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At least 577 records · Page 32

The sugar model: catalytic flow reactor dynamics of pyruvaldehyde synthesis from triose catalyzed by poly-l-lysine contained in a dialyzer

The formation of pyruvaldehyde from triose sugars was catalyzed by poly-l-lysine contained in a small dialyzer with a 100 molecular weight cut off (100 MWCO) suspended in a much larger triose substrate reservoir at pH 5.5 and 40 degrees C. The polylysine confined in the dialyzer functioned as a catalytic flow reactor that constantly brought in triose from the substrate reservoir by diffusion to offset the drop in triose concentration within the reactor caused by its conversion to pyruvaldehyde. The catalytic polylysine solution (400 mM, 0.35 mL) within the dialyzer generated pyruvaldehyde with a synthetic intensity (rate/volume) that was 3400 times greater than that of the triose substrate solution (12 mM, 120 mL) outside the dialyzer. Under the given conditions the final yield of pyruvaldehyde was greater than twice the weight of the polylysine catalyst. During the reaction the polylysine catalyst was poisoned presumably by reaction of its amino groups with aldehyde reactants and products. Similar results were obtained using a dialyzer with a 500 MWCO. The dialyzer method of catalyst containment was selected because it provides a simple and easily manipulated experimental system for studying the dynamics and evolutionary development of confined autocatalytic processes related to the origin of life under anaerobic conditions.

Biogenesis↗

Signal Design for Improved Ranging Among Multiple Transceivers

"Ultra-BOC" (where "BOC" signifies "binary offset carrier") is the name of an improved generic design of microwave signals to be used by a group of spacecraft flying in formation to measure ranges and bearings among themselves and to exchange telemetry needed for these measurements. Ultra-BOC could also be applied on Earth for diverse purposes -- for example, measuring relative positions of vehicles on highways for traffic-control purposes and determining the relative alignments of machines operating in mines and of construction machines and structures at construction sites. Ultra-BOC provides for rapid and robust acquisition of signals, even when signal-to-noise ratios are low. The design further provides that each spacecraft or other platform constantly strives to acquire and track the signals from the other platforms while simultaneously transmitting signals that provide full range, bearing, and telemetry service to the other platforms. In Ultra-BOC, unlike in other signal designs that have been considered for the same purposes, it is not necessary to maneuver the spacecraft or other platforms to obtain the data needed for resolving integer-carrier-cycle phase ambiguities.

Young, Lawrence↗

On the mechanism of soot nucleation. II. E-bridge formation at the PAH bay

A recently proposed mechanism of soot nucleation based upon the formation of a rotationally-activated dimer in the collision of an aromatic molecule and a radical leading to a stable, doubly-bonded E-bridge between them, rooted in the existence of a five-membered ring on the molecule edge, has been further investigated with a focus on the 5-6 E-bridge forming in the reaction of a PAH cyclopenta group with a bay site of another PAH. As a prototype reaction of this kind, we examined the reaction between 4-phenanthrenyl and acenaphthylene and, to project these results to larger aromatic structures, we also explored the size effect of the E-bridge forming reactions by computing the 1-naphthyl + acenaphthylene system and comparing these results with the prior results for pyrenyl + acepyrene. The two systems have been studied through high-level G3(MP2,CC)//B3LYP/6-311G(d,p) ab initio calculations of their potential energy surfaces combined with the RRKM/Master Equation calculations of reaction rate constants. With PAH monomers of similar sizes involved, the formation of E-bridge structures at the bay radical sites appeared to be faster and lead to increased nucleation rates as compared to the zigzag-forming ones. Furthermore, a model combining both the bay and zigzag rotationally-induced formation of E-bridges successfully reaches the level of nucleation fluxes comparable to those of the irreversible pyrene dimerization, thus affirming the rotationally-activated dimerization as a feasible mechanism for soot particle nucleation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anyon superconductivity from topological criticality in a Hofstadter–Hubbard model

