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At least 73 records · Page 4

Solid Fuel Burning in Steady, Strained, Premixed Flow Fields: The Graphite/Air/Methane System

A detailed numerical investigation was conducted on the simultaneous burning of laminar premixed CH4/air flames and solid graphite in a stagnation flow configuration. The graphite and methane were chosen for this model, given that they are practical fuels and their chemical kinetics are considered as the most reliable ones among solid and hydrocarbon fuels, respectively. The simulation was performed by solving the quasi-one-dimensional equations of mass, momentum, energy, and species. The GRI 2.1 scheme was used for the gas-phase kinetics, while the heterogeneous kinetics were described by a six-step mechanism including stable and radical species. The effects of the graphite surface temperature, the gas-phase equivalence ratio, and the aerodynamic strain rate on the graphite burning rate and NO, production and destruction mechanisms were assessed. Results indicate that as the graphite temperature increases, its burning rate as well as the NO, concentration increase. Furthermore, it was found that by increasing the strain rate, the graphite burning rate increases as a result of the augmented supply of the gas-phase reactants towards the surface, while the NO, concentration decreases as a result of the reduced residence time. The effect of the equivalence ratio on both the graphite burning rate and NO, concentration was found to be non-monotonic and strongly dependent on the graphite temperature. Comparisons between results obtained for a graphite and a chemically inert surface revealed that the chemical activity of the graphite surface can result to the reduction of NO through reactions of the CH3, CH2, CH, and N radicals with NO.

Egolfopoulos, Fokion N.↗

Fast Oxygen Redox Kinetics Induced by CoO 6 Octahedron With π –Interaction in P2–Type Sodium Oxides

Enhancing the kinetics of lattice oxygen redox (LOR) in P2-type layered sodium oxide cathodes is crucial for the advancement of sodium-ion batteries (SIBs) with superior energy and power densities. Electronic structure regulation stands out as a highly effective approach to address the inherent limitations of P2-type layered oxides with LOR, including sluggish kinetics, phase transitions, voltage hysteresis, and local structural distortion. In this work, a strategy involving the introduction of CoO 6 octahedra with π-interaction into Na 0.6 Li 0.1 Fe 0.3–x Co x Mn 0.6 O 2 (x = 0, 0.15, 0.3) cathodes to facilitate Na-ion transport is proposed. Furthermore, the impact of FeO 6 octahedra with σ-interaction in P2-type cathodes on electrochemical performance is comprehensively investigated. Through multimodal in-situ and ex-situ characterization techniques, it is revealed that Co–O with π-interaction effectively mitigates P2-OP4 phase transitions by strengthening Na–O, reduces voltage hysteresis, and stabilizes the local structure. Consequently, Na 0.6 Li 0.1 Co 0.3 Mn 0.6 O 2 demonstrates enhanced Na-ion diffusion kinetics, leading to improved rate performance and a reversible capacity of 55 mAh g –1 at 10 C, significantly outperforming cathodes with Fe–O σ-interaction. Moreover, when coupled with hard carbon, the full cell achieves a remarkable energy density of 395 Wh kg –1 (on cathode) at 0.1 C, with a capacity retention of 75% over 100 cycles at 1 C.

25 ENERGY STORAGE↗

Investigating the kinetic effect of prenol on iso -octane auto-ignition by means of an experimental and modeling study

A detailed experimental and kinetic modeling study was dedicated to understand the reported octane hyperboosting effect of prenol, by means of the measurement of the ignition delay times of its blends with iso -octane, and measurement of the mole fraction profiles of the fuels and intermediates inside the ULille rapid compression machine. Here, these results show that prenol addition leads to a reduction of the first-stage ignition phenomena and negative temperature coefficient behavior, which is only qualitatively captured by the model and is consistent with knock resistance improvement. It is suggested that this behavior is caused by two different factors. The first originates from gas-phase reactivity of prenol, and spans from the formation of unreactive unsaturated species through resonance-stabilized radicals, thereby constituting a competitive pathway for the radical pool generated by iso -octane. The second is of catalytic nature and cannot be captured by means of gas-phase kinetic modeling, but could also play an important role in the behavior of prenol in internal combustion engines.

