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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 919 records · Page 51
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Acetic Acid/Propionic Acid Conversion on Metal Doped Molybdenum Carbide Catalyst Beads for Catalytic Hot Gas Filtration

Catalytic hot gas filtration (CHGF) is used to precondition biomass derived fast pyrolysis (FP) vapors by physically removing reactive char and alkali particulates and chemically converting reactive oxygenates to species that are more easily upgraded during subsequent catalytic fast pyrolysis (CFP). Carboxylic acids, such as acetic acid and propionic acid, form during biomass fast pyrolysis and are recalcitrant to downstream catalytic vapor upgrading. This work developed and evaluated catalysts that can convert these acids to more upgradeable ketones at the laboratory scale. Selective catalytic conversion of these reactive oxygenates to more easily upgraded compounds can enhance bio-refinery processing economics through catalyst preservation by reduced coking from acid cracking, by preserving carbon efficiency, and through process intensification by coupling particulate removal with partial upgrading. Two metal-doped molybdenum carbide (Mo2C) supported catalyst beads were synthesized and evaluated and their performance compared with an undoped Mo2C control catalyst beads. For laboratory scale acetic acid conversion, calcium doped Mo2C supported catalyst beads produced the highest yield of acetone at ~96% at 450 °C among undoped and Ca or Ni doped catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Additively Manufactured Carbon Fiber-Reinforced Siliconized Silicon Carbide Composites Using Carbon Fiber-Reinforced Poly-Ether-Ether-Ketone (PEEK) as a Precursor

Herein, we report a method to additively manufacture carbon fiber-reinforced siliconized silicon carbide composites. The process involves the pyrolysis of a 3D-printed carbon fiber-reinforced poly-ether-ether-ketone (PEEK) composite to produce a porous carbon fiber-reinforced carbon matrix composite preform, which is subsequently infiltrated with molten silicon to obtain a carbon fiber-reinforced siliconized silicon carbide composite. A key aspect of the method is limiting polymer melt flow during pyrolysis of PEEK, which is achieved by thermally annealing the 3D-printed carbon fiber-reinforced PEEK preform in air at a temperature below PEEK’s melting temperature. Rheological and differential scanning calorimetry (DSC) measurements demonstrate that the thermal annealing treatment altered the melting behavior of PEEK, while NMR and FTIR measurements provided a mechanistic explanation for the structural changes responsible for the behavior. It was also found that dimensional changes during pyrolysis were anisotropic with greater shrinkage in the stacking direction of the material.

Yoon, Bola [ORNL] (ORCID:0000000260875373)↗
DOE OSTI2026

Polymers from Levoglucosenone and Other Anhydrosugars (CRADA Final Report)

The goal of this work is to identify promising drop-in or novel polymers that can be produced from levoglucosenone (LGO), CyreneTM, or other anhydrous sugars. LGO is a potentially important feedstock for polymers produced from renewable sources and can be produced in high yields by the company Circa from the pyrolysis of cellulose and biomass. NLR has a long history with anhydrosugars, pyrolysis and biomass-based polymers and has recently developed machine learning (ML) tools for predicting polymer properties. The DOE has recently supported efforts to identify coproducts from pyrolysis of biomass and their use in the production of performance advantaged polymers. DOE is also supporting the development of ML and molecular modeling for predicting and understanding polymer properties. NLR will leverage this expertise and experience to map out the pathways to polymers from LGO, use ML to identify the properties of novel polymers and estimate the market application space. From this effort NLR will deliver a summary report that outlines the most promising pathways based on quantitative and qualitative metrics for producing polymers from LGO.

09 BIOMASS FUELS↗
NASA NTRS1970

Polymer degradation rate control of hybrid rocket combustion

Polymer degradation to small fragments is treated as a rate controlling step in hybrid rocket combustion. Both numerical and approximate analytical solutions of the complete energy and polymer chain bond conservation equations for the condensed phase are obtained. Comparison with inert atmosphere data is very good. It is found that the intersect of curves of pyrolysis rate versus interface temperature for hybrid combustors, with the thermal degradation theory, falls at a pyrolysis rate very close to that for which a pressure dependence begins to be observable. Since simple thermal degradation cannot give sufficient depolymerization at higher pyrolysis rates, it is suggested that oxidative catalysis of the process occurs at the surface, giving a first order dependence on reactive species concentration at the wall. Estimates of the ratio of this activation energy and interface temperature are in agreement with best fit procedures for hybrid combustion data. Requisite active species concentrations and flux are shown to be compatible with turbulent transport. Pressure dependence of hybrid rocket fuel regression rate is thus shown to be describable in a consistent manner in terms of reactive species catalysis of polymer degradation.

