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NASA NTRS1994

Formation and chemical reactivity of carbon fibers prepared by defluorination of graphite fluoride

Defluorination of graphite fluoride (CFX) by heating to temperatures of 250 to 450 C in chemically reactive environments was studied. This is a new and possibly inexpensive process to produce new carbon-based materials. For example, CF 0.68 fibers, made from P-100 carbon fibers, can be defluorinated in BrH2C-CH = CH-CH2Br (1,4-dibromo-2butene) heated to 370 C, and graphitized to produce fibers with an unusually high modulus and a graphite layer structure that is healed and cross-linked. Conversely, a sulfur-doped, visibly soft carbon fiber was produced by defluorinating CF 0.9 fibers, made from P-25, in sulfur (S) vapor at 370 C and then heating to 660 C in nitrogen (N2). Furthermore, defluorination of the CF 0.68 fibers in bromine (Br2) produced fragile, structurally damaged carbon fibers. Heating these fragile fibers to 1100 C in N2 caused further structural damage, whereas heating to 150 C in bromoform (CHBr3) and then to 1100 C in N2 healed the structural defects. The defluorination product of CFX, tentatively called activated graphite, has the composition and molecular structure of graphite, but is chemically more reactive. Activated graphite is a scavenger of manganese (Mn), and can be intercalated with magnesium (Mg). Also, it can easily collect large amounts of an alloy made from copper (Cu) and type 304 stainless steel to form a composite. Finally, there are indications that activated graphite can wet metals or ceramics, thereby forming stronger composites with them than the pristine carbon fibers can form.

Hung, Ching-Cheh↗
NASA NTRS1994

The temperature of nitrogen on Pluto

With Hapke scattering theory and absorption coefficients derived from our laboratory measurements of solid N2 we have modeled the spectrum of Triton. By comparing a Hapke scattering model to the measured spectrum from Triton, we determined the temperature of the N2 on the satellite's surface to be 38 (+2, -1) K which is in accord with the measurements of Voyager 2. Applying this technique to Pluto we find that the temperature of N2 on that body is 40 +/- 2 K. Other aspects of this investigation are discussed.

Tryka, K. A.↗
NASA NTRS1993

Reevaluation of the O(+)(2P) reaction rate coefficients derived from Atmosphere Explorer C observations

O(+)(2P) is an important species for studies of the ionosphere and thermosphere: its emission at 7320 A can be used as a diagnostic of the thermospheric atomic oxygen density. Unfortunately, there are no laboratory measurements of the O and N2 reaction rates which are needed to determine the major sinks of (O+)(2p). We have recalculated the O and N2 reaction rates for O(+) (2P) using recent improvements in the solar EUV flux, cross sections, and photoelectron fluxes. For the standard solar EUV flux, the new N2 reaction rate of 3.4 +/- 1.5 x 10 exp -10 cu cm/s is close to the value obtained by Rusch et al. (1977), but the new O reaction rate of 4.0 +/- 1.9 x 10 exp -10 cu cm/sec is about 8 times larger. These new reaction rates are derived using neutral densities, electron density, and solar EUV fluxes measured by Atmosphere Explorer C in 1974 during solar minimum. The new theoretical emission rates are in good agreement with the data for the two orbits studied by Rusch et al.

Chang, T.↗
NASA NTRS1993

Wave-like perturbations observed at low altitudes by the Pioneer Venus Orbiter Neutral Mass Spectrometer during orbiter entry

Wave-like perturbations have been observed in the nightside neutral density data acquired for He, N, O, N2 and CO2 by the Pioneer Venus Orbiter Neutral Mass Spectrometer (ONMS) during entry in late 1992. The data cover an altitude range of 133-200 km from 0.5-4.5 hours local solar time and occur at medium solar activity (F(sub 10.7) = 120). The perturbations, with an effective wavelength along the orbit of about 100 to 600 km, have similar amplitudes for the various species and helium is out of phase with respect to the heavier mass species. The measurements are comparable to those observed in 1978-80 at solar maximum activity (F(sub 10.7) = 200) above 145 km. Between 133 and 160 km the rms amplitudes grow with altitude at a rate of about (1.6, 2.1, 2.7, 4.4) x 10(exp 3)/km for N, O, N2, and CO2, respectively. The average rms amplitudes above 145 km of 0.08 for N and O and 0.1 for N2 are comparable in magnitude to those observed in the earlier 1978-80 data of 0.06, 0.08, and 0.095 respectively. CO2 is an exception for which the entry value is 0.17 compared to 0.09 earlier. By combining the two overlapping data sets there is a suggestion that the CO2 amplitudes grow in value with altitude up to about 140-170 km and then decrease in amplitude. Like the earlier data, the entry data are consistent with the interpretation that the neutral density perturbations are due to gravity waves propagating upward from the lower thermosphere.