We argue that the combination of strong repulsive interactions and high magnetic fields can generate electron pairing and superconductivity. Inspired by the large lattice constants of moiré materials, which make large flux per unit cell accessible at laboratory fields, we study the triangular lattice Hofstadter-Hubbard model at one-quarter flux quantum per plaquette, where previous literature has argued that a chiral spin liquid separates a weak-coupling integer quantum Hall phase and a strong-coupling topologically trivial antiferromagnetic insulator at a density of one electron per site. We argue that topological superconductivity emerges upon doping in the vicinity of the integer quantum Hall to chiral spin liquid transition. We employ exact diagonalization and density matrix renormalization group methods to examine this theoretical scenario and find that electronic pairing indeed occurs on both sides of criticality over a remarkably broad range of interaction strengths. On the chiral spin liquid side, our results provide a concrete model realization of the long-hypothesized mechanism of anyon superconductivity. Our study thus establishes a beyond-Bardeen-Cooper-Schrieffer route to electron pairing in a well-controlled limit, relying crucially on the interplay between electron correlations and band topology.

Hubbard model↗

Diagenetic Mineralogy at Gale Crater, Mars

Three years into exploration of sediments in Gale crater on Mars, the Mars Science Laboratory rover Curiosity has provided data on several modes and episodes of diagenetic mineral formation. Curiosity determines mineralogy principally by X-ray diffraction (XRD), but with supporting data from thermal-release profiles of volatiles, bulk chemistry, passive spectroscopy, and laser-induced breakdown spectra of targeted spots. Mudstones at Yellowknife Bay, within the landing ellipse, contain approximately 20% phyllosilicate that we interpret as authigenic smectite formed by basalt weathering in relatively dilute water, with associated formation of authigenic magnetite as in experiments by Tosca and Hurowitz [Goldschmidt 2014]. Varied interlayer spacing of the smectite, collapsed at approximately 10 A or expanded at approximately 13.2 A, is evidence of localized diagenesis that may include partial intercalation of metal-hydroxyl groups in the approximately 13.2 A material. Subsequent sampling of stratigraphically higher Windjana sandstone revealed sediment with multiple sources, possible concentration of detrital magnetite, and minimal abundance of diagenetic minerals. Most recent sampling has been of lower strata at Mount Sharp, where diagenesis is widespread and varied. Here XRD shows that hematite first becomes abundant and products of diagenesis include jarosite and cristobalite. In addition, bulk chemistry identifies Mg-sulfate concretions that may be amorphous or crystalline. Throughout Curiosity's traverse, later diagenetic fractures (and rarer nodules) of mm to dm scale are common and surprisingly constant and simple in Ca-sulfate composition. Other sulfates (Mg,Fe) appear to be absent in this later diagenetic cycle, and circumneutral solutions are indicated. Equally surprising is the rarity of gypsum and common occurrence of bassanite and anhydrite. Bassanite, rare on Earth, plays a major role at this location on Mars. Dehydration of gypsum to bassanite in the dry atmosphere of Mars has been proposed but considered unlikely based on lab studies of dehydration kinetics in powdered samples. Dehydration is even less likely for bulk vein samples, as lab data show dehydration rates one to two orders of magnitude slower in bulk samples than in powders. On Mars, exposure ages of 100 Ma or more may be a significant factor in dehydration of hydrous phases.

Vaniman, David↗

New Cepheid distances to nearby galaxies based on BVRI CCD photometry. III - NGC 300

A true distance modulus of (m - M) sub 0 = 26.66 +/- 0.10 mag (corresponding to 2.1 +/- 0.1 Mpc) has been determined for the Sculptor Group spiral galaxy NGC 300. New CCD data have been obtained for a sample of known Cepheids in this galaxy from which apparent distance moduli at B, V, R, and I wavelengths are determined. Combining the data available at different wavelenghts, and assuming a true distance modulus to the LMC of 18.5 mag, a true distance modulus is obtained for NGC 300, corrected for the effects of interstellar reddening. The availability of a new distance to NGC 300 brings to five the total number of galaxies with new CCD photometry of Cepheids, useful for calibration of the Hubble constant.

