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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Calibration-Free Quantitative Analysis of Lithium-Ion Battery (LiB) Electrode Materials Using Laser-Induced Breakdown Spectroscopy (LIBS)

Recent years have seen a surge in the demand for high-performance battery electrode materials for automotive and various electronic device applications. Improving battery performance requires precise knowledge of the structure–composition properties of active electrode materials. To this effect, quantitative and precise estimation of the composition of advanced electrode materials, containing trace amounts of dopants, provide immense value toward developing next-generation high-capacity battery materials. Herein, we demonstrate the application of calibration-free laser-induced breakdown spectroscopy (LIBS) as a powerful analytical tool for rapid and reliable quantitative spectrochemical characterizations of layered Li metal oxide cathodes containing Mo and Cr dopants (<5 atom %). Specifically, we employ the LIBS using an internal calibration methodology to establish the quantitative elemental ratios of major (Ni, Mn, Co) and trace dopant (Cr, Mo) transition metals to bulk Li contents in diverse cathode material samples such as LiNi 0.5 Mn 0.5 O 2 (NM-50/50), LiNi 0.33 Mn 0.33 Co 0.33 O 2 (NMC), LiNi 0.317 Mn 0.317 Co 0.317 Cr 0.05 O 2 (Cr-doped NMC), and LiNi 0.5– x /2 Mn 0.5– x /2 Mo x O 2 ( x = 0.03, 0.04, 0.05) (Mo-doped NM-50/50) that were synthesized via sol–gel routes. The LIBS-estimated elemental compositions are in good agreement with the nominal stoichiometric values. Furthermore, ex situ LIBS characterizations presented here pave the path for future high-efficacy application of calibration-free quantitative LIBS for rapid in situ analyses of elemental composition changes in battery electrode materials under operation that need not resort to off-site analytical techniques requiring cumbersome sample preparations and/or external standards.

25 ENERGY STORAGE↗
DOE OSTI2026

Data driven investigation to understand the influence of total solids on biological biogas upgrading

In situ biogas upgrading achieves CO 2 conversion to CH 4 via hydrogenotrophic methanogenesis; however, gas-liquid mass transfer constraints limit the upgrading performance. Recognizing that optimization studies often underrepresent the effects of total solids (TS) and organic loading rate (OLR), this study undertook a holistic, statistics driven assessment of operating conditions for in situ H 2 assisted biogas upgrading, centering the analysis on TS and OLR. A dataset of 31 studies was compiled and comprised 99 observations. A rigorous analytical framework was employed, combining data standardization, fixed- and random-effects (REML) weighted regressions with cluster-robust errors, stratified analyses, and machine learning. Mixed-effects meta regression indicated that TS was the main factor explaining differences of methane fraction (CH 4 %) when considering the between studies heterogeneity. Focusing on a near-stoichiometric subset (H 2 /CO 2 ≈ 4:1), TS remained significant. Stratified results showed a stronger negative relationship between TS and CH 4 % in UASB reactors than in CSTRs, with a negative effect under mesophilic conditions and no significant effect under thermophilic conditions. A Random Forest model corroborated the statistical findings, consistently ranking H 2 /CO 2 ratio, OLR, TS, and hydrogen injection rate (HIR) as the most influential predictors. These findings delineate trends across increasing TS levels, particularly between 1% and 10%, and provide preliminary insights for TS above 15% in in situ biogas upgrading. They further provide insights for the influence of TS by reactor type and temperature, thereby advancing the evidence base for implementing biological CO 2 conversion to CH 4 in practice.

In situ biogas upgrading↗
DOE OSTI2020

Performance of a Printed Bimetallic (Stainless Steel and Bronze) Engine Head Operating under Stoichiometric and Lean Spark Ignited (SI) Combustion of Natural Gas

Additive manufacturing was used to fabricate a head for an automotive-scale single-cylinder engine operating on natural gas. The head was consisted of a bimetallic composition of stainless steel and bronze. The engine performance using the bimetallic head was compared against the stock cast iron head. The heads were tested at two speeds (1200 and 1800 rpm), two brake mean effective pressures (6 and 10 bar), and two equivalence ratios (0.7 and 1.0). The bimetallic head showed good durability over the test and produced equivalent efficiencies, exhaust temperatures, and heat rejection to the coolant to the stock head. Higher combustion temperatures and advanced combustion phasing resulted from use with the bimetallic head. The implication is that with optimization of the valve timing, an efficiency benefit may be realized with the bimetallic head.

