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Thermal metamorphism of Si2O3 - (A circumstellar dust analog)

The thermal behavior of Si2O3, the metastable condensate from SiO vapor,has been studied experimentally. Si2O3 and its successor, amorphous quartz, have previously been shown to have infrared spectral features similar to some that appear in the spectra of grains in oxygen-rich circumstellar regions. Thermal annealing experiments show that only one Si2O3 decay process operates over the range between 750-1000 K. This process is a unimolecular disproportionation. The rate of this transformation can be expressed as k/hr = 10 to the 9th exp (-40 kcal/mole/RT). By using this rate constant, it is found that a significant fraction of freshly nucleated circumstellar grains can survive passage through a typical circumstellar shell virtually unaltered in structure. It is emphasized that this is only the first in a series of laboratory experiments intended to study the metamorphism of newly condensed circumstellar material ejected into the interstellar medium. Grains similar to these might have been incorporated into the primitive solar nebula, provided that they could also survive passage through the general interstellar medium.

Nuth, J. A.↗

Trapping Ne, Ar, Kr, and Xe in Si2O3 smokes

Simple Si2O3 smokes have been condensed at both low (less than 750 K) and high (greater than 1000 K) temperature at 35 torr H2 pressure in the presence of 0, 10, 100, and 1000 microns of a noble gas mixture containing Ne, Ar, Kr, and Xe. In general, both Ne and Ar are quite loosely bound in the smokes (6.0 x 10 to the -8th and 2.6 x 10 to the -4th ccSTP/g, respectively), and are degassed at temperatures below 1200 K. Both Kr and Xe are somewhat more strongly bound at concentrations of 1.0 x 10 to the -7th and 8.2 x 10 to the -8th ccSTP/g, respectively, and in addition show a double release with a second component at a temperature of about 1875 K. With the exception that Si2O3 smokes appear to show a particular affinity for argon, possibly due to an anomalous absorption of atmospheric argon, none of the other noble gases are found in sufficient concentration to explain the gases observed in meteorites as primary circumstellar condensates. However, this data in conjunction with observations of Honda et al. (1979) do seem to show a degree of dependence between noble gas retention and chemical composition.

Nuth, Joseph A., III↗

Materials Data on Si2O3 by Materials Project

Si2O3 is beta Sn structured and crystallizes in the monoclinic C2/c space group. The structure is zero-dimensional and consists of four hydridospherosiloxane molecules. there are five inequivalent Si sites. In the first Si site, Si is bonded in a trigonal non-coplanar geometry to three O atoms. All Si–O bond lengths are 1.65 Å. In the second Si site, Si is bonded in a trigonal non-coplanar geometry to three O atoms. There is one shorter (1.64 Å) and two longer (1.65 Å) Si–O bond length. In the third Si site, Si is bonded in a trigonal non-coplanar geometry to three O atoms. There are a spread of Si–O bond distances ranging from 1.64–1.66 Å. In the fourth Si site, Si is bonded in a trigonal non-coplanar geometry to three O atoms. There is two shorter (1.65 Å) and one longer (1.66 Å) Si–O bond length. In the fifth Si site, Si is bonded in a trigonal non-coplanar geometry to three O atoms. There is two shorter (1.64 Å) and one longer (1.65 Å) Si–O bond length. There are eight inequivalent O sites. In the first O site, O is bonded in a bent 150 degrees geometry to two Si atoms. In the second O site, O is bonded in a bent 150 degrees geometry to two Si atoms. In the third O site, O is bonded in a bent 150 degrees geometry to two Si atoms. In the fourth O site, O is bonded in a bent 150 degrees geometry to two Si atoms. In the fifth O site, O is bonded in a bent 150 degrees geometry to two Si atoms. In the sixth O site, O is bonded in a bent 150 degrees geometry to two Si atoms. In the seventh O site, O is bonded in a bent 150 degrees geometry to two equivalent Si atoms. In the eighth O site, O is bonded in a bent 150 degrees geometry to two Si atoms.