Kasprzak, W. T.↗
NASA NTRS1994

Middle- and low-latitude emissions from energetic neutral atom precipitation seen from ATLAS 1 under quiet magnetic conditions

During the ATLAS 1 mission spectral observations were made at middle and low latitudes of features expected from the precipitation of energetic neutral atoms. The Imaging Spectrometric Observatory was used at night in the UV and visible with maximum gain. The tangent ray heights of the look directions ranged from near 100 km to near 200 km, and the geomagnetic conditions were quiet during the observations, which were made March 28 to April 3, 1992. The N2(+) 1N 391.4-nm and O I 130.4 and 135.6-nm emissions were observed at all latitudes, with lower emission rates at lower magnetic dip latitudes, except that enhancements in the O I lines were seen within 30 deg of the dip equator to radiative recombination of ionospheric plasma. The latitude profile observed for the N2(+) 1N emission did not show an equatorial or midlatitude peak. This implies that the source of energetic neutrals is more consistent with prompt charge exchange loss of freshly injected trapped ions with relatively low mirror heights (i.e., ions on higher L shells with equatorial pitch angle distributions nearly isotropic to the loss cone) than loss of highly eroded populations of particles with high mirror heights (i.e., ions on lower L shells with pancake equatorial pitch angle distributions). The N2(+) 1N emission rates have been compared with models of atmospheric emission due to fluxes of O/O(+) and H/H(+) in the thermosphere, as produced by energetic neutral oxygen or hydrogen atom precipitation. Energy deposition rates are inferred.

Tinsley, B. A.↗
NASA NTRS1994

Electron transport and energy degradation in the ionosphere: Evaluation of the numerical solution, comparison with laboratory experiments and auroral observations

Auroral electron transport calculations are a critical part of auroral models. We evaluate a numerical solution to the transport and energy degradation problem. The numerical solution is verified by reproducing simplified problems to which analytic solutions exist, internal self-consistency tests, comparison with laboratory experiments of electron beams penetrating a collision chamber, and by comparison with auroral observations, particularly the emission ratio of the N2 second positive to N2(+) first negative emissions. Our numerical solutions agree with range measurements in collision chambers. The calculated N(2)2P to N2(+)1N emission ratio is independent of the spectral characteristics of the incident electrons, and agrees with the value observed in aurora. Using different sets of energy loss cross sections and different functions to describe the energy distribution of secondary electrons that emerge from ionization collisions, we discuss the uncertainties of the solutions to the electron transport equation resulting from the uncertainties of these input parameters.

Lummerzheim, D.↗
NASA NTRS1995

Sensitivity of the 6300 A twilight airglow to neutral composition

The field line interhemispheric plasma (FLIP) model is used to study the 6300 A line intensity measured during three morning twilights from the McDonald Observatory in Texas. The Imaging Spectrometric Observatory (ISO) measured the 6300 A intensity during the winter of 1987 and the spring and summer of 1988. The FLIP model reproduces the measured intensity and its variation through the twilight well on each day using neutral densities from the MSIS-86 empirical model. This is in spite of the fact that different component sources dominate the integrated volume emission rate on each of the days analyzed. The sensitivity of the intensity to neutral composition is computed by varying the N2, O2, and O densities in the FLIP model and comparing to the intensity computed with the unmodified MSIS-86 densities. The ion densities change self-consistently. Thus the change in neutral composition also changes the electron density. The F2 peak height is unchanged in the model runs for a given day. The intensity changes near 100 deg SZA are comparable to within 10% when either (O2), (N2), or (O) is changed, regardless of which component source is dominant. There is strong sensitivity to changes in (N2) when dissociative recombination is dominant, virtually no change in the nighttime (SZA greater than or equal to 108 deg) intensity with (O2) doubled, and sensitivity of over 50% to doubling or halving (O) at night. When excitation by conjugate photoelectrons is the dominant nighttime component source, the relative intensity change with (O) doubled or halved is very small. This study shows the strong need for simultaneous measurements of electron density and of emissions proportional to photoelectron fluxes if the 6300 A twilight airglow is to be used to retrieve neutral densities.

