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At least 163 records · Page 9

Tracking Spatiotemporal Electric Potential in Batteries Using High-Resolution Operando X‑ray Transmission Imaging

The formation of significant concentration gradients across electrolytes in batteries affects the rate at which electrochemical reactions occur. In this work, we use high-resolution operando X-ray transmission imaging to capture spatiotemporal salt concentration profiles c(x,t) in a symmetric cell comprising a polymer electrolyte sandwiched between two lithium–indium alloy electrodes during a constant-current experiment followed by open-circuit relaxation. The decay of open-circuit potential is related to the concentration dependence of the potential across concentration cells, U. We show how operando c(x,t) data can be used to calculate the spatiotemporal electric potential “inside” the polarized electrolyte. We track the spatial- and time-dependent cell potential during the constant-current step and distinguish its two contributions: a concentration overpotential governed by U. and an ohmic contribution governed by ionic conductivity. Over most of the time window, the concentration overpotential dominates. At steady state, it is a factor of 7 larger than the ohmic contribution. Such findings indicate that efforts to design new polymer electrolytes should focus on minimizing concentration gradients.

Electrical conductivity↗

Ground System for Solar Dynamics Observatory (SDO) Mission

NASA s Goddard Space Flight Center (GSFC) has recently completed its Critical Design Review (CDR) of a new dual Ka and S-band ground system for the Solar Dynamics Observatory (SDO) Mission. SDO, the flagship mission under the new Living with a Star Program Office, is one of GSFC s most recent large-scale in-house missions. The observatory is scheduled for launch in August 2008 from the Kennedy Space Center aboard an Atlas-5 expendable launch vehicle. Unique to this mission is an extremely challenging science data capture requirement. The mission is required to capture 99.99% of available science over 95% of all observation opportunities. Due to the continuous, high volume (150 Mbps) science data rate, no on-board storage of science data will be implemented on this mission. With the observatory placed in a geo-synchronous orbit at 36,000 kilometers within view of dedicated ground stations, the ground system will in effect implement a "real-time" science data pipeline with appropriate data accounting, data storage, data distribution, data recovery, and automated system failure detection and correction to keep the science data flowing continuously to three separate Science Operations Centers (SOCs). Data storage rates of approx. 45 Tera-bytes per month are expected. The Mission Operations Center (MOC) will be based at GSFC and is designed to be highly automated. Three SOCs will share in the observatory operations, each operating their own instrument. Remote operations of a multi-antenna ground station in White Sands, New Mexico from the MOC is part of the design baseline.

Tann, Hun K.↗

Characterization of Pinhole Collimators for High-Resolution Gamma Imaging of Irradiated Fuel

Post-irradiation examination (PIE) of nuclear fuels requires imaging tools capable of resolving isotopic and spatial features with high throughput. This project contributes to a proof-of-concept effort aimed at advancing gamma emission tomography (GET) by evaluating novel fine-aperture pinhole collimators. Two Rose’s metal collimators, 100 µm (20° acceptance angle) and 350 µm (30° acceptance angle), were prototyped and characterized for their effectiveness in transporting gamma rays through the pinhole aperture. To support data collection, a Python-based data acquisition system was developed to coordinate a rotation stage, linear stage, and CZT detector, reducing latency in high-rate gamma event logging to one second per acquisition. Queue-based file writing enabled seamless real-time data capture for count rates up to 35,000 counts per second (cps). List-mode parsing algorithms were implemented to differentiate single and simultaneous gamma interactions for future tomographic reconstruction. Detector response was evaluated in both spectroscopy and list mode acquisition methods across varying source distances to confirm absolute and collimator efficiencies. Preliminary efficiency figures suggest effective collimation of gamma-rays with energies below 700 keV, with ~4% residual intensity through the aperture for Cs-137. The impact of collimator geometry on image quality is currently being evaluated. This groundwork supports the ongoing development of a sub mm resolution cone-beam CT system for imaging fuel phantoms, an essential step toward improving GET efficiency and accelerating nuclear fuel qualification efforts.

