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Experiments on Nucleation in Different Flow Regimes

The vast majority of metallic engineering materials are solidified from the liquid phase. Understanding the solidification process is essential to control microstructure, which in turn, determines the properties of materials. The genesis of solidification is nucleation, where the first stable solid forms from the liquid phase. Nucleation kinetics determine the degree of undercooling and phase selection. As such, it is important to understand nucleation phenomena in order to control solidification or glass formation in metals and alloys. Early experiments in nucleation kinetics were accomplished by droplet dispersion methods [1-6]. Dilitometry was used by Turnbull and others, and more recently differential thermal analysis and differential scanning calorimetry have been used for kinetic studies. These techniques have enjoyed success; however, there are difficulties with these experiments. Since materials are dispersed in a medium, the character of the emulsion/metal interface affects the nucleation behavior. Statistics are derived from the large number of particles observed in a single experiment, but dispersions have a finite size distribution which adds to the uncertainty of the kinetic determinations. Even though temperature can be controlled quite well before the onset of nucleation, the release of the latent heat of fusion during nucleation of particles complicates the assumption of isothermality during these experiments. Containerless processing has enabled another approach to the study of nucleation kinetics [7]. With levitation techniques it is possible to undercool one sample to nucleation repeatedly in a controlled manner, such that the statistics of the nucleation process can be derived from multiple experiments on a single sample. The authors have fully developed the analysis of nucleation experiments on single samples following the suggestions of Skripov [8]. The advantage of these experiments is that the samples are directly observable. The nucleation temperature can be measured by noncontact optical pyrometry, the mass of the sample is known, and post processing analysis can be conducted on the sample. The disadvantages are that temperature measurement must have exceptionally high precision, and it is not possible to isolate specific heterogeneous sites as in droplet dispersions.

Bayuzick, Robert J.↗

Experiments on Nucleation in Different Flow Regimes

The vast majority of metallic engineering materials are solidified from the liquid phase. Understanding the solidification process is essential to control microstructure, which in turn, determines the properties of materials. The genesis of solidification is nucleation, where the first stable solid forms from the liquid phase. Nucleation kinetics determine the degree of undercooling and phase selection. As such, it is important to understand nucleation phenomena in order to control solidification or glass formation in metals and alloys. Early experiments in nucleation kinetics were accomplished by droplet dispersion methods. Dilitometry was used by Turnbull and others, and more recently differential thermal analysis and differential scanning calorimetry have been used for kinetic studies. These techniques have enjoyed success; however, there are difficulties with these experiments. Since materials are dispersed in a medium, the character of the emulsion/metal interface affects the nucleation behavior. Statistics are derived from the large number of particles observed in a single experiment, but dispersions have a finite size distribution which adds to the uncertainty of the kinetic determinations. Even though temperature can be controlled quite well before the onset of nucleation, the release of the latent heat of fusion during nucleation of particles complicates the assumption of isothermality during these experiments. Containerless processing has enabled another approach to the study of nucleation kinetics. With levitation techniques it is possible to undercool one sample to nucleation repeatedly in a controlled manner, such that the statistics of the nucleation process can be derived from multiple experiments on a single sample. The authors have fully developed the analysis of nucleation experiments on single samples following the suggestions of Skripov. The advantage of these experiments is that the samples are directly observable. The nucleation temperature can be measured by noncontact optical pyrometry, the mass of the sample is known, and post-processing analysis can be conducted on the sample. The disadvantages are that temperature measurement must have exceptionally high precision, and it is not possible to isolate specific heterogeneous sites as in droplet dispersions. Levitation processing of refractory materials in ultra high vacuum provides an avenue to conduct these kinetic studies on single samples. Two experimental methods have been identified where ultra high vacuum experiments are possible; electrostatic levitation in ground-based experiments and electromagnetic processing in low earth orbit on TEMPUS. Such experiments, reported here, were conducted on zirconium. Liquid zirconium is an excellent solvent and has a high solubility for contaminants contained in the bulk material as well as those contaminants found in the vacuum environment. Oxides, nitrides, and carbides do not exist in the melt, and do not form on the surface of molten zirconium, for the materials and vacuum levels used in this study. Ground-based experiments with electrostatic levitation have shown that the statistical nucleation kinetic experiments are viable and yield results which are consistent with classical nucleation theory. The advantage of low earth orbit experiments is the ability to vary the flow conditions in the liquid prior to nucleation. The put-pose of nucleation experiments in TEMPUS was to examine.

