Ion beam analysis of as-received, H-implanted and post implanted annealed fusion steels

The elemental distribution for as-received (AR), H implanted (AI) and post-implanted annealed (A) Eurofer and ODS-Eurofer steels has been characterized by means of micro Particle Induced X-ray Emission (μ-PIXE), micro Elastic Recoil Detection (μ-ERD) and Secondary Ion Mass Spectrometry (SIMS). The temperature and time-induced H diffusion has been analyzed by Resonance Nuclear Reaction Analysis (RNRA), Thermal Desorption Spectroscopy (TDS), ERDA and SIMS techniques. μ-PIXE measurements point out the presence of inhomogeneities in the Y distribution for ODS-Eurofer samples. RNRA and SIMS experiments evidence that hydrogen easily outdiffuses in these steels even at room temperature. ERD data show that annealing at temperatures as low as 300 °C strongly accelerates the hydrogen diffusion process, driving out up to the 90% of the initial hydrogen.

Viabilidad técnica para la explotación y separación isotópica de Li y prospectiva en el mercado de baterías de ION-7Li y de 6Li como material base de diseño en reactores de fusión nuclear

En claro alineamiento con estrategias de sostenibilidad en el uso de recursos naturales en un escenario constante de aumento de la demanda energética mundial, el desarrollo de la tecnología energética en la Historia de la Especie Humana muestra un vector de evolución permanente desde su origen en el sentido del desarrollo y uso de nuevas fuentes energéticas con la explotación de recursos naturales de manera más eficiente: soluciones energéticas con aumento de la densidad energética (exoenergía de proceso por unidad de masa de recurso natural). Así el cambio de escala en la demanda de explotación del Litio como recurso natural se viene presentando en la última década ligada al desarrollo del mercado de las baterías "ion-Litio" y los requisitos de combustible (Deuterio y Litio) en el camino de la fusión nuclear como opción energética próxima. El análisis anticipado de las demandas sinérgicas a escala de ambos mercados aparece de enorme interés prospectivo en sus aspectos técnicos: (1) tecnologías de base para la extracción mineral y de agua marina y (2) su enriquecimiento isotópico (de interés sinérgico; 7Li para baterías eficientes ion-litio; 6Li como regenerador de tritio en ciclo de combustible en fusión nuclear) a la vez que en sus aspectos económicos. Este Proyecto realiza: (1) un ejercicio de análisis prospectivo de la demanda y de mercado para el enriquecimiento 6Li/7Li para las próximas décadas, (2) se califican los desarrollos tecnológicos específicos que van a poder permitir la producción a escala conforme a la demanda; (3) se selecciona y califica una técnica [de centrifugación / termo-difusión/ destilación combinada] como opción tecnológicamente viable para la producción a escala de formas litiadas; (4) se propone un diseño conceptual de planta de producción y finalmente (5) propone un estudio de viabilidad para la demostración de proceso y construcción de dicha planta de demostración de la nueva capacidad tecnológica. ABSTRACT Clearly aligned with sustainability strategies under growing world energy demand in the use of natural resources the development of energy technology in the history of the human species shows a vector of ongoing evolution from its origin in the sense of the development and use of new energy sources with the exploitation of natural resources in a more efficient manner. The change of scale in the demand for exploitation of Lithium as a natural resource appears during the last decade as bound to the deployment of "lithium-ion" batteries market and to the Nuclear Fusion fuels (deuterium and lithium) supply scaled demands. The prospective analysis of demands to scale in both markets appears in scene with huge prospective interest in its technical aspects: (1) base technologies for mineral and water marine extraction (2) its isotopic enrichment (synergistic interests; 7Li efficient battery Li-ion; 6Li as fusion nuclear fuel breeder (tritium) as well as in its economic aspects. This Project: (1) propose a prospective analysis exercise of the synergistic supply demand for coming decades for the enrichment of 6Li and 7Li, (2) qualifies specific technological developments ongoing to respond to supply demand; (3) select and qualifies an appropriate technique [combined centrifugation/thermo-diffusion/distillation] as technologically viable option for lithiated forms scaled-production; (4) proposes a conceptual design of production plant based on the technique and finally (5) proposes a feasibility study for the process demonstration and construction of this new technological capability Demonstration Plant.

