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At least 109 records · Page 6

Adsorbent testing and mathematical modeling of a solid amine regenerative CO2 and H2O removal system

The paper examines the design and the construction details of the test bed built for testing a solid-amine-based Regenerable CO2 Removal System (RCRS) built at the NASA/Johnson Space Center for the extended Orbiter missions. The results of tests are presented, including those for the adsorption breakthrough and the adsorption and desorption of CO2 and H2O vapor. A model for predicting the performance of regenerative CO2 and H2O vapor adsorption of the solid amine system under various operating conditions was developed in parallel with the testing of the test stand, using the coefficient of mass transfer calculated from test results. The results of simulations are shown to predict the adsorption performance of the Extended Duration Orbiter test bed fairly well. For the application to the RCRS at various operating conditions the model has to be modified.

Jeng, F. F.

Turnover of Biogenic Amines in the Hypothalamus of Rats during Pyrogen Fever

Many pharmacological studies have implicated the biogenic amines in the hypothalamus as playing a role in the production of fever, but few investigations of endogenous neurochemicals have been made during fever. Turnover rates of transmitters utilizing radioactive precursors may be one of the most accurate measurements of activity in brain regions. The present study was designed to measure the turnover of 5-hydroxytryptamine (5-HT) norepinephrine (NE) and dopamine (DA) in the hypothalamus of rats during pyrogen fever. Salmonella typhosa (Wyeth, 8 units) was previously found in our laboratory to produce a significant hyperthermia in most rats by 2.5 hours. This pyrogen (N = l2) or saline control (N = 8) was injected intraperitoneally and the rats killed 2.75 hours later. Rectal temperatures (Tr) were monitored continuously with thermocouples taped to the tail and recorded automatically every 3 minutes. Half of each group received an injection of radioactive precursors, (3)H-tryptophan (0.5 mCi) and (3)H-tryptophan (1.0 mCi), via an indwelling jugular catheter 60 minutes before killing, and the other half at 90 minutes. The rats were killed by near freezing in liquid nitrogen and the brains dissected in the cold. Turnover was measured by the method of Lane (Life Sci 21, 1101, 1977). At the time of killing most of the pyrogen group showed a significant (p < .02) increase (mean +/- s.e.m.) in Tr above pre injection levels (0.75 +/- 0.13 C, N = 10). The saline group showed no change (-0.025 +/- 0.16, N = 8), and the difference between groups was also significant. No significant differences were found in the levels of the amines between the pyrogen and saline groups. A significant difference was found in the specific activity of NE between the 60 minute pyrogen and saline groups (4.41 +/- 0.41 vs 2.6 +/- 0.51 dpm/pmole) but no change in turnover. This suggests an increased accumulation of (3)H-NE in the pyrogen group, but no change in utilization. An increased turnover of DA for the pyrogen group (44.5 vs 19.2 pmole/mg protein/hr) was found. However, DA is mainly a precursor in the hypothalamus and measurement was near the limit of sensitivity for the assay; these limitations Must be considered in interpreting this data. The most significant finding was an increase in the turnover of 5-HT in the pyrogen group (41.3 vs 7.3 pmole/mg protein/hr), indicating a resynthetization rate of 77% of the total pool per hour. These results suggest that at the time point measured, an increase in the utilization of 5-HT in the hypothalamus is-correlated with pyrogen fever.

Penn, P. E.

Crosslinking Amine-Modified Silica Aerogels with Epoxies: Mechanically Strong Lightweight Porous Materials

The mesoporous surfaces of TMOS-derived silica aerogels have been modified with amines by co-polymerization of TMOS with APTES. The amine sites have become anchors for crosslinking the nanoparticles of the skeletal backbone of the aerogel by attachment of di-, tri and tetra-functional epoxies. The resulting conformal coatings increase the density of the native aerogels by a factor of 2-3 but the strength of the resulting materials may increase by more than two orders of magnitude. Processing variables such as amount of APTES used to make the gels, the epoxy type and concentration used for crosslinking, as well as the crosslinking temperature and time were varied according to a multivariable design-of-experiments (DOE) model. It was found that while elastic modulus follows a similar trend with density, maximum strength is attained neither at the maximum density nor at the highest concentration of -NH2 groups, suggesting surface saturation effects. Aerogels crosslinked with the tri-functional epoxide always show improved strength compared with aerogels crosslinked with the other two epoxides under identical conditions. Solid C-13 NMR studies show residual unreacted epoxides, which condense with ne another by heating crosslinked aerogels at 150 C.

