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Ferguson, Frank T.

Publications and source records attributed to Ferguson, Frank T..

Great New Insights from Failed Experiments, Unanticipated Results and Embracing Controversial Observations

Experimental data and observations, whether telescopic or analytical, are never wrong, though data derived from such sources can be misinterpreted or applied inappropriately to derive conclusions that are incorrect. Given that nature always behaves according to the laws of physics and chemistry, rather than according to currently popular models and theories, experimental results should always be considered correct even when the results are far from those that one might initially expect. We discuss a number of cases where the results of experiments, even one carried out as a simple calibration measure, produced wildly different results that generally required many years of effort or contemplation to understand. On the positive side, exploration of the circumstances that produced the errant results often led to new and interesting insights concerning processes that might occur in natural environments and that were well worth the effort involved. Specifically, we show how an experiment that "failed" due to a broken conductor led to experiments that made the first refractory oxide solids containing mass independently fractionated oxygen isotopes and to 1998 predictions of the oxygen isotopic composition of the sun that were confirmed by the analysis of Genesis samples in 2011. We describe a calibration experiment that unexpectedly produced single magnetic domain iron particles. We discuss how tracking down a persistent source of "contamination" in experiments intended to produce amorphous iron and magnesium silicate smokes led to a series of studies on the synthesis of carbonaceous grain coatings that turn out to be very efficient Fischer-Tropsch catalysts and have great potential for trapping the planetary noble gases found in meteorites. We describe how models predicting the instability of silicate grains in circumstellar environments spurred new measurements of the vapor pressure of SiO partially based on previous experiments showing unexpected but systematic non-equilibrium behavior instead of the anticipated equilibrium products resembling meteoritic minerals. We trace the process that led from observations of the presence of crystalline minerals detected in the comae of some comets to the 1999 prediction of large-scale circulation of materials from the hot, innermost regions of the solar nebula out to the cold dark nebular environments where comets form. This large-scale circulation was ultimately confirmed by analyses of highly refractory Stardust samples collected from the Kuiper Belt Comet Wild 2. Finally we discuss a modern and still unresolved conflict between the assumptions built into three well known processes: the CO Self Shielding Model for mass independent isotopic fractionation of oxygen in solar system solids, rapid and thorough mixing within the solar nebula, and the efficient conversion of CO into organic coatings and volatiles on the surfaces of nebular grains via Fischer-Tropsch-type processes.

controversial↗

On the Use of Fourier Transform Infrared (FT-IR) Spectroscopy and Synthetic Calibration Spectra to Quantify Gas Concentrations in a Fischer-Tropsch Catalyst System

One possible origin of prebiotic organic material is that these compounds were formed via Fischer-Tropsch-type (FTT) reactions of carbon monoxide and hydrogen on silicate and oxide grains in the warm, inner-solar nebula. To investigate this possibility, an experimental system has been built in which the catalytic efficiency of different grain-analog materials can be tested. During such runs, the gas phase above these grain analogs is sampled using Fourier transform infrared (FT-IR) spectroscopy. To provide quantitative estimates of the concentration of these gases, a technique in which high-resolution spectra of the gases are calculated using the high-resolution transmission molecular absorption (HITRAN) database is used. Next, these spectra are processed via a method that mimics the processes giving rise to the instrumental line shape of the FT-IR spectrometer, including apodization, self-apodization, and broadening due to the finite resolution. The result is a very close match between the measured and computed spectra. This technique was tested using four major gases found in the FTT reactions: carbon monoxide, methane, carbon dioxide, and water. For the ranges typical of the FTT reactions, the carbon monoxide results were found to be accurate to within 5% and the remaining gases accurate to within 10%. These spectra can then be used to generate synthetic calibration data, allowing the rapid computation of the gas concentrations in the FTT experiments.

