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NASA NTRS1993

Catalytic crystallization of ices by small silicate smokes at temperatures less than 20K

Samples of methanol and water ices condensed from the vapor onto aluminum substrates at low temperatures (below approximately 80 K) form amorphous ices; annealing at temperatures in excess of 140-155 K is usually required to convert such amorphous samples to crystalline ices. However, we have found that when either methanol or water vapor is deposited on to aluminum substrates that have been coated with a thin (0.1-0.5 mm) layer of amorphous silicate smoke, the ices condense in crystalline form. We believe that crystalline ice forms as the result of energy liberated at the ice/silicate interface perhaps due to weak bonding of the ice at defect sites on the grains and the very high surface to volume ratio and defect density of these smokes. Annealing of amorphous water ice mixed with more volatile components such as methane, carbon monoxide, etc., has been suggested as an efficient way to produce clatherates in the outer solar nebula and thus explain the volatile content of comets and icy satellites of the outer planets. This hypothesis may need to be re-examined if amorphous ice does not form on cold silicate grains.

Moore, M.↗
NASA NTRS1994

High resolution visible to short-wave near-infrared CCD spectra of Mars during 1990

The 0.4 to 1.0 micron spectrum of Mars is dominated by a steep red, relatively featureless spectral slope. Earlier lower spectral observations interpreted the red color and the lack of absorption features in the spectra as evidence of poorly crystalline ferric oxide minerals. More recent higher spectral resolution observations and reinterpretations of older data sets have revealed measureable spectral structure, however. For example, absorption features near 0.65 and 0.86 micron were detected and spatially mapped in data obtained during the 1988 opposition. These absorptions were interpreted as evidence for crystalline hematite on Mars, occuring as an accessory phase in abundances of 3 to 6 percent in the soil. We are attempting to verify the existence of these subtle crystalline Fe(3+) absorption features and to map their spatial distribution in regions of the planet not imaged in 1988. During the 1990 opposition, we obtained imaging spectroscopic data of Mars from the University of Hawaii 2.24 m telescope at Mauna Kea Observatory. The data were obtained with the Wide Field Grism Spectrograph (WFGS), which uses an 800 x 800 CCD and a transmission grating ruled on a prism. We used a grating blazed at 4800 A in first order to obtain data from 0.50 to 0.94 micron at a spectral resolution of R = 200 to 350. The moon/Mars slit design used had projected dimensions of 0.29 x 153 inches, allowing for high spectral resolution and adequate cross-slit spatial sampling of the Martian disk.

Bell, James F., III↗
NASA NTRS1994

Real refractive indices of infrared-characterized nitric-acid/ice films: Implications for optical measurements of polar stratospheric clouds

The infrared spectra of nitric-acid/ice films representative of polar stratospheric clouds (PSCs) were collected with simultaneous optical interference measurements to determine the real refractive indices at lambda = 632 nm. Ice and amphorous nitric-acid/ice films were prepared by condensation of water and nitric acid vapors onto a wedged Al2O3 substrate. The real refractive indices of these films were determined from the optical interference of a reflected helium-neon laser during film growth. The indices of the amphorous films varied smoothly from n = 1.30 for ice to n = 1.49 for nitric acid, similar to observations in previous work. We were unable to obtain the refractive index of crystlline films during adsorption because of optical scattering caused by surface roughness. Therefore crystlline nitric acid hydrate films were prepared by annealing amphorous nitric-acid/ice films. Further heating caused desorption of the crystalline hydrate films. During desorption, the refractive indices for ice, NAM (nitric acid monohydrate), alpha- and beta-NAT (nitric acid trihydrate) films were measured using the optical interference technique. In agreement with earlier data, the real refractive indices for ice and NAM determined in desorption were n = 1.30 +/- 0.01 and n = 1.53 +/- 0.03, respectively. The real refractive indices for alpha- and beta-NAT were found to be n = 1.51 +/- 0.01 and n greater than or equal to 1.46, respectively. Our measurements also suggest that the shape of crystalline nitric acid particles may depend on whether they nucleate from the liquid or by vapor deposition. If confirmed by future studies, this observation may provide a means of distinguishing the nucleation mechanism of crystalline PSCs.