46 - INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AN↗

Conditional Entropy-Constrained Residual VQ with Application to Image Coding

This paper introduces an extension of entropy-constrained residual vector quantization (VQ) where intervector dependencies are exploited. The method, which we call conditional entropy-constrained residual VQ, employs a high-order entropy conditioning strategy that captures local information in the neighboring vectors. When applied to coding images, the proposed method is shown to achieve better rate-distortion performance than that of entropy-constrained residual vector quantization with less computational complexity and lower memory requirements. Moreover, it can be designed to support progressive transmission in a natural way. It is also shown to outperform some of the best predictive and finite-state VQ techniques reported in the literature. This is due partly to the joint optimization between the residual vector quantizer and a high-order conditional entropy coder as well as the efficiency of the multistage residual VQ structure and the dynamic nature of the prediction.

Kossentini, Faouzi↗

Test of nuclear decay rate variation due to an antineutrino flux

Unexplained variations of the decay rate parameter for weak interaction decays such as β ± decay, electron capture, as well as strong interaction α decay have been reported. Because these variations have been presented by a number of groups, at various locations, using various types of detectors, different isotopes, and over extended periods of time, some researchers have interpreted the source of these variations as not from ambient environmental factors such as temperature, pressure, and humidity but via an unexplained fundamental interaction. The state of decay rate parameter variations experiments is reviewed, and the reported results are placed into a common comparable context by defining a phenomenological cross section. After that we make decay parameter measurements as a function of time at the level of 10 -5 in the presences of an antineutrino flux with an on-off cycle time of ≈ 30 days. This level of precision requires a detailed understanding of both systematic and statistical errors; otherwise, systematic errors in the measurement may mimic the decay events of fundamental interactions. The experiment searched for variation of the $^{54}_{25}$Mn, e - capture decay rate parameter and $^{137}_{55}$Cs, β - decay rate parameter both to a level of precision of 1 part in ≈10 5 by comparing the difference between the decay rate in the presence of an antineutrino flux ≈ 3 x 10 12 $\bar{ν}$ cm -2 s -1 and no flux measurements. The experiment was located 6.53 m from the reactor core of the High Flux Isotope Reactor at the Oak Ridge National Laboratory. Two weak interaction decays, one via electron capture and the other via β - decay, were selected because the final state and the time reverse state each contain a neutrino and antineutrino, covering arguments that the antineutrino flux may interact differently or not at all in one of the cases. The $\gamma$ spectra from both decays were collected and analyzed independently. The measured variation in the decay rate parameters are found to be δλ/λ =(0.034 ± 1.38) x10 -5 for $^{54}_{25}$Mn and δλ/λ =(0.67±1.56) x10 -5 for $^{137}_{55}$Cs. These results are consistent with no measurable decay rate parameter variation due to an antineutrino flux, yielding a 68% confidence level upper limit sensitivity for $^{54}_{25}$Mn δλ/λ ≤ 1.31 x 10 -5 or σ ≤ 1.29 x10 -25 cm 2 in cross section and for $^{137}_{55}$Cs δλ/λ ≤ 2.23 x 10 -5 or σ ≤ 5.69 x10 -27 cm 2 . The cross-section upper limit obtained in these null or no observable effect measurements are ≈ 10 4 times more sensitive than past experiments reporting positive results in 54 Mn and 137 Cs. . .

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Adaptation of the TH Epsilon Mu formalism for the analysis of the equivalence principle in the presence of the weak and electroweak interaction

The TH epsilon mu formalism, used in analyzing equivalence principle experiments of metric and nonmetric gravity theories, is adapted to the description of the electroweak interaction using the Weinberg-Salam unified SU(2) x U(1) model. The use of the TH epsilon mu formalism is thereby extended to the weak interactions, showing how the gravitational field affects W sub mu (+ or -1) and Z sub mu (0) boson propagation and the rates of interactions mediated by them. The possibility of a similar extension to the strong interactions via SU(5) grand unified theories is briefly discussed. Also, using the effects of the potentials on the baryon and lepton wave functions, the effects of gravity on transition mediated in high-A atoms which are electromagnetically forbidden. Three possible experiments to test the equivalence principle in the presence of the weak interactions, which are technologically feasible, are then briefly outline: (1) K-capture by the FE nucleus (counting the emitted X-ray); (2) forbidden absorption transitions in high-A atoms' vapor; and (3) counting the relative Beta-decay rates in a suitable alpha-beta decay chain, assuming the strong interactions obey the equivalence principle.