Melendez-Alvira, D. J.↗
NASA NTRS1995

Thermal Stability of Hi-Nicalon SiC Fiber in Nitrogen and Silicon Environments

The room temperature tensile strength of uncoated and two types of pyrolytic boron nitride coated (PBN and Si-rich PBN) Hi-Nicalon SiC fibers was determined after 1 to 400 hr heat treatments to 1800 C under N2 pressures of 0.1, 2, and 4 MPa, and under 0.1 Mpa argon and vacuum environments. In addition, strength stability of both uncoated and coated fibers embedded in silicon powder and exposed to 0.1 MPa N2 for 24 hrs at temperatures to 1400 C was investigated. The uncoated and both types of BN coated fibers exposed to N2 for 1 hr showed noticeable strength degradation above 1400 C and 1600 C, respectively. The strength degradation appeared independent of nitrogen pressure, time of heat treatment, and surface coatings. TEM microstructural analysis suggests that flaws created due to SiC grain growth are responsible for the strength degradation. In contact with silicon powder, the uncoated and both types of PBN coated fibers degrade rapidly above 1350 C.

Bhatt, R. T.↗
NASA NTRS1995

High Modulus and High T(sub g) Thermally Stable Polymers from p-Ethynyl-Terminated Rigid-Rod Monomers

Novel p-ethynyl-substituted rigid rod monomers were studied by pressure Differential Scanning Calorimetry (DSC), ThermoGravimetric Analysis (TGA), IsothermoGravimetric Analysis (IGA), and TGA-IR. These monomers, 4,4'-bis(((4-ethynylphenyl)carbonyl)oxy)biphenyl, designated 1, 1,5-bis-(((4-ethynylphenyl)carbonyl)oxy)naphthalene, designated 2, and bis(4-ethynylphenyl)pyromellitimide, designated 3, were polymerized in the solid state. Thermal polymerization in N2 or air produced highly cross-linked resins with polymerization exotherms centered between 212 and 276 C. The (delta)H's of polymerization of these resins in air were found to be double those in N2. When monomers 1 and 2 were heated in air from 23 to 750 C at 10 C/min, the main decomposition product was carbon dioxide, evolving at a maximum rate between 500 and 600 C; water was also detected as a decomposition product. Void-free neat resin moldings, designated lp to 3p, were made by compression molding the monomers and then heating them. The resulting polymers were highly cross-linked, and their glass transition temperatures (T(sub g)) were much higher than their polymerization temperatures. Using ThermoMechanical Analysis (TMA), we found that polymers lp to 3p had T(sub g)'s of 422, 329, and 380 C, respectively. The thermal and thermooxidative stabilities improved when lp to 3p were postcured in N2 (the postcured polymers were designated 1pp to 3pp). The Linear Thermal Expansions (LTE) for lp and 3p were 1% between 23 and 420 C. Using rheological analysis, we could not clearly detect the T(sub g)'s of lp to 3p because their moduli dropped only slightly between 23 and 490 C and the changes in tan beta were very low. Because of high cross-link density, their moduli changed little as the resins went from a glassy to a rubbery state. Their shear storage moduli in air ranged from 0.82 (3p, 3pp) to 1.6 GPa (lpp) at 23 C, from 0.16 (2p) to 0.7GPa(lpp) at 380 C, and from 0.18(lpp)to 0.6GPa(2p) at 490 C. Finally, these novel-p-ethynyl polymers exhibited an excellent combination of high T(sub g), low LTE, and high thermooxidative stability. Most notably, 3pp lost only 3% of its initial weight when it was aged for 500 h at 288 C in air.

