Deoxidation of liquid copper: effect of phosphorus on oxygen activity

An analysis of the deoxidation of liquid copper is made by use of an Ellingham-type diagram, which incorporates data now available on interactions between copper and the deoxidant in solution. To make the diagram more quantitative information is required on interactions between oxygen and the deoxidants and the activities of component oxides in slags of interest in copper smelting.

Recrystallization and Ag3Sn Particle Redistribution During Thermomechanical Treatment of Bulk Sn-Ag-Cu Solder Alloys

Sn-Ag-Cu (SAC) solders are susceptible to appreciable microstructural coarsening during storage or service. This results in evolution of joint properties over time and thereby influences the long-term reliability of microelectronic packages. Accurate reliability prediction of SAC solders requires prediction of microstructural evolution during service. Microstructure evolution in two SAC solder alloys, such as, Sn-3.0Ag-0.5Cu (SAC 305) and Sn-1.0Ag-0.5 Cu (SAC 105), under different thermomechanical excursions, including isothermal aging at 150 degrees C and thermomechanical cycling (TMC) was studied. In general, between 200 and 600 cycles during TMC, recrystallization of the Sn matrix was observed, along with redistribution of Ag3Sn particles because of dissolution and reprecipitation. These latter effects have not been reported before. It was also observed that the Sn grains recrystallized near precipitate clusters in eutectic channels during extended isothermal aging. The relative orientation of Sn grains in proeutectic colonies did not change during isothermal aging.

Probing 2D black phosphorus by quantum capacitance measurements

Two-dimensional materials and their heterostructures have emerged as a new class of materials, not only for fundamental physics but also for electronic and optoelectronic applications. Black phosphorus (BP) is a relatively new addition to this class of materials. Its strong in-plane anisotropy makes BP a unique material for making conceptually new types of electronic devices. However, the global density of states (DOS) of BP in device geometry has not been measured experimentally. Here, we report the quantum capacitance measurements together with the conductance measurements on an hBN-protected few-layer BP (similar to six layers) in a dual-gated field effect transistor (FET) geometry. The measured DOS from our quantum capacitance is compared with density functional theory (DFT). Our results reveal that the transport gap for quantum capacitance is smaller than that in conductance measurements due to the presence of localized states near the band edge. The presence of localized states is confirmed by the variable range hopping seen in our temperature dependence conductivity. A large asymmetry is observed between the electron and hole side. This asymmetric nature is attributed to the anisotropic band dispersion of BP. Our measurements establish the uniqueness of quantum capacitance in probing the localized states near the band edge, hitherto not seen in conductance measurements.

Long-Range Stress Redistribution Resulting From Damage in Heterogeneous Media

It has been shown in CA simulations and data analysis of earthquakes that declustered or characteristic large earthquakes may occur with long-range stress redistribution. In order to understand long-range stress redistribution, we propose a linear-elastic but heterogeneous-brittle model. The stress redistribution in the heterogeneous-brittle medium implies a longer-range interaction than that in an elastic medium. Therefore, it is surmised that the longer-range stress redistribution resulting from damage in heterogeneous media may be a plausible mechanism governing main shocks.

Effects of temperature on the threshold of phosphorus for algal blooms

Algal blooms, worsening marine ecosystems and causing great economic loss, have been paid much attention to for a long time. Such environmental factors as light penetration, water temperature, and nutrient concentration are crucial in blooms processes. Among them, only nutrients can be controlled. Therefore, the threshold of nutrients for algal blooms is of great concern. To begin with, a dynamic eutrophication model has been constructed to simulate the algal growth and phosphorus cycling. The model encapsulates the essential biological processes of algal growth and decay, and phosphorus regeneration due to algal decay. The nutrient limitation is based upon commonly used Monod's kinetics. The effects of temperature and phosphorus limitation are particularly addressed. Then, we have endeavored to elucidate the threshold of phosphorus at different temperature for algal blooms. Based on the numerical simulation, the isoquant contours of change rate of alga as shown in the figure are obtained, which obviously demonstrate the threshold of nutrient at an arbitrary reasonable temperature. The larger the change rate is, the more rapidly the alga grows. If the phosphorus concentration at a given temperature remains larger than the threshold the algal biomass may increase monotonically, leading to the algal blooming. With the rising of temperature, the threshold is apparently reduced, which may explain why likely red tide disasters occur in a fine summer day. So, high temperature and sufficient phosphorus supply are the major factors which result in algal growth and blowout of red tide.

