Influence of composition on the structure, electric and magnetic properties of Pd-Mn-P and Pd-Co-P amorphous alloys

The influence of composition on the structure and on the electric and magnetic properties of amorphous Pd-Mn-P and Pd-Co-P prepared by rapid quenching techniques were investigated in terms of (1) the 3d band filling of the first transition metal group, (2) the phosphorus concentration effect which acts as an electron donor and (3) the transition metal concentration.

The structure is essentially characterized by a set of polyhedra subunits essentially inverse to the packing of hard spheres in real space. Examination of computer generated distribution functions using Monte Carlo random statistical distribution of these polyhedra entities demonstrated tile reproducibility of the experimentally calculated atomic distribution function. As a result, several possible "structural parameters" are proposed such as: the number of nearest neighbors, the metal-to-metal distance, the degree of short-range order and the affinity between metal-metal and metal-metalloid. It is shown that the degree of disorder increases from Ni to Mn. Similar behavior is observed with increase in the phosphorus concentration.

The magnetic properties of Pd-Co-P alloys show that they are ferromagnetic with a Curie temperature between 272 and 399°K as the cobalt concentration increases from 15 to 50 at.%. Below 20 at.% Co the short-range exchange interactions which produce the ferromagnetism are unable to establish a long-range magnetic order and a peak in the magnetization shows up at the lowest temperature range . The electric resistivity measurements were performed from liquid helium temperatures up to the vicinity of the melting point (900°K). The thermomagnetic analysis was carried out under an applied field of 6.0 kOe. The electrical resistivity of Pd-Co-P shows the coexistence of a Kondo-like minimum with ferromagnetism. The minimum becomes less important as the transition metal concentration increases and the coefficients of ℓn T and T^2 become smaller and strongly temperature dependent. The negative magnetoresistivity is a strong indication of the existence of localized moment.

The temperature coefficient of resistivity which is positive for Pd- Fe-P, Pd-Ni-P, and Pd-Co-P becomes negative for Pd-Mn-P. It is possible to account for the negative temperature dependence by the localized spin fluctuation model and the high density of states at the Fermi energy which becomes maximum between Mn and Cr. The magnetization curves for Pd-Mn-P are typical of those resulting from the interplay of different exchange forces. The established relationship between susceptibility and resistivity confirms the localized spin fluctuation model. The magnetoresistivity of Pd-Mn-P could be interpreted in tenns of a short-range magnetic ordering that could arise from the Rudennan-Kittel type interactions.

The ionic composition of surface waters in the English Lake District, related to bedrock geology, with some singular facts and speculation on the existence of mineral-rich groundwaters

This article is based on a survey of tarns conducted mainly in the summers of 1983 to 1985, plus a survey made in the winter of 1985, in which streams were sampled on the wide variety of rock-types occurring on the fringes of the Lake District. Differences in composition of major ions and their concentrations in the surface waters of Cumbria reflect the complex geological structure of the region. At altitudes above 300 m, on Borrowdale Volcanics and Skiddaw Slates, surface waters are derived from atmospheric precipitation, with additional inputs of some ions - especially calcium and bicarbonate - from catchment rocks and soils. In some of the low-lying large lakes on the fringes of the central fells, water composition is also dominated by inputs from upper catchments; examples are Wastwater, Ullswater and Haweswater. However in other lakes there is evidence (Derwentwater and Bassenthwaite Lake) of inputs from saline groundwater.

Elemental composition of solar energetic particles

The Low Energy Telescopes on the Voyager spacecraft are used to measure the elemental composition (2 ≤ Z ≤ 28) and energy spectra (5 to 15 MeV /nucleon) of solar energetic particles (SEPs) in seven large flare events. Four flare events are selected which have SEP abundance ratios approximately independent of energy/nucleon. The abundances for these events are compared from flare to flare and are compared to solar abundances from other sources: spectroscopy of the photosphere and corona, and solar wind measurements.