42 ENGINEERING↗

Laboratory studies of chemical and photochemical processes relevant to stratospheric ozone

The purpose of this project is to reduce the uncertainty in several key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring rate coefficients and product channels for reactions of HO(sub x) and NO(sub x) species in the temperature range 200 K to 240 K relevant to the lower stratosphere. Other areas of study have included infrared spectroscopic studies of the HO2 radical, measurements of OH radical reactions with alternative fluorocarbons, and determination of the vapor pressures of nitric acid hydrates under stratospheric conditions. The results of these studies will improve models of stratospheric ozone chemistry and predictions of perturbations due to human influences. In this annual report, we focus on our recent accomplishments in the quantitative spectroscopy of the HO2 radical. This report details the measurements of the broadening coefficients for the v(sub 2) vibrational band. Further measurements of the vapor pressures of nitric acid hydrates relevant to the polar stratospheric cloud formation indicate the importance of metastable crystalline phases of H2SO4, HNO3, and H2O. Large particles produced from these metastable phases may provide a removal mechanism for HNO3 in the polar stratosphere.

Zahniser, Mark S.↗

Kinetic analyses for solid-state phase transition of metastable amorphous-AlO x (2.5 < x ≤ 3.0) nanostructures into crystalline alumina polymorphs

Solid-solid phase change materials (SS-PCMs) hold promise for energy storage/dissipation in batteries and energetic materials. Yet, phase change kinetics for SS-PCMs undergoing metastable to semi-stable/stable phase transformations remain relatively ill-studied because trapping metastable phases remain challenging. Recently, we demonstrated the kinetic entrapment and stabilization of a highly disordered and amorphous Al-oxide phase m-AlO x @C (x~2.5-3.0) via laser ablation synthesis in solution (LASiS). We report here, to our knowledge, the first chemical kinetics analysis for S-S phase transition of the m-AlO 3 @C nanocomposites (< 5–8 nm sizes) into semi-stable equilibrium alumina phases (θ/γ-Al 2 O 3 ) via disproportionation reaction, while releasing excess trapped gases. Our results indicate the atomic density of the AlO 3 structures to be ~5–10 times less than that of the final Al 2 O 3 phases, which led to the hypothesis of a volume shrinkage process during their phase transition. Temperature-dependent X-ray diffraction studies reveal the high-temperature phase transition for m-AlO 3 → θ/γ-Al 2 O 3 to follow contracting volume kinetics model, thereby validating our earlier hypothesis. Using the geometric volume contraction model, reaction kinetics analyses from Arrhenius plots reveal the activation energy barrier for the phase transition to be ~270±11 kJ/mol. This makes the activation energy barrier nearly identical to the oxidation of micron-sized Al particles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cement and concrete as carbon sinks: Transforming a climate challenge into a carbon storage opportunity

Cement and concrete, while traditionally recognized as the main contributors to anthropogenic CO 2 emissions, also have untapped capacity to serve as substantial and scalable carbon sinks. This perspective examines how engineered mineral carbonation can transform cement-based materials into functional carbon storage systems, generating both environmental and economic value. We review the fundamental mechanisms of CO 2 uptake in cementitious systems, highlighting current limitations in reaction kinetics, phase control, and durability under varying environmental conditions. Emphasis is placed on the utilization of alkaline industrial residues and emerging magnesium-based cements, which offer synergistic pathways for carbon sequestration and circular resource use. We further assess the performance trade-offs associated with CO 2 uptake and the feasibility of deploying these technologies on industrial scales. A strategic roadmap is proposed that integrates scientific innovation, regulatory alignment, and carbon accounting in the life cycle to accelerate the adoption of carbon-storing concrete. This perspective provides a comprehensive framework to advance cement and concrete as engineered carbon sinks and supports the transition to a climate-positive construction industry.

