Vibrational characterisation of a crystallised oligoaniline: a model compound of polyaniline

NASA Astrophysics Data System (ADS)

Quillard, Sophie; Corraze, Benoı̂t; Boyer, Marie Isabelle; Fayad, Elias; Louarn, Guy; Froyer, Gérard

2001-09-01

We present a detailed study on the vibrational properties of N,N‧-diphenyl-1,4-phenylenediamine in different crystalline forms. A new triclinic form of the molecule has been obtained through appropriate recrystallization procedure. This polymorphism of the crystalline state was associated to different vibrational features. These results are discussed with regards to the possible conformations of the molecule. In order to complete the study, thin solid films of these materials were also elaborated by vacuum sublimation of the molecule, upon selected conditions of rate, deposition and thickness. Spectroscopic measurements of these layers are showed and compared to those obtained on the crystalline solid forms. We performed convenient oxidation processes of this neutral N,N‧-diphenyl-1,4-phenylenediamine (powder and thin solid film) leading to the formation of the correspondent radical cation species. A comparison with radical cation generated in solution by electrochemical oxidative method is done. Vibrational characterisations of this doped oligomer were achieved in each case and finally, the observed differences are discussed in terms of conformation.

A gel aging effect in the synthesis of open-framework gallium phosphates: structure solution and solid-state NMR of a large-pore, open-framework material† †Electronic supplementary information (ESI) available. CCDC 1577782 and 1577783. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7dt03709k

PubMed Central

Broom, Lucy K.; Clarkson, Guy J.; Guillou, Nathalie; Hooper, Joseph E.; Dawson, Daniel M.; Tang, Chiu C.; Ashbrook, Sharon E.

2017-01-01

The templated zeolite-analogue GaPO-34 (CHA structure type) crystallises from a gel precursor Ga2O3 : 2H3PO4 : 1HF : 1.7SDA : 70H2O (where SDA = structure directing agent), treated hydrothermally for 24 hours at 170 °C using either pyridine or 1-methylimizadole as SDA and one of either poorly crystalline ε-Ga2O3 or γ-Ga2O3 as gallium precursor. If the same gels are stirred for periods shorter than 2 hours but treated under identical hydrothermal conditions, then a second phase crystallises, free of GaPO-34. If β-Ga2O3 is used as a reagent only the second phase is found to crystallise, irrespective of gel aging time. The competing phase, which we denote GaPO-34A, has been structurally characterised using synchrotron powder X-ray diffraction for the pyridine material, GaPO-34A(pyr), and using single-crystal X-ray diffraction for the 1-methylimiazole material, GaPO-34A(mim). The structure of GaPO-34A(pyr), P1, a = 10.22682(6) Å, b = 12.09585(7) Å, c = 13.86713(8) Å, α = 104.6531(4)°, β = 100.8111(6)°, γ = 102.5228(6)°, contains 7 unique gallium sites and 6 phosphorus sites, with empirical formula [Ga7P6O24(OH)2F3(H2O)2]·2(C5NH6). GaPO-34A(mim) is isostructural but is modelled as a half volume unit cell, P1, a = 5.0991(2) Å, b = 12.0631(6) Å, c = 13.8405(9) Å, α = 104.626(5)°, β = 100.346(5)°, γ = 101.936(4)°, with a gallium and a bridging fluoride partially occupied and two partially occupied SDA sites. Solid-state 31P and 71Ga NMR spectroscopy confirms the structural complexity of GaPO-34A with signals resulting from overlapping lineshapes from multiple Ga and P sites, while 1H and 13C solid-state NMR spectra confirm the presence of the protonated SDA and provide evidence for disorder in the SDA. The protonated SDA is located in 14-ring one-dimensional channels with hydrogen bonding deduced from the SDA nitrogens to framework oxygen distances. Upon thermal treatment to investigate SDA removal, structure collapse occurs, which may be due the large number of bridging hydroxides and fluorides in the as-made material, and the unequal amounts of gallium and phosphorus present. PMID:29171855

Crystallisation of Ba1-xSrxZn2Si2O7 from BaO/SrO/ZnO/SiO2 glass with different ZrO2 and TiO2 concentrations

NASA Astrophysics Data System (ADS)

Vladislavova, Liliya; Kracker, Michael; Zscheckel, Tilman; Thieme, Christian; Rüssel, Christian

2018-04-01

The effect of different nucleation agents such as ZrO2 and TiO2 was investigated for a first time with respect to their crystallisation behaviour in the glass system BaO-SrO-ZnO-SiO2. In all studied glasses, a Ba1-xSrxZn2Si2O7 (0.1 ≤ x ≤ 0.9) solid solution crystallized. This phase was first described in 2015 to possess a similar structure as the high temperature phase of BaZn2Si2O7 and a thermal expansion close to zero or even negative. It may find applications e.g. as cook panels, telescope mirrors, and furnace windows. Kinetic parameters of the crystallisation process were determined by supplying different heating rates in a differential scanning calorimeter (DSC). The results were evaluated using the equations of Ozawa and Kissinger with respect to the activation energies. Furthermore, the Ozawa method was used for the determination of Avrami parameters, which provides further information on the nucleation and crystallisation processes. Scanning electron microscopy including electron backscatter diffraction (EBSD) was used to characterise the microstructure, to determine the crystallite size and the crystal orientation. For the characterisation of the occurring crystalline phases, X-ray diffraction was used.

Transitiometric analysis of solid II/solid I transition in anhydrous theophylline.

PubMed

Legendre, Bernard; Randzio, Stanislaw L

2007-10-01

For the first time, with the use of a high sensitivity, low heating rate, scanning transitiometry, it was possible to distinguish and characterise the polymorphic equilibrium transition between forms II and I in anhydrous theophylline. In this manner it was univocally proved, that forms II and I in theophylline are enantiotropically related. The temperature and enthalpy for that transition are as follows: T(trs)(II/I)=536.8+/-2.2K; Delta(trs)H(II/I)=1.99+/-0.09 kJ/mol. Making use of advantages of very slow heating rate and of a high energetic sensitivity of the transitiometer it was possible to observe in detail the polymorphic transition followed by melting of high temperature form I and to stop the solid I-liquid transition at a desired point of equilibrium. Such a solid I-liquid equilibrium could be stabilised and then displaced back to the crystallisation of form I with an adequate use of a precise temperature programming. In such a way a pure single phase of form I of theophylline was prepared. This fact was confirmed by X-ray powder diffraction patterns and calorimetric traces of fusion of the crystallised product. The temperature and enthalpy of the form I-liquid transition are as follows: T(fus)(I)=546.5+/-0.2K and Delta(fus)H(I)=29.37+/-0.29 kJ/mol.

Preparation and characterisation of hydrocortisone particles using a supercritical fluids extraction process.

PubMed

Velaga, Sitaram P; Ghaderi, Raouf; Carlfors, Johan

2002-01-14

Crystallisation and subsequent milling of pharmaceutical powders by traditional methods often cause variations in physicochemical properties thereby influencing bioavailability of the formulation. Crystallisation of drug substances using supercritical fluids (SFs) offers some advantages over existing traditional methods in controlling particle characteristics. The novel particle formation method, solution enhanced dispersion by supercritical (SEDS) fluids was used for the preparation of hydrocortisone (HC) particles. The influence of processing conditions on the solid-state properties of the particles was studied. HC, an anti-inflammatory corticosteroid, particles were prepared from acetone and methanol solutions using the SEDS process. The solutions were dispersed with supercritical CO(2), acting as an anti-solvent, through a specially designed co-axial nozzle into a pressured vessel maintained at a specific constant temperature and pressure. The temperatures and pressures studied were 40-90 degrees C and 90-180 bar, respectively. The relative flow rates of drug solution to CO(2) were varied between 0.002 and 0.03. Solid-state characterisation of particles included differential scanning calorimetry (DSC), X-ray powder diffraction (XRPD), solubility studies and scanning electron microscopy (SEM) examination. The aerodynamic properties of SEDS prepared particles were determined by a multistage liquid impinger (MLI). Particles produced from acetone solutions were crystalline needles, melting at 221+/-2 degrees C. Their morphology was independent of processing conditions. With methanol solutions, particles were flakes or needles depending on the processing temperature and pressure. This material melted at 216+/-1 degrees C, indicating a different crystal structure from the original material, in agreement with observed differences in the position and intensity of the XRPD peaks. The simulated lung deposition, using the MLI, for HC powder was improved after SEDS processing. It was possible to produce and control the crystallinity, morphology, and aerodynamic properties of HC particles with the SEDS technique. This method may be useful for the processing of inhalation powders.

Processing of carbamazepine-PEG 4000 solid dispersions with supercritical carbon dioxide: preparation, characterisation, and in vitro dissolution.

PubMed

Moneghini, M; Kikic, I; Voinovich, D; Perissutti, B; Filipović-Grcić, J

2001-07-03

The purpose of this study was to apply the attractive technique of the supercritical fluid to the preparation of solvent-free solid dispersions. In particular, the gas antisolvent crystallisation technique (GAS), using supercritical carbon dioxide as processing medium, has been considered to prepare an enhanced release dosage form for of the poorly soluble carbamazepine, employing PEG 4000 as a hydrophilic carrier. The physical characterisation of the systems using laser granulometer, powder X-ray diffraction, thermal analyses, and scanning electron microscopy was carried out in order to understand the influence of this technological process on the physical status of the drug. The results of the physical characterisation attested a substantial correspondence of the solid state of the drug before and after treatment with GAS technique, whereas a pronounced change in size and morphology of the drug crystals was noticed. The dramatic reduction of the dimensions and the better crystal shape, together with the presence of the hydrophilic polymer determined a remarkable enhancement of the in vitro drug dissolution rate.

The Temperature of the Icelandic Mantle Plume from Aluminium-in-Olivine Thermometry

NASA Astrophysics Data System (ADS)

Matthews, S.; Shorttle, O.; Maclennan, J.

2015-12-01

Temperature is a key control on the physical properties of the mantle, in particular the extent of melting during upwelling. It is not, however, a unique control on many of the parameters used to estimate mantle temperature. For example igneous crustal thickness which has often been used as a first-order proxy for mantle temperature, is also affected by mantle lithology and plume flux. Alternatives to geophysical indicators of mantle temperature are petrological thermometers. However, these record crystallisation temperatures, therefore a series of assumptions about the coupled melt- solid mantle thermal history must be made when calculating back to mantle potential temperature. In this study we investigate how these assumptions may affect mantle temperature estimates and how crystallisation temperatures may offer insights into the melting and melt transport processes, focussing on a new set of crystallisation temperature estimates we have made on primitive Icelandic basalts.We used the aluminium-in-olivine thermometer of Coogan et al. (2014) to estimate crystallisation temperatures of olivine phenocrysts in a suite of samples from the Northern Volcanic Zone (NVZ) of Iceland. The data suggest that within a single volcanic system crystallisation temperature depends strongly on the olivine forsterite content, thus the history of melt evolution, and how the eruption samples this, must be considered when extrapolating to mantle temperature. To assess the influence of the assumptions required to obtain mantle temperature we constructed a simple thermal model incorporating varying proportions of lherzolite, pyroxenite and harzburgite undergoing decompression melting. A trade off between increasing mantle temperature and decreasing pyroxenite (or increasing harzburgite) in the source is observed. Using this dataset and our model, calculations reveal a potential temperature of 1470±130 °C for Iceland, and a temperature excess of 150±40 °C relative to ambient mantle. These estimates are consistent with temperatures estimated using crustal thickness and melt chemistry.

Drowning-out crystallisation of sodium sulphate using aqueous two-phase systems.

PubMed

Taboada, M E; Graber, T A; Asenjo, J A; Andrews, B A

2000-06-23

A novel method to obtain crystals of pure, anhydrous salt, using aqueous two-phase systems was studied. A concentrated salt solution is mixed with polyethylene glycol (PEG), upon which three phases are formed: salt crystals, a PEG-rich liquid and a salt-rich liquid. After removal of the solid salt, a two-phase system is obtained. Both liquid phases are recycled, allowing the design of a continuous process, which could be exploited industrially. The phase diagram of the system water-Na2SO4-PEG 3350 at 28 degrees C was used. Several process alternatives are proposed and their economic potential is discussed. The process steps needed to produce sodium sulphate crystals include mixing, crystallisation, settling and, optionally, evaporation of water. The yield of sodium sulphate increases dramatically if an evaporation step is used.

Particle Engineering in Pharmaceutical Solids Processing: Surface Energy 
Considerations

PubMed Central

Williams, Daryl R.

2015-01-01

During the past 10 years particle engineering in the pharmaceutical industry has become a topic of increasing importance. Engineers and pharmacists need to understand and control a range of key unit manufacturing operations such as milling, granulation, crystallisation, powder mixing and dry powder inhaled drugs which can be very challenging. It has now become very clear that in many of these particle processing operations, the surface energy of the starting, intermediate or final products is a key factor in understanding the processing operation and or the final product performance. This review will consider the surface energy and surface energy heterogeneity of crystalline solids, methods for the measurement of surface energy, effects of milling on powder surface energy, adhesion and cohesion on powder mixtures, crystal habits and surface energy, surface energy and powder granulation processes, performance of DPI systems and finally crystallisation conditions and surface energy. This review will conclude that the importance of surface energy as a significant factor in understanding the performance of many particulate pharmaceutical products and processes has now been clearly established. It is still nevertheless, work in progress both in terms of development of methods and establishing the limits for when surface energy is the key variable of relevance. PMID:25876912

Sodium sulfate crystallisation monitoring using IR thermography

NASA Astrophysics Data System (ADS)

Vazquez, P.; Thomachot-Schneider, C.; Mouhoubi, K.; Bodnar, J.-L.; Avdelidis, N. P.; Charles, D.; Benavente, D.

2018-03-01

In this work, the evaporation of sodium sulfate droplets with different concentrations and at different temperatures were studied using infrared thermography (IRT). IRT allows to detect the evaporation evolution, the crystal growth and for the first time, to observe in vivo the heat release related to sodium sulfate crystallisation. A detailed study revealed that dendritic Thenardite III crystals appeared at the edge of all the crystallised droplets, though they showed a fast increase of temperature related to crystallisation only when a hydrated phase crystallised also from the droplet. The observation of the heat of crystallisation is thus directly related to the supersaturation of the droplet and consequently to temperature. In addition, IRT detection is circumscribed by the location of crystallisation. The heat can be observed and measured only when the crystallisation occurs in the interface solution - air.

Aqueous trifluorethanol solutions simulate the environment of DNA in the crystalline state.

PubMed

Kypr, J; Chládková, J; Zimulová, M; Vorlícková, M

1999-09-01

We took 28 fragments of DNA whose crystal structures were known and used CD spectroscopy to search for conditions stabilising the crystal structures in solution. All 28 fragments switched into their crystal structures in 60-80% aqueous trifluorethanol (TFE) to indicate that the crystals affected the conformation of DNA like the concentrated TFE. The fragments crystallising in the B-form also underwent cooperative TFE-induced changes that took place within the wide family of B-form structures, suggesting that the aqueous and crystal B-forms differed as well. Spermine and magnesium or calcium cations, which were contained in the crystallisation buffers, promoted or suppressed the TFE-induced changes of several fragments to indicate that the crystallisation agents can decide which of the possible structures is adopted by the DNA fragment in the crystal.

Force of crystallisation-development during CaO hydration: theory vs. experiment and the role of fluid transport

NASA Astrophysics Data System (ADS)

Wolterbeek, Tim; van Noort, Reinier; Spiers, Chris

2017-04-01

When chemical reactions that involve an increase in solid volume proceed in a confined space, this may under certain conditions lead to the development of a so-called force of crystallisation (FoC). In other words, reaction can result in stress being exerted on the confining boundaries of the system. In principle, any thermodynamic driving force that is able to produce a supersaturation with respect to a solid product can generate a FoC, as long as precipitation can occur under confined conditions, i.e. within load-bearing grain contacts. Well-known examples of such reactions include salt damage, where supersaturation is caused by evaporation and surface curvature effects, and a wide range of mineral reactions where the solid products comprise a larger volume than the solid reactants. Frost heave, where crystallisation is driven by fluid under-cooling, i.e. temperature change, is a similar process. In a geological context, FoC-development is widely considered to play an important role in pseudomorphic replacement, vein formation, and reaction-driven fracturing. Chemical reactions capable of producing a FoC such as the hydration of CaO (lime), which is thermodynamically capable of producing stresses in the GPa range, also offer obvious engineering potential. Despite this, relatively few studies have been conducted where the magnitude of the FoC is determined directly. Indeed, the maximum stress obtainable by CaO hydration has not been validated or determined experimentally. Here we report uni-axial compaction/expansion experiments performed in an oedometer-type apparatus on pre-compacted CaO powder, at 65 °C and at atmospheric pore fluid pressure. Using this set-up, the FoC generated during CaO hydration could be measured directly. Our results show FoC-induced stresses reaching up to 153 MPa, with the hydration reaction stopping or slowing down significantly before completion. Failure to achieve the GPa stresses predicted by thermodynamic theory is attributed to competition between FoC development and its inhibiting effect on reaction progress. Our microstructural observations indicate that hydration-induced stresses caused the shut-down of pathways for water into the sample, thereby hampering ongoing reaction and limiting the magnitude of stress build-up to the values observed.

Mirror Symmetry Breaking by Chirality Synchronisation in Liquids and Liquid Crystals of Achiral Molecules.

PubMed

Tschierske, Carsten; Ungar, Goran

2016-01-04

Spontaneous mirror symmetry breaking is an efficient way to obtain homogeneously chiral agents, pharmaceutical ingredients and materials. It is also in the focus of the discussion around the emergence of uniform chirality in biological systems. Tremendous progress has been made by symmetry breaking during crystallisation from supercooled melts or supersaturates solutions and by self-assembly on solid surfaces and in other highly ordered structures. However, recent observations of spontaneous mirror symmetry breaking in liquids and liquid crystals indicate that it is not limited to the well-ordered solid state. Herein, progress in the understanding of a new dynamic mode of symmetry breaking, based on chirality synchronisation of transiently chiral molecules in isotropic liquids and in bicontinuous cubic, columnar, smectic and nematic liquid crystalline phases is discussed. This process leads to spontaneous deracemisation in the liquid state under thermodynamic control, giving rise to long-term stable symmetry-broken fluids, even at high temperatures. These fluids form conglomerates that are capable of extraordinary strong chirality amplification, eventually leading to homochirality and providing a new view on the discussion of emergence of uniform chirality in prebiotic systems. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The application of ATR-FTIR spectroscopy and multivariate data analysis to study drug crystallisation in the stratum corneum.

PubMed

Goh, Choon Fu; Craig, Duncan Q M; Hadgraft, Jonathan; Lane, Majella E

2017-02-01

Drug permeation through the intercellular lipids, which pack around and between corneocytes, may be enhanced by increasing the thermodynamic activity of the active in a formulation. However, this may also result in unwanted drug crystallisation on and in the skin. In this work, we explore the combination of ATR-FTIR spectroscopy and multivariate data analysis to study drug crystallisation in the skin. Ex vivo permeation studies of saturated solutions of diclofenac sodium (DF Na) in two vehicles, propylene glycol (PG) and dimethyl sulphoxide (DMSO), were carried out in porcine ear skin. Tape stripping and ATR-FTIR spectroscopy were conducted simultaneously to collect spectral data as a function of skin depth. Multivariate data analysis was applied to visualise and categorise the spectral data in the region of interest (1700-1500cm -1 ) containing the carboxylate (COO - ) asymmetric stretching vibrations of DF Na. Spectral data showed the redshifts of the COO - asymmetric stretching vibrations for DF Na in the solution compared with solid drug. Similar shifts were evident following application of saturated solutions of DF Na to porcine skin samples. Multivariate data analysis categorised the spectral data based on the spectral differences and drug crystallisation was found to be confined to the upper layers of the skin. This proof-of-concept study highlights the utility of ATR-FTIR spectroscopy in combination with multivariate data analysis as a simple and rapid approach in the investigation of drug deposition in the skin. The approach described here will be extended to the study of other actives for topical application to the skin. Copyright © 2016 Elsevier B.V. All rights reserved.

Zircon and monazite petrochronologic record of prolonged amphibolite to granulite facies metamorphism in the Ivrea-Verbano and Strona-Ceneri Zones, NW Italy

NASA Astrophysics Data System (ADS)

Guergouz, Celia; Martin, Laure; Vanderhaeghe, Olivier; Thébaud, Nicolas; Fiorentini, Marco

2018-05-01

In order to improve the understanding of thermal-tectonic evolution of high-grade terranes, we conducted a systematic study of textures, REE content and U-Pb ages of zircon and monazite grains extracted from migmatitic metapelites across the amphibolite to granulite facies metamorphic gradient exposed in the Ivrea-Verbano and Strona-Ceneri Zones (Italy). This study documents the behaviour of these accessory minerals in the presence of melt. The absence of relict monazite grains in the metasediments and the gradual decrease in the size of inherited zircon grains from amphibolite to granulite facies cores indicate partial to total dissolution of accessory minerals during the prograde path and partial melting. The retrograde path is marked by (i) growth of new zircon rims (R1 and R2) around inherited cores in the mesosome, (ii) crystallisation of stubby zircon grains in the leucosome, especially at granulite facies, and (iii) crystallisation of new monazite in the mesosome. Stubby zircon grains have a distinctive fir-tree zoning and a constant Th/U ratio of 0.20. Together, these features reflect growth in the melt; conversely, the new zircon grains with R1 rims have dark prismatic habits and Th/U ratios < 0.1, pointing to growth in solid residues. U-Pb ages obtained on both types are similar, indicating contemporaneous growth of stubby zircon and rims around unresorbed zircon grains, reflecting the heterogeneous distribution of the melt at the grain scale. In the Ivrea-Verbano Zone the interquartile range (IQR) of U-Pb ages on zircon and monazite are interpreted to represent the length of zircon and monazite crystallisation in the presence of melt. Accordingly, they provide an indication on the minimum duration for high-temperature metamorphism and partial melting of the lower crust: 20 Ma and 30 Ma in amphibolite and granulite facies, respectively. In amphibolite facies, zircon crystallisation between 310 and 294 Ma (IQR) is interpreted to reflect metamorphic peak condition and earlier retrograde history; conversely, monazite crystallisation between 297 and 271 Ma (IQR) reflects cooling under 750 °C to a temperature close to the solidus. In granulite facies, zircon crystallisation between 295 and 265 Ma (IQR) is interpreted to reflect high-temperature conditions, which were attained after peak of metamorphism during isothermal decompression and subsequent cooling under 850-950 °C. The observed decrease of U-Pb ages in metamorphic zircon and monazite from amphibolite to granulite facies (i.e. from the middle to the lower crust) is interpreted to record slow cooling and crystallisation of the Variscan orogenic root at the transition from orogenic collapse to opening of the Tethys Ocean.

Magmatism and crustal extension: Constraining activation of the ductile shearing along the Gediz detachment, Menderes Massif (western Turkey)

NASA Astrophysics Data System (ADS)

Rossetti, Federico; Asti, Riccardo; Faccenna, Claudio; Gerdes, Axel; Lucci, Federico; Theye, Thomas

2017-06-01

The Menderes Massif of western Turkey is a key area to study feedback relationships between magma generation/emplacement and activation of extensional detachment tectonics. Here, we present new textural analysis and in situ U-(Th)-Pb titanite dating from selected samples collected in the transition from the undeformed to the mylonitized zones of the Salihli granodiorite at the footwall of the Neogene, ductile-to-brittle, top-to-the-NNE Gediz-Alaşheir (GDF) detachment fault. Ductile shearing was accompanied by the fluid-mediated sub-solidus transformation of the granodiorite to orthogneiss, which occurred at shallower crustal levels and temperatures compatible with the upper greenschist-to-amphibolite facies metamorphic conditions (530-580 °C and P < 2 GPa). The syn-tectonic metamorphic overgrowth of REE-poor titanite on pristine REE-rich igneous titanite offers the possibility to constrain the timing of magma crystallisation and solid-state shearing at the footwall of the Gediz detachment. The common Pb corrected 206Pb/238U (206Pb*/238U) ages and the REE re-distribution in titanite that spatially correlates with the Th/U zoning suggests that titanite predominantly preserve open-system ages during fluid-assisted syn-tectonic re-crystallisation in the transition from magma crystallization and emplacement (at 16-17 Ma) to the syn-tectonic, solid-state shearing (at 14-15 Ma). A minimum time lapse of ca. 1-2 Ma is then inferred between the crustal emplacement of the Salihli granodiorite and nucleation of the ductile extensional shearing along the Gediz detachment. The reconstruction of the cooling history of the Salihli granodiorite documents a punctuated evolution dominated by two episodes of rapid cooling, between 14 Ma and 12 Ma ( 100 °C/Ma) and between 3 and 2 Ma ( 105 °C/Ma). We relate the first episode to nucleation and development of post-emplacement of ductile shearing along the GDF and the second to brittle high-angle faulting, respectively. Our dataset suggests that in the Menderes Massif the activation of ductile extension was a consequence, rather than the cause, of magma emplacement in the extending crust.

Soft matter in hard confinement: phase transition thermodynamics, structure, texture, diffusion and flow in nanoporous media.

PubMed

Huber, Patrick

2015-03-18

Spatial confinement in nanoporous media affects the structure, thermodynamics and mobility of molecular soft matter often markedly. This article reviews thermodynamic equilibrium phenomena, such as physisorption, capillary condensation, crystallisation, self-diffusion, and structural phase transitions as well as selected aspects of the emerging field of spatially confined, non-equilibrium physics, i.e. the rheology of liquids, capillarity-driven flow phenomena, and imbibition front broadening in nanoporous materials. The observations in the nanoscale systems are related to the corresponding bulk phenomenologies. The complexity of the confined molecular species is varied from simple building blocks, like noble gas atoms, normal alkanes and alcohols to liquid crystals, polymers, ionic liquids, proteins and water. Mostly, experiments with mesoporous solids of alumina, gold, carbon, silica, and silicon with pore diameters ranging from a few up to 50 nm are presented. The observed peculiarities of nanopore-confined condensed matter are also discussed with regard to applications. A particular emphasis is put on texture formation upon crystallisation in nanoporous media, a topic both of high fundamental interest and of increasing nanotechnological importance, e.g. for the synthesis of organic/inorganic hybrid materials by melt infiltration, the usage of nanoporous solids in crystal nucleation or in template-assisted electrochemical deposition of nano structures.

Soft matter in hard confinement: phase transition thermodynamics, structure, texture, diffusion and flow in nanoporous media

NASA Astrophysics Data System (ADS)

Huber, Patrick

2015-03-01

Spatial confinement in nanoporous media affects the structure, thermodynamics and mobility of molecular soft matter often markedly. This article reviews thermodynamic equilibrium phenomena, such as physisorption, capillary condensation, crystallisation, self-diffusion, and structural phase transitions as well as selected aspects of the emerging field of spatially confined, non-equilibrium physics, i.e. the rheology of liquids, capillarity-driven flow phenomena, and imbibition front broadening in nanoporous materials. The observations in the nanoscale systems are related to the corresponding bulk phenomenologies. The complexity of the confined molecular species is varied from simple building blocks, like noble gas atoms, normal alkanes and alcohols to liquid crystals, polymers, ionic liquids, proteins and water. Mostly, experiments with mesoporous solids of alumina, gold, carbon, silica, and silicon with pore diameters ranging from a few up to 50 nm are presented. The observed peculiarities of nanopore-confined condensed matter are also discussed with regard to applications. A particular emphasis is put on texture formation upon crystallisation in nanoporous media, a topic both of high fundamental interest and of increasing nanotechnological importance, e.g. for the synthesis of organic/inorganic hybrid materials by melt infiltration, the usage of nanoporous solids in crystal nucleation or in template-assisted electrochemical deposition of nano structures.

Formation and crystallisation of a liquid jet in a film exposed to a tightly focused laser beam

NASA Astrophysics Data System (ADS)

Anisimov, S. I.; Zhakhovsky, V. V.; Inogamov, N. A.; Murzov, S. A.; Khokhlov, V. A.

2017-06-01

This paper considers the effect of an ultrashort laser pulse on a thin gold film on a glass substrate at a focal spot size near 1 μm. We analyse the motion and thermal history of a film that has peeled off from the substrate in the heating spot as a consequence of melting. The detached zone is shown to form a domeshaped bump whose motion is hindered by surface tension. After the dome stops and turns back, towards the substrate, a jet begins to grow on its top. Concurrently, because of the heat dissipation in the film, melt recrystallisation begins, involving first the dome and then the jet. The liquid part of the jet elongates and breaks up into droplets because of the Plateau-Rayleigh instability development. The formation of a neck and the detachment of the last droplet occur in the solidification zone between the crystalline and liquid parts of the jet. The propagation of the crystallisation zone in the jet leads the necking process, so neck disruption occurs in the solid phase under nonequilibrium crystallisation conditions (the melt temperature is hundreds of kelvins lower than the melting point), at limiting mechanical stress and at high deformation rates. As a result, the jet transforms into a high needle with an extremely small tip radius (a few nanometres).

Staged storage and magma convection at Ambrym volcano, Vanuatu

NASA Astrophysics Data System (ADS)

Sheehan, Fionnuala; Barclay, Jenni

2016-08-01

New mineral-melt thermobarometry and mineral chemistry data are presented for basaltic scoriae erupted from the Mbwelesu crater of Ambrym volcano, Vanuatu, during persistent lava lake activity in 2005 and 2007. These data reveal crystallisation conditions and enable the first detailed attempt at reconstruction of the central magma plumbing system of Ambrym volcano. Pressures and temperatures of magma crystallisation at Ambrym are poorly constrained. This study focuses on characterising the magma conditions underlying the quasi-permanent lava lakes at the basaltic central vents, and examines petrological evidence for magma circulation. Mineral-melt equilibria for clinopyroxene, olivine and plagioclase allow estimation of pressures and temperatures of crystallisation, and reveal two major regions of crystallisation, at 24-29 km and 11-18 km depth, in agreement with indications from earthquake data of crustal storage levels at c. 25-29 km and 12-21 km depth. Temperature estimates are 1150-1170 °C for the deeper region, and 1110-1140 °C in the mid-crustal region, with lower temperatures of 1090-1100 °C for late-stage crystallisation. More primitive plagioclase antecrysts are thought to sample a slightly more mafic melt at sub-Moho depths. Resorption textures combined with effectively constant mafic mineral compositions suggest phenocryst convection in a storage region of consistent magma composition. In addition, basalt erupted at Ambrym has predominantly maintained a constant composition throughout the volcanic succession. This, coupled with recurrent periods of elevated central vent activity on the scale of months, suggest frequent magmatic recharge via steady-state melt generation at Ambrym.

A Computational Approach to Modeling Magma Ocean Evolution in 2-D and 3-D

NASA Astrophysics Data System (ADS)

Tackley, P. J.; Louro Lourenço, D. J.; Fomin, I.

2017-12-01

Models of magma ocean evolution have typically been performed in 1-D (e.g. Abe, PEPI 1997; Solomatov and Stevenson, JGR 1993; Elkins-Tanton EPSL 2008). However, 1-D models may miss important aspects of the process, in particular the possible development of solid-state convection before the magma ocean has completely crystallised, and possible large-scale overturn driven by thermal and/or compositional gradients. On the other hand, fully resolving magma ocean evolution in 2-D or 3-D would be extremely challenging due to the small time-scales and length-scales associated with turbulent convection in the magma and the extreme viscosity contrast between regions of high melt fraction and regions of low melt fraction, which are separated by a rheological threshold associated with the solid forming an interconnected matrix. Here, an intermediate approach to treat these has been implemented within the framework of the mantle convection code StagYY (Tackley, PEPI 2008). The basic approach is to resolve processes that occur in the mostly solid state (i.e. below the rheological threshold) while parameterising processes that occur in the mostly liquid state, based largely on the works of Y. Abe. Thus, turbulent convection in magma-rich regions is treated using an effective thermal conductivity based on mixing-length theory, and segregation of solid and liquid is treated using Darcy's law for low melt fractions or crystal settling (offset by vigorous convection) for high melt fractions. At the outer surface a combined radiative-conductive heat balance is implemented, including the temperature drop over a very thin ( cm) thermal boundary layer and reduction of radiative heat loss by an atmosphere. Key to the whole process is petrology: the coexisting compositions of magma and solid under various conditions including possible fractionation, and for this different approaches have been parameterised ranging from a simple basalt-harzburgite parameterisation to a bi-eutectic lower mantle melting model based on ab initio and laboratory experiments.

