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At least 325 records · Page 18

Is There a Speed Limit?

Fundamental barriers limiting the rate of the growth of crystals suitable for processing into cost efficient effective solar cells are discussed. The physical conditions which permit the growth of sheet directly from the melt are explored to identify the factors which control the growth rate. These criteria are edge defined film fed growth, free meniscus growth and inclined interface growth with specific reference to the effects that increase of speed has on those aspects of the resulting material that bear on the quality of the solar cells made from it. Useful directions for future research are indicated.

Chalmers, B.↗

Single Crystal Membranes

Single crystal a- and c-axis tubes and ribbons of sodium beta-alumina and sodium magnesium beta-alumina were grown from sodium oxide rich melts. Additional experiments grew ribbon crystals containing sodium magnesium beta, beta double prime, beta triple prime, and beta quadruple prime. A high pressure crystal growth chamber, sodium oxide rich melts, and iridium for all surfaces in contact with the melt were combined with the edge-defined, film-fed growth technique to grow the single crystal beta-alumina tubes and ribbons. The crystals were characterized using metallographic and X-ray diffraction techniques, and wet chemical analysis was used to determine the sodium, magnesium, and aluminum content of the grown crystals.

Stormont, R. W.↗

Materials Science Laboratory - Columnar-to-Equiaxed Transition in Solidification Processing and Microstructure Formation in Casting of Technical Alloys under Diffusive and Magnetically Controlled Convective Conditions

The Materials Science Laboratory - Columnar-to-Equiaxed Transition in Solidification Processing and Microstructure Formation in Casting of Technical Alloys under Diffusive and Magnetically Controlled Convective Conditions (MSL-CETSOL and MICAST) are two investigations which supports research into metallurgical solidification, semiconductor crystal growth (Bridgman and zone melting), and measurement of thermo-physical properties of materials. This is a cooperative investigation with the European Space Agency (ESA) and National Aeronautics and Space Administration (NASA) for accommodation and operation aboard the International Space Station (ISS). Research Summary: Materials Science Laboratory - Columnar-to-Equiaxed Transition in Solidification Processing (CETSOL) and Microstructure Formation in Casting of Technical Alloys under Diffusive and Magnetically Controlled Convective Conditions (MICAST) are two complementary investigations which will examine different growth patterns and evolution of microstructures during crystallization of metallic alloys in microgravity. The aim of these experiments is to deepen the quantitative understanding of the physical principles that govern solidification processes in cast alloys by directional solidification.

Gandin, Charles-Andre↗

Effects of a Rotating Magnetic Field on Gas Transport During Detached Crystal Growth in Space

During the detached Bridgman growth of semiconductor crystals, the melt has a short free surface which is detached from the ampoule wall near the crystal-melt interface, thus eliminating the crystal defects caused by contact with the ampoule wall. Recent modelling has indicated that initiation and continuation of detached growth depends on the rate of transport of dissolved gas from the crystal-melt interface, where gas is rejected into the melt, to the detached free surface, where evaporating gas maintains the pressure on the free surface. Here we use numerical modelling to investigate whether the application of a rotating magnetic field increases or decreases the transport of rejected gas to the detached free surface. Unfortunately the results show that a rotating magnetic field almost always decreases the evaporation rate at the detached free surface. The exception is an insignificant increase for a short period at the beginning of crystal growth for a few circumstances. The evaporation rate decreases as the strength of the rotating magnetic field is increased.

Walker, John S.↗

Fatigue crack growth resistance of a mesoscale composite microstructure Haynes 282 fabricated via electron beam melting additive manufacturing

Materials synthesis via additive manufacturing gives unprecedented control over the solidified microstructure. While a number of studies have demonstrated the ability to produce spatially varying microstructures, little work exists to understand the behavior of such “composite” materials. In this work, we utilized electron beam melting to process Ni-based superalloy Haynes 282 and produce compact tension samples with a spatially varying mesoscale structure. Fatigue crack growth experiments reveal that the crack growth rate is dependent on the degree of microstructural heterogeneity. This work demonstrates that the crack growth resistance can be tailored within a component using electron beam melting additive manufacturing.