Meador, Mary Ann B.

Catalytic dehydrogenation of amine borane complexes

A method of generating hydrogen includes the steps of providing an amine borane (AB) complex, at least one hydrogen generation catalyst, and a solvent, and mixing these components. Hydrogen is generated. The hydrogen produced is high purity hydrogen suitable for PEM fuel cells. A hydrolytic in-situ hydrogen generator includes a first compartment that contains an amine borane (AB) complex, a second container including at least one hydrogen generation catalyst, wherein the first or second compartment includes water or other hydroxyl group containing solvent. A connecting network permits mixing contents in the first compartment with contents in the second compartment, wherein high purity hydrogen is generated upon mixing. At least one flow controller is provided for controlling a flow rate of the catalyst or AB complex.

Mohajeri, Nahid

Catalytic dehydrogenation of amine borane complexes

A method of generating hydrogen includes the steps of providing an amine borane (AB) complex, at least one hydrogen generation catalyst, and a solvent, and mixing these components Hydrogen is generated. The hydrogen produced is high purity hydrogen suitable for PEM fuel cells. A hydrolytic in-situ hydrogen generator includes a first compartment that contains an amine borane (AB) complex, a second container including at least one hydrogen generation catalyst, wherein the first or second compartment includes water or other hydroxyl group containing solvent. A connecting network permits mixing contents in the first compartment with contents in the second compartment, wherein high purity hydrogen is generated upon mixing. At least one flow controller is provided for controlling a flow rate of the catalyst or AB complex.

Mohajeri, Nahid

Primordial Synthesis of Amines and Amino Acids in a 1958 Miller H2S-Rich Spark Discharge Experiment

Archived samples from a previously unreported 1958 Stanley Miller electric discharge experiment containing hydrogen sulfide (H2S) were recently discovered and analyzed using high-performance liquid chromatography and time-of-flight mass spectrometry. We report here the detection and quantification of primary amine-containing compounds in the original sample residues, which were produced via spark discharge using a gaseous mixture of H2S, CH4, NH3, and CO2. A total of 23 amino acids and 4 amines, including 7 organosulfur compounds, were detected in these samples. The major amino acids with chiral centers are racemic within the accuracy of the measurements, indicating that they are not contaminants introduced during sample storage. This experiment marks the first synthesis of sulfur amino acids from spark discharge experiments designed to imitate primordia! environments. The relative yield of some amino acids, in particular the isomers of aminobutyric acid, are the highest ever found in a spark discharge experiment. The simulated primordial conditions used by Miller may serve as a model for early volcanic plume chemistry and provide insight to the possible roles such plumes may have played in abiotic organic synthesis. Additionally, the overall abundances of the synthesized amino acids in the presence of H2S are very similar to the abundances found in some carbonaceous meteorites, suggesting that H2S may have played an important role in prebiotic reactions in early solar system environments.

Parker, Eric T.

Performance Characterization and Simulation of Amine-Based Vacuum Swing Sorption Units for Spacesuit Carbon Dioxide and Humidity Control

