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JANNAF 36th Combustion Subcommittee Meeting

Volume 11, the second of three volumes is a compilation of 33 unclassified/unlimited-distribution technical papers presented at the Joint Army-Navy-NASA-Air Force (JANNAF) 36th Combustion Subcommittee held jointly with the 24 Airbreathing Propulsion Subcommittee and 18th Propulsion Systems Hazards Subcommittee. The meeting was held on 18-21 October 1999 at NASA Kennedy Space Center and The DoubleTree Oceanfront Hotel, Cocoa Beach, Florida. Topics covered include gun solid propellant ignition and combustion, Electrothermal Chemical (ETC) propulsion phenomena, liquid propellant gun combustion and barrel erosion, gas phase propellant combustion, kinetic and decomposition phenomena and liquid and hybrid propellant combustion behavior.

Fry, Ronald S.↗

Kinetics of nitric oxide formation and decomposition

Experiments on shock wave structure were conducted in the 12 inch shock tube facility, and it is shown that this work was motivated by the need for improved kinetics for the modeling of NO production in space shuttle flow fields. The experiments on shock structure involved simultaneous observations of pressure and temperature on the wall of the shock tube during reflection of normal shock waves in inert gases.

Kruger, C. H.↗

Nonequilibrium shock wave structure, 1. Kinetics of nitric oxide formation and decomposition, 2

Theoretical and numerical aspects of molecular flow simulation focussed on the development of collision models for diatomic and triatomic gases undergoing rotational excitation and energy exchange. A laser absorption technique is proposed and analyzed as sufficiently sensitive for measuring rotational populations in a nonequilibrium shock wave. Also reported is a survey of available literature on NO chemical rate data in preparation for experiments on NO decompensation kinetics in atmospheric pollution.

Kruger, C. H.↗

Kinetics and Mechanism of the CIO + CIO Reaction: Pressure and Temperature Dependences of the Bimolecular and Termolecular Channels andThermal Decomposition of Chlorine Peroxide, CIOOCI

The kinetics and mechanism of the CIO + CIO reaction and the thermal decomposition of CIOOCI were studied using the flash photolysis/long path ultraviolet absorption technique. Pressure and temperature dependences were determined for the rate coefficients for the bimolecular and termolecular reaction channels, and for the thermal decompositon of CIOOCI.

Kinetics Thermal Decomposition Biomolecul↗

Interactions of Hydrazine and Blowby Gases

The interactions between hydrazine and blowby gases from pyrovalves was explored in this research project. Investigating the decomposition chemistry of hydrazine through detailed chemical kinetic modeling is a project started last summer while participating in the Summer Faculty Fellowship program. During the 1999-2000 academic year, the chemical kinetic mechanism for hydrazine decomposition developed while a SFF at NASA's White Sands Test Facility was further revised and validated against the limited experimental data in the literature. This mechanism was then used in assessing the effects of blowby gas species on hydrazine decomposition. The combustion products introduced into the fuel line by pyrovalve actuation consist primarily of hydrogen gas. Hydrogen is also a product of the decomposition of hydrazine. Additional gaseous chemical species are introduced into the fuel, as well as metals and metal salts that deposit onto the walls of the fuel line. The deposition process is undoubtedly very rapid, and exothermic. Therefore, the major focus of this summer's work was examining the effects of hydrogen presence on hydrazine decomposition, with some representative calculations including the remaining gaseous species found to exist in blowby gases. Since hydrogen is a product of hydrazine decomposition, all reactions necessary to evaluate its effect on hydrazine decomposition chemistry were in the original mechanism developed. However, the mechanism needed to be considerably expanded to include the reactions of the other gaseous blowby species with hydrazine, all the intermediate species formed in its decomposition, and each other. The expanded mechanism consists of 70 species interacting via a network of 452 reactions. Calculations with molecular hydrogen introduced into hydrazine gas in an inert bath gas indicate that H2 presence as an initial reactant in substantial amounts can dramatically impact the decomposition process for hydrazine. The other gaseous blowby species (CO, CO2, H2O, CH4, O2, and N2) were found to have little effect compared to the inclusion of hydrogen itself as an initial reagent. This result is undoubtedly due, in part, to the fact that the blowby gas used in these calculations consisted of 94.6% H2. A more rigorous examination of the behavior of the full detailed mechanism under a variety of conditions was not performed.

