SEARCH · Search NASA
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Explore the source record for details and available documents.
Abstract Asymmetric carbon molecular sieve (CMS) hollow fiber membranes with tunable micro‐ and macro‐structural morphologies for energy efficient propylene‐propane separation are reported here. A sub‐glass transition temperature (sub‐Tg) thermal oxidative crosslinking strategy enables simultaneous optimization of the intrinsic molecular sieving properties while also reducing the thickness of the CMS “skin” derived from the 6FDA : BPDA/DAM polyimide precursors. Such synergistic tuning of CMS microstructure and macroscopic morphology of CMS hollow fibers enables significantly increased propylene permeance (reaching 186.5 GPU) while maintaining an appealing propylene/propane selectivity of 13.3 for 50/50 propylene/propane mixed gas feeds. Our findings reveal a more refined and versatile tool than available with previous O 2 ‐doping pretreatments. The advanced approach here should be broadly useful to other polyimide precursors and diverse gas pairs.
Abstract Asymmetric carbon molecular sieve (CMS) hollow fiber membranes with tunable micro‐ and macro‐structural morphologies for energy efficient propylene‐propane separation are reported here. A sub‐glass transition temperature (sub‐Tg) thermal oxidative crosslinking strategy enables simultaneous optimization of the intrinsic molecular sieving properties while also reducing the thickness of the CMS “skin” derived from the 6FDA : BPDA/DAM polyimide precursors. Such synergistic tuning of CMS microstructure and macroscopic morphology of CMS hollow fibers enables significantly increased propylene permeance (reaching 186.5 GPU) while maintaining an appealing propylene/propane selectivity of 13.3 for 50/50 propylene/propane mixed gas feeds. Our findings reveal a more refined and versatile tool than available with previous O 2 ‐doping pretreatments. The advanced approach here should be broadly useful to other polyimide precursors and diverse gas pairs.
Abstract Hierarchically porous materials containing sub-nm ultramicropores with molecular sieving abilities and microcavities with high gas diffusivity may realize energy-efficient membranes for gas separations. However, rationally designing and constructing such pores into large-area membranes enabling efficient H 2 separations remains challenging. Here, we report the synthesis and utilization of hybrid carbon molecular sieve membranes with well-controlled nano- and micro-pores and single zinc atoms and clusters well-dispersed inside the nanopores via the carbonization of supramolecular mixed matrix materials containing amorphous and crystalline zeolitic imidazolate frameworks. Carbonization temperature is used to fine-tune pore sizes, achieving ultrahigh selectivity for H 2 /CO 2 (130), H 2 /CH 4 (2900), H 2 /N 2 (880), and H 2 /C 2 H 6 (7900) with stability against water vapor and physical aging during a continuous 120-h test.
The University of Wisconsin High Spectral Resolution Lidar (HSRL) provides unambiguous measurements of backscatter cross section, backscatter phase function, depolarization, and optical depth. This is accomplished by dividing the lidar return into separate particulate and molecular contributions. The molecular return is then used as a calibration target. We have modified the HSRL to use an I2 molecular absorption filter to separate aerosol and molecular signals. This allows measurement in dense clouds. Useful profiles extend above the cloud base until the two way optical depth reaches values between 5 and 6; beyond this, photon counting errors become large. In order to observe multiple scattering, the HSRL includes a channel which records the combined aerosol and molecular lidar return simultaneously with the spectrometer channel measurements of optical properties. This paper describes HSRL multiple scattering measurements from both water and ice clouds. These include signal strengths and depolarizations as a function of receiver field of view. All observations include profiles of extinction and backscatter cross sections. Measurements are also compared to predictions of a multiple scattering model based on small angle approximations.
Ultra-high molecular weight (UHMW, >10 6 g mol −1 ) vinyl polymers are increasingly accessible through photoiniferter polymerization, yet their behavior in electrospinning has received comparatively little attention. Here, we explore the electrospinning of UHMW poly(methyl acrylate), poly(methyl methacrylate), poly(N,N-dimethylacrylamide), and poly(styrene-co-pentafluorostyrene) synthesized by photoiniferter polymerization, with number-average molecular weights (M n ) greater than 1000 kDa and dispersities below 1.4. UHMW polymers form stable Taylor cones and discrete fibers at solution concentrations as low as 0.5 wt% due to their large number of entanglements, a threshold unachievable with low molecular weight (M n = 20–54 kDa) polymers of the same chemistry. Using poly(methyl methacrylate) and poly(styrene-co-pentafluorostyrene) as model systems, we demonstrate that fiber diameter can be tuned from 350 nm to 20 μm through systematic variation of polymer concentration (0.01 to 4 wt%) and flow rate (0.5 to 10 mL h −1 ). Additionally, we find that collector rotation rate governs fiber alignment, with highly aligned mats obtained with drum rotation speeds of 1000 RPM. Reversing the polarity of the electric field during electrospinning reorients the surface chemistry of these fiber mats without altering their microscale morphology, shifting the water contact angle by 7° (89° to 96°) and providing a two-fold binding capacity enhancement in cationic dye uptake. These results show that the high entanglement densities of UHMW vinyl polymers shift the accessible electrospinning window to dilute solutions and that electric-field polarity is a useful lever to control the surface chemistry in the resulting fibers.