A computational approach to modelling magma ocean evolution in 2-D and 3-D

NASA Astrophysics Data System (ADS)

Tackley, Paul; Lourenco, Diogo; Fomin, Ilya

2017-04-01

Models of magma ocean evolution have typically been performed in 1-D (e.g. Abe, PEPI 1997; Solomatov and Stevenson, JGR 1993; Elkins-Tanton EPSL 2008). However, 1-D models may miss important aspects of the process, in particular the possible development of solid-state convection before the magma ocean has completely crystallised, and possible large-scale overturn driven by thermal and/or compositional gradients. On the other hand, fully resolving magma ocean evolution in 2-D or 3-D would be extremely challenging due to the small time-scales and length-scales associated with turbulent convection in the magma and the extreme viscosity contrast between regions of high melt fraction and regions of low melt fraction, which are separated by a rheological threshold associated with the solid forming an interconnected matrix. Here, an intermediate approach to treat these has been implemented within the framework of the mantle convection code StagYY (Tackley, PEPI 2008). The basic approach is to resolve processes that occur in the mostly solid state (i.e. below the rheological threshold) while parameterising processes that occur in the mostly liquid state, based largely on the works of Y. Abe. Thus, turbulent convection in magma-rich regions is treated using an effective thermal conductivity based on mixing-length theory, and segregation of solid and liquid is treated using Darcy's law for low melt fractions or crystal settling (offset by vigorous convection) for high melt fractions. At the outer surface a combined radiative-conductive heat balance is implemented, including the temperature drop over a very thin ( cm) thermal boundary layer and reduction of radiative heat loss by an atmosphere. Key to the whole process is petrology: the coexisting compositions of magma and solid under various conditions including possible fractionation, and for this different approaches have been parameterised ranging from a simple basalt-harzburgite parameterisation to a bi-eutectic lower mantle melting model based on ab initio and laboratory experiments.

Hen Egg-White Lysozyme Crystallisation: Protein Stacking and Structure Stability Enhanced by a Tellurium(VI)-Centred Polyoxotungstate

PubMed Central

Bijelic, Aleksandar; Molitor, Christian; Mauracher, Stephan G; Al-Oweini, Rami; Kortz, Ulrich; Rompel, Annette

2015-01-01

As synchrotron radiation becomes more intense, detectors become faster and structure-solving software becomes more elaborate, obtaining single crystals suitable for data collection is now the bottleneck in macromolecular crystallography. Hence, there is a need for novel and advanced crystallisation agents with the ability to crystallise proteins that are otherwise challenging. Here, an Anderson–Evans-type polyoxometalate (POM), specifically Na6[TeW6O24]⋅22 H2O (TEW), is employed as a crystallisation additive. Its effects on protein crystallisation are demonstrated with hen egg-white lysozyme (HEWL), which co-crystallises with TEW in the vicinity (or within) the liquid–liquid phase separation (LLPS) region. The X-ray structure (PDB ID: 4PHI) determination revealed that TEW molecules are part of the crystal lattice, thus demonstrating specific binding to HEWL with electrostatic interactions and hydrogen bonds. The negatively charged TEW polyoxotungstate binds to sites with a positive electrostatic potential located between two (or more) symmetry-related protein chains. Thus, TEW facilitates the formation of protein–protein interfaces of otherwise repulsive surfaces, and thereby the realisation of a stable crystal lattice. In addition to retaining the isomorphicity of the protein structure, the anomalous scattering of the POMs was used for macromolecular phasing. The results suggest that hexatungstotellurate(VI) has great potential as a crystallisation additive to promote both protein crystallisation and structure elucidation. PMID:25521080

A thermodynamic approach to model the caloric properties of semicrystalline polymers

NASA Astrophysics Data System (ADS)

Lion, Alexander; Johlitz, Michael

2016-05-01

It is well known that the crystallisation and melting behaviour of semicrystalline polymers depends in a pronounced manner on the temperature history. If the polymer is in the liquid state above the melting point, and the temperature is reduced to a level below the glass transition, the final degree of crystallinity, the amount of the rigid amorphous phase and the configurational state of the mobile amorphous phase strongly depend on the cooling rate. If the temperature is increased afterwards, the extents of cold crystallisation and melting are functions of the heating rate. Since crystalline and amorphous phases exhibit different densities, the specific volume depends also on the temperature history. In this article, a thermodynamically based phenomenological approach is developed which allows for the constitutive representation of these phenomena in the time domain. The degree of crystallinity and the configuration of the amorphous phase are represented by two internal state variables whose evolution equations are formulated under consideration of the second law of thermodynamics. The model for the specific Gibbs free energy takes the chemical potentials of the different phases and the mixture entropy into account. For simplification, it is assumed that the amount of the rigid amorphous phase is proportional to the degree of crystallinity. An essential outcome of the model is an equation in closed form for the equilibrium degree of crystallinity in dependence on pressure and temperature. Numerical simulations demonstrate that the process dependences of crystallisation and melting under consideration of the glass transition are represented.

Reversible monolayer-to-crystalline phase transition in amphiphilic silsesquioxane at the air-water interface

DOE PAGES

Banerjee, R.; Sanyal, M. K.; Bera, M. K.; ...

2015-02-17

We report on the counter intuitive reversible crystallisation of two-dimensional monolayer of Trisilanolisobutyl Polyhedral Oligomeric SilSesquioxane (TBPOSS) on water surface using synchrotron x-ray scattering measurements. Amphiphilic TBPOSS form rugged monolayers and Grazing Incidence X-ray Scattering (GIXS) measurements reveal that the in-plane inter-particle correlation peaks, characteristic of two-dimensional system, observed before transition is replaced by intense localized spots after transition. The measured x-ray scattering data of the non-equilibrium crystalline phase on the air-water interface could be explained with a model that assumes periodic stacking of the TBPOSS dimers. These crystalline stacking relaxes upon decompression and the TBPOSS layer retains its initialmore » monolayer state. The existence of these crystals in compressed phase is confirmed by atomic force microscopy measurements by lifting the materials on a solid substrate.« less

Crystallising Experiences among Young Elite Dancers

ERIC Educational Resources Information Center

Pickard, Angela; Bailey, Richard

2009-01-01

Crystallising experiences are defined as memorable reactions an individual has to some quality or feature of an activity or domain that yields a long-term change in the individual performance and their view of themselves (Walters & Gardner, 1986; Freeman, 1999). This paper explores the nature and consequences of crystallising experiences from…

The effect of amino acid excipients on morphology and solid-state properties of multi-component spray-dried formulations for pulmonary delivery of biomacromolecules.

PubMed

Sou, Tomás; Kaminskas, Lisa M; Nguyen, Tri-Hung; Carlberg, Renée; McIntosh, Michelle P; Morton, David A V

2013-02-01

For a dry powder carrier platform to be suitable for pulmonary delivery of potent biomacromolecules, it has to be aerosolisable and capable of stabilising the biomacromolecules. In the present study, strategies aiming to produce a multi-component spray-dried powder formulation with a stable amorphous glassy matrix containing mannitol, trehalose, glycine and alanine, while using leucine as a particle formation and aerosolisation enhancing agent were investigated. The results from in vitro aerosolisation studies demonstrated high fine particle fractions (FPFs) from several formulations. Scanning electronic micrographs (SEMs) revealed distinct morphological features of these formulations in response to increasing leucine concentration: from the apparent insufficiency for discrete particle formation, to reduced particle agglomeration, to increased surface corrugation. X-ray powder diffraction (XRPD) results indicated that partially ordered leucine resulting from self-assembly on the particle surface is important for the amino acid to function effectively as an encapsulating agent. This may also play a role in inhibiting crystallisation of other components within the formulation. In conclusion, the results suggest that with suitable particle size, good dispersibility and solid-state properties, selected trehalose/leucine combinations appear to have good potential for development into a universal carrier platform for pulmonary delivery of potent biomacromolecules and the work highlights areas deserving further investigation. Copyright © 2012 Elsevier B.V. All rights reserved.

Progress with polycrystalline silicon thin-film solar cells on glass at UNSW

NASA Astrophysics Data System (ADS)

Aberle, Armin G.

2006-01-01

Polycrystalline Si (pc-Si) thin-film solar cells on glass have long been considered a very promising approach for lowering the cost of photovoltaic (PV) solar electricity. In recent years there have been dramatic advances with this PV technology, and the first commercial modules (CSG Solar) are expected to hit the marketplace in 2006. The CSG modules are based on solid-phase crystallisation of plasma-enhanced chemical vapor deposition (PECVD) -deposited amorphous Si. Independent research in the author's group at the University of New South Wales (UNSW) during recent years has led to the development of three alternative pc-Si thin-film solar cells on glass—EVA, ALICIA and ALICE. Cell thickness is generally about 2 μm. The first two cells are made by vacuum evaporation, whereas ALICE cells can be made by either vacuum evaporation or PECVD. Evaporation has the advantage of being a fast and inexpensive Si deposition method. A crucial component of ALICIA and ALICE cells is a seed layer made on glass by metal-induced crystallisation of amorphous silicon (a-Si). The absorber layer of these cells is made by either ion-assisted Si epitaxy (ALICIA) or solid-phase epitaxy of a-Si (ALICE). This paper reports on the status of these three new thin-film PV technologies. All three solar cells seem to be capable of voltages of over 500 mV and, owing to their potentially inexpensive and scalable fabrication process, have significant industrial appeal.

Structure Formation of Ultrathin PEO Films at Solid Interfaces—Complex Pattern Formation by Dewetting and Crystallization

PubMed Central

Braun, Hans-Georg; Meyer, Evelyn

2013-01-01

The direct contact of ultrathin polymer films with a solid substrate may result in thin film rupture caused by dewetting. With crystallisable polymers such as polyethyleneoxide (PEO), molecular self-assembly into partial ordered lamella structures is studied as an additional source of pattern formation. Morphological features in ultrathin PEO films (thickness < 10 nm) result from an interplay between dewetting patterns and diffusion limited growth pattern of ordered lamella growing within the dewetting areas. Besides structure formation of hydrophilic PEO molecules, n-alkylterminated (hydrophobic) PEO oligomers are investigated with respect to self-organization in ultrathin films. Morphological features characteristic for pure PEO are not changed by the presence of the n-alkylgroups. PMID:23385233

High-resolution EPMA X-ray images of mother liquid inclusions in a Pd2Ga single crystal

NASA Astrophysics Data System (ADS)

Müller, D.; Schwerin, J.; Gille, P.; Fehr, K. T.

2014-03-01

During crystal growth from solution inclusions of different compositions were trapped at the rim of a Pd2Ga single crystal. Their fine-grained (< 5 μm) internal structure demands special requirements for electron microprobe analysis, realized by low-voltage (5 keV) element mapping applying a step size of 0.138 μm for each pixel. It can be shown, that these inclusions represent an isolated chemical system, and that crystallisation upon cooling follows the expected thermodynamic phase relations. Thus the final composition in the centre of the inclusion consists of a small-scale mixture of PdGa and Pd5Ga3 evolved out of a solid-solid decomposition of Pd5Ga4.

Hen egg-white lysozyme crystallisation: protein stacking and structure stability enhanced by a Tellurium(VI)-centred polyoxotungstate.

PubMed

Bijelic, Aleksandar; Molitor, Christian; Mauracher, Stephan G; Al-Oweini, Rami; Kortz, Ulrich; Rompel, Annette

2015-01-19

As synchrotron radiation becomes more intense, detectors become faster and structure-solving software becomes more elaborate, obtaining single crystals suitable for data collection is now the bottleneck in macromolecular crystallography. Hence, there is a need for novel and advanced crystallisation agents with the ability to crystallise proteins that are otherwise challenging. Here, an Anderson-Evans-type polyoxometalate (POM), specifically Na6 [TeW6 O24 ]⋅22 H2 O (TEW), is employed as a crystallisation additive. Its effects on protein crystallisation are demonstrated with hen egg-white lysozyme (HEWL), which co-crystallises with TEW in the vicinity (or within) the liquid-liquid phase separation (LLPS) region. The X-ray structure (PDB ID: 4PHI) determination revealed that TEW molecules are part of the crystal lattice, thus demonstrating specific binding to HEWL with electrostatic interactions and hydrogen bonds. The negatively charged TEW polyoxotungstate binds to sites with a positive electrostatic potential located between two (or more) symmetry-related protein chains. Thus, TEW facilitates the formation of protein-protein interfaces of otherwise repulsive surfaces, and thereby the realisation of a stable crystal lattice. In addition to retaining the isomorphicity of the protein structure, the anomalous scattering of the POMs was used for macromolecular phasing. The results suggest that hexatungstotellurate(VI) has great potential as a crystallisation additive to promote both protein crystallisation and structure elucidation. © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Analysis of thickness dependent on crystallization kinetics in thin isotactic-polysterene films

NASA Astrophysics Data System (ADS)

Khairuddin

2016-11-01

Crystalliaztion kinetics of thin film of Isotactic Polysterene (it-PS) films has been studied. Thin PET films having thickness of 338, 533, 712, 1096, 1473, and 2185 A° were prepared by using spin-cast technique. The it-PS crystals were grown on Linkam-hostage in the temperature range 130-240°C with an interval of 10°C. The crystal growths are measured by optical microscopy in lateral direction. It was found that a substantial thickness dependence on crystallisation rate. The analysis using fitting technique based on theory crystal growth of Lauritzen-Hoffman showed that the fitting technique could not resolve to predict the mechanism controlling the thickness dependence on the rate of crystallisation. The possible reasons were due to the crystallisation rate varies with the type of crystals (smooth, rough, overgrowth terrace), and the crystallisation rate changes with the time of crystallisation.

Release mechanism of insulin encapsulated in trehalose ester derivative microparticles delivered via inhalation.

PubMed

Davidson, Iain G; Langner, Eric J; Plowman, Steven V; Blair, Julian A

2003-03-26

The aim of this study was to evaluate properties of amorphous oligosaccharide ester derivative (OED) microparticles in order to determine drug release mechanisms in the lung. Trehalose OEDs with a wide range of properties were synthesised using conventional methods. The interaction of spray dried amorphous microparticles (2-3 microm) with water was investigated using attenuated total reflectance Fourier transform infra-red spectroscopy (ATR-FTIR) and dynamic vapour sorption (DVS). The in vivo performance of insulin/OED microparticles was assessed using a modified Higuchi kinetic model. A modified Hansen solvent parameter approach was used to analyse the interactions with water and in vivo trends. In water or high humidity, OED powders absorb water, lose relaxation energy and crystallise. The delay of the onset of crystallisation depends on the OED and the amount of water present. Crystallisation follows first order Arrhenius kinetics and release of insulin from OED microparticles closely matches the degree of crystallisation. The induction period depends on dispersive interactions between the OED and water while crystallisation is governed by polarity and hydrogen bonding. Drug release from OED microparticles is, therefore, controlled by crystallisation of the matrix on contact with water. The pulmonary environment was found to resemble one of high humidity rather than a liquid medium. Copyright 2003 Elsevier Science B.V.

Role for syn-eruptive plagioclase disequilibrium crystallisation in basaltic magma ascent dynamics

NASA Astrophysics Data System (ADS)

La Spina, Giuseppe; Burton, Mike; de'Michieli Vitturi, Mattia; Arzilli, Fabio

2017-04-01

Magma ascent dynamics in volcanic conduits play a key role in determining the eruptive style of a volcano. The lack of direct observations inside the conduit means that numerical conduit models, constrained with observational data, provide invaluable tools for quantitative insights into complex magma ascent dynamics. The highly nonlinear, interdependent processes involved in magma ascent dynamics require several simplifications when modelling their ascent. For example, timescales of magma ascent in conduit models are typically assumed to be much longer than crystallisation and gas exsolution for basaltic eruptions. However, it is now recognized that basaltic magmas may rise fast enough for disequilibrium processes to play a key role on the ascent dynamics. The quantification of the characteristic times for crystallisation and exsolution processes are fundamental to our understanding of such disequilibria and ascent dynamics. Using observations from Mount Etna's 2001 eruption and a magma ascent model we are able to constrain timescales for crystallisation and exsolution processes. Our results show that plagioclase reaches equilibrium in 1-2 h, whereas ascent times were 1 h. Furthermore, we have related the amount of plagioclase in erupted products with the ascent dynamics of basaltic eruptions. We find that relatively high plagioclase content requires crystallisation in a shallow reservoir, whilst a low plagioclase content reflects a disequilibrium crystallisation occurring during a fast ascent from depth to the surface. Using these new constraints on disequilibrium plagioclase crystallisation we also reproduce observed crystal abundances for different basaltic eruptions: Etna 2002/2003, Stromboli 2007 (effusive eruption) and 1930 (paroxysm) and different Pu'u' O'o eruptions at Kilauea (episodes 49-53). Therefore, our results show that disequilibrium processes play a key role on the ascent dynamics of basaltic magmas and cannot be neglected when describing basaltic eruptions. Quantifying the characteristic times for crystallisation and exsolution represents a major step towards a more complete, realistic and general model of basaltic volcanism

Chemical reactions and morphological stability at the Cu/Al2O3 interface.

PubMed

Scheu, C; Klein, S; Tomsia, A P; Rühle, M

2002-10-01

The microstructures of diffusion-bonded Cu/(0001)Al2O3 bicrystals annealed at 1000 degrees C at oxygen partial pressures of 0.02 or 32 Pa have been studied with various microscopy techniques ranging from optical microscopy to high-resolution transmission electron microscopy. The studies revealed that for both oxygen partial pressures a 20-35 nm thick interfacial CuAlO2 layer formed, which crystallises in the rhombohedral structure. However, the CuAlO2 layer is not continuous, but interrupted by many pores. In the samples annealed in the higher oxygen partial pressure an additional reaction phase with a needle-like structure was observed. The needles are several millimetres long, approximately 10 microm wide and approximately 1 microm thick. They consist of CuAlO2 with alternating rhombohedral and hexagonal structures. Solid-state contact angle measurements were performed to derive values for the work of adhesion. The results show that the adhesion is twice as good for the annealed specimen compared to the as-bonded sample.

Study on crystallization kinetics and phase evolution in Li2O-Al2O3-GeO2-P2O5 glass-ceramics system

NASA Astrophysics Data System (ADS)

Das, Anurup; Dixit, Anupam; Goswami, Madhumita; Mythili, R.; Hajra, R. N.

2018-04-01

To address the safety issues related to liquid electrolyte and improve the battery performance, Solid State Electrolytes (SSEs) are now in frontier area of research interest. We report here synthesis of Li-SSE based on Li2O-Al2O3-GeO2-P2O5 (LAGP) system with NASICON structure. Glass sample with nominal composition Li1.5Al0.5Ge1.5P2.5Si0.5O12 was prepared by melt-quenching technique. Non-isothermal crystallization kinetics was studied using DSC and activation energy of crystallisation was calculated to be ˜ 246 kJ/mol using Kissinger's equation. XRD of heat treated samples show the formation of required LiGe2(PO4)3 phase along with other minor phases. Compositional analysis using SEM-EDX confirms enrichment of Ge and Si along the grain boundaries.

The degassing and crystallisation behaviour of basaltic lavas

NASA Astrophysics Data System (ADS)

Applegarth, L. J.; Tuffen, H.; Pinkerton, H.; James, M. R.

2010-12-01

Degassing is a fundamental volcanic process that can play a major role in controlling eruptive styles. Volatile loss during magma ascent and decompression increases the liquidus temperature of the residual melt, resulting in undercooling that can trigger crystallisation (1,2). Late-stage crystallisation and vesiculation are significant factors in controlling the eruptive behaviour of volcanoes of intermediate composition (2), but their effects on basaltic volcanic activity have yet to be fully investigated. We present the results of experiments designed to measure the degassing and crystallisation behaviour of volcanic rocks at temperatures up to 1250°C, using thermo-gravimetric analysis coupled with differential scanning calorimetry and mass spectrometry (TGA-DSC-MS). During TGA-DSC-MS analysis, volatiles released from a sample under a controlled heating programme are identified in a mass spectrometer whilst changes to the sample weight and heat flow are simultaneously recorded. By subjecting samples of basaltic lava and bombs to two heating cycles, we have shown that the onset of degassing (mass loss) is systematically followed by crystallisation (exothermic events) on the first heating cycle. During the second cycle, when the sample has been fully degassed, no mass loss or crystallisation are recorded. Our results also highlight complexities in the processes; in some cases up to four pulses of degassing and crystallisation have been identified during a single heating cycle. Our results allow us to measure the total volatile content of samples, the onset temperatures of degassing and crystallisation and the time lag between the two processes, and the enthalpy, hence percentage, of crystallisation taking place. These results have important implications for our understanding of basaltic volcanic eruptions. During effusive basaltic eruptions, lava can travel many kilometres, threatening property and infrastructure. The final areal flow extent is partly dependent on the highly variable rheology. Cooling strongly affects rheology, but is mainly restricted to thermal boundary layers. Degassing-induced undercooling and crystallisation, however, may alter the bulk rheology (1), and may have contrasting effects. Rapid microlite growth may lead to crystal-crystal interactions, and the development of non-linear rheological properties such as a yield strength (3,4), which will impede advance. Alternatively, the latent heat of crystallisation may reduce the viscosity of the residual melt and suppress further crystal nucleation (5), tending to render the lava more mobile. As yet, the complex effects of degassing on the crystallisation, and hence rheological, behaviour of basaltic melts are not yet sufficiently well constrained for inclusion in the current generation of numerical lava flow models. An improved understanding of these processes is a critical step in improving our ability to forecast flow behaviour. 1. Sparks, R.S.J. and Pinkerton, H. (1978) Nature, 276, 385. 2. Blundy, J. and Cashman, K.V. (2001) Contrib. Mineral. Petrol. 140, 631. 3. Marsh, B.D. (1981) Contrib. Mineral. Petrol. 78, 85. 4. Bagdassarov, N. and Pinkerton, H. (2004) J. Volcanol. Geotherm. Res. 132, 115. 5. Brandeis, G., Jaupart, C., and Allegre, C.J. (1984) J. Geophys. Res. 89(B12), 10161.

Compaction and Crystallisation in Magma Chambers: Towards a Model of the Skaergaard Intrusion

NASA Astrophysics Data System (ADS)

McKenzie, D. P.

2010-12-01

The equations governing the conservation of mass, momentum and energy are first simplified by using the extended Boussinesq approximation, and then solved numerically to study the time dependent behaviour of a compacting solidifying layer at the base of a magma chamber when variations in the horizontal plane can be neglected. The most important result is that the concept of a trapped liquid fraction, which has been widely used to model the bulk composition of layered intrusions, is a useful concept to describe the steady state behaviour of compacting layers. The result is at first sight surprising, because there is relative movement between the melt and crystals during compaction, and the system is therefore open. The reason why it is correct is because both the melt and the crystals are moving downwards in a frame fixed to the upper surface of the compacting layer. Since the mass of all elements must be conserved, what goes into the top of the layer as melt and solid must come out of its bottom as a solid when the behaviour is not time dependent. However, when time dependent behaviour occurs the concept of a trapped liquid fraction ceases to be useful. The governing equations are then used to model the concentration of phosphorous in the lower part of the Skaergaard intrusion, where it behaves incompatibly. The observed behaviour requires the viscosity of the solid part of the compacting layer to have a viscosity of about 10^18 Pa s.

Influence of enzymatic and chemical interesterification on crystallisation properties of refined, bleached and deodourised (RBD) palm oil and RBD palm kernel oil blends.

PubMed

Norizzah, Abd Rashid; Nur Azimah, Kamarulzaman; Zaliha, Omar

2018-04-01

Interesterification reaction involves rearrangement of the fatty acid radicals on the glycerol backbone, either randomly (chemical interesterification) or regioselectivity (enzymatic interesterification). Refined, bleached and deodourised palm oil (RBDPO) and palm kernel oil (RBDPKO) were blended in ratios from 25:75 to 75:25 (wt/wt). All blends were subjected to enzymatic (EI) and chemical interesterification (CI) using Lipozyme TL IM (4% w/w) and sodium methoxide (0.2% m/m) as the catalysts, respectively. The effect of EI and CI on the triacylglycerol (TAG) composition, thermal behaviour, polymorphism, crystal morphology and crystallisation kinetics were studied. The aim of this research is to characterise the nature of crystals in food product for certain desired structure. The crystallisation behaviour discussed in this study involves microstructure (PLM), polymorphism (XRD), thermal properties and crystallisation kinetics by DSC. The alteration in TAG composition was greater after CI as compared to EI with the reduction of LaLaLa (from 11.00% to 5.15%) and POO (from 14.28% to 4.87%). The DSC complete melting and crystallisation temperature of blend with 75% PO increased after CI, from 39.58 °C to 41.67 °C and from -30.84 °C to -28.33 °C, respectively. EI contributed to finer crystals than CI. However, the β' and β polymorph mixture and crystallisation kinetics (n = 2) of PO-PKO blends did not change after CI and EI. The knowledge on controlling crystallisation of RBDPO and RBDPKO blends is vital for proper processing condition like margarine production. Copyright © 2018 Elsevier Ltd. All rights reserved.

Studies of isothermal crystallisation kinetics of sunflower hard stearin-based confectionery fats.

PubMed

Bootello, Miguel A; Hartel, Richard W; Levin, Madeline; Martínez-Blanes, Jose M; Real, Concepción; Garcés, Rafael; Martínez-Force, Enrique; Salas, Joaquín J

2013-08-15

The crystallisation and polymorphic properties of three sunflower hard stearins (SHSs) and cocoa butter equivalents (CBEs) formulated by blending SHSs and palm mid fraction (PMF) were studied and compared with those from cocoa butter (CB), to explore their possibilities as confectionery fats. The isothermal crystallisation kinetics of these fats were examined by pNMR and DSC at three different temperatures. All samples studied displayed a two-step crystallisation profile that could be fitted to an exponential-Gompertz equation. Stop-and-return DSC studies showed that SHSs and CBEs exhibited different crystallisation mechanisms according to their triacylglycerol composition, with a quick formation of metastable crystals, followed by a polymorphic transition to the more stable β or β' forms. X-ray diffraction (XRD) was used to investigate the polymorphic forms of tempered SHSs and CBEs in the long term. In all cases the resulting fats displayed short spacing patterns associated with β polymorphism. These formulations based on SHSs and PMF met all the requirements to be considered as CBEs; therefore they could be used as an alternative to traditional confectionery fats. Copyright © 2013 Elsevier Ltd. All rights reserved.

Coarse-grained modelling of triglyceride crystallisation: a molecular insight into tripalmitin tristearin binary mixtures by molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Pizzirusso, Antonio; Brasiello, Antonio; De Nicola, Antonio; Marangoni, Alejandro G.; Milano, Giuseppe

2015-12-01

The first simulation study of the crystallisation of a binary mixture of triglycerides using molecular dynamics simulations is reported. Coarse-grained models of tristearin (SSS) and tripalmitin (PPP) molecules have been considered. The models have been preliminarily tested in the crystallisation of pure SSS and PPP systems. Two different quenching procedures have been tested and their performances have been analysed. The structures obtained from the crystallisation procedures show a high orientation order and a high content of molecules in the tuning fork conformation, comparable with the crystalline α phase. The behaviour of melting temperatures for the α phase of the mixture SSS/PPP obtained from the simulations is in qualitative agreement with the behaviour that was experimentally determined.

DFT calculations in the assignment of solid-state NMR and crystal structure elucidation of a lanthanum(iii) complex with dithiocarbamate and phenanthroline.

PubMed

Gowda, Vasantha; Laitinen, Risto S; Telkki, Ville-Veikko; Larsson, Anna-Carin; Antzutkin, Oleg N; Lantto, Perttu

2016-12-06

The molecular, crystal, and electronic structures as well as spectroscopic properties of a mononuclear heteroleptic lanthanum(iii) complex with diethyldithiocarbamate and 1,10-phenanthroline ligands (3 : 1) were studied by solid-state 13 C and 15 N cross-polarisation (CP) magic-angle-spinning (MAS) NMR, X-ray diffraction (XRD), and first principles density functional theory (DFT) calculations. A substantially different powder XRD pattern and 13 C and 15 N CP-MAS NMR spectra indicated that the title compound is not isostructural to the previously reported analogous rare earth complexes with the space group P2 1 /n. Both 13 C and 15 N CP-MAS NMR revealed the presence of six structurally different dithiocarbamate groups in the asymmetric unit cell, implying a non-centrosymmetric packing arrangement of molecules. This was supported by single-crystal X-ray crystallography showing that the title compound crystallised in the triclinic space group P1[combining macron]. In addition, the crystal structure also revealed that one of the dithiocarbamate ligands has a conformational disorder. NMR chemical shift calculations employing the periodic gauge including projector augmented wave (GIPAW) approach supported the assignment of the experimental 13 C and 15 N NMR spectra. However, the best correspondences were obtained with the structure where the atomic positions in the X-ray unit cell were optimised at the DFT level. The roles of the scalar and spin-orbit relativistic effects on NMR shielding were investigated using the zeroth-order regular approximation (ZORA) method with the outcome that already the scalar relativistic level qualitatively reproduces the experimental chemical shifts. The electronic properties of the complex were evaluated based on the results of the natural bond orbital (NBO) and topology of the electron density analyses. Overall, we apply a multidisciplinary approach acquiring comprehensive information about the solid-state structure and the metal-ligand bonding of the heteroleptic lanthanum complex.

Fatty acid bile acid conjugates (FABACs)—New molecules for the prevention of cholesterol crystallisation in bile

PubMed Central

Gilat, T; Somjen, G; Mazur, Y; Leikin-Frenkel, A; Rosenberg, R; Halpern, Z; Konikoff, F.

2001-01-01

BACKGROUND—Cholesterol gall stones are a frequent disease for which at present surgery is the usual therapy. Despite the importance of bile acids it has become evident that phospholipids are the main cholesterol solubilisers in bile. Even phospholipid components, such as fatty acids, have anticrystallising activity.
AIM—To synthesise fatty acid bile acid conjugates (FABACs) and study their effects on cholesterol crystallisation in bile in vitro and in vivo.
METHODS—FABACs were prepared by conjugation of cholic acid at position 3 with saturated fatty acids of variable chain length using an amide bond. Cholesterol crystallisation and its kinetics (crystal observation time, crystal mass) were studied in model bile, pooled enriched human bile, and fresh human bile using FABACs with saturated fatty acids of varying chain length (C-6 to C-22). Absorption of FABACs into blood and bile was tested in hamsters. Prevention of biliary cholesterol crystallisation in vivo was tested in hamsters and inbred mice.
RESULTS—FABACs strongly inhibited cholesterol crystallisation in model as well as native bile. The FABACs with longer acyl chains (C-16 to C-22) were more effective. At a concentration of 5 mM, FABACs almost completely inhibited cholesterol crystallisation in fresh human bile for 21 days. FABACs were absorbed and found in both portal and heart blood of hamsters. Levels in bile were 2-3 times higher than in blood, indicating active secretion. Appreciable levels were found in the systemic circulation 24-48 hours after a single administration. Ingested FABACs completely prevented the formation of cholesterol crystals in the gall bladders of hamsters and mice fed a lithogenic diet.
CONCLUSIONS—FABACs are potent inhibitors of cholesterol crystallisation in bile. They are absorbed and secreted into bile and prevent the earliest step of cholesterol gall stone formation in animals. These compounds may be of potential use in cholesterol gall stone disease in humans.


Keywords: gall stones; bile; phospholipids; cholesterol crystallisation; fatty acid bile acid conjugates PMID:11115826

A constitutive law for degrading bioresorbable polymers.

PubMed

Samami, Hassan; Pan, Jingzhe

2016-06-01

This paper presents a constitutive law that predicts the changes in elastic moduli, Poisson's ratio and ultimate tensile strength of bioresorbable polymers due to biodegradation. During biodegradation, long polymer chains are cleaved by hydrolysis reaction. For semi-crystalline polymers, the chain scissions also lead to crystallisation. Treating each scission as a cavity and each new crystal as a solid inclusion, a degrading semi-crystalline polymer can be modelled as a continuum solid containing randomly distributed cavities and crystal inclusions. The effective elastic properties of a degrading polymer are calculated using existing theories for such solid and the tensile strength of the degrading polymer is predicted using scaling relations that were developed for porous materials. The theoretical model for elastic properties and the scaling law for strength form a complete constitutive relation for the degrading polymers. It is shown that the constitutive law can capture the trend of the experimental data in the literature for a range of biodegradable polymers fairly well. Copyright © 2016 Elsevier Ltd. All rights reserved.

Crystallisation via novel 3D nanotemplates as a tool for protein purification and bio-separation

NASA Astrophysics Data System (ADS)

Shah, Umang V.; Jahn, Niklas H.; Huang, Shanshan; Yang, Zhongqiang; Williams, Daryl R.; Heng, Jerry Y. Y.