Melissaris, Anastasios P.↗
NASA NTRS1996

Products of Dissociative Recombination in the Ionosphere

SRI International undertook a novel experimental measurement of the product states formed by dissociative recombination (DR) of O2(+), NO(+), and N2(+) as a function of both electron energy and reactant ion vibrational level. For these measurements we used a recently developed experimental technique for measuring dissociation product distributions that allows both the branching ratios to be accurately determined and the electronic and rovibrational state composition of the reactant ions to be specified. DR is the dominant electron loss mechanism in all regions of the ionosphere. In this process, electron attachment to the molecular ion produces an unstable neutral molecule that rapidly dissociates. For a molecular ion such as O2(+), the dissociation recombination reaction is (1) O2(+) + e yields O + O + W. The atomic products of this reaction, in this case two oxygen atoms, can be produced in a variety of excited states and with a variety of kinetic energies, as represented by W in Eq. (1). These atoms are not only active in the neutral chemistry of the ionosphere, but are also especially important because their optical emissions are often used to infer in situ concentrations of the parent molecular ion and ambient electron densities. Many laboratory measurements have been made of DR reaction rates under a wide range of electron temperatures, but very little is known about the actual distributions among the final states of the atomic products. This lack of knowledge seriously limits the validity and effectiveness of efforts to model both natural and man-made ionospheric disturbances. Bates recently identified major deficiencies in the currently accepted branching ratios for O2(+) as they relate to blue and green line emission measurements in the nocturnal F-region. During our two-year effort, we partially satisfied our ambitious goals. We constructed and operated a variable pressure, electron-impact ion source and a high pressure, hollow-cathode discharge ion source for O2(+), NO(+), and N2(+) beams. Translational spectroscopy of the products of dissociative charge transfer in Cs vapor was used to accurately assay the composition of the O2(+) and NO(+) beams and to develop a methodology for the vibrationally controlled preparation of the ground state ion beams. Attempts to assay the N2(+) beam revealed a novel two-electron process in the charge transfer reactions. A coaxial electron gun for the DR measurements was constructed following an extensive numerical design of the fields. Tests of the gun, however, found substantial perturbations of the magnetic fields by the soft iron (CMI-C) assembly containing the Langmuir probe that locates the electron beam. Hydrogen annealing of the iron failed to eliminate the field perturbations, necessitating the removal of the probe assembly. During this work on the coaxial electron gun, we discovered that predissociated high Rydberg states of O2 could be produced by subjecting the molecules to a sudden perturbation by an electromagnetic field. This technique allowed a measurement of the product branching to the atomic limits for the lowest seven vibrational levels of O2(+).

