Engineering topics
Publications and source records attributed to Blake, D. F..
X-Ray Diffraction (XRD) is the most direct and accurate method for determining mineralogy. The CHEMIN XRD/XRF instrument has shown promising results on a variety of mineral and rock samples. Additional information is contained in the original extended abstract.
Health effects from Martian dusts will be a concern for any manned Mars missions. Nuisance dusts plagued the Apollo astronauts, but dusts of more hazardous mineralogy, in habitats occupied by Mars astronauts weakened by a long-duration mission, may be more than a nuisance. Chemical hazards in Martian regolith attributable to S, Cl, Br, Cd, and Pb are known or strongly suspected to be present, but terrestrial studies of the health effects of dusts indicate that accurate determination of mineralogy is a critical factor in evaluating inhalation hazards. Mineral inhalation hazards such as the Group-I carcinogenic zeolite erionite, which is demonstrated to cause mesothelioma, cannot be identified by chemical analysis alone. Studies of palagonite analogs raise the possibility that erionite may occur on Mars. In addition to health effects concerns, environmental mineralogy has significant importance in resource extraction, groundwater use, and sustained agriculture. The high sulfur and chlorine content of Martian regolith will affect all of these uses, but the nature of mineralogic reservoirs for S and Cl will determine their uptake and concentration in extracted groundwater and in agricultural applications of regolith. Wet chemistry experiments planned for the Mars Environmental Compatibility Assessment (MECA) will define some of the consequences of water/soil interaction, but an understanding of the mineralogic basis for water-rock reactions is needed to understand the mechanisms of reaction and to apply the results of a few experiments to larger scales and different conditions.
Vapor-deposited amorphous water ice when warmed above the glass transition temperature (120-140 K), is a viscous liquid which exhibits a viscosity vs temperature relationship different from that of liquid water at room temperature. New studies of thin water ice films now demonstrate that viscous liquid water persists in the temperature range 140-210 K. where it coexists with cubic crystalline ice. The liquid character of amorphous water above the glass transition is demonstrated by (1) changes in the morphology of water ice films on a nonwetting surface observed in transmission electron microscopy (TEM) at around 175 K during slow warming, (2) changes in the binding energy of water molecules measured in temperature programmed desorption (TPD) studies, and (3) changes in the shape of the 3.07 micrometers absorption band observed in grazing angle reflection-absorption infrared spectroscopy (RAIRS) during annealing at high temperature. whereby the decreased roughness of the water surface is thought to cause changes in the selection rules for the excitation of O-H stretch vibrations. Because it is present over such a wide range of temperatures, we propose that this form of liquid water is a common material in nature. where it is expected to exist in the subsurface layers of comets and on the surfaces of some planets and satellites.
Electron diffraction studies of vapor-deposited water ice have characterized the dynamical structural changes during crystallization that affect volatile retention in cometary materials. Crystallization is found to occur by nucleation of small domains, while leaving a significant part of the amorphous material in a slightly more relaxed amorphous state that coexists metastably with cubic crystalline ice. The onset of the amorphous relaxation is prior to crystallization and coincides with the glass transition. Above the glass transition temperature, the crystallization kinetics are consistent with the amorphous solid becoming a "strong" viscous liquid. The amorphous component can effectively retain volatiles during crystallization if the volatile concentration is approximately 10% or less. For higher initial impurity concentrations, a significant amount of impurities is released during crystallization, probably because the impurities are trapped on the surfaces of micropores. A model for crystallization over long timescales is described that can be applied to a wide range of impure water ices under typical astrophysical conditions if the fragility factor D, which describes the viscosity behavior, can be estimated.
Films of vapor deposited water ice at low temperature (T<30 K) show a number of interesting structural changes during a gradual warmup. We would like to talk about the structure of the low temperature high density amorphous form of water ice, the process of crystallization, and some recent work on the morphological changes of water ice films at high temperature. The studies of the high density amorphous form are from in-situ electron microscopy as well as numerical simulations of molecular dynamics and have lead to new insights into the physical distinction between this high density amorphous form and the low density amorphous form. For the process of crystallization, we propose a model that describes the crystallization of water ice from the amorphous phase to cubic ice in terms of the nucleation of small domains in the ice. This model agrees well with the behavior of water ice in our electron microscopy studies and finds that pure water above the glass transition is a strong liquid. In more recent work, we have concentrated on temperatures above the crystallization temperature and we find interesting morphological changes related to the decrease in viscosity of the amorphous component in the cubic crystalline regime. Given enough time, we would like to put these results in an astrophysical context and discuss some observed features of the frost on interstellar grains and the bulk ice in comets.