Freedman, Wendy L.↗

Arylethynyl Substituted 9,lO-Anthraquinones: Tunable Stokes Shifts by Substitution and Solvent Polarity

2-Arylethynyl- and 2,6- and 2,7-diarylethynyl-substituted 9,lO-anthraquinones were synthesized via Sonogashira coupling reactions of 2-bromo-, 2,6-dibromo-, and 2,7-dibromo-9,10- anthraquinone with para-substituted phenylacetylenes. While the redox properties of those compounds are almost insensitive to substitution, their absorption maxima are linearly related to the Hammett constants with different slopes for electron donors and electron acceptors. ABI compounds are photoluminescent both in solution (quantum yields of emission <= 6 %), and as solids. The emission spectra have the characteristics of charge-transfer bands with large Stokes shifts (100-250 nm). The charge-transfer character of the emitting state is supported by large dipole moment differences between the ground and the excited state as concluded on the basis of molecular modeling and Lippert-Mataga correlations of the Stokes shifts with solvent polarity. Maximum Stokes shifts are attained by both electron-donating and -withdrawing groups. This is explained by a destabilization of the HOMO by electron donors and a stabilization of the LUMO by electron acceptors. X-ray crystallographic analysis of, for example, 2,7-bisphenylethynfl- 9,lO-anthraquinone reveals a monoclinic P21In space group and no indication for pi-overlap that would promote quenching, thus explaining emission from the solid state. Representative reduced forms of the title compounds were isolated as stable acetates of the corresponding dihydrs-9,10- anthraquinones. The emission of these compounds is blue-shifted relative to the parent oxidized forms and is attributed to internal transitions in the dihydro-9,lO-anthraquinone core.

Yang, Jinhua↗

High-Temperature Properties of Piezoelectric Langatate Single Crystals

Langasite type crystals belong to non-polar point group of 32 and do not show any phase transformations up to the melting temperature. Langatate (La3Ga(5.5)Ta(0.5)O14) demonstrates piezoelectric activity better than quartz and possesses attractive properties for high temperature sensors, resonators and filter applications. High-quality and colorless langatate crystals were grown by the Czochralski technique. The electromechanical and electrical properties of langatate crystals in different crystallographic directions were characterized at elevated temperature. The piezoelectric coefficient along x-axis was 7 pC/N as measured by a Berlincourt meter for a plate geometry with an aspect ratio of 10:1. The dielectric constant did not exhibit any significant temperature dependence (K33 approx. 21 at 30 C and K33 approx. 23 at 600 C). Loss tangent at 100 kHz remained <0.003 up to 300 C and <0.65 at 600 C. The dielectric properties along the y-axis were similar and its temperature dependence was analogous to the x-axis. Electromechanically, the inactive z-axis exhibited no resonance with K33 approx. 84 at room temperature, decreasing down to approx. 49 at 600 C. Resistivity of these crystals along x-axis decreased from approx. 6x10(exp 11) omega-cm at room temperature, to approx. 1.6x10(exp 6) omega-cm at 600 C.

Sehirlioglu, Alp↗

A Thorough Characterization of the Tellurocyanate Anion

Tellurocyanate, [TeCN] − , is the heaviest group 16 congener of the cyanate anion, [OCN] − . Due to the relative instability of the C─Te bond, tellurocyanate chemistry has seen only scarce attention. Here, we present the facile synthesis and thorough characterization of [K@crypt-222][TeCN]. The anion is essentially linear with interatomic distances C─N = 1.150(6)Å and C─Te = 2.051(4)Å, thus approximating a C≡N triple bond and for C─Te a bond order between 1 and 2. Fully 13 C and 15 N labeled [Te 13 C 15 N] − allowed for the extraction of chemical shifts and all possible coupling constants ( 13 C = 77.8 ppm, 15 N = 285.7 ppm, 125 Te = −566 ppm, 1 J 13C-15N = 8 Hz, 1 J 13C-125Te = 748 Hz, 2 J1 5N-125Te = 55 Hz), which were also determined independently by quantum chemical calculations. In the series [ChCN] − (Ch = O─Te), [TeCN] − shows the strongest spin-orbit coupling (SOC) induced heavy-atom effect on the light-atom shielding (SO-HALA-effect). In contrast, 15 N shifts are also well described without considering relativistic effects and/or SOC. Negative-ion photoelectron spectroscopy was used to extract the electron affinity (EA = 3.034 eV) and spin-orbit splitting (3807 cm −1 ) of [TeCN] • . These values continue the trends of falling EA and rising SOC in the series [ChCN] • .