A new class of polyimides and copolyimides made from substituted benzidines and aromatic dianhydrides and other aromatic diamines. The polyimides obtained with said diamines are distinguished by excellent thermal, excellent solubility, excellent electrical properties such as very low dielectric constants, excellent clarity and mechanical properties making the polyimides ideally suited as coating materials for microelectronic apparatii, as membranes for selective molecular or gas separation, as fibers in molecular composites, as high tensile strength, high compression strength fibers, as film castable coatings, or as fabric components.
The physical characteristics of the transition region separating the molecular and the atomic medium in interstellar clouds are studied using H I 21-cm and CO J = 1-0 data. Strong evidence is found for general heating of the surface layers of molecular clouds and for the existence of large heated neutral atomic halos around the molecular clouds. The heating of the molecular cloud surface is manifested through the general existence of limb brightening in the CO emission, with a characteristic depth of 1.7 pc, dependent on the Galactic latitude. The heated H I halos have a characteristic depth of 4.7 pc and a maximal extent of about 10 pc.
Membrane technologies have made critical advances in resource recovery, water purification, and energy systems. However, it is difficult to systematically tune properties of traditional polymer membranes, and researchers have struggled to deliver challenging, advanced separations using these platforms. In recent years, membranes based on 2D materials have drawn attention for molecular-scale separations due to their unique properties, most notably their tunable nanoscale interlayer properties. Among the diverse family of 2D materials, phyllosilicates, a broad class of naturally abundant clay minerals, offer significant advantages in cost and scalability over synthetic 2D materials, positioning them as promising candidates for advanced membrane technologies. Their inherent structural and chemical properties, strategies for tailoring selective transport pathways, and recent advancements across applications including ion separation, water treatment, and energy conversion are discussed. Finally, key challenges and opportunities are outlined to guide future research in leveraging phyllosilicate membranes for high-performance separation technologies.
High energy, high intensity molecular beam flow is analyzed, using a skimmer which is a small inlet where the beam is separated from the core flow
The gravity receptors of all vertebrates utilize a 'test mass' consisting of a complex arrangement of mineral and organic substance that lies over the sensory receptor areas. In most vertebrates, the mineral is a polymorph of calcium carbonate in the form of minute, single crystals called otoconia. An investigation is conducted to determine the number of proteins in otoconial complexes and their molecular weights. The investigation makes use of a microdisk gel electrophoresis method reported by Gainer (1971). The most important finding of the reported research is that analysis of the proteins of the organic material of the otoconial complexes is possible when sensitive microanalytical methods are employed. Further modification of the basic technique employed and the inclusion of other sensitive staining methods should mean that, in the future, protein separation by molecular weight will be possible in sample pools containing only two otoconial masses.
Bipolar membrane (BPM) electrochemical processes are a promising platform for carbon dioxide (CO 2 ) separations, but the molecular level thermodynamic and kinetic understanding of CO 2 -to-bicarbonate (HCO 3 − ) transformation remain poorly understood. This study employs a multiscale computational approach to systematically explore the adsorption and reactive transformation of CO 2 in five anion exchange ionomer systems. Classical molecular dynamics (MD) simulation results demonstrate that polymers with imidazolium groups significantly reduce CO 2 diffusion and enhance (OH − )–CO 2 interactions due to stronger electrostatic and π-interactions. Compared to the commonly used quaternary ammonium ionomers, imidazolium-functionalized ionomers show improved CO 2 proximity and interaction strength. Ab initio MD and density functional theory (DFT) calculations reveal that the benzyl-substituted imidazolium (IM-Ben) substantially reduces the energy barrier for HCO 3 − formation (∼72 meV lower) compared to the alkyl-substituted IM-nBu, while also mitigating imidazolium deprotonation under moderate hydration conditions. Transition state analysis shows IM-Ben forms more extensive hydrogen-bonding networks, which stabilize the transition state structure and contribute to a lower energy barrier for bicarbonate formation. These findings highlight the advantage of the adjacent benzyl moiety in enabling efficient CO 2 -to-bicarbonate transformation via hydrated hydroxide ion counterions, offering mechanistic insights and clear molecular design principles for optimizing anion exchange ionomers at bipolar membrane interfaces for electrochemical CO 2 separation applications.