42 ENGINEERING↗
NASA NTRS2014

High-Precision Measurement of Eu/Eu* in Geological Glasses via LA-ICP-MS Analysis

Elemental fractionation during laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis has been historically documented between refractory and volatile elements. In this work, however, we observed fractionation between light rare earth elements (LREEs) and heavy rare earth elements (HREEs) when using ablation strategies involving large spot sizes (greater than 100 millimeters) and line scanning mode. In addition: (1) ion yields decrease when using spot sizes above 100 millimeters; (2) (Eu/Eu*)(sub raw) (i.e. Europium anomaly) positively correlates with carrier gas (He) flow rate, which provides control over the particle size distribution of the aerosol reaching the ICP; (3) (Eu/Eu*)(sub raw) shows a positive correlation with spot size, and (4) the changes in REE signal intensity, induced by the He flow rate change, roughly correlate with REE condensation temperatures. The REE fractionation is likely driven by the slight but significant difference in their condensation temperatures. Large particles may not be completely dissociated in the ICP and result in preferential evaporation of the less refractory LREEs and thus non-stoichiometric particle-ion conversion. This mechanism may also be responsible for Sm-Eu-Gd fractionation as Eu is less refractory than Sm and Gd. The extent of fractionation depends upon the particle size distribution of the aerosol, which in turn is influenced by the laser parameters and matrix. Ablation pits and lines defined by low aspect ratios produce a higher proportion of large particles than high aspect ratio ablation, as confirmed by measurements of particle size distribution in the laser induced aerosol. Therefore, low aspect ratio ablation introduces particles that cannot be decomposed and/or atomized by the ICP and thus results in exacerbated elemental fractionation. Accurate quantification of REE concentrations and Eu/Eu* requires reduction of large particle production during laser ablation. For the reference materials analyzed in this work, the 100 millimeters spot measurements of Eu/Eu* agreed with GeoRem preferred values within 3 percent. Our long-term analyses of Eu/Eu* in MPI-DING glass KL-2G and USGS glass BIR-1G were reproducible at 3 percent (2 RSD).

geological glasses↗
NASA NTRS1983

Temperature-dependent ion mixing and diffusion during sputtering of thin films of CrSi2 on silicon

Measurements of sputtering yields and composition profiles have been carried out using backscattering spectrometry for samples of CrSi2 on Si irradiated wth 200-keV Xe ions. When the CrSi2 layer is thinner than the ion range, the sputtering yield ratio of Si to Cr increases from 3.5 for room-temperature irradiation to 65 at 290 C. For a thick sample, the corresponding increase is from 2.4 to 4.0 only. These changes are explained in terms of a rise in the Si surface concentration ot 290 C. The driving force for this process seems to be the establishment of stoichiometric CrSi2 compound. Transport of Si to the surface is by ion mixing in the thin sample and thermal diffusion through the thick layer.

Shreter, U.↗
DOE OSTI2021

Intermediate Sr 2 Co 1.5 Fe 0.5 O 6-δ Tetragonal Structure between Perovskite and Brownmillerite as a Model Catalyst with Layered Oxygen Deficiency for Enhanced Electrochemical Water Oxidation

The generation of hydrogen in an environmentally benign way is highly essential to meet future energy demands. However, in the process of splitting water electrochemically, sluggish kinetics of the oxygen evolution reaction (OER) curtails its applicability, as it drags energy input. Herein, we synthesized SrCo-Fe-O oxides to optimize their OER activity by varying the Co/Fe ratio. Among them, Sr 2 Co 1.5 Fe 0.5 O 6-δ exhibited the best OER catalytic activity in the series, with an overpotential of 318 mV at 10 mA cm -2 and Tafel slope of 44.8 mV dec -1 . High-resolution neutron powder diffraction analysis identified an intermediate structure between the perovskite and brownmillerite, with alternating layers of disorderly orientated oxygen-deficient tetrahedra and fully stoichiometric octahedra. The unique stacking of tetrahedral and octahedral units facilitates desired interactions between the electrode surface and electrolyte. Theoretical calculations revealed that increased covalency of Co 3d and O 2p in Sr 2 Co 1.5 Fe 0.5 O 6-δ oxide is another primary contributor to its augmented water oxidation ability. As a model for developing catalysts with such an intermediate structure, the synergetic effect of oxygen vacancy and hybridization between Co 3d and O 2p assured the Sr 2 Co 1.5 Fe 0.5 O 6-δ oxide as a better catalyst for its enhanced OER activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2001