Meagher, Nancy E.↗

Recovery and separation of precious metals from space

During the past year a viable procedure centered around centrifugal partition chromatography (CPC), a multistage liquid-liquid partitioning technique for the separation of precious metals (Pt, Pd, Rh, Ir, Os, Ru), was developed. Stable and inexpensive ligands that can be readily recycled to achieve the separations of the precious metals were identified. The separation methods developed so far yield three separate fractions: Pt, Pd, and Rh-Ir. The Rh-Ir pair can be separated in a subsequent run. The total amount of precious metals separated in a single experiment varied from 1 to 50 mg. The factors affecting the efficiencies of these separations were studied. The kinetics of the decomposition of the complex and the ion pair have a major bearing on these efficiencies, with slow kinetics resulting in poor efficiencies. The methods for the improvement of the efficiencies were also investigated. For example, significant improvement in the efficiencies and separation times for Pt and Pd were achieved by the use of chloride gradient in the mobile phase. Two papers were published and talks were presented on our work at the FACSS meeting in Anaheim, Oct. 1991, and at the Pittsburgh Conference in New Orleans, Mar. 1992.

Freiser, H.↗

The rate of pyrite decomposition on the surface of Venus

We report the results of a detailed experiment study of the kinetics and mechanism of pyrite (FeS2) chemical weathering under Venus surface conditions. Pyrite is thermodynamically unstable on the surface of Venus and will spontaneously decompose to pyrrhotite (Fe7S8) because the observed S2 partial pressure in the lower atmosphere of Venus is lower than the S2 vapor pressure over coexisting pyrite and pyrrhotite. Pyrite decomposition kinetics were studied in pure CO2 and CO2 gas mixtures along five isotherms in the temperature range 390-531 C. In all gas mixtures studied, pyrite thermally decomposes to pyrrhotite (Fe7S8), which on continued heating loses sulfur to form more Fe-rich pyrrhotites. During this process the pyrrhotites are also being oxidized to form magnetite (Fe3O4), which converts to maghemite (gamma-Fe2O3), and then to hematite (alpha-Fe2O3). The reaction rates for pyrite thermal decomposition to pyrrhotite were determined by measuring the weight loss. The thickness of the unreacted pyrite in the samples provided a second independent reaction rate measurement. Finally, Mossbauer spectra done on 42 of the 115 experimental samples provided a third set of independent reaction rate data. Pyrite decomposition follows zero-order kinetics and is independent of the amount of pyrite present. The rate of pyrite decomposition is apparently independent of the gas compositions used and of the CO2 number density over a range of a factor of 40. The derived activation energy of approximately 150 kJ/mole is the same in pure CO2, two different CO-CO2 mixtures, and a ternary CO-SO2-CO2 mixture. Based on data for a CO-CO2-SO2 gas mixture with a CO number density approximately 10 times higher than at the surface of Venus and a SO2 number density approximately equal to that at the surface of Venus, the rate of pyrite destruction on the surface of Venus varies from about 1225 +/- 238 days/cm at the top of Maxwell Montes (approximately 660 K) to about 233 +/- 133 days/cm in the plains of Venus (approximately 740 K). These lifetimes are very short on a geological time scale and show that pyrite cannot exist on the surface of Venus for any appreciable length of time.

Fegley, B., Jr.↗

Production and analysis of thermal decomposition products from polymeric materials

A description is presented of a strategy for analyzing the combustion process and the degradation products which are formed. One of three primary objectives in the study of polymer degradation is related to the characterization of the material to be studied and the investigation of the thermal behavior of the material. Another objective is concerned with the definition of the nature of the decomposition process by identification and quantitation of the degradation products. The third objective involves the determination of the mechanism and kinetics of the decomposition process. The methods of sample degradation include pyrolysis, oxidative degradation, flaming combustion, and the use of large-scale combustion chambers. Methods of chemical separation and identification are considered, taking into account low-boiling volatiles, high-boiling volatiles, and ancillary techniques.

