Results for “Pyrolysis” — Page 17

NASA NTRS2011

Evaluation of Sorbents for Acetylene Separation in Atmosphere Revitalization Loop Closure

State-of-the-art carbon dioxide reduction technology uses a Sabatier reactor to recover water from metabolic carbon dioxide. In order to maximize oxygen loop closure, a byproduct of the system, methane, must be reduced to recover hydrogen. NASA is currently exploring a microwave plasma methane pyrolysis system for this purpose. The resulting product stream of this technology includes unreacted methane, product hydrogen, and acetylene. The hydrogen and the small amount of unreacted methane resulting from the pyrolysis process can be returned to the Sabatier reactor thereby substantially improving the overall efficiency of the system. However, the acetylene is a waste product that must be removed from the pyrolysis product. Two materials have been identified as potential sorbents for acetylene removal: zeolite 4A, a commonly available commercial sorbent, and HKUST-1, a newly developed microporous metal. This paper provides an explanation of the rationale behind acetylene removal and the results of separation testing with both materials.

Abney, Morgan B.↗

NASA NTRS2013

Investigating the Origin of Chlorohydrocarbons Detected by the Sample Analysis at Mars (SAM) Instrument at Rocknest

The search for organic compounds on Mars, including molecules of either abiotic or biological origin is one of the key goals of the Mars Science Laboratory (MSL) mission. Previously the Viking and Phoenix Lander missions searched for organic compounds, but did not find any definitive evidence of martian organic material in the soils. The Viking pyrolysis gas chromatography mass spectrometry (GCMS) instruments did not detect any organic compounds of martian or exogenous origin above a level of a few parts-per-billion (ppb) in the near surface regolith at either landing site [1]. Viking did detect chloromethane and dichloromethane at pmol levels (up to 40 ppb) after heating the soil samples up to 500 C (Table 1), although it was originally argued that the chlorohydrocarbons were derived from cleaning solvents used on the instrument hardware, and not from the soil samples themselves [1]. More recently, it was suggested that the chlorohydrocarbons detected by Viking may have been formed by oxidation of indigenous organic matter during pyrolysis of the soil in the presence of perchlorates [2]. Although it is unknown if the Viking soils contained perchlorates, Phoenix did reveal relatively high concentrations (~0.6 wt%) of perchlorate salt in the icy regolith [3], therefore, it is possible that the chlorohydrocarbons detected by Viking were produced, at least partially, during the experiments [2,4]. The Sample Analysis at Mars (SAM) instrument suite on MSL analyzed the organic composition of the soil at Rocknest in Gale Crater using a combination of pyrolysis evolved gas analysis (EGA) and GCMS. One empty cup procedural blank followed by multiple EGA-GCMS analyses of the Rocknest soil were carried out. Here we will discuss the results from these SAM measurements at Rocknest and the steps taken to determine the source of the chlorohydrocarbons.

Glavin, D.↗

NASA NTRS2013

Evidence for Perchlorates and the Origin of Chlorinated Hydrocarbons Detected by SAM at the Rocknest Aeolian Deposit in Gale Crater

Four individual sample portions from a single scoop of the Rocknest aeolian deposit were sieved ( 150 m) and delivered to the Sample Analysis at Mars (SAM) instrument by the Mars Science Laboratory rover's sample acquisition system. The samples were analyzed separately by the SAM pyrolysis evolved gas and gas chromatography mass spectrometry analysis modes. Several chlorinated hydrocarbons including chloromethane, dichloromethane, trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of 0.01 to 2.3 nanomole.The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N-methyl-N- (tert-butyldimethylsilyl)trifluoroacetamide (MTBSTFA), a chemical that leaked from a derivatization cup inside SAM.The best candidate for the oxychloride phase in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated species measured by SAM, although other chlorine bearing phases are being considered. Laboratory pyrolysis experiments suggest that reaction of martian chlorine with organic carbon from MTBSTFA can explain the presence of the chloromethanes and a chloromethylpropene also detected by SAM.However, we cannot exclude the possibility that traces of organic carbon of either martian or exogenous origin contributed to some of the chloromethanes measured by SAM. Although the alteration history and exposure age of the Rocknest deposit is unknown, it is possible that oxidative degradation of complex organic matter by ionizing radiation or other chemical processes in Rocknest has occurred.

