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At least 37 records · Page 2

Ultrafast Photoflash Synthesis of High-Entropy Oxide Nanoparticles

High-entropy metal oxides (HEOs) have recently received growing attention for broad energy conversion and storage applications due to their tunable properties. HEOs typically involve the combination of multiple metal cations in a single oxide lattice, thus bringing distinctive structures, controllable elemental composition, and tunable functional properties. Many synthesis methods for HEOs have been reported, such as solid-state reactions and carbon thermal shock methods. These methods frequently are energy-intensive or require relatively expensive heating equipment. In this work, we report an ultrafast photoflash synthesis method for HEO nanoparticles on diverse substrates. The energy input is provided by a commercial Xe photoflash unit, which triggers exothermic reactions to convert metal salt precursors to HEO nanoparticles within tens of milliseconds. The formation of HEO nanoparticles is attributed to the ultrafast heating (∼106 K/s) and cooling (∼105 K/s) rates of the photoflash and overall high temperature (>1000 K) during the ultrafast synthesis process. When the synthesized CoNiFeCrMn oxide (HEO) is tested as an oxygen evolution reaction electrocatalyst, it shows similar activity to similar materials prepared by other methods. We believe this photoflash synthesis provides a simple method for many others to synthesize diverse HEOs and explore their properties and potential applications.

exothermic reaction synthesis

Mixing and non-equilibrium chemical reaction in a compressible mixing layer

The effects of compressibility, chemical reaction exothermicity, and non-equilibrium chemical modeling in a reacting plane mixing layer were investigated by means of two dimensional direct numerical simulations. The chemical reaction was irreversible and second order of the type A + B yields Products + Heat. The general governing fluid equations of a compressible reacting flow field were solved by means of high order finite difference methods. Physical effects were then determined by examining the response of the mixing layer to variation of the relevant non-dimensionalized parameters. The simulations show that increased compressibility generally results in a suppressed mixing, and consequently a reduced chemical reaction conversion rate. Reaction heat release was found to enhance mixing at the initial stages of the layer growth, but had a stabilizing effect at later times. The increased stability manifested itself in the suppression or delay of the formation of large coherent structures within the flow. Calculations were performed for a constant rate chemical kinetics model and an Arrhenius type kinetic prototype. The choice of the model was shown to have an effect on the development of the flow. The Arrhenius model caused a greater temperature increase due to reaction than the constant kinetic model. This had the same effect as increasing the exothermicity of the reaction. Localized flame quenching was also observed when the Zeldovich number was relatively large.

Steinberger, Craig J.

Advances and Challenges in Low‐Temperature Upcycling of Waste Polyolefins via Tandem Catalysis

Abstract Polyolefin waste is the largest polymer waste stream that could potentially serve as an advantageous hydrocarbon feedstock. Upcycling polyolefins poses significant challenges due to their inherent kinetic and thermodynamic stability. Traditional methods, such as thermal and catalytic cracking, are straightforward but require temperatures exceeding 400 °C for complete conversion because of thermodynamic constraints. We summarize and critically compare recent advances in upgrading spent polyolefins and model reactants via kinetic (and thermodynamic) coupling of the endothermic C─C bond cleavage of polyolefins with exothermic reactions including hydrogenation, hydrogenolysis, metathesis, cyclization, oxidation, and alkylation. These approaches enable complete conversion to desired products at low temperatures (<300 °C). The goal is to identify challenges and possible pathways for catalytic conversions that minimize energy and carbon footprints.

C-C cleavage

Graphite oxidation at low temperature in subsonic air.

Coupled mass loss and heat transfer was studied experimentally for thin two inch diameter graphite disks heated as high as 2800 F in a flow of ambient air at velocities of 97 to 717 ft/sec. Oxidation was predominately reaction rate controlled with rate constants which were determined experimentally for POCO AXF 5Q, ATJ, ATJS, and an AVCO 3D Orthogonal material. The specimen thermal response was used with an energy balance to obtain the influence of mass loss and chemical reactions on the heat transfer. Specimen heating due to exothermic reactions correlates qualitatively with an approximate theory.

Knight, D. D.

