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At least 109 records · Page 6

Contact Angles and Surface Tension of Germanium-Silicon Melts

Precise knowledge of material parameters is more and more important for improving crystal growth processes. Two important parameters are the contact (wetting) angle and the surface tension, determining meniscus shapes and surface-tension driven flows in a variety of methods (Czochralski, EFG, floating-zone, detached Bridgman growth). The sessile drop technique allows the measurement of both parameters simultaneously and has been used to measure the contact angles and the surface tension of Ge(1-x)Si(x) (0 less than or equal to x less than or equal to 1.3) alloys on various substrate materials. Fused quartz, Sapphire, glassy carbon, graphite, SiC, carbon-based aerogel, pyrolytic boron nitride (pBN), AIN, Si3N4, and polycrystalline CVD diamond were used as substrate materials. In addition, the effect of different cleaning procedures and surface treatments on the wetting behavior were investigated. Measurements were performed both under dynamic vacuum and gas atmospheres (argon or forming gas), with temperatures up to 1100 C. In some experiments, the sample was processed for longer times, up to a week, to investigate any changes of the contact angle and/or surface tension due to slow reactions with the substrate. For pure Ge, stable contact angles were found for carbon-based substrates and for pBN, for Ge(1-x)Si(x) only for pBN. The highest wetting angles were found for pBN substrates with angles around 170deg. For the surface tension of Ge, the most reliable values resulted in gamma(T) = (591- 0.077 (T-T(sub m)) 10(exp -3)N/m. The temperature dependence of the surface tension showed similar values for Ge(1-x)Si(x), around -0.08 x 10(exp -3)N/m K, and a compositional dependence of 2.2 x 10(exp -3)N/m at%Si.

Croell, A.↗

Wetting Angles and Surface Tension of Ge(1-x)Si(x) Melts on Different Substrate Materials

The wetting angles and the surface tension of Ge(1-x)Si(x) melts (0.02 less than x less than 0.13) have been measured on various substrate materials using the sessile drop technique. Fused quartz, sapphire, SiC, glassy carbon, pBN, AIN, and Si3N4 have been used as substrates. The highest and most stable wetting angles were found for pBN substrates with 164 +/- 8 deg., either under forming gas with an additional carbon getter in the system or under active vacuum. The surface tension measurements resulted in a value of +2.2 x 10(exp -3) N/m.at%Si for the concentration dependence delta(gamma)/(delta)C. For the composition range measured, the temperature dependence (delt)gamma/(delta)T showed values similar to those of pure Ge, on average -0.07 x 10(exp -3) N/mK.

Croell, A.↗

Ru(sub 2)Ge(sub 3): Crystal Growth and Come Properties

Large samples of Ru(sub 2)Ge(sub 3) were grown from Ge-rich off-stoichiometric melts at a temperature close to 1460 C by a vertical gradient freeze method in graphite and glassy carbon crucibles.

off-stoichiometric melt twinning crack formation h↗

Computational and Experimental Study of Li-doped Ionic Liquids at Electrified Interfaces

We evaluate the influence of Li-salt doping on the dynamics, capacitance, and structure of three ionic liquid electrolytes, [pyr14][TFSI], [pyr13][FSI], and [EMIM][BF4], using molecular dynamics and polarizable force fields. In this respect, our focus is on the properties of the electric double layer (EDL) formed by the electrolytes at the electrode surface as a function of surface potential (Psi). The rates of EDL formation are found to be on the order of hundreds of picoseconds and only slightly influenced by the addition of Li-salt. The EDLs of three electrolytes are shown to have different energy storage capacities, which we relate to the EDL formation free energy. The differential capacitance obtained from our computations exhibits asymmetry about the potential of zero charge and is consistent with the camel-like profiles noted from mean field theories and experiments on metallic electrodes. The introduction of Li-salt reduces the noted asymmetry in the differential capacitance profile. Complementary experimental capacitance measurements have been made on our three electrolytes in their neat forms and with Li-salt. The measurements, performed on glassy carbon electrodes, produce U-like profiles, and Li-salt doping is shown to strongly affect capacitance at high magnitudes of Psi. Differences in the theoretical and experimental shapes and magnitudes of capacitance are rationalized in terms of the electrode surface and pseudocapacitive effects. In both neat and Li-doped liquids, the details of the computational capacitance profile are well described by Psi-induced changes in the density and molecular orientation of ions in the molecular layer closest to the electrode. Our results suggest that the addition of Li+ induces disorder in the EDL, which originates from the strong binding of anions to Li+. An in-depth analysis of the distribution of Li+ in the EDL reveals that it does not readily enter the molecular layer at the electrode surface, preferring instead to be localized farther away from the surface in the second molecular layer. This behavior is validated through an analysis of the free energy of Li+ solvation as a function of distance from the electrode. Free energy wells are found to coincide with localized concentrations of Li+, the depths of which increase with Psi and suggest a source of impedance for Li+ to reach the electrode.