Middlebrook, Ann M.↗
NASA NTRS1994

Silicate emission feature in the spectrum of comet Mueller 1993a

An 8- to 13-micron spectrum of comet Mueller 1993a, a dynamically new comet, was acquired when the comet was at R = 2 AU. Strong, structured silicate emission is present, closely resembling that seen in Comet P/Halley at smaller R. For the first time in a new comet, the 11.2-micron peak of crystalline olivine was detected, demonstrating that crystalline olivine particles were widespread in the solar nebula. Crystalline olivine particles could have formed in the inner protosolar nebula at temperatures greater than 1200 K; extensive radial mixing would have been required to transport these grains to the region of comet formation. Either there was more radial mixing in the solar nebula than some current theories predict or the olivine grains have a presolar origin.

Hanner, Martha S.↗
NASA NTRS1995

The growth of cubic silicon carbide on a compliant substrate

Research has shown that silicon carbide grown on silicon and 6H silicon carbide has problems associated with these substrates. This is because silicon and silicon carbide has a 20% lattice mismatch and cubic silicon carbide has not been successfully achieved on 6H silicon carbide. We are investigating the growth of silicon carbide on a compliant substrate in order to grow defect free silicon carbide. This compliant substrate consists of silicon/silicon dioxide with 1200 A of single crystal silicon on the top layer. We are using this compliant substrate because there is a possibility that the silicon dioxide layer and the carbonized layer will allow the silicon lattice to shrink or expand to match the lattice of the silicon carbide. This would improve the electrical properties of the film for the use of device fabrication. When trying to grow silicon carbide, we observed amorphous film. To investigate, we examined the process step by step using RHEED. RHEED data showed that each step was amorphous. We found that just by heating the substrate in the presence of hydrogen it changed the crystal structure. When heated to 1000 C for 2 minutes, RHEED showed that there was an amorphous layer on the surface. We also heated the substrate to 900 C for 2 minutes and RHEED data showed that there was a deterioration of the single crystalline structure. We assumed that the presence of oxygen was coming from the sides of the silicon dioxide layer. Therefore, we evaporated 2500 A of silicon to all four edges of the wafer to try to enclose the oxygen. When heating the evaporated wafer to 900 C the RHEED data showed single crystalline structure however at 1000 C the RHEED data showed deterioration of the single crystalline structure. We conclude that the substrate itself is temperature dependent and that the oxygen was coming from the sides of the silicon dioxide layer. We propose to evaporate more silicon on the edges of the wafer to eliminate the escape of oxygen. this will allow us to grow single crystal cubic silicon carbide.

Mitchell, Sharanda↗
NASA NTRS1995

Material processing of convection-driven flow field and temperature distribution under oblique gravity

A set of mathematical formulation is adopted to study vapor deposition from source materials driven by heat transfer process under normal and oblique directions of gravitational acceleration with extremely low pressure environment of 10(exp -2) mm Hg. A series of time animation of the initiation and development of flow and temperature profiles during the course of vapor deposition has been obtained through the numerical computation. Computations show that the process of vapor deposition has been accomplished by the transfer of vapor through a fairly complicated flow pattern of recirculation under normal direction gravitational acceleration. It is obvious that there is no way to produce a homogeneous thin crystalline films with fine grains under such a complicated flow pattern of recirculation with a non-uniform temperature distribution under normal direction gravitational acceleration. There is no vapor deposition due to a stably stratified medium without convection for reverse normal direction gravitational acceleration. Vapor deposition under oblique direction gravitational acceleration introduces a reduced gravitational acceleration in vertical direction which is favorable to produce a homogeneous thin crystalline films. However, oblique direction gravitational acceleration also induces an unfavorable gravitational acceleration along horizontal direction which is responsible to initiate a complicated flow pattern of recirculation. In other words, it is necessary to carry out vapor deposition under a reduced gravity in the future space shuttle experiments with extremely low pressure environment to process vapor deposition with a homogeneous crystalline films with fine grains. Fluid mechanics simulation can be used as a tool to suggest most optimistic way of experiment with best setup to achieve the goal of processing best nonlinear optical materials.