Most water ice in the universe is in a form which does not occur naturally on Earth and of which only minimal amounts have been made in the laboratory. We have encountered this 'high-density amorphous ice' in electron diffraction experiments of low-temperature (T less than 30 K) vapor-deposited water and have subsequently modeled its structure using molecular dynamics simulations. The characteristic feature of high-density amorphous ice is the presence of 'interstitial' oxygen pair distances between 3 and 4 A. However, we find that the structure is best described as a collapsed lattice of the more familiar low-density amorphous form. These distortions are frozen in at temperatures below 38 K because, we propose, it requires the breaking of one hydrogen bond, on average, per molecule to relieve the strain and to restructure the lattice to that of low-density amorphous ice. Several features of astrophysical ice analogs studied in laboratory experiments are readily explained by the structural transition from high-density amorphous ice into low-density amorphous ice. Changes in the shape of the 3.07 gm water band, trapping efficiency of CO, CO loss, changes in the CO band structure, and the recombination of radicals induced by low-temperature UV photolysis all covary with structural changes that occur in the ice during this amorphous to amorphous transition. While the 3.07 micrometers ice band in various astronomical environments can be modeled with spectra of simple mixtures of amorphous and crystalline forms, the contribution of the high-density amorphous form nearly always dominates.
A series of surface-modified clays containing nanophase (np) iron/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these 'Mars-soil analogs' were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxyl mineral such as 'green rust', or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable meaghemite (gamma-Fe203) by mild heat treatment and then to nanophase hematite (aplha-Fe203) by extensive heat treatment. Their chemical reactivity offers a plausible mechanism for the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxide and silicate phase surfaces. The mode of formation of these (nanophase) iron oxides on Mars is still unknown.
A series of surface-modified clays containing nanophase (np) iron oxide/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these "Mars-soil analogs" were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging, specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The clay acted as an effective matrix, both chemically and sterically, preventing the major part of the synthesized iron oxides from ripening, i.e., growing and developing larger crystals. The precipitated iron oxides appear as isodiametric or slightly elongated particles in the size range 1-10 nm, having large specific surface area. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxy mineral such as "green rust," or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable maghemite (gamma-Fe2O3) by mild heat treatment and then to nanophase hematite (alpha-Fe2O3) by extensive heat treatment. After mild heating, the iron-enriched clay became slightly magnetic, to the extent that it adheres to a hand-held magnet, as was observed with Mars soil. The chemical reactivity of the iron-enriched clays strongly resembles, and offers a plausible mechanism for, the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxides and silicate phase surfaces. The reflectance spectrum of the clay-iron preparations in the visible range is generally similar to the reflectance curves of bright regions on Mars. This strengthens the evidence for the predominance of nanophase iron oxides/oxyhydroxides in Mars soil. The mode of formation of these nanophase iron oxides on Mars is still unknown. It is puzzling that despite the long period of time since aqueous weathering took place on Mars, they have not developed from their transitory stage to well-crystallized end-members. The possibility is suggested that these phases represent a continuously on-going, extremely slow weathering process.
As determined by impactor samplers flown on ER-2 and DC-8 aircraft, black carbon aerosol (BCA) mass loadings in the stratosphere average 0.6 nanograms per standard cubic meter, or 0.01 percent of the total aerosol. Upper tropospheric BCA increases to 0.3 percent. Low stratospheric concentration is commensurate with present commercial air traffic fuel consumption, given the following assumptions: the BCA emissions are 0.1 grams per kilogram of fuel consumed, 10 percent of route mileage is above the tropopause, and average BCA stratospheric residence time is about one year. Taking BCA into account, the stratospheric single scatter albedo is about 0.99. Using parameters for planned supersonic commercial aircraft, whose emissions will be predominantly in the stratosphere, it is shown that such traffic will double stratospheric BCA concentration. This would reduce the aerosol single scattering albedo by one percent, and double the BCA surface area that is available for heterogeneous chemistry.
Iron-enriched smectites have been suggested as important mineral compounds of the Martian soil. They were shown to comply with the chemical analysis of the Martian soil, to simulate many of the findings of the Viking Labeled Release Experiments on Mars, to have spectral reflectance in the VIS-NIR strongly resembling the bright regions on Mars. The analogy with Mars soil is based, in a number of aspects, on the nature and behavior of the iron oxides and oxyhydroxides deposited on the surface of the clay particles. A summary of the properties of these iron phases and some recent findings are presented. Their potential relevance to Mars surface processes is discussed.
Interplanetary dust particles (IDPs) are among the most pristine and primitive extraterrestrial materials available for direct study. Most of the stratospheric particles selected for study from the JSC Curatorial Collection were chondritic in composition (major element abundances within a factor of two of chondritic meteorites) because this composition virtually ensures that the particle is from an extraterrestrial source. It is likely that some of the most interesting classes of IDP's have not been recognized simply because they are not chondritic or do not fit established criteria for extraterrestrial origin. Indeed, mass spectroscopy data from the Giotto Flyby of comet Halley indicate that a substantial fraction of the dust is in the submicron size range and that a majority of these particles contain C, H, O, and/or N as major elements. The preponderance of CHON particles in the coma of Halley implies that similar particles may exist in the JSC stratospheric dust collection. However, the JSC collection also contains a variety of stratospheric contaminants from terrestrial sources which have these same characteristics. Because established criteria for extraterrestrial origin may not apply to such particles in individual cases, and integrated approach is required in which a variety of analysis techniques are applied to the same particle. Non-chondritic IDP's, like their chondritic counterparts, can be used to elucidate pre- and early solar system processes and conditions. The study of non-chondritic IDP's may additionally yield unique information which bears on the nature of cometary bodies and the processing of carbonaceous and other low atomic number materials. A suite of complementary techniques, including Low Voltage Scanning Electron Microscopy (LVSEM), Energy-Dispersive X-ray Microanalysis (EDX), Secondary Ion Mass Spectrometry (SIMS) isotope-ratio imaging and Analytical Electron Microscopy (AEM), were utilized to accomplish the following two objectives: (1) to develop criteria for the unequivocal identification of extraterrestrial non-chondritic IDP's; and (2) to infer IDP parent body, solar nebula, and pre-solar conditions through the study of phases, textures, and components contained within non-chondritic IDP's. The general approach taken is designed to maximize the total information obtained from each particle. Techniques will be applied in order from least destructive to most destructive.