Cosby, Philip↗
NASA NTRS1997

Kinetics and Thermochemistry of the Br((sup 2)P3/2) + NO2 Association Reaction

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the Br((sup 2)P3/2) + NO2 association reaction as a function of temperature (259-432 K) pressure (12.5 - 700 Torr), and buffer gas identity (He, Ar, H2, N2, CO2, CF4, SF6). The reaction is found to be in the falloff regime between third and second order over the entire range of conditions investigated. At temperatures below 350 K, the association reaction is found to be irreversible on the time scale of the experiment (approximately 30 ms). At higher temperatures reversible addition is observed, allowing equilibrium constants for BrNO2 formation and dissociation to be determined. Second- and third-law analyses of the equilibrium data are in only fair agreement and lead to the following thermochemical parameters for the association reaction: Delta-H(298) = 19.6 +/- 1.7 kcal/mol, Delta-H(0) = -18.6 +/- 2.0 kcal/mol, Delta-S(298) = 29.3 +/- 4.2 cal/mol/K, Delta-H(sub f)(sub 298)(BrNO2) = 17.0 +/-1.8 kcal/mol(uncertainties are 2 sigma estimates of absolute accuracy). The value for Delta-H(0) determined in this study has been employed to calculate k(sub 0)(sup SC), the low-pressure third-order rate coefficient in the strong collision limit, by using the method of Troe; calculated values of k(sub 0)(sup SC) are inconsistent with experimental results unless Delta-H(0) is assigned a value near the lower limit derived from analysis of the high-temperature approach to equilibrium data, i.e. delta-H(0) approximately equals -16.6 kcal/mol. A potential source of systematic error in the calculation of both k(sub 0)(sup SC) and the absolute entropy of BrNO2 results from the complete lack of knowledge of the energies and degeneracies of the electronic states of BrNO3. The procedure developed by Troe and co-workers has been employed to extrapolate experimental falloff curves to the low- and high-pressure limits. Derived values for k(sub 0)(M,298K) in units of 10(exp -31) cm(exp 6)/sq molecule/s range from 2.75 for M = He to 6.54 for M = CO2; 2 sigma uncertainties are estimated to be +/- 20%. Values for k(sub 0)(N2,T) in units of 10(exp -31) cm(exp 6)/sq molecule/s are 5.73 at 259 K, 4.61 at 298 K, and 3.21 at 346 K; the observed temperature dependence for k(sub 0)(N2,T) is consistent with the theoretical temperature dependence for Beta(sub c)k(sub 0)(sup SC). Values for k(sub infinity)(T) in units of 10(exp -11) cu cm/molecule/s are 2.86 at 259 K, 3.22 at 298 K, and 3.73 at 346 K; 2 sigma uncertainties are estimated to be a factor of 2. Approximate falloff parameters in a convenient format for atmospheric modeling are also derived.

Kreutter, K. D.↗
NASA NTRS1998

Evaluation of Relative Sensitivity of SAW and Flexural Plate Wave Devices for Atmospheric Sensing

The objective of this project is to evaluate the suitability of the ultrasonic flexural plate wave (FPW) device as the detector in a gas chromatograph (GC). Of particular interest is the detection of nitrous oxide (N2O). From experimental results we conclude analyte detection is achieved through two mechanisms: changes in gas density, and mass loading of the device membrane due to the sorption of gas molecules. Reducing the dead volume of the FPW chamber increased the FPW response. A comparison of the FPW response to that of the surface acoustic wave (SAW) detector provided with the GC (made by MSI, Microsensor Technologies, Inc.), shows that for unseparated N2O in N2, the FPW exhibits a sensitivity that is at least 550 times greater than that of the SAW device. A Porapak Q column was found to separate N2O from its carrier gas, N2 or He. With the Porapak Q column, a coated FPW detected 1 ppm N2O in N2 or He, with a response magnitude of 7 Hz. A coated SAW exhibited a response of 25 Hz to pure N2O. The minimal detectable N2O concentrations of the sensors were not evaluated.

White, Richard M.↗
NASA NTRS1995

Photochemistry of Triton's Atmosphere and Ionosphere

The photochemistry of 32 neutral and 21 ion species in Triton's atmosphere is considered. Parent species N2, CH4, and CO (with a mixing ratio of 3 x 10(exp -4) in our basic model) sublime from the ice with rates of 40, 208, and 0.3 g/sq cm/b.y., respectively. Chemistry below 50 km is driven mostly by photolysis of methane by the solar and interstellar medium Lyman-alpha photons, producing hydrocarbons C2H4, C2H6, and C2H2 which form haze particles with precipitation rates of 135, 28, and 1.3 g/sq cm/b.y., respectively. Some processes are discussed which increase the production of HCN (by an order of magnitude to a value of 29 g/sq cm/b.y.) and involve indirect photolysis of N2 by neutrals. Reanalysis of the measured methane profiles gives an eddy diffusion coefficient K = 4 x 10(exp 3)sq cm/s above the tropopause and a more accurate methane number density near the surface, (3.1 +/- 0.8)x IO(exp 11)/cu cm. Chemistry above 200 km is driven by the solar EUV radiation (lambda less than 1000 A) and by precipitation of magnetospheric electrons with a total energy input of 10(exp 8) W (based on thermal balance calculations). The most abundant photochemical species are N, H2, H, 0, and C. They escape with the total rates of 7.7 x 10(exp 24)/ s, 4.5 x 10(exp 25)/s, 2.4 x 10(exp 25)/s, 4.4 x 10(exp 22)/s, and 1.1 x 10(exp 24), respectively. Atomic species are transported to a region of 50-200 km and drive the chemistry there. Ionospheric chemistry explains the formation of an E region at 150-240 km with HCO(+) as a major ion, and of an F region above 240 km with a peak at 320 km and C(+) as a major ion. The ionosphere above 500 km consists of almost equal densities of C(+) and N(+) ions. The model profiles agree with the measured atomic nitrogen and electron density profiles. A number of other models with varying rate coefficients of some reactions, differing properties of the haze particles (chemically passive or active), etc., were developed. These models show that there are four basic unknown values which have strong impacts on the composition and structure of the atmosphere and ionosphere. These values and their plausible ranges are the CO mixing ratio f(sub co) = 10(exp -4) - 10(exp -3), the magnetospheric electron energy input (1 +/- 0.5) x 10(exp 8) W, the rate coefficient of charge-exchange reaction N2(+) + C(kappa) = 10(exp -11) - 10(exp -10)cu cm/s, and the ion escape velocity upsilon(sub i) approx. equals 150 cm/s.