Outwardly Propagating Flames at Elevated Pressures

Spherical, outwardly-propagating flames of CH4-O2-inert and H2-O2-inert mixtures were experimentally studied in a high pressure apparatus. Stretch-free flame speeds and Markstein lengths were extracted for a wide range of pressures and equivalence ratios for spherically-symmetric, smooth flamefronts and compared to numerical computations with detailed chemistry and transport, as well as existing data in the literature. Wrinkle development was examined for propagating flames that were unstable under our experimental conditions. Hydrodynamic cells developed for most H2-air and CH4-air flames at elevated pressures, while thermal-diffusive instabilities were also observed for lean and near-stoichiometric hydrogen flames at pressures above atmospheric. Strategies in suppressing or delaying the onset of cell formation have been assessed. Buoyancy effects affected sufficiently off-stoichiometric CH4 mixtures at high pressures.

Law, C. K.↗
DOE OSTI2025

Alternate InP synthesis with aminophosphines: solution–liquid–solid nanowire growth

Indium phosphide nanowires are important components in high-speed electronics and optoelectronics, including photodetectors and photovoltaics. However, most syntheses either use high-temperature and costly vapor-phase methodology or highly toxic and pyrophoric tris(trimethylsilyl)phosphine. To expand on the success of the aminophosphine-based InP colloidal quantum dot synthesis, we developed a synthesis for thin (~11 nm) zinc blende InP nanowires at 180 °C using indium tris(trifluoroacetate) and tris(diethylamino)phosphine. A flat nanoribbon morphology was identified by transmission electron and atomic force microscopy analysis, with the stoichiometric (110) lattice plane exposed. Nanowire growth proceeded through a solution–liquid–solid mechanism from in situ-formed indium metal nanoparticles. Molecular byproducts of tris(oleylamino)phosphine oxide and N-oleyltrifluoroacetamide observed by 31 P and 19 F NMR spectroscopy inform a proposed mechanism of indium reduction by the aminophosphine. Morphological control over the nanowire product was achieved by varying the phosphorus injection to control the aspect ratio, the In : P ratio to toggle between nanowires and multipods, and the pre-hot injection evacuation step to favor a quantum dot product. Furthermore, replacing the indium precursor with indium tris(trifluoromethanesulfonate) was found to make bulk zinc blende InP nanowires with an average diameter of >250 nm and tens of microns in length.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Structural stability, elemental ordering, and transport properties of layered ScTaN 2

Ternary transition metal (TM) nitrides have gained significant attention in thin film research due to their promising properties for a broad range of applications. Particularly, some of the ternary TM nitrides have been predicted to adopt layered structures that make them interesting for thermoelectric conversion and quantum materials applications. Unfortunately, synthesis of TM ternary nitride films by physical vapor deposition often favors disordered 3D structures rather than the predicted 2D-like layered structure. In this study, we investigate the structural interplay in the Sc-Ta-N ternary system using a combinatorial approach. Combinatorial libraries S⁢c 𝑥 ⁢T⁢a 1−𝑥 ⁢N are synthesized following a two-step method: First, deposit film precursors by cosputtering and then process the resulting 3D-structured samples with rapid thermal annealing. Synchrotron grazing-incidence wide-angle x-ray scattering on films annealed at 1200 ⁢°⁢C for 20 min leads to the nucleation of ScTaN 2 layered structure (𝑃⁢6 3 /𝑚⁢𝑚⁢𝑐) near stoichiometry. We find that the layered structure can accommodate large off-stoichiometry in the Ta-rich region (𝑥 < 0.5), facilitated by the alloying with quasi-isostructural Ta 5 ⁢N 6 compound that exists on a composition tie line at 𝑥 = 0. While focusing on ScTaN 2 , we estimate the long-range order parameter in near-stoichiometric films to be 0.86, corresponding to a fraction of Sc/Ta antisites of 7%. Transport measurements on ScTaN 2 reveal a nearly temperature-independent high carrier density (10 21 c⁢m −3 ), suggesting a heavily doped semiconductor or semimetallic character, consistent with a small positive Seebeck coefficient of +19 µV/K. The carrier mobility at 2 K is relatively small (9.5c⁢m 2 V −1 s −1 ) and the residual-resistivity ratio is minor, suggesting that electrical conduction is dominated by defects or disorder. Measured magnetoresistance suggests possible weak antilocalization at 2 K. This paper highlights the interplay between ScTaN 2 and Ta 5 ⁢N 6 crystal structures in stabilizing layered materials, emphasizes the importance of cation order/disorder for potential tunable alloys, and suggests that ScTaN 2 is a promising platform for exploring electronic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2024