Phosphorus substituted hydroxylamine and hydroxamic acid derivatives: synthesis and reactivity

Dedicated to Prof. Julio Alvarez-Builla on the occasion of his 65th anniversary.

Potential Application of Adsorptive Media to Enhance Phosphorus Uptake in Stormwater Basins and Wetlands at Lake Tahoe : literature review. Report to the University of California Davis Tahoe Research Group

Phosphorus removal by wetlands and basins in Lake Tahoe may be improved through designing these systems to filter storm water through media having higher phosphorus removal capabilities than local parent material. Substrates rich in iron, aluminum and calcium oftentimes have enhanced phosphorus removal. These substrates can be naturally occurring, byproducts of industrial or water treatment processes, or engineered. Phosphorus removal fundamentally occurs through chemical adsorption and/or precipitation and much of the phosphorus can be irreversibly bound. In addition to these standard media, other engineered substrates are available to enhance P removal. One such substrate is locally available in Reno and uses lanthanum coated diatomaceous earth for arsenate removal. This material, which has a high positive surface charge, can also irreversibly remove phosphorus. Physical factors also affect P removal. Specifically, specific surface area and particle shape affect filtration capacity, contact area between water and the surface area, and likelihood of clogging and blinding. A number of substrates have been shown to effectively remove P in case studies. Based upon these studies, promising substrates include WTRs, blast furnace slag, steel furnace slag, OPC, calcite, marble Utelite and other LWAs, zeolite and shale. However, other nonperformance factors such as environmental considerations, application logistics, costs, and potential for cementification narrow the list of possible media for application at Tahoe. Industrial byproducts such as slags risk possible leaching of heavy metals and this potential cannot be easily predicted. Fly ash and other fine particle substrates would be more difficult to apply because they would need to be blended, making them less desirable and more costly to apply than larger diameter media. High transportation costs rule out non-local products. Finally, amorphous calcium products will eventually cementify reducing their effectiveness in filtration systems. Based upon these considerations, bauxite, LWAs and expanded shales/clays, iron-rich sands, activated alumina, marble and dolomite, and natural and lanthanum activated diatomaceous earth are the products most likely to be tested for application at Tahoe. These materials are typically iron, calcium or aluminum based; many have a high specific surface area; and all have low transportation costs. (PDF contains 21 pages)

Beta-Hydroxyimino Phosphorus Derivatives. An Efficient Tool in Organic Synthesis

[EN] The purpose of this review article is to illustrate synthetic aspects of functionalized phosphorus derivatives containing an oximo moiety at the beta-position. First section will be focused on the synthesis of phosphine oxides, phosphonates or phosphonium salts containing an oxime group. The synthesis of these derivatives comprises the carbon–phosphorus single bond construction by reaction of haloximes with phosphorus derivatives, nucleophilic addition of phosphorus reagents to carbonyl compounds, or nucleophilic addition of phosphorus reagents to nitro olefins. This section will also concentrate on the most practical routes for the synthesis of the target compounds, through carbon–nitrogen double bond formation, which are as follows: condensation processes of carbonyl compounds and hydroxylamine derivatives or addition of hydroxylamines to allenes or alkynes. The preparative use of beta-oximo phosphorus derivatives as synthetic intermediates will be discussed in a second section, comprising olefination reaction, oxidation of oximes to nitrile oxides by reaction at the C-N double bond of the oxime moiety, oxidation of these substrates to nitrosoalkenes, reduction to the corresponding hydroxylamines and some reactions at the hydroxyl group of the hydroxyimino moiety.

Origin of Th/U variations in chondritic meteorites

Isotope dilution thorium and uranium analyses of the Harleton chondrite show a larger scatter than previously observed in equilibrated ordinary chondrites (EOC). The linear correlation of Th/U with 1/U in Harleton (and all EOC data) is produced by variation in the chlorapatite to merrillite mixing ratio. Apatite variations control the U concentrations. Phosphorus variations are compensated by inverse variations in U to preserve the Th/U vs. 1/U correlation. Because the Th/U variations reflect phosphate ampling, a weighted Th/U average should converge to an improved solar system Th/U. We obtain Th/U=3.53 (1_-mean=0.10), significantly lower and more precise than previous estimates.

To test whether apatite also produces Th/U variation in CI and CM chondrites, we performed P analyses on the solutions from leaching experiments of Orgueil and Murchison meteorites.

A linear Th/U vs. 1/U correlation in CI can be explained by redistribution of hexavalent U by aqueous fluids into carbonates and sulfates.