Calculations of ion-molecule deuterium fractionation reactions involving HD

Gas-phase chemical models of deuterium fractionation in dense interstellar clouds utilize a small number of exothermic reactions to achieve fractionation. Although HD is a major repository of deuterium, it appears not to exchange deuterium with many molecular ions. Useful semiquantitative reasons have been given for the unusual lack of reactivity of exothermic ion-HD deuterium exchange systems, but quantum chemical studies are needed to understand these ideas in more detail and to determine if the lack of reactivity pertains at very low temperatures not studied in the laboratory, or whether tunneling can drive the reactions. Accordingly, the potential energy surfaces of three representative ion-molecule exchange reactions involving protonated ions and HD have been investigated with ab initio quantum chemical techniques. Our results generally confirm the semiquantitative picture as to which reactions are likely to occur and show that tunneling at low temperatures is unlikely to alter this picture.

Maluendes, Sergio A.

Intumescent-ablators as improved thermal protection materials

Nitroaromatic amine-based intumescent coatings were improved with regard to their thermal protection ability by adding endothermic decomposing fillers with endotherms at or near the exothermic reaction of the intumescent agent, since the effectiveness of the intumescent coatings without fillers is reduced by the exothermic behavior of the coatings during thermal activation. Fillers were dispersed directly in the base coating. Potassium fluoborate, ammonium fluoborate, zinc borate, and ammonium oxalate function as endothermic ablative materials at specific temperature regions, and also enhance the char formation during the intumescent process.

Sawko, P. M.

Nitrogen dioxide produced by self-sustained pyrolysis of nitrous oxide

Apparatus is developed for achieving continuous self-sustaining pyrolysis reaction in the production of nitrogen dioxide from nitrous oxide. The process becomes self-sustaining because of the exothermic reaction and the regenerative heating of the gases in the pyrolysis chamber.

Sabol, A. P.

Differential scanning calorimetry of coal

Differential scanning calorimetry studies performed during the first year of this project demonstrated the occurrence of exothermic reactions associated with the production of volatile matter in or near the plastic region. The temperature and magnitude of the exothermic peak were observed to be strongly affected by the heating rate, sample mass and, to a lesser extent, by sample particle size. Thermal properties also were found to be influenced by oxidation of the coal sample due to weathering effects.

Gold, P. I.

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.

Ambient cure polyimide foams

Flame and temperature resistant polyimide foams are prepared by the reaction of an aromatic dianhydride, (pyromellitic dianhydride) with an aromatic polyisocyanate, (polymethylene polyphenylisocyanate), in the presence of an inorganic acid and furfuryl alcohol. Usable acids include dilute sulfuric acid, dilute nitric acid, hydrochloric acid, polyphosphoric acid, and phosphoric acid, with the latter being preferred. The dianhydride and the isocyanate in about equimolar proportions constitute about 50% of the reaction mixture, the rest being made up with the acid and the alcohol in a ratio of about 1:10. An exothermic reaction between the acid and the alcohol provides the heat necessary for the other components to polymerize without recourse to external heat sources. The mixture can be sprayed on any surface to form polymeric foam in locations where the application of heat is not practical or possible, for instance, between walls or on mine tunnel surfaces.

Sawko, P. M.

A detailed investigation of proposed gas-phase syntheses of ammonia in dense interstellar clouds

The initial reactions of the Herbst and Klemperer (1973) and the Dalgarno (1974) schemes (I and II, respectively) for the gas-phase synthesis of ammonia in dense interstellar clouds were investigated. The rate of the slightly endothermic reaction between N(+) and H2 to yield NH(+) and H (scheme I) under interstellar conditions was reinvestigated under thermal and nonthermal conditions based on laboratory data. It was found that the relative importance of this reaction in synthesizing ammonia is determined by how the laboratory data at low temperature are interpreted. On the other hand, the exothermic reaction between N and H3(+) to form NH2(+) + H (scheme II) was calculated to possess significant activation energy and, therefore, to have a negligible rate coefficient under interstellar conditions. Consequently, this reaction cannot take place appreciably in interstellar clouds.

Herbst, Eric

Energy Distribution among Reaction Products. III: The Method of Measured Relaxation Applied to H + Cl2

The method of measured relaxation is described for the determination of initial vibrational energy distribution in the products of exothermic reaction. Hydrogen atoms coming from an orifice were diffused into flowing chlorine gas. Measurements were made of the resultant ir chemiluminescence at successive points along the line of flow. The concurrent processes of reaction, diffusion, flow, radiation, and deactivation were analyzed in some detail on a computer. A variety of relaxation models were used in an attempt to place limits on k(nu prime), the rate constant for reaction to form HCl in specified vibrational energy levels: H+Cl2 yields (sup K(nu prime) HCl(sub nu prime) + Cl. The set of k(?) obtained from this work is in satisfactory agreement with those obtained by another experimental method (the method of arrested relaxation described in Parts IV and V of the present series.