2017-07-01

This study reports an experimental validation of the surface preferential nucleation of proteins on the basis of a relationship between nucleant pore diameter and protein hydrodynamic diameter. The validated correlation was employed for the selection of nucleant pore diameter to crystallise a target protein from binary, equivolume protein mixture. We report proof-of-concept preliminary experimental evidence for the rational approach for crystallisation of a target protein from a binary protein mixture on the surface of 3D nanotemplates with controlled surface porosity and narrow pore-size distribution selected on the basis of a relationship between the nucleant pore diameter and protein hydrodynamic diameter. The outcome of this study opens up an exciting opportunity for exploring protein crystallisation as a potential route for protein purification and bio-separation in both technical and pharmaceutical applications.

The impact of N,N-dimethyldodecylamine N-oxide (DDAO) concentration on the crystallisation of sodium dodecyl sulfate (SDS) systems and the resulting changes to crystal structure, shape and the kinetics of crystal growth.

PubMed

Summerton, Emily; Hollamby, Martin J; Zimbitas, Georgina; Snow, Tim; Smith, Andrew J; Sommertune, Jens; Bettiol, Jeanluc; Jones, Christopher; Britton, Melanie M; Bakalis, Serafim

2018-05-19

At low temperatures stability issues arise in commercial detergent products when surfactant crystallisation occurs, a process which is not currently well-understood. An understanding of the phase transition can be obtained using a simple binary SDS (sodium dodecyl sulfate) + DDAO (N,N-dimethyldodecylamine N-oxide) aqueous system. It expected that the crystallisation temperature of an SDS system can be lowered with addition of DDAO, thus providing a route to improve detergent stability. Detergent systems are typically comprised of anionic surfactants, non-ionic surfactants and water. This study explores the crystallisation of a three component system consisting of sodium dodecyl sulfate (SDS), N,N-dimethyldodecylamine N-oxide (DDAO), and water using wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC) and confocal Raman microscopy. The presence of DDAO lowered the crystallisation temperature of a 20 wt% SDS system. For all aqueous mixtures of SDS + DDAO at low temperatures, SDS hydrated crystals, SDS.1/2H 2 O or SDS·H 2 O, formed. SDS hydrates comprising of layers of SDS separated by water layers. DDAO tended to reside in the vicinity of these SDS crystals. In the absence of DDAO an additional intermediary hydrate structure, SDS.1/8H 2 O, formed whereas for mixed SDS + DDAO systems no such structure was detected during crystallisation. Copyright © 2018. Published by Elsevier Inc.

Crystallisation kinetics study in stabilisation treatment of sol-gel derived 45S5 bioglass

NASA Astrophysics Data System (ADS)

Prakrathi, S.; Matin, Mallikarjun; Kiran, P.; Manne, Bhaskar; Ramesh, M. R.

2018-04-01

Solgel gel derived bioglasses require stabilisation heat treatment to decompose nitrates and to improve mechanical stability. While decomposing nitrate phases especially in solgel derived 45S5 bioglass, it is difficult to avoid crystallisation of silicate crystalline phases (Na2CaSi2O6, Na2Ca2Si3O9) due to overlapping of nitrates decomposition and silicates crystallisation temperatures. Control of such crystallinity amount in bioglasses is at most important during stabilisation as it affects the dissolution rates of bioglassesin body fluids. Controlling and quantifying of this crystallinity helps in engineering bioglasses for specific period in application. In this work, synthesis of 45S5 bioglass through solgel method is presented. Here, temperature and time dependent crystallisation kinetics were estimated using a quality parameter derived from X-ray diffraction (XRD) patterns of bioglass during stabilisation treatment. Quality parameter derived from XRD patterns is termed as IPB which is the ratio of integral area of peaks to the integral area of background. It is proposed that IPB can be used as quality parameter to assess crystallinity and to study crystallisation kinetics in bioglasses.

Development of a digital video-microscopy technique to study lactose crystallisation kinetics in situ.

PubMed

Arellano, María Paz; Aguilera, José Miguel; Bouchon, Pedro

2004-11-15

Polarised light microscopy was employed non-invasively to monitor lactose crystallisation from non-seeded supersaturated solutions in real time. Images were continuously recorded, processed and characterised by image analysis, and the results were compared with those obtained by refractometry. Three crystallisation temperatures (10, 20 and 30 degrees C) and three different levels of initial relative supersaturation (C/C(s)=1.95; 2.34; 3.15) were investigated. Induction times using the imaging technique proved to be substantially lower than those determined using refractive index. Lactose crystals were isolated digitally to determine geometrical parameters of interest, such as perimeter, diameter, area, roundness and Feret mean, and to derive crystal growth rates. Mean growth rates obtained for single crystals were fitted to a combined mass transfer model (R(2)=0.9766). The model allowed the effects of temperature and supersaturation on crystallisation rate to be clearly identified. It also suggested that, in this set of experiments, surface integration seemed to be the rate controlling step. It is believed that a similar experimental set-up could be implemented in a real food system to characterise a particular process where crystallisation control is of interest and where traditional techniques are difficult to implement.

Effect of Na2O on Crystallisation Behaviour and Heat Transfer of Fluorine-Free Mould Fluxes

NASA Astrophysics Data System (ADS)

Yang, Jian; Zhang, Jianqiang; Sasaki, Yasushi; Ostrovski, Oleg; Zhang, Chen; Cai, Dexiang; Kashiwaya, Yoshiaki

Most of the commercial mould fluxes contain fluorides which bring about serious environmental problems. The major challenge in the application of fluorine-free mould fluxes is to control the heat transfer from the strand to copper mould which is closely related to crystallisation behaviour. In this study, the effects of Na2O on the crystallisation behaviour and heat transfer of CaO-SiO2-Na2O-B2O3-TiO2-Al2O3-MgO-Li2O mould fluxes were investigated using single /double hot thermocouple technique (SHTT/DHTT) and infrared emitter technique (IET), respectively. Continuous cooling transformation (CCT) and time-temperature transformation (TTT) diagrams constructed using SHTT showed that the increase of Na2O concentration led to higher critical cooling rate and shorter incubation time. The crystallisation behaviour in a thermal gradient was examined using DHTT. The heat flux measured by IET showed that the increase of Na2O concentration decreased the heat flux when Na2O was lower than 9 mass% but the further increase of Na2O raised the heat flux. The relationship between flux crystallisation and heat transfer was also discussed.

Influence of solvent polarity and supersaturation on template-induced nucleation of carbamazepine crystal polymorphs

NASA Astrophysics Data System (ADS)

Parambil, Jose V.; Poornachary, Sendhil K.; Tan, Reginald B. H.; Heng, Jerry Y. Y.

2017-07-01

Studies on the use of template surfaces to induce heterogeneous crystal nucleation have gained momentum in recent years-with potential applications in selective crystallisation of polymorphs and in the generation of seed crystals in a continuous crystallisation process. In developing a template-assisted solution crystallisation process, the kinetics of homogeneous versus heterogeneous crystal nucleation could be influenced by solute-solvent, solute-template, and solvent-template interactions. In this study, we report the effect of solvents of varying polarity on the nucleation of carbamazepine (CBZ) crystal polymorphs, a model active pharmaceutical ingredient. The experimental results demonstrate that functionalised template surfaces are effective in promoting crystallisation of either the metastable (form II) or stable (form III) polymorphs of CBZ only in moderately (methanol, ethanol, isopropanol) and low polar (toluene) solvents. A solvent with high polarity (acetonitrile) is thought to mask the template effect on heterogeneous nucleation due to strong solute-solvent and solvent-template interactions. The current study highlights that a quality-by-design (QbD) approach-considering the synergistic effects of solute concentration, solvent type, solution temperature, and template surface chemistry on crystal nucleation-is critical to the development of a template-induced crystallisation process.

Thermodynamic modelling of a membrane distillation crystallisation process for the treatment of mining wastewater.

PubMed

Nathoo, Jeeten; Randall, Dyllon Garth

2016-01-01

Membrane distillation (MD) could be applicable in zero liquid discharge applications. This is due to the fact that MD is applicable at high salinity ranges which are generally outside the scope of reverse osmosis (RO) applications, although this requires proper management of precipitating salts to avoid membrane fouling. One way of managing these salts is with MD crystallisation (MDC). This paper focuses on the applicability of MDC for the treatment of mining wastewater by thermodynamically modelling the aqueous chemistry of the process at different temperatures. The paper is based on the typical brine generated from an RO process in the South African coal mining industry and investigates the effect water recovery and operating temperature have on the salts that are predicted to crystallise out, the sequence in which they will crystallise out and purities as a function of the water recovery. The study confirmed the efficacy of using thermodynamic modelling as a tool for investigating and predicting the crystallisation aspects of the MDC process. The key finding from this work was that, for an MDC process, a purer product can be obtained at higher operating temperatures and recoveries because of the inverse solubility of calcium sulphate.

Utilisation of adsorption and desorption for simultaneously improving protein crystallisation success rate and crystal quality

NASA Astrophysics Data System (ADS)

Guo, Yun-Zhu; Sun, Li-Hua; Oberthuer, Dominik; Zhang, Chen-Yan; Shi, Jian-Yu; di, Jiang-Lei; Zhang, Bao-Liang; Cao, Hui-Ling; Liu, Yong-Ming; Li, Jian; Wang, Qian; Huang, Huan-Huan; Liu, Jun; Schulz, Jan-Mirco; Zhang, Qiu-Yu; Zhao, Jian-Lin; Betzel, Christian; He, Jian-Hua; Yin, Da-Chuan

2014-12-01

High-quality protein crystals of suitable size are an important prerequisite for applying X-ray crystallography to determine the 3-dimensional structure of proteins. However, it is often difficult to obtain protein crystals of appropriate size and quality because nucleation and growth processes can be unsuccessful. Here, we show that by adsorbing proteins onto porous polystyrene-divinylbenzene microspheres (SDB) floating on the surface of the crystallisation solution, a localised high supersaturation region at the surface of the microspheres and a low supersaturation region below the microspheres can coexist in a single solution. The crystals will easily nucleate in the region of high supersaturation, but when they grow to a certain size, they will sediment to the region of low supersaturation and continue to grow. In this way, the probability of crystallisation and crystal quality can be simultaneously increased in a single solution without changing other crystallisation parameters.

Alkali metal complexes of a phosphine-borane-stabilised carbanion: influence of co-ligands on structure.

PubMed

Izod, Keith; Wills, Corinne; Clegg, William; Harrington, Ross W

2007-09-07

The adducts [[(Me(3)Si)(2){Me(2)P(BH(3))}C]K(L)(n)](m) [L = THF, n = 0.5, m = infinity (2a); L = tmeda (2b), pmdeta (2c), n = 1, m = 2] may be synthesised by treatment of solvent-free [[(Me(3)Si)(2){Me(2)P(BH(3))}C]K](infinity) (2) with the corresponding Lewis base (tmeda = N,N,N',N'-tetramethylethylenediamine; pmdeta = N,N,N',N'',N''-pentamethyldiethylenetriamine). X-Ray crystallography reveals that, whereas 2 crystallises with a complex 2-dimensional sheet structure, 2a crystallises as a ribbon-type one-dimensional polymer and both 2b and 2c crystallise as dimers. The corresponding complex with 12-crown-4, [K(12-crown-4)(2)][(Me(3)Si)(2){Me(2)P(BH(3))}C] (2d) crystallises as a separated ion pair. The complexes [[(Me(3)Si)(2){Me(2)P(BH(3))}C]M(pmdeta)](n) [M = Na, n = 1 (6); M = Rb, n = 2 (7)] may be synthesised by treatment of [(Me(3)Si)(2){Me(2)P(BH(3))}C]M with pmdeta. Whereas crystallises as a discrete monomer, compound 7 crystallises as a dimer. Compounds 2, 2a-2d, 6, 7 and the corresponding caesium derivative [[(Me(3)Si)(2){Me(2)P(BH(3))}C]Cs(pmdeta)](2) () provide an opportunity to consider the influence of the ionic radius of the metal and the nature of the co-ligands on the structures of alkali metal complexes of a phosphine-borane-stabilised carbanion.

Penetration enhancement of ibuprofen from supersaturated solutions through human skin.

PubMed

Iervolino, M; Cappello, B; Raghavan, S L; Hadgraft, J

2001-01-05

Systematic investigations on the diffusion of ibuprofen (IBU) from supersaturated solutions through human epidermis are reported. Significant flux enhancement was obtained from supersaturated solutions compared to the saturated solution. Hydroxypropyl methylcellulose (HPMC), when used as an additive was found to be effective in maintaining the high activity state at high degrees of saturation (DS). The increase in the flux was proportional to the DS. In the presence of 2-hydroxypropyl-beta-cyclodextrin (CD) at DS 2 and 3 a lower flux was observed compared to HPMC. At DS 5 a higher flux enhancement was found suggesting that CD might act as a penetration enhancer at certain CD/drug ratios. Studies on the mechanism of stabilisation of HPMC and CD on IBU crystallisation from supersaturated systems showed that HPMC acts as a growth inhibitor and habit modifier whereas CD does not influence the crystallisation process.

Are metastable, precrystallisation, density-fluctuations a universal phenomena?

PubMed

Heeley, Ellen L; Poh, C Kit; Li, Wu; Maidens, Anna; Bras, Wim; Dolbnya, Igor P; Gleeson, Anthony J; Terrill, Nicolas J; Fairclough, J Patrick A; Olmsted, Peter D; Ristic, Rile I; Hounslow, Micheal J; Ryan, Anthony J

2003-01-01

In-situ observations of crystallisation in minerals and organic polymers have been made by simultaneous, time-resolved small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS) techniques. In isotactic polypropylene slow quiescent crystallisation shows the onset of large scale ordering prior to crystal growth. Rapid crystallisations studied by melt extrusion indicate the development of well resolved oriented SAXS patterns associated with long range order before the development of crystalline peaks in the WAXS region. Block copolymers self-assemble into mesophases in polymer melts above a critical chain length (or above a critical temperature) and this self-assembly process is shown to be susceptible to an incipient crystallisation. Mesophase formation is observed at anomalously high temperatures in ethylene-oxide containing block copolymers below the normal melting point of the polyoxy ethylene chains. Formation of calcium carbonate from aqueous solutions of sodium carbonate and calcium nitrate is observed to be a two-stage process and precipitation proceeds by the production of an amorphous metastable phase. This phase grows until it is volume filling and leads to the formation of the two polymorphs Calcite and Vaterite. These three sets of results suggest pre-nucleation density fluctuations, leading to a metastable phase, play an integral role in all three classes of crystallisation. In due course, this phase undergoes transformation to "normal" crystals.

Timing of Crystallisation of the Lunar Magma Ocean Constrained by the Oldest Zircon

NASA Technical Reports Server (NTRS)

Nemchin, A.; Timms, N.; Pidgeon, R.; Geisler, T.; Reddy, S.; Meyer, C.

2009-01-01

The presently favoured concept for the early evolution of the Moon involves consolidation of debris from a giant impact of a Mars sized body with Earth forming a primitive Moon with a thick global layer of melt referred to as the Lunar Magma Ocean1 . It is widely accepted that many significant features observed on the Moon today are the result of crystallisation of this magma ocean. However, controversy exists over the precise timing and duration of the crystallisation process. Resolution of this problem depends on the establishment of precise and robust key crystallisation time points. We report a 4417 6 Myr old zircon in lunar breccia sample 72215,195, which provides a precisely determined younger limit for the solidification of the Lunar Magma Ocean. A model based on these data, together with the age of the Moon forming giant impact, defines an exponential time frame for crystallisation and suggests formation of anorthositic crust after about 80-85% of the magma ocean was solidified. In combination with other zircon ages the 4417 +/- 6 Myr age also suggests that the very small (less than a few per cent) residual portion of the magma ocean continued to solidify during the following 300-500 m.y.

Psychedelics and the science of self-experience.

PubMed

Nour, Matthew M; Carhart-Harris, Robin L

2017-03-01

Altered self-experiences arise in certain psychiatric conditions, and may be induced by psychoactive drugs and spiritual/religious practices. Recently, a neuroscience of self-experience has begun to crystallise, drawing upon findings from functional neuroimaging and altered states of consciousness occasioned by psychedelic drugs. This advance may be of great importance for psychiatry. © The Royal College of Psychiatrists 2017.

Magnetic nanoparticles through organometallic synthesis: evolution of the magnetic properties from isolated nanoparticles to organised nanostructures.

PubMed

Dumestre, Fréderic; Martinez, Susana; Zitoun, David; Fromen, Marie-Claire; Casanove, Marie-José; Lecante, Pierre; Respaud, Marc; Serres, Arnaud; Benfield, Robert E; Amiens, Catherine; Chaudret, Bruno

2004-01-01

Co and NiFe nanoparticles (2.7 to 3.3 nm mean diameter) of narrow size distribution have been obtained through the decomposition of organometallic precursors in organic solutions of long alkyl chain ligands, namely oleic acid and hexadecylamine. Materials of various volume fractions were produced. The particles have been structurally characterised by WAXS. Both adopt the bulk structure: HCP in the case of cobalt; a mixture of FCC and BCC for NiFe. Their aptitude to self-assemble either on flat supports or in bulk solid state has been investigated by means of TEM and SAXS. This study suggests the crystallisation of the nanoparticles upon solvent evaporation, especially a local FCC arrangement was observed for the NiFe material. Magnetic measurements (SQUID) confirm this tendency. The blocking temperature depends on the metal volume fraction, i.e. on the anisotropy generated by the dipolar couplings (Ki). We show that, for dense samples, the particles of high intrinsic anisotropy, Ku, (Co) still display an individual behaviour while the soft ones (NiFe) display a collective behaviour.

Towards the synthesis of prenylated phloroglucinol derivatives: An X-ray crystallographic and DFT study of unexpected reaction products

NASA Astrophysics Data System (ADS)

Akerman, Matthew P.; Mkhize, Zimbili; van Heerden, Fanie R.

2018-07-01

Owing to their bioactivity and prevalence in medicinal plant extracts, prenylated phloroglucinols have garnered significant interest. Towards the synthesis of prenylated phloroglucinol derivatives, 2,4,6-trihydroxy-3-(3-methylbut-2-enyl)acetophenone is required as an intermediate. Herein, this was synthesised by a tandem Claisen-Cope rearrangement reaction on 2,4-bis(methoxymethoxy)-6-(3-methylbut-2-enyloxy)acetophenone and a subsequent hydrolysis to remove protecting groups. This reaction yielded the desired product as well as three by-products. Two of these by-products were isomeric chromane derivatives (2 and 3) and the third was a methoxy derivative (4). These compounds have been studied by single crystal X-ray crystallography and DFT methods. Compound (2) crystallised in the P21/c space group with two hydrogen-bonded molecules in the asymmetric unit (Z = 8). Compound (4) crystallised in the Pbca space group with a single molecule in the asymmetric unit (Z = 8). Both compounds formed extensive supramolecular structures supported by hydrogen bonds in the solid state. Compound (2) forms a simple one-dimensional hydrogen-bonded chain co-linear with the a-axis. Compound (4) forms a two-dimensional supramolecular structure comprising "pentameric" hydrogen-bonded motifs linked by additional H-bonds to form the supramolecular structure. Both structures showed intramolecular hydrogen bonds between the acetyl oxygen and adjacent OH group. DFT simulations were used to probe the relative energies of the molecules and hydrogen bonds. These simulations showed that the intramolecular hydrogen bond has a substantial stabilising effect with an interaction strength of 70.64 kJ mol-1. The formation of the hydrogen-bonded dimer of (2) from which the supramolecular structure is formed has a ΔHassoc constant of -42.32 kJ mol-1, illustrating that the formation of the hydrogen-bonded structure is energetically favourable.

Assessing the shock state of the lunar highlands: Implications for the petrogenesis and chronology of crustal anorthosites.

PubMed

Pernet-Fisher, J F; Joy, K H; Martin, D J P; Donaldson Hanna, K L

2017-07-19

Our understanding of the formation and evolution of the primary lunar crust is based on geochemical systematics from the lunar ferroan anorthosite (FAN) suite. Recently, much effort has been made to understand this suite's petrologic history to constrain the timing of crystallisation and to interpret FAN chemical diversity. We investigate the shock histories of lunar anorthosites by combining Optical Microscope (OM) 'cold' cathodoluminescence (CL)-imaging and Fourier Transform Infrared (FTIR) spectroscopy analyses. In the first combined study of its kind, this study demonstrates that over ~4.5 Ga of impact processing, plagioclase is on average weakly shocked (<15 GPa) and examples of high shock states (>30 GPa; maskelynite) are uncommon. To investigate how plagioclase trace-element systematics are affected by moderate to weak shock (~5 to 30 GPa) we couple REE+Y abundances with FTIR analyses for FAN clasts from lunar meteorite Northwest Africa (NWA) 2995. We observe weak correlations between plagioclase shock state and some REE+Y systematics (e.g., La/Y and Sm/Nd ratios). This observation could prove significant to our understanding of how crystallisation ages are evaluated (e.g., plagioclase-whole rock Sm-Nd isochrons) and for what trace-elements can be used to differentiate between lunar lithologies and assess magma source compositional differences.

In situ dynamic observations of perovskite crystallisation and microstructure evolution intermediated from [PbI6]4- cage nanoparticles

NASA Astrophysics Data System (ADS)

Hu, Qin; Zhao, Lichen; Wu, Jiang; Gao, Ke; Luo, Deying; Jiang, Yufeng; Zhang, Ziyi; Zhu, Chenhui; Schaible, Eric; Hexemer, Alexander; Wang, Cheng; Liu, Yi; Zhang, Wei; Grätzel, Michael; Liu, Feng; Russell, Thomas P.; Zhu, Rui; Gong, Qihuang

2017-06-01

Hybrid lead halide perovskites have emerged as high-performance photovoltaic materials with their extraordinary optoelectronic properties. In particular, the remarkable device efficiency is strongly influenced by the perovskite crystallinity and the film morphology. Here, we investigate the perovskites crystallisation kinetics and growth mechanism in real time from liquid precursor continually to the final uniform film. We utilize some advanced in situ characterisation techniques including synchrotron-based grazing incident X-ray diffraction to observe crystal structure and chemical transition of perovskites. The nano-assemble model from perovskite intermediated [PbI6]4- cage nanoparticles to bulk polycrystals is proposed to understand perovskites formation at a molecular- or nano-level. A crystallisation-depletion mechanism is developed to elucidate the periodic crystallisation and the kinetically trapped morphology at a mesoscopic level. Based on these in situ dynamics studies, the whole process of the perovskites formation and transformation from the molecular to the microstructure over relevant temperature and time scales is successfully demonstrated.

In situ dynamic observations of perovskite crystallisation and microstructure evolution intermediated from [PbI6]4− cage nanoparticles

PubMed Central

Hu, Qin; Zhao, Lichen; Wu, Jiang; Gao, Ke; Luo, Deying; Jiang, Yufeng; Zhang, Ziyi; Zhu, Chenhui; Schaible, Eric; Hexemer, Alexander; Wang, Cheng; Liu, Yi; Zhang, Wei; Grätzel, Michael; Liu, Feng; Russell, Thomas P.; Zhu, Rui; Gong, Qihuang

2017-01-01

Hybrid lead halide perovskites have emerged as high-performance photovoltaic materials with their extraordinary optoelectronic properties. In particular, the remarkable device efficiency is strongly influenced by the perovskite crystallinity and the film morphology. Here, we investigate the perovskites crystallisation kinetics and growth mechanism in real time from liquid precursor continually to the final uniform film. We utilize some advanced in situ characterisation techniques including synchrotron-based grazing incident X-ray diffraction to observe crystal structure and chemical transition of perovskites. The nano-assemble model from perovskite intermediated [PbI6]4− cage nanoparticles to bulk polycrystals is proposed to understand perovskites formation at a molecular- or nano-level. A crystallisation-depletion mechanism is developed to elucidate the periodic crystallisation and the kinetically trapped morphology at a mesoscopic level. Based on these in situ dynamics studies, the whole process of the perovskites formation and transformation from the molecular to the microstructure over relevant temperature and time scales is successfully demonstrated. PMID:28635947

Promoting crystallisation of the Salmonella enteritidis fimbriae 14 pilin SefD using deuterium oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Bing; Garnett, James A.; Lee, Wei-chao

Highlights: Black-Right-Pointing-Pointer The benefits of D{sub 2}O in screening for crystallisation was explored. Black-Right-Pointing-Pointer The crystal structures of the SefD pilin in both H{sub 2}O and D{sub 2}O reveal differences. Black-Right-Pointing-Pointer Crystallisation improvements are explained by altered interactions in D{sub 2}O crystals. Black-Right-Pointing-Pointer D{sub 2}O is useful additive in sparse-matrix screening for crystallisation. -- Abstract: The use of heavy water (D{sub 2}O) as a solvent is commonplace in many spectroscopic techniques for the study of biological macromolecules. A significant deuterium isotope effect exists where hydrogen-bonding is important, such as in protein stability, dynamics and assembly. Here we illustrate the usemore » of D{sub 2}O in additive screening for the production of reproducible diffraction-quality crystals for the Salmonella enteritidis fimbriae 14 (SEF14) putative tip adhesin, SefD.« less

An automated parallel crystallisation search for predicted crystal structures and packing motifs of carbamazepine.

PubMed

Florence, Alastair J; Johnston, Andrea; Price, Sarah L; Nowell, Harriott; Kennedy, Alan R; Shankland, Norman

2006-09-01

An automated parallel crystallisation search for physical forms of carbamazepine, covering 66 solvents and five crystallisation protocols, identified three anhydrous polymorphs (forms I-III), one hydrate and eight organic solvates, including the single-crystal structures of three previously unreported solvates (N,N-dimethylformamide (1:1); hemi-furfural; hemi-1,4-dioxane). Correlation of physical form outcome with the crystallisation conditions demonstrated that the solvent adopts a relatively nonspecific role in determining which polymorph is obtained, and that the previously reported effect of a polymer template facilitating the formation of form IV could not be reproduced by solvent crystallisation alone. In the accompanying computational search, approximately half of the energetically feasible predicted crystal structures exhibit the C=O...H--N R2(2)(8)dimer motif that is observed in the known polymorphs, with the most stable correctly corresponding to form III. Most of the other energetically feasible structures, including the global minimum, have a C=O...H--N C(4) chain hydrogen bond motif. No such chain structures were observed in this or any other previously published work, suggesting that kinetic, rather than thermodynamic, factors determine which of the energetically feasible crystal structures are observed experimentally, with the kinetics apparently favouring nucleation of crystal structures based on the CBZ-CBZ R2(2)(8) motif. (c) 2006 Wiley-Liss, Inc. and the American Pharmacists Association.

The devitrification of a LAS glass matrix studied by X-ray powder diffraction

NASA Astrophysics Data System (ADS)

Rocherullé, Jean; Bénard-Rocherullé, Patricia

2002-06-01

The crystallisation kinetics of a Li 0.6Al 0.1Si 0.6O 1.65 glass matrix has been performed by means of X-ray powder diffraction. Data diffraction have shown the simultaneous formation of two crystalline phases Li 2SiO 3 and Li 0.6Al 0.6Si 2.4O 6 (so-called virgilite) for heat treatments conducted at 700 and 750 °C. The kinetic parameters of crystallisation have been determined for each phase from several time-dependent X-ray diffraction studies. The two values of the Avrami exponent, close to 1.5, suggest that crystallisation is controlled by a diffusion process, the nucleation being non-existent in the temperature range from 700 to 750 °C. With regard to the activation energy of the overall crystallisation phenomenon, the values obtained, close to 175 kJ mol -1, provide to this glass a relative ability to crystallise compared to others glasses from MSiAlO systems, where M is an alkaline-earth or a rare-earth element. With respect to the Li 0.6Al 0.6Si 2.4O 6 phase, long time heat treatments at 750 °C have revealed a phase transition from the hexagonal symmetry to the tetragonal one. The corresponding value of the Avrami exponent (i.e., 1) suggests a diffusionless transformation with a one-dimensional growth.

Airborne chemistry: acoustic levitation in chemical analysis.

PubMed

Santesson, Sabina; Nilsson, Staffan

2004-04-01

This review with 60 references describes a unique path to miniaturisation, that is, the use of acoustic levitation in analytical and bioanalytical chemistry applications. Levitation of small volumes of sample by means of a levitation technique can be used as a way to avoid solid walls around the sample, thus circumventing the main problem of miniaturisation, the unfavourable surface-to-volume ratio. Different techniques for sample levitation have been developed and improved. Of the levitation techniques described, acoustic or ultrasonic levitation fulfils all requirements for analytical chemistry applications. This technique has previously been used to study properties of molten materials and the equilibrium shape()and stability of liquid drops. Temperature and mass transfer in levitated drops have also been described, as have crystallisation and microgravity applications. The airborne analytical system described here is equipped with different and exchangeable remote detection systems. The levitated drops are normally in the 100 nL-2 microL volume range and additions to the levitated drop can be made in the pL-volume range. The use of levitated drops in analytical and bioanalytical chemistry offers several benefits. Several remote detection systems are compatible with acoustic levitation, including fluorescence imaging detection, right angle light scattering, Raman spectroscopy, and X-ray diffraction. Applications include liquid/liquid extractions, solvent exchange, analyte enrichment, single-cell analysis, cell-cell communication studies, precipitation screening of proteins to establish nucleation conditions, and crystallisation of proteins and pharmaceuticals.

In situ dynamic observations of perovskite crystallisation and microstructure evolution intermediated from [PbI 6] 4– cage nanoparticles

DOE PAGES

Hu, Qin; Zhao, Lichen; Wu, Jiang; ...

2017-06-21

Hybrid lead halide perovskites have emerged as high-performance photovoltaic materials with their extraordinary optoelectronic properties. In particular, the remarkable device efficiency is strongly influenced by the perovskite crystallinity and the film morphology. Here, we investigate the perovskites crystallisation kinetics and growth mechanism in real time from liquid precursor continually to the final uniform film. We utilize some advanced in situ characterisation techniques including synchrotron-based grazing incident X-ray diffraction to observe crystal structure and chemical transition of perovskites. The nano-assemble model from perovskite intermediated [PbI 6] 4– cage nanoparticles to bulk polycrystals is proposed to understand perovskites formation at a molecular-more » or nano-level. A crystallisation-depletion mechanism is developed to elucidate the periodic crystallisation and the kinetically trapped morphology at a mesoscopic level. Based on these in situ dynamics studies, the whole process of the perovskites formation and transformation from the molecular to the microstructure over relevant temperature and time scales is successfully demonstrated.« less

An integrated zircon geochronological and geochemical investigation into the Miocene plutonic evolution of the Cyclades, Aegean Sea, Greece: part 2—geochemistry

NASA Astrophysics Data System (ADS)

Bolhar, Robert; Ring, Uwe; Kemp, Anthony I. S.; Whitehouse, Martin J.; Weaver, Steve D.; Woodhead, Jon D.; Uysal, I. Tonguc; Turnbull, Rose

2012-12-01

Zircons from 14 compositionally variable granitic rocks were examined in detail using CL image-guided micro-analysis to unravel the complex magmatic history above the southward retreating Hellenic subduction zone system in the Aegean Sea. Previously published U-Pb ages document an episodic crystallisation history from 17 to 11 Ma, with peraluminous (S-type) granitic rocks systematically older than closely associated metaluminous (I-type) granitic rocks. Zircon O- and Hf isotopic data, combined with trace element compositions, are highly variable within and between individual samples, indicative of open-system behaviour involving mantle-derived melts and evolved supracrustal sources. Pronounced compositional and thermal fluctuations highlight the role of magma mixing and mingling, in accord with field observations, and incremental emplacement of distinct melt batches coupled with variable degrees of crustal assimilation. In the course of partial fusion, more fertile supracrustal sources dominated in the earlier stages of Aegean Miocene magmatism, consistent with systematically older crystallisation ages of peraluminous granitic rocks. Differences between zircon saturation and crystallisation temperatures (deduced from zircon Ti concentrations), along with multimodal crystallisation age spectra for individual plutons, highlight the complex and highly variable physico-compositional and thermal evolution of silicic magma systems. The transfer of heat and juvenile melts from the mantle varied probably in response to episodic rollback of the subducting lithospheric slab, as suggested by punctuated crystallisation age spectra within and among individual granitic plutons.

Early evolution and dynamics of Earth from a molten initial stage

NASA Astrophysics Data System (ADS)

Lourenço, Diogo L.; Tackley, Paul J.