Bonding analysis↗

Soil incubation methods lead to large differences in inferred methane production temperature sensitivity

Abstract Quantifying the temperature sensitivity of methane (CH 4 ) production is crucial for predicting how wetland ecosystems will respond to climate warming. Typically, the temperature sensitivity (often quantified as a Q 10 value) is derived from laboratory incubation studies and then used in biogeochemical models. However, studies report wide variation in incubation-inferred Q 10 values, with a large portion of this variation remaining unexplained. Here we applied observations in a thawing permafrost peatland (Stordalen Mire) and a well-tested process-rich model ( ecosys ) to interpret incubation observations and investigate controls on inferred CH 4 production temperature sensitivity. We developed a field-storage-incubation modeling approach to mimic the full incubation sequence, including field sampling at a particular time in the growing season, refrigerated storage, and laboratory incubation, followed by model evaluation. We found that CH 4 production rates during incubation are regulated by substrate availability and active microbial biomass of key microbial functional groups, which are affected by soil storage duration and temperature. Seasonal variation in substrate availability and active microbial biomass of key microbial functional groups led to strong time-of-sampling impacts on CH 4 production. CH 4 production is higher with less perturbation post-sampling, i.e. shorter storage duration and lower storage temperature. We found a wide range of inferred Q 10 values (1.2–3.5), which we attribute to incubation temperatures, incubation duration, storage duration, and sampling time. We also show that Q 10 values of CH 4 production are controlled by interacting biological, biochemical, and physical processes, which cause the inferred Q 10 values to differ substantially from those of the component processes. Terrestrial ecosystem models that use a constant Q 10 value to represent temperature responses may therefore predict biased soil carbon cycling under future climate scenarios.

54 ENVIRONMENTAL SCIENCES↗

The effect of oxygen fugacity on the solubility of carbon-oxygen fluids in basaltic melt

The solubility of CO2-CO fluids in a midocean ridge basalt have been measured at 1200 C, 500-1500 bar, and oxygen fugacities between NNO and NNO-4. In agreement with results of previous studies, the results reported here imply that, at least at low pressures, CO2 dissolves in basaltic melt only in the form of carbonate groups. The dissolution reaction is heterogeneous, with CO2 molecules in the fluid reacting directly with reactive oxygens in the melt to produce CO3(2-). CO, on the other hand, is insoluble, dissolving neither as carbon, molecular CO, nor CO3(2-). It is shown that, for a given pressure and temperature, the concentration of dissolved carbon-bearing species in basaltic melt in equilibrium with a carbon-oxygen fluid is proportional to the mole fraction of CO2 in the fluid, which is a function of fO2. At low pressures CO2 solubility is a linear function of CO2 fugacity at constant temperatures.

Pawley, Alison R.↗

Xerogel-Derived Ni Electrocatalysts for the Hydrogen Evolution Reaction in Alkaline Media

Anion exchange membrane water electrolyzers (AEMWEs) represent a promising technology for hydrogen production. The big advantage of the technology is that it allows for the use of platinum group metal-free (PGM-free) electrocatalysts at both electrodes, including catalysts for the hydrogen evolution reaction (HER) at the cathode. In addition to fulfilling the cost requirement, PGM-free HER catalysts need to meet the activity and durability targets of the AEMWEs. Here, in this work, we developed several carbon-supported, xerogel-derived nickel (Ni) HER electrocatalysts and evaluated the effect of various synthesis conditions, such as the type of carbon support, Ni-to-carbon ratio, and heat-treatment temperature and time, on their performance. Scanning transmission electron microscopy combined with energy-dispersive X-ray spectroscopy (STEM-EDS), X-ray diffraction spectroscopy (XRD), and X-ray photoelectron spectroscopy (XPS) revealed the formation of Ni nanoparticles with an oxygen-rich layer on the outside. Durability of the best-performing catalyst was assessed via a constant-current hold at 10 mA cm –2 over 100 h. This catalyst was found to be more active and durable than the reference PGM-free material, a commercial Ni catalyst supported on a Vulcan XC-72. The catalyst was also tested in the cathode of a fully PGM-free AEMWE, allowing to reach 1.90 V (1.84 V HFR-free) at 1 A cm –2 at 80 °C.