36 MATERIALS SCIENCE↗

Kinetic Controls on Formation of Textures in Rapidly Cooled Rocks

The crystallization of silicate melts is a complex process involving melts usually produced by partial melting and cooling environments that are rapid in volcanic lavas or so slow as to be auto-metamorphic in plutonic regimes. The volcanic lavas are amenable to laboratory study as are chondrules that comprise the bulk of chondritic meteorites. Dynamic crystallization studies of basalt and chondrule melts have shown that nucleation has a more profound effect on the final texture than the cooling or crystal growth rates. The sequence of crystal shapes grown at increasing degrees of supercooling (DELTA T) or cooling rate demonstrates the effect of increasing growth rate. Equant or euhedral crystals become skeletal, then dendritic and ultimately spherulitic indicating the nucleation temperature and the DELTA T when growth began. Because crystals cannot grow until they nucleate, cooling rate does not always correlate with crystal growth rate and thus crystal shape. Silicate melts cooled at the same rate can have drastically different textures depending on the temperature of nucleation. A dynamic crystallization study of basaltic rocks shows that basaltic lavas must erupt with sufficient crystals present in the melt to act as nuclei and foster growth. With nuclei present, growth will begin when the temperature drops below the liquidus temperature and typical basaltic textures such as intersertal, intergranular or subophitic will form. If nuclei are not present, crystallization will not begin immediately and the DELTA T will increase until embryos in the melts become nuclei. The DELTA T present when grow begins dictates the growth rate and the crystal shapes and thus the rock texture. If nucleation is delayed, growth will take place at high DELTA T and the crystals will favor skeletal or dendritic shapes. Chondrules are usually considered crystallized melt droplets and clearly some are, but most are not. Most chondrules have porphyritic textures that cannot develop from totally melted droplets because nucleation is delayed during cooling and growth occurs at high DELTA T and the resulting textures are dendritic or spherulitic. The porphyritic textures will develop only if the chondrule is partially molten and begins to crystallize immediately upon cooling. Chondrule compositions are close to komatiites and these studies bear on the origin of their textures as well.

Lofgren, Gary E.↗

Thermocapillary flow and natural convection in a melt column with an unknown melt/solid interface

A vertical melt column set up between an upper heating rod and a lower sample rod, i.e., the so-called half-zone system, is a convenient experimental tool for studying convection in the melt in floating-zone crystal growth. In order to help understand the convection observed in the melt column, a computer model has been developed to describe steady state, axisymmetrical thermocapillary flow and natural convection in the melt. The governing equations and boundary conditions are expressed in general non-orthogonal curvilinear coordinates in order to accurately treat the unknown melt/solid interface as well as all other physical boundaries in the system. The effects of key dimensionless variables on the following items are discussed: (1) convection and temperature distribution in the melt; (2) the shape of the melt/solid interface; (3) the height of the melt column. These dimensionless variables are the Grashof, Marangoni and Prandtl numbers.

Lan, C. W.↗

Formation of a Martian Pyroxenite: A Comparative Study of the Nakhlite Meteorites and Theo's Flow

The unusual composition of the nakhlites, a group of pyroxenitic martian meteorites with young ages, presents an opportunity to learn about nonbasaltic magmatic activity on another planet. However, the limited number of these meteorites makes unraveling their history difficult. A promising terrestrial analog for the formation of the nakhlites is Theo's Flow in Ontario, Canada. This atypical, 120 m-thick flow differentiated in place, forming distinct layered lithologies of peridotite, pyroxenite, and gabbro. Theo's pyroxenite and the nakhlites share strikingly similar petrographies, with concentrated euhedral to subhedral augite grains set in a plagioclase-rich matrix. These two suites of rocks also share specific petrologic features, mineral and whole-rock compositional features, and size and spatial distributions of cumulus grains. The numerous similarities suggest that the nakhlites formed by a similar mechanism in a surface lava flow or shallow intrusion. Their formation could have involved settling of crystals in a phenocryst-laden flow or in situ nucleation and growth of pyroxenes in an ultramafic lava flow. The latter case is more likely and requires steady-state nucleation and growth of clusters of pyroxene grains (and olivine in the nakhlites), circulating in a strongly convecting melt pool, followed by settling and continued growth in a thickening cumulate pile. Trapped pockets of intercumulus liquid in the pile gradually evolved, finally growing Fe-enriched rims on cumulus grains. With sufficient evolution, the melt reached plagioclase supersaturation, causing rapid growth of plagioclase sprays and late-stage mesostasis growth.