36 MATERIALS SCIENCE↗

Materials Data on Fe(Si2O3)2 by Materials Project

FeSiO3(SiO)3 crystallizes in the triclinic P1 space group. The structure is one-dimensional and consists of one FeSiO3 ribbon oriented in the (1, 0, 0) direction and one SiO ribbon oriented in the (1, 0, 0) direction. In the FeSiO3 ribbon, Fe is bonded in a rectangular see-saw-like geometry to four O atoms. There are a spread of Fe–O bond distances ranging from 1.83–2.09 Å. Si is bonded in a trigonal non-coplanar geometry to three O atoms. There is one shorter (1.65 Å) and two longer (1.68 Å) Si–O bond length. There are three inequivalent O sites. In the first O site, O is bonded in a 3-coordinate geometry to two equivalent Fe and one Si atom. In the second O site, O is bonded in a bent 120 degrees geometry to two equivalent Si atoms. In the third O site, O is bonded in a water-like geometry to two equivalent Fe atoms. In the SiO ribbon, there are three inequivalent Si sites. In the first Si site, Si is bonded in a single-bond geometry to one O atom. The Si–O bond length is 1.64 Å. In the second Si site, Si is bonded in a single-bond geometry to one O atom. The Si–O bond length is 1.69 Å. In the third Si site, Si is bonded to four O atoms to form corner-sharing SiO4 tetrahedra. There are a spread of Si–O bond distances ranging from 1.64–1.66 Å. There are three inequivalent O sites. In the first O site, O is bonded in a bent 150 degrees geometry to two Si atoms. In the second O site, O is bonded in a bent 120 degrees geometry to two Si atoms. In the third O site, O is bonded in a bent 120 degrees geometry to two equivalent Si atoms.

36 MATERIALS SCIENCE↗

Properties of various silicon oxide phases in thin films

Layers of SiO2 with reproducible properties can be manufactured relatively easily today. In the case of SiO and Si2O3 layers, it is necessary to carefully check all of the manufacturing parameters for producing layers with reproducible properties. The properties of the layers in the case of SiO2 do conform to expectations. In the case of Si2O3 and SiO, they can be understood at least qualitatively. Additional interesting models are available for a quantitative understanding.

Ritter, E.↗

Experimental studies of the vapor phase nucleation of refractory compounds. I - The condensation of SiO

The critical partial pressure of SiO necessary to initiate avalanche nucleation in the SiO-H2 system is measured as a function of the ambient temperature in the range 750-1000 K. Results show that the condensate produced at low temperatures is Si2O3, while a mixture of Si2O3 and amorphous SiO2 is produced at high temperatures. A surface energy of approximately 500 ergs/sq cm for the particles is found by analyzing the critical partial pressure vs temperature using classical nucleation theory. It is concluded that classical nucleation theory is not applicable to this system, because several inconsistencies in the thermodynamic analysis are demonstrated, and it is suggested that a kinetic theory of nucleation may be the preferential way to describe the condensation process.

Nuth, J. A.↗

Condensation of nonequilibrium phases of refractory silicates from the vapor

Silicon monoxide solid was evaporated in a bell jar containing reducing, neutral, or oxidizing atmospheres at pressures of a few torr. The vapor invariably condensed as smoke-sized particles of silicon sesquioxide, Si2O3. The condensation of a solid whose composition differs from that of the parent gas and is apparently the least stable of the three solid species illustrates the importance of specific nucleation effects in the condensation process. This result has significant implications for theories of formation of grains in space.

Day, K. L.↗

A spectroscopic study of intermediates in the condensation of refractory smokes: Matrix isolation experiments SiO

The infrared and Raman spectra of N2 matrix isolated silicon oxides are investigated. The vibrational frequencies of SiO, Si2O2, and Si3O3 were identified and assigned on the basis of normal coordinate analyses. Heating the solid to 50 K (evaporating the matrix) leaves a residue whose infrared spectrum is identical to that of a smoke condensed at ambient temperatures. Further heating of the sample to 500 K leads to significant changes in the band shapes. Investigations of the infrared spectra at several stages of the diffusion process result in the proposal of a mechanism for the transition from molecular properties to those of the residue (bulk) material, which is characterized as Si2O3.

Khanna, R. K.↗

A spectroscopic study of intermediates in the condensation of refractory smokes - Matrix isolation experiments of SiO

The infrared and Raman spectra of N2 matrix-isolated silicon oxides were investigated. The vibrational frequencies of SiO, Si2O2, and Si3O3 were identified and assigned on the basis of normal coordinate analyses. Heating the solid to approximately 50 K (evaporating the matrix) leaves a residue whose infrared spectrum is identical to that of a smoke condensed at ambient temperatures. Further heating of the sample to approximately 500 K leads to significant changes in the band shapes. Investigations of the infrared spectra at several stages of the diffusion process enable a mechanism to be proposed for the transition from molecular properties to those of the residue (bulk) material, which has been characterized as Si2O3.

