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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.

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At least 703 records · Page 39

Direct observation on supersonic microprojectile penetration of carbon fiber composites with ultrafast synchrotron X-ray phase contrast imaging

High-speed penetration into carbon fiber composites is of fundamental importance to materials science and impact engineering, but research along this line suffers considerably from the lack of direct experimental observations. Here we investigate such penetration dynamics of a unidirectional carbon fiber reinforced epoxy (UCFRE) composite, with a combination of in situ, ultrafast, synchrotron phase contrast imaging and finite element (FE) analysis. The experiments yield the first direct observation on projectile trajectories and fiber-scale deformation and damage in the UCFRE composites during supersonic microprojectile penetration, for different fiber orientations (0 degrees - 90 degrees from the impact direction) and projectile velocities (600 - 850 m.s -1 ), at unprecedented temporal (~ 100 ps) and spatial (5 μm) resolutions. The maximum penetration depth decreases with increasing fiber orientation angles, as a result of anisotropic damage evolution in the composite sample. Strain localizations are prone to develop along a direction perpendicular to the fiber orientation, while the damage or cavity region, along the fiber direction. FE modeling with a three-dimensional Hashin criterion yields consistent projectile trajectory and cavity morphology with the experimental results. Finally, with increasing fiber orientation angles, damage analyses show a transition in the damage mode from fiber compression to matrix compression damage, in line with the increasing maximum penetration depth.

36 MATERIALS SCIENCE↗

Printed graphene oxide-based membranes for gas separation and carbon capture

Graphene oxide (GO)-based separation membranes have demonstrated the great potential to separate molecules and ions by the interlayer spacing with tunable nano-sized channels. The scalable fabrication of GO-based gas separation membranes, however, remains challenging, although a few preparation approaches have been reported. Here in this work, we present for the first time that the co-solvent ink-jet printing, as a fast and scalable method, can be utilized for scalable GO-based gas separation membrane preparation. Large-area (>100 cm 2 ), ultrathin, and high-quality GO membrane was successfully deposited on commercial polysulfone (PS) support, and characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and X-ray diffraction, et al., Selective hydrogen (H 2 ) and helium (He) transport over carbon dioxide (CO 2 ) and nitrogen (N 2 ) was demonstrated for the printed GO membrane. To further explore the separation potential of the printed GO-based gas membrane, additives for facilitated molecular transport were incorporated during the membrane printing process. By inserting CO 2 -philic agents into the printed GO membrane, highly efficient separation of CO 2 from N 2 was achieved with CO 2 /N 2 selectivity of 70 and CO 2 permeance as high as 2,500 GPU. The strategy proposed here may provide guidance for large-scale GO-based gas separation membrane production and a versatile approach for applying other functional 2-dimensional materials towards the membrane separation application.

42 ENGINEERING↗

Reduced-order condensed-phase kinetic models for polyethylene, polypropylene and polystyrene thermochemical recycling

Thermochemical recycling of plastic waste (PW) into chemicals and energy vectors requires coupling particle and reactor-scale simulations to accurate condensed phase pyrolysis mechanisms for each constituent. This work proposes a methodology to derive reduced-order condensed-phase kinetic models from validated semi-detailed kinetic mechanisms. Two types of kinetic models are obtained for polyethylene (PE), polypropylene (PP) and polystyrene (PS): reduced semi-detailed models and multi-step fully lumped ones. These families offer different compromises between accuracy and computational cost. The former employ 50–100 gas + liquid species and describe both the radical degradation and the detailed carbon distribution of the products. Conversely, the latter involves 5–10 species per polymer tracking only the main petroleum cuts. The kinetic mechanisms are complemented by the definition of thermochemical properties of gas, liquid, and solid-phase species, accounting for phase-transitions through pseudo-chemical reactions. Model validations are performed by comparison with experimental data and the original semi-detailed mechanisms in terms of mass loss, heat fluxes and product distribution profiles. The resulting CHEMKIN-like condensed-phase models are attached as Supplementary Material and as a GitHub repository. Extending the proposed approach to other polymers and coupling it with existing subsets in the CRECK kinetic framework (e.g., biomass, PVC, PET) offers a powerful tool to model thermochemical recycling of PW and biomass/PW mixtures.