Carbon storage↗

Complexes of tubulin oligomers and tau form a viscoelastic intervening network cross-bridging microtubules into bundles

Abstract The axon-initial-segment (AIS) of mature neurons contains microtubule (MT) fascicles (linear bundles) implicated as retrograde diffusion barriers in the retention of MT-associated protein (MAP) tau inside axons. Tau dysfunction and leakage outside of the axon is associated with neurodegeneration. We report on the structure of steady-state MT bundles in varying concentrations of Mg 2+ or Ca 2+ divalent cations in mixtures containing αβ-tubulin, full-length tau, and GTP at 37 °C in a physiological buffer. A concentration-time kinetic phase diagram generated by synchrotron SAXS reveals a wide-spacing MT bundle phase (B ws ), a transient intermediate MT bundle phase (B int ), and a tubulin ring phase. SAXS with TEM of plastic-embedded samples provides evidence of a viscoelastic intervening network (IN) of complexes of tubulin oligomers and tau stabilizing MT bundles. In this model, αβ-tubulin oligomers in the IN are crosslinked by tau’s MT binding repeats, which also link αβ-tubulin oligomers to αβ-tubulin within the MT lattice. The model challenges whether the cross-bridging of MTs is attributed entirely to MAPs. Tubulin-tau complexes in the IN or bound to isolated MTs are potential sites for enzymatic modification of tau, promoting nucleation and growth of tau fibrils in tauopathies.

59 BASIC BIOLOGICAL SCIENCES↗

Molybdenite in calcium-aluminum-rich inclusions in the Allende meteorite

The first observations of molybdenite in a meteorite have been made in two Ca-Al-rich inclusions in the Allende chondrite. The mineral occurs as single individuals completely enclosed in high Ni metal (62-64.5 wt. % Ni). The association with refractories is consistent with thermodynamic calculations which predict that Mo is a high temperature condensate even when nucleation constraints are imposed on the formation of a metal phase. Kinetic factors (including nucleation constraints) appear to have played an important role in the formation of molybdenite and the associated sulfides, magnetite and high nickel metal.

Fuchs, L. H.↗

Precision of NO2 photolysis rate measurements

Gas-phase kinetic calculations indicate that actinometric measurements of the rate of solar photolysis of NO2 in nitrogen can be in error by +5 to -15% or more, unless odd oxygen N2O5 chemistry, and trace oxygen content are considered. A field experiment confirms that the effect of the quartz tube on the measured photolysis rate is less than 1.7%.

Dickerson, R. R.↗

Autoignition of Fuel-Oxidizer Mixtures in Microgravity

Microgravity autoignition phenomena that may be influenced by chemically significant walls as well as by photochemically significant radiative fields are examined. First, the limitations of quasi-steady autoignition theory in providing information needed for the characterization of autoignition temperature fields are discussed. Time-dependent autoignition theory is then used to analyze the autoignition behavior of a reactive system where both wall catalysis and gas phase kinetic rates are significant. Space-time trajectories of temperature and species concentrations for such cases are presented

Berlad, A. L.↗

Photo-sensitized ignition of hydrogen/oxygen mixtures for hypersonic flight vehicles

An approach toward improving supersonic ignition and combustion efficiency was investigated under a feasibility program with NASA-Ames. The idea is to selectively irradiate targetted species in the combustion zone. The ensuing photodissociation reactions produce highly reactive radicals which modify the gas phase kinetics. The overall objective of this research was to demonstrate photosensitized ignition of H2/O2 mixtures, and to gain a preliminary understanding of the ignition mechanism, especially as it pertains to the concept of supersonic combustion. To this end, a series of experiments were performed with a model sensitizer, NO2. At subatmospheric pressures and moderate temperatures (above 100 F), mixtures of H2/O2/NO2 are ignitable by a pulsed eximer laser at 308 nm, 115 to 200 mJ. Ignitability was found to be a function of NO2 pressure, temperature, laser energy per pulse, and laser lens focal length (fluence at focal volume). Mixtures could not be ignited in the absence of the sensitizer. While increasing temperature improved sensitized ignition in the lower temperature range, a retarding effect was observed at the highest temperatures. To more thoroughly understand these thermal effects, the UV-Vis and IR spectra of NO2 and H2/O2/NO2 mixtures were studied over the temperature range 70 to 900 F. Initially, increasing temperature shifts the N2O4 in a reversible reaction to 2 NO2 equilibrium toward NO2, favoring photochemical ignition. However, at still higher temperature, NO2 converts to non-absorbing NO + 1/2 O2, thus preventing photosensitized ignition.