Understanding the interplay between excimer formation and symmetry-breaking charge separation is important for optimizing charge separation in organic photovoltaic materials. To explore this connection, we synthesized four 1,6,7,12-tetrakis( p -X-phenoxy)perylene-(3,4:9,10)-bisdicarboximide cofacially stacked dimers, where X = MeO, tert -butyl, Br, and CF 3 . Steady-state spectroscopy reveals H-type aggregation and excimer formation in all four dimers, while transient absorption spectroscopy shows relatively small changes in their excited-state absorptions. However, time-resolved fluorescence (TRF) spectroscopy shows that relaxation occurs from an initial Frenkel exciton-dominated excimer state to one in which charge transfer (CT) character contributes. Relaxation to the lower-lying state with CT character is attributed to a combination of structural and charge distribution changes elicited by varying the substituents. Finally, this study illustrates how subtle changes in charge distribution and structure can combine to influence the excited state dynamics that influence charge separation in molecular dimers.
The course of organic chemical evolution preceding the emergence of life on earth is discussed based on evidence of processes occurring in interstellar space, the solar system and the primitive earth. Following a brief review of the equilibrium condensation model for the origin and evolution of the solar system, consideration is given to the nature and organic chemistry of interstellar clouds, comets, Jupiter, meteorites, Venus and Mars, and the prebiotic earth. Major issues to be resolved in the study of organic chemical evolution on earth are identified regarding condensation and accretion in the solar nebula, early geological evolution, the origin and evolution of the atmosphere, organic production rates, organic-inorganic interactions, environmental fluctuations, phase separation and molecular selectivity.
The High Spectral Resolution Lidar (HSRL) was operated from a roof-top site in Madison, Wisconsin. The transmitter configuration used to acquire the case study data produces about 50 mW of ouput power and achieved eye-safe, direct optical depth, and backscatter cross section measurements with 10 min averaging times. A new continuously pumped, injection seeded, frequency doubled Nd:YAG laser transmitter reduces time-averaging constraints by a factor of about 10, while improving the aerosol-molecular signal separation capabilities and wavelength stability of the instrument. The cirrus cloud backscatter-phase functions have been determined for the October 27-28, 1986 segment of the HSRL FIRE dataset. Features exhibiting backscatter cross sections ranging over four orders of magnitude have been observed within this 33 h period. During this period, cirrus clouds were observed with optical thickness ranging from 0.01 to 1.4. The altitude relationship between cloud top and bottom boundaries and the optical center of the cloud is influenced by the type of formation observed.
Spectrophotometric observations of SN 1987A from the Kuiper Airborne Observatory are presented for five epochs at 60, 260, 415, 615, and 775 days after the explosion. The low-resolution (lambda/Delta lambda = 50-100) spectra of SN 1987A are combined with data from other wavelengths to model the continuum, subtract the continuum from the spectra to determine line strengths and reveal molecular bands, separate the atomic continuum radiation from the dust continuum, and derive constraints on the grain temperatures and optical depths. A scenario for the evolution of SN 1987A and that of the ejecta from which it arises is obtained on the basis of the analysis of the continuum emission.
A computational method was devised to explore the relationship between charge separation, geometry, molecular dipole moment, polarizability, and hyperpolarizabilities in comjugated organic molecules. It is shown that bond length alternation (the average difference in length between single and double bonds in the molecule) is a key structurally observable parameter that can be correlated with hyperpolarizabilities and is thus relevant to the optimizaton of molecules and materials.
Covalent organic frameworks (COFs) enable molecular-level design of nanochannels for selective separation in pressure-driven membrane processes. Through variation of building blocks and, subsequently, the pore structure and chemistry, membrane performance can be tailored. This study employs nonequilibrium molecular dynamics simulations to theoretically demonstrate the tunable selectivity of COF membranes through a bottom-up functionalization approach. Water and salt transport are evaluated for six β-ketoenamine-linked COFs with varying multilayer thicknesses. For the thinnest multilayer (0.64–0.72 nm), all COFs exhibit low sodium sulfate (Na 2 SO 4 ) rejection (55–66%). However, 20 stacked sheets (6.4–7.2 nm) provide 67–98% rejection, with the sulfonated COF providing the highest Na 2 SO 4 rejection. Analysis of time-resolved ion density profiles reveals that solute rejection is primarily governed by interfacial exclusion arising from pore size and functional group chemistry. Although increasing salt rejection compromises water permeance, the permeance of all COF membranes is at least two orders of magnitude greater than that of a commercially available nanofiltration membrane. Overall, this work guides the rational design of COF membranes for aqueous salt separation.