kinetics↗

Non-premixed counterflow methane flames in DC/AC/NS electric fields

The response of counterflow diffusion flames to sub-breakdown DC and AC electric fields, as well as their superposition with ns pulse discharge waveforms, is studied in the plane-to-plane electrode geometry. Sub-breakdown DC and low-frequency AC electric fields cause the flame displacement toward the grounded electrode, in the direction of the applied field, indicating that the body force on the positive ions exceeds that on the electrons and negative ions. As the AC frequency increases, the flame response becomes less pronounced, due to the reduction of the electrohydrodynamic (EHD) body force impulse over the AC half-period. The electric field in the electrode gap is determined by ps Electric Field Induced Second Harmonic (E-FISH) generation, with absolute calibration using sub-breakdown ns pulses overlapped with the measured electric field waveform. The results show that the electric field distribution across the flame in the current saturation regime follows the Laplacian field. This indicates that the space charge density in the gap is too low to distort the applied DC or AC field, consistent with the kinetic modeling predictions. Combining a nanosecond pulse discharge with a sub-breakdown DC field generates a diffuse plasma across the entire gap. Time-resolved and spatially resolved measurements of the electric field in the discharge indicate the ionization wave propagation between the electrodes. The present results do not exhibit a detectable flame displacement enhancement by ns discharge pulses combined with a sub-breakdown field, observed previously. Kinetic modeling calculations show that the absence of this effect in the plane-to-plane geometry is due to the rapid plasma self-shielding. This indicates that alternative electrode geometries limiting the self-shielding would be more effective for the plasma / electric field enhanced flameholding and flame stabilization applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

BODIPY based A-D-A molecules: Effect of CF3 group substitution at meso phenyl group

Two pairs of A-D-A molecules have been created with fluorene and benzodithiophene as the central donor subunits and terminal BODIPY units, functionalized with either a 4-methylphenyl or 4-trifluoromethylphenyl group at the meso position. The effect of the para substituent of the meso phenyl group on the photophysical properties of these molecules is studied through steady state absorption and fluorescence spectroscopy as well as femtosecond transient absorption and time resolved fluorescence spectroscopy techniques. Applicability of these molecules as donors in solution processed solar cell active layers was investigated through time resolved microwave conductivity measurements on blends with PC60BM acceptor, which shows a varying yield of charge transfer with choice of substituent. Transient absorption spectroscopy is then employed to investigate the role of the 4-trifluoromethylphenyl group in altering the efficiency of charge transfer from these A-D-A molecules to PC60BM. The results show a consistent picture of picosecond charge transfer and a component of a few hundred ps geminate recombination that results in a small yield of long-lived free charges optimized for the methylphenyl derivatives.

36 MATERIALS SCIENCE↗

Statorless mixed flow turbine for transonic pulsating inflow

Effective harvesting of power from high speed highly transient inflows such as the outflow of rotating detonation combustors (RDCs) is key to achieving their promised cycle efficiency step jump. To increase power density and efficiency simultaneously, a concept that can directly ingest transonic outflow, addressing the choking is needed, i.e. without additional transition elements. A new statorless design was assessed using a comprehensive approach to quantify all contributions to loss generation in transient flows, locally and globally. The turbine rotor was designed under steady flow conditions with a genetic algorithm. The comparison of power and loss generation between steady and unsteady flow results shows that a design methodology under steady-state conditions is suitable to characterize the performance of different designs. Three design families were further assessed under highly transient transonic conditions including traveling shock waves with a relative total pressure amplitude of 149.6% around the mean value and inflow angle variations from -26.5 deg to +51.8 deg. The oblique shock impinging on the pressure side (PS) of the turbine augments the shaft power extraction. When the oblique shock reflects between the pressure side and suction side (SS), its strength diminishes. This paper provides design guidelines on efficient turbine work extraction from the shocks emanating from detonation combustors.

rotating detonation engines↗

Promising performance of sulfide catholytes compared to halide alternatives in NMC811 cathodes for sheet-type sulfide solid-state batteries

Sulfide-based solid-state batteries (SSBs) show promise in achieving energy densities over 350 Wh/kg, yet challenges persist with their incorporation of high-voltage, nickel-rich layered oxide cathodes, such as LiNi₀.₈Mn₀.₁Co₀.₁O₂ (NMC811), due to the poor oxidation stability of sulfide solid-state electrolytes (SSEs) like Li₆PS₅Cl (LPSCl). Although halide SSEs such as Li₃InCl₆ (LIC) and Li₃YCl₆ (LYC) have previously shown promise in stabilizing high-voltage NMC cathodes, our research reveals that sulfide SSE catholytes, particularly when combined with surface-coated NMC cathodes, deliver superior performance. Here, this investigation assesses the cycling stability of various catholytes—LPSCl, LIC, Li₁₀GeP₂S₁₂ (LGPS), combined LIC-LPSCl, and LYC-LPSCl—in SSBs with LiNbO₃-coated NMC811 cathodes against sheet-type LPSCl separators. Findings indicate that while LGPS-based cathodes maintain higher capacity retention, they yield lower deliverable capacity, and LIC cathodes experience significant electrochemical degradation. Importantly, our results underscore that sulfide SSE catholytes, in conjunction with LiNbO₃-coated cathodes, optimize the cathode-electrolyte interphase (CEI), enhancing both kinetics and mass transport. These insights provide a strategic direction for optimizing catholyte composition in the development of sheet-type sulfide-based SSBs.