2014-05-01

It is now well established that most of the terrestrial planets underwent a magma ocean stage during their accretion. On Earth, it is probable that at the end of accretion, giant impacts like the hypothesised Moon-forming impact, together with other sources of heat such as conversion of gravitational energy of formation into heat, heat losses from the core at the core-mantle boundary, radioactive decay, electromagnetic induction heating and tidal heating, melted a substantial part of the mantle. The thermal and chemical evolution of the resulting magma ocean most certainly had dramatic consequences on the history of the planet, influencing the chemical composition of the mantle after differentiation, the style of tectonic regime prevailing in the solid-state mantle and its habitability. Considerable research has been done on magma oceans using 1-D models (e.g.: Abe, PEPI 1997; Solomatov, Treat. Geophys. 2007; Elkins-Tanton, EPSL 2008). However, its dynamics, evolution from a molten state to the present day solid state, and crystallisation are still not fully understood and are more complex than a 1-D formulation. Recent advances in computational methods and resources allow us to address numerically more complex problems, with higher resolution and multiple physics incorporated. Moreover, new developments in mineral physics that indicate that melt can be denser than solid at high pressures (e.g.: de Koker et al., EPSL 2013) can have very important impacts on the classical views of the solidification of magma oceans (Labrosse et al., Nature 2007). The goal of our study is to understand and characterise the influence of melting on the long-term thermo-chemical evolution of rocky planet interiors, starting from an initial molten state (magma ocean). Our approach is to test existing published 1-D parameterisations of magma ocean dynamics and extend them into 2-D models. We will address this problem using the numerical code StagYY (Tackley, PEPI 2008), which uses a finite-volume scheme for advection of temperature, a multigrid solver to obtain a velocity-pressure solution at each timestep, tracers to track composition, and a treatment of partial melting and crustal formation. Additional enhancements are needed in the code and are related to the physics and parameterisation of melting.

Solvothermal synthesis of a new 3-D mixed-metal sulfide framework, (H1.33tren)[In2.67Sb1.33S8]·tren

NASA Astrophysics Data System (ADS)

Lampkin, John D.; Powell, Anthony V.; Chippindale, Ann M.

2016-11-01

A new indium(III) antimony(V) sulfide, (H1.33tren)[In2.67Sb1.33S8]·tren, has been prepared solvothermally at 433 K. The compound crystallises in the tetragonal space group I-42d (lattice parameters, a=12.6248(5) and c=19.4387(18) Å at 150 K) and contains adamantane-like T2 supertetrahedral units comprised of corner-sharing InS45- and SbS43- tetrahedra. The adamantane-like units are then linked through sulfur vertices to generate an open, 3-D framework structure containing large pores in which neutral, protonated tren (tris(2-aminoethylene)amine) molecules reside. The presence of the organic components was confirmed by solid-state 13C NMR (10 kHz), combustion and thermogravimetric analysis. The band gap, obtained from UV-vis diffuse reflectance measurements, is 2.7(2) eV. Stirring with either water or alkali-metal salt solution leads to removal of the neutral tren molecules and an 9% reduction in unit-cell volume on formation of (H1.33tren)[In2.67Sb1.33S8]·(H2O)4.

Quantum simulations and many-body physics with light.

PubMed

Noh, Changsuk; Angelakis, Dimitris G

2017-01-01

In this review we discuss the works in the area of quantum simulation and many-body physics with light, from the early proposals on equilibrium models to the more recent works in driven dissipative platforms. We start by describing the founding works on Jaynes-Cummings-Hubbard model and the corresponding photon-blockade induced Mott transitions and continue by discussing the proposals to simulate effective spin models and fractional quantum Hall states in coupled resonator arrays (CRAs). We also analyse the recent efforts to study out-of-equilibrium many-body effects using driven CRAs, including the predictions for photon fermionisation and crystallisation in driven rings of CRAs as well as other dynamical and transient phenomena. We try to summarise some of the relatively recent results predicting exotic phases such as super-solidity and Majorana like modes and then shift our attention to developments involving 1D nonlinear slow light setups. There the simulation of strongly correlated phases characterising Tonks-Girardeau gases, Luttinger liquids, and interacting relativistic fermionic models is described. We review the major theory results and also briefly outline recent developments in ongoing experimental efforts involving different platforms in circuit QED, photonic crystals and nanophotonic fibres interfaced with cold atoms.

Drug carrier systems for solubility enhancement of BCS class II drugs: a critical review.

PubMed

Kumar, Sumit; Bhargava, Deepak; Thakkar, Arti; Arora, Saahil

2013-01-01

Poor aqueous solubility impedes a drug's bioavailability and challenges its pharmaceutical development. Pharmaceutical development of drugs with poor water solubility requires the establishment of a suitable formulation layout among various techniques. Various approaches have been investigated extensively to improve the aqueous solubility and poor dissolution rate of BCS class II and IV drugs. In this literature review, novel formulation options, particularly for class II drugs designed for applications such as micronization, self-emulsification, cyclodextrin complexation, co-crystallisation, super critical fluid technology, solubilisation by change in pH, salt formation, co-solvents, melt granulation, and solid dispersion, liposomal/niosomal formulations, are discussed in detail to introduce biopharmaceutical challenges and recent approaches to facilitate more efficient drug formulation and development.

Uptake of pharmaceuticals by sorbent-amended struvite fertilisers recovered from human urine and their bioaccumulation in tomato fruit.

PubMed

de Boer, Marissa A; Hammerton, Michelle; Slootweg, J Chris

2018-04-15

Struvite precipitation is a well-documented method for recovering up to 98% of phosphorus from urine, which is one of the main nutrients in fertilizers besides nitrogen and potassium. Shortcomings of this process, however, are the low nitrogen recovery ratio and the possible uptake of pharmaceuticals from urine. In this work, the NH 4 + adsorbent materials biochar and zeolite are coupled with struvite precipitation to increase the N-recovery of struvite from 5.7% to 9.8%. Since nitrogen is one of the main nutrients in fertilisers, this increase is of significance for its potential commercial use. In addition, urine is spiked with pharmaceuticals to measure the consequential uptake in struvite-based fertilisers and crops afterwards. Five fertilisers are prepared by nutrient recovery from spiked urine using: (1) struvite crystallisation, (2) struvite crystallisation combined with N adsorption on zeolite, (3) struvite crystallisation combined with N adsorption on biochar, (4) N adsorption on zeolite without struvite crystallisation, and (5) N adsorption on biochar without struvite crystallisation. The fertiliser with the highest purity product and the lowest uptake of pharmaceuticals was struvite combined with zeolite. Next, the contaminated struvite-sorbent fertilisers are tested in a crop trial in which the bioaccumulation of pharmaceuticals in edible plant tissue (tomatoes) is measured. This bioaccumulation in tomato fruit biomass from each of the spiked fertilisers in the crop trial was found to be lower than 0.0003% in all cases, far below the acceptable daily intake (ADI) levels (750 kg of dry tomatoes should be consumed per day to reach the ADI limit). Consequently, the subsequent risk to human health from tomato fruit grown using urine derived struvite-sorbent fertilisers is found to be insignificant. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Optical system for the Protein Crystallisation Diagnostics Facility (PCDF) on board the ISS

NASA Astrophysics Data System (ADS)

Joannes, Luc; Dupont, Olivier; Dewandel, Jean-Luc; Ligot, Renaud; Algrain, Hervé

2004-06-01

The Protein Crystallisation Diagnostic Facility (PCDF) is a multi-user facility to study the protein crystallisation under the conditions of micro-gravity onboard the International Space Station (ISS) Columbus facility. Large size protein crystals will growth under reduced gravity in thermally controlled reactors. A combination of diagnostic tools like video system, microscope, interferometer, and light scattering device shall help to understand the growth phenomena. Common methods of protein crystallisation shall be performed in PCDF: Dialysis where the protein solution and the salt solution are separated by a semi-permeable membrane. Extended Length Dialysis Batch where the saturation to get crystals is achieved by changing the concentration of the protein in the sample liquid. The overall ESA project is leaded by EADS Space Transportation, Friedrichshafen, Germany. Lambda-X is responsible for the Optical System (OS), with Verhaert Design and Development as sub-contractor for the mechanical design. The OS includes different compact parts: Original illumination systems based on LEDs of difference colours; Quantitative Mach-Zehnder interferometers to measure the concentration distribution around crystals; Imaging assemblies to visualize the protein volume with different field of views. The paper concentrates on the description of each part, and in particular on the imaging assembly which allow switching from one field of view to another by passive elements only.

Thermal Evolution and Crystallisation Regimes of the Martian Core

NASA Astrophysics Data System (ADS)

Davies, C. J.; Pommier, A.

2015-12-01

Though it is accepted that Mars has a sulfur-rich metallic core, its chemical and physical state as well as its time-evolution are still unconstrained and debated. Several lines of evidence indicate that an internal magnetic field was once generated on Mars and that this field decayed around 3.7-4.0 Gyrs ago. The standard model assumes that this field was produced by a thermal (and perhaps chemical) dynamo operating in the Martian core. We use this information to construct parameterized models of the Martian dynamo in order to place constraints on the thermochemical evolution of the Martian core, with particular focus on its crystallization regime. Considered compositions are in the FeS system, with S content ranging from ~10 and 16 wt%. Core radius, density and CMB pressure are varied within the errors provided by recent internal structure models that satisfy the available geodetic constraints (planetary mass, moment of inertia and tidal Love number). We also vary the melting curve and adiabat, CMB heat flow and thermal conductivity. Successful models are those that match the dynamo cessation time and fall within the bounds on present-day CMB temperature. The resulting suite of over 500 models suggest three possible crystallization regimes: growth of a solid inner core starting at the center of the planet; freezing and precipitation of solid iron (Fe- snow) from the core-mantle boundary (CMB); and freezing that begins midway through the core. Our analysis focuses on the effects of core properties that are expected to be constrained during the forthcoming Insight mission.

Theoretical and Experimental Studies of N,N-Dimethyl-N'-Picryl-4,4'-Stilbenediamine.

PubMed

Papper, Vladislav; Wu, Yuanyuan; Kharlanov, Vladimir; Sukharaharja, Ayrine; Steele, Terry W J; Marks, Robert S

2018-01-01

N,N-dimethyl-N'-picryl-4,4'-stilbenediamine (DMPSDA) was prepared, purified and crystallised in a form of black lustrous crystals, and its absorption and fluorescence spectra were recorded in cyclohexane, acetonitrile and dimethyl sulfoxide. Non-emissive intramolecular charge transfer state (ICT) was clearly observed in this molecule in all three solvents. Theoretical calculations demonstrating a betaine electronic structure of the trinitrophenyl group in the ground state of the molecule and a charge transfer nature of the long wavelength transition S 0  → S 1 supported the experimental observations of the ICT formation in the molecule.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Qin; Zhao, Lichen; Wu, Jiang

Hybrid lead halide perovskites have emerged as high-performance photovoltaic materials with their extraordinary optoelectronic properties. In particular, the remarkable device efficiency is strongly influenced by the perovskite crystallinity and the film morphology. Here, we investigate the perovskites crystallisation kinetics and growth mechanism in real time from liquid precursor continually to the final uniform film. We utilize some advanced in situ characterisation techniques including synchrotron-based grazing incident X-ray diffraction to observe crystal structure and chemical transition of perovskites. The nano-assemble model from perovskite intermediated [PbI 6] 4– cage nanoparticles to bulk polycrystals is proposed to understand perovskites formation at a molecular-more » or nano-level. A crystallisation-depletion mechanism is developed to elucidate the periodic crystallisation and the kinetically trapped morphology at a mesoscopic level. Based on these in situ dynamics studies, the whole process of the perovskites formation and transformation from the molecular to the microstructure over relevant temperature and time scales is successfully demonstrated.« less

Characterisation of a garnet population from the Sikkim Himalaya: implications for the mechanisms and rates of porphyroblast crystallisation

NASA Astrophysics Data System (ADS)

George, Freya; Gaidies, Fred

2016-04-01

Analysis of porphyroblast distribution in metamorphic rocks yields insight into the processes controlling metamorphic reaction rates. By coupling this textural record with microprobe analysis and phase-equilibria and diffusion modelling, a detailed view of the nucleation and growth history of metamorphic minerals can be obtained. In this study, we comprehensively characterise the 3D distribution and compositional variation of a garnet population in a garnet-grade pelitic schist of the Lesser Himalayan Sequence (Sikkim), in order to investigate both the rates and kinetic controls of porphyroblastic crystallisation. Quantification of the size, shape and spatial distribution of garnet using high-resolution μ-computed X-ray tomography and statistical analysis reveals a log-normal crystal size distribution, systematic variation of aspect ratio with crystal size, and a significantly clustered garnet texture in the study sample. The latter is indicative of interface-controlled nucleation and growth, with nucleation sites controlled principally by a heterogeneous precursor assemblage. At length-scales less than 0.7 mm, there is evidence for adjacent grains that are on average smaller than the mean size of the population; this minor ordering is attributed to secondary redistribution of porphyroblast centers and reduction of crystal sizes due to syn-kinematic growth and resorption, respectively. Geochemical traverses through centrally sectioned garnet crystals of variable size highlight several features: (1) core compositions of even the smallest crystals preserve primary prograde growth zonation, with little evidence for diffusional modification in any crystal size; (2) rim compositions are within error between grains, suggestive of sample-scale equilibration of the growth medium at the time of cessation of crystallisation; (3) different grains of equal radii display equivalent compositional zoning; and (4) gradients of compositional profiles display a steepening trend in progressively smaller grain sizes, converse to anticipated trends based on classic kinetic crystallisation theory. The observed systematic behaviour is interpreted to reflect interface-controlled rates of crystallisation, with a decrease in the rate of crystal growth of newly nucleated grains as the crystallisation interval proceeds. Numerical simulations of garnet growth successfully reproduce observed core and rim compositions, and simulations of intracrystalline diffusion yield rapid heating/cooling rates along the P-T path, in excess of 100 °C/Ma. Radial garnet crystallisation is correspondingly rapid, with minimum growth rates of 1.5 mm/Ma in the smallest crystals. Simulations suggest progressive nucleation of new generations of garnet occurred with an exponentially decreasing frequency along the prograde path; however, measured gradients indicate that core compositions developed more slowly than predicted by the model, potentially resulting in a more evenly distributed pattern of nucleation.

Primary welding and crystallisation textures preserved in the intra-caldera ignimbrites of the Permian Ora Formation, northern Italy: implications for deposit thermal state and cooling history

NASA Astrophysics Data System (ADS)

Willcock, M. A. W.; Cas, R. A. F.

2014-06-01

Exceptional exposure through a Permian intra-caldera ignimbrite fill within the 42 × 40 km Ora caldera (>1,290 km3 erupted volume) provides an opportunity to study welding textures in a thick intra-caldera ignimbrite succession. The ignimbrite succession records primary dense welding, a simple cooling unit structure, common crystallisation zones, and remarkably preserves fresh to slightly hydrated glass in local vitrophyre zones. Evidence for primary syn- and post-emplacement welding consists of (a) viscously deformed and sintered juvenile glass and relict shard textures; (b) complete deposit welding; (c) subtle internal welding intensity variations; (d) vitrophyre preserved locally at the base of the ignimbrite succession; (e) persistent fiamme juvenile clast shapes throughout the succession at the macroscopic and microscopic scales, defining a moderate to well-developed eutaxitic texture; (f) common undulating juvenile clast (pumice) margins and feathery terminations; (g) a general loss of deposit porosity; and (h) perlitic fracturing. A low collapsing or fountaining explosive eruption column model is proposed to have facilitated the ubiquitous welding of the deposit, which in turn helped preserve original textures. The ignimbrite succession preserves no evidence of a time break through the sequence and columnar joints cross-gradational ignimbrite lithofacies boundaries, so the ignimbrite is interpreted to represent a simple cooling unit. Aspect ratio and anisotropy of magnetic susceptibility (AMS) analyses through stratigraphic sections within the thick intra-caldera succession and at the caldera margin reveal variable welding compaction and strain profiles. Significantly, these data show that welding degree/intensity may vary in an apparently simple cooling unit because of variations in eruption process recorded in differing lithofacies. These data imply complex eruption, emplacement, and cooling processes. Three main crystallisation textural zones are identified in the ignimbrite succession: localised vitrophyre zones, widespread microcrystalline to sparsely spherulitic pseudomorphed vitriclastic textural zones, and thick granophyric zones. These zones record a typical spectrum from rapid to prolonged cooling. The non-uniform crystallisation patterns reflect variations in deposit thickness, the relative position of deposits within the larger ignimbrite succession, the type of substrate material, and the degree of confinement in the intra-caldera setting. We support previous work suggesting that traditional welding classifications (e.g. Smith, US Geological Survey Professional Paper 354-F 1960b) are most appropriate for use within altered and/or ancient ignimbrite successions.

Atypical effects of incorporated surfactants on stability and dissolution properties of amorphous polymeric dispersions.

PubMed

Al-Obaidi, Hisham; Lawrence, M Jayne; Buckton, Graham

2016-11-01

To understand the impact of ionic and non-ionic surfactants on the dissolution and stability properties of amorphous polymeric dispersions using griseofulvin (GF) as a model for poorly soluble drugs. Solid dispersions of the poorly water-soluble drug, griseofulvin (GF) and the polymers, poly(vinylpyrrolidone) (PVP) and poly(2-hydroxypropyl methacrylate) (PHPMA), have been prepared by spray drying and bead milling and the effect of the ionic and non-ionic surfactants, namely sodium dodecyl sulphate (SDS) and Tween-80, on the physico-chemical properties of the solid dispersions studied. The X-ray powder diffraction data and hot-stage microscopy showed a fast re-crystallisation of GF. While dynamic vapour sorption (DVS) measurements indicated an increased water uptake, slow dissolution rates were observed for the solid dispersions incorporating surfactants. The order by which surfactants free dispersions were prepared seemed critical as indicated by DVS and thermal analysis. Dispersions prepared by milling with SDS showed significantly better stability than spray-dried dispersions (drug remained amorphous for more than 6 months) as well as improved dissolution profile. We suggest that surfactants can hinder the dissolution by promoting aggregation of polymeric chains, however that effect depends mainly on how the particles were prepared. © 2016 Royal Pharmaceutical Society.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ben Yahia, Hamdi, E-mail: benyahia.hamdi@voila.fr; Rodewald, Ute Ch.; Boulahya, Khalid

Graphical abstract: The new compounds RE{sub 4}O{sub 4}[AsO{sub 4}]Cl (RE = La, Pr, Nd, Sm, Eu, Gd) were synthesised by solid state reaction via a salt flux route and investigated by HRTEM, SAED, and single crystal X-ray diffraction. - Highlights: • We discovered the series of RE{sub 4}O{sub 4}[AsO{sub 4}]Cl (RE = La, Pr, Nd, Sm, Eu, Gd) compounds. • The RE{sub 4}O{sub 4}[AsO{sub 4}]Cl single crystals were grown using NaCl/KCl flux. • The RE{sub 4}O{sub 4}[AsO{sub 4}]Cl structures were solved using single crystal X-ray diffraction data. • The layered RE{sub 4}O{sub 4}[AsO{sub 4}]Cl compounds were further characterized using HRTEMmore » and SAED. • We observed an alternation of ordered-[RE{sub 4}O{sub 4}]{sup 4+} and disordered-[ClAsO{sub 4}]{sup 4–} layers. - Abstract: The new compounds RE{sub 4}O{sub 4}[AsO{sub 4}]Cl (RE = La, Pr, Nd, Sm, Eu, Gd) were synthesised by solid state reaction via a salt flux route and investigated by HRTEM, SAED, and single crystal X-ray diffraction. The samples crystallise with a tetragonal cell, space group P4{sub 2}/mnm and Z = 2. Their crystal structure consists of an alternation of [RE{sub 4}O{sub 4}]{sup 4+} and [ClAsO{sub 4}]{sup 4–} layers. The [RE{sub 4}O{sub 4}]{sup 4+} layer contains ORE{sub 4/4} tetrahedra which share common edges. The anions AsO{sub 4}{sup 3–} and Cl{sup –} are located between these layers in disordered manner. SAED and HRTEM experiments confirmed this structural model and enabled us to propose an ordered model for the [ClAsO{sub 4}]{sup 4–} layers.« less

Solid-state structure of 1-(diaminomethylene)thiouron-1-ium propionate

NASA Astrophysics Data System (ADS)

Janczak, Jan

2017-10-01

The single crystals of 1-(diaminomethylene)thiouron-1-ium propionate suitable for the X-ray analysis were grown using a solution growth technique room temperature. The compound crystallises in the centrosymmetric C2/c space group of the monoclinic system. The conformation of the 1-(diaminomethylene)thiouron-1-ium cation is not strictly planar, but slightly twisted. Both planar arms of the cation are oppositely rotated by 2.1(1)° around the Csbnd N bonds involving the central N atom. The propionate(-) anion is also non-planar, the carboxylate group is turned by 4.3(1)° in relation to the planar carbon chain. The arrangement of oppositely charged components, i.e. 1-(diaminomethylene)thiouron-1-ium cations and propionate(-) anions in the crystal is mainly determined by ionic and Nsbnd H⋯O hydrogen bonding interactions forming two-dimensional network aligned to (100) plane. The neighbouring 2D layers interact via much weaker Nsbnd H⋯S hydrogen bonds forming three-dimensional hydrogen bonded network. Hirshfeld surface and the analysis of 2D fingerprint plots are illustrating both quantitatively and qualitatively interactions governing the supramolecular assemblies. The compound was also characterised by the FT-IR and Raman spectroscopy. The vibrational assignments have been supported by the isotopic frequency shift.

Structural characterisation of the Li argyrodites Li7PS6 and Li7PSe6 and their solid solutions: quantification of site preferences by MAS-NMR spectroscopy.

PubMed

Kong, Shiao Tong; Gün, Ozgül; Koch, Barbara; Deiseroth, Hans Jörg; Eckert, Hellmut; Reiner, Christof

2010-05-03

Li(7)PS(6) and Li(7)PSe(6) belong to a class of new solids that exhibit high Li(+) mobility. A series of quaternary solid solutions Li(7)PS(6-x)Se(x) (0 < or = x < or = 6) were characterised by X-ray crystallography and magic-angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy. The high-temperature (HT) modifications were studied by single-crystal investigations (both F43m, Z=4, Li(7)PS(6): a=9.993(1) A, Li(7)PSe(6): a=10.475(1) A) and show the typical argyrodite structures with strongly disordered Li atoms. HT-Li(7)PS(6) and HT-Li(7)PSe(6) transform reversibly into low-temperature (LT) modifications with ordered Li atoms. X-ray powder diagrams show the structures of LT-Li(7)PS(6) and LT-Li(7)PSe(6) to be closely related to orthorhombic LT-alpha-Cu(7)PSe(6). Single crystals of the LT modifications are not available due to multiple twinning and formation of antiphase domains. The gradual substitution of S by Se shows characteristic site preferences closely connected to the functionalities of the different types of chalcogen atoms (S, Se). High-resolution solid-state (31)P NMR is a powerful method to differentiate quantitatively between the distinct (PS(4-n)Se(n))(3-) local environments. Their population distribution differs significantly from a statistical scenario, revealing a pronounced preference for P-S over P-Se bonding. This preference, shown for the series of LT samples, can be quantified in terms of an equilibrium constant specifying the melt reaction Se(P)+S(2-) <==>S(P)+Se(2-), prior to crystallisation. The (77)Se MAS-NMR spectra reveal that the chalcogen distributions in the second and third coordination sphere of the P atoms are essentially statistical. The number of crystallographically independent Li atoms in both LT modifications was analysed by means of (6)Li{(7)Li} cross polarisation magic angle spinning (CPMAS).

Use of heat of adsorption to quantify amorphous content in milled pharmaceutical powders.

PubMed

Alam, Shamsul; Omar, Mahmoud; Gaisford, Simon

2014-01-01

Isothermal calorimetry operated in gas perfusion mode (IGPC) is often used to quantify the amorphous content of pharmaceutical powders. Typically, the calibration line is constructed using the heat of crystallisation as the sample is exposed to high levels of a plasticising vapour. However, since the physical form to which the amorphous fraction crystallises may be dependent on the presence of any crystalline seed, the calibration line is often seen to be non-linear, especially as the amorphous content of the sample approaches 100% w/w. Redesigning the experiment so that the calibration line is constructed with the heat of adsorption is an alternative approach that, because it is not dependent upon crystallisation to a physical form should ameliorate this problem. The two methods are compared for a model compound, salbutamol sulphate, which forms either a hydrate or an anhydrate depending on the amorphous content. The heat of adsorption method was linear between amorphous contents of 0 and 100% w/w and resulted in a detection limit of 0.3% w/w and a quantification limit of 0.92% w/w. The heat of crystallisation method was linear only between amorphous contents of 0 and 80% w/w and resulted in a detection limit of 1.7% w/w and a quantification limit of 5.28% w/w. Thus, the use of heat of adsorption is shown to be a better method for quantifying amorphous contents to better than 1% w/w. Copyright © 2013 Elsevier B.V. All rights reserved.

The influence of solution environment on the nucleation kinetics and crystallisability of para-aminobenzoic acid.

PubMed

Turner, T D; Corzo, D M C; Toroz, D; Curtis, A; Dos Santos, M M; Hammond, R B; Lai, X; Roberts, K J

2016-10-05

The influence of solvent type on the solution thermodynamics, nucleation-kinetics and crystal growth of alpha para-aminobenzoic acid (PABA) crystallising from supersaturated ethanol, acetonitrile and water solutions, is examined using poly-thermal analysis of the metastable zone width. Application of a recently proposed model for analysis of crystallisation kinetics (J. Cryst. Growth, 2010, 312, 698-704) indicates a solvent and concentration dependence of the nucleation mechanism and key nucleation parameters for the alpha form of PABA. The mechanism of nucleation is found to change from instantaneous to progressive with decreasing concentration and also when changing the solvent from ethanol to acetonitrile to water. The dependence of the nucleation mechanism is correlated to the kinetic component of the nucleation rate through calculated values of instantaneously nucleated crystallites, which increase from 1.40 × 10 9 m -3 in ethanol to 1.08 × 10 10 m -3 in acetonitrile to 2.58 × 10 10 m -3 in water. This in combination with low calculated number concentrations of interfacial tension between 1.13 and 2.71 mJ m -2 , supports the conclusion that the kinetic component of the nucleation rate is more limiting when crystallising PABA from ethanol solutions in comparison to water solutions. This finding is further supported by molecular dynamics simulations of the solvation free energy of PABA, which is found to be greatest in water, -42.4 kJ mol -1 and lowest in ethanol, -58.5 kJ mol -1 .

Solution based synthesis of mixed-phase materials in the Li2TiO3-Li4SiO4 system

NASA Astrophysics Data System (ADS)

Hanaor, Dorian A. H.; Kolb, Matthias H. H.; Gan, Yixiang; Kamlah, Marc; Knitter, Regina

2015-01-01

As candidate tritium breeder materials for use in the ITER helium cooled pebble bed, ceramic multiphasic compounds lying in the region of the quasi-binary lithium metatitanate-lithium orthosilicate system may exhibit mechanical and physical advantages relative to single phase materials. Here we present an organometallic solution-based synthesis procedure for the low-temperature fabrication of compounds in the Li2TiO3-Li4SiO4 region and investigate phase stability and transformations through temperature varied X-ray diffraction and scanning calorimetry. Results demonstrate that the metatitanate and metasilicate phases Li2TiO3 and Li2SiO3 readily crystallise in nanocrystalline form at temperatures below 180 °C. Lithium deficiency in the region of 5% results from Li sublimation from Li4SiO4 and/or from excess Li incorporation in the metatitanate phase and brings about a stoichiometry shift, with product compounds exhibiting mixed lithium orthosilicate/metasilicate content towards the Si rich region and predominantly Li2TiO3 content towards the Ti rich region. Above 1150 °C the transformation of monoclinic to cubic γ-Li2TiO3 disordered solid-solution occurs while the melting of silicate phases indicates a likely monotectic type system with a solidus line in the region 1050-1100 °C. Synthesis procedures involving a lithium chloride precursor are not likely to be a viable option for breeder pebble synthesis as this route was found to yield materials with a more significant Li-deficiency exhibiting the crystallisation of the Li2TiSiO5 phase at intermediate compositions.

Komatiites and nickel sulfide ores of the Black Swan area, Yilgarn Craton, Western Australia. 4. Platinum group element distribution in the ores, and genetic implications

NASA Astrophysics Data System (ADS)

Barnes, Stephen J.

2004-11-01

The Black Swan komatiite sequence, in the Eastern Goldfields province of the Archaean Yilgarn Craton in Western Australia, is a body of dominantly olivine-rich cumulates with lesser volumes of spinifex textured rocks, interpreted as a section through an extensive komatiite lava flow field. The sequence hosts a number of nickel sulfide orebodies, including the Silver Swan massive shoot and the Cygnet and Black Swan disseminated orebodies. The massive sulfide orebodies of the Black Swan Succession are pervasively depleted in all platinum group elements (PGEs), particularly Pt and Pd, despite very high Ni contents. This depletion cannot be explained by R-factor variations, which would also require relatively low Ni tenors. The PGE depletion could be explained in part if the ores are enriched in a monosulfide solid solution (MSS) cumulate component, but requires some additional fractional segregation of sulfide melt upstream from the site of deposition. The Silver Swan orebody shows a remarkably consistent vertical zonation in PGE contents, particularly in Ir, Ru, Rh, Os, which increase systematically from very low levels at the stratigraphic base of the sulfide body to maxima corresponding roughly with the top of a lower layer of the orebody rich in silicate inclusions. Platinum shows the opposite trend, but is somewhat modified by remobilisation during talc carbonate alteration. A similar pattern is also observed in the adjacent White Swan orebody. This zonation is interpreted and modelled as the result of fractional crystallisation of MSS from the molten sulfide pool. The strong IPGE depletion towards the base of the orebody may be a consequence of sulfide liquid crystallisation in an inverted thermal gradient, between a thin rapidly cooling upper rind of komatiite lava and a hot substrate.

A Dual-Porosity, In Situ Crystallisation Model For Fast-Spreading Mid-Ocean Ridge Magma Chambers Based Upon Direct Observation From Hess Deep

NASA Astrophysics Data System (ADS)

MacLeod, C. J.; Lissenberg, C. J.

2014-12-01

We propose a revised magma chamber model for fast-spreading mid-ocean ridges based upon a synthesis of new data from a complete section of lower crust from the East Pacific Rise, reconstructed from samples collected from the Hess Deep rift valley during cruise JC21. Our investigation includes detailed sampling across critical transitions in the upper part of the plutonic section, including the inferred axial melt lens (AML) within the dyke-gabbro transition. We find that an overall petrological progression, from troctolite and primitive gabbro at the base up into evolved (oxide) gabbro and gabbronorite at the top of the lower crustal section, is mirrored by a progressive upward chemical fractionation as recorded in bulk rock and mineral compositions. Crystallographic preferred orientations measured using EBSD show that the downward increase in deformation of mush required in crystal subsidence models is not observed. Together these observations are consistent only with a model in which crystallisation of upward migrating evolving melts occurs in situ in the lower crust. Over-enrichment in incompatible trace element concentrations and ratios above that possible by fractional crystallisation is ubiquitous. This implies redistribution of incompatible trace elements in the lower crust by low porosity, near-pervasive reactive porous flow of interstitial melt moving continuously upward through the mush pile. Mass balance calculations reveal a significant proportion of this trace element enriched melt is trapped at mid-crustal levels. Mineral compositions in the upper third to half of the plutonic section are too evolved to represent the crystal residues of MORB. Erupted MORB therefore must be fed from melts sourced in the deeper part of the crystal mush pile, and which must ascend rapidly without significant modification in the upper plutonics or AML. From physical models of mush processes we posit that primitive melts are transported through transient, high porosity channels generated by gravitational instabilities that periodically overturn and drain crystallising melt bodies (sills) from deeper levels of the lower crustal mush. We conclude that magma chambers are characterised by melt delivery to the deep crust, followed by in situ crystallisation of melts transported upwards via a dual-porosity system.

The effect of ultrasonic intensity on the crystal structure of palm oil.