08 HYDROGEN↗

Spin-free formulation of the multireference driven similarity renormalization group: A benchmark study of first-row diatomic molecules and spin-crossover energetics

We report a spin-free formulation of the multireference (MR) driven similarity renormalization group (DSRG) based on the ensemble normal ordering of Mukherjee and Kutzelnigg (1997). This ensemble averages over all microstates of a given total spin quantum number, and therefore, it is invariant with respect to SU(2) transformations. As such, all equations may be reformulated in terms of spin-free quantities and they closely resemble those of spin-adapted closed-shell coupled cluster (CC) theory. The current implementation is used to assess the accuracy of various truncated MR-DSRG methods (perturbation theory up to third order and iterative methods with single and double excitations) in computing the constants of 33 first-row diatomic molecules. The accuracy trends for these first-row diatomics are consistent with our previous benchmark on a small subset of closed-shell diatomic molecules. We then present the first MR-DSRG application on transition-metal complexes by computing the spin splittings of the [Fe(H 2 O) 6 ] 2+ and [Fe(NH 3 ) 6 ] 2+ molecules. A focal point analysis (FPA) shows that third-order perturbative corrections are essential to achieve reasonably converged energetics. The FPA based on the linearized MR-DSRG theory with one- and two-body operators and up to a quintuple- ζ basis set predicts the spin splittings of [Fe(H 2 O) 6 ] 2+ and [Fe(NH 3 ) 6 ] 2+ to be –35.7 and –17.1 kcal mol –1 , respectively, showing good agreement with the results of local CC theory with singles, doubles, and perturbative triples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

ISMIP6 Antarctica: a multi-model ensemble of the Antarctic ice sheet evolution over the 21st century

Abstract. Ice flow models of the Antarctic ice sheet are commonly used to simulate its future evolution in response to different climate scenarios and assess the mass loss that would contribute to future sea level rise. However, there is currently no consensus on estimates of the future mass balance of the ice sheet, primarily because of differences in the representation of physical processes, forcings employed and initial states of ice sheet models. This study presents results from ice flow model simulations from 13 international groups focusing on the evolution of the Antarctic ice sheet during the period 2015–2100 as part of the Ice Sheet Model Intercomparison for CMIP6 (ISMIP6). They are forced with outputs from a subset of models from the Coupled Model Intercomparison Project Phase 5 (CMIP5), representative of the spread in climate model results. Simulations of the Antarctic ice sheet contribution to sea level rise in response to increased warming during this period varies between −7.8 and 30.0 cm of sea level equivalent (SLE) under Representative Concentration Pathway (RCP) 8.5 scenario forcing. These numbers are relative to a control experiment with constant climate conditions and should therefore be added to the mass loss contribution under climate conditions similar to present-day conditions over the same period. The simulated evolution of the West Antarctic ice sheet varies widely among models, with an overall mass loss, up to 18.0 cm SLE, in response to changes in oceanic conditions. East Antarctica mass change varies between −6.1 and 8.3 cm SLE in the simulations, with a significant increase in surface mass balance outweighing the increased ice discharge under most RCP 8.5 scenario forcings. The inclusion of ice shelf collapse, here assumed to be caused by large amounts of liquid water ponding at the surface of ice shelves, yields an additional simulated mass loss of 28 mm compared to simulations without ice shelf collapse. The largest sources of uncertainty come from the climate forcing, the ocean-induced melt rates, the calibration of these melt rates based on oceanic conditions taken outside of ice shelf cavities and the ice sheet dynamic response to these oceanic changes. Results under RCP 2.6 scenario based on two CMIP5 climate models show an additional mass loss of 0 and 3 cm of SLE on average compared to simulations done under present-day conditions for the two CMIP5 forcings used and display limited mass gain in East Antarctica.