Pacey, P. D.

The compositional structure and the effects of exothermicity in an unpremixed planar jet flame

Results are presented of direct numerical simulations (DNS) of a randomly perturbed compressible, spatially developing planar jet under the influence of a finite rate Arrhenius chemical reaction of the type F + O yields Product + Heat. The objectives of the simulations are to assess the compositional structure of the flame and to determine the influence of reaction exothermicity by means of statistical sampling of the data generated by DNS. It is shown that even with this idealized kinetics model, the simulated results exhibit features in accordance with experimental data. These results indicate that the Damkoehler number is an important parameter in determining the statistical composition of the reacting field, and that the results are insensitive to the mechanism by which this parameter is varied. It is demonstrated that as the intensity of mixing is increased and the effect of finite rate chemistry is more pronounced, the magnitudes of the ensemble mean and rms of the product mass fraction decrease, and those of the reactants mass fraction increase. Also, at higher mixing rates the joint probability density functions of the reactants' mass fractions shift towards higher values within the composition domain indicating a lower reactedness. These trends are consistent with those observed experimentally and are very useful in portraying the statistical structure of non-equilibrium diffusion flames. The DNS generated data are also utilized to examine the applicability of the 'laminar diffusion flamelet model' in predicting the rate of the reactant conversion with finite rate chemistry. This examination indicates that the bounds of the product formation scale reasonably well with those obtained by the flamelet model. However, in the range of the relatively low values of the Damkoehler numbers considered, the scatter of the results is substantially more than that to be completely determined by the closure.

Steinberger, C. J.

The compositional structure and the effects of exothermicity in a nonpremixed planar jet flame

Results are presented of direct numerical simulation (DNS) of a randomly perturbed compressible, spatially developing two-dimensional planar jet under the influence of a finite rate chemical reaction of the type F + O yields product. The objectives of the simulations are to assess the compositional structure of the flame and to determine the influence of reaction exothermicity by means of statistical sampling of the DNS generated data. It is shown that even with this idealized kinetics model the simulated results exhibit features in accord with experimental data. These results indicate that the Damkohler number is an important parameter in determining the statistical composition of the reacting field and that the results are not very sensitive to the mechanism by which this parameter is varied. It is demonstrated that as the intensity of mixing is increased and the effect of finite rate chemistry is more pronounced, the magnitudes of the ensemble mean and variance of the product mass fraction decrease and those of the reactants' mass fraction increase. Also, at higher mixing rates the joint probability density functions of the reactants' mass fractions shift towards higher values within the composition domain, indicating a lower reactedness.

Steinberger, C. J.

Measurements of the inert Hugoniot and observation of mechanical ignition in Ni(V) + Al reactive multilayers via x-ray diffraction

This study investigates the inert Hugoniot response, mechanical ignition, and reaction dynamics of Ni(V)+Al multilayers during longitudinal, laser-driven shock compression experiments. Ni(V)+Al multilayers, known for their self-propagating exothermic reactions, were subjected to longitudinal stresses exceeding 50 GPa using the laser shock facility within the Dynamic Compression Sector (DCS) at the Advanced Photon Source (APS). In situ x-ray diffraction (XRD) revealed that Ni(V) and Al were not in equilibrium during compression, with stress discrepancies attributed to twinning, grain structure effects, and/or dislocation density. However, the measured inert Hugoniot closely matched prior experimental and computational studies, confirming the utility of XRD for measuring the equation of state of thin, complex materials. Additionally, reaction was observed at significantly higher stresses than reported previously using laser-launched flyers. This discrepancy suggests a strong influence of externally imposed shear stress on reaction thresholds, which likely arose from deviations in flyer planarity during past experiments. Full reaction of the multilayer occurred within 40 ns after shock-wave passage, evidenced by complete melting of the constituents. Eulerian hydrocode simulations replicated experimental conditions, providing insights into equilibrium dynamics and experimental artifacts. The results highlight how even small shear forces facilitate ignition in Ni(V)+Al multilayers at lower stresses.