Fennelly, A. J.↗

In situ TEM observation of calcium silicate hydrate nanostructure at high temperatures

Fire poses a substantial threat to concrete structures because calcium silicate hydrate (C-S-H) is not thermally stable at high temperatures. Herein, in situ TEM at temperatures from 20 to 800 °C was conducted to study the thermal-induced structural changes in C-S-H. We captured C-S-H shrinks at an average rate of 0.02 μm{sup 2}/{sup o}C upon heating with three stages observed, including induction, constant, and rapid periods. Our observation revealed that an 800 nm pore could be healed during pore structure evolution owing to the reconstruction and deformation among C-S-H blocks. The Ca/Si ratio was dropped at higher temperatures because of the leakage of calcium ions from the C-S-H structure to form CaO precipitates. The temperature-driven phase transformation and degradation were also detected using electron diffraction that C-S-H was transformed into metastable calcium silicate minerals above 800 °C. This work provides insights into the nanoscale transformation of C-S-H at high temperatures.

36 MATERIALS SCIENCE↗

Chemical Doppelgangers in GALAH DR3: The Distinguishing Power of Neutron-capture Elements among Milky Way Disk Stars

The observed chemical diversity of Milky Way stars places important constraints on Galactic chemical evolution and the mixing processes that operate within the interstellar medium. Recent works have found that the chemical diversity of disk stars is low. For example, the Apache Point Observatory Galactic Evolution Experiment (APOGEE) "chemical doppelganger rate," or the rate at which random pairs of field stars appear as chemically similar as stars born together, is high, and the chemical distributions of APOGEE stars in some Galactic populations are well-described by two-dimensional models. However, limited attention has been paid to the heavy elements (Z > 30) in this context. In this work, we probe the potential for neutron-capture elements to enhance the chemical diversity of stars by determining their effect on the chemical doppelganger rate. We measure the doppelganger rate in GALactic Archaeology with HERMES DR3, with abundances rederived using The Cannon, and find that considering the neutron-capture elements decreases the doppelganger rate from ~2.2% to 0.4%, nearly a factor of 6, for stars with –0.1 < [Fe/H] < 0.1. While chemical similarity correlates with similarity in age and dynamics, including neutron-capture elements does not appear to select stars that are more similar in these characteristics. Our results highlight that the neutron-capture elements contain information that is distinct from that of the lighter elements and thus add at least one dimension to Milky Way abundance space. This work illustrates the importance of considering the neutron-capture elements when chemically characterizing stars and motivates ongoing work to improve their atomic data and measurements in spectroscopic surveys.

79 ASTRONOMY AND ASTROPHYSICS↗

Spacesuit Evaporator-Absorber-Radiator (SEAR)

For decades advanced spacesuit developers have pursued a regenerable, robust non-venting system for heat rejection. Toward this end, this paper investigates linking together two previously developed technologies, namely NASA's Spacesuit Water Membrane Evaporator (SWME), and Creare's lithium chloride Heat Pump Radiator (HPR). Heat from a liquid cooled garment is transported to SWME that provides cooling through evaporation. The SEAR is evacuated at the onset of operations and thereafter, the water vapor absorption rate of the HPR maintains a low pressure environment for the SWME to evaporate effectively. This water vapor captured by solid LiCl in the HPR with a high enthalpy of absorption, results in sufficient temperature lift to reject most of the heat to space by radiation. After the sortie, the HPR would be heated up in a regenerator to drive off and recover the absorbed evaporant. A one-fourth scale prototype was built and tested in vacuum conditions at a sink temperature of 250 K. The HPR was able to stably reject 60 W over a 7-hour period. A conceptual design of a full-scale radiator is proposed. Excess heat rejection above 240 W would be accomplished through venting of the evaporant. Loop closure rates were predicted for various exploration environment scenarios.