Catholyte↗

Synthesis and morphological characterization of linear and miktoarm star poly(solketal methacrylate)- block -polystyrene copolymers

The synthesis, molecular characterization, and morphological evaluation of AB n, (n = 2,3) miktoarm star block copolymers consisting of poly(glycerol monomethacrylate) (PGMA) and polystyrene (PS) with varying molecular weights and compositions is described. The system is known to demonstrate a remarkably high Flory-Huggins interaction parameter. The corresponding linear diblock copolymer analogues, were synthesized as well, and comparisons with regard to feature dimensions and morphologies are provided. Well-ordered nanostructures of various morphologies were formed with domain spacing as low as 7.2 nm. Different morphologies were attained by some of the topological isomers indicating that in miktoarm star block copolymers the phase boundaries were strongly shifted. Additionally, a triblock ABA analogue was studied to investigate the effect of triblock copolymer conformations. Noteworthy is that for copolymers with different macromolecular architecture leading to similar morphology; different domain spacings were obtained. The synthesis of all the samples was carried out by high-vacuum anionic polymerization techniques. Molecular characterization with Size Exclusion Chromatography (SEC) and Proton Nuclear Magnetic Resonance Spectroscopy ( 1 H NMR) confirmed well-defined copolymers obtained. The morphological characterization was accomplished by Small-Angle X-ray Scattering (SAXS). In conclusion, the observations from this study highlight the potential of incorporating macromolecular architecture in the self-assembly of strongly immiscible block copolymers to attain ultra-small nanofeatures with desired morphologies.

36 MATERIALS SCIENCE↗

Third-body stabilization of supercritical CO 2 in CO oxidation: development and application of a ReaxFF force field for the CO/O/CO 2 system

Supercritical CO 2 (scCO 2 ) plays a crucial role as a solvent in separation processes, advanced power cycles, and materials processing. Nonetheless, the atomistic comprehension of how the dense scCO 2 matrix influences the fundamental reaction of carbon monoxide (CO) is still insufficiently explored. Experimental studies and molecular dynamics (MD) simulations frequently fail to detect the highly reactive, transient intermediates, such as atomic oxygen (O), that drive these reactions. Here, to address this issue, we have developed a novel ReaxFF reactive force field for the CO 2 /CO/O system. The force field parameters were calibrated using density functional theory and second-order Møller-Plesset calculations to model CO 2 crystal properties, intermolecular interactions, bond dissociation curves, and reaction energy barriers. The force field reproduces the cohesive energy of the CO 2 crystal, the pressure characteristics of bulk scCO 2 , the equation-of-state behavior over a wide pressure–density range, the pressure dependence of the C–O bond length under compression, and the structural properties of liquid and scCO 2 , as documented by experiments, ab-initio MD, and prominent non-reactive models. The force field was subsequently applied to study the CO + O → CO 2 reaction. In a dilute environment, the reaction is inefficient as the newly formed CO 2 rapidly dissociates due to excess kinetic and potential energy acquired from the exothermic reaction. Conversely, in a dense scCO 2 environment, the surrounding matrix acts as an efficient third body, stabilizing the emerging CO2 product via molecular collisions. Statistical analysis confirms an average excess energy dissipation of 133.9 ± 3.6 kcal/mol over 112.4 ± 17.9 ps. Kinetic energy decomposition reveals that ∼ 92% of the excess kinetic energy is stored in internal (rotational and vibrational) degrees of freedom. This ReaxFF force field establishes a mechanistic foundation for third-body stabilization in dense reactive environments.