DNS of Flame Stabilization Dynamics of a Swirl-Stabilized Spray Burner Using Sustainable Aviation Fuels

Concern for emission reduction has motivated the development of new cost-effective alternative sustainable aviation fuels (SAFs). Drop-in SAFs with blends of the certified and the alternative fuels are beneficial because they do not require engine modifications for use in current aviation engines. Combustion characteristics are of particular concern when comparing a new fuel with Jet-A. Lean blow-off and flame stabilization have been identified to be governed by the fuel propensity to autoignition, i.e. derived cetane number. However, fundamental investigation is required to identify the impact of derived cetane number on the combustion mode of flame stabilization in a realistic combustor. The combustion mode has also a direct impact on turbulent combustion modeling closures. DNS simulations are performed in the low-Mach solver of the Pele Suite called PeleLMeX. Lagrangian multi-phase modeling is used to capture the liquid spray injection of Jet-A (reference fuel) and C1 as a representative of a low cetane number SAF. Adaptive Mesh Refinement (AMR) is used to enable a more efficient simulation of a more realistic domain size and embedded boundary treatment is used to model a bluff-body geometry. Local extinction and edge flame propagation were observed for both fuels. The edge flame propagation mode was quantified in terms of a Damkohler number defined as the ratio between progress variable reaction rate and its diffusive flux. Initial analysis suggests that a mixed mode combustion occurs for the edge flame propagation, with flame propagation assisted by ignition and autoignition co-existing for both Jet-A and C1 flames. The analysis of the extinction region shows a larger progress variable for Jet-A which can further increase the local displacement speed and present a faster reignition of the stoichiometric mixture fraction.

adaptive mesh refinement↗
NASA NTRS1960

Kinetic Parameters for the Hydrogen and Ethylene Flames from Flashback Measurements

Values for the flame activation energy and an overall reaction order have been obtained for premixed hydrogen-oxygen and ethylene-oxygen flames with nitrogen and with argon as diluents; the values come from measurements of the change with pressure and flame temperature of the critical boundary velocity gradient for flashback. Measurements have been made for rich and stoichiometric hydrogen flames and for lean and stoichiometric ethylene flames. For hydrogen flames with nitrogen diluent an overall order of 2*3 is found; for ethylene flames with nitrogen diluent, the order obtained is 1*8. With argon diluent, values for the order are about 10 per cent lower for each flame. With nitrogen diluent the flame activation energy apparently increases with flame temperature; this increase is not found with argon diluent. For hydrocarbon flames the assumption that the initial equivalence ratio equals the effective equivalence ratio in the flame leads to an order of reaction with respect to oxygen that is considerably larger than unity. For hydrogen flames, that assumption is consistent with an oxygen order of unity.