Ion charge number and flux saturation effects in the corona of a laser-irradiated pellet

The quasisteady structure of the corona of a laser-irradiated pellet is completely determined for arbitrary Z, (ion charge number} and re/ra (ratio of critical and ablation radii), and for heat-flux saturation factor/above approximately 0.04. The ion-to-electron temperature ratio at rc grows sensibly with Z,; all other quantities depend weakly and nonmonotonically on Z,. For rc /ra close to unity, and all Z, of interest (Z, < 47}, the flow is subsonic at rc. For a given laser power W, flux saturation may decrease (low/) or increase (high/) the ablation pressure Pa relative to the value obtained when saturation is not considered; in some cases a decrease in/with W fixed increases Pa. For intermediate^ ~0.1), Pa cc (W/r* )2/3 p\n\pc = critical density), independently of rc/ra; for/~0.6, Pa «s larger by a factor of about [rc/raf13. For rjra > 1.2 roughly, the mass ablation rate is C{Z,) [{m/kZ.f^Kr^Pl) l,\ independent of pc and/, and barely dependent on Z,(m, is ion mass; k, Boltzmann's constant; K, conductivity coefficient; and C, a tabulated function).

Self-consistent, nonlocal electron heat flux at arbitrary ion charge number

A single, nonlocal expression for the electron heat flux, which closely reproduces known results at high and low ion charge number 2, and “exact” results for the local limit at all 2, is derived by solving the kinetic equation in a narrow, tail-energy range. The solution involves asymptotic expansions of Bessel functions of large argument, and (Z-dependent)order above or below it, corresponding to the possible parabolic or hyperbolic character of the kinetic equation; velocity space diffusion in self-scattering is treated similarly to isotropic thermalization of tail energies in large Z analyses. The scale length H characterizing nonlocal effects varies with Z, suggesting an equal dependence of any ad hoc flux limiter. The model is valid for all H above the mean-free path for thermal electrons.

Modelling of chloride penetration into non-saturated concrete: Case study application for real marine off shore structures

The aim of this paper is to explain the chloride concentration profiles obtained experimentally from control samples of an offshore platform after 25 years of service life. The platform is located 12 km off the coast of the Brazilian province Rio Grande do Norte, in the north-east of Brazil. The samples were extracted at different orientations and heights above mean sea level. A simple model based on Fick’s second law is considered and compared with a finite element model which takes into account transport of chloride ions by diffusion and convection. Results show that convective flows significantly affect the studied chloride penetrations. The convection velocity is obtained by fitting the finite element solution to the experimental data and seems to be directly proportional to the height above mean sea level and also seems to depend on the orientation of the face of the platform. This work shows that considering solely diffusion as transport mechanism does not allow a good prediction of the chloride profiles. Accounting for capillary suction due to moisture gradients permits a better interpretation of the material’s behaviour.

Modelling of chloride penetration into non-saturated concrete: case study application for real marine offshore structures

The aim of this paper is to explain the chloride concentration profiles obtained experimentally from control samples of an offshore platform after 25 years of service life. The platform is located 12 km off the coast of the Brazilian province Rio Grande do Norte, in the north-east of Brazil. The samples were extracted at different orientations and heights above mean sea level. A simple model based on Fick’s second law is considered and compared with a finite element model which takes into account transport of chloride ions by diffusion and convection. Results show that convective flows significantly affect the studied chloride penetrations. The convection velocity is obtained by fitting the finite element solution to the experimental data and seems to be directly proportional to the height above mean sea level and also seems to depend on the orientation of the face of the platform. This work shows that considering solely diffusion as transport mechanism does not allow a good prediction of the chloride profiles. Accounting for capillary suction due to moisture gradients permits a better interpretation of the material’s behaviour

Optimizing phosphorus diffusion for photovoltaic applications: peak doping, inactive phosphorus,gettering, and contact formation

The phosphosilicate glass (PSG), fabricated by tube furnace diffusion using a POCl3 source, is widely used as a dopant source in the manufacturing of crystalline silicon solar cells. Although it has been a widely addressed research topic for a long time, there is still lack of a comprehensive understanding of aspects such as the growth, the chemical composition, possible phosphorus depletion, the resulting in-diffused phosphorus profiles, the gettering behavior in silicon, and finally the metal-contact formation. This paper addresses these different aspects simultaneously to further optimize process conditions for photovoltaic applications. To do so, a wide range of experimental data is used and combined with device and process simulations, leading to a more comprehensive interpretation. The results show that slight changes in the PSG process conditions can produce high-quality emitters. It is predicted that PSG processes at 860 °C for 60 min in combination with an etch-back and laser doping from PSG layer results in high-quality emitters with a peak dopant density Npeak = 8.0 × 1018 cm−3 and a junction depth dj = 0.4 μm, resulting in a sheet resistivityρsh = 380 Ω/sq and a saturation current-density J0 below 10 fA/cm2. With these properties, the POCl3 process can compete with ion implantation or doped oxide approaches.