Chatfield, D. A.↗

Homogeneous nucleation kinetics

Homogeneous nucleation kinetics are rederived in a manner fundamentally similar to the approach of classical nucleation theory with the following modifications and improvements. First, the cluster is a parent phase cluster and does not require energization to the parent state. Second, the thermodynamic potential used to describe phase stability is a continuous function along the pathway of phase decomposition. Third, the kinetics of clustering corresponds directly to the diffusional flux of monomers through the cluster distribution and are formally similar to classical theory with the resulting kinetic equation modified by two terms in the preexponential factor. These terms correct for the influence of a supersaturation dependent clustering within the parent phase and for the influence of an asymmetrical cluster concentration as a function of cluster size at the critical cluster size. Fourth, the supersaturation dependence of the nucleation rate is of the same form as that given by classical nucleation theory. This supersaturation dependence must however be interpreted in terms of a size dependent surface tension. Finally, there are two scaling laws which describe supersaturation to either constant nucleation rate or to the thermodynamically determined physical spinodal.

Rasmussen, D. H.↗

Viscosity Relaxation in Molten HgZnTe

Rotating cup measurements of the viscosity of the pseudo-binary melt, HgZnTe have shown that the isothermal liquid with zinc mole fraction 0.16 requires tens of hours of equilibration time before a steady viscous state can be achieved. Over this relaxation period, the viscosity at 790 C increases by a factor of two, while the viscosity at 810 C increases by 40%. Noting that the Group VI elements tend to polymerize when molten, we suggest that the viscosity of the melt is enhanced by the slow formation of Te atom chains. To explain the build-up of linear Te n-mers, we propose a scheme, which contains formation reactions with second order kinetics that increase the molecular weight, and decomposition reactions with first order kinetics that inactivate the chains. The resulting rate equations can be solved for the time dependence of each molecular weight fraction. Using these molecular weight fractions, we calculate the time dependence of the average molecular weight. Using the standard semi-empirical relation between polymer average molecular weight and viscosity, we then calculate the viscosity relaxation curve. By curve fitting, we find that the data imply that the rate constant for n-mer formation is much smaller than the rate constant for n-mer deactivation, suggesting that Te atoms only weakly polymerize in molten HgZnTe. The steady state toward which the melt relaxes occurs as the rate of formation of an n-mer becomes exactly balanced by the sum of the rate for its deactivation and the rate for its polymerization to form an (n+1)-mer.

Su, Ching-Hua↗

38th JANNAF Combustion Subcommittee Meeting

This volume, the first of two volumes, is a collection of 55 unclassified/unlimited-distribution papers which were presented at the Joint Army-Navy-NASA-Air Force (JANNAF) 38th Combustion Subcommittee (CS), 26 th Airbreathing Propulsion Subcommittee (APS), 20th Propulsion Systems Hazards Subcommittee (PSHS), and 21 Modeling and Simulation Subcommittee. The meeting was held 8-12 April 2002 at the Bayside Inn at The Sandestin Golf & Beach Resort and Eglin Air Force Base, Destin, Florida. Topics cover five major technology areas including: 1) Combustion - Propellant Combustion, Ingredient Kinetics, Metal Combustion, Decomposition Processes and Material Characterization, Rocket Motor Combustion, and Liquid & Hybrid Combustion; 2) Liquid Rocket Engines - Low Cost Hydrocarbon Liquid Rocket Engines, Liquid Propulsion Turbines, Liquid Propulsion Pumps, and Staged Combustion Injector Technology; 3) Modeling & Simulation - Development of Multi- Disciplinary RBCC Modeling, Gun Modeling, and Computational Modeling for Liquid Propellant Combustion; 4) Guns Gun Propelling Charge Design, and ETC Gun Propulsion; and 5) Airbreathing - Scramjet an Ramjet- S&T Program Overviews.

Fry, Ronald S.↗

CuInS2 Films Deposited by Aerosol-Assisted Chemical Vapor Deposition Using Ternary Single-Source Precursors