PubMed

Patrick, Maria; Blindt, Renoo; Janssen, Jo

2004-05-01

It has been known for a long time that both the crystal structure and kinetics of crystallisation can be affected by ultrasound. In the past systems used have relied on high power ultrasonic probes to produce crystals. The majority of these probes produce cavitation in the system and it has been difficult to differentiate between effects caused by the ultrasound alone or by the cavitation produced by ultrasound on the crystal structure. Some materials, such as fats, are very susceptible to the production of free radicals that lead to "off-flavours" being obtained. These "off-flavours" are easily produced when the standard high power probes are used. This has meant that, although the crystal structure of the final product might be improved, the presence of 'off' flavours has prevented ultrasound being considered as a commercial technique for the crystallisation of edible fats. At Unilever R&D a system has been developed which can investigate the effect of ultrasound on the crystallisation of fats under controlled conditions covering a range of intensities and cooling rates. The intensity levels used were both below and above the cavitational threshold. By keeping the cooling regime constant it has been possible to show that the structure of the final product can vary from a material looking similar to cottage cheese through to a fine cream simply by varying the ultrasonic intensity. This paper describes the effect of ultrasound on both the crystal structure and kinetics of palm oil crystallisation at intensities below and above the cavitational threshold.

The record of mantle heterogeneity preserved in Earth's oceanic crust

NASA Astrophysics Data System (ADS)

Burton, K. W.; Parkinson, I. J.; Schiano, P.; Gannoun, A.; Laubier, M.

2017-12-01

Earth's oceanic crust is produced by melting of the upper mantle where it upwells beneath mid-ocean ridges, and provides a geographically widespread elemental and isotopic `sample' of Earth's mantle. The chemistry of mid-ocean ridge basalts (MORB), therefore, holds key information on the compositional diversity of the upper mantle, but the problem remains that mixing and reaction during melt ascent acts to homogenise the chemical variations they acquire. Nearly all isotope and elemental data obtained thus far are for measurements of MORB glass, and this represents the final melt to crystallise, evolving in an open system. However, the crystals that are present are often not in equilibrium with their glass host. Melts trapped in these minerals indicate that they crystallised from primitive magmas that possess diverse compositions compared to the glass. Therefore, these melt inclusions preserve information on the true extent of the mantle that sources MORB, but are rarely amenable to precise isotope measurement. An alternative approach is to measure the isotope composition of the primitive minerals themselves. Our new isotope data indicates that these minerals crystallised from melts with significantly different isotope compositions to their glass host, pointing to a mantle source that has experienced extreme melt depletion. These primitive minerals largely crystallised in the lower oceanic crust, and our preliminary data for lower crustal rocks and minerals shows that they preserve a remarkable range of isotope compositions. Taken together, these results indicate that the upper mantle sampled by MORB is extremely heterogeneous, reflecting depletion and enrichment over much of Earth's geological history.

Granular compaction and the topology of pore deformation

NASA Astrophysics Data System (ADS)

Saadatfar, Mohammad; Takeuchi, Hiroshi; Hanifpour, Maryam; Robins, Vanessa; Francois, Nicolas; Hiraoka, Yasuaki

2017-06-01

The mechanism of crystallisation in highly dissipative materials such as foams or granular materials is still widely unknown. In macroscopic granular materials high levels of energy need to be injected to overcome the natural propensity of these dissipative materials to form amorphous structures [1, 2]. The transition from disordered to ordered packings in such systems triggers a wide range of geometrical, topological and mechanical changes at multi length scales [3]. Formation of cavities and patterns by aggregates of grains and their evolution during this transition requires a complete topological description of the system. Here, crystallisation of three-dimensional packings of frictional spheres is studied at the grain scale with x-ray tomography. Using a novel and powerful topological tool, Persistent Homology, we describe the complete formation process of perfect tetrahedral and octahedral patterns: the two building blocks of FCC and HCP crystalline arrangements. Additionally we present possible and allowable deformations of these components that accurately reproduce the main topological features of the system. These results give new insights into the crystallisation of these highly dissipative materials.

Planetoid core crystallisation and fractionation - Evidence from the Agpalilik mass of the Cape York iron meteorite shower

NASA Astrophysics Data System (ADS)

Esbensen, K. H.; Buchwald, V. F.

1982-09-01

Metallographic and chemical study of the Agpalik mass of the Cape York iron meteorite shower reveals evidence of the mode of crystallization and fractionation of key elements consistent with a dendritic solidification of at least part of the once fully molten parent body's metallic core. Chemical gradients of Ir and Au are assessed across an 85 cm section that is inferred to be perpendicular to the parent body's gravitational field, and are interpreted as representing a dendritic growth mode. The characteristic elongated and orientated sulfide nodules found in Agpalik signify trapped liquid of the latest stages of crystallization. Detailed mineralogical and chemical characterization of the Agpalik liquid-solid transformation products allow modelling of the entire crystallization history commencing with dendritic metal precipitation through an ultimate troilite-taenite-Cu eutectic, representing a crystallization range spanning approximately 1350-700 C.

Solid-state supramolecular structure formed between the 1-(diaminomethylene)thiourea and mellitic acid

NASA Astrophysics Data System (ADS)

Janczak, Jan

2018-07-01

The single crystals of hexakis(1-(diaminomethylene)thiouron-1-ium) benzene-1,2,3,4,5,6-hexacarboxylate (mellitate(6-)) tetrahydrate suitable for the X-ray analysis were grown using a solution growth technique at room temperature. The compound crystallises in centrosymmetric space group of the triclinic system. The conformation of six crystallographically independent 1-(diaminomethylene)thiouron-1-ium cations is not strictly planar, but twisted. Both planar arms of the cations are oppositely rotated by 6.1(1) ÷ 20.9(1)o around the Csbnd N bonds involving the central N atom. All of the carboxylate groups of mellitate(6-) anion are inclined to the plane of aromatic six-membered carbon ring by 43.0(1) ÷ 72.0(1)o. Oppositely charged components i.e. 1-(diaminomethylene)thiouron-1-ium cations and mellitate(6-) anion interact each other via Nsbnd H⋯O hydrogen bonds forming hexakis(1-(diaminomethylene)thiouron-1-ium) mellitate units that further interact with the water molecules forming hexakis(1-(diaminomethylene)thiouron-1-ium) mellitate tetrahydrate supramolecular architecture. Hirshfeld surface and the analysis of 2D fingerprint plots are used for illustrate both qualitatively and quantitatively interactions between the units governing the supramolecular assemblies. The compound was also characterised by vibrational spectroscopy. The vibrational assignment have been supported by the isotopic frequency shift.

Solid-state supramolecular structure of tetrakis(1-(diaminomethylene)thiouron-1-ium) pyromellate

NASA Astrophysics Data System (ADS)

Janczak, Jan

2018-03-01

The single crystals of tetrakis(1-(diaminomethylene)thiouron-1-ium) pyromellate suitable for the X-ray analysis were grown using a solution growth technique at room temperature. The compound crystallises in the centrosymmetric space group P21/c of the monoclinic system. Asymmetric unit consists of half of the tetrakis(1-(diaminomethylene)thiouron-1-ium) pyromellate molecule. Both independent parts of the 1-(diaminomethylene)-thiouron-1-ium cations are not strictly planar, but twisted. Both planar arms of the cation are oppositely rotated around the Csbnd N bonds involving the central N atom of the cation. The arrangement of the oppositely charged components, i.e. 1-(diaminomethylene)-thiouron-1-ium cations and pyromellate(4-) anion is determined by the Nsbnd H⋯O hydrogen bonds with R22(8) and R21(6) graphs forming supramolecular tetrakis(1-(diaminomethylene)-thiouron-1-ium) pyromellate units that further interact each other forming three dimensional hydrogen bonded network. Hirshfeld surface and the analysis of the 2D-fingerprint plots are illustrating both qualitatively and quantitatively interactions governing the formation of the supramolecular tetrakis(1-(diaminomethylene)-thiouron-1-ium) pyromellate complex as well as the mutual arrangement of the supramolecules in the crystal. The compound was also characterized by the FT-IR and Raman spectroscopy. Assignment of the bands have been supported by the isotropic frequency shift.

Fabrication of hierarchical feather-mimetic polymer nanofibres

NASA Astrophysics Data System (ADS)

Ouyang, Shenshen; Wang, Tao; Zhong, Longgang; Peng, Meiling; Yao, Juming; Wang, Sheng

2018-01-01

In this study, hierarchically feather-mimetic structures formed of poly(m-phenylene isophthalamide) (PMIA) nanofibres were prepared by electrospinning and subsequent crystallisation for superwettability applications. X-ray diffraction measurementsand scanning electron microscopy show that a feather-mimetic structure of crystallised nanoflakes was formed following a hydrothermal treatment process. The nanoflakes formed a nanosized fine texture on top of a coarser-textured membrane, which greatly improved the membrane roughness and yielded a hierarchical topography. After fluorination, the membrane exhibited superamphiphobicity, with surface contact angles of 151° and 136° for water and hexadecane, respectively. The method provides new insight for the design and development of functional bionic membranes based on PMIA.

Development of modal layering in granites: a case study from the Carna Pluton, Connemara, Ireland

NASA Astrophysics Data System (ADS)

McKenzie, Kirsty; McCarthy, William; Hunt, Emma

2016-04-01

Modal layering in igneous rocks uniquely record dynamic processes operating in magma chambers and also host a large proportion of Earth's strategic mineral deposits. This research investigates the origin of biotite modal layering and primary pseudo-sedimentary structures in felsic magmas, by using a combination of Crystal Size Distribution (CSD) analysis and Electron Probe Microanalysis (EPMA) to determine the mechanisms responsible for the development of these structures in the Carna Pluton, Connemara, Ireland. The Carna Pluton is a composite granodiorite intrusion and is one of five plutons comprising the Galway Granite Complex (425 - 380 Ma). Prominent 30 cm thick modal layers are defined by sharp basal contacts to a biotite-rich (20%) granite, which grades upward over 10 cm into biotite-poor, alkali-feldspar megacrystic granite. The layering strikes parallel to, and dips 30-60° N toward the external pluton contact. Pseudo-sedimentary structures (cross-bedding, flame structures, slumping and crystal graded bedding) are observed within these layers. Petrographic observations indicate the layers contain euhedral biotite and fresh undeformed quartz and feldspar. Throughout the pluton, alkali-feldspar phenocrysts define a foliation that is sub-parallel to the strike of biotite modal layers. Together these observations indicate that the intrusion's concentric foliation, biotite layers and associated structures formed in the magmatic state and due to a complex interaction between magma flow and crystallisation processes. Biotite CSDs (>250 crystals per sample) were determined for nine samples across three biotite-rich layers in a single unit. Preliminary CSD results suggest biotite within basal contacts accumulated via fractional crystallisation within an upward-growing crystal pile, likely reflecting the yield strength of the magma as a limiting factor to gravitational settling of biotite. This is supported by the abrupt decrease in mean biotite crystal size across the contact, compared to the biotite crystals in the megacrystic granite below. CSD results provide additional evidence for in-situ textural coarsening of biotite. This study proposes a new model for the crystallisation dynamics of the Carna Pluton. During emplacement, 2 - 5 cm alkali-feldspar megacrysts were aligned and fractional crystallisation was the primary mechanism driving the formation of biotite modal layers. Pseudo-sedimentary structures are interpreted to have formed due to the entrainment of biotite crystals within a necessarily highly fluid magma chamber. However, this interpretation is difficult to reconcile with the high viscosities commonly associated with granitic melts. To test this hypothesis, ongoing EPMA analysis on biotite F content and Fe/(Fe+Mg) ratios will assess whether the magma viscosity could have been low enough to produce these features via flow processes; or whether expansion of the pluton and tilting of planar primary magmatic layers, prior to solidification, could be responsible.

Crystallisation regimes and kinetics in experimentally decompressed dacitic magma

NASA Astrophysics Data System (ADS)

Blum-Oeste, N.; Schmidt, B. C.; Webb, S. L.

2011-12-01

Kinetic processes during magma ascent may have a strong influence on the eruption style. In water bearing dacitic magmas decompression induced exsolution of water and accompanying crystallisation of plagioclase are the main processes which drive the system towards a new equilibrium state. We present new data on the evolution of residual glass composition and crystal size distributions of plagioclase from decompression experiments. Experiments have been conducted in cold seal pressure vessels at 850°C on a natural dacite composition from Taapaca volcano (N. Chile). After an initial equilibration at 2kbar decompression rates between 6.3 and 450bar/h were applied to final pressures between 50 and 1550bar where samples were rapidly quenched. Complementary equilibrium experiments were done at corresponding pressures. The glass composition evolves from the initial state towards the equilibrium at the final pressure. The completeness of this re-equilibration depends on run duration and reaction rates. We introduce the "re-equilibration index" (REI), a fraction between 0 (initial state) and 1 (final state) which allows comparison of chemical components in terms of re-equilibration at different decompression rates. REI divided by the decompression duration gives the "re-equilibration rate" (RER). The REI varies among oxides and it decreases with increasing decompression rate. The highest REIs of ~0.9 have been found for MgO, K2O and Al2O3 at 6.3bar/h whereas Na2O shows the lowest number with 0.25 at this decompression rate. Towards faster decompression all REIs tend to decrease which shows a decreasing completeness of re-equilibration. At 450bar/h the highest REIs are ~0.25. RERs increase from below ~0.005/h at 6.3bar/h up to almost 0.08/h for Al2O3 at 450bar/h. The variability of RERs of different oxides also increases with decompression rates. At 450bar/h the RERs reach from <0.005/h up to 0.08/h. Although RERs strongly increase from low to high decompression rates, this does not compensate for the decreasing duration available for re-equilibration as REIs clearly show. The volume fraction of plagioclase decreases from ~21% at 6.3bar/h to ~16% at 450bar/h which fits the decrease in REIs. The population density of small crystals decreases whereas the population density of larger crystals increases from slow to fast decompression. This reflects a transition from nucleation controlled crystallisation at slow decompression to a growth dominated regime at fast decompression. As RERs show re-equilibration is faster in the growth dominated regime. Although this transition in nucleation processes might be counter-intuitive it can be explained by the observation of slightly higher water concentrations at fast decompression rates resulting in higher liquidus temperatures and thus lower undercooling.

LA-ICP-MS trace element mapping: insights into the crystallisation history of a metamorphic garnet population

NASA Astrophysics Data System (ADS)

George, Freya; Gaidies, Fred

2017-04-01

In comparison to our understanding of major element zoning, relatively little is known about the incorporation of trace elements into metamorphic garnet. Given their extremely slow diffusivities and sensitivity to changing mineral assemblages, the analysis of the distribution of trace elements in garnet has the potential to yield a wealth of information pertaining to interfacial attachment mechanisms during garnet crystallisation, the mobility of trace elements in both garnet and the matrix, and trace element geochronology. Due to advances in the spatial resolution and analytical precision of modern microbeam techniques, small-scale trace element variations can increasingly be documented and used to inform models of metamorphic crystallisation. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) in particular, can be used to rapidly quantify a wide range of elemental masses as a series of laser rasters, producing large volumes of spatially constrained trace element data. In this study, we present LA-ICP-MS maps of trace element concentrations from numerous centrally-sectioned garnets representative of the crystal size-distribution of a single sample's population. The study sample originates from the garnet-grade Barrovian zone of the Lesser Himalayan Sequence in Sikkim, northeast India, and has been shown to have crystallised garnet within a single assemblage between 515 ˚C and 565˚C, with no evidence for accessory phase reaction over the duration of garnet growth. Previous models have indicated that the duration of garnet crystallisation was extremely rapid (<1 Myr), with negligible diffusional homogenisation of major divalent cations. Consequently, the trace element record likely documents the primary zonation generated during garnet growth. In spite of straightforward (i.e. concentrically-zoned) major element garnet zonation, trace elements maps are characterised by significant complexity and variability. Y and the heavy rare earth elements are strongly enriched in crystal cores, where there is overprinting of the observed internal fabric, and exhibit numerous concentric annuli towards crystal rims. Conversely, the medium rare earth elements (e.g. Gd, Eu and Sm) exhibit bowl-shaped zoning from core to rim, with no annuli, and core and rim compositions of the medium rare earth elements are the same throughout the population within crystals of differing size. Cr exhibits pronounced spiral zoning, and the average Cr content increases towards garnet rims. In all cases, spirals are centered on the geometric core of the crystals. These LA-ICP-MS maps highlight the complexity of garnet growth over a single prograde event, and indicate that there is still much to be learnt from the analysis of garnet using ever-improving analytical methods. We explore the potential causes of the variations in the distribution of trace elements in garnet, and assess how these zoning patterns may be used to refine our understanding of the intricacies of garnet crystallisation and the spatial and temporal degree of trace element equilibration during metamorphism.

Method of Estimating Continuous Cooling Transformation Curves of Glasses

NASA Technical Reports Server (NTRS)

Zhu, Dongmei; Zhou, Wancheng; Ray, Chandra S.; Day, Delbert E.

2006-01-01

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.

The effect of titanite crystallisation on Eu and Ce anomalies in zircon and its implications for the assessment of porphyry Cu deposit fertility

NASA Astrophysics Data System (ADS)

Loader, Matthew A.; Wilkinson, Jamie J.; Armstrong, Robin N.

2017-08-01

The redox sensitivity of Ce and Eu anomalies in zircon has been clearly demonstrated by experimental studies, and these may represent an important tool in the exploration for porphyry Cu deposits which are thought to be derived from oxidised magmas. These deposits are significant because they are the source of much of the world's copper and almost all of the molybdenum and rhenium, key elements in many modern technologies. However, Ce and Eu anomalies in zircon are also affected by the co-crystallisation of REE bearing phases, such as titanite. Here, we report the trace element chemistry of zircons from titanite-bearing intrusions associated with mineralisation at the world class Oyu Tolgoi porphyry Cu-Au deposit (Mongolia). Based on these data, we suggest that neither zircon Eu/Eu*, nor Ce4+/Ce3+ are robust proxies for melt redox conditions, because they are both too strongly dependent on melt REE concentrations, which are usually poorly constrained and controlled by the crystallisation of titanite and other REE-bearing phases. In spite of this, Eu/Eu* can broadly distinguish between fertile and barren systems, so may still be an indicator of porphyry magma fertility, and a useful tool for exploration.

Memory and comprehension for health information among older adults: distinguishing the effects of domain-general and domain-specific knowledge.

PubMed

Chin, Jessie; Payne, Brennan; Gao, Xuefei; Conner-Garcia, Thembi; Graumlich, James F; Murray, Michael D; Morrow, Daniel G; Stine-Morrow, Elizabeth A L

2015-01-01

While there is evidence that knowledge influences understanding of health information, less is known about the processing mechanisms underlying this effect and its impact on memory. We used the moving window paradigm to examine how older adults varying in domain-general crystallised ability (verbal ability) and health knowledge allocate attention to understand health and domain-general texts. Participants (n = 107, age: 60-88 years) read and recalled single sentences about hypertension and about non-health topics. Mixed-effects modelling of word-by-word reading times suggested that domain-general crystallised ability increased conceptual integration regardless of text domain, while health knowledge selectively increased resource allocation to conceptual integration at clause boundaries in health texts. These patterns of attentional allocation were related to subsequent recall performance. Although older adults with lower levels of crystallised ability were less likely to engage in integrative processing, when they did, this strategy had a compensatory effect in improving recall. These findings suggest that semantic integration during reading is an important comprehension process that supports the construction of the memory representation and is engendered by knowledge. Implications of the findings for theories of text processing and memory as well as for designing patient education materials are discussed.

Influence of crystallised igneous intrusions on fault nucleation and reactivation during continental extension

NASA Astrophysics Data System (ADS)

Magee, Craig; McDermott, Kenneth G.; Stevenson, Carl T. E.; Jackson, Christopher A.-L.

2014-05-01

Continental rifting is commonly accommodated by the nucleation of normal faults, slip on pre-existing fault surfaces and/or magmatic intrusion. Because crystallised igneous intrusions are pervasive in many rift basins and are commonly more competent (i.e. higher shear strengths and Young's moduli) than the host rock, it is theoretically plausible that they locally intersect and modify the mechanical properties of pre-existing normal faults. We illustrate the influence that crystallised igneous intrusions may have on fault reactivation using a conceptual model and observations from field and subsurface datasets. Our results show that igneous rocks may initially resist failure, and promote the preferential reactivation of favourably-oriented, pre-existing faults that are not spatially-associated with solidified intrusions. Fault segments situated along strike from laterally restricted fault-intrusion intersections may similarly be reactivated. This spatial and temporal control on strain distribution may generate: (1) supra-intrusion folds in the hanging wall; (2) new dip-slip faults adjacent to the igneous body; or (3) sub-vertical, oblique-slip faults oriented parallel to the extension direction. Importantly, stress accumulation within igneous intrusions may eventually initiate failure and further localise strain. The results of our study have important implications for the structural of sedimentary basins and the subsurface migration of hydrocarbons and mineral-bearing fluids.

Crystallisation sequence and magma evolution of the De Beers dyke (Kimberley, South Africa)

NASA Astrophysics Data System (ADS)

Soltys, Ashton; Giuliani, Andrea; Phillips, David

2018-06-01

We present petrographic and mineral chemical data for a suite of samples derived from the De Beers dyke, a contemporaneous, composite intrusion bordering the De Beers pipe (Kimberley, South Africa). Petrographic features and mineral compositions indicate the following stages in the evolution of this dyke: (1) production of antecrystic material by kimberlite-related metasomatism in the mantle (i.e., high Cr-Ti phlogopite); (2) entrainment of wall-rock material during ascent through the lithospheric mantle, including antecrysts; (3) early magmatic crystallisation of olivine (internal zones and subsequently rims), Cr-rich spinel, rutile, and magnesian ilmenite, probably on ascent to the surface; and (4) crystallisation of groundmass phases (i.e., olivine rinds, Fe-Ti-rich spinels, perovskite, apatite, monticellite, calcite micro-phenocrysts, kinoshitalite-phlogopite, barite, and baddeleyite) and the mesostasis (calcite, dolomite, and serpentine) on emplacement in the upper crust. Groundmass and mesostasis crystallisation likely forms a continuous sequence with deuteric/hydrothermal modification. The petrographic features, mineralogy, and mineral compositions of different units within the De Beers dyke are indistinguishable from one another, indicating a common petrogenesis. The compositions of antecrysts (i.e., high Cr-Ti phlogopite) and magmatic phases (e.g., olivine rims, magnesian ilmenite, and spinel) overlap those from the root zone intrusions of the main Kimberley pipes (i.e., Wesselton, De Beers, Bultfontein). However, the composition of these magmatic phases is distinct from those in `evolved' intrusions of the Kimberley cluster (e.g., Benfontein, Wesselton water tunnel sills). Although the effects of syn-emplacement flow processes are evident (e.g., alignment of phases parallel to contacts), there is no evidence that the De Beers dyke has undergone significant pre-emplacement crystal fractionation (e.g., olivine, spinel, ilmenite). This study demonstrates the requirement for detailed petrographic and mineral chemical studies to assess whether individual intrusions are in fact `evolved'; and that dykes are not necessarily produced by differentiated magmas.

Prediction of the glass transition in aqueous solutions of simple amides by molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Kreck, Cara A.; Mandumpal, Jestin B.; Mancera, Ricardo L.

2011-01-01

Some simple amides in aqueous solution are used in the cryopreservation of biological tissues as they are believed to promote the vitrification of water, inhibiting its crystallisation and the ensuing damage from ice formation. Molecular dynamics annealing simulations reveal a broadening in the glass transition of aqueous acetamide and N-methylacetamide solutions, suggesting a thermodynamic stabilisation of the glassy state, which may be responsible for their increased tendency of vitrification and their cryoprotective ability. By contrast, aqueous formamide solutions do not exhibit broadening of the glass transition; instead, it is shifted to lower temperatures, which explains their lack of vitrification properties.

How do Kakortokites form? Additional evidence from the Ilimaussaq Complex, S. Greenland

NASA Astrophysics Data System (ADS)

Hunt, E. J.; Finch, A. A.; Donaldson, C. H.

2012-04-01

The Ilímaussaq Complex, South Greenland, contains some of the most evolved igneous rocks in the world and is widely considered to represent one of the largest deposits of rare-earth elements, Ta, Nb and Zr. Our work is focused on the kakortokite layered series at the base of the complex. The layered series is composed of 29 repetitive 3-layer units (named -11 to +17, Bohse et al. 1971), successively enriched in arfvedsonite, eudialyte and nepheline. Despite a large body of work on the development of the kakortokite series, no consensus on the process/processes that produced the layering has been forthcoming. We present the preliminary findings of a combined petrographical, quantitative textural and geochemical analysis on the kakortokite series, initially focused on layer 0. Although many of the hypotheses for the formation of these rocks invoke a pressure change, the enrichment of the series in volatile constituents (CH4 and H; Konnerup-Madsen, 2001) has led many authors to suggest crystallisation occurred in a closed system, with processes of gravitational settling formed the layering. Crystal size distribution (CSD) analysis, performed on hand-digitised photomicrographs, provides insight into processes of crystal nucleation and growth. The results indicate that simple cumulate settling is untenable for layer 0. Instead the plot gradients indicate that the arfvedsonite in the black kakortokite crystallised in situ above a sharp boundary to the white kakortokite. The CSD plots for the alkali feldspars indicate secondary nucleation occurred, with the small crystal size fraction forming in situ. The feldspar phenocrysts also exhibit embayment textures indicating partial resorption. These graphs are consistent with a model whereby an influx of hotter magma results in the partial thermal erosion of the underlying white kakortokite, followed by in situ crystallisation of arfvedsonite above the melt infiltration boundary, followed by in situ crystallisation of eudialyte. Then nepheline and alkali feldspar crystallised through multiple modes of nucleation, developing the characteristic layering. Geochemical trends described by Pfaff et al. (2008) support an open system replenishment model during the formation of layer 0, and potentially also layers +4 and +8. To further this work we intend to apply this combined approach to investigate the formation of individual layers, scaling these processes into a model for the development of the Ilímaussaq complex. Bohse et al. (1971). Rapport Grønlands Geologiske Undergesølgelse, 36, 43 pp. Konnerup-Madsen (2001). Geology Greenland Surv. Bull., 190, 159-166. Pfaff et al. (2008). Lithos, 106, 280-296.

Cumulate xenoliths from St. Vincent, Lesser Antilles Island Arc: a window into upper crustal differentiation of mantle-derived basalts

NASA Astrophysics Data System (ADS)

Tollan, P. M. E.; Bindeman, I.; Blundy, J. D.

2012-02-01

In order to shed light on upper crustal differentiation of mantle-derived basaltic magmas in a subduction zone setting, we have determined the mineral chemistry and oxygen and hydrogen isotope composition of individual cumulus minerals in plutonic blocks from St. Vincent, Lesser Antilles. Plutonic rock types display great variation in mineralogy, from olivine-gabbros to troctolites and hornblendites, with a corresponding variety of cumulate textures. Mineral compositions differ from those in erupted basaltic lavas from St. Vincent and in published high-pressure (4-10 kb) experimental run products of a St. Vincent high-Mg basalt in having higher An plagioclase coexisting with lower Fo olivine. The oxygen isotope compositions (δ18O) of cumulus olivine (4.89-5.18‰), plagioclase (5.84-6.28‰), clinopyroxene (5.17-5.47‰) and hornblende (5.48-5.61‰) and hydrogen isotope composition of hornblende (δD = -35.5 to -49.9‰) are all consistent with closed system magmatic differentiation of a mantle-derived basaltic melt. We employed a number of modelling exercises to constrain the origin of the chemical and isotopic compositions reported. δ18OOlivine is up to 0.2‰ higher than modelled values for closed system fractional crystallisation of a primary melt. We attribute this to isotopic disequilibria between cumulus minerals crystallising at different temperatures, with equilibration retarded by slow oxygen diffusion in olivine during prolonged crustal storage. We used melt inclusion and plagioclase compositions to determine parental magmatic water contents (water saturated, 4.6 ± 0.5 wt% H2O) and crystallisation pressures (173 ± 50 MPa). Applying these values to previously reported basaltic and basaltic andesite lava compositions, we can reproduce the cumulus plagioclase and olivine compositions and their associated trend. We conclude that differentiation of primitive hydrous basalts on St. Vincent involves crystallisation of olivine and Cr-rich spinel at depth within the crust, lowering MgO and Cr2O3 and raising Al2O3 and CaO of residual melt due to suppression of plagioclase. Low density, hydrous basaltic and basaltic andesite melts then ascend rapidly through the crust, stalling at shallow depth upon water saturation where crystallisation of the chemically distinct cumulus phases observed in this study can occur. Deposited crystals armour the shallow magma chamber where oxygen isotope equilibration between minerals is slowly approached, before remobilisation and entrainment by later injections of magma.

Impact of triacylglycerol composition on shear-induced textural changes in highly saturated fats.

PubMed

Gregersen, Sandra B; Andersen, Morten D; Hammershøj, Marianne; Wiking, Lars

2017-01-15

This study demonstrates a strong interaction between triacylglycerol (TAG) composition and effects of shear rate on the microstructure and texture of fats. Cocoa butter alternatives with similar saturated fat content, but different major TAGs (PPO-, PSO-, SSO-, POP- and SOS-rich blends) were evaluated. Results show how shear can create a harder texture in fat blends based on symmetric monounsaturated TAGs (up to ∼200%), primarily due to reduction in crystal size, whereas shear has little effect on hardness of asymmetric monounsaturated TAGs. Such differences could not be ascribed to differences in the degree of supercooling, but was found to be a consequence of differences in the crystallisation behaviour of different TAGs. The fractal dimension was evaluated by dimensional detrended fluctuation analysis and Fourier transformation of microscopy images. However, the concept of fractal patterns was found to be insufficient to describe microstructural changes of fat blends with high solid fat content. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electronic structure and glass forming ability in early and late transition metal alloys

NASA Astrophysics Data System (ADS)

Babić, E.; Ristić, R.; Figueroa, I. A.; Pajić, D.; Skoko, Ž.; Zadro, K.

2018-03-01

A correlation between the change in magnetic susceptibility (Δχexp) upon crystallisation of Cu-Zr and Hf metallic glasses (MG) with their glass forming ability (GFA) observed recently, is found to apply to Cu-Ti and Zr-Ni alloys, too. In particular, small Δχexp, which reflects similar electronic structures, ES, of glassy and corresponding crystalline alloys, corresponds to high GFA. Here, we studied Δχexp for five Cu-Ti and four Cu-Zr and Ni-Zr MGs. The fully crystalline final state of all alloys was verified from X-ray diffraction patterns. The variation of GFA with composition in Cu-Ti, Cu-Zr and Cu-Hf MGs was established from the variation of the corresponding critical casting thickness, dc. Due to the absence of data for dc in Ni-Zr MGs their GFA was described using empirical criteria, such as the reduced glass transition temperature. A very good correlation between Δχexp and dc (and/or other criteria for GFA) was observed for all alloys studied. The correlation between the ES and GFA showed up best for Cu-Zr and NiZr2 alloys where direct data for the change in ES (ΔES) upon crystallisation are available. The applicability of the Δχexp (ΔES) criterion for high GFA (which provides a simple way to select the compositions with high GFA) to other metal-metal MGs (including ternary and multicomponent bulk MGs) is briefly discussed.

Synergism between urinary prothrombin fragment 1 and urine: a comparison of inhibitory activities in stone-prone and stone-free population groups.

PubMed

Webber, Dawn; Rodgers, Allen L; Sturrock, Edward D

2002-09-01

South African blacks rarely form kidney stones compared with whites. This study investigated whether purified urinary prothrombin fragment 1 (UPTF1) derived from blacks is a more potent inhibitor of calcium oxalate crystallisation than that from whites. UPTF1 was purified from the urine of both population groups and their inhibitory activities were compared in a cross-over design in which each protein was tested in ultrafiltered urine from both population groups. Coulter Multisizer, [14C]-oxalate deposition and scanning electron microscopy experiments were used to monitor crystallisation. The study has demonstrated for the first time that UPTF1 promotes nucleation and that inhibitory activity is synergistically dependent upon urine composition. The activity of the whites' UPTF1 was greater than that of the blacks in the whites' urine (e.g. particle size decrease: 31.7% vs. 25.2%), while the blacks' UPTF1 was superior to that of the whites in the blacks' urine (e.g. particle size decrease: 46.5% vs. 32.4%). In addition, when tested in their respective endogenous urines, the blacks' UPTF1 demonstrated superior inhibitory activity on an absolute scale (e.g. particle size decrease: 46.5% vs. 31.7%). Thus, the urine composition of black South Africans may influence their UPTF1 conformation, conferring greater efficacy for inhibition of calcium oxalate crystallisation.

Estimation of the nucleation kinetics for the anti-solvent crystallisation of paracetamol in methanol/water solutions

NASA Astrophysics Data System (ADS)

Ó'Ciardhá, Clifford T.; Frawley, Patrick J.; Mitchell, Niall A.