54 ENVIRONMENTAL SCIENCES↗

Mechanistic investigation of the aerobic oxidation of 2-pyridylacetate coordinated to a Ru(ii) polypyridyl complex

A new ruthenium polypyridyl complex, [Ru(bpy) 2 (acpy)] + (acpy = 2-pyridylacetate, bpy = 2,2'-bipyridine), was synthesized and fully characterized. Distinct from the previously reported analog, [Ru(bpy) 2 (pic)] + (pic = 2-pyridylcarboxylate), the new complex is unstable under aerobic conditions and undergoes oxidation to yield the corresponding α-keto-2-pyridyl-acetate (acpyoxi) coordinated to the Ru II center. The reaction is one of the few examples of C–H activation at mild conditions using O 2 as the primary oxidant and can provide mechanistic insights with important implications for catalysis. Theoretical and experimental investigations of this aerobic oxidative transformation indicate that it takes place in two steps, first producing the α-hydroxo-2-pyridyl-acetate analog and then the final product. The observed rate constant for the first oxidation was in the order of 10 -2 h -1 . The reaction is hindered in the presence of coordinating solvents indicating the role of the metal center in the process. Theoretical calculations at the M06-L level of theory were performed for multiple reaction pathways in order to gain insights into the most probable mechanism. Our results= indicate that O 2 binding to [Ru(bpy) 2 (acpy)] + is favored by the relative instability of the six-ring chelate formed by the acpy ligand and the resulting Ru III -OO˙- superoxo is stabilized by the carboxylate group in the coordination sphere. C–H activation by this species involves high activation free energies (ΔG ‡ = 41.1 kcal mol -1 ), thus the formation of a diruthenium μ-peroxo intermediate, [(Ru III (bpy) 2 (O-acpy)) 2 O 2 ] 2+ via interaction of a second [Ru(bpy) 2 (acpy)] + was examined as an alternative pathway. The dimer yields two Ru IV =O centers with a low ΔG ‡ of 2.3 kcal mol -1 . The resulting Ru IV =O species can activate C–H bonds in acpy (ΔG ‡ = 23.1 kcal mol -1 ) to produce the coordinated α-hydroxo-2-pyridylacetate. Further oxidation of this intermediate leads to the α-keto-2-pyridyl-acetate product. The findings provide new insights into the mechanism of C–H activation catalyzed by transition-metal complexes using O 2 as the sole oxygen source.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Pn magnitude scale m b ( Pn ) for earthquakes along the equatorial Mid-Atlantic Ridge

We developed a short-period Pn magnitude scale m b (Pn) for earthquakes along the equatorial Mid-Atlantic Ridge. Due to low signal-to-noise ratios, teleseismic body wave magnitude and long-period surface wave magnitude cannot be confidently determined for small earthquakes of m b < 4. Local magnitude scales are also not useful for these events because the oceanic environment does not allow the propagation of crustal phases. However, regional high-frequency Pn waves from these small- to moderate-size (m b 3–6) earthquakes are well recorded in the equatorial Atlantic region and can be used to assign magnitudes. We measured over 2041 Pn peak amplitudes on vertical records from about 21 stations in northeastern Brazil and 11 stations in western Africa in the distance range of 700–3700 km. We analysed data from 189 events from the global centroid moment tensor catalogue to tie our m b (Pn) scale to M w so that seismic moments can be readily estimated. Pn arrivals show apparent group velocity between 7.9 km s –1 at short ranges (~1000 km) and up to 9.1 km s –1 at 3500 km. The measured peak amplitudes have a frequency between 0.8 and 3 Hz at 1000–1800 km, but at greater distances, 1800–3700 km, they show a remarkably consistent frequency of about 0.8 Hz. The peak amplitude attenuates at a higher rate at short distances (~0.65 magnitude units between 700 and 2000 km) but attenuates at a lower rate at long distances (~0.35 magnitude units between 2000 and 3700 km). The low rate of amplitude decay with distance and nearly constant frequency content of the peak amplitudes suggest that Pn waves propagate efficiently in the lower part of the upper mantle in the equatorial Atlantic Ocean basins. Furthermore, these are important attributes of oceanic Pn waves that can be used to assign magnitude for small- to moderate-size earthquakes in the equatorial mid-Atlantic region. The estimated station corrections correlate well with upper mantle low-velocity anomalies, especially in Brazil.