Chowdhury, Emdadul Haque [Pennsylvania State Univ.↗

Technique for an improved and time-resolved carbon areal density measurement with a single channel diagnostic for inertial confinement fusion

Measurement of the areal density and velocity of the carbon ablator shell during peak burn in inertial confinement fusion give powerful information on the state of the ablator and where in the trajectory of implosion it reaches peak burn. Detailed comparison of the absolute densities and velocities of the carbon in implosions has been prevented by the limited ability to resolve shot-to-shot variation within a shot series or within a campaign. Here, a new approach using a single, ultra fast (~10 ps) gamma ray channel can massively reduce uncertainties and will provide insights on improvements to target and drive variables. Small improvements in these experimental design parameters may result in much greater yields.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

First-principles-derived transport properties of Molten chloride salts

Molten salts have many applications ranging from a heat transfer medium in both generation IV nuclear reactor designs and the solar industry to thermal storage systems. While molten salts show promising properties for these applications, there still exists a knowledge gap for the transport properties of molten salts at elevated temperatures. This work uses ab initio Molecular Dynamics to investigate the transport properties of KCl, LiCl, KCl-LiCl eutectic, NaCl, MgCl 2 , and NaCl-MgCl 2 eutectic molten salt systems. Further, the properties presented here are the diffusion coefficient, viscosity, and isochoric heat capacity. These properties are compared to experimental data where available and other computational work in cases where no experimental data is available. This is the first work to explore timescales over 100 ps via AIMD for the determination of transport properties in molten salts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced ionic conductivity and lack of paddle-wheel effect in pseudohalogen-substituted Li argyrodites

Superionic conductors are key to the development of safe and high-energy-density, all-solid-state batteries. Using a combined theoretical and experimental approach, we explore the feasibility of increasing the ionic conductivity through pseudohalogen substitution in the Li argyrodite structure. Under the guidance of calculated thermodynamic stability, BH 4 -substituted Li argyrodite, Li 5.91 PS 4.91 (BH 4 ) 1.09 , was successfully synthesized via a mechanochemical method. As-synthesized BH 4- substituted Li argyrodite displays an ionic conductivity of 4.8 mS/cm at 25°C. Ab initio molecular dynamics simulation trajectory analysis was used to investigate how BH 4 facilitates Li-ion diffusion and indicates only a weak correlation with the B–H bond motion. Here, we find that the enhanced conductivity mainly originates from the weak interaction between Li and BH 4 and find no evidence of a paddle-wheel effect from the polyanion. This work provides insight into how cluster ions enhance Li diffusion and systematically describes how to explore superionic conductors with pseudohalogen substitution.

25 ENERGY STORAGE↗

Persistent hot carrier diffusion in boron arsenide single crystals imaged by ultrafast electron microscopy

Cubic boron arsenide (BAs) is promising for microelectronics thermal management because of its high thermal conductivity. Recently, its potential as an optoelectronic material is also being explored. However, it remains challenging to measure its photocarrier transport properties because of small sizes of available high-quality crystals. Here, we use scanning ultrafast electron microscopy (SUEM) to directly visualize the diffusion of photocarriers in BAs single crystals. Surprisingly, we observed ambipolar diffusion at low optical fluence with persistent hot carrier dynamics for above 200 ps, which can likely be attributed to the large frequency gap between acoustic and optical phonons, the same feature that is responsible for the high thermal conductivity. At higher optical fluence, we observed spontaneous electron-hole separation. Our results show BAs is an attractive optoelectronic material combining high thermal conductivity and excellent photocarrier transport properties. Finally, our study also demonstrates the capability of SUEM to probe photocarrier transport in emerging materials.

36 MATERIALS SCIENCE↗

Liquid chromatography at critical conditions (LCCC): Capabilities and limitations for polymer analysis

This paper investigates liquid chromatography at critical condition (LCCC) for polymer analysis. Based on controversial claims on the separation of cyclic polymers from linear analogues in the literature, the efficiency of LCCC for separation and purity analysis is questioned. Polyisobutylene (PIB) and poly(3,6-dioxa-1,8-octanedithiols) (polyDODT) were used for the study. Here, the structure of low molecular weight cyclic and linear polyDODT was demonstrated by MALDI-ToF. NMR did not show the presence of thiol end groups in higher molecular weight PIB-disulfide and polyDODT samples, so they were considered cyclic polymers. When a low molecular weight polyDODT oligomer with only traces of cycles, as demonstrated by MALDI-ToF, was mixed with an M n = 27K g/mol cyclic sample, LCCC did not detect the presence of linear oligomers at 6 wt%. Based on the data presented here, it can be concluded that the LCCC method is not capable of measuring < 6 wt% linear contamination so earlier claims for cyclic polystyrene (PS) samples purified by LCCC having < 3 % linear contaminants are questioned.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optoelectronic and material properties of solution-processed Earth-abundant Cu 2 BaSn(S, Se) 4 films for solar cell applications