2011-08-01

In this work the primary nucleation kinetics have been estimated for the anti-solvent crystallisation of paracetamol in methanol-water solutions from metastable zone widths (MSZW) and induction times at 25 °C. Laser back-scattering via a focused beam reflectance Measurement (FBRM ®) is utilised to detect the onset of nucleation. The theoretical approach of Kubota was employed to estimate the nucleation kinetics, which accounts for the sensitivity of the nucleation detection technique. This approach is expanded in this work to analyse the induction time for an anti-solvent crystallisation process. Solvent composition is known to have a significant impact on the measured induction times and MSZW. The induction time in this paper was measured from 40% to 70% mass water and the MSZW is measured from 40% to 60% mass water. The primary focus of the paper was to gauge the extent of how solvent composition affects nucleation kinetics so that this effect may be incorporated into a population balance model. Furthermore, the effects of solvent composition on the estimated nucleation rates are investigated. The primary nucleation rates were found to decrease with dynamic solvent composition, with the extent of their reduction linked to the gradient of the solubility curve. Finally, both MSZW and induction time methods have been found to produce similar estimates for the nucleation parameters.

Do "inhibitors of crystallisation" play any role in the prevention of kidney stones? A critique.

PubMed

Robertson, William G

2017-02-01

A critical examination of data in the literature and in as yet unpublished laboratory records on the possible role of so-called inhibitors of crystallisation in preventing the formation of calcium-containing kidney stones leads to the following conclusions. So-called inhibitors of spontaneous "self-nucleation" are unlikely to play any role in the initiation of the crystallisation of CaOx or CaP in urine because excessive urinary supersaturation of urine with respect to these salts dominates the onset of "self-nucleation" within the normal time frame of the transit of tubular fluid through the nephron (3-4 min). Inhibitors of the crystal growth of CaOx crystals may or may not play a significant role in the prevention of CaOx stone-formation since once again excessive supersaturation of urine can overwhelm any potential effect of the inhibitors on the growth process. However, they may play a role as inhibitors of crystal growth at lower levels of metastable supersaturation when the balance between supersaturation and inhibitors is more equal. Inhibitors of CaOx crystal aggregation may play a significant role in the prevention of stones, since they do not appear to be strongly affected by excessive supersaturation, either in vitro or in vivo. Inhibitors of CaOx crystal binding to renal tubular epithelium may exist but further studies are necessary to elucidate their importance in reducing the risk of initiating stones in the renal tubules. Inhibitors of CaOx crystal binding to Randall's Plaques and Randall's Plugs may exist but further studies are necessary to elucidate their importance in reducing the risk of initiating stones on renal papillae. There may be an alternative explanation other than a deficiency in the excretion of inhibitors for the observations that there is a difference between CaOx crystal size and degree of aggregation in the fresh, warm urines of normal subjects compared those in urine from patients with recurrent CaOx stones. This difference may depend more on the site of "self-nucleation" of CaOx crystals in the renal tubule rather than on a deficiency in the excretion of so-called inhibitors of crystallisation by patients with CaOx stones. The claim that administration of potassium citrate, potassium magnesium citrate or magnesium hydroxide reduces the rate of stone recurrence may be due to the effect of these forms of medication on the supersaturation of urine with respect to CaOx and CaP rather than to any increase in "inhibitory activity" attributed to these forms of treatment. In summary, there is a competition between supersaturation and so-called inhibitors of crystallisation which ultimately determines the pattern of crystalluria in stone-formers and normals. If the supersaturation of urine with respect to CaOx reaches or exceeds the 3-4 min formation product of that salt, then it dominates the crystallisation process both in terms of "self-nucleation" and crystal growth but appears to have little or no effect on the degree of aggregation of the crystals produced. At supersaturation levels of urine with respect to CaOx well below the 3-4 min formation product of that salt, the influence of inhibitors increases and some may affect not only the degree of aggregation but also the crystal growth of any pre-formed crystals of CaOx at these lower levels of metastability.

Crystallisation of mela-aillikites of the Narsaq region, Gardar alkaline province, south Greenland and relationships to other aillikitic carbonatitic associations in the province

NASA Astrophysics Data System (ADS)

Upton, B. G. J.; Craven, J. A.; Kirstein, L. A.

2006-11-01

Aillikites (carbonated, melilite-free ultramafic lamprophyres grading to carbonatites) are minor components of the Gardar alkaline igneous province. They occur principally as minor intrusions and as clasts in diatremes, but more voluminous aillikitic intrusions crop out near the Ilímaussaq Complex, which they predate by a few million years. These larger intrusions were emplaced at 1160 ± 5 Ma. They are essentially carbonate-free and, consisting almost wholly of ferromagnesian silicate and oxide minerals, are mela-aillikites. Typically the mela-aillikites are fine-grained rocks composed largely of olivine, clinopyroxene, phlogopite and magnetite that crystallised in open systems, permitting loss of volatile-rich residues. The petrography is highly complex, involving at least 28 mineral species. Pyroxenitic veins were emplaced while the host-rocks were still at high temperatures and represent channels through which fluorinated silico-carbonatitic residual melts escaped, with exsolving CO 2 as propellant. Precipitation of Ca-rich minerals including monticellite, perovskite, vesuvianite, wollastonite and cuspidine was a result of dissociation of the calcium carbonate in the residual melts. Late-stage crystallisation was in a highly oxidising environment in which the 'common minerals' attain extreme compositions (almost pure forsterite, ferrian-diopside, highly magnesian ilmenite, Ba-Ti-rich phlogopite and Sr-rich kaersutite). Spatially associated diatremes may be vents through which CO 2-rich gases erupted. The whole-rock compositions are considered to be well removed from those of co-existing melts: compaction and expulsion of highly mobile residual melts is inferred to have left the mela-aillikites as aberrant cumulates. The mela-aillikites are a late-Gardar manifestation of the aillikitic magmatism that occurred intermittently in the province for over 120 Ma. Repetitive formation of metasomite vein systems in the deep lithospheric mantle is postulated. These readily fusible metasomites had short residence histories, experiencing either adiabatic melting or thermal melting as a result of plume activity. The abnormally large volumes of ultramafic lamprophyre magma, from which the mela-aillikites crystallised, may denote the culmination of metasomatic processes in the closing stages of the evolution of the Gardar Province.

Evidence for the presence of carbonate melt during the formation of cumulates in the Colli Albani Volcanic District, Italy

NASA Astrophysics Data System (ADS)

Shaw, Cliff S. J.

2018-06-01

Fergusite and syenite xenoliths and mafic lapilli from two locations in the Villa Senni ignimbrite of the Colli Albani Volcanic District show evidence for fractionation of a silicate magma that led to exsolution of an immiscible carbonate melt. The fergusite xenoliths are divided into two groups on the basis of their clinopyroxene compositions. Group 1 clinopyroxene records the crystallisation of a silicate melt and enrichment of the melt in Al, Ti and Mn and depletion in Si as well as enrichment in incompatible trace elements. The second group of clinopyroxene compositions (group 2) comes mainly from Ba-F-phlogopite- and Ti-andradite-bearing fergusites. They have significantly higher Si and lower Al and Ti and, like the coexisting phlogopite and garnet are strongly enriched in Mn. The minerals in the fergusites containing group 2 clinopyroxene are enriched in Ba, Sr, Cs, V and Li all of which are expected to partition strongly into a carbonate melt phase relative to the coexisting silicate melt. The compositional data suggest that the group 1 fergusites record sidewall crystallisation of CO2-rich silicate melt and that once the melt reached a critical degree of fractionation, carbonate melt exsolved. The group 2 fergusites record continued crystallisation in this heterogeneous silicate - carbonate melt system. Composite xenoliths of fergusite and thermometamorphic skarn record contact times of hundreds to a few thousand years indicating that fractionation and assimilation was relatively rapid.

The influence of crystallised Fe3O4 on the magnetic properties of coprecipitation-derived ferrimagnetic glass-ceramics.

PubMed

Bretcanu, O; Spriano, S; Verné, E; Cöisson, M; Tiberto, P; Allia, P

2005-07-01

Ferrimagnetic glass-ceramics are potential candidates for magnetic induction hyperthermia, which is one form of inducing deep-regional hyperthermia, by using a magnetic field. The aim of this work was to analyse the influence of the amount of crystallised magnetite on the magnetic properties of glass-ceramic samples. Thus, two different ferrimagnetic glass-ceramics with the composition of the system Na(2)O-CaO-SiO(2)-P(2)O(5)-FeO-Fe(2)O(3) were prepared by melting at 1500 degrees C for 30 min of the coprecipitation-derived starting products. The X-ray diffraction patterns show the presence of nanometric magnetite crystals in a glassy matrix after cooling from melting temperature. The estimated amount of crystallised magnetite varies between 20 and 45 wt.%, as a function of the chemical composition. The morphology of the crystals was studied by scanning electron micrography and transmission electron micrography. Glass transition temperature and thermal stability were investigated by differential thermal analysis. Magnetic hysteresis cycles were analysed using a vibrating sample magnetometer with a maximum applied field of 17 kOe, at room temperature, in quasi-static conditions. Calorimetric measurements were carried out using a magnetic induction furnace. The power losses estimated from calorimetric measurements under a magnetic field of 40 kA/m and 440 kHz are 65 W/g for the glass-ceramic with lower iron oxides content and 25 W/g for the glass-ceramic with higher iron oxide content.

Stabilisation of Ce-Cu-Fe amorphous alloys by addition of Al

NASA Astrophysics Data System (ADS)

Kelhar, Luka; Ferčič, Jana; Boulet, Pascal; Maček-Kržmanc, Marjeta; Šturm, Sašo; Lamut, Martin; Markoli, Boštjan; Kobe, Spomenka; Dubois, Jean-Marie

2016-10-01

The present work describes the formation of amorphous alloys in the (Al1-xCex)62Cu25Fe13 quaternary system (0 ≤ x ≤ 1). When the amount of Ce falls in the range 0.67 ≤ x ≤ 0.83, the alloys obtained exhibit a completely amorphous structure confirmed by powder X-ray diffraction. Otherwise, at compositions x = 0.5, 0.58, 0.92 and 1, a primary crystalline phase forms together with an amorphous matrix. The crystallisation temperature (Tx) decreases with increasing Ce content, varying from 593 K for x = 0.5-383 K for x = 1. Composition x = 0.75 is considered as the best glass former, exhibiting a large supercooled liquid region of 40 K width that precedes crystallisation. In order to form bulk amorphous alloys, ribbons with this later composition were consolidated into few millimetre thick discs using pulsed electric current sintering at different temperatures, yet preserving the amorphous structure. Meanwhile, increasing temperature above 483 K triggers crystallisation of a primary phase isostructural to AlCe3. Further increase in the temperature up to 573 K yields a higher fraction of the crystalline phase. Testing mechanical properties, using nanoindentation, revealed that both elastic modulus (E) and hardness (H) depend on the Al content, ranging from E = 85.6 ± 3.7 GPa and H = 6.2 ± 0.7 GPa for x = 0.5 down to E = 39.8 ± 1.0 GPa and H = 3.1 ± 0.2 GPa for x = 0.92.

Thermal Convection in a Creeping Solid With Melting/Freezing Interfaces at Either or Both Boundaries

NASA Astrophysics Data System (ADS)

Labrosse, S.; Morison, A.; Deguen, R.; Alboussiere, T.; Tackley, P. J.; Agrusta, R.

2017-12-01

Thermal convection in the solid mantles of the Earth, other terrestrial planets and icy satellites sets in while it is still crystallising from a liquid layer (see abstract by Morison et al, this conference). The existence of an ocean (water or magma) either or both below and above the solid mantle modifies the conditions applying at the boundary since matter can flow through it by changing phase. Adapting the boundary conditions developed for the dynamics of the inner core by Deguen et al (GJI 2013) to the plane layer and the spherical shell, we solve the linear stability problem and obtain weakly non-linear solutions as well as direct numerical solutions in both geometries, with a liquid-solid phase change at either or both boundaries. The phase change boundary condition is controlled by a dimensionless number, Φ , which when small, allows easy flow through the boundary while the classical non-penetrating boundary condition is recovered for large values. If both boundaries have a phase change, the preferred wavelength of the flow is large, i.e. λ ∝Φ -1/2 in a plane layer and degree 1 in a spherical shell, and the critical Rayleigh number is of order Φ . The heat transfer efficiency, as measured by the dependence of the Nusselt number on the Rayleigh number also increases indefinitely for decreasing values of Φ . If only one boundary has a phase change condition, the critical wavelength is increased by about a factor 2 and the critical Rayleigh number is decreased by about a factor 4. The dynamics is controlled entirely by the boundary layer opposite to the phase change interface and the geometry of the flow. This model provides a natural explanation for the emergence of degree 1 convection in thin ice layers and implies a style of early mantle dynamics on Earth very different from what is classically envisioned.

Magma accumulation or second boiling - Investigating the ongoing deformation field at Montserrat, West Indies

NASA Astrophysics Data System (ADS)

Collinson, Amy; Neuberg, Jurgen; Pascal, Karen

2016-04-01

For over 20 years, Soufriere Hills Volcano, Montserrat has been in a state of volcanic unrest. Intermittent periods of dome building have been punctuated by explosive eruptions and dome collapse events, endangering the lives of the inhabitants of the island. The last episode of active magma extrusion was in February 2010, and the last explosive event (ash venting) in March 2012. Despite a lack of eruptive activity recently, the volcano continues to emit significant volumes of SO2 and shows an ongoing trend of island inflation. Through the aid of three-dimensional numerical modelling, using a finite element method, we explore the potential sources of the ongoing island inflation. We consider both magmatic (dykes and chamber) and tectonic sources. Whilst a magmatic source suggests the possibility for further eruption, a tectonic source may indicate cessation of volcanic activity. We show that a magmatic source is the most likely scenario, and illustrate the effect of different sources (shapes, characters and depths) on the surface displacement. Furthermore, through the inclusion of topographic data, we investigate how the topography may affect the displacement pattern at the surface. We investigate the conflicting scenarios of magma chamber resupply versus second boiling - crystallisation-induced degassing. Based on numerical modelling results, we suggest the required pressurisation is too high for crystallisation-induced degassing to be the dominant process - thereby suggesting magma accumulation may be ongoing. However, we show that second boiling may be a contributing factor, particularly when taking into account the local tectonics and regional stretching.

Lanthanide(II) complexes of a phosphine-borane-stabilised carbanion.

PubMed

Izod, Keith; Clegg, William; Harrington, Ross W

2010-08-07

The reaction between two equivalents of the potassium salt [(Me(3)Si)(2){Me(2)P(BH(3))}C]K (4) and SmI(2)(THF)(2) in refluxing THF yields the dialkylsamarium(II) compounds [(Me(3)Si)(2){Me(2)P(BH(3))}C](2)Sm(THF) (5a) or [(Me(3)Si)(2){Me(2)P(BH(3))}C](2)Sm(THF)(3) (5b), depending on the crystallisation conditions, in good yield as air- and moisture-sensitive crystalline solids. X-ray crystallography shows that, whereas both alkyl ligands chelate the samarium(II) ion in 5a, in 5b one alkyl ligand chelates the metal centre and one binds the metal only through its borane hydrogen atoms. The reaction between YbI(2) and two equivalents of 4 in refluxing benzene yields the solvent-free dialkylytterbium(II) compound [(Me(3)Si)(2){Me(2)P(BH(3))}C](2)Yb (8). In contrast to 5a and 5b, compound 8 reacts rapidly with THF to give the free phosphine-borane (Me(3)Si)(2){Me(2)P(BH(3))}CH as the only identifiable product.

Adapting phase-switch Monte Carlo method for flexible organic molecules

NASA Astrophysics Data System (ADS)

Bridgwater, Sally; Quigley, David

2014-03-01

The role of cholesterol in lipid bilayers has been widely studied via molecular simulation, however, there has been relatively little work on crystalline cholesterol in biological environments. Recent work has linked the crystallisation of cholesterol in the body with heart attacks and strokes. Any attempt to model this process will require new models and advanced sampling methods to capture and quantify the subtle polymorphism of solid cholesterol, in which two crystalline phases are separated by a phase transition close to body temperature. To this end, we have adapted phase-switch Monte Carlo for use with flexible molecules, to calculate the free energy between crystal polymorphs to a high degree of accuracy. The method samples an order parameter , which divides a displacement space for the N molecules, into regions energetically favourable for each polymorph; which is traversed using biased Monte Carlo. Results for a simple model of butane will be presented, demonstrating that conformational flexibility can be correctly incorporated within a phase-switching scheme. Extension to a coarse grained model of cholesterol and the resulting free energies will be discussed.

Experimental evidence of a liquid-liquid transition in interfacial water

NASA Astrophysics Data System (ADS)

Zanotti, J.-M.; Bellissent-Funel, M.-C.; Chen, S.-H.

2005-07-01

At ambient pressure, bulk liquid water shows an anomalous increase of thermodynamic quantities and apparent divergences of dynamic properties on approaching a temperature Ts of 228 K. At normal pressure, supercooled water spontaneously freezes below the homogeneous nucleation temperature, TH = 235 K. Upon heating, the two forms of Amorphous Solid Water (ASW), LDA (Low Density Amorphous Ice) and HDA (High Density Amorphous Ice), crystallise above TX = 150 K. As a consequence, up to now no experiment has been able to explore the properties of liquid water in this very interesting temperature range between 150 and 235 K. We present nanosecond-time-scale measurements of local rotational and translational dynamics of interfacial, non-crystalline, water from 77 to 280 K. These experimental dynamic results are combined with calorimetric and diffraction data to show that after exhibiting a glass transition at 165 K, interfacial water experiences a first-order liquid-liquid transition at 240 K from a low-density to a high-density liquid. This is the first direct evidence of the existence of a liquid-liquid transition involving water.

Thermostabilisation of membrane proteins for structural studies

PubMed Central

Magnani, Francesca; Serrano-Vega, Maria J.; Shibata, Yoko; Abdul-Hussein, Saba; Lebon, Guillaume; Miller-Gallacher, Jennifer; Singhal, Ankita; Strege, Annette; Thomas, Jennifer A.; Tate, Christopher G.

2017-01-01

The thermostability of an integral membrane protein in detergent solution is a key parameter that dictates the likelihood of obtaining well-diffracting crystals suitable for structure determination. However, many mammalian membrane proteins are too unstable for crystallisation. We developed a thermostabilisation strategy based on systematic mutagenesis coupled to a radioligand-binding thermostability assay that can be applied to receptors, ion channels and transporters. It takes approximately 6-12 months to thermostabilise a G protein-coupled receptor (GPCR) containing 300 amino acid residues. The resulting thermostabilised membrane proteins are more easily crystallised and result in high-quality structures. This methodology has facilitated structure-based drug design applied to GPCRs, because it is possible to determine multiple structures of the thermostabilised receptors bound to low affinity ligands. Protocols and advice are given on how to develop thermostability assays for membrane proteins and how to combine mutations to make an optimally stable mutant suitable for structural studies. PMID:27466713

Crystallisation of alpha-crustacyanin, the lobster carapace astaxanthin-protein: results from EURECA

NASA Astrophysics Data System (ADS)

Zagalsky, P. F.; Wright, C. E.; Parsons, M.

1995-08-01

Crystallisation of alpha-crustacyanin, the lobster carapace astaxanthin-protein was attempted under microgravity conditions in EURECA satellite using liquid-liquid diffusion with polyethyleneglycol (PEG) as precipitant; in a second reaction chamber phenol and dioxan were used as additives to prevent composite crystal growth. Crystals of alpha-crustacyanin grown under microgravity from PEG were larger than those grown terrestrially in the same apparatus under otherwise identical conditions. On retrieval, the crystals from PEG were shown to be composite and gave a powder diffraction pattern. The second reaction chamber showed leakage on retrieval and had also been subjected to rapid temperature variation during flight. Crystal fragments were nevertheless recovered but showed a powder diffraction pattern. It is concluded, certainly for liquid-liquid diffusion using PEG alone, that, for crustacyanin, although microgravity conditions resulted in an increase in dimensions of crystals, a measurable improvement in molecular ordering was not achieved.

Influence of mixing and ultrasound frequency on antisolvent crystallisation of sodium chloride.

PubMed

Lee, Judy; Ashokkumar, Muthupandian; Kentish, Sandra E

2014-01-01

Ultrasound is known to promote nucleation of crystals and produce a narrower size distribution in a controlled and reproducible manner for the crystallisation process. Although there are various theories that suggest cavitation bubbles are responsible for sonocrystallisation, most studies use power ultrasonic horns that generate both intense shear and cavitation and this can mask the role that cavitation bubbles play. High frequency ultrasound from a plate transducer can be used to examine the effect of cavitation bubbles without the intense shear effect. This study reports the crystal size and morphology with various mixing speeds and ultrasound frequencies. The results show high frequency ultrasound produced sodium chloride crystals of similar size distribution as an ultrasonic horn. In addition, ultrasound generated sodium chloride crystals having a more symmetrical cubic structure compared to crystals produced by a high shear mixer. Copyright © 2013 Elsevier B.V. All rights reserved.

The fine art of integral membrane protein crystallisation.

PubMed

Birch, James; Axford, Danny; Foadi, James; Meyer, Arne; Eckhardt, Annette; Thielmann, Yvonne; Moraes, Isabel

2018-05-18

Integral membrane proteins are among the most fascinating and important biomolecules as they play a vital role in many biological functions. Knowledge of their atomic structures is fundamental to the understanding of their biochemical function and key in many drug discovery programs. However, over the years, structure determination of integral membrane proteins has proven to be far from trivial, hence they are underrepresented in the protein data bank. Low expression levels, insolubility and instability are just a few of the many hurdles one faces when studying these proteins. X-ray crystallography has been the most used method to determine atomic structures of membrane proteins. However, the production of high quality membrane protein crystals is always very challenging, often seen more as art than a rational experiment. Here we review valuable approaches, methods and techniques to successful membrane protein crystallisation. Copyright © 2018 Diamond Light Source LTD. Published by Elsevier Inc. All rights reserved.

Analysis of X-ray structures of matrix metalloproteinases via chaotic map clustering.

PubMed

Giangreco, Ilenia; Nicolotti, Orazio; Carotti, Angelo; De Carlo, Francesco; Gargano, Gianfranco; Bellotti, Roberto

2010-10-08

Matrix metalloproteinases (MMPs) are well-known biological targets implicated in tumour progression, homeostatic regulation, innate immunity, impaired delivery of pro-apoptotic ligands, and the release and cleavage of cell-surface receptors. With this in mind, the perception of the intimate relationships among diverse MMPs could be a solid basis for accelerated learning in designing new selective MMP inhibitors. In this regard, decrypting the latent molecular reasons in order to elucidate similarity among MMPs is a key challenge. We describe a pairwise variant of the non-parametric chaotic map clustering (CMC) algorithm and its application to 104 X-ray MMP structures. In this analysis electrostatic potentials are computed and used as input for the CMC algorithm. It was shown that differences between proteins reflect genuine variation of their electrostatic potentials. In addition, the analysis has been also extended to analyze the protein primary structures and the molecular shapes of the MMP co-crystallised ligands. The CMC algorithm was shown to be a valuable tool in knowledge acquisition and transfer from MMP structures. Based on the variation of electrostatic potentials, CMC was successful in analysing the MMP target family landscape and different subsites. The first investigation resulted in rational figure interpretation of both domain organization as well as of substrate specificity classifications. The second made it possible to distinguish the MMP classes, demonstrating the high specificity of the S1' pocket, to detect both the occurrence of punctual mutations of ionisable residues and different side-chain conformations that likely account for induced-fit phenomena. In addition, CMC demonstrated a potential comparable to the most popular UPGMA (Unweighted Pair Group Method with Arithmetic mean) method that, at present, represents a standard clustering bioinformatics approach. Interestingly, CMC and UPGMA resulted in closely comparable outcomes, but often CMC produced more informative and more easy interpretable dendrograms. Finally, CMC was successful for standard pairwise analysis (i.e., Smith-Waterman algorithm) of protein sequences and was used to convincingly explain the complementarity existing between the molecular shapes of the co-crystallised ligand molecules and the accessible MMP void volumes.

Origins of anisotropic seismic attenuation of the inner core - intrinsic anelasticity of hcp iron alloy

NASA Astrophysics Data System (ADS)

Redfern, Simon

2015-04-01

Earth's inner core is elastically anisotropic, with seismology showing faster wave propagation along the polar axis compared to the equatorial plane. Some inner core studies report anisotropic seismic attenuation. Attenuation of body-waves has, previously, been postulated to be due to scattering by anisotropic microstructure, but recent normal mode studies also show strong anisotropic attenuation (Mäkinen et al. 2014). This suggests that the anisotropic attenuation is a result of the intrinsic (and anisotropic) anelastic properties of the solid iron alloy forming Earth's inner core. Here, I consider the origins of inner core anisotropic attenuation. Possibilities include grain boundary relaxation, dislocation bowing/glide, or point defect (alloying element) relaxations. The inner core is an almost perfect environment for near-equilibrium crystallisation, with very low temperature gradients across the inner core, low gravity, and slow crystallisation rates. It is assumed that grain sizes may be of the order of hundreds of metres. This implies vanishingly small volumes of grain boundary, and insignificant grain boundary relaxation. The very high homologous temperature and the absence of obvious deviatoric stress, also leads one to conclude that dislocation densities are low. On the other hand, estimates for light element concentrations are of the order of a few % with O, S, Si, C and H at various times being suggested as candidate elements. Light element solutes in hcp metals contribute to intrinsic anelastic attenuation if they occur in sufficient concentrations to pair and form elastic dipoles. Switching of dipoles under the stress of a passing seismic wave will result in anelastic mechanical loss. Such attenuation has been measured in hcp metals in the lab, and is anisotropic due to the intrinsic elastic anisotropy of the host lattice. Such solute pair relaxations result in a "Zener effect", which is suggested here to be responsible for observed anisotropic seismic attenuation. Zener relaxation magnitude scales with solute concentration and is consistent with around 5% light element. Variations in attenuation are expected in a core with spatially varying concentrations of light element, and attenuation tomography of the inner core could, therefore, be employed to map chemical heterogeneity.

Intrinsic Aniostropic Anelasticity of Hcp Iron Due to Light Element Solute Atoms

NASA Astrophysics Data System (ADS)

Redfern, S. A. T.

2014-12-01

Earth's inner core is elastically anisotropic, with seismology showing faster wave propagation along the polar axis compared to the equatorial plane. Some inner core studies report anisotropic seismic attenuation. Attenuation of body-waves has, previously, been postulated to be due to scattering by anisotropic microstructure, but recent normal mode studies also show strong anisotropic attenuation (Mäkinen et al. 2014). This suggests that the anisotropic attenuation is a result of the intrinsic (and anisotropic) anelastic properties of the solid iron alloy forming Earth's inner core. Here, I consider the origins of inner core anisotropic attenuation. Possibilities include grain boundary relaxation, dislocation bowing/glide, or point defect (alloying element) relaxations. The inner core is an almost perfect environment for near-equilibrium crystallisation, with very low temperature gradients across the inner core, low gravity, and slow crystallisation rates. It is assumed that grain sizes may be of the order of hundreds of metres. This implies vanishingly small volumes of grain boundary, and insignificant grain boundary relaxation. The very high homologous temperature and the absence of obvious deviatoric stress, also leads one to conclude that dislocation densities are low. On the other hand, estimates for light element concentrations are of the order of a few % with O, S, Si, C and H at various times being suggested as candidate elements. Light element solutes in hcp metals contribute to intrinsic anelastic attenuation if they occur in sufficient concentrations to pair and form elastic dipoles. Switching of dipoles under the stress of a passing seismic wave will result in anelastic mechanical loss. Such attenuation has been measured in hcp metals in the lab, and is anisotropic due to the intrinsic elastic anisotropy of the host lattice. Such solute pair relaxations result in a "Zener effect", which is suggested here to be responsible for observed anisotropic seismic attenuation. Zener relaxation magnitude scales with solute concentrationand is consistent with around 5% loght element. Variations in attenuation are expected in a core with spatially varying concentrations of light element, and attenuation tomography of the inner core could, therefore, be employed to map chemical heterogeneity.

Low-pressure differentiation of tholeiitic lavas as recorded in segregation veins from Reykjanes (Iceland), Lanzarote (Canary Islands) and Masaya (Nicaragua)

NASA Astrophysics Data System (ADS)

Martin, E.; Sigmarsson, O.

2007-11-01

Segregation veins are common in lava sheets and result from internal differentiation during lava emplacement and degassing. They consist of evolved liquid, most likely replaced by gas-filter pressing from a ˜50% crystallised host lava. Pairs of samples, host lavas and associated segregation veins from the Reykjanes Peninsula (Iceland), Lanzarote (Canary Islands) and the Masaya volcano (Nicaragua) show extreme mineralogical and compositional variations (MgO in host lava, segregation veins and interstitial glass ranges from 8-10 wt%, 3-6 wt%, and to less than 0.01 wt%, respectively). These samples allow the assessment of the internal lava flow differentiation mechanism, since both the parental and derived liquid are known in addition to the last magma drops in the form of late interstitial glasses. The mineralogical variation, mass-balance calculated from major- and trace element composition, and transitional metal partition between crystals and melts are all consistent with fractional crystallisation as the dominant differentiation mechanism. The interstitial glasses are highly silicic (SiO2 = 70-80 wt%) and represent a final product of high-degree (75-97%) fractional crystallisation of olivine tholeiite at a pressure close to one atmosphere. The tholeiitic liquid-line-of-decent and the composition of the residual melts are governed by the K2O/Na2O of the initial basaltic magma. The granitic minimum is reached if the initial liquid has a high K2O/Na2O whereas trondhjemitic composition is the final product of magma with low initial K2O/Na2O.

Bioisosteric ferrocenyl-containing quinolines with antiplasmodial and antitrichomonal properties

USDA-ARS?s Scientific Manuscript database

A series of ferrocenyl'containing quinolines and ferrocenylamines were prepared and fully characterized. The molecular structures of two ferrocenyl'containing quinolines, determined using single'crystal x'ray diffraction, revealed that the compounds crystallise in a folded conformation. The compound...

Phyllosilicate weathering pathways in chlorite-talc bearing soil parent materials, D.R. Congo: early findings.

NASA Astrophysics Data System (ADS)

Dumon, Mathijs; Oostermeyer, Fran; Timmermans, Els; De Meulemeester, Aschwin; Mees, Florias; Van Driessche, Isabel; Erens, Hans; Bazirake Mujinya, Basile; Van Ranst, Eric

2015-04-01

The study of the formation and transformation of clay minerals is of the upmost importance to understand soil formation and to adjust land-use management to the land surface conditions. These clay minerals determine to a large extent the soil physical and chemical properties. It is commonly observed that over time the mineralogy of any parent material is transformed to a simple assemblage composed mostly of Al and Fe oxides and low-activity clays, e.g. kaolinite. This is especially obvious in the humid tropics, which have been protected from glacial erosion, allowing deep, highly weathered soils to form. Despite the abundant presence of kaolinite in these soils, its formation pathways are still under debate: either neoformation by dissolution-crystallisation reactions or solid-state transformation of 2:1 phyllosilicates. To elucidate this, weathering sequences in a unique 40 m core taken below a termite mound, reaching a talc-chlorite bearing substrate in the Lubumbashi area, Katanga, DR Congo are being investigated in detail using a.o. quantitative X-ray diffraction analysis, chemical characterization, micromorphology and µXRF-scanning with the main objective to improve the understanding of the formation pathways of kaolinite subgroup minerals in humid tropical environments. Based on an initial characterization of the core, two zones of interest were selected for more detailed analysis, for which the early findings will be presented. The first zone extends from ca. 9 m to 11 m below the surface is dominated by kaolinite but shows early traces of primary talc and micas. The second zone extends from 34 to 36 m below the surface and contains large amounts of chlorite, with smaller amounts of talc, micas and kaolinite.

Neuroanatomical correlates of intelligence in healthy young adults: the role of basal ganglia volume.