Mars Rover↗

NASA NTRS2016

Conversion and Extraction of Insoluble Organic Materials in Meteorites

We endeavor to develop and implement methods in our laboratory to convert and extract insoluble organic materials (IOM) from low car-bon bearing meteorites (such as ordinary chondrites) and Precambrian terrestrial rocks for the purpose of determining IOM structure and prebiotic chemistries preserved in these types of samples. The general scheme of converting and extracting IOM in samples is summarized in Figure 1. First, powdered samples are solvent extracted in a micro-Soxhlet apparatus multiple times using solvents ranging from non-polar to polar (hexane - non-polar, dichloromethane - non-polar to polar, methanol - polar protic, and acetonitrile - polar aprotic). Second, solid residue from solvent extractions is processed using strong acids, hydrochloric and hydrofluoric, to dissolve minerals and isolate IOM. Third, the isolated IOM is subjected to both thermal (pyrolysis) and chemical (oxidation) degradation to release compounds from the macromolecular material. Finally, products from oxidation and pyrolysis are analyzed by gas chromatography - mass spectrometry (GCMS). We are working toward an integrated method and analysis scheme that will allow us to determine prebiotic chemistries in ordinary chondrites and Precambrian terrestrial rocks. Powerful techniques that we are including are stepwise, flash, and gradual pyrolysis and ruthenium tetroxide oxidation. More details of the integrated scheme will be presented.

Locke, Darren R.↗

NASA NTRSDate not supplied

Analysis of Mars 2020 Entry with Coupled Material Response and CFD

When computing the response of an ablating thermal protection system during entry, the aerothermal environment and material response are traditionally computed independently, with the introduction of a blowing correction term in the material response model to account for the outgassing of char and pyrolysis gases. This study presents an approach, where the pyrolysis blowing gases, calculated within the PATO material response code [1], are integrated into the DPLR hypersonic CFD code [2] via a blowing boundary condition. This methodology employs an iterative process, whereby the blown pyrolysis gas products from PATO are incorporated into DPLR, refining surface heating predictions. The NEQAIR code is used to compute radiative heating [3]. The method is applied in computing 3D material response of the Mars 2020 entry. When compared with uncoupled material response, the coupled simulations show a lower surface heat flux initially and a higher heat flux at peak heating as shown in Fig. 1. This is in agreement with previous work using a sphere case with environments from MSL [4].

Heat Transfer↗

NASA NTRSDate not supplied

Material Characterization and Modeling of Room Temperature Vulcanizing Silicone

Room Temperature Vulcanizing silicone (RTV) is a high-temperature adhesive that has successfully been used as a gap-filler between Thermal Protection System (TPS) tiles for heatshields on numerous missions. It is also used to bond instrumentation plugs such as temperature and pressure sensors into the heatshields. While RTV has been traditionally assumed to be a non-porous and non-ablating material, numerous experiments have shown that RTV pyrolyzes and becomes highly porous as it is heated. Heating RTV has also shown swelling, or intumescence, which can pose unique problems that lead to roughness induced boundary-layer transition, surface oxide formation and contamination of heat shield sensors. Therefore, it is crucial to understand and model the intumescence phenomenon of RTV. As data for RTV material properties is limited, the first step in modeling RTV is to collect material properties such as pyrolysis mass-loss, microstructure change, virgin and char porosity, etc. which was performed in our initial study. Additionally, thermomechanical properties such as Young’s modulus and Poisson ratio are required for modeling the intumescence of RTV, which were taken from literature and the coefficient of thermal expansion was collected using in-situ heating and Micro Computed Tomography (µ-CT) in previous studies. Finally, numerous other properties such as pyrolysis gas properties, virgin and char thermal conductivity and specific heat were compiled from previous experiments and literature into a material database that can be used for simulations. In Porous Material Analysis Toolbox based on OpenFOAM (PATO) [4], structural mechanics coupled with material response was used for simulating the intumescence of RTV as it is heated. However, since the permeability of the material is very low, the pyrolysis gas creates an internal pressure build-up as the material is being heated, significantly contributing to the deformation of the material. To correctly characterize this phenomenon, additional physics models were implemented into PATO's stress analysis solver, and results were compared with RTV dilatometry test data as a preliminary verification case. Future work will include experiments of RTV at the Plasmatron X facility and the in-situ heating cell with µ-CT, and improvement of simulation tools to more accurately model RTV intumescence.