Khanna, R. K.↗

Lunar and Planetary Science Conference, 18th, Houston, TX, Mar. 16-20, 1987, Proceedings

Papers on lunar and planetary science are presented, including petrogenesis and chemistry of lunar samples, geology and petrogenesis of the Apollo 15 landing site, lunar geology and applications, cratering records and cratering effects, differentiated meteorites, chondritic meteorites and asteroids, extraterrestrial grains, Venus, Mars, and icy satellites. The importance of lunar granite and KREEP in very high potassium basalt petrogenesis, indentifying parent plutonic rocks from lunar breccia and soil fragments, glasses in ancient and young Apollo 16 regolith breccias, the formation of the Imbrium basin, the chemistry and petrology of the Apennine Front, lunar mare ridges, studies of Rima Mozart, electromagnetic energy applications in lunar resource mining and construction, detecting a periodic signal in the terrestrial cratering record, and a search for water on the moon, are among the topics discussed. Other topics include the bidirectional reflectance properties of Fe-Ni meteorites, the nature and origin of C-rich ordinary chondrites and chondritic clasts, the dehydration kinetics of shocked serpentine, characteristics of Greenland Fe/Ni cosmic grains, electron microscopy of a hydrated interplanetary dust particle, trapping Ne, Ar, Kr, and Xe in Si2O3 smokes, gossans on Mars, and a model of the porous structure of icy satellites.

Ryder, Graham↗

Experimental studies of circumstellar, interstellar and interplanetary refractory grain analogs

Experimental techniques for studying the processes which occur during the life cycle of a refractory grain are reviewed. Consideration is given to the construction of a differentially-pumped beam-mass spectrometer which is expected to determine the relative stability of small clusters in the Fe-Mg-Si-O and Ca-Ti-Al-O systems as a function of temperature and pressure. Also, a smoke generator has been constructed to produce gram quantities of amorphous grains for use in thermal annealing and hydrous alteration studies of smokes containing Fe-Mg-Al-Ti-Ca-Si-O and Cl. Topics of the studies include the properties of grains produced in a flow condensation apparatus, the sorption efficiency of Si2O3 smokes for AR gas, the processing of ices containing refractory precursors such as SiH4 or Fe(CO)5 plus water, and the residue from 1 MeV bombardment and warming of an amorphous Fe-SiO smoke.

Nuth, J. A.↗

Laboratory studies of refractory metal oxide smokes

Studies of the properties of refractory metal oxide smokes condensed from a gas containing various combinations of SiH4, Fe(CO)5, Al(CH3)3, TiCl4, O2 and N2O in a hydrogen carrier stream at 500 K greater than T greater than 1500 K were performed. Ultraviolet, visible and infrared spectra of pure, amorphous SiO(x), FeO(x), AlO(x) and TiO(x) smokes are discussed, as well as the spectra of various co-condensed amorphous oxides, such as FE(x)SiO(y) or Fe(x)AlO(y). Preliminary studies of the changes induced in the infrared spectra of iron-containing oxide smokes by vacuum thermal annealing suggest that such materials become increasingly opaque in the near infrared with increased processing: hydration may have the opposite effect. More work on the processing of these materials is required to confirm such a trend: this work is currently in progress. Preliminary studies of the ultraviolet spectra of amorphous Si2O3 and MgSiO(x) smokes revealed no interesting features in the region from 200 to 300 nm. Studies of the ultraviolet spectra of both amorphous, hydrated and annealed SiO(x), TiO(x), AlO(x) and FeO(x) smokes are currently in progress. Finally, data on the oxygen isotopic composition of the smokes produced in the experiments are presented, which indicate that the oxygen becomes isotopically fractionated during grain condensation. Oxygen in the grains is as much as 3 percent per amu lighter than the oxygen in the original gas stream. The authors are currently conducting experiments to understand the mechanism by which fractionation occurs.

Nuth, Joseph A.↗

Trapping of noble gases in proton-irradiated silicate smokes

We have measured Ne, Ar, Kr, and Xe in Si2O3 'smokes' that were condensed on Al substrates, vapor-deposited with various mixtures of CH4, NH3, H2O3 and noble gases at 10 K and subsequently irradiated with 1 MeV protons to simulate conditions during grain mantle formation in interstellar clouds. Neither Ne nor Ar is retained by the samples upon warming to room temperature, but Xe is very efficiently trapped and retained. Kr is somewhat less effectively retained, typically depleted by factors of about 10-20 relative to Xe. Isotopic fractionation favoring the heavy isotopes of Xe and Kr of about 5-10-percent/amu is observed. Correlations between the specific chemistry of the vapor deposition and heavy noble gas retention are most likely the result of competition by the various species for irradiation-produced trapping sites. The concentration of Xe retained by some of these smokes exceeds that observed in phase Q of meteorites and, like phase Q, they do not seem to be carriers of the light noble gases.

Nichols, R. H., Jr.↗