In modeling cometary ice, the properties of clathrate hydrates were used to explain anomalous gas release at large radial distances from the Sun, and the retention of particular gas inventories at elevated temperatures. Clathrates may also have been important early in solar system history. However, there has never been a reasonable mechanism proposed for clathrate formation under the low pressures typical of these environments. For the first time, it was shown that clathrate hydrates can be formed by warming and annealing amorphous mixed molecular ices at low pressures. The complex microstructures which occur as a result of clathrate formation from the solid state may provide an explanation for a variety of unexplained phenomena. The vacuum and imaging systems of an Hitachi H-500H Analytical Electron Microscope was modified to study mixed molecular ices at temperatures between 12 and 373 K. The resulting ices are characterized by low-electron dose Transmission Electron Microscopy (TEM) and Selected Area Electron Diffraction (SAED). The implications of these results for the mechanical and gas release properties of comets are discussed. Laboratory IR data from similar ices are presented which suggest the possibility of remotely observing and identifying clathrates in astrophysical objects.
The properties of clathrate hydrates were used to explain the complex and poorly understood physical processes taking place within cometary nuclei and other icy solar system bodies. Most of all the experiments previously conducted used starting compositions which would yield clathrate types I hydrates. The main criterion for type I vs. type II clathrate hydrate formation is the size of the guest molecule. The stoichiometry of the two structure types is also quite different. In addition, the larger molecules which would form type II clathrate hydrates typically have lower vapor pressures. The result of these considerations is that at temperatures where we identified clathrate formation (120-130 K), it is more likely that type II clathrate hydrates will form. We also formed clathrate II hydrates of methanol by direct vapor deposition in the temperature range 125-135 K.
Ices of various kinds (H2O, CO, CO2, CH4, NH3, CH3OH, etc.) comprise a volumetrically significant proportion of objects in the solar system (comets, outer planets, planetary rings, satellites) as well as in interstellar space (astrophysical ices). The refinement of analytical electron microscopy (AEM) procedures for storing, preparing and analyzing ices and other materials at cryogenic temperatures is discussed. These procedures will be essential to the successful analysis of returned comet nucleus samples.
This paper describes the damage structure induced in natural CaF2 by the electron beam when using TEM. The observed 10-20 nm periodic features with coherent fringe patterns and the pronounced loss of fluorine found after the TEM exposure of 100-line-oriented and 111-oriented sections of CaF2 provides support for the mechanism of damage by decomposition of CaF2 into 2F and Ca, with the Ca precipitates maintaining a close topotaxial relationship with the parent CaF2.
The resolution of available low-voltage SEM (LVSEM) models used in the characterization of interplanetary dust particles (IDPs) is limited by a number of factors including energy spread in the electron source, beam brightness, scanning electron detector geometry, and various lens aberrations. This paper describes an improved model of LVSEM which offers an increased resolution at low voltage. The improvements include a cold cathode FE source which has an extremely low inherent energy spread and high brightness, a second condenser lens to converge the beam and maintain an optimum aperture half-angle, and a detector optimized for low-voltage scanning-electron collection. To reduce lens aberrations, the specimen is immersed in the objective lens field. The features of several IDP samples observed using the images obtained with this LVSEM model are described.
The paper describes a method for embedding, sectioning, and observing two types of extraterrestrial materials, including hydrated interplanetary dust particles (IDPs) and carbonaceous chondrite meteorites. The technique, which produces large thin areas suitable for both high-resolution imaging and thin-film microanalysis, was applied to study the petrology of the IDP Ames-DE C86-11, the Murchison carbonaceous chondrite matrix, and the Allende dark inclusion. The technique makes it possible to maintain delicate interfaces, boundaries, and phase relationships between grains. Because phases are held in place, layer lattice silicates and other minerals with strong preferred orientations can be viewed in any orientation, including the orientation normal to their basal planes.
A simple hand-held grinding fixture is discussed which can produce microtome mounts of hard materials, oriented interfaces, and powders embedded in a 5/16-in plastic rod. The device has been used for the ultramicrotomy of meteorite samples, 10-50 micron interplanetary dust particles, and thin films on plastic. Results are presented for a layer lattice silicate from the Murchison carbonaceous chondrite, illustrating the resolution and structural detail that can be obtained with the method.