Controlling carbon dioxide (CO2) and water (H2O) vapor concentrations in a space suit is critical to ensuring an astronauts safety, comfort, and capability to perform extra-vehicular activity (EVA) tasks. Historically, this has been accomplished using lithium hydroxide (LiOH) and metal oxide (MetOx) canisters. Lithium hydroxide is a consumable material that requires priming with water before it becomes effective at removing carbon dioxide. MetOx is regenerable through a power-intensive thermal cycle but is significantly heavier on a volume basis than LiOH. As an alternative, amine-based vacuum swing beds are under aggressive development for EVA applications. The vacuum swing units control atmospheric concentrations of both CO2 and H2O through fully-regenerative process. The current concept, referred to as the rapid cycle amine (RCA), has resulted in numerous laboratory prototypes. Performance of these prototypes have been assessed experimentally and documented in previous reports. To support developmental e orts, a first principles model has also been established for the vacuum swing sorption technology. For the first time in several decades, a major re-design of Portable Life Support System (PLSS) for the extra-vehicular mobility unit (EMU) is underway. NASA at Johnson Space Center built and tested an integrated PLSS test bed of all subsystems under a variety of simulated EVA conditions of which the RCA prototype played a significant role. The efforts documented herein summarize RCA test performance and simulation results for single and variable metabolic rate experiments in an integrated context. In addition, a variety of off-nominal tests were performed to assess the capability of the RCA to function under challenging circumstances. Tests included high water production experiments, degraded vacuum regeneration, and deliberate valve/power failure and recovery.

Swickrath, Michael J.

Rapid Cycle Amine (RCA 2.0) System Development

The Rapid Cycle Amine (RCA) system is a low power assembly capable of simultaneously removing carbon dioxide (CO2) and humidity from an influent air steam and subsequent regeneration when exposed to a vacuum source. Two solid amine sorbent beds are alternated between an uptake mode and a regeneration mode. During the uptake mode, the sorbent is exposed to an air steam (ventilation loop) to adsorb CO2 and water vapor, while during the regeneration mode, the sorbent rejects the adsorbed CO2 and water vapor to a vacuum source. The two beds operate such that while one bed is in the uptake mode, the other is in the regeneration mode, thus continuously providing an on-service sorbent bed by which CO2 and humidity may be removed. A novel valve assembly provides a simple means of diverting the process air flow through the uptake bed while simultaneously directing the vacuum source to the regeneration bed. Additionally, the valve assembly is designed to allow for switching between uptake and regeneration modes with only one moving part while minimizing gas volume losses to the vacuum source by means of an internal pressure equalization step during actuation. The process can be controlled by a compact, low power controller design with several modes of operation available to the user. Together with NASA, United Technologies Corporation Aerospace Systems has been developing RCA 2.0 based on performance and design feedback on several sorbent bed test articles and valve design concepts. A final design was selected in November 2011 and fabricated and assembled between March and August 2012, with delivery to NASA-JSC in September 2012. This paper will provide an overview on the RCA system design and results of pre-delivery testing.

Papale, William

Rapid Cycle Amine (RCA 2.0) System Development

The Rapid Cycle Amine (RCA) system is a low-power assembly capable of simultaneously removing carbon dioxide (CO2) and humidity from an influent air steam and subsequent regeneration when exposed to a vacuum source. Two solid amine sorbent beds are alternated between an uptake mode and a regeneration mode. During the uptake mode, the sorbent is exposed to an air steam (ventilation loop) to adsorb CO2 and water (H2O) vapor, whereas during the regeneration mode, the sorbent rejects the adsorbed CO2 and H2O vapor to a vacuum source. The two beds operate such that while one bed is in the uptake mode, the other is in the regeneration mode, thus continuously providing an on-service sorbent bed by which CO2 and humidity may be removed. A novel valve assembly provides a simple means of diverting the process air flow through the uptake bed while simultaneously directing the vacuum source to the regeneration bed. Additionally, the valve assembly is designed to allow for switching between uptake and regeneration modes with only one moving part while minimizing gas volume losses to the vacuum source by means of an internal pressure equalization step during actuation. The process can be controlled by a compact, low-power controller design with several modes of operation available to the user. Together with NASA Johnson Space Center, Hamilton Sundstrand Space Systems International, Inc. has been developing RCA 2.0 based on performance and design feedback on several sorbent bed test articles and valve design concepts. A final design of RCA 2.0 was selected in November 2011 and fabricated and assembled between March and August 2012, with delivery to NASA Johnson Space Center in September 2012. This paper provides an overview of the RCA system design and results of pre-delivery testing.