Fine, B.↗
DOE OSTI2024

A chemical kinetic analysis of knock propensity of methanol-to-gasoline fuel

Production of low carbon gasoline-like fuels such as methanol-to-gasoline (MTG) is a promising approach to achieve rapid greenhouse gas emission reduction of the transportation sector. Despite the fact that gasoline that meets the ASTM D4814 standard for automotive spark-ignition engine fuel can be readily produced from these processes, it is unclear how the composition of MTG may affect engine performance and emissions. Here, in this paper, a surrogate for an MTG is used to numerically study the effects of gasoline composition on knock propensity and on the sensitivity of knock to thermal and fuel stratification, to oxygen dilution and to nitric oxide from exhaust gas recirculation of residual gases. Simulations were performed in ANSYS CHEMKIN-PRO using a comprehensive chemical kinetic mechanism for gasoline surrogates, and results of the MTG surrogate were compared against those of a petroleum-based regular E10 gasoline, termed PACE-20. A premium-grade MTG fuel was also formulated by adding ethanol to the MTG surrogate, and results were compared against those of four premium-grade, gasoline-like fuels representative of future alternative gasoline formulations. Surrogates and mechanism were evaluated by comparison against experimental engine data, and the model showed high accuracy at stoichiometric conditions (mean absolute error of ignition timing equal to 1.46 crank angle degrees) but larger deviations at lean conditions (mean absolute error of ignition timing equal to 5.52 crank angle degrees). Despite the fact that the MTG surrogate has a RON 1.1 units higher than that of PACE-20, it may show higher knock propensity at medium temperature conditions due to a less intense NTC behavior. MTG autoignition was more temperature- and equivalence ratio-sensitive than that of PACE20, suggesting that MTG can benefit more from naturally-occurring thermal stratification or from induced fuel stratification of the end gas to mitigate knock intensity. The sensitivity of autoignition reactivity to oxygen dilution and to NO concentration was higher for MTG than for regular gasoline at medium loads, but the opposite trend was observed at high loads due to the effect of pressure on the low-temperature chemistry of regular gasoline. Approximately 14 % vol ethanol content was required to upgrade the octane rating of MTG from regular grade to premium grade. Adding 13.6 % vol ethanol made the fuel autoignition less sensitive to both oxygen dilution and NO content (ignition time varies approx. 17 % and 50 % less with oxygen dilution and NO addition, respectively, when adding ethanol at high engine loads).

02 PETROLEUM↗
DOE OSTI2020

Ni Nanoparticles on CeO 2 (111): Energetics, Electron Transfer, and Structure by Ni Adsorption Calorimetry, Spectroscopies, and Density Functional Theory

The morphology, interfacial bonding energetics and charge transfer of Ni clusters and nanoparticles on slightly-reduced CeO 2-x (111) surfaces at 100 to 300 K have been studied using single crystal adsorption calorimetry (SCAC), low-energy ion scattering spectroscopy (LEIS), Xray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and density functional theory (DFT). The initial heat of adsorption of Ni vapor decreased with the extent of pre-reduction (x) of the CeO 2-x (111), showing that stoichiometric ceria adsorbs Ni more strongly than oxygen vacancies. On CeO 1.95 (111) at 300 K, the heat dropped quickly with coverage in the first 0.1 ML, attributed to nucleation of Ni clusters on stoichiometric steps, followed by the Ni particles spreading onto less favorable terrace sites. At 100 K, the clusters nucleate on terraces due to slower diffusion. Adsorbed Ni monomers are in the +2 oxidation state, and they bind by ~45 kJ/mol more strongly to step sites than terraces. The measured heat of adsorption versus average particle size on terraces is favorably compared to DFT calculations. The Ce 3d XPS lineshape showed an increase in Ce 3+ /Ce 4+ ratio with Ni coverage, providing the number of electrons donated to the ceria per Ni atom. The charge transferred per Ni is initially large but strongly decreases with increasing cluster size for both experiments and DFT, and shows large differences between clusters at steps versus terraces. This charge is localized on the interfacial Ni and Ce atoms in their atomic layers closest to the interface. This knowledge is crucial to understanding the nature of the active sites on the surface of Ni-CeO 2 catalysts for which metal-oxide interactions play a very important role in the activation of O-H and C-H bonds. In conclusion, the changes in these interactions with Ni particle size (metal loading) and the extent of reduction of the ceria help to explain how previously reported catalytic activity and selectivity change with these same structural details.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Performance Comparison of LPG and Gasoline in an Engine Configured for EGR-Loop Catalytic Reforming