Krasnopolsky, Vladimir A.↗
NASA NTRS1995

Photochemistry of Triton's Atmosphere and Ionosphere

The photochemistry of 32 neutral and 21 ion species in Triton's atmosphere is considered. Parent species N2, CH4, and CO (with a mixing ratio of 3 x 10(exp -4) in our basic model) sublime from the ice with rates of 40, 208, and 0.3 g/sq cm/b.y., respectively. Chemistry below 50 km is driven mostly by photolysis of methane by the solar and interstellar medium Lyman-alpha photons, producing hydrocarbons C2H4, C2H6, and C2H2 which form haze particles with precipitation rates of 135, 28, and 1.3 g/sq cm/b.y., respectively. Some processes are discussed which increase the production of HCN (by an order of magnitude to a value of 29 g/sq cm/b.y.) and involve indirect photolysis of N2 by neutrals. Reanalysis of the measured methane profiles gives an eddy diffusion coefficient K = 4 x 10(exp 3) sq cm/s above the tropopause and a more accurate methane number density near the surface, (3.1 +/- 0.8) x 10(exp 11)/cc cm. Chemistry above 200 km is driven by the solar EUV radiation (lambda less than 1000 A)) and by precipitation of magnetospheric electrons with a total energy input of 10(exp 8) W (based on thermal balance calculations). The most abundant photochemical species are N, H2, H, O, and C. They escape with the total rates of 7.7 x 10(exp 24)/ s, 4.5 x 10(exp 25)/ s, 2.4 x 10(exp 25)/ s, 4.4 x 10(exp 22)/ s, and 1.1 x 10(exp 24)/ s, respectively. Atomic species are transported to a region of 50-200 km and drive the chemistry there. Iono- spheric chemistry explains the formation of an E region at 150-240 km with HCO(+) as a major ion, and of an F region above 240 km with a peak at 320 km and C(+) as a major ion. The ionosphere above 500 km consists of almost equal densities of C(+) and N(+) ions. The model profiles agree with the measured atomic nitrogen and electron density profiles. A number of other models with varying rate coefficients of some reactions, differing properties of the haze particles (chemically passive or active), etc., were developed. These models show that there are four basic unknown values which have strong impacts on the composition and structure of the atmosphere and ionosphere. These values and their plausible ranges are the CO mixing ratio f(sub co) = 10(exp -4)- 10(exp -3), the magnetospheric electron energy input (1 +/- 0.5) x 10(exp 8) W, the rate coefficient of charge-exchange reaction N2(+) + Ck = 10(exp -11)-10(exp -10)cc cm/s, and the ion escape velocity upselon(sub i) approx. 150 cm/s.

Krasnopolsky, Vladimir A.↗
NASA NTRS1960

The Interactions Between Nitrogen and Oxygen Molecules

Lippincott's delta-function model for atomic interactions is analyzed, both physically and mathematically, and extended, by differentiation between K- and L-shell electrons and the introduction of a variable parameter in the expression for the delta-function strength, to cover homonuclear molecules more complex than hydrogen. In addition, modifications are made which allow treatments of diatomic, heteronuclear molecules. This theory, in conjunction with a reasonably extensive study of resonance, dispersion, and configuration interaction phenomena, as well as the use of simple quantum mechanical arguments, is then applied to the N2-N2, N2-O2, and O2-O2 interactions.