Induction of epithelial chloride secretion by channel-forming cryptdins 2 and 3

Salt and water secretion from intestinal epithelia requires enhancement of anion permeability across the apical membrane of Cl− secreting cells lining the crypt, the secretory gland of the intestine. Paneth cells located at the base of the small intestinal crypt release enteric defensins (cryptdins) apically into the lumen. Because cryptdins are homologs of molecules known to form anion conductive pores in phospholipid bilayers, we tested whether these endogenous antimicrobial peptides could act as soluble inducers of channel-like activity when applied to apical membranes of intestinal Cl− secreting epithelial cells in culture. Of the six peptides tested, cryptdins 2 and 3 stimulated Cl− secretion from polarized monolayers of human intestinal T84 cells. The response was reversible and dose dependent. In contrast, cryptdins 1, 4, 5, and 6 lacked this activity, demonstrating that Paneth cell defensins with very similar primary structures may exhibit a high degree of specificity in their capacity to elicit Cl− secretion. The secretory response was not inhibited by pretreatment with 8-phenyltheophyline (1 μM), or dependent on a concomitant rise in intracellular cAMP or cGMP, indicating that the apically located adenosine and guanylin receptors were not involved. On the other hand, cryptdin 3 elicited a secretory response that correlated with the establishment of an apically located anion conductive channel permeable to carboxyfluorescein. Thus cryptdins 2 and 3 can selectively permeabilize the apical cell membrane of epithelial cells in culture to elicit a physiologic Cl− secretory response. These data define the capability of cryptdins 2 and 3 to function as novel intestinal secretagogues, and suggest a previously undescribed mechanism of paracrine signaling that in vivo may involve the reversible formation of ion conductive channels by peptides released into the crypt microenvironment.

Transmembrane topology of a CLC chloride channel

CLC chloride channels form a large and conserved gene family unrelated to other channel proteins. Knowledge of the transmembrane topology of these channels is important for understanding the effects of mutations found in human myotonia and inherited hypercalciuric kidney stone diseases and for the interpretation of structure–function studies. We now systematically study the topology of human ClC-1, a prototype CLC channel that is defective in human myotonia. Using a combination of in vitro glycosylation scanning and protease protection assays, we show that both N and C termini face the cytoplasm and demonstrate the presence of 10 (or less likely 12) transmembrane spans. Difficult regions were additionally tested by inserting cysteines and probing the effect of cysteine-modifying reagents on ClC-1 currents. The results show that D3 crosses the membrane and D4 does not, and that L549 between D11 and D12 is accessible from the outside. Further, since the modification of cysteines introduced between D11 and D12 and at the extracellular end of D3 strongly affect ClC-1 currents, these regions are suggested to be important for ion permeation.

Selective Perturbation of Apical Membrane Traffic by Expression of Influenza M2, an Acid-activated Ion Channel, in Polarized Madin–Darby Canine Kidney Cells

The function of acidification along the endocytic pathway is not well understood, in part because the perturbants used to modify compartmental pH have global effects and in some cases alter cytoplasmic pH. We have used a new approach to study the effect of pH perturbation on postendocytic traffic in polarized Madin–Darby canine kidney (MDCK) cells. Influenza M2 is a small membrane protein that functions as an acid-activated ion channel and can elevate the pH of the trans-Golgi network and endosomes. We used recombinant adenoviruses to express the M2 protein of influenza virus in polarized MDCK cells stably transfected with the polymeric immunoglobulin (Ig) receptor. Using indirect immunofluorescence and immunoelectron microscopy, M2 was found to be concentrated at the apical plasma membrane and in subapical vesicles; intracellular M2 colocalized partly with internalized IgA in apical recycling endosomes as well as with the trans-Golgi network marker TGN-38. Expression of M2 slowed the rate of IgA transcytosis across polarized MDCK monolayers. The delay in transport occurred after IgA reached the apical recycling endosome, consistent with the localization of intracellular M2. Apical recycling of IgA was also slowed in the presence of M2, whereas basolateral recycling of transferrin and degradation of IgA were unaffected. By contrast, ammonium chloride affected both apical IgA and basolateral transferrin release. Together, our data suggest that M2 expression selectively perturbs acidification in compartments involved in apical delivery without disrupting other postendocytic transport steps.