Hung, R. J.↗
NASA NTRS1993

Diacetylene and Polydiacetylene Derivatives of 2-Methyl-4-Nitroaniline for Second-Harmonic Generation

A novel diacetylene derivative of 2-Methyl-4-NitroAniline (MNA), a well-known material for Second-Harmonic Generation (SHG), is synthesized. This monomer DiAcetylene MethylNitroAniline, (DAMNA) is characterized by means of the Kurtz technique at 1064 nm and is found to have an SHG powder efficiency 62.5 % that of MNA itself. Thin crystalline films of DAMNA are grown onto quartz, Teflon, and Kapton substrates by means of vapor deposition in vacuum. These films are then polymerized in the solid state by exposure to long-wavelength UV radiation to give crystalline polydiacetylene thin films (PDAMNA). The films are next characterized for SHG, using an unpolymerized DAMNA film as a reference. Interestingly, films grown onto Teflon exhibit greater orientation and significantly greater SHG than those grown onto quartz and Kapton. This result is promising in that it demonstrates the potential of PDAMNA as both a crystalline and polymeric material for SHG applications, in which highly oriented thin films are desired. Computational modeling (usingAM1) is also carried out on DAMNA and is compared to the experimental results.

Paley, M. S.↗
NASA NTRS1996

Soot Precursor Material: Visualization Via Simultaneous LIF-LII and Characterization Via TEM

Simultaneous combined laser-induced fluorescence and laser-induced incandescence (LIF-LII) images are presented for both a normal and inverse diffusion flame. The excitation wavelength dependence distinguishes the LIF and LII signals in images from the normal diffusion flame while the temporal decay distinguishes the signals in images of the inverse diffusion flame. Each flame presents a minimum in the combined LIF-LII intensity in a region separating the fuel pyrolysis and soot containing regions. Opacity, geometric in definition, and extent of crystallinity measured through both bright and dark field Transmission Electron Microscopy (TEM) characterizes the thermophoretically sampled material from within this minimal LIF-LII intensity region. TEM analysis reveals rather different soot processes occurring within the normal and inverse diffusion flame. In the normal diffusion flame, rapid chemical and physical coalescence of PAHs results in initial formation of soot precursor particles that are highly crystalline and evolve toward fully formed soot. In the inverse diffusion flame, rapid coalescence of pyrolysis products occurs, producing tarlike, globular structures equivalent in size to fully formed soot aggregates but with markedly less crystallinity than normal-appearing soot. These different material properties are interpreted as reflecting different relative rates of chemical and physical coalescence of fuel pyrolysis products versus carbonization. Significantly, these TEM images support qualitative photophysical arguments suggesting that, in general, this 'dark' region observed in the LIF-LII images demarcates a transitional region in which a fundamental change in the material the material chemical/physical properties occurs between solid carbonaceous soot and condensed or gaseous molecular growth material.

VanderWal, Randall L.↗
NASA NTRS1997

Chemical and Thermal Analysis

Work during the past three years has included significant research in several areas aimed at further clarification of the aging and chemical failure mechanism of thermoplastics (PVDF or Tefzel) for pipes. Among the areas investigated were the crystallinity changes associated with both the Coflon and Tefzel after various simulated environmental exposures using X-Ray diffraction analysis. We have found that significant changes in polymer crystallinity levels occur as a function of the exposures. These crystallinity changes may have important consequences on the fracture, fatigue, tensile, and chemical resistance of the materials. We have also noted changes in the molecular weight distribution and the increased crosslinking of the Coflon material using Gel Permeation Chromatographic Analysis. Again these changes may result in variations in the mechanical and chemical properties in the material. We conducted numerous analytical studies with methods including X-ray Diffraction, Gel Permeation Chromatography, Fourier Transform Infrared Spectroscopy, and Differential Scanning Calorimetry. We investigated a plethora of aged samples of both Tefzel and Coflon that were forwarded from MERL. Pressurized tests were performed on powdered PVDF in a modified Fluid A, which we will call A-2. In this case the ethylene diamine concentration was increased to 3 percent in methanol. Coflon pipe sections and powdered Coflon were exposed in pressure cells at 1700 psi at three separate test temperatures.