Copper barium thioselenostannate, Cu 2 BaSnS 4-x Se x (CBTSSe), absorbers employ low-toxicity and abundant metals while offering low-cost manufacturing options, controllable stoichiometry and band gap tunability (from 2 eV at x = 0 to 1.55 eV at x = 3). CBTSSe can therefore be considered a prospective candidate for maintaining or improving upon the advantages of already commercialized Cu(In,Ga)(S,Se) 2 (CIGSSe) and CdTe absorbers. Here, we focus on solution-deposited stoichiometric CBTSSe films with band gap of 1.59 eV (x ≈ 3) and explore the fundamental film properties. Temperature- and excitation-dependent photoluminescence studies reveal a dominant defect emission at ~1.5 eV and a second deep defect feature at 1.15 eV. From time-resolved terahertz measurements, we find a charge carrier (electron and hole sum) mobility of ~140 cm 2 /Vs—i.e., comparable to values in CIGSSe or Cu 2 ZnSnS 4-x Se x (CZTSSe)—as well as a two-component minority carrier lifetime. A longer-lived lifetime component (~2 ns) arises from bulk recombination. However, strong recombination at the (bare) surface leads to a ~50 ps lifetime, inferior to state-of-the-art CIGSSe or CZTSSe absorbers. This recombination issue may worsen for CBTSSe/CdS interfaces, due to a cliff-like band alignment with 0.6 eV band offset, as revealed by ultraviolet photoemission spectroscopy. A low number of charge carriers within the absorber further contributes to a high series resistance. Employing these films, we also report the highest performance achieved from solution-processed trigonal CBTSSe thin-film photovoltaic devices, with open circuit voltage, short-circuit current density, fill factor and efficiency of 470 mV, 14.3 mA/cm 2 , 43.6% and 2.9%, respectively. The physical measurements provided on the stoichiometric solution-processed CBTSSe absorber further point to critical areas for future improvement of CBTSSe and related photovoltaic cells in the quest for higher efficiency devices based on earth abundant metals.

14 SOLAR ENERGY↗

Phonon lifetimes and mode softening in cubic Cs 2 AgBiBr 6

Metal halide perovskites (MHPs) have emerged as noteworthy candidates for photovoltaic applications in recent years. Their high power-conversion efficiency is largely attributed to the structure-function relationship, which is not well understood. In this study, we examine the low-frequency phonons of the double perovskite Cs 2 AgBiBr 6 using neutron inelastic scattering. We find that the acoustic phonon lifetimes decrease from 16 to 3 ps along Γ to X, which is indicative of significant anharmonicity that contributes to the ultralow thermal conductivity. Additionally, we observe a linear temperature dependence of the square of the zone-center soft optical phonon energy, which is consistent with a weakly first-order displacive cubic-tetragonal structural phase transition. These results provide a deeper understanding of the lattice dynamics and phase transitions in MHPs as well as the effects of anharmonicity by comparison with prototypical hybrid organic-inorganic MHPs, (CH 3 NH 3 ) PbX 3 (X = Br, I).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Timing and synchronization of the DUNE neutrino detector

The DUNE neutrino experiment far detector has a fiducial mass of 40 kt. The O(1 M) readout channels are distributed over the 4 x 10kt modules and need to be synchronized to O(10 ns) with a reliable, simple, affordable system. For the majority of channels a simple DC-balanced protocol is used, with clock and synchronization information encoded on the same fibre. The remaining channels use “White Rabbit” (IEEE-1588). Small scale tests show a timing jitter of <100 ps. The DUNE timing system has been successfully prototyped at the ProtoDUNE-SP detector at CERN.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

The CLAS12 Central Time-of-Flight system

The Central Time-of-Flight system for the large-acceptance CLAS12 spectrometer in Hall B at the Thomas Jefferson National Accelerator Facility is described. The system consists of a hermetic barrel of 48 scintillation counters at a radius of 25 cm from the beamline. The wedge-shaped counters are 3.4 cm wide, 3.0 cm thick, and 90 cm long, and span a range of polar angles relative to the center of the nominal target location from roughly 35° to 125°. The counters reside in the 5-T field of the CLAS12 superconducting solenoid. The bars are read out via bent light guides 1 m long on the upstream end of the counters and 1.6 m long on the downstream end. The phototubes are shielded by a multi-layer dynamical magnetic shield system to reduce the local fringe fields in the range from 400 G to 1000 G down to the level of 0.2 G at the location of the photocathodes. The average effective time resolution of the counters is 80 ps.

47 OTHER INSTRUMENTATION↗