The selected SEP composition results may be described by an average composition plus a systematic flare-to-flare deviation about the average. For each of the four events, the ratios of the SEP abundances to the four-flare average SEP abundances are approximately monotonic functions of nuclear charge Z in the range 6 ≤ Z ≤ 28. An exception to this Z-dependent trend occurs for He, whose abundance relative to Si is nearly the same in all four events.

The four-flare average SEP composition is significantly different from the solar composition determined by photospheric spectroscopy: The elements C, N and O are depleted in SEPs by a factor of about five relative to the elements Na, Mg, Al, Si, Ca, Cr, Fe and Ni. For some elemental abundance ratios (e.g. Mg/O), the difference between SEP and photospheric results is persistent from flare to flare and is apparently not due to a systematic difference in SEP energy/nucleon spectra between the elements, nor to propagation effects which would result in a time-dependent abundance ratio in individual flare events.

The four-flare average SEP composition is in agreement with solar wind abundance results and with a number of recent coronal abundance measurements. The evidence for a common depletion of oxygen in SEPs, the corona and the solar wind relative to the photosphere suggests that the SEPs originate in the corona and that both the SEPs and solar wind sample a coronal composition which is significantly and persistently different from that of the photosphere.

The isotopic composition of energetic particles emitted from a large solar flare

We report measurements of isotope abundance ratios for 5-50 MeV/nuc nuclei from a large solar flare that occurred on September 23, 1978. The measurements were made by the Heavy Isotope Spectrometer Telescope (HIST) on the ISEE-3 satellite orbiting the Sun near an Earth-Sun libration point approximately one million miles sunward of the Earth. We report finite values for the isotope abundance ratios ¹³C/¹²C, ¹⁵N/¹⁴N, ¹⁸O/¹⁶O, ²²Ne/ ²⁰Ne, ²⁵Mg/²⁴Mg, and ²⁶Mg/²⁴Mg, and upper limits for the isotope abundance ratios ³He/⁴He, ¹⁴C/¹²C, ¹⁷O/¹⁶O, and ²¹Ne/²⁰Ne.

We measured element abundances and spectra to compare the September 23, 1978 flare with other flares reported in the literature. The flare is a typical large flare with "low" Fe/O abundance (≤ 0.1).

For ¹³C/¹²C, ¹⁵N/¹⁴N, ¹⁸O/¹⁶O, ²⁵Mg/ ²⁴Mg, and ²⁶Mg/²⁴Mg, our measured isotope abundance ratios agree with the solar system abundance ratios of Cameron (1981). For neon we measure ²²Ne/²⁰Ne = 0.109 + 0.026 - 0.019, a value that is different with confidence 97.5% from the abundance measured in the solar wind by Geiss at al. (1972) of ²²Ne/²⁰Ne = 0.073 ± 0.001. Our measurement for ²²Ne/²⁰Ne agrees with the isotopic composition of the meteoritic component neon-A.

Separate arguments appear to rule out simple mass fractionation in the solar wind and in our solar energetic particle measurements as the cause of the discrepancy in the comparison of the apparent compositions of these two sources of solar material.

A balloon measurement of the isotopic composition of galactic cosmic ray boron, carbon, and nitrogen

The isotopic compositions of galactic cosmic ray boron, carbon, and nitrogen have been measured at energies near 300 MeV amu^-1, using a balloon-borne instrument at an atmospheric depth of ~5 g cm^-2. The calibrations of the detectors comprising the instrument are described. The saturation properties of the cesium iodide scintilla tors used for measurement of particle energy are studied in the context of analyzing the data for mass. The achieved rms mass resolution varies from ~ 0.3 amu at boron to ~ 0.5 amu at nitrogen, consistent with a theoretical analysis of the contributing factors. Corrected for detector interactions and the effects of the residual atmosphere, the results are ^(10)B/B = 0.33^(+0.17)_(-0.11), ^(13)C/C = 0.06^(+0.13)_(-0.01), and ^(15)N/N = 0.42 (+0.19)_(-0.17). A model of galactic propagation and solar modulation is described. Assuming a cosmic ray source composition of solar-like isotopic abundances, the model predicts abundances near earth consistent with the measurements.