Stickler, D. B.↗
NASA NTRS1972

Demonstration of the range over which the Langley Research Center digital computer charring ablation program (CHAP) can be used with confidence: Comparisons of CHAP predictions and test data for three ablation materials

Comparisons of ablation calculations with the charring ablation computer code and ablation test data are presented over a wide range of environmental conditions in air for three materials: low-density nylon phenolic, Avcoat 5026-39HC/G, and a filled silicon elastomer. Heat fluxes considered range from over 500 Btu/sq ft-sec to less than 50 Btu/sq ft-sec. Pressures range from 0.5 atm to .004 atm. Enthalpies range from about 2000 Btu/lb to 18000 Btu/lb. Predictions of recession, pyrolysis penetration, and thermocouple responses are considered. Recession predictions for nylon phenolic are good as steady state is approached, but strongly transient cases are underpredicted. Pyrolysis penetrations and thermocouple responses are very well predicted. Recession amounts for Avcoat and silicone elastomer are less well predicted, although high heat flux cases near steady state are fairly satisfactory. Pyrolysis penetrations and thermocouple responses are very well predicted.

Moyer, C. B.↗
NASA NTRS1972

Analysis of Surveyor 3 television cable

A sample of cable described as four inches of TV cable, fabric wrapped, which had been exposed to the atmosphere for an unknown period of time, was subjected to extensive chemical analyses for the various components. The fabric was tested using attenuated total reflectance, chloroform extract, aqueous extraction, pyrolysis infrared, and reflectance spectroscopy. The wire insulation was tested using pyrolysis infrared, pyrolysis gas chromatography, differential thermal analysis, attenuated total reflectance subsurface, and tensile tests. Corrosion was also observed in parts of certain wires.

Gross, F. C.↗
NASA NTRS1972

Numerical analysis of the transient response of an axisymmetric ablative char layer considering internal flow effects

The differential equations governing the transient response of the char layer of an ablating axisymmetric body, internal pyrolysis gas flow effects being considered, have been derived. These equations have been expanded into finite difference form and programed for numerical solution on a digital computer. Numerical results compare favorably with simplified exact solutions. The complete numerical analysis was used to obtain solutions for two representative body shapes subjected to a typical entry heating environment. Pronounced effects of the lateral flow of pyrolysis gases on the mass flow field within the char layer and the associated surface and pyrolysis interface recession rates are shown.

Pittman, C. M.↗
NASA NTRS1972

A Numerical Analysis of the Transient Response of an Ablation System Including Effects of Thermal Nonequilibrium, Mass Transfer and Chemical Kinetics

The differential equations governing the transient response of a one-dimensional ablative thermal protection system undergoing stagnation ablation are derived. These equations are for thermal nonequilibrium effects between the pyrolysis gases and the char layer and kinetically controlled chemical reactions and mass transfer between the pyrolysis gases and the char layer. The boundary conditions are written for the particular case of stagnation heating with surface removal by oxidation or sublimation and pyrolysis of the uncharred layer occurring in a plane. The governing equations and boundary conditions are solved numerically using the modified implicit method (Crank-Nicolson method). Numerical results are compared with exact solutions for a number of simplified cases. The comparison is favorable in each instance.

Clark, R. K.↗
NASA NTRS1973

An analysis of a charring ablator with thermal nonequilibrium, chemical kinetics, and mass transfer

The differential equations governing the transient response of a one-dimensional ablative thermal protection system are presented for thermal nonequilibrium between the pyrolysis gases and the char layer and with finite rate chemical reactions occurring. The system consists of three layers (the char layer, the uncharred layer, and an optical insulation layer) with concentrated heat sinks at the back surface and between the second and third layers. The equations are solved numerically by using a modified implicit finite difference scheme to obtain solutions for the thickness of the charred and uncharred layers, surface recession and pyrolysis rates, solid temperatures, porosity profiles, and profiles of pyrolysis-gas temperature, pressure, composition, and flow rate. Good agreement is obtained between numerical results and exact solutions for a number of simplified cases. The complete numerical analysis is used to obtain solutions for an ablative system subjected to a constant heating environment. Effects of thermal, chemical, and mass transfer processes are shown.