Bue, Grant C.↗

3D microstructure design of lithium-ion battery electrodes assisted by X-ray nano-computed tomography and modelling

Driving range and fast charge capability of electric vehicles are heavily dependent on the 3D microstructure of lithium-ion batteries (LiBs) and substantial fundamental research is required to optimise electrode design for specific operating conditions. Here we have developed a full microstructure-resolved 3D model using a novel X-ray nano-computed tomography (CT) dual-scan superimposition technique that captures features of the carbon-binder domain. This elucidates how LiB performance is markedly affected by microstructural heterogeneities, particularly under high rate conditions. The elongated shape and wide size distribution of the active particles not only affect the lithium-ion transport but also lead to a heterogeneous current distribution and non-uniform lithiation between particles and along the through-thickness direction. Building on these insights, we propose and compare potential graded-microstructure designs for next-generation battery electrodes. To guide manufacturing of electrode architectures, in-situ X-ray CT is shown to reliably reveal the porosity and tortuosity changes with incremental calendering steps.

33 ADVANCED PROPULSION SYSTEMS↗

The Physics behind Precipitation Onset Bias in CMIP6 Models: The Pseudo-Entrainment Diagnostic and Trade-Offs between Lapse Rate and Humidity

Conditional instability and the buoyancy of plumes drive moist convection but have a variety of representations in model convective schemes. Vertical thermodynamic structure information from Atmospheric Radiation Measurement (ARM) sites and reanalysis (ERA5), satellite-derived precipitation (TRMM3b42), and diagnostics relevant for plume buoyancy are used to assess climate models. Previous work has shown that CMIP6 models represent moist convective processes more accurately than their CMIP5 counterparts. However, certain biases in convective onset remain pervasive among generations of CMIP modeling efforts. Here we diagnose these biases in a cohort of nine CMIP6 models with sub-daily output, assessing conditional instability in profiles of equivalent potential temperature θ e and saturation equivalent potential temperature θ es in comparison to a plume model with different mixing assumptions. Most models capture qualitative aspects of the θ es vertical structure, including a substantial decrease with height in the lower free troposphere associated with the entrainment of subsaturated air. We define a “pseudo-entrainment” diagnostic that combines subsaturation and a θ es measure of conditional instability similar to what entrainment would produce under the small-buoyancy approximation. This captures the trade-off between larger θ es lapse rates (entrainment of dry air) and small subsaturation (permits positive buoyancy despite high entrainment). This pseudo-entrainment diagnostic is also a reasonable indicator of the critical value of integrated buoyancy for precipitation onset. Models with poor θ e /θ es structure (those using variants of the Tiedtke Scheme) or low entrainment runs of CAM5, and models with low subsaturation, such as NASA-GISS, lie outside the observational range in this diagnostic.

54 ENVIRONMENTAL SCIENCES↗

SATS Enhanced Capabilities and Demonstration of Improved Ramp Rates for In-Cell Testing