Meador, Willard E., Jr.↗
NASA NTRS1993

Wave-Like Perturbations Observed at Low Altitudes by the Pioneer Venus Orbiter Neutral Mass Spectrometer During Orbiter Entry

Wave-like perturbations have been observed in the nightside neutral density data acquired for He, N, O, N2 and CO2 by the Pioneer Venus Orbiter Neutral Mass Spectrometer (ONMS) during entry in late 1992. The data cover an altitude range of 133-200 km from 0.5-4.5 hours local solar time and occur at medium solar activity (F(sub 10.7) = 120) The perturbations, with an effective wavelength along the orbit of about 100 to 600 km, have similar amplitudes for the various species and helium is out of phase with respect to the heavier mass species. The measurements are comparable to those observed in 1978-80 at solar maximum activity (F(sub 10.7) = 200) above 145 km. Between 133 and 160 km the rms amplitudes grow with altitude at a rate of about (1.6, 2.1, 2.7, 4.4) x 10(exp -3)/ km for N, O, N2, and CO2 respectively. The average rms amplitudes above 145 km of 0.08 for N and O and 0.1 for N2 are comparable in magnitude to those observed in the earlier 1978-80 data of 0.06, 0.08 and 0.095 respectively. CO2 is an exception for which the entry value is 0.17 compared to 0.09 earlier. By combining the two overlapping data sets there is a suggestion that the CO2 amplitudes grow in value with altitude up to about 140-170 km and then decrease in amplitude. Like the earlier data, the entry data are consistent with the interpretation that the neutral density perturbations are due to gravity waves propagating upward from the lower thermosphere. Earlier data sampled a higher altitude region where dissipation is important in limiting and ultimately reversing the growth of gravity waves while the lower altitude entry data probed the region where growth of these waves can be observed.

Kasprzak, W. T.↗
NASA NTRS1997

Study of the solid-phase thermal decomposition of NTO using Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry (STMBMS)

The solid phase thermal reaction chemistry of NTO between 190 and 250 C is presently being evaluated by utilizing STMBMS, a technique that enables the authors to measure the vapor pressure of NTO and to explore the reaction mechanisms and chemical kinetics associated with the NTO thermal decomposition process. The vapor pressure of NTO is expressed as Log(sub 10) p(torr) = 12.5137 + 6,296.553(1/t(k)) and the Delta-H(sub subl) = 28.71 +/- 0.07 kcal/mol (120.01 +/- 0.29 kJ/mol). The pyrolysis of NTO results in the formation of gaseous products and a condensed-phase residue. The identity of the major gaseous products and their origin from within the NTO molecules are determined based on the results from pyrolysis of NTO, NTO-3-C-13, NTO-1,2- (15)N2 and NTO-(2)H2. Identification of the products show the major gaseous products to be N2, CO2, NO, HNCO, H2O and some N2O, CO, HCN and NH3. The N2 is mostly derived from the N-1 and N-2 positions with some being from the N-4 and N-1 or N-2 positions. The CO2 is derived from both carbons in the NTO molecule in comparable amounts. The residue has an elemental formula of C(2.1)H(.26)N(2.9)O and FTIR analysis suggests that the residue is polyurea- and polycarbamate- like in nature. The temporal behaviors of the rates of formation of the gaseous products indicate that the overall thermal decomposition of NTO in the temperature range evaluated involves four major processes: (1) NTO sublimation; (2) an apparent solid-solid phase transition between 190 and 195 C; (3) a decomposition regime induced by the presence of exogenous H2O at the onset of decomposition; and (4) a decomposition regime that occurs at the onset of decomposition and continues until the depletion of NTO. Decomposition pathways that are consistent with the data are presented.