Papale, William

Rapid Cycle Amine (RCA) 3.0 System Development

The Rapid Cycle Amine (RCA) 3.0 system is currently under development by NASA, the Lyndon B. Johnson Space Center (JSC) in conjunction with United Technologies Corporation Aerospace Systems (UTAS). The RCA technology is a new carbon dioxide (CO2) and humidity removal system that has been baselined for the Advanced Extravehicular Mobility Unit (AEMU) Portable Life Support System. The evolution of the RCA development has progressed through several iterations of technology readiness levels including RCA 1.0, RCA 2.0, and RCA 3.0 test articles. The RCA is an advancement over currently technologies due to its unique regeneration capability. The RCA is capable of simultaneously removing CO2 and humidity from an influent air steam and subsequent regeneration when exposed to a vacuum source. The RCA technology uses two solid amine sorbent beds in an alternating fashion to adsorb CO2 and water (uptake mode) and desorb CO2 and water (regeneration mode) at the same time. The two beds operate in an efficient manner so that while one bed is in the uptake mode, the other is in the regeneration mode, thus continuously providing an on-service sorbent bed by which CO2 and humidity may be removed. The RCA 2.0 and 3.0 test articles were designed with a novel valve assembly which allows for switching between uptake and regeneration modes with only one moving part while minimizing gas volume losses to the vacuum source by means of an internal pressure equalization step during actuation. The RCA technology also is low power, small, and has performed extremely well in all development testing thus far. A final design was selected for the RCA 3.0, fabricated, assembled, and performance tested in 2014 with delivery to NASAJSC in January 2015. This paper will provide an overview on the RCA 3.0 system design and results of pre-delivery testing with references to the development of RCA 1.0 and RCA 2.0.

Chullen, Cinda

Design and Development Comparison of Rapid Cycle Amine 1.0, 2.0, and 3.0

The development of the Rapid Cycle Amine (RCA) swing-bed technology for carbon dioxide (CO2) removal has been in progress since favorable results were published in 1996. Shortly thereafter, a prototype was designed, developed, and tested successfully and delivered to Johnson Space Center in 1999. An improved prototype was delivered to NASA in 2006 and was notated as RCA 1.0 and sized for the extravehicular activity (EVA). The new RCA swing-bed technology is a regenerative system which employs two alternating solid-amine sorbent beds to remove CO2 and water. The two- bed design employs a chemisorption process whereby the beds alternate between adsorbtion and desorbsion. This process provides for an efficient operation of the RCA so that while one bed is in adsorb (uptake) mode, the other is in the desorb (regeneration) mode. The RCA has now progressed through several iterations of technology readiness levels. Test articles have now been designed, developed, and tested for the advanced space suit portable life support system (PLSS) including RCA 1.0, RCA 2.0, and RCA 3.0. The RCA 3.0 was the most recent RCA fabrication and was delivered to NASA-JSC in June 2015. The RCA 1.0 test article was designed with a pneumatically actuated linear motion spool valve. The RCA 2.0 and 3.0 test articles were designed with a valve assembly which allows for switching between uptake and regeneration modes while minimizing gas volume losses to the vacuum source. RCA 2.0 and 3.0 also include an embedded controller design to control RCA operation and provide the capability of interfacing with various sensors and other ventilation loop components. The RCA technology is low power, small, and has fulfilled all test requirements levied upon the technology during development testing thus far. This paper will provide an overreview of the design and development of RCA 1.0, 2.0 and 3.0 including detail differences between the design specifications of each.