This report presents the development of the second-generation Severe Accident Test Station, referred to as SATS 2.0. SATS 2.0 represents a major advancement in addressing critical research needs for the United States nuclear industry, particularly in relation to fuel fragmentation, relocation, and dispersal (FFRD) concerns associated with the nuclear industry’s goal to extend fuel burnup beyond a peak rod average of 62 GWd/tU. The central objective of SATS 2.0 was the deployment a new furnace capable of achieving heating rates up to 100°C/s. This achievement addresses critical capability gaps, enabling assessment of prioritized research objectives established by the Electric Power Research Institute’s (EPRI) Collaborative Research on Advanced Fuel Technologies (CRAFT) working group. These research objectives are directly related to high-burnup loss-of-coolant accident (LOCA) conditions and the effects of prolonged exposure to elevated temperatures, both of which are crucial to enhancing nuclear safety and efficiency. The SATS 2.0 system builds upon prior experience with the original SATS system, which focused on evaluating accident-tolerant fuel (ATF) cladding concepts during accident conditions. However, the new system not only expands upon prior core capabilities by achieving higher heating rates with a better furnace but also plans to incorporate novel auxiliary systems to create a versatile platform for addressing current research needs. For example, a system was developed for the quantification and characterization of fission gas released during high-temperature transients. Additionally, in situ measurement capabilities were developed, such as digital image correlation which enabled the real-time capture of strain related to balloon and burst events and fiber-optic sensors that allowed for high-fidelity characterization of temperature gradients. Demonstration tests of the new 12-lamp furnace achieved heating rates up to 120°C/s. Notably, SATS 2.0 demonstrated its capacity to simulate LOCA burst tests at different pressures, yielding burst data that align with historical empirical models. Moreover, the system exhibited its capability to simulate complex conditions observed in anticipated operational occurrences, while effectively mitigating temperature overshoots. These accomplishments mark significant progress toward overcoming FFRD challenges and advancing the United States nuclear industry's safety basis and technical capabilities for extended burnup.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Impacts of Permeability Heterogeneity and Background Flow on Supercritical CO 2 Dissolution in the Deep Subsurface

Motivated by CO 2 capture and sequestration (CCS) design considerations, we consider the coupled effects of permeability heterogeneity and background flow on the dissolution of a supercritical CO 2 lens into an underlying deep, confined aquifer. We present the results of a large-scale Monte Carlo simulation study examining the interaction of background flow rate and three parameters describing multi-Gaussian log-permeability fields: mean, variance, and correlation length. Hundreds of high-resolution simulations were performed using the PFLOTRAN finite volume software to model CO 2 dissolution in a kilometer-scale aquifer over 1,000 years. Predictive dimensionless scaling relationships relating CO 2 dissolution rate to heterogeneity statistics, Rayleigh (Ra) and Péclet (Pe) numbers were developed for both gravitationally dominated free convection to background flow-dominated forced convection regimes. An empirical criterion, Pe = Ra 3/4 , was discovered for regime transition. All simulations converged quickly to a quasi-steady, approximately linear dissolution rate. However, this rate displayed profound variability between permeability field realizations sharing the same heterogeneity statistics, even under mild permeability heterogeneity. In general, increased heterogeneity was associated with a lower mean and higher variance of dissolution rate, undesirable from a CCS design perspective. The relationship between dissolution rate and background flow was found to be complex and nonlinear. Dimensionless scaling relationships were uncovered for a number of special cases. Results call into question the validity of the Boussinesq approximation in the context of modest-to-high background flow rates and the general applicability of numerical simulations without background flow.

42 ENGINEERING↗

An experimental, theoretical, and kinetic modeling study of post-flame oxidation of ammonia