Bulluck, J. W.↗
NASA NTRS1996

Chemical and Thermal Analysis

Work has included significant research in several areas aimed at further clarification of the aging and chemical failure mechanism of thermoplastics (PVDF or Tefzel) for pipes. Among the areas investigated were the crystallinity changes associated with both the Coflon and Tefzel after various simulated environmental exposures using X-Ray diffraction analysis. We have found that significant changes in polymer crystallinity levels occur as a function of the exposures. These crystallinity changes may have important consequences on the fracture, fatigue, tensile, and chemical resistance of the materials. We have also noted changes in the molecular weight distribution of the Coflon material using a dual detector Gel Permeation Analysis. Again these changes may result in variation in the mechanical and chemical properties in the material. We conducted numerous analytical studies with methods including X-Ray Diffraction, Gel Permeation Chromatography, Fourier Transform Infrared Spectroscopy, Thermogravimetric Analysis, and Differential Scanning Calorimetry. We investigated a number of aged samples of both Tefzel and Coflon that were forwarded from MERL. Pressurized tests were performed in a modified Fluid G, which we will call G2. In this case the ethylene diamine concentration was increased to 3 percent in methanol. Coflon pipe sections and powdered Coflon were exposed in pressure cells at 1700 psi at three separate test temperatures, 70 C, 110 C, and 130 C. The primary purpose of the pressure tests in Fluid G2 was to further elucidate the aging mechanism of PVDF degradation.

Bulluck, J. W.↗
NASA NTRS1996

International Research Project on the Effects of Chemical Ageing of Polymers on Performance Properties: Chemical and Thermal Analysis

Work during the past six months has included significant research in several areas aimed at further clarification of the aging and chemical failure mechanism of thermoplastics (PVDF or Tefzel) pipes. Among the areas investigated were the crystallinity changes associated with both the Coflon and Tefzel after various simulated environmental exposures using X-ray diffraction analysis. We have found that significant changes in polymer crystallinity levels occur as a function of the exposures. These crystallinity changes may have important consequences on the fracture, fatigue, tensile, and chemical resistance of the materials. We have also noted small changes in the molecular weight distribution. Again these changes may result in variations in the mechanical and chemical properties in the material. We conducted numerous analytical studies with methods including X-ray Diffraction, Gel Permeation Chromatography, Fourier Transform Infrared Spectroscopy, Ultra- Violet Scanning Analysis, GC/Mass Spectrometry, Differential Scanning Calorimetry and Thermomechanical Analysis. In the ultra-violet analysis we noted the presence of an absorption band indicative of triene formation. We investigated a number of aged samples of both Tefzel and Coflon that were forwarded from MERL. We also cast films at SWT and subjected these films to a refluxing methanol 1% ethylene diamine solution. An updated literature search was conducted using Dialog and DROLLS to identify any new papers that may have been published in the open literature since the start of this project. The updated literature search and abstracts are contained in the Appendix section of this report.

Bulluck, J. W.↗
NASA NTRS1999

Space Weathering in the Fine Size Fractions of Lunar Soils: Soil Maturity Effects