Haskins, Justin B.↗

Below Band-Gap Laser Ablation of Diamond for Transmission Electron Microscopy

A 248-nm excimer laser was used to thin naturally occurring type 1a diamond substrates at normal and glancing (22 deg) incidence. Perforation of a 250 micron thick substrate was achieved in about 15 minutes at normal incidence. Whilst the substrate thinned at glancing incidence was found to have large electron-transparent areas, that thinned at normal incidence required additional argon milling to achieve electron transparency. X-ray photoelectron spectroscopy of the back surface of the diamond failed to detect any graphite or glassy carbon, confirming that damage due to laser ablation occurs only at the incident surface. Samples prepared using this technique imaged in the transmission electron microscope were observed to have retained the nitrogen platelets

Posthill, J. B.↗

Wetting Properties of Molten Salts

Wettability is a key piece of information in understanding the behavior of molten salts at material interfaces. Wettability is most easily characterized by contact angle which is measurable using the sessile drop method. A modified sessile drop method was used to measure the contact angle of the LiCl-KCl eutectic at varying temperatures on Nickel 200, Hastelloy C276, Glassy Carbon, and MACOR machinable ceramic. The contact angle was used with existing surface temperature data to find the work of adhesion at various temperatures. Finally, problems encountered during the experiment are listed and possible improvements are provided.

36 MATERIALS SCIENCE↗

Mixed-Polarity Copolymers Based on Ethylene Oxide and Cyclic Carbonate: Insights into Li-Ion Solvation and Conductivity

Here, this study investigates the relationship between polarity and ionic conductivity in random and block copolymer electrolytes comprising highly flexible oligo(ethylene oxide) methyl ether methacrylate (OEM) and highly polar but glassy glycerol carbonate methacrylate (GCMA) monomers, blended with either lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium triflate. Interestingly, the high polarity of GCMA did not significantly enhance ionic dissociation, and the random copolymers (POEM-r-PGCMA) showed similar or lower ionic conductivities than the POEM homopolymer. Further analysis revealed that Li + only interacts with OEM and its counterion, not with GCMA. The less-intermixed and weakly phase-separated block copolymer (POEM-b-PGCMA) exhibited even lower conductivities than the random copolymer. Our results suggest that Li + solvation occurs only in the POEM-rich phase and that the larger PGCMA regions, depleted of Li + , disrupt long-range ion transport. These findings provide valuable insights into the design of polymer electrolytes and how segmental mobility and functional groups with contrasting polarities affect ion transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The dust around R Coronae Borealis type stars

Measurements taken by the International Ultraviolet Explorer spacecraft of the stars RY Sgr and R CrB have been analyzed using Mie theory. The extinction data, which show a 2400-2500 A peak, are consistent with a distribution of 5-60 nm glassy or amorphous carbon particles obscuring the stellar flux. The data are also fairly consistent with a cloud ejection model. Since the extinction data lack the commonly observed peak at 2170 A, it is proposed that this difference is due to the conditions present when the dust condenses. Interstellar carbon grains appear to originate in normal carbon stars which are carbon and hydrogen rich. In contrast, the grains around R CrB type stars seem to condense from a carbon-rich and hydrogen-poor vapor.

Hecht, J. H.↗

Tuning the Mechanical Properties of Crosslinked Copolymers via Sequence and Solvent‐Selective Swelling for Vat Photopolymerization