Clark, R. K.↗
NASA NTRS1972

An evaluation of pyrolytic techniques with regard to the Apollo 11, 12 and 14 lunar samples analyses.

The first technique involved pyrolysis at 700 C under an inert atmosphere in a flowing He system at normal pressure. The products were collected at liquid nitrogen temperature and then allowed to pass instantaneously into a combined capillary gas chromatograph-mass spectrometer. The second technique consisted of a vacuum pyrolysis where the sample was first degassed at 150 C and then pyrolized at 500 C and 1000 C consecutively. The products were again collected at liquid nitrogen temperature and then they were directly introduced to the ion source of the mass spectrometer through a modified gas inlet system. The experiments have shown the importance of taking into account the factors that influence pyrolytic degradation and/or the synthesis of products. Pyrolysis of Apollo 14 lunar fines and scrapings from an astronaut's glove gave different products by mass spectroscopy and showed different looking flaky materials upon scanning electron microscopy.

Nagy, B.↗
NASA NTRS1978

Smoke toxicity methodology

The toxicity of pyrolysis products for aircraft interior materials must be within some reasonable limit. The toxicity of pyrolysis products from five candidate aircraft materials is evaluated. The most important part of this study was to demonstrate that pyrolysis of materials could be controlled and biological endpoints are reproducible.

Dilley, J. V.↗
NASA NTRS1979

Some effects of gas adsorption on the high temperature volatile release behavior of a terrestrial basalt, tektite and lunar soil

Mass pyrograms obtained from high-temperature, mass psectrometric pyrolysis of a glassy theoleiitic submarine basalt and a tektite, ground in air to less than 64 microns, have shown N2 and SO release patterns very similar to those from the pyrolysis of mature lunar soil fines. The N2 and CO release behavior from the terrestrial samples reproduces the biomodal, high-temperature (approximately 700 and 1050 C) features from the lunar samples. Unground portions of the basalt and tektite show no release of N2 and CO during pyrolysis. Grinding also alters the release behavior and absolute amounts of H2O and CO2. It is suggested that adsorption of atmospheric gases in addition to solar wind implantation of ions may account for the wide range of values in previously reported concentrations of carbon and nitrogen from lunar fines.

Graham, D. G.↗
NASA NTRS1987

Gas chromatographic instrumentation for the analysis of aerosols and gases in Titan's atmosphere

Instrumentation presently being developed by NASA for the collection and analysis of organic gases and aerosols in Titan's atmosphere is described together with the results of the preliminary experiments. For the aerosols, stepwise pyrolysis was shown to be a suitable method for preparing complex organic material for gas chromatography (GC), and a pyrolysis-gas chromatograph was developed and successfully used to analyze a simulated Titan aerosol. Atmospheric gases will be collected by a low-pressure gas sampling system using large-volume sample loops and analyzed by GC. The results of preliminary studies using a 20 cu cm sampling system and a very sensitive metastable ionization detector showed that hydrocarbon components at the 10 ppb level can be detected. Studies are in progress on shortening the overall analysis time by improving the pyrolysis system, the gas sampling system, and the associated gas chromatograph. Further development of the gas sampling system is planned to ensure rapid collection of samples adequate for analysis by GC over the entire range of pressures to be encountered during the probe's descent.

Scattergood, T. W.↗
NASA NTRS1986

Role of minerals in thermal alteration of organic matter. II - A material balance

The paper presents the results of pyrolysis experiments which were carried out on Green River and Monterey Formation kerogens with and without calcite, illite, or montmorillonite at 300 C for 2 to 1,000 hours under dry and hydrous conditions. The data reveal significant differences in the products generated by pyrolysis of kerogens with and without minerals. Both illite and montmorillonite adsorb a considerable portion of the generated bitumen. In the case of calcite, the pyrolysis products are similar to those from kerogen heated alone, and bitumen adsorption is negligible.