Friedman, R. C.↗

Formation and fate of freshwater on an ice floe in the Central Arctic

The melt of snow and sea ice during the Arctic summer is a significant source of relatively fresh meltwater. The fate of this freshwater, whether in surface melt ponds or thin layers underneath the ice and in leads, impacts atmosphere–ice–ocean interactions and their subsequent coupled evolution. Here, we combine analyses of datasets from the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition (June–July 2020) for a process study on the formation and fate of sea ice freshwater on ice floes in the Central Arctic. Our freshwater budget analyses suggest that a relatively high fraction (58 %) is derived from surface melt. Additionally, the contribution from stored precipitation (snowmelt) outweighs by 5 times the input from in situ summer precipitation (rain). The magnitude and rate of local meltwater production are remarkably similar to those observed on the prior Surface Heat Budget of the Arctic Ocean (SHEBA) campaign, where the cumulative summer freshwater production totaled around 1 m during both. A relatively small fraction (10 %) of freshwater from melt remains in ponds, which is higher on more deformed second-year ice (SYI) compared to first-year ice (FYI) later in the summer. Most meltwater drains laterally and vertically, with vertical drainage enabling storage of freshwater internally in the ice by freshening brine channels. In the upper ocean, freshwater can accumulate in transient meltwater layers on the order of 0.1 to 1 m thick in leads and under the ice. The presence of such layers substantially impacts the coupled system by reducing bottom melt and allowing false bottom growth; reducing heat, nutrient, and gas exchange; and influencing ecosystem productivity. Regardless, the majority fraction of freshwater from melt is inferred to be ultimately incorporated into the upper ocean (75 %) or stored internally in the ice (14 %). Terms such as the annual sea ice freshwater production and meltwater storage in ponds could be used in future work as diagnostics for global climate and process models. For example, the range of values from the CESM2 climate model roughly encapsulate the observed total freshwater production, while storage in melt ponds is underestimated by about 50 %, suggesting pond drainage terms as a key process for investigation.

54 ENVIRONMENTAL SCIENCES↗

Single crystals of selected titanates and tungstates

The compound preparation and crystal growth of a number of mixed titanate compositions was investigated. None of the compounds studied were found to melt congruently and therefore, crystal growth was extremely difficult. Various single crystal preparation methods always resulted in mixed phases from which 1-2 mm size crystals could be separated. It is concluded from this study that before successful single crystal growth can be accomplished, a detailed study of the phase diagrams in each of the systems of interest must be completed.

Loiacono, G. M.↗

Materials science and manufacturing in space: The NBS program of ground based research

National Bereau of Standards work for NASA in support of NASA's Space Processing Program is described. The objectives of the NBS program are to perform ground-based studies of those aspects of space that could possibly provide a unique environment for making materials more perfect or more pure. The approach taken deals primarily with experimental and theoretical studies of the possible effects of the absence of gravitational forces on those materials preparation processes where the presence of gravity may be important in reducing perfection or purity. The materials preparation processes studied comprise 6 tasks in the areas of crystal growth, purification and chemical processing, and the preparation of composites. They are: (1) crystal perfection in Czochralski growth; (2) evaporative preparation of ultrahigh purity materials; (3) vacuum effects in the preparation of composite materials; (4) melt shape in weightless crystal growth; (5) vapor transport synthesis and crystal growth of oxides; and (6) surface traction and other surface phenomena.