The post -flame oxidation rate of ammonia was investigated in a novel atmospheric pressure flow reactor at temperatures of 1280 ± 16 K and as a function of residence time and mixture composition (1-10% O 2 , dry and moist). The experimental results, as well as selected data from literature, were analyzed using an updated detailed chemical kinetic model. The medium temperature, very lean conditions enhance the importance of reactions of the nitroxyl (HNO) intermediate. High-level theory was used to calculate the rate constant for HNO + NH 2 , indicating that this step is significantly faster than values used in literature. Furthermore, a trajectory based approach was used to determine collision efficiencies for selected bath gases for HNO + M. The experimental results show that the NH 3 oxidation rate increases with temperature and O 2 concentration, while the presence of water vapor slightly inhibits reaction. Formation of NO and N 2 O was strongly promoted at higher levels of O 2 . Modeling results agreed well with the measurements, except at the lowest level of O 2 . The predicted oxidation rate of NH 3 was shown to result from a delicate balance between chain branching and terminating steps involving NH 2 , H 2 NO, and HNO. Recent theoretical work on reactions of these species by Klippenstein and coworkers and Stagni et al. was instrumental in improving modeling predictions. After initiation, NO reached a pseudo -steady-state level, where the pathways to NO were largely balanced by the NH 2 + NO reaction. Nitric oxide was partly oxidized to NO 2 , with the NH 2 + NO 2 reaction responsible for most of the N 2 O formation. Novelty and significance statement: This study provides the first detailed kinetic analysis of the lean postflame oxidation of ammonia, based on time -resolved flow reactor data in a novel reactor. In addition to the post -flame oxidation rate of ammonia, data for formation of NO and N 2 O were compared with modeling predictions. The medium temperature, very lean conditions enhance the importance of reactions of the HNO and H 2 NO intermediates. Inclusion in the model of results from recent high-level theoretical work, including present calculations for HNO + NH 2 and HNO + M, was crucial for capturing the observed behavior. It is argued that the post -initiation steady-state NH 3 oxidation rates constitute important data for model validation, along with ignition delays and laminar flame speeds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deposition pressure dependent structural and optoelectronic properties of ex-situ boron-doped poly-Si/SiO x passivating contacts based on sputtered silicon

Among common methods to form polycrystalline silicon (poly-Si) films for passivating-contact solar cells, physical vapor deposition, in particular sputtering, is the safest one as it does not require any toxic gaseous precursors. One of the critical parameters to control the properties of sputtered silicon films is their deposition pressure. In this work, structural and optoelectronic characteristics of ex-situ boron-doped poly-Si/SiO x passivating contacts, formed from sputtered intrinsic amorphous silicon (a-Si) deposited at different pressures on top of SiO x /c-Si substrates and subjected to a high-temperature boron diffusion step, are investigated. The deposition rate and density of the as-deposited a-Si films increase with reducing pressure. Low-temperature photoluminescence spectra captured from the as-deposited samples at different pressures do not show typical emissions from hydrogenated a-Si. Meanwhile, their Fourier-transform infrared absorption spectra all show Si–H stretching modes, indicating that hydrogen had been initially incorporated into the chemical SiO x layers and eventually hydrogenated the a-Si/SiO x interfaces during the sputtering process. After the high-temperature boron-diffusion step, all hydrogen-related peaks disappear. Lower pressure films (1.5 and 2.5 mTorr) show more consistent improved performance after hydrogen treatments, compared to higher pressure films (4 and 5 mTorr). Overall, the resultant passivating contacts at 2.5 mTorr achieve a low single-side recombination current density Jo of ~9 fA/cm 2 , whereas their contact resistivity is still low at 15 mO cm 2 .

14 SOLAR ENERGY↗

Cautionary Notes on Cosmogenic W-182 and Other Nuclei in Lunar Samples

Leya et al. (2000) showed that neutron capture on Ta-181 results in a production rate of Ta-182 (decays with a half-life of 114 days to W-182) sufficiently high to cause significant shifts in W-182 abundances considering the neutron fluences due to the cosmic ray cascade that were known to occur near the lunar surface. Leya et al. concluded that this cosmogenic production of W-182 may explain the large positive epsilon(sub W-182) values that Lee et al. (1997) had reported in some lunar samples rather than being produced from decay of now extinct Hf-182 (bar tau = 13 x 10(exp 6) yr). If the large range in epsilon(sub W-182) of lunar samples (0 to +11 in whole rock samples) was due to decay of now extinct Hf-182, it would require a very early time of formation and differentiation of the lunar crust-mantle system (with high Hf/W ratios) during the earliest stages of Earth s accretion. This result was both surprising and difficult to understand. The ability to explain these results by a more plausible mechanism is therefore very attractive. In a recent report Lee et al. (2002) showed that there were excesses of W-182 and that epsilon(sub W-182) was correlated with the Ta/W ratios in the mineral phases of individual lunar rock samples. This is in accord with W-182 variations in lunar samples being produced by cosmic-ray induced neutron capture on Ta-182.