PubMed

Rhein, Cosima; Mühle, Christiane; Richter-Schmidinger, Tanja; Alexopoulos, Panagiotis; Doerfler, Arnd; Kornhuber, Johannes

2014-01-01

In neuropsychiatric diseases with basal ganglia involvement, higher cognitive functions are often impaired. In this exploratory study, we examined healthy young adults to gain detailed insight into the relationship between basal ganglia volume and cognitive abilities under non-pathological conditions. We investigated 137 healthy adults that were between the ages of 21 and 35 years with similar educational backgrounds. Magnetic resonance imaging (MRI) was performed, and volumes of basal ganglia nuclei in both hemispheres were calculated using FreeSurfer software. The cognitive assessment consisted of verbal, numeric and figural aspects of intelligence for either the fluid or the crystallised intelligence factor using the intelligence test Intelligenz-Struktur-Test (I-S-T 2000 R). Our data revealed significant correlations of the caudate nucleus and pallidum volumes with figural and numeric aspects of intelligence, but not with verbal intelligence. Interestingly, figural intelligence associations were dependent on sex and intelligence factor; in females, the pallidum volumes were correlated with crystallised figural intelligence (r = 0.372, p = 0.01), whereas in males, the caudate volumes were correlated with fluid figural intelligence (r = 0.507, p = 0.01). Numeric intelligence was correlated with right-lateralised caudate nucleus volumes for both females and males, but only for crystallised intelligence (r = 0.306, p = 0.04 and r = 0.459, p = 0.04, respectively). The associations were not mediated by prefrontal cortical subfield volumes when controlling with partial correlation analyses. The findings of our exploratory analysis indicate that figural and numeric intelligence aspects, but not verbal aspects, are strongly associated with basal ganglia volumes. Unlike numeric intelligence, the type of figural intelligence appears to be related to distinct basal ganglia nuclei in a sex-specific manner. Subcortical brain structures thus may contribute substantially to cognitive performance.

Characterisation and in vitro stability of low-dose, lidocaine-loaded poly(vinyl alcohol)-tetrahydroxyborate hydrogels.

PubMed

Abdelkader, D H; Osman, M A; El-Gizawy, S A; Faheem, A M; McCarron, P A

2016-03-16

Poly(vinyl alcohol) hydrogels cross-linked with the tetrahydroxyborate anion possess textural and rheological properties that can be used as novel drug-loaded vehicles for application to traumatic wounds. However, addition of soluble drug substances causes concentration-dependent phase separation and rheological changes. The aim of this work was to investigate the effect of adding a local anaesthetic, but keeping the concentration low in an attempt to prevent these changes. Cross-linked hydrogels prepared from three grades of poly(vinyl alcohol) were characterised rheologically. Temperature sweep studies showed an elevated complex viscosity upon moving from 25°C to 80°C, which remained high for 48 h following completion of the cycle. Adhesion to model dermal surfaces achieved a maximum of 2.62 N cm(-2) and were greater than that observed to epidermal substrates, with a strong dependence on the rate of detachment used during testing. An optimised formulation (6% w/w PVA (31-50; 99) and 2% w/w THB) containing lidocaine hydrochloride loaded to an upper maximum concentration of 1.5% w/w was assessed for phase separation and drug crystallisation. After six months, crystallisation was present in formulations containing 0.7% and 1.5% lidocaine HCl. Changes in pH in response to increases in lidocaine loading were low. Drug release was shown to operate via a non-Fickian process for all three concentrations, with 60% occurring after approximately 24h. It can be concluded that using a low concentration of lidocaine hydrochloride in hydrogels based on poly(vinyl alcohol) will result in crystallisation. Furthermore, these hydrogels are unlikely to induce rapid anaesthesia due to the low loading and slow release kinetics. Copyright © 2016 Elsevier B.V. All rights reserved.

Emerging applications of spark plasma sintering in all solid-state lithium-ion batteries and beyond

NASA Astrophysics Data System (ADS)

Zhu, Hongzheng; Liu, Jian

2018-07-01

Solid-state batteries have received increasing attention due to their high safety aspect and high energy and power densities. However, the development of solid-state batteries is hindered by inferior solid-solid interfaces between the solid-state electrolyte and electrode, which cause high interfacial resistance, reduced Li-ion and electron transfer rate, and limited battery performance. Recently, spark plasma sintering (SPS) is emerging as a promising technique for fabricating solid-state electrolyte and electrode pellets with clean and intimate solid-solid interfaces. During the SPS process, the unique reaction mechanism through the combination of current, pressure and high heating rate allow the formation of desirable solid-solid interfaces between active material particles. Herein, this work focuses on the overview of the application of SPS for fabricating solid-state electrolyte and electrode in all solid-state Li-ion batteries, and beyond, such as solid-state Li-S and Na-ion batteries. The correlations among SPS parameters, interfacial resistance, and electrochemical properties of solid-state electrolytes and electrodes are discussed for different material systems. In the end, we point out future opportunities and challenges associated with SPS application in the hot area of solid-state batteries. It is expected that this timely review will stimulate more fundamental and applied research in the development of solid-state batteries by SPS.

EFFECTS OF LASER RADIATION ON MATTER. LASER PLASMA: Laser—ultrasonic formation of melts of high-speed tool steels

NASA Astrophysics Data System (ADS)

Gureev, D. M.

1994-09-01

A study was made of the influence of ultrasonic vibrations on the processes of heat and mass transfer, and of structure formation during ultrafast crystallisation of laser melts of T1 high-speed tool steel. Acoustic flows which appeared in laser melts effectively smoothed out the temperature inhomogeneities and flattened the relief of the molten surface even when the laser radiation acted for just ~1 ms. The transformation of the mechanical energy of ultrasonic vibrations into heat increased the depth of the laser melt baths and suppressed crack formation. The observed changes in the structural and phase composition appeared as a change in the microhardness of the solidified laser melts. The geometry of coupling of ultrasound into a laser melt influenced the changes in the microhardness, suggesting a need for a more detailed analysis of the structure formation processes in the course of ultrafast crystallisation of laser melts in an ultrasonic field.

Progress and prospect on failure mechanisms of solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Ma, Jun; Chen, Bingbing; Wang, Longlong; Cui, Guanglei

2018-07-01

By replacing traditional liquid organic electrolyte with solid-state electrolyte, the solid-state lithium batteries powerfully come back to the energy storage field due to their eminent safety and energy density. In recent years, a variety of solid-state lithium batteries based on excellent solid-state electrolytes are developed. However, the performance degradation of solid-state lithium batteries during cycling and storing is still a serious challenge for practical application. Therefore, this review summarizes the research progress of solid-state lithium batteries from the perspectives of failure phenomena and failure mechanisms. Additionally, the development of methodologies on studying the failure mechanisms of solid-state lithium batteries is also reviewed. Moreover, some perspectives on the remaining questions for understanding the failure behaviors and achieving long cycle life, high safety and high energy density solid-state lithium batteries are presented. This review will help researchers to recognize the status of solid-state lithium batteries objectively and attract much more research interest in conquering the failure issues of solid-state lithium batteries.

Solid oxide fuel cells fueled with reducible oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chuang, Steven S.; Fan, Liang Shih

A direct-electrochemical-oxidation fuel cell for generating electrical energy includes a cathode provided with an electrochemical-reduction catalyst that promotes formation of oxygen ions from an oxygen-containing source at the cathode, a solid-state reduced metal, a solid-state anode provided with an electrochemical-oxidation catalyst that promotes direct electrochemical oxidation of the solid-state reduced metal in the presence of the oxygen ions to produce electrical energy, and an electrolyte disposed to transmit the oxygen ions from the cathode to the solid-state anode. A method of operating a solid oxide fuel cell includes providing a direct-electrochemical-oxidation fuel cell comprising a solid-state reduced metal, oxidizing themore » solid-state reduced metal in the presence of oxygen ions through direct-electrochemical-oxidation to obtain a solid-state reducible metal oxide, and reducing the solid-state reducible metal oxide to obtain the solid-state reduced metal.« less

Compatibility between strontium-doped ferrite cathode and metallic interconnects in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Miguel-Pérez, Verónica; Martínez-Amesti, Ana; Arriortua, María Isabel

2015-04-01

One of the most important issues related to the performance of solid oxide fuel cells (SOFCs) is the chromium poisoning of the perovskite-type materials used as cathodes by the gaseous chromium species from metallic interconnects. In this study, powder mixtures of LSF40-Cr2O3 were heated at 800 °C and 1000 °C in air and were subsequently analysed by X-ray powder diffraction. For all the mixtures, the crystallisation of SrCrO4 was observed. In addition, the degradation occurring between three alloys with different compositions, Crofer 22 APU, SS430 and Conicro 4023 W 188, as metallic interconnects and La0.6Sr0.4FeO3 (LSF40) ceramic material as a cathode was studied. The results show significant chromium deposition and the formation of SrCrO4, LaCrO3 and La2O3 that block the active LSF40 electrode surface and degrade the stack (YSZ/SDC/LSF40/Interconnect) performance. LSF40 assembled with SS430 exhibited substantial Cr deposition. The deposition of the Cr species and the reaction with the LSF40 cathode is related to the composition of the oxide scales formed at each metallic interconnect and at the same time is related to the composition of the alloys. The best results obtained were for the half-cell (YSZ/SDC/LSF40) in contact with Conicro 4023 W 188 and Crofer 22 APU after heat treatment in air at 800 °C for 100 h.

The Ni-rich part of the Al–Ge–Ni phase diagram

PubMed Central

Jandl, Isabella; Reichmann, Thomas L.; Richter, Klaus W.

2013-01-01

The Ni-rich part of the ternary system Al–Ge–Ni (xNi > 50 at.%) was investigated by means of optical microscopy, powder X-ray diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscopy (SEM). The two isothermal sections at 550 °C and 700 °C were determined. Within these two sections a new ternary phase, designated as τ4, AlyGe9−yNi13±x (hP66, Ga3Ge6Ni13-type) was detected and investigated by single crystal X-ray diffraction. Another ternary low temperature phase, τ5, was found only in the isothermal section at 550 °C around the composition AlGeNi4. This compound was found to crystallise in the Co2Si type structure (oP12, Pnma). The structure was identified by Rietveld refinement of powder data. The NiAs type (B8) phase based on binary Ge3Ni5 revealed an extended solid solubility of Al and the two isotypic compounds AlNi3 and GeNi3 form a complete solid solution. Based on DTA results, six vertical sections at 55, 60, 70, 75 and 80 at.% Ni and at a constant Al:Ni ratio of 1:3 were constructed. Furthermore, the liquidus surface projection and the reaction scheme (Scheil diagram) were completed by combining our results with previous results from the Ni-poor part of the phase diagram. Six invariant ternary reactions were identified in the Ni-rich part of the system. PMID:27087754

Mantle-derived trace element variability in olivines and their melt inclusions

NASA Astrophysics Data System (ADS)

Neave, David A.; Shorttle, Oliver; Oeser, Martin; Weyer, Stefan; Kobayashi, Katsura

2018-02-01

Trace element variability in oceanic basalts is commonly used to constrain the physics of mantle melting and the chemistry of Earth's deep interior. However, the geochemical properties of mantle melts are often overprinted by mixing and crystallisation processes during ascent and storage. Studying primitive melt inclusions offers one solution to this problem, but the fidelity of the melt-inclusion archive to bulk magma chemistry has been repeatedly questioned. To provide a novel check of the melt inclusion record, we present new major and trace element analyses from olivine macrocrysts in the products of two geographically proximal, yet compositionally distinct, primitive eruptions from the Reykjanes Peninsula of Iceland. By combining these macrocryst analyses with new and published melt inclusion analyses we demonstrate that olivines have similar patterns of incompatible trace element (ITE) variability to the inclusions they host, capturing chemical systematics on intra- and inter-eruption scales. ITE variability (element concentrations, ratios, variances and variance ratios) in olivines from the ITE-enriched Stapafell eruption is best accounted for by olivine-dominated fractional crystallisation. In contrast, ITE variability in olivines and inclusions from the ITE-depleted Háleyjabunga eruption cannot be explained by crystallisation alone, and must have originated in the mantle. Compatible trace element (CTE) variability is best described by crystallisation processes in both eruptions. Modest correlations between host and inclusion ITE contents in samples from Háleyjabunga suggest that melt inclusions can be faithful archives of melting and magmatic processes. It also indicates that degrees of ITE enrichment can be estimated from olivines directly when melt inclusion and matrix glass records of geochemical variability are poor or absent. Inter-eruption differences in olivine ITE systematics between Stapafell and Háleyjabunga mirror differences in melt inclusion suites, and confirm that the Stapafell eruption was fed by lower degree melts from greater depths within the melting region than the Háleyjabunga eruption. Although olivine macrocrysts from Stapafell are slightly richer in Ni than those from Háleyjabunga, their overall CTE systematics (e.g., Ni/(Mg/Fe), Fe/Mn and Zn/Fe) are inconsistent with being derived from olivine-free pyroxenites. However, the major element systematics of Icelandic basalts require lithological heterogeneity in their mantle source in the form of Fe-rich and hence fusible domains. We thus conclude that enriched heterogeneities in the Icelandic mantle are composed of modally enriched, yet nonetheless olivine-bearing, lithologies and that olivine CTE contents provide an incomplete record of lithological heterogeneity in the mantle. Modally enriched peridotites may therefore play a more important role in oceanic magma genesis than previously inferred.

S-type rhyolites from the Tolmie Igneous Complex, Australia: deep crust origins and shallow crustal evolution

NASA Astrophysics Data System (ADS)

Clemens, J. D.; Birch, W. D.

2010-05-01

The Late Devonian Tolmie Igneous Complex, in Central Victoria, Australia, is composed mainly of Ba-rich (up to 3000 ppm) S-type rhyolite ignimbrites with SiO2 varying from 69 to 79 wt% and low Mg#s (1 to 43). Two main ignimbrite flows fill the Wabonga Caldera, the Ryans Creek and the overlying Toombullup Ignimbrites, totalling 750 to 1000 km3 in volume. The tectonic environment is late post-tectonic continental extension, with rifting and normal faulting. However, the volcanism was unimodal, without associated mafic lavas or pyroclastic rocks. Devonian red-beds underlie the Complex, Carboniferous, red-bed basins overlie the volcanic rocks, and some mafic lavas are present in the overlying red-bed sequences. The presence of almandine-rich garnet phenocrysts with rutile, in the Ryans Creek, implies minimum pressures of magma generation of 0.9 - 1.0 GPa. The Toombullup Ignimbrite contains two generations of garnet phenocrysts and three of orthopyroxene. Grt+Opx assemblages in the Toombullup imply early magmatic temperatures near 1000 ° C. The early phenocryst assemblage of Grt+Opx+Pl+Qtz constrains early magmatic crystallisation to around 0.4 GPa. Later Grt+Opx+Crd+Pl+Bt+Qtz assemblages suggest crystallisation at around 0.3 GPa and 750 to 800 ° C. The presence of ferroan Opx+Fa as late microphenocrysts suggest continued crystallisation at around 0.15 GPa and 800 ° C. Thus the magmas may were generated by high-T contact anatectic partial melting of Ba-enriched quartzofeldspathic metasediments near the base of the continental crust, during extension and mantle upwelling. There is then a record of partial crystallisation during ascent to shallow crustal pressures, where the felsic magmas evolved and interacted prior to eruption. Geochemical variations in the Complex suggest that there are at least 3 separate magma groups. Mafic-felsic magma mixing and restite unmixing can be ruled out as processes responsible for the variation. The chemistry of the magmas is interpreted to be the result of a complex interplay between partial melting of heterogeneous source rocks, variable entrainment of peritectic phases formed during the melting reactions and some crystal fractionation involving garnet, orthopyroxene, plagioclase and accessory minerals (Ap, Mon, Ilm, Zrn). The implication of these rocks for the local geology is that pre-Palaeozoic supracrustal rocks must have been carried to the base of the crust but escaped high-grade metamorphism and partial melting for 100s of millions of years after the orogenic events that brought them to those depths.

On the state of crystallography at the dawn of the electron microscopy revolution.

PubMed

Higgins, Matthew K; Lea, Susan M

2017-10-01

While protein crystallography has, for many years, been the most used method for structural analysis of macromolecular complexes, remarkable recent advances in high-resolution electron cryo-microscopy led to suggestions that 'the revolution will not be crystallised'. Here we highlight the current success rate, speed and ease of modern crystallographic structure determination and some recent triumphs of both 'classical' crystallography and the use of X-ray free electron lasers. We also outline fundamental differences between structure determination using X-ray crystallography and electron microscopy. We suggest that crystallography will continue to co-exist with electron microscopy as part of an integrated array of methods, allowing structural biologists to focus on fundamental biological questions rather than being constrained by the methods available. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Education and Self-Change

ERIC Educational Resources Information Center

Kristjansson, Kristjan

2008-01-01

This paper explores three psychological theories of self--Kenneth Gergen's theory of the crystallised self, Carol Dweck's theory of the incremental self and William Swann's theory of the homeostatic self--for their ability to account for personal change in general, and radical self-change in particular. Special attention is paid to their…

New insights into the early stages of silica-controlled barium carbonate crystallisation

NASA Astrophysics Data System (ADS)

Eiblmeier, Josef; Schürmann, Ulrich; Kienle, Lorenz; Gebauer, Denis; Kunz, Werner; Kellermeier, Matthias

2014-11-01

Recent work has demonstrated that the dynamic interplay between silica and carbonate during co-precipitation can result in the self-assembly of unusual, highly complex crystal architectures with morphologies and textures resembling those typically displayed by biogenic minerals. These so-called biomorphs were shown to be composed of uniform elongated carbonate nanoparticles that are arranged according to a specific order over mesoscopic scales. In the present study, we have investigated the circumstances leading to the continuous formation and stabilisation of such well-defined nanometric building units in these inorganic systems. For this purpose, in situ potentiometric titration measurements were carried out in order to monitor and quantify the influence of silica on both the nucleation and early growth stages of barium carbonate crystallisation in alkaline media at constant pH. Complementarily, the nature and composition of particles occurring at different times in samples under various conditions were characterised ex situ by means of high-resolution electron microscopy and elemental analysis. The collected data clearly evidence that added silica affects carbonate crystallisation from the very beginning (i.e. already prior to, during, and shortly after nucleation), eventually arresting growth on the nanoscale by cementation of BaCO3 particles within a siliceous matrix. Our findings thus shed light on the fundamental processes driving bottom-up self-organisation in silica-carbonate materials and, for the first time, provide direct experimental proof that silicate species are responsible for the miniaturisation of carbonate crystals during growth of biomorphs, hence confirming previously discussed theoretical models for their formation mechanism.Recent work has demonstrated that the dynamic interplay between silica and carbonate during co-precipitation can result in the self-assembly of unusual, highly complex crystal architectures with morphologies and textures resembling those typically displayed by biogenic minerals. These so-called biomorphs were shown to be composed of uniform elongated carbonate nanoparticles that are arranged according to a specific order over mesoscopic scales. In the present study, we have investigated the circumstances leading to the continuous formation and stabilisation of such well-defined nanometric building units in these inorganic systems. For this purpose, in situ potentiometric titration measurements were carried out in order to monitor and quantify the influence of silica on both the nucleation and early growth stages of barium carbonate crystallisation in alkaline media at constant pH. Complementarily, the nature and composition of particles occurring at different times in samples under various conditions were characterised ex situ by means of high-resolution electron microscopy and elemental analysis. The collected data clearly evidence that added silica affects carbonate crystallisation from the very beginning (i.e. already prior to, during, and shortly after nucleation), eventually arresting growth on the nanoscale by cementation of BaCO3 particles within a siliceous matrix. Our findings thus shed light on the fundamental processes driving bottom-up self-organisation in silica-carbonate materials and, for the first time, provide direct experimental proof that silicate species are responsible for the miniaturisation of carbonate crystals during growth of biomorphs, hence confirming previously discussed theoretical models for their formation mechanism. Electronic supplementary information (ESI) available: Additional titration data (Fig. S1 and S2) and further results from TEM-EDX analyses (Fig. S3-S8). See DOI: 10.1039/c4nr05436a

Coordinated garbage collection for raid array of solid state disks

DOEpatents

Dillow, David A; Ki, Youngjae; Oral, Hakki S; Shipman, Galen M; Wang, Feiyi

2014-04-29

An optimized redundant array of solid state devices may include an array of one or more optimized solid-state devices and a controller coupled to the solid-state devices for managing the solid-state devices. The controller may be configured to globally coordinate the garbage collection activities of each of said optimized solid-state devices, for instance, to minimize the degraded performance time and increase the optimal performance time of the entire array of devices.

Petrological and experimental evidence for differentiation of water-rich magmas beneath St. Kitts, Lesser Antilles

NASA Astrophysics Data System (ADS)

Melekhova, Elena; Blundy, Jon; Martin, Rita; Arculus, Richard; Pichavant, Michel

2017-12-01

St. Kitts lies in the northern Lesser Antilles, a subduction-related intraoceanic volcanic arc known for its magmatic diversity and unusually abundant cognate xenoliths. We combine the geochemistry of xenoliths, melt inclusions and lavas with high pressure-temperature experiments to explore magma differentiation processes beneath St. Kitts. Lavas range from basalt to rhyolite, with predominant andesites and basaltic andesites. Xenoliths, dominated by calcic plagioclase and amphibole, typically in reaction relationship with pyroxenes and olivine, can be divided into plutonic and cumulate varieties based on mineral textures and compositions. Cumulate varieties, formed primarily by the accumulation of liquidus phases, comprise ensembles that represent instantaneous solid compositions from one or more magma batches; plutonic varieties have mineralogy and textures consistent with protracted solidification of magmatic mush. Mineral chemistry in lavas and xenoliths is subtly different. For example, plagioclase with unusually high anorthite content (An≤100) occurs in some plutonic xenoliths, whereas the most calcic plagioclase in cumulate xenoliths and lavas are An97 and An95, respectively. Fluid-saturated, equilibrium crystallisation experiments were performed on a St. Kitts basaltic andesite, with three different fluid compositions ( XH2O = 1.0, 0.66 and 0.33) at 2.4 kbar, 950-1025 °C, and fO2 = NNO - 0.6 to NNO + 1.2 log units. Experiments reproduce lava liquid lines of descent and many xenolith assemblages, but fail to match xenolith and lava phenocryst mineral compositions, notably the very An-rich plagioclase. The strong positive correlation between experimentally determined plagioclase-melt KdCa-Na and dissolved H2O in the melt, together with the occurrence of Al-rich mafic lavas, suggests that parental magmas were water-rich (> 9 wt% H2O) basaltic andesites that crystallised over a wide pressure range (1.5-6 kbar). Comparison of experimental and natural (lava, xenolith) mafic mineral composition reveals that whereas olivine in lavas is predominantly primocrysts precipitated at low-pressure, pyroxenes and spinel are predominantly xenocrysts formed by disaggregation of plutonic mushes. Overall, St. Kitts xenoliths and lavas testify to mid-crustal differentiation of low-MgO basalt and basaltic andesite magmas within a trans-crustal, magmatic mush system. Lower crustal ultramafic cumulates that relate parental low-MgO basalts to primary, mantle -derived melts are absent on St. Kitts.

A review of lithium and non-lithium based solid state batteries

NASA Astrophysics Data System (ADS)

Kim, Joo Gon; Son, Byungrak; Mukherjee, Santanu; Schuppert, Nicholas; Bates, Alex; Kwon, Osung; Choi, Moon Jong; Chung, Hyun Yeol; Park, Sam

2015-05-01

Conventional lithium-ion liquid-electrolyte batteries are widely used in portable electronic equipment such as laptop computers, cell phones, and electric vehicles; however, they have several drawbacks, including expensive sealing agents and inherent hazards of fire and leakages. All solid state batteries utilize solid state electrolytes to overcome the safety issues of liquid electrolytes. Drawbacks for all-solid state lithium-ion batteries include high resistance at ambient temperatures and design intricacies. This paper is a comprehensive review of all aspects of solid state batteries: their design, the materials used, and a detailed literature review of various important advances made in research. The paper exhaustively studies lithium based solid state batteries, as they are the most prevalent, but also considers non-lithium based systems. Non-lithium based solid state batteries are attaining widespread commercial applications, as are also lithium based polymeric solid state electrolytes. Tabular representations and schematic diagrams are provided to underscore the unique characteristics of solid state batteries and their capacity to occupy a niche in the alternative energy sector.

Effects of shock and Martian alteration on Tissint hydrogen isotope ratios and water content

NASA Astrophysics Data System (ADS)

Hallis, L. J.; Huss, G. R.; Nagashima, K.; Taylor, G. J.; Stöffler, D.; Smith, C. L.; Lee, M. R.

2017-03-01

The Tissint meteorite, a picritic shergottite, fell to Earth in Morocco on the 18th of July 2011, and is only the fifth Martian meteorite witnessed to fall. Hydrogen isotope ratios and water contents are variable within different minerals in Tissint. Ringwoodite and shock melt pockets contain elevated D/H ratios relative to terrestrial values (δD = 761-4224‰). These high ratios in recrystallized phases indicate significant implantation of hydrogen from the D-rich Martian atmosphere during shock. In contrast, although olivine has detectable water abundances (230-485 ppm), it exhibits much lower D/H ratios (δD = +88 to -150‰), suggesting this water was not implanted from the Martian atmosphere. The minimal terrestrial weathering experienced by Tissint gives confidence that the olivine-hosted water has a Martian origin, but its high concentration indicates direct inheritance from the parental melt is improbable, especially given the low pressure of olivine crystallisation. Incorporation of a low δD crustal fluid, or deuteric alteration during crystallisation, could explain the relatively high water contents and low D/H ratios in Tissint olivine.

Radiation grafting of various water-soluble monomers on ultra-high molecular weight polyethylene powder. Part II: Thermal, FTIR and morphological characterisation

NASA Astrophysics Data System (ADS)

Aydınlı, Bahattin; Tin c̡er, Teoman

2001-10-01

Radiation induced grafted polyacrylic acid (PAA), polymethacrylic acid (PMAA), polyacrylamide (PAAm), poly N,N-dimethyl acrylamide (PNDAAm) and poly 1-vinyl-2 pyrrolidone (PVP) on ultra-high molecular weight polyethylene (UHMWPE) were characterised by DSC, FTIR and SEM analysis. While the effect of irradiation on pure UHMWPE was found to increase crystallinity and cause higher enthalpy of crystallisation, grafted UHMWPE powders showed lower crystallinity and enthalpy of crystallisation. In all grafted UHMWPE there existed secondary transitions corresponding to grafting polymers in the first run of DSC above 60°C and they became clearer at a higher grafting level. In the second run of DSC some Tg values appeared to shift to higher temperatures while some were not detected. FTIR analysis indicated the presence of water-soluble polymers in the grafted UHMWPE. The characteristic peaks of water-soluble polymers became sharper in the grafted UHMWPE. SEM analysis revealed that the grafting occurs both on fiber and microparticles of UHMWPE while flowing characteristic of powder is retained.

Supramolecular hydrogen-bonding network in 1-(diaminomethylene)thiouron-1-ium 4-hydroxybenzenesulfonate crystal

NASA Astrophysics Data System (ADS)

Perpétuo, Genivaldo J.; Gonçalves, Rafael S.; Janczak, Jan

2015-09-01

The single crystals of 1-(diaminomethylene)thiouron-1-ium 4-hydroxybenzenesulfonate were grown using a solution growth technique. The compound crystallises in the centrosymmetric P21/c space group of the monoclinic system. The conformation of the 1-(diaminomethylene)thiouron-1-ium cation is not strictly planar, but twisted. Both arms of the cation are oppositely rotated by 8.5(1)° around the Csbnd N bonds involving the central N atom. The arrangement of oppositely charged components, i.e. 1-(diaminomethylene)thiouron-1-ium cations and 4-hydroxybenzenesulfonate anions in the crystal is mainly determined by ionic and hydrogen-bonding interactions forming supramolecular network. The possible hydrogen-bonding interactions between cation and anion units were analysed on the basis of molecular orbital calculations. The obtained deuterated analogue crystallises similar as H-compound in the monoclinic system (P21/c) with quite similar lattice parameters. The compound was also characterised by the FT-IR and Raman spectroscopies. The characteristic bands of the functional and skeletal groups of the protiated and deuterated analogue of 1-(diaminomethylene)thiouron-1-ium 4-hydroxybenzenesulfonate are discussed.

Ceramic Electrolyte Membrane Technology: Enabling Revolutionary Electrochemical Energy Storage

DTIC Science & Technology

2015-10-05

ion batteries . Solid-state Li- ion batteries could significantly improve safety and eliminate the need for complex...advancing ceramic electrolyte technology for use in solid-state Li- ion batteries . Solid-state Li- ion batteries could significantly improve safety and...technology for use in solid-state Li- ion batteries and high specific energy Li-S and Li- air batteries . Solid-state Li- ion batteries could

Nature of diffraction fringes originating in the core of core-shell nanoparticle Cu/SiO2 and formation mechanism of the structures

NASA Astrophysics Data System (ADS)

Radnaev, A. R.; Kalashnikov, S. V.; Nomoev, A. V.