Tannenbaum, Eli↗
NASA NTRS1987

The role of minerals in the thermal alteration of organic matter. III - Generation of bitumen in laboratory experiments

A series of pyrolysis experiments, utilizing two different immature kerogens (from the Monterey and Green River Formations) mixed with common sedimentary minerals (calcite, illite, or Na-montmorillonite), was conducted to study the impact of the mineral matrix on the bitumen that was generated. Calcite has no significant influence on the thermal evolution of bitumen and also shows virtually no adsorption capacity for any of the pyrolysate. In contrast, montmorillonite (M) and illite, to a lesser extent, alter bitumen during dry pyrolysis. M and illite also display strong adsorption capacities for the polar constituents of bitumen. By this process, hydrocarbons are substantially concentrated within the pyrolysate that is not strongly adsorbed on the clay matrices. The effects of the clay minerals are significantly reduced during hydrous pyrolysis. The strong adsorption capacities of M and illite, as well as their thermocatalytic properties, may in part explain why light oils and gases are generated from certain argillaceous source-rock assemblages, whereas heavy immature oils are often derived from carbonate source rocks.

Huizinga, Bradley J.↗
NASA NTRS1988

A mass spectrometric study of the simultaneous reaction mechanism of TMIn and PH3 to grow InP

The reaction mechanisms for the growth of InP from various mixtures of trimethyl indium (TMIn) and PH3 by OMVPE were investigated using mass spectrometry and a D2 ambient for isotopic labeling of the reaction products. It was found that, whereas TMIn alone pyrolyzes homogeneously, forming CH3D, and PH3 alone pyrolyzes heterogeneously, producing H2, the pyrolysis reactions of TMIn and PH3 together are completely different. The pyrolysis temperatures of both TMIn and PH3 are reduced (by 50 C for TMIn and 225 C for PH3), and the sole product is CH4 at high values of the PH3/TMIn ratio. The pyrolysis reaction is shown to be coupled (as evidenced by the equal depletion of TMIn and PH3 from the vapor) and, at temperatures below 400 C, heterogeneous.

Buchan, N. I.↗
NASA NTRS1990

Two Radiative/Thermochemical Instruments

Measurements of absorption and emission complement thermal measurements. Two laboratory instruments for research in combustion and pyrolysis equipped for radiative as well as thermal measurements. One instrument essentially differential scanning calorimeter (DSC) modified to detect radiation emitted by flames. Provides means to evaluate limits of flammability of materials exhibiting exothermic reactions in DSC's. Other instrument used to determine pyrolysis properties of specimens exposed to various gases by measurement of infrared absorption spectra of pyrolysis products.

Tapphorn, Ralph M.↗
NASA NTRS1993

A model of concurrent flow flame spread over a thin solid fuel

A numerical model is developed to examine laminar flame spread and extinction over a thin solid fuel in lowspeed concurrent flows. The model provides a more precise fluid-mechanical description of the flame by incorporating an elliptic treatment of the upstream flame stabilization zone near the fuel burnout point. Parabolic equations are used to treat the downstream flame, which has a higher flow Reynolds number. The parabolic and elliptic regions are coupled smoothly by an appropriate matching of boundary conditions. The solid phase consists of an energy equation with surface radiative loss and a surface pyrolysis relation. Steady spread with constant flame and pyrolysis lengths is found possible for thin fuels and this facilitates the adoption of a moving coordinate system attached to the flame with the flame spread rate being an eigen value. Calculations are performed in purely forced flow in a range of velocities which are lower than those induced in a normal gravity buoyant environment. Both quenching and blowoff extinction are observed. The results show that as flow velocity or oxygen percentage is reduced, the flame spread rate, the pyrolysis length, and the flame length all decrease, as expected. The flame standoff distance from the solid and the reaction zone thickness, however, first increase with decreasing flow velocity, but eventually decrease very near the quenching extinction limit. The short, diffuse flames observed at low flow velocities and oxygen levels are consistent with available experimental data. The maximum flame temperature decreases slowly at first as flow velocity is reduced, then falls more steeply close to the quenching extinction limit. Low velocity quenching occurs as a result of heat loss. At low velocities, surface radiative loss becomes a significant fraction of the total combustion heat release. In addition, the shorter flame length causes an increase in the fraction of conduction downstream compared to conduction to the fuel. These heat losses lead to lower flame temperatures, and ultimately, extinction. This extinction mechanism differs from that of blowoff, where the flame is unable to be stabilized due to the high flow velocity.

Ferkul, Paul V.↗