Bayuzick, R. J.↗

In situ identification of the Martian surface material and its interaction with the Martian atmosphere using DTA/GC

Little is known about the mineralogy of the martian surface material. Several techniques have been suggested as candidates for the in situ identification of the martian surface material. The most promising of these techniques include differential thermal analysis (DTA) coupled with gas chromatography (GC) and differential scanning calorimetry (DSC) coupled with either mass spectrometry (MS) or GC. Our studies showed that differential thermal analysis coupled with gas chromatography (DTA/GC) is a more appropriate analytical technique than DSC/MS or DSC/GC to identify the mineralogy of the martian surface material in situ. DTA/GC can be regarded as an advancement from pyrolytic GC analyses that were successfully flown on previous missions, but have supplied only limited mineralogical information.

Mancinelli, R. L.↗

Evaluation of methods for rapid determination of freezing point of aviation fuels

Methods for identification of the more promising concepts for the development of a portable instrument to rapidly determine the freezing point of aviation fuels are described. The evaluation process consisted of: (1) collection of information on techniques previously used for the determination of the freezing point, (2) screening and selection of these techniques for further evaluation of their suitability in a portable unit for rapid measurement, and (3) an extensive experimental evaluation of the selected techniques and a final selection of the most promising technique. Test apparatuses employing differential thermal analysis and the change in optical transparency during phase change were evaluated and tested. A technique similar to differential thermal analysis using no reference fuel was investigated. In this method, the freezing point was obtained by digitizing the data and locating the point of inflection. Results obtained using this technique compare well with those obtained elsewhere using different techniques. A conceptual design of a portable instrument incorporating this technique is presented.

Mathiprakasam, B.↗

Phase diagram and electrical behavior of silicon-rich iridium silicide compounds

The iridium-silicon phase diagram on the silicon-rich side was investigated by means of X-ray powder diffraction, density, differential thermal analysis, metalography, microprobe analysis, and electrical resistivity. Attempts were made to prepare eight previously reported silicon-rich iridium silicide compounds by arc melting and Bridgman-like growth. However, microprobe analysis identified only four distinct compositions: IrSi, Ir3Si4, Ir3Si5 and IrSi sub about 3. The existence of Ir4Si5 could not be confirmed in this study, even though the crystal structure has been previously reported. Differential thermal analysis (DTA) in conjunction with X-ray powder diffraction confirm polymorphism in IrSi sub about 3, determined to have orthorhombic and monoclinic unit cells in the high and low temperature forms. A eutectic composition alloy of 83 +/- 1 atomic percent silicon was observed between IrSi sub about 3 and silicon. Ir3Si4 exhibits distinct metallic behavior while Ir3Si5 is semiconducting. Both and IrSi and IrSi sub about 3 exhibit nearly temperature independent electrical resistivities on the order of 5-10 x 10 exp -6 ohms-m.

Allevato, C. E.↗

Mineralogical aspects of terrestrial weathering effects in chondrites from Allan Hills, Antarctica

The work reported here represents a first attempt at comparing the mineralogical aspects of weathering effects in selected Antarctic chondrites with those present in a petrologically similar chondrite which was weathered in the Arizona desert. The methods of analysis employed include X-ray diffractometry, differential thermal analysis, and reflectance spectrophotometry. It is found that the dominant weathering products in the rocks are complex, multiple-phase, hydrous ferric oxides which formed by alteration of Ni-Fe metal and sulfide particles under the influence of liquid water. The Fe-oxide weathering products may comprise approximately 15-20 wt % of the most intensely weathered samples although the same samples contain not more than 5% goethite as the only well-crystallized hydrous ferric oxide.

Gooding, J. L.↗

Processing of Lunar Soil Simulant for Space Exploration Applications

NASA's long-term vision for space exploration includes developing human habitats and conducting scientific investigations on planetary bodies, especially on Moon and Mars. To reduce the level of up-mass processing and utilization of planetary in-situ resources is recognized as an important element of this vision. Within this scope and context, we have undertaken a general effort aimed primarily at extracting and refining metals, developing glass, glass-ceramic, or traditional ceramic type materials using lunar soil simulants. In this paper we will present preliminary results on our effort on carbothermal reduction of oxides for elemental extraction and zone refining for obtaining high purity metals. In additions we will demonstrate the possibility of developing glasses from lunar soil simulant for fixing nuclear waste from potential nuclear power generators on planetary bodies. Compositional analysis, x-ray diffraction patterns and differential thermal analysis of processed samples will be presented.

