine elementary state-to-state relaxation pathways, and locate higher excited vibrational states. Systems currently under investigation include SF6 and vinyl chloride. In suitable cases, the probe beam can be a tunable visible or UV source, such as a dye laser. Fluorescence spectroscopy can then be used to monitor the transient absorptions produced by multiple-photon excitation. Among the systems which can be examined are biacetyl and glyoxal.
In spite of the conduction of numerous studies regarding the vinylidene free radical, its role and importance as a reactive intermediate is not well characterized. Laufer (1980, 1983) has reported the absorption spectrum of metastable H2CC(3B2), the lowest excited state, in the vacuum ultraviolet and has measured several aspects of its quenching properties. The present study provides a measurement of the extinction coefficient of H2CC(3B2). Knowledge of the vinylidene concentration is required to convert readily available absorption data into an extinction coefficient or cross section. In the current work, the H2CC(3B2) concentration was determined in an investigation of the photodissociation of vinyl chloride.
Space technology is contributing to air pollution control primarily through improved detectors and analysis methods. Miniaturized mass spectrometer is under development to monitor vinyl chloride and other hydrocarbon contaminants in an airborne laboratory. Miniaturized mass spectrometer can be used to protect personnel in naval and medical operations as well as aboard aircraft.