Lavid, Moshe↗

Radiation-Controlled, Opposed-Flow Flame Spread in a Microgravity Environment

The effects of surface and gas-phase radiation on the rate and the structure of laminar flame spread over thin fuels are investigated using a flame-spread model which consists of the continuity, momentum, species, and energy equations in the gas and the continuity and energy equations in the solid. Numerical calculations, complemented by scaling arguments, show that, at high velocities of the oxidizer flow, radiation effects are unimportant; the spread rate decreases with increasing opposing velocity due to finite-rate gas-phase kinetics. However, radiation becomes progressively important when the opposing velocity is below a certain value: the flame cools, shrinks in size, and its spread rate falls sharply with decreasing opposing velocity.

Bhattacharjee, Subrata↗

Laboratory Studies of Chemical and Photochemical Processes Relevant to Stratospheric Ozone

The purpose of this project is to reduce the uncertainty in several key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring rate coefficients and product channels for reactions of HOx and NOx species in the temperature range 200 K to 240 K relevant to the lower stratosphere. Other areas of study have included infrared spectroscopic studies of the HO radical, measurements of OH radical reactions with alternative fluorocarbons, and determination of the vapor pressures of nitric acid hydrates under stratospheric conditions. The results of these studies will improve models of stratospheric ozone chemistry and predictions of perturbations due to human influences.

Zahniser, Mark S.↗

Laboratory Studies of Chemical and Photochemical Processes Relevant to Stratospheric Ozone

The purpose of this project is to reduce the uncertainty in several key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring rate coefficients and product channels for reactions of HO(x) and NO(x) species in the temperature range 200 K to 240 K relevant to the lower stratosphere. The results of these studies will improve models of stratospheric ozone chemistry and predictions of perturbations due to human influences. The second year's effort has focussed the design and construction of the proposed high pressure flow reactor on three separate areas: (1) the construction of the high pressure flow reactor; (2) characterization of the turbulent flow profile; and (3) demonstration of the instrument by measuring HO2 + NO2 and HO2 + NO reaction rate coefficients.

Villalta, Peter W.↗

34th JANNAF Combustion Subcommittee Meeting: MURI Technology - Volume 2

This volume is a compilation of 48 unclassified/unlimited distribution papers presented at the 1997 meeting of the JANNAF 34th Combustion Subcommittee (CS) held jointly with the Propulsion Systems Hazards Subcommittee (PSHS), and the Airbreathing Propulsion Subcommittee. Proceedings of the CS, PSHS and APS meetings are published separately by CPIA. The CS Meeting Proceedings are published in four volumes. The JANNAF papers contained in this volume contributed to the Second Year Progress Review of the Multidisciplinary University Research Initiative Program (MURI) on 'Novel New Ingredients to Stabilize Rocket Motors'. Technical progress made on this program was presented as JANNAF CS papers contained in Volumes 2 and 4. Papers contained in this volume review bi-plateau propellant combustion, AP and metal combustion, solid propellant combustion instability fundamentals and motor applications, gas-phase and condensed-phase kinetics, and measurement techniques.

Fry, Ronald S.↗

Laboratory Studies of Chemical and Photochemical Processes Relevant to Stratospheric Ozone

This is the final report for this project. Its purpose is to reduce the uncertainty in rate coefficients for key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring the rate coefficients for the reactions of HO2 + O3, and HO2 + NO2 in the temperature range (200-240 K) relevant to the lower stratosphere. In order to accomplish this, a high pressure turbulent flow tube reactor was built and its flow characteristics were quantified. The instrument was coupled with tunable diode laser spectroscopy for HO2 detection. Room temperature measurements of the HO2 + NO2 rate coefficients over the pressure range of 50-300 torr agree well with previous measurements. Preliminary measurements of the HO2 + O, rate coefficients at 50 - 300 Torr over the temperature range of 208-294 K agree with the NASA evaluation from 294-225 K but deviate significantly (50 % higher) at approximately 210 K.