Passaglia, E.↗

Radial segregation induced by natural convection and melt/solid interface shape in vertical Bridgman growth

The roles of natural convection in the melt and the shape of the melt/solid interface on radial dopant segregation are analyzed for a prototype of vertical Bridgman crystal growth system by finite element methods that solve simultaneously for the velocity field in the melt, the shape of the solidification isotherm, and the temperature distribution in both phases. Results are presented for crystal and melt with thermophysical properties similar to those of gallium-doped germanium in Bridgman configurations with melt below (thermally destabilizing) and above (stabilizing) the crystal. Steady axisymmetric flow are classified according to Rayleigh number as either being nearly the growth velocity, having a weak cellular structure or having large amplitude cellular convention. The flows in the two Bridgman configurations are driven by different temperature gradients and are in opposite directions. Finite element calculations for the transport of a dilute dopant by these flow fields reveal radial segregation levels as large as sixty percent of the mean concentration. Segregation is found most severe at an intermediate value of Rayleigh number above which the dopant distribution along the interface levels as the intensity of the flow increases.

Chang, C. J.↗

Spinel-silicate co-crystallization relations in sample 15555

The results on the crystallization history of medium-grained mare basalt sample 15555,171, based on microprobe analyses (Dalton, 1973) of host and inclusion mineral pairs are summarized with emphasis placed on that part of the crystallization history during which chromite and ulvospinel were crystallizing. Compositional data on pyroxene olivine, chromite and ulvospinel in 15555,171 were collected using microprobe; data are based on corrected counts ratios for nine elements. It is concluded that systematic chemical relations between host and inclusion minerals suggest continuous in situ nucleation and growth of these minerals; that the data allow the possibility of some minerals, especially chromite, settling out of the melt during crystallization; and that the chromite to ulvospinel transition is correlated with a compositional change of the melt resulting from nucleation and growth of plagioclase.

Dalton, J.↗

Silicon dendritic web growth

Technological goals for a silicon dendritic web growth program effort are presented. Principle objectives for this program include: (1) grow long web crystals front continuously replenished melt; (2) develop temperature distribution in web and melt; (3) improve reproductibility of growth; (4) develop configurations for increased growth rates (width and speed); (5) develop new growth system components as required for improved growth; and (6) evaluate quality of web growth.

Duncan, S.↗

The Detached Bridgman Process: Application for the Growth of Low-Defect Germanium Crystals

During crystal growth in the vertical Bridgman process, both the melt and the growing crystal are in contact with the ampoule wall. The different thermal coefficients of expansion of the crystal and the ampoule wall can lead to stresses, crystal defects, and not rarely to cracks and/or polycrystalline growth in the crystal. The detached Bridgman process is characterized by the fact that the melt meniscus frees itself from the ampoule wall and the crystal can be grown without wall contact with the ampoule. After the effect of detachment was observed due to the reduced force of gravity during the early experiments under microgravity conditions, in the past few years the Bridgman process likewise has been successfully used to grow at least partially detached under 1g-condition. If the requirements for detaching the melt meniscus from the ampoule wall are not fulfilled by the material-specific parameters (like e.g. wetting behavior between ampoule and melt and the growth angle of the crystal), detachment can be obtained also by the imposition of suitable pressure ratios in the growth ampoule. In the context of this paper, the growth of germanium by the detached and vertical Bridgman processes in pyrolytic boron nitride crucibles will be reported, Typical gap widths between ampoule wall and detached grown crystals are approximately 10-50 microns. Compared to the crystals grown with wall contact, a reduction of the etch pit density of approximately two orders of magnitude could be obtained by growing with the detached process.