The effects of space weathering on the optical properties of lunar materials have been well documented. These effects include a reddened continuum slope, lowered albedo, and attenuated absorption features in reflectance spectra of lunar soils as compared to finely comminuted rocks from the same Apollo sites. However, the regolith processes that cause these effects are not well known, nor is the petrographic setting of the products of these processes fully understood. A Lunar Soil Characterization Consortium has been formed with the purpose of systematically integrating chemical and mineralogical data with the optical properties of lunar soils. Understanding space-weathering effects is critical in order to fully integrate the lunar sample collection with remotely-sensed data from recent robotic missions (e.g., Lunar Prospector, Clementine, and Galileo) We have shown that depositional processes (condensation of impact-derived vapors, sputter deposits, accreted impact material, e.g., splash glass, spherules, etc.) are a major factor in the modification of the optical surfaces of lunar regolith materials. In mature soils, it is the size and distribution of the nanophase metal in the soil grains that has the major effect on optical properties. In this report, we compare and contrast the space-weathering effects in an immature and a mature soil with similar elemental compositions. For this study, we analyzed <10 micron sieve fractions of two Apollo 17 soils, 79221 (mature, Is/FeO = 81) and 71061 (immature, Is/FeO = 14). Details of the sieving procedures and allocation scheme are given else where. The results of other detailed chemical, mineralogical, and spectroscopic analyses of these soil samples are reported elsewhere. A representative sample of each soil was embedded in low-viscosity epoxy, and thin sections (about 70nm thick) were obtained through ultra microtomy. The thin sections used for these analyses typically contained cross sections of up to 500 individual grains. The thin sections were studied using a JEOL 2010 transmission electron microscope (TEM) equipped with a thin window energy-dispersive X-ray (EDX) spectrometer. An individual thin section was selected from each soil, and for each grain in the section we determined (1) the elemental composition by EDX; (2) whether the grain was crystalline or glassy using electron diffraction and darkfield imaging; (3) the presence or absence of rims and accreted material; and (4) the distribution of nanophase Fe where present. Most of the categories are self-evident; however, we divide the agglutinate derived material into agglutinitic glass (glass with approximately the same composition as the bulk soil that contains nanophase Fe with or without vesicles) and agglutinate fragments, which are composed of crystalline grains and agglutinitic glass. Lithic fragments are defined as polymineralic grains with no glass. Pyroxene grains have been divided into high- and low-Ca groups. As expected, there are a number of differences in the petrography of the <10-microns fractions of 79221 and 71061 given the great difference in their respective maturities, but we focus here on two major distinctions: agglutinate content and the number of grains with micropatina. Slightly over 50% of the particles in 79221 consist of agglutinitic glass and agglutinate fragments, while the remainder are predominantly crystalline mineral grains. The agglutinic glass particles contain abundant nanophase Fe and vesicles. Angular particles are rare, with most showing smooth, rounded exteriors, Of the mineral grains analyzed thus far, over 90% of the grains have amorphous rims that contain nanophase Fe (these rims are believed to have formed by vapor deposition and irradiation effects). The nanophase Fe in these rims probably accounts for a significant fraction of the increase in Is/FeO measured in these size fractions. In addition to the rims, the majority of particles also show abundant accreted material in the form of glass splashes and spherules that also contain nanophase Fe. In stark contrast, the surfaces of the mineral grains in the 71061 sample are relatively prisitine, as only about 14% of the mineral grains in the sample exhibited amorphous rims. Furthermore, the mineral particles are more angular and show greater surface roughness than in the mature sample. Accreted material on particle surfaces is rare. Agglutinitic material is a major component of the 71061 sample; however, nanophase Fe and vesicles are not as well developed as in the 79221 sample. It is now recognized that nanophase Fe is probably the main agent in modifying the optical properties of lunar soil grains. The most important result of this study is the observation that in the fine size fractions of mature soils, nearly every grain has nanophase Fe within 100 run of the particle surface. (Additional Information contained in original)

Keller, L. P.↗
NASA NTRS1999

Spectral Behavior of Hematite at Visible/Near Infrared and Midinfrared Wavelengths

The oxide mineral hematite alpha-Fe2O3) is present on Mars as evidenced by spectroscopy using visible/near infrared (VNIR) and midinfrared (MIR) wavelengths. The physical nature of this surficial hematite varies from fine-grained, crystalline red hematite (red-Hm) in certain martian bright regions, to coarser-grained, crystalline gray hematite (gray-Hm) in the Sinus Meridiani equatorial site discovered in the Mars Global Surveyor Thermal Emission Spectrometer (MGS-TES) data. The VNIR spectra require that the red hematite is present in amounts subordinate to a second ferric pigment, which accounts for the general shape and position of the martian ferric absorption edge. By analogy with palagonitic tephra and synthetic samples, the pigment is a nanophase ferric oxide, possibly nanophase hematite (np-Hm). The purpose of this abstract is to document the physicospectral properties of hematite in the VNIR (0.35 to 2.2 microns) and MIR (5 to 25 microns) with respect to the terms "nanophase" and "crystalline", "red" and "gray", and "fine-grained" and "coarse-grained". We will show that different "types" of hematite (no-, red-, and gray-Hm) have different spectral responses in the VNIR and MIR regions and that these differences are important for inferring the types of hematite and their relative proportions from remotely sensed spectra of Mars. Because hematite is an alteration product that forms through many different geologic processes, determination of the type of hematite provides important clues about the style and diversity of martian weathering processes.