Secondary Organic Aerosol Composition Studies Using Mass Spectrometry

Trace volatile organic compounds emitted by biogenic and anthropogenic sources into the atmosphere can undergo extensive photooxidation to form species with lower volatility. By equilibrium partitioning or reactive uptake, these compounds can nucleate into new aerosol particles or deposit onto already-existing particles to form secondary organic aerosol (SOA). SOA and other atmospheric particulate matter have measurable effects on global climate and public health, making understanding SOA formation a needed field of scientific inquiry. SOA formation can be done in a laboratory setting, using an environmental chamber; under these controlled conditions it is possible to generate SOA from a single parent compound and study the chemical composition of the gas and particle phases. By studying the SOA composition, it is possible to gain understanding of the chemical reactions that occur in the gas phase and particle phase, and identify potential heterogeneous processes that occur at the surface of SOA particles. In this thesis, mass spectrometric methods are used to identify qualitatively and qualitatively the chemical components of SOA derived from the photooxidation of important anthropogenic volatile organic compounds that are associated with gasoline and diesel fuels and industrial activity (C12 alkanes, toluene, and o-, m-, and p-cresols). The conditions under which SOA was generated in each system were varied to explore the effect of NO_x and inorganic seed composition on SOA chemical composition. The structure of the parent alkane was varied to investigate the effect on the functionalization and fragmentation of the resulting oxidation products. Relative humidity was varied in the alkane system as well to measure the effect of increased particle-phase water on condensed-phase reactions. In all systems, oligomeric species, resulting potentially from particle-phase and heterogeneous processes, were identified. Imines produced by reactions between (NH₄)₂SO₄ seed and carbonyl compounds were identified in all systems. Multigenerational photochemistry producing low- and extremely low-volatility organic compounds (LVOC and ELVOC) was reflected strongly in the particle-phase composition as well.

Chemical composition of Iraq water resources (abbreviated translation) [Translation from: Vodnye Resursy 1975(4,) 173-185]

This abbreviated translation summarises the chemical composition of Iraq water resources. Among the described water bodies are the River Euphrates, Shatt al Arab River and a number of standing waters.

Species composition and relative abundance of zooplanktivorous haplochromines in the northern portion of Lake Victoria (Uganda)

Recent surveys have indicated an increase in haplochromine biomass recorded from the bottom trawl and in the beam trawl. The haplochromines recovering in the offshore waters belong to three species in the zooplanktivorous trophic group: Yssichromis laparogramma (Greenwood and Gee), Yssichromis fusiformis (Greenwood and Gee) and Astatotilapia lacrimosa (Boulenger). In this paper, the species composition and relative abundance of the zooplanktivorous haplochromines recorded from the bottom and frame trawl surveys in the various parts of the Ugandan waters of Lake Victoria are discussed.

Composition and bulk properties of Dorset river gravels

Considerable interest has been expressed in the composition of the stream gravels, the movement of bed materials and the relationship of sediment composition, packing and siltation of void space to invertebrate ecology. In the autumn of 1982, freeze-samples of gravel were obtained in Dorset streams. Data were required on the depth of salmonid egg pocke and were part of a broader investigation of regional variation in the independent variables of salmonid fish length, gravel size, current velocity and the resultant dependent variable ~egg burial depth. The Dorset river gravels examined are bimodal. The grain size distribution may be resolved into two near-normal frequency distributions interpreted as representing a primary framework or lattice of gravel particles into which a secondary matrix population of sand particles has penetrated.

The changing chemical composition of chalk streams and rivers

The area studied was the River Frome system below Dorchester. The main river has its origins mainly in chalk springs, although some of its tributaries have surface run-off from farm lands and heath-lands. Thus the chemistry of the river is affected by changes in land practice and differences in the geology of the catchment area. Regular chemical analysis of chalk waters started at the River Laboratory in 1964, Regular weekly analyses have been carried out since 1965 at Bere Stream (a small chalk stream) and the River Frome (a large chalk stream); also single samples have been analysed to provide preliminary information. In 1970-71 an attempt was made to discover the contribution each main source made to the flow and chemical composition of the River Frome. Results of these investigations are presented in the paper.