Chullen, Cinda

Design and Development Comparison of Rapid Cycle Amine 1.0, 2.0, and 3.0

The development of the Rapid Cycle Amine (RCA) swing-bed technology for carbon dioxide (CO2) removal has been in progress since favorable results were published in 1996. Shortly thereafter, a prototype was designed, developed, and tested successfully and delivered to Johnson Space Center in 1999. An improved prototype (RCA 1.0) was delivered to NASA in 2006 and sized for the extravehicular activity (EVA). The RCA swing-bed technology is a regenerative system which employs two alternating solid-amine sorbent beds to remove CO2 and water. The two-bed design employs a chemisorption process whereby the beds alternate between adsorption and desorption. This process provides for an efficient RCA operation that enables one bed to be in adsorb (uptake) mode, while the other is in the desorb (regeneration) mode. The RCA has progressed through several iterations of technology readiness levels. Test articles have now been designed, developed, and tested for the advanced space suit portable life support system (PLSS) including RCA 1.0, RCA 2.0, and RCA 3.0. The RCA 3.0 was the most recent RCA fabrication and was delivered to NASA-JSC in June 2015. The RCA 1.0 test article was designed with a pneumatically actuated linear motion spool valve. The RCA 2.0 and 3.0 test articles were designed with a valve assembly which allows for switching between uptake and regeneration modes while minimizing gas volume losses to the vacuum source. RCA 2.0 and 3.0 also include an embedded controller design to control RCA operation and provide the capability of interfacing with various sensors and other ventilation loop components. The RCA technology is low power, small, and has fulfilled all test requirements levied upon the technology during development testing thus far. This paper will provide an overview of the design and development of RCA 1.0, 2.0 and 3.0 including detail differences between the design specifications of each. Nomenclature.

Chullen, Cinda

Effect of Tube-Based X-Ray Microtomography Imaging on the Amino Acid and Amine Content of the Murchison CM2 Chondrite

X-ray and synchrotron X-ray micro-computed tomography (micro-CT) are increasingly being used for three dimensional reconnaissance imaging of chondrites and returned extraterrestrial material prior to detailed chemical and mineralogical analyses. Although micro-CT imaging is generally considered to be a non-destructive technique since silicate and metallic minerals in chondrites are not affected by X-ray exposures at the intensities and wavelengths typically used, there are concerns that the use of micro-CT could be detrimental to the organics in carbonaceous chondrites. We recently conducted a synchrotron micro-CT experiment on a powdered sample of the Murchison CM2 carbonaceous chondrite exposed to a monochromatic high energy (approximately 48 kiloelectronvolts) total X-ray radiation dose of approximately 1 kilogray (kGy) using the Advanced Photon Source beamline 13-BMD (13-Bending Magnet-D Beamline) at Argonne National Laboratory and found that there were no detectable changes in the amino acid abundances or enantiomeric compositions in the chondrite after exposure relative to a Murchison control sample that was not exposed. However, lower energy bremsstrahlung X-rays could interact more with amino acids and other lower molecular weight amines in meteorites. To test for this possibility, three separate micro-CT imaging experiments of the Murchison meteorite using the GE Phoenix v/tome/x s 240 kilovolt microfocus high resolution tungsten target X-ray tube instrument at the American Museum of Natural History (AMNH) were conducted and the amino acid abundances and enantiomeric compositions were determined. We also investigated the abundances of the C1-C5 amines in Murchison which were not analyzed in the first study.

Microtomography Imaging

H 2 O and CO 2 Sorption in Ion-Exchange Sorbents: Distinct Interactions in Amine Versus Quaternary Ammonium Materials

This article examines how water (H₂O) and carbon dioxide (CO₂) interact with two classes of ion-exchange sorbents — a primary amine sorbent and a quaternary ammonium (QA⁺) sorbent — using calorimetry, thermal gravimetric analysis, gas analysis, and molecular modeling. Here, the QA⁺ sorbent exhibits stronger binding to both H₂O and CO₂ but also shows thermal stability limitations. Mixed-gas experiments reveal that humidity strongly influences CO₂ uptake and that moisture-driven sorbent regeneration enables cyclic moisture swing CO₂ capture, with implications for low-energy CO₂ separation from dilute gas streams.