Crystallography

Diffusion Driven Combustion Waves in Porous Media

Filtration of gas containing oxidizer, to the reaction zone in a porous medium, due, e.g., to a buoyancy force or to an external pressure gradient, leads to the propagation of Filtration combustion (FC) waves. The exothermic reaction occurs between the fuel component of the solid matrix and the oxidizer. In this paper, we analyze the ability of a reaction wave to propagate in a porous medium without the aid of filtration. We find that one possible mechanism of propagation is that the wave is driven by diffusion of oxidizer from the environment. The solution of the combustion problem describing diffusion driven waves is similar to the solution of the Stefan problem describing the propagation of phase transition waves, in that the temperature on the interface between the burned and unburned regions is constant, the combustion wave is described by a similarity solution which is a function of the similarity variable x/square root of(t) and the wave velocity decays as 1/square root of(t). The difference between the two problems is that in the combustion problem the temperature is not prescribed, but rather, is determined as part of the solution. We will show that the length of samples in which such self-sustained combustion waves can occur, must exceed a critical value which strongly depends on the combustion temperature T(sub b). Smaller values of T(sub b) require longer sample lengths for diffusion driven combustion waves to exist. Because of their relatively small velocity, diffusion driven waves are considered to be relevant for the case of low heat losses, which occur for large diameter samples or in microgravity conditions, Another possible mechanism of porous medium combustion describes waves which propagate by consuming the oxidizer initially stored in the pores of the sample. This occurs for abnormally high pressure and gas density. In this case, uniformly propagating planar waves, which are kinetically controlled, can propagate, Diffusion of oxidizer decreases the wave velocity. In addition to the reaction and diffusion layers, the uniformly propagating wave structure includes a layer with a pressure gradient, where the gas motion is induced by the production or consumption of the gas in the reaction as well as by thermal expansion of the gas. The width of this zone determines the scale of the combustion wave in the porous medium.

Aldushin, A. P.

Ambient cure polyimide foams prepared from aromatic polyisocyanates, aromatic polycarboxylic compounds, furfuryl alcohol, and a strong inorganic acid

Flame and temperature resistant polyimide foams are prepared by the reaction of an aromatic dianhydride, e.g., pyromellitic dianhydride, with an aromatic polyisocyanate, e.g., polymethylene polyphenylisocyanate (PAPI) in the presence of an inorganic acid and a lower molecular weight alcohol, e.g., dilute sulfuric acid or phosphoric acid and furfuryl alcohol. The exothermic reaction between the acid and the alcohol provides the heat necessary for the other reactants to polymerize without the application of any external heat. Such mixtures, therefore, are ideally suited for in situ foam formation, especially where the application of heat is not practical or possible.

Sawko, Paul M.

Catalyzed Combustion of Bipropellants for Micro-Spacecraft Propulsion

This paper addresses the need to understand the physics and chemistry involved in propellant combustion processes in micro-scale combustors for propulsion systems on micro-spacecraft. These spacecraft are planned to have a mass less than 50 kilograms with attitude control estimated to be in the 10 milli-Newton thrust class. These combustors are anticipated to be manufactured using Micro Electrical Mechanical Systems (MEMS) technology and are expected to have diameters approaching the quenching diameter of the propellants. Combustors of this size are expected to benefit significantly from surface catalysis processes. Miniature flame tube apparatus is chosen for this study because microtubes can be easily fabricated from known catalyst materials and their simplicity in geometry can be used in fundamental simulations for validation purposes. Experimentally, we investigated the role of catalytically active surfaces within 0.4 and 0.8 mm internal diameter microtubes, with special emphases on ignition processes in fuel rich gaseous hydrogen and gaseous oxygen. Flame thickness and reaction zone thickness calculations predict that the diameters of our test apparatus are below the quenching diameter of the propellants in sub-atmospheric tests. Temperature and pressure rise in resistively heated platinum and palladium microtubes was used as an indication of exothermic reactions. Specific data on mass flow versus preheat temperature required to achieve ignition are presented. With a plug flow model, the experimental conditions were simulated with detailed gas-phase chemistry, thermodynamic properties, and surface kinetics. Computational results generally support the experimental findings, but suggest an experimental mapping of the exit temperature and composition is needed.

Schneider, Steven J.