Infrared Spectroscopy↗

Vapor Pressure and Evaporation Coefficient of Silicon Monoxide over a Mixture of Silicon and Silica

The evaporation coefficient and equilibrium vapor pressure of silicon monoxide over a mixture of silicon and vitreous silica have been studied over the temperature range (1433 to 1608) K. The evaporation coefficient for this temperature range was (0.007 plus or minus 0.002) and is approximately an order of magnitude lower than the evaporation coefficient over amorphous silicon monoxide powder and in general agreement with previous measurements of this quantity. The enthalpy of reaction at 298.15 K for this reaction was calculated via second and third law analyses as (355 plus or minus 25) kJ per mol and (363.6 plus or minus 4.1) kJ per mol respectively. In comparison with previous work with the evaporation of amorphous silicon monoxide powder as well as other experimental measurements of the vapor pressure of silicon monoxide gas over mixtures of silicon and silica, these systems all tend to give similar equilibrium vapor pressures when the evaporation coefficient is correctly taken into account. This provides further evidence that amorphous silicon monoxide is an intimate mixture of small domains of silicon and silica and not strictly a true compound.

Ferguson, Frank T.↗

A Model of Silicate Grain Nucleation and Growth in Circumstellar Outflows

Based on its abundance, high bond energy, and recent measurements of its vapor pressure SiO is a natural candidate for dust nucleation in circumstellar outflows around asymptotic giant branch stars. In this paper, we describe a model of the nucleation and growth of silicate dust in such outflows. The sensitivity of the model to varying choices of poorly constrained chemical parameters is explored, and the merits of using scaled rather than classical nucleation theory are briefly considered, An elaboration of the model that includes magnesium and iron as growth species is then presented and discussed. The composition of the bulk of the grains derived from the model is consistent with olivines and pyroxenes, but somewhat metal-rich grains and very small, nearly pure SiO grains are also produced,

Paquette, John A.↗

Fischer-Tropsch-Type Production of Organic Materials in the Solar Nebula: Studies Using Graphite Catalysts and Measuring the Trapping of Noble Gases

The formation of abundant carbonaceous material in meteorites is a long standing problem and an important factor in the debate on the potential for the origin of life in other stellar systems. The Fischer-Tropsch-type (FTT) catalytic reduction of CO by hydrogen was once the preferred model for production of organic materials in the primitive solar nebula. We have demonstrated that many grain surfaces can catalyze both FTT and HB-type reactions, including amorphous iron and magnesium silicates, pure silica smokes as well as several minerals. Graphite is not a particularly good FTT catalyst, especially compared to iron powder or to amorphous iron silicate. However, like other silicates that we have studied, it gets better with exposure to CO. N2 and H2 over time: e.g., after formation of a macromolecular carbonaceous layer on the surfaces of the underlying gains. While amorphous iron silicates required only 1 or 2 experimental runs to achieve steady state reaction rates, graphite only achieved steady state after 6 or more experiments. We will present results showing the catalytic action of graphite grains increasing with increasing number of experiments and will also discuss the nature of the final "graphite" grains aster completion of our experiments.

Nuth, Joseph A., III↗

Catalytic Metal Free Production of Large Cage Structure Carbon Particles: A Candidate for Hydrogen Storage

We will demonstrate that carbon particles consisting of large cages can be produced without catalytic metal. The carbon particles were produced in CO gas as well as by introduction of 5% methane gas into the CO gas. The gas-produced carbon particles were able to absorb approximately 16.2 wt% of hydrogen. This value is 2.5 times higher than the 6.5 wt% goal for the vehicular hydrogen storage proposed by the Department of Energy in the USA. Therefore, we believe that this carbon particle is an excellent candidate for hydrogen storage for fuel cells.

Kimura, Yuki↗

Is the 21-micron Feature Observed in Some Post-AGB Stars Caused by the Interaction Between Ti Atoms and Fullerenes?

Recent measurements of fullerenes and Ti atoms recorded in our laboratory have demonstrated the presence of an infrared feature near 21 pm. The feature observed has nearly the same shape and position as is observed for one of the most enigmatic features in post-asymptotic giant blanch (AGB) stars. In our experimental system large cage carbon particles, such as large fullerenes, were produced from CO gas by the Boudouard reaction. Large-cage carbon particles intermixed with Ti atoms were produced by the evaporation of a Ti metal wrapped carbon electrode in CO gas. The infrared spectra of large fullerenes interacting with Ti atoms show a characteristic feature at 20.3 micron that closely corresponds to the 20.1 micron feature observed in post-AGB stars. Both the lab- oratory and stellar spectra also show a small but significant peak at 19.0 micron, which is attributed to fullerenes. Here, we propose that the interaction between fullerenes and Ti atoms may be a plausible explanation for the 21-micron feature seen in some post-AGB stars.