Yin, Qingzhu↗

Modeling Advanced Strippers for CO2 Capture from Gas-Fired Power Plants using Aqueous Piperazine

Energy performance of 5 m piperazine was evaluated with an advanced stripper at the pilot scale, accounting for heat loss. Modeling studies indicated that heat loss at locations other than the heat source impacted the heat duty. For strippers with excess packing, the column was the most important source of heat loss, and values as low as 0.03 GJ/hr can cause pinch and reabsorption of CO2. Solvents like 5 m PZ are more affected by heat loss in the column due to a top-side temperature pinch at high lean loading. Heat loss impacts NGCC CO2 capture more than coal-based CO2 capture. Surface temperature measurements pilot plants showed that heat loss was 50-75% controlled by natural convection. Measured heat loss was correlated with steam flowrate and wind speed and ranged from 8126 to 219668 Btu/hr, representing 35% of the measured heat rate on average. Net heat duty linearly varied with CO2 removal at low lean loading and was similar for coal and NGCC conditions at fixed removal. At 90% removal, net heat duty was about 2.5 GJ/t with 4 and 12% CO2 in the flue gas. 7 At NGCC conditions, strippers with finite packing can benefit from a flashing feed to the top of the column by using a hot bypass. A flashing feed was linked to a reduction in irreversibility of the stripper from temperature driving forces. It also reduces heat duty by up to 6% at fixed packing height and reduces packing requirement for a fixed steam heater size compared to a warm bypass. Lean loading and lean solvent rate were effective handles to maximize profitability of a fixed stripper design at low gas price. High ambient temperature operation can benefit from low pressure stripping to about 0.18 lean loading at 150 ℃ to maintain the cyclic capacity at reduced rich loading. At low gas price, the capture plant was able to maximize profitability even with a high heat duty of 2.7-3.1 GJ/t at a lean loading of 0.2-0.22 mol/mol. Heat recovery by partial water vapor condensation in a gas-liquid exchanger can be replaced by a direct contact condenser (DCC). The DCC improved gas cooling and reduced heat duty compared to the CO2 exchanger at 0.2 lean loading. The DCC when used with a 150 ℃/5.5 bar stripper can reduce the cost of capture compared to the base case by $3- 4/tonne at 15 ft of packing (optimum) but increases cost of capture by $6/tonne with a 120 ℃/2 bar stripper and 10 ft of packing (optimum). The DCC can work effectively with a solvent with a high heat of absorption and thermal stability.

Suresh Babu, Athreya↗

Theoretical and kinetic modeling study of hydrazine oxidation

The present work constitutes the first theoretical and kinetic modeling study of hydrazine oxidation, which may be important for burnout in ammonia-fueled combustion. The kinetics of the oxidation of N 2 H 4 , N 2 H 3 and tHNNH by molecular oxygen were investigated via a quantum chemistry/canonical transition state theory approach. Geometries and anharmonic frequencies were obtained with density functional theory, and energies from coupled cluster calculations (CCSD(T)) extrapolated to the infinite basis set limit, with corrections for core-valence electron correlation, scalar relativistic effects, and higher level correlation up to lambda coupled cluster, CCSDT(Q) Λ . The key reactions occurred on the N 2 H 4 O 2 potential energy surface, where the results indicated a fast reaction of N 2 H 3 with HO 2 via singlet adducts to yield tHNNH + H 2 O 2 and HNN(H)O + H 2 O, while reaction on the triplet surface proceeds via a bound complex followed by a tight, submerged barrier to yield N 2 H 4 + O 2 . The results were incorporated in a detailed reaction mechanism, which was used to interpret the shock tube results from Michel and Wagner (1965) on the effect of O 2 on hydrazine conversion at 1100–1400 K. The kinetic model captured qualitatively the observed behavior, but underestimated the reaction rate under oxidizing conditions. The hydrazine pyrolysis chemistry dominated conversion at reducing conditions and/or high temperature. At oxidizing conditions and intermediate temperatures (≲ 1400 K), reactions of N 2 -amines with HO 2 and O 2 were important for the oxidation rate.

Ab initio calculations↗