Minier, L.↗
NASA NTRS1997

Cratering on Titan: A Pre-Cassini Perspective

The NASA-ESA Cassini mission, comprising a formidably instrumented orbiter and parachute-borne probe to be launched this October, promises to reveal a crater population on Titan that has been heretofore hidden by atmospheric haze. This population on the largest remaining unexplored surface in the solar system will be invaluable in comparative planetological studies, since it introduces evidence of the atmospheric effects of cratering on an icy satellite. Here, I highlight some impact features we may hope to find and could devote some modeling effort toward. Titan in a Nutshell: Radius= 2575 km. Density= 1880 kg/cubic m consistent with rock-ice composition. Surface pressure = 1.5 bar. Surface gravity = 1.35 m/square s Atmosphere -94% N2 6% CH, Surface temperature = 94K Tropopause temperature = 70K at 40 km alt. Probable liquid hydrocarbon deposits exist on or near the surface.Titan in a Nutshell: Radius= 2575 km. Density= 1880 kg/cubic m consistent with rock-ice composition. Surface pressure = 1.5 bar. Surface gravity = 1.35 m/square s; Atmosphere about 94% N2 6% CH, Surface temperature = 94K Tropopause temperature = 70K at 40 km alt. Probable liquid hydrocarbon deposits exist on or near the surface. Titan is comparable to Callisto and Ganymede for strength/gravity, Mars/Earth/Venus for atmospheric interaction, and Hyperion, Rhea, and Iapetus for impactor distribution. The leading/trailing asymmetry of crater density from heliocentric impactors is expected to be about 5-6, in the absence of resurfacing. Any Saturnocentric impactor population is likely to alter this. In particular the impact disruption of Hyperion is noted; because of the 3:4 orbital resonance with Titan, fragments from the proto-Hyperion breakup would have rapidly accreted onto Titan. Titan's resurfacing history is of course unknown. The disruption of impactors into fragments that individually create small craters is expected to occur. A crude estimate suggests a maximum separation of about 2 km (compared with 4 km on Venus, or 0.5 km on Earth). Crater chains are unlikely on Titan, since impactors must pass close enough to Saturn to be tidally disrupted; as a result, they would suffer aerodynamic disruption. Crater counting on adjacent satellites gives densities of about 200 per 10 (exp 6) square km for 20-km-diameter craters. However, the presence of a thick atmosphere leads to atmospheric shielding, depleting the relative abundance of small craters. This has been evaluated by models, and the relative abundance of small craters may be due to a diagnostic atmospheric collapse. A number of radar-dark "splotches" have been detected on Venus; these have been attributed to the interaction of the surface with the atmospheric shockwave produced by the Tunguska-like explosion of a bolide in the atmosphere. Simple analogy suggests that similar features might occur on Titan, but the shocked mass density (which controls the momentum coupling between the surface and the shockwave) of Titan's cold N2 atmosphere is about 20x smaller than that of Venus's hot CO2 atmosphere. Unless ice is much more easily turned to rubble than is rock, such features seem less probable on Titan. When the energy deposited by an impact forms a fireball with an equilibrate greater than one scale height, the fireball expands upward and can distribute ejecta. on ballistic exoatmospheric trajectories. On Venus this process is believed to be responsible for the parabolic features; the interaction of various-sized particles falling through the atmosphere with the zonal wind field winnows the particles to form a parabolic deposit. Although such a process is possible on Titan, the large scale height at higher altitudes would make it more difficult. Comparison with craters on other icy satellites suggests that craters on Titan will be fairly shallow (depth/diameter about 0.1) and craters greater than 10 km in diameter will have central peaks or domed bases, perhaps with central pits. The formation of ejecta. blankets may involve the atmosphere in a significant way, both by restraining the expansion of the ejecta cloud and by influencing the thermal history of the ejecta. Compared with Venus, Titan's atmosphere will chill an impact melt somewhat quickly, so the long ejecta flows seen on Venus seem less likely, detailed modeling needs to be performed to determine the impact melt production. Crater topography on Titan may be highlighted by the influence of liquids forming crater lakes. Craters with central peaks will typically form ring-shaped lakes, although horseshoe-shaped takes may be common; domed craters with central pits may even form bullseye lakes with islands with central ponds. If liquids have covered a substantial part of Titan's surface for a substantial period, hydroblemes and tsunami deposits may be common.

Lorenz, R. D.↗