Block copolymers (BCPs) offer distinct advantages for vat photopolymerization by enabling mechanically programmable network structures through microphase-separated morphologies that can be kinetically trapped during curing, yielding properties unattainable in homogeneous resins. However, the respective roles of repeat-unit sequence and solvent environment, together with their interplay in directing network formation and mechanical performance, remain unclear. Here, we synthesize a series of CO 2 -based polycarbonate copolymers comprising a crosslinkable glassy poly(vinyl cyclohexene carbonate) (PVCHC, A block) and a non-crosslinkable soft poly(propylene carbonate) (PPC, B block). The polymer sequence is systematically varied (ABA, BAB, and statistical), and solvent choice controls block-selective swelling to jointly control gelation behavior, microphase morphology, and mechanical response through changes in the accessibility and local environment of photocrosslinkable vinyl groups during network formation, as revealed by photorheology and small angle x-ray scattering. By tuning polymer sequence and curing solvent, we transform nominally identical formulations from brittle to highly ductile materials, achieving a three-orders-of-magnitude range in toughness (0.003 to 9.1 MJ m −3 ). These results establish clear structure–processing–property relationships and identify polymer sequence and selective solvation as powerful strategies for programming both printability and performance of block copolymer resins for additive manufacturing.

additive manufacturing↗

Hybridized polymer matrix composites

Methods of improving the fire resistance of graphite epoxy composite laminates were investigated with the objective of reducing the volume of loose graphite fibers disseminated into the airstream as the result of a high intensity aircraft fuel fire. Improvements were sought by modifying the standard graphite epoxy systems without significantly negating their structural effectiveness. The modifications consisted primarily of an addition of a third constituent material such as glass fibers, glass flakes, carbon black in a glassy resin. These additions were designed to encourage coalescense of the graphite fibers and thereby reduce their aerodynamic float characteristics. A total of 38 fire tests were conducted on thin (1.0 mm) and thick (6.0 mm) hybrid panels.

Henshaw, J.↗

A review of rare earth elements and yttrium in coal ash: Content, modes of occurrences, combustion behavior, and extraction methods

Rare earth elements and yttrium (REY) have attracted considerable attention over the last decade because of their vital roles in clean energy, consumer product, national defense and security applications, among other uses. Due to the retention of REY during coal burning, coal combustion ash is considered as potential alternative sources for REY. Understanding the content, speciation, retention and/or transformation behavior of REY during coal combustion not only expands our knowledge of the combustion behavior of the trace elements in coal, but also provides basis for modeling REY partitioning during coal combustion and for developing economically viable REY recovery technologies. This review makes a critical summary of recent progress in the study of REY in coal ash. The contents and the extraction potentials of REY in coal ash derived from 15 major coal-producing countries worldwide were summarized and evaluated. Various analytical methods for determining REY bulk contents and speciation, together with the solid sample pretreatment, analytical accuracy and precision, advantages and disadvantages were summarized and compared. Modern analytical approaches combined indirect methods (e.g., sequential extraction) shed light on the physical distribution, mineralogy, and the chemical state of REY in coal ash. Three types of REY occurrences in coal ash, including Si-Al glassy association, discrete minerals or compounds, and organic association (bound with unburned carbon) were defined in the review. The glassy association can be further divided into REY minerals closely bound to glass phases and dispersed throughout the glassy structure. REY partitioning in various emission streams, the size distribution, and their enrichment behavior in coal ash were discussed. Additionally, thermal behavior and transformation of various REY forms in coal during combustion process, including organic-associated REY, REY phosphates, REY carbonates, clay-bound REY and among others were summarized. Two possible retention mechanisms of REY by aluminosilicate glass at boiler temperature were proposed: the incorporation of the individual REY phases into the glass as inclusions and the diffusion of REY phases throughout Si-Al glass structures in the melting process. Feed coal mineral types, mineral-mineral associations, boiler conditions, and other factors control the retention process. After coal combustion, the speciation of REY in fly ash may be modified by the reactions of REY phases with flue gas components. Further, an overview of REY transformation mechanisms during coal combustion was deeply discussed. Finally, current extraction techniques for REY recovery from coal combustion ash were introduced. Future outlooks and research problems were also identified.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamical States of Low Temperature Cirrus

Low ice crystal concentration and sustained in-cloud supersaturation, commonly found in cloud observations at low temperature, challenge our understanding of cirrus formation. Heterogeneous freezing from effloresced ammonium sulfate, glassy aerosol, dust and black carbon are proposed to cause these phenomena; this requires low updrafts for cirrus characteristics to agree with observations and is at odds with the gravity wave spectrum in the upper troposphere. Background temperature fluctuations however can establish a dynamical equilibrium between ice production and sedimentation loss (as opposed to ice crystal formation during the first stages of cloud evolution and subsequent slow cloud decay) that explains low temperature cirrus properties. This newly-discovered state is favored at low temperatures and does not require heterogeneous nucleation to occur (the presence of ice nuclei can however facilitate its onset). Our understanding of cirrus clouds and their role in anthropogenic climate change is reshaped, as the type of dynamical forcing will set these clouds in one of two preferred microphysical regimes with very different susceptibility to aerosol.