Polycrystalline CuInS2 films were deposited by aerosol-assisted chemical vapor deposition using both solid and liquid ternary single-source precursors (SSPs) which were prepared in-house. Films with either (112) or (204/220) preferred orientation, had a chalcopyrite structure, and (112)-oriented films contained more copper than (204/220)-oriented films. The preferred orientation of the film is likely related to the decomposition and reaction kinetics associated with the molecular structure of the precursors at the substrate. Interestingly, the (204/220)-oriented films were always In-rich and were accompanied by a secondary phase. From the results of post-growth annealing, etching experiments, and Raman spectroscopic data, the secondary phase was identified as an In-rich compound. On the contrary, (112)-oriented films were always obtained with a minimal amount of the secondary phase, and had a maximum grain size of about 0.5 micron. Electrical and optical properties of all the films grown were characterized. They all showed p-type conduction with an electrical resistivity between 0.1 and 30 Omega-cm, and an optical band gap of approximately 1.46 eV +/- 0.02, as deposited. The material properties of deposited films revealed this methodology of using SSPs for fabricating chalcopyrite-based solar cells to be highly promising.

Jin, Michael↗

CuInS2 Films Deposited by Aerosol-Assisted Chemical Vapor Deposition Using Ternary Single-Source Precursors

Polycrystalline CuInS2 films were deposited by aerosol-assisted chemical vapor deposition using both solid and liquid ternary single-source precursors (SSPs) prepared in-house. Films with either (112) or (204/220) preferred orientation were obtained, and compositional analysis showed that (112)-oriented films contained more copper than (204/220)-oriented films. Using X-ray diffraction, the signature of chalcopyrite structure was often confirmed for (112)-oriented films. The preferred orientation of the film is likely related to the decomposition and reaction kinetics associated with the molecular structure of the precursors at the substrate. Interestingly, the (204/220)-oriented films were always accompanied by a secondary phase, which was identified as an unknown In-rich compound from the results of post-growth annealing, etching experiments, and Raman spectroscopic data. By increasing Cu to In ratio in the film, (112)-oriented films were obtained with a maximum grain size of about 0.5 micrometers, and their X-ray diffractions did not show any observable signature of the In secondary phase. Electrical and optical properties of all the films grown were characterized. They all showed p-type conduction with an electrical resistivity between 0.1 omega cm and 30 omega cm, and an optical band gap of 1.46eV +/- 0.02, as deposited. The material properties of deposited films revealed this methodology of using SSPs for fabricating chalcopyrite-based solar cells to be highly promising.

Jin, Michael H.-C.↗

Critical analysis of nitramine decomposition data: Activation energies and frequency factors for HMX and RDX decomposition

A summary of a literature review on thermal decomposition of HMX and RDX is presented. The decomposition apparently fits first order kinetics. Recommended values for Arrhenius parameters for HMX and RDX decomposition in the gaseous and liquid phases and for decomposition of RDX in solution in TNT are given. The apparent importance of autocatalysis is pointed out, as are some possible complications that may be encountered in interpreting extending or extrapolating kinetic data for these compounds from measurements carried out below their melting points to the higher temperatures and pressure characteristic of combustion.

Schroeder, M. A.↗

Factors influencing organic carbon preservation in marine sediments

The organic matter that escapes decomposition is buried and preserved in marine sediments, with much debate as to whether the amount depends on bottom-water O2 concentration. One group argues that decomposition is more efficient with O2, and hence, organic carbon will be preferentially oxidized in its presence, and preserved in its absence. Another group argues that the kinetics of organic matter decomposition are similar in the presence and absence of O2, and there should be no influence of O2 on preservation. A compilation of carbon preservation shows that both groups are right, depending on the circumstances of deposition. At high rates of deposition, such as near continental margins, little difference in preservation is found with varying bottom-water O2. It is important that most carbon in these sediments decomposes by anaerobic pathways regardless of bottom-water O2. Hence, little influence of bottom-water O2 on preservation would, in fact, be expected. As sedimentation rate drops, sediments deposited under oxygenated bottom water become progressively more aerobic, while euxinic sediments remain anaerobic. Under these circumstances, the relative efficiencies of aerobic and anaerobic decomposition could affect preservation. Indeed, enhanced preservation is observed in low-O2 and euxinic environments. To explore in detail the factors contributing to this enhanced carbon preservation, aspects of the biochemistries of the aerobic and anaerobic process are reviewed. Other potential influences on preservation are also explored. Finally, a new model for organic carbon decomposition, the "pseudo-G" model, is developed. This model couples the degradation of refractory organic matter to the overall metabolic activity of the sediment, and has consequences for carbon preservation due to the mixing together of labile and refractory organic matter by bioturbation.

Non-NASA Center↗