TPS↗

NASA NTRSDate not supplied

Material Properties and Modeling of Room Temperature Vulcanizing Silicone

Room Temperature Vulcanizing silicone (RTV) is a high-temperature adhesive that has successfully been used as a gap-filler between Thermal Protection System (TPS) tiles for heatshields on numerous missions. It is also used to bond instrumentation plugs such as temperature and pressure sensors into the heatshields. While RTV has been traditionally assumed to be a non-porous and non-ablating material, numerous experiments have shown that RTV pyrolyzes and becomes highly porous as it is heated. Heating RTV has also shown swelling, or intumescence, which can pose unique problems that lead to roughness induced boundary-layer transition, surface oxide formation and contamination of heat shield sensors. Therefore, it is crucial to understand and model the intumescence phenomenon of RTV. As data for RTV material properties is limited, the first step in modeling RTV is to collect material properties such as pyrolysis mass-loss, microstructure change, virgin and char porosity, etc. which was performed in our initial study. Additionally, thermomechanical properties such as Young’s modulus and Poisson ratio are required for modeling the intumescence of RTV, which were taken from literature and the coefficient of thermal expansion was collected using in-situ heating and Micro Computed Tomography (µ-CT) in previous studies. Finally, numerous other properties such as pyrolysis gas properties, virgin and char thermal conductivity and specific heat were compiled from previous experiments and literature into a material database that can be used for simulations. In Porous Material Analysis Toolbox based on OpenFOAM (PATO) [4], structural mechanics coupled with material response was used for simulating the intumescence of RTV as it is heated. However, since the permeability of the material is very low, the pyrolysis gas creates an internal pressure build-up as the material is being heated, significantly contributing to the deformation of the material. To correctly characterize this phenomenon, additional physics models were implemented into PATO's stress analysis solver, and results were compared with RTV dilatometry test data as a preliminary verification case. Future work will include experiments of RTV at the Plasmatron X facility and the in-situ heating cell with µ-CT, and improvement of simulation tools to more accurately model RTV intumescence.

PATO↗

NASA NTRSDate not supplied

Analysis of Mars 2020 Entry with Coupled Material Response and CFD

When computing the response of an ablating thermal protection system during entry, the aerothermal environment and material response are traditionally computed independently, with the introduction of a blowing correction term in the material response model to account for the outgassing of char and pyrolysis gases. This study presents an approach, where the pyrolysis blowing gases, calculated within the PATO material response code, are integrated into the DPLR hypersonic CFD code via a blowing boundary condition. This methodology employs an iterative process, whereby the blown pyrolysis gas products from PATO are incorporated into DPLR, refining surface heating predictions. The NEQAIR code is used to compute radiative heating. The method is applied in computing 3D material response of the Mars 2020 entry. When compared with uncoupled material response, the coupled simulations show a lower surface heat flux initially and a higher heat flux at peak heating as shown in Fig. 1. This is in agreement with previous work using a sphere case with environments from MSL.

Heat Transfer↗

NASA NTRSDate not supplied

Kinetic Model Development of the Carbon Vapor Deposition Reactor to Predict Performance Versus Design

To enable complete closure of a Sabatier-based atmosphere revitalization system where oxygen recovery is predicated by carbon dioxide reduction to methane and water, there must be a means of recovering the hydrogen from the byproduct methane. Honeywell’s carbon vapor deposition (CVD) reactor is a potential technology that provides a thermochemical means by which methane decomposes at high temperatures (> 1,000 °C) into hydrogen, solid carbon, and a small percentage of hydrocarbons. This advanced methane pyrolysis reactor utilizes a carbon fiber substrate to capture and immobilize the solid pyrolytic carbon rather than allowing continuation toward undesirable soot. The CVD reactor is a highly dynamic system whose characteristic geometry changes while operating. The reactor model was developed to provide predictive performance assessment capabilities at different operating conditions, geometries, and configurations to aid in technology development. Modeling of the CVD reactor considered the multitude of simultaneous and interdependent physicochemical processes that are entailed, including: (1) the homogeneous gas-phase pyrolysis reactions, (2) the heterogeneous deposition reactions, and (3) the transport of gaseous species in the reactor domains. A 1-D CVD reactor model was developed based on a general packed-bed, axial-dispersion plug flow reactor model with a solid substrate balance to account for carbon deposition. The model includes 59 species and 243 reactions constituting the methane pyrolysis reaction network, carbon deposition, and interconversions of oxygenate species. The reactor model was compared to brassboard test data, where it was shown to be able to capture the pertinent physicochemical phenomena as evidenced by its agreement with short-duration run data (i.e., looking at different temperature and flow rate conditions), as well as trend agreement with the brassboard reactor’s long-duration test data. Recommendations are provided on further model development steps as well as its use cases.