Single-molecule protein folding: Diffusion fluorescence resonance energy transfer studies of the denaturation of chymotrypsin inhibitor 2

We report single-molecule folding studies of a small, single-domain protein, chymotrypsin inhibitor 2 (CI2). CI2 is an excellent model system for protein folding studies and has been extensively studied, both experimentally (at the ensemble level) and theoretically. Conformationally assisted ligation methodology was used to synthesize the proteins and site-specifically label them with donor and acceptor dyes. Folded and denatured subpopulations were observed by fluorescence resonance energy transfer (FRET) measurements on freely diffusing single protein molecules. Properties of these subpopulations were directly monitored as a function of guanidinium chloride concentration. It is shown that new information about different aspects of the protein folding reaction can be extracted from such subpopulation properties. Shifts in the mean transfer efficiencies are discussed, FRET efficiency distributions are translated into potentials, and denaturation curves are directly plotted from the areas of the FRET peaks. Changes in stability caused by mutation also are measured by comparing pseudo wild-type CI2 with a destabilized mutant (K17G). Current limitations and future possibilities and prospects for single-pair FRET protein folding investigations are discussed.

Screen-printed electrode-based electrochemical detector coupled with in-situ ionic-liquid-assisted dispersive liquid–liquid microextraction for determination of 2,4,6-trinitrotoluene

A novel method is reported, whereby screen-printed electrodes (SPELs) are combined with dispersive liquid–liquid microextraction. In-situ ionic liquid (IL) formation was used as an extractant phase in the microextraction technique and proved to be a simple, fast and inexpensive analytical method. This approach uses miniaturized systems both in sample preparation and in the detection stage, helping to develop environmentally friendly analytical methods and portable devices to enable rapid and onsite measurement. The microextraction method is based on a simple metathesis reaction, in which a water-immiscible IL (1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [Hmim][NTf2]) is formed from a water-miscible IL (1-hexyl-3-methylimidazolium chloride, [Hmim][Cl]) and an ion-exchange reagent (lithium bis[(trifluoromethyl)sulfonyl]imide, LiNTf2) in sample solutions. The explosive 2,4,6-trinitrotoluene (TNT) was used as a model analyte to develop the method. The electrochemical behavior of TNT in [Hmim][NTf2] has been studied in SPELs. The extraction method was first optimized by use of a two-step multivariate optimization strategy, using Plackett–Burman and central composite designs. The method was then evaluated under optimum conditions and a good level of linearity was obtained, with a correlation coefficient of 0.9990. Limits of detection and quantification were 7 μg L−1 and 9 μg L−1, respectively. The repeatability of the proposed method was evaluated at two different spiking levels (20 and 50 μg L−1), and coefficients of variation of 7 % and 5 % (n = 5) were obtained. Tap water and industrial wastewater were selected as real-world water samples to assess the applicability of the method.

Ion balance in waters through inductively coupled plasma optical emission spectrometry

Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) has been employed to carry out the determination of both major anions and cations in water samples. The anion quantification has been performed by means of a new automatic accessory. In this device chloride has been determined by continuously adding a silver nitrate solution. As a result solid silver chloride particles are formed and retained on a nylon filter inserted in the line. The emission intensity is read at a silver characteristic wavelength. By plotting the drop in silver signal versus the chloride concentration, a straight line is obtained. As regards bicarbonate, this anion has been on-line transformed into carbon dioxide with the help of a 2.0 mol L−1 nitric acid stream. Carbon signal is linearly related with bicarbonate concentration. Finally, information about sulfate concentration has been achieved by means of the measurement of sulfur emission intensity. All the steps have been simultaneously and automatically performed. With this setup detection limits have been 1.0, 0.4 and 0.09 mg L−1 for chloride, bicarbonate and sulfate, respectively. Furthermore, it affords good precision with RSD below 6 %. Cation (Ca, Mg, Na and K) concentration, in turn, has been obtained by simultaneously reading the emission intensity at characteristic wavelengths. The obtained limits of detection have been 8 × 10−3, 2 × 10−3, 8 × 10−4 and 10−2 mg L−1 for sodium, potassium, magnesium and calcium, respectively. As regards sample throughput, about 30 samples h−1 can be analysed. Validation results have revealed that the obtained concentrations for these anions are not significantly different as compared to the data provided by conventional methods. Finally, by considering the data for anions and cations, precise ion balances have been obtained for well and mineral water samples.