Solubility and Diffusivity of Water in Lunar Basalt, and Chemical Zonation in Olivine-Hosted Melt Inclusions

I report the solubility and diffusivity of water in lunar basalt and an iron-free basaltic analogue at 1 atm and 1350 °C. Such parameters are critical for understanding the degassing histories of lunar pyroclastic glasses. Solubility experiments have been conducted over a range of fO₂ conditions from three log units below to five log units above the iron-wüstite buffer (IW) and over a range of pH₂/pH₂O from 0.03 to 24. Quenched experimental glasses were analyzed by Fourier transform infrared spectroscopy (FTIR) and secondary ionization mass spectrometry (SIMS) and were found to contain up to ~420 ppm water. Results demonstrate that, under the conditions of our experiments: (1) hydroxyl is the only H-bearing species detected by FTIR; (2) the solubility of water is proportional to the square root of pH₂O in the furnace atmosphere and is independent of fO₂ and pH₂/pH₂O; (3) the solubility of water is very similar in both melt compositions; (4) the concentration of H₂ in our iron-free experiments is <3 ppm, even at oxygen fugacities as low as IW-2.3 and pH₂/pH₂O as high as 24; and (5) SIMS analyses of water in iron-rich glasses equilibrated under variable fO₂ conditions can be strongly influenced by matrix effects, even when the concentrations of water in the glasses are low. Our results can be used to constrain the entrapment pressure of the lunar melt inclusions of Hauri et al. (2011).

Diffusion experiments were conducted over a range of fO₂ conditions from IW-2.2 to IW+6.7 and over a range of pH₂/pH₂O from nominally zero to ~10. The water concentrations measured in our quenched experimental glasses by SIMS and FTIR vary from a few ppm to ~430 ppm. Water concentration gradients are well described by models in which the diffusivity of water (D^*_water) is assumed to be constant. The relationship between D^*_water and water concentration is well described by a modified speciation model (Ni et al. 2012) in which both molecular water and hydroxyl are allowed to diffuse. The success of this modified speciation model for describing our results suggests that we have resolved the diffusivity of hydroxyl in basaltic melt for the first time. Best-fit values of D^*_water for our experiments on lunar basalt vary within a factor of ~2 over a range of pH₂/pH₂O from 0.007 to 9.7, a range of fO₂ from IW-2.2 to IW+4.9, and a water concentration range from ~80 ppm to ~280 ppm. The relative insensitivity of our best-fit values of D^*_water to variations in pH₂ suggests that H₂ diffusion was not significant during degassing of the lunar glasses of Saal et al. (2008). D^*_water during dehydration and hydration in H₂/CO₂ gas mixtures are approximately the same, which supports an equilibrium boundary condition for these experiments. However, dehydration experiments into CO₂ and CO/CO₂ gas mixtures leave some scope for the importance of kinetics during dehydration into H-free environments. The value of D^*_water chosen by Saal et al. (2008) for modeling the diffusive degassing of the lunar volcanic glasses is within a factor of three of our measured value in our lunar basaltic melt at 1350 °C.

In Chapter 4 of this thesis, I document significant zonation in major, minor, trace, and volatile elements in naturally glassy olivine-hosted melt inclusions from the Siqueiros Fracture Zone and the Galapagos Islands. Components with a higher concentration in the host olivine than in the melt (MgO, FeO, Cr₂O₃, and MnO) are depleted at the edges of the zoned melt inclusions relative to their centers, whereas except for CaO, H₂O, and F, components with a lower concentration in the host olivine than in the melt (Al₂O₃, SiO₂, Na₂O, K₂O, TiO₂, S, and Cl) are enriched near the melt inclusion edges. This zonation is due to formation of an olivine-depleted boundary layer in the adjacent melt in response to cooling and crystallization of olivine on the walls of the melt inclusions concurrent with diffusive propagation of the boundary layer toward the inclusion center.