In prior work, the EGR loop catalytic reforming strategy developed by ORNL has been shown to provide a relative brake engine efficiency increase of more than 6% by minimizing the thermodynamic expense of the reforming processes, and in some cases achieving thermochemical recuperation (TCR), a form of waste heat recovery where waste heat is converted to usable chemical energy. In doing so, the EGR dilution limit was extended beyond 35% under stoichiometric conditions. In this investigation, a Microlith®-based metal-supported reforming catalyst (developed by Precision Combustion, Inc. (PCI)) was used to reform the parent fuel in a thermodynamically efficient manner into products rich in H2 and CO. We were able to expand the speed and load ranges relative to previous investigations: from 1,500 to 2,500 rpm, and from 2 to 14 bar break mean effective pressure (BMEP). Experiments were conducted to determine the effects of the H/C ratio of the fuel on H2 production and on the engine efficiency in order to compare E10 gasoline (H/C = 1.95) and liquified petroleum gas (LPG), comprised primarily of propane (H/C = 2.67). Additionally, the compression ratio of the engine was increased to ascertain whether further efficiency improvements could be realized based on a reduced knock propensity of the dilute EGR mixture with the reformed fuel. Both the gasoline and propane reforming strategies provided efficiency gains up to 1.85 percentage points and further efficiency improvements with the increased compression ratio were realized. The fuel specific effects of gasoline vs. LPG, the effect of engine operating condition on reforming, and knock limits of the reformed mixture are discussed in detail.

33 ADVANCED PROPULSION SYSTEMS↗
NASA NTRS1996

Quick-Mixing Studies Under Reacting Conditions

The low-NO(x) emitting potential of rich-burn/quick-mix/lean-burn )RQL) combustion makes it an attractive option for engines of future stratospheric aircraft. Because NO(x) formation is exponentially dependent on temperature, the success of the RQL combustor depends on minimizing high temperature stoichiometric pocket formation in the quick-mixing section. An experiment was designed and built, and tests were performed to characterize reaction and mixing properties of jets issuing from round orifices into a hot, fuel-rich crossflow confined in a cylindrical duct. The reactor operates on propane and presents a uniform, non-swirling mixture to the mixing modules. Modules consisting of round orifice configurations of 8, 9, 10, 12, 14, and 18 holes were evaluated at a momentum-flux ratio of 57 and jet-to-mainstream mass-flaw ratio of 2.5. Temperatures and concentrations of O2, CO2, CO, HC, and NO(x) were obtained upstream, down-stream, and within the orifice plane to determine jet penetration as well as reaction processes. Jet penetration was a function of the number of orifices and affected the mixing in the reacting system. Of the six configurations tested, the 14-hole module produced jet penetration close to the module half-radius and yielded the best mixing and most complete combustion at a plane one duct diameter from the orifice leading edge. The results reveal that substantial reaction and heat release occur in the jet mixing zone when the entering effluent is hot and rich, and that the experiment as designed will serve to explore satisfactorily jet mixing behavior under realistic reacting conditions in future studies.

Leong, May Y.↗
DOE OSTI2020

Rapid and Simultaneous Characterization of Drug Conjugation in Heavy and Light Chains of a Monoclonal Antibody Revealed by High-Resolution Ion Mobility Separations in SLIM

Antibody-drug conjugates (ADCs) have recently gained traction in the biomedical community due to their promise for human therapeutics and an alternative to chemotherapy for cancer. Crucial metrics for ADC efficacy, safety, and selectivity are their drug-antibody ratios (DARs). However, DAR characterization (i.e., determining the average number of conjugated drugs on the antibody) through analytical methods remains challenging due to the heterogeneity of drug conjugation as well as the numerous post-translational modifications possible in the monoclonal antibody. In this work, we report on the use of high-resolution ion mobility spectrometry separations in our structures for lossless ion manipulations coupled to mass spectrometry (SLIM IMS-MS) platform for the rapid and simultaneous characterization of the drug load profile (i.e., stoichiometric distribution of the number of conjugated drugs present on the mAb), determination of the weighted average DAR in both the heavy and light chains of a model antibody-drug conjugate, and calculation of the overall DAR of the ADC. After chemical reduction of the ADC and a subsequent 31.5 meter SLIM IMS separation the various drug bound antibody species could be well resolved for both chains. Furthermore, we also show that higher resolution separations were possible with SLIM IMS as compared to ones performed on a commercially available (~1 meter) drift tube IMS-MS platform. Interestingly, additional gas-phase substructures become evident with longer path length SLIM IMS, potentially providing insight related to how drug conjugation may alter the structural properties of a monoclonal antibody and thus affect its overall potency and/or selectivity for a given antigen. We expect high-resolution SLIM IMS separations will augment the existing toolbox for ADC characterization, particularly for structural confirmation to enable the rapid optimization of DAR for a given ADC and thus better understand its potential toxicity and potency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