Rare earth and trace elements in igneous and metamorphic minerals of oceanic gabbros from the Mid-Atlantic Ridge

SIMS analyses have been carried out on clinopyroxenes, plagioclases and amphiboles of six gabbroic samples from Holes 921-924 of the Ocean Drilling Program Leg 153 sited in the MARK area of the Mid-Atlantic Ridge at the ridge-transform intersection, to investigate the rare earth, trace and volatile element distribution in the lower ocean crust during igneous crystallization and higher grade metamorphic conditions. The metagabbros underwent granulite to subgreenschist facies conditions through three main tectono-metamorphic phases: (1) ductile regime (750 < T < 1000 °C and P = 0.3 GPa); (2) transitional regime (600 < T < 700 °C and P = 0.2 GPa); (3) brittle regime (350 < T < 600 °C and P < 0.2 GPa). Igneous clinopyroxenes show Cl-chondrite normalized patterns depleted in LREE, and nearly flat for HREE. The rare earth and trace element distributions in igneous clinopyroxenes and plagioclases indicate that these minerals act as REE reservoirs, and comprise the main contribution to the overall rock content. The abundances in igneous minerals reflect the degree of fractionation of the parent liquids. In metamorphic clinopyroxenes recrystallized in anhydrous assemblages, the REE and trace elements patterns mimic those of the primary ones. Conversely, clinopyroxerie re-equilibrated in amphibolebearing assemblages shows a significant increase in REE, Ti, Zr, Y and V, a negative Eu anomaly, and slight decreases in Sr and Ba. An overall increase of REE and some trace elements is evident in hydrous assemblages, with preferential partitioning in the amphibole. It shows high Ti (18196-22844 ppm), LREE depleted patterns and LaN/SmN = 0.10-0.33, LaN/YbN = 0.10-0.30. Amphiboles from granoblastic assemblages show homogeneous patterns with no or a positive anomaly for TiN and negative anomalies for SrN and ZrN. Volatiles in amphibole are low, with Cl/F < 1; H2O% is significantly lower than the stoichiometric ratio (1.33-1.53%). The composition of the clinopyroxene and amphibole recrystallized in low-strain domains records evidence of incomplete re-equilibration, and element diffusion and partitioning is in part controlled by the textural site. The possible origins of the fluids involved in the metamorphic recrystallization are discussed: (1) remobilization from igneous amphibole; (2) exsolution from evolved melts; (3) introduction of seawater-derived fluids modified in rock-dominated systems; (4) injection of highly evolved hydrous melts during the metamorphic process.

Geochemistry, isotopic ratios and aldehyde concentrations of frost flowers, snow and ice near Barrow, Alaska

Frost flowers, intricate featherlike crystals that grow on refreezing sea ice leads, have been implicated in lower atmospheric chemical reactions. Few studies have presented chemical composition information for frost flowers over time and many of the chemical species commonly associated with Polar tropospheric reactions have never been reported for frost flowers. We undertook this study on the sea ice north of Barrow, Alaska to quantify the major ion, stable oxygen and hydrogen isotope, alkalinity, light absorbance by soluble species, organochlorine, and aldehyde composition of seawater, brine, and frost flowers. For many of these chemical species we present the first measurements from brine or frost flowers. Results show that major ion and alkalinity concentrations, stable isotope values, and major chromophore (NO3- and H2O2) concentrations are controlled by fractionation from seawater and brine. The presence of these chemical species in present and future sea ice scenarios is somewhat predictable. However, aldehydes, organochlorine compounds, light absorbing species, and mercury (part 2 of this research and Sherman et al. (2012, doi:10.1029/2011JD016186)) are deposited to frost flowers through less predictable processes that probably involve the atmosphere as a source. The present and future concentrations of these constituents in frost flowers may not be easily incorporated into future sea ice or lower atmospheric chemistry scenarios. Thinning of Arctic sea ice will likely present more open sea ice leads where young ice, brine, and frost flowers form. How these changing ice conditions will affect the interactions between ice, brine, frost flowers and the lower atmosphere is unknown.