58 GEOSCIENCES↗

KAO observations of SN1987A

Explosion calculations of SN1987A generate pictures of Rayleigh-Taylor fingers of radioactive Ni-56 (Ni-56 yields Co-56 yields Fe-56) which are boosted to velocities of several thousand km/s. From the KAO observations of the mid-IR iron lines, a picture of the iron in the ejecta emerges which is consistent with the 'frothy iron fingers' having expanded to fill about 50% of the metal-rich volume of the ejecta (nu(sub m) less than or equal to 2500 km/s). The ratio of the nickel line intensities I(sub (Ni I)7.5 micron)/I(sub (Ni II)6.6 microns) yields a high ionization fraction of x(sub Ni) greater than or equal to 0.9 in the volume associated with the iron-group elements at day 415, before dust condenses in the ejecta. From the KAO observations of the dust's thermal emission (2 microns to 100 microns), it is deduced that when the grains condense, their infrared radiation is trapped, their apparent opacity is gray, and they have a surface area filling factor of about 50%. The dust emission from SN1987A is featureless: no 9.7 micron silicate feature, nor PAH features, nor dust emission features of any kind are seen at any time. The total dust opacity increases with time even though the surface area filling factor and the dust/gas ratio remain constant. This suggests that the dust forms along coherent structures which can maintain their radial line-of-sight opacities, i.e., along fat fingers. The coincidence of the filling factor of the dust and the filling factor of the iron strongly suggests that the dust condenses within the iron, and therefore the dust is iron-rich. It only takes approximately 10(exp -4) solar mass of dust for the ejecta to be optically thick out to approximately 100 microns; a lower limit of 4 x 10(exp -4) solar mass of condensed grains exists in the metal-rich volume, but much more dust could be present. The episode of dust formation started at about 539 days and proceeded rapidly, so that by 600 days 45% of the bolometric luminosity was being emitted in the IR; by 775 days, 86% of the bolometric luminosity was being reradiated by the dust. Measurements of the bolometric luminosity of SN1987A from 1000 to 2300 days are based on 10 micron and 20 micron photometry and rely on the suppositions that the IR emission is a graybody (proven to be true by the KAO observations at 615 and 775 days) and that the dust temperature drops to and remainsat 150 K. The late-time bolometric luminosity is stronger than that expected from the radioactive decay of Co-56, Co-57, Ti-44, and Na-22 and the late-time dust temperatures are consistent with the presence of a compact object.

Wooden, Diane H.↗

Method of Estimating Continuous Cooling Transformation Curves of Glasses

A method is proposed for estimating the critical cooling rate and continuous cooling transformation (CCT) curve from isothermal TTT data of glasses. The critical cooling rates and CCT curves for a group of lithium disilicate glasses containing different amounts of Pt as nucleating agent estimated through this method are compared with the experimentally measured values. By analysis of the experimental and calculated data of the lithium disilicate glasses, a simple relationship between the crystallized amount in the glasses during continuous cooling, X, and the temperature of undercooling, (Delta)T, was found to be X = AR(sup-4)exp(B (Delta)T), where (Delta)T is the temperature difference between the theoretical melting point of the glass composition and the temperature in discussion, R is the cooling rate, and A and B are constants. The relation between the amount of crystallisation during continuous cooling and isothermal hold can be expressed as (X(sub cT)/X(sub iT) = (4/B)(sup 4) (Delta)T(sup -4), where X(sub cT) stands for the crystallised amount in a glass during continuous cooling for a time t when the temperature comes to T, and X(sub iT) is the crystallised amount during isothermal hold at temperature T for a time t.

Zhu, Dongmei↗