Air Revitalization↗

NASA NTRSDate not supplied

Effect of Aromaticity on Soot Formation: A Reactive Molecular Dynamics Study

This study investigates the formation of soot from n-dodecane and its blend with m-xylene under pyrolytic and low-oxygen conditions with reactive molecular dynamics (MD) simulations. ReaxFF force field is used to simulate the interactions of fuel and oxygen molecules at engine-relevant conditions (2500-3500 K and 70-75 bar). Fuel molecules with carbon atom density of 0.03 g/cm 3 are dispersed into a cube and constant temperature simulations are carried out with a Nosé-Hoover thermostat. Pyrolysis of n-dodecane and the chemical pathway towards the formation of aromatic hydrocarbons are investigated. The initial pyrolysis rate of n-dodecane is observed to be slightly higher with the addition of aromatic compounds and oxygen. While the first aromatics formed from the decomposed n-dodecane are phenyl radicals at 2500 K, decomposition of the aliphatic fuel compound is observed to be necessary to build a carbon cluster, and eventually soot. Morphological properties of the created soot particles are also analyzed. The maturity, size and aromatics content of the soot particle are slightly affected with the addition of m-xylene and oxygen at 3500 K within the 3 ns simulation time possibly due the formation of larger and more condensed aromatic rings, resulting in larger soot molecules. The outcomes of this study provide important insights into the formation mechanism of soot and its morphological characteristics depending on varying fuel concentrations at pyrolysis and low oxygen engine conditions. Results of this analysis will further contribute to the understanding of contrail formation on generated soot particles originated from the combustion of different chemical components with particle chemistry matching companion experiments.

soot formation↗

NASA NTRSDate not supplied

An Overview of Experiments in The Entry Systems Modeling Project

The Entry Systems Modeling (ESM) project has invested in experiments designed to enhance understanding of salient interactions between thermal protection materials (TPS) and mission-relevant planetary entry environments. An arc-jet campaign has been carried out at the Aerodynamic Heating Facility (AHF) to investigate the spallation of fiber particles as a function of gas composition and to measure the effect of pyrolysis gas flow on the in-depth temperature response of phenolic impregnated carbon ablator (PICA). Moreover, fundamental insights into the pyrolysis and oxidation mechanisms of the phenolic binding agent of FiberForm will be discussed. Finally, two new apparatus developed at NASA will be presented that were designed to interrogate phenomena associated with the production of gases and particles generated under simulated flight conditions.

Material Response↗

NASA NTRSDate not supplied

An Overview of Experiments in The Entry Systems Modeling Project

The Entry Systems Modeling (ESM) project has invested in experiments designed to enhance understanding of salient interactions between thermal protection materials (TPS) and mission-relevant planetary entry environments. An arc-jet campaign has been carried out at the Aerodynamic Heating Facility (AHF) to investigate the spallation of fiber particles as a function of gas composition and to measure the effect of pyrolysis gas flow on the in-depth temperature response of phenolic impregnated carbon ablator (PICA). Moreover, fundamental insights into the pyrolysis and oxidation mechanisms of the phenolic binding agent of FiberForm will be discussed. Finally, two new apparatus developed at NASA will be presented that were designed to interrogate phenomena associated with the production of gases and particles generated under simulated flight conditions.