Concentration profiles of some components in the melt inclusions exhibit multicomponent diffusion effects such as uphill diffusion (CaO, FeO) or slowing of the diffusion of typically rapidly diffusing components (Na₂O, K₂O) by coupling to slow diffusing components such as SiO₂ and Al₂O₃. Concentrations of H2O and F decrease towards the edges of some of the Siqueiros melt inclusions, suggesting either that these components have been lost from the inclusions into the host olivine late in their cooling histories and/or that these components are exhibiting multicomponent diffusion effects.

A model has been developed of the time-dependent evolution of MgO concentration profiles in melt inclusions due to simultaneous depletion of MgO at the inclusion walls due to olivine growth and diffusion of MgO in the melt inclusions in response to this depletion. Observed concentration profiles were fit to this model to constrain their thermal histories. Cooling rates determined by a single-stage linear cooling model are 150–13,000 °C hr^-1 from the liquidus down to ~1000 °C, consistent with previously determined cooling rates for basaltic glasses; compositional trends with melt inclusion size observed in the Siqueiros melt inclusions are described well by this simple single-stage linear cooling model. Despite the overall success of the modeling of MgO concentration profiles using a single-stage cooling history, MgO concentration profiles in some melt inclusions are better fit by a two-stage cooling history with a slower-cooling first stage followed by a faster-cooling second stage; the inferred total duration of cooling from the liquidus down to ~1000 °C is 40 s to just over one hour.

Based on our observations and models, compositions of zoned melt inclusions (even if measured at the centers of the inclusions) will typically have been diffusively fractionated relative to the initially trapped melt; for such inclusions, the initial composition cannot be simply reconstructed based on olivine-addition calculations, so caution should be exercised in application of such reconstructions to correct for post-entrapment crystallization of olivine on inclusion walls. Off-center analyses of a melt inclusion can also give results significantly fractionated relative to simple olivine crystallization.

All melt inclusions from the Siqueiros and Galapagos sample suites exhibit zoning profiles, and this feature may be nearly universal in glassy, olivine-hosted inclusions. If so, zoning profiles in melt inclusions could be widely useful to constrain late-stage syneruptive processes and as natural diffusion experiments.

Aspects of the washout of salmonid eggs. 6. Information on gravel composition , redd sites, the dimensions of redds and the depth of egg burial

Sampling was concentrated on the North Moor region and the series of ditches which drained this area to the Bristol Channel. Although most ditches were not deep the mud substratum precluded sampling from within the habitat. All samples were taken with a pond net from the banks. Efforts were made to sample each part of the habitat although in some ditches the macrophyte growth was so intense as to make sampling difficult particularly of the sediments. Organisms were identified on the 10 sampling sites.

La lucha de bandos en el País Vasco: de los Parientes Mayores a la Hidalguía Universal. Guipúzcoa, de los bandos a la Provincia (s. XIV a XVI)

La historiografía tradicional acuñó el término Lucha de Bandos para referirse a los enfrentamientos internobiliarios que tuvieron lugar en el País Vasco entre el bando de los oñacinos y el de los gamboínos durante los siglos XIV y XV. La renovación historiográfica que fue cuajando durante los primeros años 70 demostró, sin embargo, que semejantes enfrentamientos ocultaban otros que contraponían a los grupos sociales antagónicos tanto en el mundo rural como en las villas en una amplia tipología de conflictos hasta el punto que, en la actualidad, tendemos a equiparar Lucha de Bandos y conflictividad social. Los trabajos que recoge este libro son el resultado de un nuevo acercamiento al problema, a la luz de las nuevas propuestas que durante los últimos años han aportado otros autores en el tratamiento de problemas similares en otras latitudes. En su mayoría fueron presentados los días 4 y 5 de diciembre de 1997 en Vitoria durante un Symposium sobre la Lucha de Bandos en el País Vasco. Con una especial atención al caso guipuzcoano, se abordan, entre otras, distintas cuestiones relacionadas con la historiografía, las fuentes, la definición y significado de Pariente Mayor, las bases materiales de su poder, la constitución de oligarquías municipales en las villas, los movimientos migratorios, la “revolución de los precios” o la dimensión política de la hidalguía universal. En conjunto se ofrece una visión diacrónica que observa las transformaciones sociales, económicas y políticas que conoció la sociedad guipuzcoana al final de la Lucha de Bandos, al compás del nacimiento y de los primeros pasos de una “sociedad igualitaria”.