Unlike CI and EOC, whole rock Th/U variations in CMs are mostly due to Th variations. A Th/U vs. 1/U linear correlation suggested by previous data for CMs is not real. We distinguish 4 components responsible for the whole rock Th/U variations: (1) P and actinide-depleted matrix containing small amounts of U-rich carbonate/sulfate phases (similar to CIs); (2) CAIs and (3) chondrules are major reservoirs for actinides, (4) an easily leachable phase of high Th/U. likely carbonate produced by CAI alteration. Phosphates play a minor role as actinide and P carrier phases in CM chondrites.

Using our Th/U and minimum galactic ages from halo globular clusters, we calculate relative supernovae production rates for ²³²Th/²³⁸U and ²³⁵U/²³⁸U for different models of r-process nucleosynthesis. For uniform galactic production, the beginning of the r-process nucleosynthesis must be less than 13 Gyr. Exponentially decreasing production is also consistent with a 13 Gyr age, but very slow decay times are required (less than 35 Gyr), approaching the uniform production. The 15 Gyr Galaxy requires either a fast initial production growth (infall time constant less than 0.5 Gyr) followed by very low decrease (decay time constant greater than 100 Gyr), or the fastest possible decrease (≈8 Gyr) preceded by slow in fall (≈7.5 Gyr).

Nitrogen and phosphorus forms in water and the food requirements of algae. [Translation from: Wiadomosci Ekologiczne 19 238-244, 1973. ]

When dissolved in water, compounds of nitrogen and phosphorus ought to contain the basic assimilated food requirements for autotrophic plants and therefore autotrophic algae. This article summarises the occurrence of nitrogen in water, how species of algae utilize nitrogen and phosphorus forms for growth and the capacities of algae to adapt to environments of different nutrient wealth. This topic has unquestionable importance not only for the purpose of survival of a species but also in deciding indirectly about the stability of ecosystems.

I. Configurational stability and redistribution equilibria in organomagnesium compounds. II. Redistribution equilibria in organocadmium compounds

I. CONFIGURATIONAL STABILITY AND REDISTRIBUTION EQUILIBRIA IN ORGANOMAGNESIUM COMPOUNDS

The dependence of the rate of inversion of a dialkylmagnesium compound on the solvent has been studied.

Examination of the temperature dependence of the nuclear magnetic resonance spectrum of 1-phenyl-2-propylmagnesium bromide in diethyl ether solution indicates that inversion of configuration at the methylene group of this Grignard reagent occurs with an approximate rate of 2 sec^-1 at room temperature. This is the first example of a rapid inversion rate in a secondary Grignard reagent.

The rates of exchange of alkyl groups between dineopentylmagnesium and di-s-butylmagnesium, bis-(2-methylbutyl)-magnesium and bis-(4, 4-dimethyl-2-pentyl)-magnesium respectively in diethyl ether solution were found to be fast on the nmr time scale. However, the alkyl group exchange rate was found to be slow in a diethyl ether solution of dineopentylmagnesium and bis-(2-methylbutyl)-magnesium containing N, N, N', N'-tetramethylethylenediamine. The unsymmetrical species neopentyl-2-methylbutyl-magnesium was observed at room temperature in the nmr spectrum of the solution containing the diamine.

II. REDISTRIBUTION EQUILIBRIA IN ORGANOCADMIUM COMPOUNDS

The exchange of methyl groups in dimethylcadmium has been studied by nuclear magnetic resonance spectroscopy. Activation parameters for the methyl group exchange have been measured for a neat sample and for a solution in tetrahydrofuran. The exchange is faster in the basic solvent tetrahydrofuran relative to the neat sample and in tetrahydrofuran solution is retarded by the solvating agent N, N, N’, N’-tetramethylethylenediamine and greatly increased by cadmium bromide. The addition of methanol to a solution of dimethylcadmium in tetrahydrofuran appears to have very little effect on the rate of exchange. The exchange was found to proceed with retention of configuration. The rate-limiting step for the exchange of methyl groups in a basic solvent appears to be the dissociation of coordinating solvent from dimethylcadmium.

The equilibrium between methylcadmium bromide, dimethylcadmium and cadmium bromide in tetrahydrofuran solution has also been studied. At room temperature the interconversion of the species is very fast on the nmr time scale but at -100° distinct absorptions for methylcadmium bromide and imethylcadmium are observed.

The species ethylmethylcadmium has been observed in the nmr spectrum.

The rate of exchange of vinyl groups in a solution of divinylcadmium in tetrahydrofuran has been found to be fast on the nmr time scale.