Lane, Melissa D.↗
NASA NTRS1999

Spectral Behavior of Hematite at Visible/Near Infrared and Midinfrared Wavelengths

The oxide mineral hematite alpha-Fe2O3) is present on Mars as evidenced by spectroscopy using visible/near infrared (VNIR) and midinfrared (MIR) wavelengths. The physical nature of this surficial hematite varies from fine-grained, crystalline red hematite (red-Hm) in certain martian bright regions, to coarser-grained, crystalline gray hematite (gray-Hm) in the Sinus Meridiani equatorial site discovered in the Mars Global Surveyor Thermal Emission Spectrometer (MGS-TES) data. The VNIR spectra require that the red hematite is present in amounts subordinate to a second ferric pigment, which accounts for the general shape and position of the martian ferric absorption edge. By analogy with palagonitic tephra and synthetic samples, the pigment is a nanophase ferric oxide, possibly nanophase hematite (np-Hm). The purpose of this abstract is to document the physicospectral properties of hematite in the VNIR (0.35 to 2.2 mm) and MIR (5 to 25 mm) with respect to the terms "nanophase" and "crystalline", "red" and "gray", and "fine-grained" and "coarse-grained". We will show that different "types" of hematite (np-, red-, and gray-Hm) have different spectral responses in the VNIR and MIR regions and that these differences are important for inferring the types of hematite and their relative proportions from remotely sensed spectra of Mars. Because hematite is an alteration product that forms through many different geologic processes, determination of the type of hematite provides important clues about the style and diversity of martian weathering processes. Additional information is contained in the original extended abstract.

Lane, M. D.↗
NASA NTRS2001

Retrieval of Polar Stratospheric Cloud Microphysical Properties From Lidar Measurements: Dependence on Particle Shape Assumptions

Knowledge of particle sizes and number densities of polar stratospheric clouds (PSCs) is highly important, because they are critical parameters for the modeling of the ozone chemistry of the stratosphere. In situ measurements of PSC particles are rare. the main instrument for the accumulation of PSC data are lidar systems. Therefore the derivation of some microphysical properties of PSCS from the optical parameters measured by lidars would be highly beneficial for ozone research. Inversion of lidar data obtained in the presence of PSCs formed from crystalline particles type 11 and the various nitric acid tri Ydrrate (NAT) types cannot be easily accomplished, because a suitable scattering theory for small faceted crystals has not been readily available tip to now. As a consequence, the T-matrix method is commonly used for the interpretation of these PSC lidar data. Here the assumption is made that the optical properties of an ensemble of spheroids resemble those of crystalline PSCs, and microphysical properties of the PSC are inferred from the optical signatures of the PSC at two or more wavelengths. The problem with the T-matrix approach is that the assumption of spheroidal instead of faceted particles can lead to dramatically wrong results: Usually cloud particle properties are deduced from analysis of lidar profiles of backscatter ratio and depolarization ratio. The particle contribution to the backscatter ratio is given by the product of the particle number density and the backscattering cross section. The latter is proportional to the value of the particle's scattering phase function at 180 degrees scattering angle. At 180 degrees however, the phase functions of rough, faceted crystals and of spheroids with same maximum dimension differ by a factor of 6. From this it follows that for a PSC consisting of faceted crystals, the particle number density is underestimated by roughly the same factor if spheroidal particles are unrealistically assumed. We are currently developing a retrieval technique for determining the microphysical parameters of crystalline PSCs that takes into account the faceted shape of the PSC particles. This approach utilizes finite-difference time-domain (FDTD) calculations of particle optical properties. The accuracy and the free choice of the shape of the scattering particle make the FDTD technique a promising tool for the inversion of PSC lidar data. A first comparison of FDTD and T-matrix calculations will be presented.