Villalta, P. W.↗

Computational and Experimental Study of Energetic Materials in a Counterflow Microgravity Environment

Counterflow diffusion flames are studied for various fuels flowing against decomposition products from solid ammonium perchlorate (AP) pellets in order to obtain fundamental understanding of composite propellant flame structure and chemistry. We illustrate this approach through a combined experimental and numerical study of a fuel mixture consisting of C2H4 CO + H2, and C2H2 + C2H4 flowing against solid AP. For these particular AP-fuel systems, the resulting flame zone simulates the various flame structures that are ex+ to exist between reaction products from Ap crystals and a hydrocarbon binder. As in all our experimental studies, quantitative species and temperature profiles have been measured between the fuel exit and AP surface. Species measured included CN, NH, NO, OH, N2, CO2, CO, H2, CO, HCl, and H2O. Temperature was measured using a thermocouple at the exit, spontaneous Raman scattering measurements throughout the flame, OH rotational population distributions, and NO vibrational population distributions. The burning rate of AP was also measured as a function of strain rate, given by the separation distance between the AP surface and the gaseous hydrocarbon fuel tube exit plane. This distance was nominally set at 5 mm, although studies have been performed for variations in separation distance. The measured 12 scalars are compared with predictions from a detailed gas-phase kinetics model consisting of 86 species and 531 reactions. Model predictions are found to be in good agreement with experiment and illustrate the type of kinetic features that may be expected to occur in propellants when AP particle size distributions are varied. Furthermore, the results constitute the continued development of a necessary database and validation of a comprehensive model for studying more complex AP-solid fuel systems in microgravity. Exploratory studies have also been performed with liquid and solid fuels at normal gravity. Because of melting (and hence dripping) and deep thermal wave penetration into the liquid, these experiments were found feasible, but not used for obtaining quantitative data. Microgravity experiments are needed to eliminate the dripping and boiling phenomena of these systems at normal gravity. Microgravity tests in the NASA Glenn 2.2 second drop tower were performed (1) to demonstrate the feasibility of performing propellant experiments using the NASA Glenn microgravity facilities, (2) to develop the operational procedures for safe handing of the energetic materials and disposal of their toxic combustion by-products and (3) to obtain initial measurements of the AP burning rate and flame structure under microgravity conditions. Experiments were conducted on the CH4/AP system previously studied at normal gravity using a modified design of the counterflow burner and a NASA Glenn Pig Rig, i.e., one of the existing drop rigs for general-purpose usage. In these experiments, the AP burning rate was measured directly with a linear variable differential transducer (LVDT) and video imaging of the flame structure was recorded ignition was achieved by hot wires stretched across the AP surfaces. Initial drop tower combustion data show that with the same burner separation distance and flow conditions of the normal gravity experiments, the AP burning rate is approximately a factor of two lower. This difference is likely a result of radiation effects, but further tests with longer test times need to be conducted to verify that steady state conditions were achieved under microgravity conditions.

Takahashi, Fumiaki↗

Astrochemistry and the Role of Laboratory and Theoretical Support

We emphasize some current needs of astrochemists for laboratory data. The data are urgently required both to detect molecules in assorted regions and to produce robust models of these regions. Three areas of laboratory-based research are particularly crucial and yet are not being studied in the United States: (i) reactions more complex than the formation of molecular hydrogen occurring on interstellar grain analogs, (ii) molecular spectroscopy in the THz (far-infrared) region of the electromagnetic spectrum, and (iii) gas-phase kinetics of reactions leading to complex molecules. Without solid knowledge of many unstudied but key reactions, both in the gas and on grains, astrochemists will not be in position to keep up with the large amount of new information expected to come from the next generation of telescopes.

Herbst, E.↗