Methane Pyrolysis and Disposing Off Resulting Carbon

Sabatier/Electrolysis (S/E) is a leading process for producing methane and oxygen for application to Mars ISPP. One significant problem with this process is that it produces an excess of methane for combustion with the amount of oxygen that is produced. Therefore, one must discard roughly half of the methane to obtain the proper stoichiometric methane/oxygen mixture for ascent from Mars. This is wasteful of hydrogen, which must be brought from Earth and is difficult to transport to Mars and store on Mars. To reduced the problem of transporting hydrogen to Mars, the S/E process can be augmented by another process which reduces overall hydrogen requirement. Three conceptual approaches for doing this are (1) recover hydrogen from the excess methane produced by the S/E process, (2) convert the methane to a higher hydrocarbon or other organic with a lower H/C ratio than methane, and (3) use a separate process (such as zirconia or reverse water gas shift reaction) to produce additional oxygen, thus utilizing all the methane produced by the Sabatier process. We report our results here on recovering hydrogen from the excess methane using pyrolysis of methane. Pyrolysis has the advantage that it produces almost pure hydrogen, and any unreacted methane can pass through the S/E process reactor. It has the disadvantage that disposing of the carbon produced by pyrolysis presents difficulties. Hydrogen may be obtained from methane by pyrolysis in the temperature range 10000-12000C. The main reaction products are hydrogen and carbon, though very small amounts of higher hydrocarbons, including aromatic hydrocarbons are formed. The conversion efficiency is about 95% at 12000C. One needs to distinguish between thermodynamic equilibrium conversion and conversion limited by kinetics in a finite reactor.

Sharma, P. K.↗
NASA NTRS1999

Methane Pyrolysis and Disposing Off Resulting Carbon

Sabatier/Electrolysis (S/E) is a leading process for producing methane and oxygen for application to Mars ISPP. One significant problem with this process is that it produces an excess of methane for combustion with the amount of oxygen that is produced. Therefore, one must discard roughly half of the methane to obtain the proper stoichiometric methane/oxygen mixture for ascent from Mars. This is a waste of hydrogen, which must be brought from Earth and is difficult to transport to Mars and store on Mars. To reduce the problem of transporting hydrogen to Mars, the S/E process can be augmented by another process which reduces overall hydrogen requirement. Three conceptual approaches for doing this are (i) recover hydrogen from the excess methane produced by the S/E process, (ii) convert the methane to a higher hydrocarbon or other organic with a lower H/C ratio than methane, and (iii) use a separate process (such as zirconia or reverse water gas shift reaction) to produce additional oxygen, thus utilizing all the methane produced by the Sabatier process. We report our results here on recovering hydrogen from the excess methane using pyrolysis of methane. Pyrolysis has the advantage that it produces almost pure hydrogen, and any unreacted methane can pass through the S/E process reactor. It has the disadvantage that disposing of the carbon produced by pyrolysis presents difficulties. The goals of a research program on recovery of hydrogen from methane are (in descending priority order): 1) Study the kinetics of pyrolysis to arrive at a pyrolysis reactor design that produces high yields in a confined volume at the lowest possible operating temperature; 2) Study the kinetics of carbon burnoff to determine whether high yields can be obtained in a confined volume at acceptable operating temperatures; and 3) Investigate catalytic techniques for depositing carbon as a fine soot which can be physically separated from the reactor. In the JPL program, we have made significant measurements in regard to goal 1, cursory measurements in regard to goal 2, and would plan to pursue goal 3 if additional resources are secured.

Sharma, P. K.↗