Reichardt, Susanne↗
NASA NTRS2001

Grain Properties of Comet C/1995 O1 (Hale-Bopp) Deduced Through Computational Techniques

We present the computational analysis of the 7.6 - 13.2 micrometer infrared (IR) spectrophotometry (R approximately equal to 120) of comet C/1995 O1 (Hale-Bopp) in conjunction with concurrent observations which extend the spectral energy distribution from the near-infrared to far-infrared wavelengths. The observations include temporal epochs pre-perihelion, (1996 October UT and 1997 February UT), near perihelion (1997 April UT), and postperihelion (1997 June UT). Through the computational modeling of small amorphous carbon, and crystalline and amorphous silicate grains in Hale-Bopp's coma, we find that as the comet approached perihelion, the grain size distribution (the Hanner modified power law) steepened (N = 3.4 pre-perihelion, to N = 3.7 near and post-perihelion) along with an increase in the fractal porosity of larger (greater than 1 micrometer) grains. The peak of the grain size distribution remained constant (ap = 0.2 micrometer) at each epoch. We attribute the emergence of the 9.3 micrometer peak near perihelion to crystalline orthopyroxeno grains released from inside the nucleus. Crystalline silicates (olivine and orthopyroxene) make up about 30% (by mass) of the submicron sized (less than 1 micrometer) dust grains in Hale-Bopp's coma during each epoch.

Harker, David E.↗
NASA NTRS2002

Cometary Science After Hale-Bopp

Comets and the chondritic porous interplanetary dust particles (CP IDPs) that they shed in their comae are reservoirs of primitive solar nebula materials. The high porosity and fragility of cometary grains and CP IDPs, and anomalously high deuterium contents of pyroxene-rich CP IDPs imply these aggregate particles contain significant interstellar grain components. Spectrophotometry of comets at thermal IR wavelengths (3-40 microns) reveal the presence of a warm (near-IR) featureless emission modeled by amorphous carbon grains, and mid-IR and far-IR broad and narrow resonances modeled by chondritic (50% Fe and 50% Mg) amorphous and Mg-rich crystalline silicate minerals, respectively. Cometary amorphous silicate resonances are well matched by IR spectra of CP IDPs dominated by 0.1 micron spherules of Glass with Embedded Metal and Sulfides (GEMS) that are thought to be the interstellar Fe-bearing amorphous silicates produced in the cooling outflows of Asymptotic Giant Branch (AGB) stars. Acid-etched microtomed CP IDP samples, however, show that both the carbon phase (aliphatic) and the amorphous silicate phase (Mg-rich) are not optically absorbing while the embedded Fe nanoparticles make the IDPs dark. The CP IDPs suggest either significant processing has occurred in the ISM or that the AGB amorphous silicates have Mg-rich stoichiometry and possibly grew on Fe particle condensates. Cometary crystalline silicate resonances are well matched by IR spectra of laboratory submicron Mg-rich olivine crystals, [Mg(sub y),Fe(sub 1-y)]2SiO4 with y/ge0.85, and in the case of Hale-Bopp at r(sub h) less than or equal to approx. 1.5 AU, by Mg-rich pyroxene crystals, [Mg(sub x),Fe(sub 1-x)]SiO3 with x/ge0.85. While a fraction of AGB stardust (less than or equal to 15%) are Mg-rich crystals, this interstellar star dust component is insufficient to account for the deduced abundance of crystalline minerals in comet dust. An insufficient source of ISM Mg-rich crystals leads to the inference that Mg-rich crystals in comets may be hot, early solar nebula condensates that traveled large radial distances out to the comet-forming zone.

Wooden, Diane H.↗
NASA NTRS2003

Twinning, Epitaxy and Domain Switching in Ferroelastic Inclusion Compounds

Our research is in the area of solid-state organic chemistry, which lies at the interface between physical organic chemistry and materials science. We use crystalline solids as models to probe fundamental issues about physical processes, molecular interactions and chemical reactions that are important for fabrication, stabilization and application of technological materials. Much of our most recent work has focused on the phenomena of ferroelastic and ferroelectric domain switching, in which application of an external force or electric field to a crystal causes the molecules inside the crystal to reorient, in tandem, to a new orientational state. To better understand and control the domain switching process, we have designed and synthesized over twenty closely related, ferroelastic organic crystals. Our approach has been to use crystalline inclusion compounds, in which one molecule (the guest) is trapped within the crystalline framework of a second molecule (the host). By keeping the host constant and varying the proportions and kinds of guests, it has been possible to tailor these materials so that domain switching is rapid and reversible (which is desirable for high technology applications). Inclusion compounds therefore serve as powerful systems for understanding the specific molecular mechanisms that control domain switching.

Hollingsworth, Mark D.↗