Barahona, D.↗

A Diversity of Calcium-Rich Carbonates in EETA 79001

Carbonate minerals of martian origin are present in several martian meteorites in trace concentrations (less than 1 percent) and possess unique isotopic signatures that suggest that the martian environment and/or isotopic reservoirs are very different from the Earth’s. Carbonates are most common in the older martian meteorites (ALH 84001 and the nakhlites), however, there have been reports of carbonate in the younger shergottites including EETA 79001 (Mars meteorite Elephant Moraine 79001). Acidification studies of Zagami and Shergotty have shown that CO2 is released suggesting that carbonate phases are present in these meteorites, but the origin of these phases is controversial. The young ages of the shergottites makes them important samples for understanding the modern martian environment. The carbonates in EETA 79001 are the best-characterized secondary minerals in a shergottite, but their origin remains controversial. Gooding et al. argued that two types of carbonate occur with-in the glassy parts of the meteorite. One type, nearly pure CaCO3 associated with Ca-sulfate shows textural evidence for being present in the rock prior to it being shocked, suggesting formation on Mars. The second was more abundant and consists of Ca-rich carbonate, possibly with finely intergrown Mg-phosphate, but does not possess any textural relationships indicative of a martian origin. Carbon and oxygen isotopic studies of this carbonate yielded oxygen isotopes that potentially suggest a martian origin as well

Niles, P. B.↗

Simulation of lunar carbon chemistry. II - Lunar winds contribution

Simulation experiments, computations, and analysis of glassy agglutinates show that a directly condensed lunar wind vapor phase is strongly depleted in carbon and sulfur compounds and may recrystallize rapidly in the lunar thermal cycle and separate from host crystals. Factors preventing identification of low-energy species implanted from the lunar atmosphere are discussed. Computational results indicate that the implanted lunar winds carbon originates both from the vapor phases injected into the lunar atmosphere during thermal metamorphism of mature lunar soil grains and from direct volatization of impacting micrometeorites. It is suggested that microglass splashes and tiny crystalline grains possibly attached to the surface of coarser grains do not affect the characteristics of solar wind carbon chemistry in the lunar soil.

Bibring, J. P.↗

Calcium carbonate and calcium sulfate in Martian meteorite EETA79001

Chips of glassy Lithology C of EETA79001 were studied by scanning electron microscopy and energy dispersive X-ray spectroscopy to determine the mineralogy and petrogenesis of the glass that was shown by others to contain trapped Mars-like gases. Calcium carbonite was identified as massive to acicular crystals for which Ca, C, and O were the major elements. Calcium sulfate was identified as prismatic-acicular crystals with Ca and S as the major elements.

Gooding, J. L.↗

Distributed Mafic Rock Resources for Carbon Mineralization in Arizona

Ex-situ carbon mineralization is a process by which CO2 is reacted with alkaline silicate minerals and rocks to produce stable carbonate materials, which can be used for other industrial processes. Arizona, U.S.A., hosts abundant surficial mafic rocks in three young volcanic fields, Geronimo-San Bernardino, San Francisco, and Springerville, and other distributed locations throughout the state. We created a Mafic Rock Resource Inventory (MRRI) that categorizes geochemical, physical, and textural characteristics of a diverse suite of surficial mafic rock samples and provide a benchmark reaction dataset parameterizing the temperature, pressure, and pH conditions best suited ex-situ mineralization in different rock types. MRRI data is publicly available online via a map-viewer. We establish two reaction condition sets, varied in temperature, pressure, and pH, where crystal-rich and glassy rocks reach maximum reaction extent and different carbonate phases are formed. Systematic ex-situ mineralization experiments on 21 diverse rock types show trends in geochemical, mineralogical, and reactivity behavior and establish maximum effective capture capacity. From this, scoria cones in three Arizona volcanic fields have a ~62 Gt effective CO₂ storage capacity with one of the fields having a ~42 Gt storage capacity in lava flows. Reactivity results have applications to alkaline mafic rock resources exposed globally, including producing additional effective storage capacity estimates and scaled commercialization of mafic rock ex-situ mineralization, should reaction extents be improved through advances in mineralization techniques. MRRI data were used to create a Direct Air Capture to Mineralization (DACM) systems model, technoeconomic analysis, and life-cycle assessment. These documents are presented as three appendices.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