Kimura, Yuki↗

Formation of TiC-core, Graphitic-mantle Grains from CO Gas

We demonstrate a new formation route for TiC-core, graphitic-mantle spherules that does not require c-atom addition and the very long timescales associated with such growth (Bernatowicz et al. 1996). Carbonaceous materials can also be formed from C2H2 and its derivatives, as well as from CO gas. In this paper, we will demonstrate that large cage structure carbon particles can be produced from CO gas by the Boudouard reaction. Since the sublimation temperature for such fullerenes is low, the large cages can be deposited onto previously-nucleated TiC and produce TiC-core, graphitic-mantle spherules. New constraints for the formation conditions and the timescale for the formation of TiC-core, graphitic-mantle spherules are suggested by the results of this study. In particular, TiC-core, graphitic-mantle grains found in primitive meteorites that have never experienced hydration could be mantled by fullerenes or carbon nanotubes rather than by graphite. In situ observations of these grains in primitive anhydrous meteoritic matrix could confirm or refute this prediction and would demonstrate that the graphitic mantle on such grains is a metamorphic feature due to interaction of the pre-solar fullerenes with water within the meteorite matrix.

Kimura, Yuki↗

Initial Measurement of the Vapor Pressures of Simple Refractory Materials: Cu and Fe

It has become increasingly clear over the past decade that high temperature processes played important roles in the Primitive Solar Nebula. Unfortunately, basic data, such as the vapor pressures of iron or SiO have not been measured over the appropriate temperature range (near T approximately equal to 2000K), but must be extrapolated from lower temperature measurements often made more than 50 years ago. The extrapolation of the available data to higher temperatures can be quite complex and can depend on other factors such as the oxygen fugacity or the presence of hydrogen gas. Moreover, modern technology has made possible more accurate measurements of such quantities over a wider temperature range. We recently acquired a commercial Thermo-Cahn Thermogravimetric system capable of vacuum operation to 1700 C and measurement of mass change with microgram accuracy in a 100g sample or smaller. In this paper, we will report our progress in learning to make vapor pressure measurements using this system.

Nuth, Joseph A., III↗

Vapor Transport Within the Thermal Diffusion Cloud Chamber

A review of the equations used to determine the 1-D vapor transport in the thermal diffusion cloud chamber (TDCC) is presented. These equations closely follow those of the classical Stefan tube problem in which there is transport of a volatile species through a noncondensible, carrier gas. In both cases, the very plausible assumption is made that the background gas is stagnant. Unfortunately, this assumption results in a convective flux which is inconsistent with the momentum and continuity equations for both systems. The approximation permits derivation of an analytical solution for the concentration profile in the Stefan tube, but there is no computational advantage in the case of the TDCC. Furthermore, the degree of supersaturation is a sensitive function of the concentration profile in the TD CC and the stagnant background gas approximation can make a dramatic difference in the calculated supersaturation. In this work, the equations typically used with a TDCC are compared with very general transport equations describing the 1-D diffusion of the volatile species. Whereas no pressure dependence is predicted with the typical equations, a strong pressure dependence is present with the more general equations given in this work. The predicted behavior is consistent with observations in diffusion cloud experiments. It appears that the new equations may account for much of the pressure dependence noted in TDCC experiments, but a comparison between the new equations and previously obtained experimental data are needed for verification.

Ferguson, Frank T.↗

STARDUST - A simulation experiment of cosmic dust analogues production in microgravity conditions

The condensation of solid materials from the vapor phase is important in several scientific fields such as chemical vapor deposition, air pollution and the formation of refractory cosmic dust around stars. Conventional studies of refractory grain formation, using high temperature furnace and shock tube techniques, are restricted to short time scales and suffer from buoyancy induced convection that limit their accuracy. In order to simulate more accurately the condensation of refractory grains near stars and to investigate the advantages of performing condensation studies in microgravity conditions, an experimental investigation was undertaken. This work reports the experimental equipment currently used. The results from the first flight series and particle aggregation modelling efforts are presented briefly.

Ferguson, Frank T.↗