Varcum↗

NASA NTRSDate not supplied

Updates to PATO’s Thermo-Mechanical Model

The solid mechanics module within the Porous material Analysis Toolbox (PATO) material response code was updated to model the stress contribution from both internal pressure and pyrolysis shrinkage as function of material’s decomposition. Incorporating these physical phenomena, alongside the previously included temperature dependent mechanical properties, thermal expansion, and aerodynamic loads, allows for a more accurate thermo-mechanical behavior modeling of Thermal Protection System (TPS) materials, which is critical to assess spallation risks during atmospheric entry. This poster outlines the workflow for obtaining the necessary PATO inputs, derived from dilatometry experiments, which are used to model the stress field in TPS materials due to thermal expansion and pyrolysis shrinkage. Furthermore, to analyze the relevance of the stress contribution from the internal pressure, a study was conducted using TACOT with different permeability values.

TPS↗

NASA NTRS1961

Thermal Decomposition of Some Linear Perfluoroalkanes in an Inconel Tube

The products of the pyrolysis reactions of perfluoropropane, perfluoroethane, and carbon tetrafluoride in an Inconel bomb are described. The values for the energy of activation and frequency factor for the first-order pyrolysis reactions are respectively: (1) 80 kcal. per mole and 2x10(exp14) sec.(exp-1) for perfluoropropane; (2) 53 kcal. per mole and 3x10(exp7) sec.(exp-1) for perfluoroethane; and (3) 96 kcal. per mole and 4x10(exp13) sec.(exp-1) for carbon tetrafluoride.

PERFLUOROALKANE↗

NASA NTRS1972

Compounds of the organogenic elements in Apollo 11 and 12 lunar samples - A review.

Investigations of low molecular weight compounds of the organogenic elements on lunar samples are reviewed. The three general techniques of vacuum pyrolysis, acid hydrolysis, and crushing have been employed by most investigators. Vacuum pyrolysis of lunar fines produce a variety of gaseous species which are either: (1) indigenous, (2) solar wind products and/or (3) chemical reaction products of mineral phases found in the lunar samples. Acid hydrolysis of lunar fines using deuterium-labeled acids yields evidence for indigenous methane and ethane. Methane and ethane found in the lunar fines are largely derived from the solar wind with only trace amounts indigenous to the samples. Crushing experiments with lunar fines and breccias produce methane, ethane, hydrogen, nitrogen, hydrogen sulfide and the rare gases.

Gibson, E. K., Jr.↗

NASA NTRS1972

Compounds of carbon and other volatile elements in Apollo 14 and 15 samples.

DF dissolution and pyrolysis showed that the indigenous methane and ethane contents in Apollo 14 and 15 lunar samples correlated with the amounts of solar wind gases and the deutero-carbon reaction gases. Pyrolysis evolved mainly CO and N2 and lower amounts of CO2. Other compounds detected and quantitated by these techniques were DCN, HCN, CS2, D2S, and PD3.

Holland, P. T.↗

NASA NTRS1974

Carbon, nitrogen and sulfur in lunar fines 15012 and 15013 - Abundances, distributions and isotopic compositions

Lunar fines 15012,16 and 15013,3 were analyzed by stepwise pyrolysis and acid hydrolysis as well as complete combustion in oxygen to determine carbon, nitrogen and sulfur. In addition, hydrogen was analysed during pyrolysis as well as during hydrolysis. By comparison of the distribution frequencies of C, N, S, H2 and Fe with He-4, considered to have arisen from solar wind contribution, it is concluded that nitrogen and hydrogen have largely a solar origin. Carbon has a significant solar contribution, and metallic iron may have resulted from solar wind interaction with ferrous minerals on the lunar surface. Sulfur probably has a predominantly lunar origin. There is no direct evidence for meteorotic contribution to these samples. Solar wind interaction also has a marked effect on the stable isotope distribution of C-13/C-12, N-15/N-14, and S-34/S-32. In all cases, the heavy isotope was most enriched in the smallest grain-size fraction.

Chang, S.↗

NASA NTRS1975

A users manual for a revised version of the Langley charring ablator program

A computer program is described that will compute the transient response of a thermal protection material to a prescribed heat input at the surface. The program has the capability of analyzing pyrolysis gas chemical kinetics in detail and treating pyrolysis reactions-in-depth. Deposition of solid products produced by chemical reactions in the gas phase is included in the analysis. An outline is given for the theory. detailed operating instructions for the computer program are included.

Stroud, C. W.↗