Agenda única de saúde: a busca do acesso universal e a garantia do direito à saúde

Este trabalho visa identificar os determinantes da ampliação de demandas judiciais contra os gestores do SUS. Em sua maioria (85%) relacionam-se ao fornecimento de medicamentos e são geradas, no âmbito do Judiciário, pelo entendimento daquele órgão que o Poder Público está descumprindo o direito à saúde constitucionalmente adquirido. Foi realizada uma revisão bibliográfica acerca de sistemas nacionais de saúde com princípios constitutivos básicos semelhantes aos do SUS, tendo sido selecionados o Canadá, Colômbia e Espanha. O objetivo foi observar se àqueles sistemas apresentam as dificuldades experimentadas pelo SUS, ou se existe, no sistema nacional, alguma peculiaridade. Foram analisados os artigos da Constituição de 1988 relativos à saúde, observando-se em vários deles pouca clareza na descrição de conceitos que parecem dar margem a múltiplos entendimentos dos atores envolvidos com a implementação do SUS. Desenvolveuse uma pesquisa quali-quantitativa: o 1 componente foi realizado por meio de entrevistas com atores chave, representantes do Executivo, Legislativo, Judiciário, Órgãos de Classe, Conselhos de Saúde e Gestores. A etapa quantitativa foi realizada a partir da coleta, sistematização e análise de dados acerca das demandas judiciais chegadas aos gestores do SUS localizados no Rio de Janeiro (SMS, SESDEC e NERJ). Os entendimentos dos entrevistados mostraram-se muito distintos e bastante relacionados com seus locais de atuação. Foi observado que o Judiciário, grosso modo, ratifica as prescrições médicas, determinando aos gestores, tornados réus, o fornecimento de produtos de saúde que vão desde os medicamentos essenciais até os de dispensação excepcional e mesmo, algumas substâncias importadas. As liminares não atendem as padronizações definidas pelas Políticas Nacionais de Assistência Farmacêutica, nem as que dizem respeito às relações pactuadas entre os gestores nem a responsabilização existente por nível de gestão. Tais questões têm gerado um tensionamento permanente entre o Executivo da saúde, Judiciário e população, uma vez que o cumprimento das determinações judiciais representa, para o gestor, uma necessidade de realocação orçamentária para a aquisição de medicamentos não planejados, que pode determinar a não realização de ações programáticas prioritárias. Parece que estas ações do Judiciário, ainda que legítimas, não necessariamente favorecem a equidade de acesso ao SUS. Por último, foram definidos 3 núcleos causais para a ampliação das demandas judiciais de saúde: o 1, derivado da pouca clareza de alguns conceitos constitucionais determinada pela falta de consenso político quando dos trabalhos da ANC, que deixaram estas definições para regulamentações posteriores, que não ocorreram; o 2, representado pela não contestação da maior parcela das prescrições médicas, pelo Judiciário, o que parece demonstrar o poder das profissões, medicina e direito, e, a inexistência de regulação do exercício profissional pelo Estado e o 3, determinado pela pouca articulação no SUS entre a gestão financeira e da atenção à saúde, o que parece impedir que os gestores atuem como protagonistas destas situações, deixando de promover articulações entre os Poderes do Estado, Instituições, Órgãos de Classe e a sociedade para definição de estratégias comuns voltadas à resolução dos problemas apontados neste estudo.