36 MATERIALS SCIENCE

Supramolecular Complexation-Enhanced CO 2 Chemisorption in Amine-Derived Sorbents

A supramolecular complexation approach is developed to improve the CO 2 chemisorption performance of solvent-lean amine sorbents. Operando spectroscopy techniques reveal the formation of carbamic acid in the presence of a crown ether. Here, the reaction pathway is confirmed by theoretical simulation, in which the crown ether acts as a proton acceptor and shuttle to drive the formation and stabilization of carbamic acid. Improved CO 2 capacity and diminished energy consumption in sorbent regeneration are achieved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Closed‐Loop Recycling of Poly(pentylene Adipate‐ co ‐Terephthalate) via Amine‐Catalyzed Methanolysis

Advancing circularity through effective chemical recycling strategies is essential for enabling the sustainable use of emerging biodegradable polyesters in film applications. In this context, poly(pentylene adipate-co-terephthalate) with a 40/60 adipate-to-terephthalate ratio (PPeAT60), a significantly stiffer and partially biobased copolyester recently reported by our team, offers improved mechanical performance and processability compared to commercial poly(butylene adipate-co-terephthalate), while providing a platform to evaluate advanced recycling approaches for film applications. Here, this study describes depolymerization of PPeAT60 through amine-catalyzed methanolysis, followed by the repolymerization of the recovered monomers. The resulting repolymerized material exhibited a molar mass distribution, chemical structure, and thermal stability comparable to the virgin polymer, confirming the technical feasibility of the methanolysis-based recycling route. Both polymers displayed nearly identical melting, glass transition, and decomposition temperatures, crystallinity, and modulus, demonstrating full structural and mechanical reproducibility after recycling. Variations in crystallization kinetics, elongation at break, and barrier properties likely arise from trace impurities (<1%) introduced during processing acting as nucleating and stress-inducing agents. Overall, these results demonstrate that PPeAT60 retains its key properties after chemical recycling, establishing methanolysis as a promising platform for recycling of this partially biobased polymer that may be able to replace both conventional polyolefins and PBAT in flexible packaging applications.

09 BIOMASS FUELS

Chemical recycling of post-consumer polyester wastes using a tertiary amine organocatalyst

Recycling diverse waste plastics poses challenges due to complex sorting and processing, resulting in high costs and inefficiency. To tackle this, we present a metal-free catalytic sorting method for targeted deconstruction of polyester from post-consumer plastic waste, encompassing textiles, plastic mixtures, and multilayer packaging materials. This method employs N-methylpiperidine, a tertiary amine catalyst in methanol, to depolymerize polyethylene terephthalate (PET). Operating under these conditions (160°C, 1 h), we achieve 100% yields of dimethyl terephthalate and ethylene glycol. This technique also effectively breaks down other polyesters, including polylactic acid, polycarbonate, and polybutylene terephthalate, yielding high-yield monomers at relatively low temperatures. Through comprehensive nuclear magnetic resonance (NMR) analysis, we propose that N-methylpiperidine’s role is in enhancing methanol nucleophilicity and activating PET’s ester bond. Our insights advance the chemical recycling of post-consumer plastic waste, offering a potentially simple and efficient path to closing the polyester production loop.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Amine-Assisted Ligand-Exchange Method to Enhance Photovoltaic Parameters in FAPbI3 Nanocrystal Solar Cells

Perovskite colloidal nanocrystals (PeNCs) have exceptional optoelectronic properties and phase stability, making them promising for photovoltaic applications. However, insulating ligands on PeNC surfaces limit the current density and reduce the power conversion efficiency (PCE) in PeNC solar cells (SCs). This study introduces an amine-assisted ligand-exchange (ALE) strategy using 3-phenyl-1-propylamine (3P1P) to effectively remove long ligands from PeNC films. ALE reduced long-chain ligand density without increasing the number of defect states and therefore reduced the exciton-binding energy of FAPbI3 NC films. These changes facilitated exciton dissociation and charge transport in FAPbI3 PeNC SCs. The facilitation of exciton dissociation was due to the increased magnetic dipole interaction between excitons after the ALE process. The use of ALE achieved FAPbI3 PeNC SCs that had an improved short-circuit current density of 17.98 mA/cm2 and a PCE of 15.56% with improved stability after the treatment and negligible hysteresis. This work provides new insight into engineering PeNC films.

amines