Sen, Subhayu↗

Crystallization Kinetics of Calcium-magnesium Aluminosilicate (CMAS) Glass

The crystallization kinetics of a calcium-magnesium aluminosilicate (CMAS) glass with composition relevant for aerospace applications, like air-breathing engines, were evaluated using differential thermal analysis (DTA) in powder and bulk forms. Activation energy and frequency factor values for crystallization of the glass were evaluated. X-ray diffraction (XRD) was used to investigate the onset of crystallization and the phases that developed after heat treating bulk glass at temperatures ranging from 690 to 960 deg for various times. Samples annealed at temperatures below 900 deg remained amorphous, while specimens heat treated at and above 900 deg exhibited crystallinity originating at the surface. The crystalline phases were identified as wollastonite (CaSiO3) and aluminum diopside (Ca(Mg,Al) (Si,Al)2O6). Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were employed to examine the microstructure and chemical compositions of crystalline phases formed after heat treatment.

X-ray diffraction (XRD)↗

Definition of exobiology experiments for future Mars missions

During the past year we have concentrated on two objectives. The first objective is ongoing and is to define the experimental parameters that are necessary to conduct autonomously a mineralogical analysis of the Martian surface in situ using differential thermal analysis coupled with gas chromatography (DTA/GC). The rationale in support of this objective is that proper interpretation of the mineralogical data from the DTA/GC can be used to better describe the present and past environments of Mars, leading to a better assessment of the probability of life evolving on Mars. To meet these objectives we have analyzed a number of samples collected from nature using the DTA/GC. One of the more significant findings was that in samples of desert varnish we detected magnetite and maghemite that may serve as potential biomarkers applicable to DTA/GC analyses of Martian surface material during landed missions. The second objective follows from the first and is to better understand microbe-environment interactions by determining the response of microbes to changes in their environment, including extreme desiccation and solar UV-radiation. The rationale behind this is to develop hypotheses regarding what may have happened to life that may have arose on Mars, and microbial life that may get to the surface of Mars via spacecraft, or meteors from Earth. To accomplish this objective we have exposed microbes, collected from NaCl and gypsum-halite crystals, to the space environment aboard the ESA-German Biopan facility for 15 days. The most significant finding was that these microbes survived the exposure better than others.

Mancinelli, Rocco L.↗

Magnetite: What it reveals about the origin of the banded iron formations

Magnetite, Fe3O4 is produced abiotically and biotically. Abiotically, magnetite is a late magmatic mineral and forms as a consequence of the cooling of iron rich magma. Biotically, magnetite is produced by several organisms, including magnetotactic bacteria. Hematite, Fe2O3, is also produced abiotically and biotically. Abiotically, hematite rarely occurs as a primary mineral in igneous rocks, but is common as an alteration product, fumarole deposit, and in some metamorphosed Fe-rich rocks. Biotically, hematite is produced by several types of microorganisms. Biologically-produced magnetite and hematite are formed under the control of the host organism, and consequently, have characteristics not found in abiotically produced magnetite and hematite crystals. To determine if the magnetite and hematite in the Banded Iron Formation was biologically or abiotically produced, the characteristics of biologically-produced magnetite and hematite (concentrated from Aquaspirillum magnetotacticum) and abiotically-produced magnetite and hematite obtained from Wards Scientific Supply Company, were compared with characteristics of magnetite and hematite concentrated from the Gunflint Banded Iron Formation (Ontario, Canada) using thermal and crystallographic analytical techniques. Whole rock analysis of the Gunflint Banded Iron Formation by x-ray diffraction (XRD) and differential thermal analysis (DTA) revealed the presence of quartz, hematite, siderite and dolomite as the major minerals, and magnetite, greenalite, pyrite, pyrrhotite and apatite as the minor minerals. Analysis of a crude magnetic fraction of the Gunflint showed the minerals quartz, hematite, siderite, dolomite, and magnetite. Analysis of the crude magnetic fraction from Aquaspirillum magnetotacticum revealed organic compounds plus hematite and magnetite. The mineral identification and particle size distribution data obtained from the DTA along with XRD data indicate that the magnetite and hematite from the Gunflint BIF share some similarities with biologically formed magnetite and hematite.

Schwartz, D. E.↗

Preparation and Characterization of the Skutterudite-Related Phase Ru0.5Pd0.5 Sb3

A new skutterudite phase Ru0.5Pd0.5 Sb3 was prepared. It adds to the many materials with the skutterudite structure that have shown a good potential for thermoelectric applications. Single- phase polycrystalline samples were prepared and characterized by x-ray analysis, electron probe microanalysis, density, sound velocity, thermal expansion coefficient, and differential thermal analysis measurements.

ternary↗