Schweizer, M.↗

Petrographic Evidence for Rapid Heating and Cooling During Chrondrule Formation

The chondrule cooling rates used in most chondrule-formation models appear to be too low. Recent petrographic evidence indicates that the amount of crystal (especially olivine) growth that occurred after the last melting event was about 30 smaller than the grain sizes simulated in order to estimate cooling rates. The smaller amount of growth leads to an upwards revision of cooling rates by about a factor of 1000. Most chondrules are porphyritic. They consist of large and small crystals of olivine and, less commonly, pyroxene immersed in a mesostasis having a plagioclase-rich composition. In the most primitive chondrites the mesostasis is often vitreous. Because the large majority of chondrules contain FeS, it is clear that the nebula had cooled below the FeS condensation temperature (ca. 650 K) before chondrule formation occurred. The high FeO/(FeO+MgO) ratios of some chondrules require still lower nebular temperatures (less than 500 K). The traditional view has been that porphyritic chondrules formed in a single heating/cooling event and many laboratory experiments have been carried out in various kinds of kinds of furnaces to try to simulate the formation of chondrules textures in a single heating/cooling cycle. These furnace experiments have been used to infer the cooling rates of chondrules during the temperature range at which olivine crystallized from the melt. Most of these inferred values are in the range 0.01-1 K per second. These low cooling rates are problematical because there is no long-term nebular environment that yields such values. In transparent regions chondrules would cool at rates orders of magnitude higher, whereas in an opaque nebular disk the cooling rates would be many orders of magnitude lower. And these latter conditions are not suitable locations for chondrule formation because such high temperatures would cause the complete evaporation of chondrules (which have melting temperatures about 600 K higher than their evaporation temperatures). During the last several years several kinds of petrographic evidence indicating rapid chondrule cooling have been recognized. These include thin overgrowths on relict grains, clusters of small crystals that grew following the most recent melting event, and fragments preserving shardlike shapes that would have been hidden had several tens of micrometers of new growth occurred following the last melting event. And there are other indications of rapid cooling including the preservation of volatiles such as FeS and one case where the modeling of O-isotopic and FeO/(FeO+MgO) gradients indicated a high cooling rate.

Wasson, J. T.↗

Using defects as a ‘fossil record’ to help interpret complex processes during additive manufacturing: as applied to raster-scanned electron beam powder bed additively manufactured Ti–6Al–4V

Abstract Defects in parts produced by additive manufacturing, instead of simply being perceived as deleterious, can act as important sources of information associated with the complex physical processes that occur during materials deposition and subsequent thermal cycles. Indeed, they act as materials-state ‘fossil’ records of the dynamic AM process. The approach of using defects as epoch-like records of prior history has been developed while studying additively manufactured Ti–6Al–4V and has given new insights into processes that may otherwise remain either obscured or unquantified. Analogous to ‘epochs,’ the evolution of these defects often is characterized by physics that span across a temporal length scale. To demonstrate this approach, a broad range of analyses including optical and electron microscopy, X-ray computed tomography, energy-dispersive spectroscopy, and electron backscatter diffraction have been used to characterize a raster-scanned electron beam Ti–6Al–4V sample. These analysis techniques provide key characteristics of defects such as their morphology, location within the part, complex compositional fields interacting with the defects, and structures on the free surfaces of defects. Observed defects have been classified as banding, spherical porosity, and lack of fusion. Banding is directly related to preferential evaporation of Al, which has an influence on mechanical properties. Lack-of-fusion defects can be used to understand columnar grain growth, fluid flow of melt pools, humping, and spattering events. Graphical abstract

36 MATERIALS SCIENCE↗

A new cyclic carbonate enables high power/ low temperature lithium-ion batteries

The modern lithium-ion battery (LIB) configuration was enabled by the "magic chemistry" between ethylene carbonate (EC) and graphitic carbon anode. Despite the constant changes of cathode chemistries with improved energy densities, EC-graphite combination remained static during the last three decades. While the interphase generated by EC protects the fragile graphitic structure, the intrinsic disadvantages of EC (high viscosity, high melting point, excessive interphase growth) lead to mediocre power density and poor performances of LIB at sub-zero temperatures, where lithium depositions form upon charging. Such performance compromises arise from the fundamental dilemma between requiring effective interphase protection and high impedance from excessive growth of interphase. In this work, we designed and synthesized a "double EC" molecule as electrolyte additive to resolve the above dilemma. Erythritol bis(carbonate) (EBC) possesses lower LUMO energy level than EC and hence tends to decompose prior to EC reduction, but its weak solvation toward Li + restricts the extent of its reduction, thus minimizing the interphase thickness and the corresponding impedances. Electrolytes containing EBC enables both the charging and discharging of ampere-size LIB pouch cells at sub-zero temperatures from 0 to -20°C, demonstrating that the key approach to improve low temperature performances lies in how to tailor interphasial chemistry rather than the bulk electrolyte composition.

25 ENERGY STORAGE↗