2016-05-01

This article is devoted to the analysis of the reasons for the occurrence of diffraction fringes in the cores of the core-shell nanoparticles Cu/SiO2. Moiré and diffraction fringes are observed while studying the nanoparticle cores under a transmission electron microscope. The formation of diffraction fringes is closely connected to the mechanism of nanoparticle formation under study and appears to be its consequence, letting us develop a hypothesis of metastable phase formation in nanoparticle cores. In our opinion, the emergence of diffraction fringes in cores of copper is connected to clasterisation in solid solution oversaturated with silicon α-Cu with the diffused interphase state. Only copper and oxygen (oxygen is presented as oxides in such types of copper as M0 - up to 0.01%; and M1 - up to 0.03%), Copper and silicon with oxygen in a stoichiometric proportion that is only sufficient for silicon dioxide formation (SiO2), Copper and silicon with oxygen in an amount that is sufficient not only for silicon dioxide formation, but also for the dissolution of silicon in the α-Cu solid solution, The amount of silicon in the alloy is not sufficient for the total fixation of oxygen contained in copper, Copper, oxygen and silicon whose contamination is greater than 8 wt.%. In the first case, the top-cut of oxygen in α-Cu solid solution is 0.03% at the temperature of 1066 °C. At slow cooling, secondary recrystallisation leads to the formation of equilibrium Cu2O on the line of the ultimate solubility (Figure 1a - line of maximum solubility of oxygen in copper). In the case of fast cooling fixation of oversaturated, single-phase, non-equilibrium α-Cu, solid solution (heat-treated) takes place, which contains saluted oxygen in an interstice crystal lattice of copper.Room temperature for nonferrous alloys (metals) is sufficient for the diffusive mobility of atoms, but insufficient for the formation of an equilibrium phase and stable phase of Cu2O. This is why diffusion of oxygen atoms in certain areas (clusters) with their increased diffusion of oxygen atoms in certain areas (clusters) with their increased number has been suggested [4]. At the same time, there is a boundary between the stable phase of α-Cu and 'pre-precipitations' containing oxygen, but not having the full value oxide: red copper ore, Cu2O (Figure 1b - solvus of suggested metastable phase). In this case, diffraction fringes can be treated as 'pre-precipitations' in the form of Guinier-Preston zones with diffuse interfaces and a stable α-Cu phase.In the second case, all oxygen and silicon after condensation and crystallisation are fixed in the form of amorphous SiO2 on the core surface of copper. As far as there are no atoms of saluted oxygen or silicon in copper, there are no conditions for the formation of non-equilibrium structures. Consequently, the diffraction pattern of nanoparticle cores is not observed (Figure 2a).In the third case, in the presence of quite a large amount of silicon in the stoichiometric drop, the process of copper oxide formation is not possible, because all the oxygen is used for the production of silicon dioxide since the sensitivity of oxygen to silicon is higher than to copper. This can be explained by the difference in Gibbs energy for the oxidising reaction of components. At the temperature of 25 °C it is 29.0 J/(g mol) - for copper, and 80.8 J/(g mol) for silicon. Silicon dioxide occurring due to the oxygen content in copper will be displaced on the surface of the drop in the form of ash, forming the SiO2 shell [24]. The reason lies in the lower specific density of silicon (approximately 2.2 g/cm3) compared to copper (8.92 g/cm3). This is why, in our case, it is appropriate to study the system where there is no influence of oxygen on the crystallisation of the Cu-Si system [5]. In the cores of such nanoparticles, prominent diffraction fringes can be observed in the α-Cu core (Figure 3b).Analysis of the Cu-Si phase diagram (Figure 3) shows that the maximum solubility of silicon α-Cu at the temperature 552 °C comprises 4.65 wt.% Si. This part of the Cu-Si phase diagram containing up to 8 wt.% silicon represents a classical example of the well-studied phase diagram of Al-Cu components, with the formation of Guinier-Preston zones in the quenched aluminium alloy [25].Single-phase solid solution of silicon α-Cu is fixed at fast cooling in our case. During its formation, cooling and natural ageing of the nanoparticle core, and redistribution of silicon into certain areas, takes place, forming metastable clusters in the matrix with high silicon content. They seem to be 'pre-precipitations' of the γ-phase of copper, though they really are not. In our opinion, diffraction fringes observed in these particles appear to be metastable phases according to Guinier-Preston zone type, i.e. α-Cu area with excessive silicon content.For nonferrous alloys, room temperature is sufficient for diffusive mobility of atoms of the saluted component [19]. Clusters are formed both at the time of cooling and in the long-term process (i.e. natural ageing). Provided that it is not a new phase, but rather the area of the initial matrix α-Cu solid solution enriched with dissolved silicon, such areas may be treated as Guinier-Preston zones. In contrast to intermediate phases with qualitatively new structures, characterised by their own lattices, Guinier-Preston zones have the same lattice as the matrix solution, but are deformed because of the difference in the atomic diameters of the solute and solvent. There is no clear boundary between the zone and solid solution by which it is surrounded. Compared to concentration fluctuations that appear continuously and are diffused by thermal motion, Guinier-Preston zones are stable for a long time (at low temperatures, for an intermediate amount of time). Experiments have shown that, with the increase of ageing duration, zone sizes are also increased. Furthermore, larger zones grow due to dissolution of the smaller ones, i.e. the same way as in coagulation of crystal grains in the solid state (i.e. collective crystallisation) [19]. The number of the zones at the given ageing temperature does not depend on the alloy composition.In some alloys, Guinier-Preston zones appear immediately after heat treatment or even during the cooling after heat treatment. At the same time, intermediate phases and stable phases appear after the incubation interval. All these facts show that Guinier-Preston zones are different to intermediate and stable phases. This is why Guinier-Preston zones are often called 'pre-precipitations' to differentiate them from real precipitations of intermediate and stable phases with a qualitatively new structure [19].Unlike such a structured approach that treats Guinier-Preston zones as 'pre-precipitations' from a thermodynamic point of view, they can be treated as independent stable phases, intermediate between the matrix solution and the stable phase. Consequently, these zones can be treated as the second phase that is in metastable equilibrium with the matrix solution.Moreover, a Guinier-Preston zone in the dual Cu-Si system with limited solubility of silicon in solid state can have its own line limit of solubility km (Figure 3). Metastable phases with a high content of silicon in the α-Cu matrix crystalline lattice appear below this line.Provided that the Guinier-Preston zone is treated as a phase, at the moment of its origin, the change of the free energy of the alloy is as follows: ΔU = -ΔUtot + ΔUsurf + ΔUel (Utot - total energy of the system, Usurf - surface energy of the crystal, Uel - elastic energy component). Because of the coherence property of the zone and the matrix, the ΔUsurf component can be neglected as its value is very small. Then, at relatively high oversaturation, the energy barrier for the origin of the Guinier-Preston zone should be relatively small, which explains the occurrence of clusters immediately after heat treatment or even at the moment of cooling and following natural ageing.The fact that Guinier-Preston zones can easily appear throughout the whole volume of the matrix solid solution and give the structure of equable decay with high density is of high practical value for us (Figure 2b).Thus, diffraction fringes in copper cores of core-shell nanoparticles should be treated as the second metastable phase, which is in equilibrium with the matrix solid solution. Similar to the exfoliation curve km in the solid solution α-Cu, the solvus curve for γ-Cu with intermediate 'pre-precipitations' can be built. The structure of the boundary with the matrix differentiates Guinier-Preston zones from other intermediate phases. These zones are fully coherent extractions, which is why their boundary with the matrix is poorly defined.As the rate accuracy of basal spacing with the method of electronic diffraction does not exceed 1 Å, according to the data it is not possible to evaluate accurately the change dα-Cu in diffraction fringes of the nanoparticle core; phase nonuniformity of structures has been suggested [26]. This is why it is necessary to treat such structures as solid solutions of α-Cu matrix, with the presence of metastable phases with the deformed crystal lattice.In the fourth case, formation of core-shell nanoparticle Cu/SiO2 happens much like in the third case, but due to the fact the amount of silicon is insufficient for the total fixation of oxygen and copper, a transition zone containing Cu2O is formed. Moiré in such particles are observed at the possible placing of double diffraction from two or more crystals of solid solution α-Cu (Figure 4a) [3]. The nanoparticle according to SAED analysis is very much like a 'sandwich': core α-Cu (Figure 4b, basal spacing d(111) ≈ 2.0 Å, corresponding to the tabular data for Cu), transition zone - copper oxide Cu2O (Figure 5a, basal spacing d(111) ≈ 2.4 Å) and shell - amorphous silicon dioxide, according to the EDAX data, the content of oxygen in this area is greater than 12% [11]. High copper oxide (CuO) was discovered only on the surface of the nanoparticle shell SiO2 (Figure 5b, basal spacing d(111) ≈ 2.5 Å).In the fifth case, when the silicon content is from 8.3-8.5 wt.% to 13 wt.%, copper with silicon in solid state at room temperature forms a continuous series of solid solutions of copper α, γ, ɛ and η. Silicon containing more than 13 wt.% copper undergoes eutectic decomposition only at (η″ + Si) [5]; structurally, such a solution contains eutectics in eutectics. In the obtained powder of nanoparticles, there are no modifications of solid solutions of copper, except for α-Cu.

Syntheses, spectroscopic characterization, crystal structure and natural rubber vulcanization activity of new disulfides derived from sulfonyldithiocarbimates

NASA Astrophysics Data System (ADS)

Alves, Leandro de Carvalho; Rubinger, Mayura Marques Magalhães; Tavares, Eder do Couto; Janczak, Jan; Pacheco, Elen Beatriz Acordi Vasques; Visconte, Leila Lea Yuan; Oliveira, Marcelo Ribeiro Leite

2013-09-01

The compounds (Bu4N)2[(4-RC6H4SO2NCS2)2] [Bu4N = tetrabutylammonium cation; R = H (1), F (2), Cl (3) and Br (4)] and (Ph4P)2[(4-RC6H4SO2NCS2)2]ṡH2O [Ph4P = tetraphenylphosphonium cation and R = I (5)] were synthesized by the reaction of the potassium dithiocarbimates (4-RC6H4SO2NCS2K2ṡ2H2O) with I2 and Bu4NBr or Ph4PCl. The IR data were consistent with the formation of the dithiocarbimatodisulfides anions. The NMR spectra showed the expected signals for the cations and anions in a 2:1 proportion. The structures of compounds 1-5 were determined by the single crystal X-ray diffraction. The compounds 2, 3 and 4 are isostructural and crystallise in the centrosymmetric space group C2/c of the monoclinic system. Compound 1 crystallises in the monoclinic system in the space group of P21/n and the compound 5 crystallises in the centrosymmetric space group P-1 of the triclinic system. The complex anions of compounds 2, 3 and 4 exhibit similar conformations having twofold symmetry, while in 1 and 5 the anions exhibit C1 symmetry. The activity of the new compounds in the vulcanization of the natural rubber was evaluated and compared to the commercial accelerators ZDMC, TBBS and TMTD. These studies confirm that the sulfonyldithiocarbimato disulfides anions are new vulcanization accelerators, being slower than the commercial accelerators, but producing a greater degree of crosslinking, and scorch time values compatible with good processing safety for industrial applications. The mechanical properties, stress and tear resistances were determined and compared to those obtained with the commercial accelerators.

Thermobarometry of Whangarei volcanic field lavas, New Zealand: Constraints on plumbing systems of small monogenetic basalt volcanoes

NASA Astrophysics Data System (ADS)

Shane, Phil; Coote, Alisha

2018-04-01

The intra-plate, basaltic Whangarei volcanic field (WVF) is a little-studied cluster of Quaternary monogenetic volcanoes in northern New Zealand. Clinopyroxene-melt equilibria provides an insight to the ascent and storage of the magmas that is not evident from whole-rock-scale geochemistry. Basalts from two of the younger volcanoes contain a population of equilibrium and disequilibrium clinopyroxene phenocrysts. Many of the crystals are resorbed, and are characterised by diffuse, patchy zoning, and low MgO (Mg#70-80) and Cr2O3 contents. Such crystals also occur as relic cores in other phenocrysts. These grew in a magma that was more evolved than that of the host rock composition. Equilibrium clinopyroxenes are enriched in MgO (Mg#83-88) and Cr2O3 ( 0.4-0.9 wt%), and occur as reverse-zoned crystals, and rim/mantle overgrowths on relic cores of other crystals. These crystals and rim/mantles zones nucleated in magma with a composition similar to that of the host rock. The textural relationships demonstrate that a mafic magma intruded a more silicic resident magma, resulting in crystal-exchange and entrainment of antecrysts. Clinopyroxene-melt equilibria indicate that the crystallisation occurred at temperatures in the range 1135-1195 °C, and pressures in the range 290-680 MPa. The dominant pressure mode (400-550 MPa) equates to depths of about 15-19 km which coincides with a present-day body of partial melt in the crust. Higher pressures indicated by subordinate crystal populations indicate staged ascent and crystallisation above the Moho ( 26 km depth). Thus, the magmatic system is envisaged as a crystal mush column through the lower and mid crust. Such crystallisation histories are perhaps not expected in low flux, monogenetic magma systems, and reflect the importance of the crustal density structure beneath the volcanoes. Future activity could be preceded by seismic events in the lower crust as the magmas intrude localised crystal mush bodies.

Neuroanatomical Correlates of Intelligence in Healthy Young Adults: The Role of Basal Ganglia Volume

PubMed Central

Rhein, Cosima; Mühle, Christiane; Richter-Schmidinger, Tanja; Alexopoulos, Panagiotis; Doerfler, Arnd; Kornhuber, Johannes

2014-01-01

Background In neuropsychiatric diseases with basal ganglia involvement, higher cognitive functions are often impaired. In this exploratory study, we examined healthy young adults to gain detailed insight into the relationship between basal ganglia volume and cognitive abilities under non-pathological conditions. Methodology/Principal Findings We investigated 137 healthy adults that were between the ages of 21 and 35 years with similar educational backgrounds. Magnetic resonance imaging (MRI) was performed, and volumes of basal ganglia nuclei in both hemispheres were calculated using FreeSurfer software. The cognitive assessment consisted of verbal, numeric and figural aspects of intelligence for either the fluid or the crystallised intelligence factor using the intelligence test Intelligenz-Struktur-Test (I-S-T 2000 R). Our data revealed significant correlations of the caudate nucleus and pallidum volumes with figural and numeric aspects of intelligence, but not with verbal intelligence. Interestingly, figural intelligence associations were dependent on sex and intelligence factor; in females, the pallidum volumes were correlated with crystallised figural intelligence (r = 0.372, p = 0.01), whereas in males, the caudate volumes were correlated with fluid figural intelligence (r = 0.507, p = 0.01). Numeric intelligence was correlated with right-lateralised caudate nucleus volumes for both females and males, but only for crystallised intelligence (r = 0.306, p = 0.04 and r = 0.459, p = 0.04, respectively). The associations were not mediated by prefrontal cortical subfield volumes when controlling with partial correlation analyses. Conclusions/Significance The findings of our exploratory analysis indicate that figural and numeric intelligence aspects, but not verbal aspects, are strongly associated with basal ganglia volumes. Unlike numeric intelligence, the type of figural intelligence appears to be related to distinct basal ganglia nuclei in a sex-specific manner. Subcortical brain structures thus may contribute substantially to cognitive performance. PMID:24699871

Effects of Nutritional Interventions during Pregnancy on Infant and Child Cognitive Outcomes: A Systematic Review and Meta-Analysis

PubMed Central

Taylor, Rachael M.; Fealy, Shanna M.; Bisquera, Alessandra; Smith, Roger; Collins, Clare E.; Evans, Tiffany-Jane

2017-01-01

Background: Epidemiological studies have demonstrated that folate, iodine and iron intake during pregnancy impacts on foetal brain development and cognitive function. However, in human studies, the relationship with other dietary nutrients is less clear. Objective: This systematic review aims to critically appraise the current literature and meta-analyses results from nutritional interventions during pregnancy that aimed to optimise infant and child cognitive outcomes. Design: Ten electronic databases were searched for articles published up to August 2017. The search was limited to articles published in English. Randomised controlled trials (RCTs) testing the impact of any nutritional intervention (dietary counselling, education, nutrient supplementation, fortified foods and/or foods) during pregnancy on cognitive outcomes of children (<10 years old). Two independent reviewers assessed study eligibility and quality using the American Dietetic Association quality criteria checklist for primary research. Standardised mean differences were used for nine cognitive domains to measure effects for meta-analyses. Results: A total of 34 RCTs were included (21 studies included children aged less than 35 months, 10 studies included children aged 36–60 months and 3 studies included children aged 61–119 months). The types of nutritional interventions included nutrient supplements, whole foods, fortified foods and nutrition education. The following nine cognition outcomes: attention, behaviour, crystallised intelligence, fluid intelligence, global cognition, memory, motor skills, visual processing, and problem solving were not significantly impacted by nutritional interventions, although 65% of studies conducted post-hoc data analyses and were likely to be underpowered. Although, long chain polyunsaturated fatty acids (LCPUFA) supplementation was associated with a marginal increase in crystallised intelligence (Effect size (ES): 0.25; 95% confidence interval (95% CI): −0.04, 0.53), the effect was not statistically significant (p = 0.09), with significant study heterogeneity (p = 0.00). Conclusions: LCPUFA supplementation may be associated with an improvement in child crystallised intelligence, however further research is warranted. The remaining eight cognition domains were not significantly impacted by maternal nutritional interventions. PMID:29156647

Ar-Ar dating and petrogenesis of the Early Miocene Taşkapı-Mecitli (Erciş-Van) granitoid, Eastern Anatolia Collisional Zone, Turkey

NASA Astrophysics Data System (ADS)

Oyan, Vural

2018-06-01

The Early Miocene Taşkapı-Mecitli granitoid that is located in the northern section of the Eastern Anatolia Collision Zone has typical I-type, metaluminous and calk-alkaline characteristics. It also contains mafic microgranular / magmatic enclaves (MMEs). New Ar-Ar dating results show that the age of the Taşkapı-Mecitli granitoid is ∼23 Ma and it crystallised in the Early Miocene, in contrast to its previously known Cretaceous age. Identical crystallisation ages (∼23 Ma), similar mineral assemblages and geochemical compositions, and indistinguishable isotopic compositions of MMEs and host rocks imply that the MMEs are most consistent with a cumulate origin formed at earlier stages of the same magmatic system that produced the Taşkapı-Mecitli granitoid. MELTS modelling suggests that magma of the Taşkapı-Mecitli granitoid was the result of fractionation under a crustal pressure of 4 kbar, with a H2O content of 1.5%. EC-AFC model calculation reveals that the Taşkapı-Mecitli granitoid includes from 0.5% to 2% crustal assimilation rates. These rates indicate that crustal contamination can be negligible when compared to fractional crystallisation in the evolution of the magma beneath the Taşkapı-Mecitli granitoid. The partial melting model calculations and MORB-normalised trace element concentrations of the least evolved samples of the Taşkapı-Mecitli granitoid are consistent with those of mafic melts obtained from partial melting of interacting mantle- lower crust with a melting degree of 18%. The age (23 Ma) of the post- or syn-collisional Taşkapı-Mecitli granitoid suggests that the collision between Arabian and Eurasian plates could be before/around ∼23 Ma (Late Oligocene to Early Miocene).

A laboratory study of the nucleation kinetics of nitric acid hydrates under stratospheric conditions

NASA Astrophysics Data System (ADS)

James, Alexander D.; Murray, Benjamin J.; Plane, John M. C.

2016-04-01

Measurements of the kinetics of crystallisation of ternary H2O-H2SO4-HNO3 mixtures to produce nitric acid hydrate phases, as occurs in the lower stratosphere, have been a long-standing challenge for investigators in the laboratory. Understanding polar stratospheric chlorine chemistry and thereby ozone depletion is increasingly limited by descriptions of nucleation processes. Meteoric smoke particles have been considered in the past as heterogeneous nuclei, however recent studies suggest that these particles will largely dissolve, leaving mainly silica and alumina as solid inclusions. In this study the nucleation kinetics of nitric acid hydrate phases have been measured in microliter droplets at polar stratospheric cloud (PSC) temperatures, using a droplet freezing assay. A clear heterogeneous effect was observed when silica particles were added. A parameterisation based on the number of droplets activated per nuclei surface area (ns) has been developed and compared to global model data. Nucleation experiments on identical droplets have been performed in an X-Ray Diffractometer (XRD) to determine the nature of the phase which formed. β-Nitric Acid Trihydrate (NAT) was observed alongside a mixture of Nitric Acid Dihydrate (NAD) phases. It is not possible to determine whether NAT nucleates directly or is formed by a phase transition from NAD (likely requiring the presence of a mediating liquid phase). Regardless, these results demonstrate the possibility of forming NAT on laboratory timescales. In the polar stratosphere, sulfuric acid (present at several weight percent of the liquid under equilibrium conditions) could provide such a liquid phase. This study therefor provides insight into previous discrepancies between phases formed in the laboratory and those observed in the atmosphere. It also provides a basis for future studies into atmospheric nucleation of solid PSCs.

Packaging of solid state devices

DOEpatents

Glidden, Steven C.; Sanders, Howard D.

2006-01-03

A package for one or more solid state devices in a single module that allows for operation at high voltage, high current, or both high voltage and high current. Low thermal resistance between the solid state devices and an exterior of the package and matched coefficient of thermal expansion between the solid state devices and the materials used in packaging enables high power operation. The solid state devices are soldered between two layers of ceramic with metal traces that interconnect the devices and external contacts. This approach provides a simple method for assembling and encapsulating high power solid state devices.

Successive mixing and mingling of magmas in a plutonic complex of Northeast Brazil

NASA Astrophysics Data System (ADS)

Neves, S. P.; Vauchez, A.

1995-02-01

Field and petrographic evidence together with major element geochemistry suggest that mixing and mingling of magmas of contrasting compositions were important petrogenetic processes in the Fazenda Nova/Serra da Japeganga plutonic complex of Northeast Brazil. The complex was emplaced at pressures of 300-500 MPa in amphibolite facies metamorphic rocks of Neoproterozoic age and consists of three main rock types: (1) coarse-grained granite; (2) porphyritic granite and (3) diorite to quartz-monzodiorite. The latter two make up the Fazenda Nova batholith which is located on the northwestern side of the sinistral, NE-trending, Fazenda Nova strike-slip shear zone. NE-plunging stretching lineations in the shear zone suggest that this batholith represents an uplifted, and therefore deeper, portion of the complex. The structure of the complex reflects the stratigraphy in a magma chamber, with the porphyritic granite above the diorite and below the coarse-grained granite. The porphyritic granite has a uniform composition, intermediate in mafic mineral content, quartz, and majorelements between the coarse-grained granite and the diorite. It is free of disequilibrium mineral assemblages, and locally displays gradational contacts with the overlain coarse-grained granite. Most elements display linear correlation with SiO 2 in Harker diagrams. These features are interpreted as resulting from mixing of almost crystal-free felsic and intermediate magmas. Fluid dynamic calculations using the coarse-grained granite and the silica-poorest diorite as end-members in the mixing process show that mechanical mixing was possible, and thermal modelling suggests that the formation of an homogeneous hybrid may have been achieved in less than 50,000 yr. The diorites contain corroded K-feldspar megacrysts, and range in composition from low to relatively high silica contents, partly overlapping with the porphyritic granite. This suggests that a new mixing event occurred during the crystallisation of the porphyritic granite, this time producing a heterogeneous, xenocryst-bearing, dioritic hybrid. Abundant enclaves of diorite in the porphyritic granite, despite their textural diversity, are typically devoid of chilled margins, and were therefore formed relatively early in the crystallisation history of the granite. They are interpreted as liquid droplets separated from the heterogeneous hybrid magma through convection currents and incorporated in the, crystallising granitic magma. Subsequently, during the crystallisation of the porphyritic granite, mafic magma supply to the batholith continued at a declining rate, probably assisted by the development of the Fazenda Nova shear zone. This leads to the production of stromatitic-like structures, with alternating bands of mutually contaminated granite and diorite, then to the intrusion of contorted synplutonic dykes, and, finally, of late-stage dykes, some of which with chilled finer-grained margins.

Solid state recorders for airborne reconnaissance

NASA Astrophysics Data System (ADS)

Klang, Mark R.

2003-08-01

Solid state recorders have become the recorder of choice for meeting airborne ruggedized requirements for reconnaissance and flight test. The cost of solid state recorders have decreased over the past few years that they are now less expense than the traditional high speed tape recorders. CALCULEX, Inc manufactures solid state recorders called MONSSTR (Modular Non-volatile Solid State Recorder). MONSSTR is being used on many different platforms such as F/A-22, Global Hawk, F-14, F-15, F-16, U-2, RF-4, and Tornado. This paper will discuss the advantages of using solid state recorders to meet the airborne reconnaissance requirement and the ability to record instrumentation data. The CALCULEX recorder has the ability to record sensor data and flight test data in the same chassis. This is an important feature because it eliminates additional boxes on the aircraft. The major advantages to using a solid state recorder include; reliability, small size, light weight, and power. Solid state recorders also have a larger storage capacity and higher bandwidth capability than other recording devices.

The solid-state terahertz spectrum of MDMA (Ecstasy) - A unique test for molecular modeling assignments

NASA Astrophysics Data System (ADS)

Allis, Damian G.; Hakey, Patrick M.; Korter, Timothy M.

2008-10-01

The terahertz (THz, far-infrared) spectrum of 3,4-methylene-dioxymethamphetamine hydrochloride (Ecstasy) is simulated using solid-state density functional theory. While a previously reported isolated-molecule calculation is noteworthy for the precision of its solid-state THz reproduction, the solid-state calculation predicts that the isolated-molecule modes account for only half of the spectral features in the THz region, with the remaining structure arising from lattice vibrations that cannot be predicted without solid-state molecular modeling. The molecular origins of the internal mode contributions to the solid-state THz spectrum, as well as the proper consideration of the protonation state of the molecule, are also considered.

Intelligence and Personality as Predictors of Divergent Thinking: The Role of General, Fluid and Crystallised Intelligence

ERIC Educational Resources Information Center

Batey, Mark; Chamorro-Premuzic, Tomas; Furnham, Adrian

2009-01-01

Two studies examined the relationships between measures of intelligence, personality and divergent thinking (DT) in student samples. Study one investigated the incremental validity of measures of IQ and fluid intelligence with the Big Five Personality Inventory with regards to DT. Significant relationships of DT to fluid intelligence, Extraversion…

Proofreading as an Index of Crystallised Intelligence

ERIC Educational Resources Information Center

Furnham, Adrian

2010-01-01

This paper reports on four studies that were all concerned with cognitive and non-cognitive correlates of proofreading (PR) ability. A new, five-minute PR test was devised and piloted. In the first pilot study (N = 191) it was correlated with a verbal reasoning test. In the second study (N = 103) PR scores were regressed onto measures of…

Solid state lighting devices and methods with rotary cooling structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koplow, Jeffrey P.

Solid state lighting devices and methods for heat dissipation with rotary cooling structures are described. An example solid state lighting device includes a solid state light source, a rotating heat transfer structure in thermal contact with the solid state light source, and a mounting assembly having a stationary portion. The mounting assembly may be rotatably coupled to the heat transfer structure such that at least a portion of the mounting assembly remains stationary while the heat transfer structure is rotating. Examples of methods for dissipating heat from electrical devices, such as solid state lighting sources are also described. Heat dissipationmore » methods may include providing electrical power to a solid state light source mounted to and in thermal contact with a heat transfer structure, and rotating the heat transfer structure through a surrounding medium.« less

Architecture and method for a burst buffer using flash technology

DOEpatents

Tzelnic, Percy; Faibish, Sorin; Gupta, Uday K.; Bent, John; Grider, Gary Alan; Chen, Hsing-bung

2016-03-15

A parallel supercomputing cluster includes compute nodes interconnected in a mesh of data links for executing an MPI job, and solid-state storage nodes each linked to a respective group of the compute nodes for receiving checkpoint data from the respective compute nodes, and magnetic disk storage linked to each of the solid-state storage nodes for asynchronous migration of the checkpoint data from the solid-state storage nodes to the magnetic disk storage. Each solid-state storage node presents a file system interface to the MPI job, and multiple MPI processes of the MPI job write the checkpoint data to a shared file in the solid-state storage in a strided fashion, and the solid-state storage node asynchronously migrates the checkpoint data from the shared file in the solid-state storage to the magnetic disk storage and writes the checkpoint data to the magnetic disk storage in a sequential fashion.

Heterogeneous uptake of ammonia and dimethylamine into sulfuric and oxalic acid particles

NASA Astrophysics Data System (ADS)

Sauerwein, Meike; Keung Chan, Chak

2017-05-01

Heterogeneous uptake is one of the major mechanisms governing the amounts of short-chain alkylamines and ammonia (NH3) in atmospheric particles. Molar ratios of aminium to ammonium ions detected in ambient aerosols often exceed typical gas phase ratios. The present study investigated the simultaneous uptake of dimethylamine (DMA) and NH3 into sulfuric and oxalic acid particles at gaseous DMA / NH3 molar ratios of 0.1 and 0.5 at 10, 50 and 70 % relative humidity (RH). Single-gas uptake and co-uptake were conducted under identical conditions and compared. Results show that the particulate dimethyl-aminium/ammonium molar ratios (DMAH / NH4) changed substantially during the uptake process, which was severely influenced by the extent of neutralisation and the particle phase state. In general, DMA uptake and NH3 uptake into concentrated H2SO4 droplets were initially similarly efficient, yielding DMAH / NH4 ratios that were similar to DMA / NH3 ratios. As the co-uptake continued, the DMAH / NH4 gradually dropped due to a preferential uptake of NH3 into partially neutralised acidic droplets. At 50 % RH, once the sulfate droplets were neutralised, the stronger base DMA displaced some of the ammonium absorbed earlier, leading to DMAH / NH4 ratios up to four times higher than the corresponding gas phase ratios. However, at 10 % RH, crystallisation of partially neutralised sulfate particles prevented further DMA uptake, while NH3 uptake continued and displaced DMAH+, forming almost pure ammonium sulfate. Displacement of DMAH+ by NH3 has also been observed in neutralised, solid oxalate particles. The results can explain why DMAH / NH4 ratios in ambient liquid aerosols can be larger than DMA / NH3, despite an excess of NH3 in the gas phase. An uptake of DMA to aerosols consisting of crystalline ammonium salts, however, is unlikely, even at comparable DMA and NH3 gas phase concentrations.

Review—Practical Challenges Hindering the Development of Solid State Li Ion Batteries

DOE PAGES

Kerman, Kian; Luntz, Alan; Viswanathan, Venkatasubramanian; ...

2017-06-09

Solid state electrolyte systems boasting Li+ conductivity of >10 mS cm -1 at room temperature have opened the potential for developing a solid state battery with power and energy densities that are competitive with conventional liquid electrolyte systems. The primary focus of this review is twofold. First, differences in Li penetration resistance in solid state systems are discussed, and kinetic limitations of the solid state interface are highlighted. Second, technological challenges associated with processing such systems in relevant form factors are elucidated, and architectures needed for cell level devices in the context of product development are reviewed. Specific research vectorsmore » that provide high value to advancing solid state batteries are outlined and discussed.« less

Solid state division progress report, period ending February 29, 1980

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1980-09-01

Research is reported concerning theoretical solid state physics; surface and near-surface properties of solids; defects in solids; transport properties of solids; neutron scattering; crystal growth and characterization; and isotope research materials.

Two chain gallium fluorodiphosphates: synthesis, structure solution, and their transient presence during the hydrothermal crystallisation of a microporous gallium fluorophosphate.

PubMed

Millange, Franck; Walton, Richard I; Guillou, Nathalie; Loiseau, Thierry; O'Hare, Dermot; Férey, Gérard

2002-04-21

Two novel gallium fluorodiphosphates have been isolated and their structures solved ab initio from powder X-ray diffraction data; the materials readily interconvert under hydrothermal conditions, and are metastable with respect to an open-framework zeolitic gallium fluorophosphate, during the synthesis of which they are present as transient intermediates.

Ball-free mechanochemistry: in situ real-time monitoring of pharmaceutical co-crystal formation by resonant acoustic mixing.

PubMed

Michalchuk, Adam A L; Hope, Karl S; Kennedy, Stuart R; Blanco, Maria V; Boldyreva, Elena V; Pulham, Colin R

2018-04-17

Resonant acoustic mixing (RAM) is a new technology designed for intensive mixing of powders that offers the capability to process powders with minimal damage to particles. This feature is particularly important for mixing impact-sensitive materials such as explosives and propellants. While the RAM technique has been extensively employed for the mixing of powders and viscous polymers, comparatively little is known about its use for mechanosynthesis. We present here the first in situ study of RAM-induced co-crystallisation monitored using synchrotron X-ray powder diffraction. The phase profile of the reaction between nicotinamide and carbamazepine in the presence of a small amount of water was monitored at two different relative accelerations of the mixer. In marked contrast to ball-milling techniques, the lack of milling bodies in the RAM experiment does not hinder co-crystallisation of the two starting materials, which occurred readily and was independent of the frequency of oscillation. The reaction could be optimised by enhancing the number of reactive contacts through mixing and comminution. These observations provide new insight into the role of various experimental parameters in conventional mechanochemistry using liquid-assisted grinding techniques.

Carotid disease at age 73 and cognitive change from age 70 to 76 years: A longitudinal cohort study

PubMed Central

Allerhand, Michael; Eadie, Elizabeth; Thomas, Avril; Corley, Janey; Pattie, Alison; Taylor, Adele; Shenkin, Susan D; Cox, Simon; Gow, Alan; Starr, John M; Deary, Ian J

2016-01-01

Cognitive decline and carotid artery atheroma are common at older ages. In community-dwelling subjects, we assessed cognition at ages 70, 73 and 76 and carotid Doppler ultrasound at age 73, to determine whether carotid stenosis was related to cognitive decline. We used latent growth curve models to examine associations between four carotid measures (internal carotid artery stenosis, velocity, pulsatility and resistivity indices) and four cognitive ability domains (memory, visuospatial function, crystallised intelligence, processing speed) adjusted for cognitive ability at age 11, current age, gender and vascular risk factors. Amongst 866 participants, carotid stenosis (median 12.96%) was not associated with cognitive abilities at age 70 or cognitive decline from age 70 to 76. Increased ICA pulsatility and resistivity indices were associated with slower processing speed (both P < 0.001) and worse visuospatial function (P = 0.036, 0.031, respectively) at age 70, and declining crystallised intelligence from ages 70 to 76 (P = 0.008, 0.006, respectively). The findings suggest that vascular stiffening, rather than carotid luminal narrowing, adversely influences cognitive ageing and provides a potential target for ameliorating age-related cognitive decline. PMID:28155579

Carotid disease at age 73 and cognitive change from age 70 to 76 years: A longitudinal cohort study.

PubMed

Wardlaw, Joanna M; Allerhand, Michael; Eadie, Elizabeth; Thomas, Avril; Corley, Janey; Pattie, Alison; Taylor, Adele; Shenkin, Susan D; Cox, Simon; Gow, Alan; Starr, John M; Deary, Ian J

2017-08-01

Cognitive decline and carotid artery atheroma are common at older ages. In community-dwelling subjects, we assessed cognition at ages 70, 73 and 76 and carotid Doppler ultrasound at age 73, to determine whether carotid stenosis was related to cognitive decline. We used latent growth curve models to examine associations between four carotid measures (internal carotid artery stenosis, velocity, pulsatility and resistivity indices) and four cognitive ability domains (memory, visuospatial function, crystallised intelligence, processing speed) adjusted for cognitive ability at age 11, current age, gender and vascular risk factors. Amongst 866 participants, carotid stenosis (median 12.96%) was not associated with cognitive abilities at age 70 or cognitive decline from age 70 to 76. Increased ICA pulsatility and resistivity indices were associated with slower processing speed (both P < 0.001) and worse visuospatial function ( P = 0.036, 0.031, respectively) at age 70, and declining crystallised intelligence from ages 70 to 76 ( P = 0.008, 0.006, respectively). The findings suggest that vascular stiffening, rather than carotid luminal narrowing, adversely influences cognitive ageing and provides a potential target for ameliorating age-related cognitive decline.

Reaction pathways towards the formation of dolomite-analogues at ambient conditions

NASA Astrophysics Data System (ADS)

Pimentel, Carlos; Pina, Carlos M.

2016-04-01

In this paper we present results of a study of the crystallisation behaviour of the dolomite-analogues norsethite and PbMg(CO3)2 at room temperature and atmospheric pressure. Whereas precipitation of norsethite was previously obtained by mixing solutions (Hood et al., 1974; Pimentel and Pina, 2014a,b), we report, for the first time, the synthesis of PbMg(CO3)2 by using the same method. The formation of both phases was promoted by ageing slurries for periods of time ranging from a few days (norsethite) up to 6 months (PbMg(CO3)2). The crystallisation of both norsethite and PbMg(CO3)2 occurs by sequences of dissolution-precipitation reactions involving several amorphous and crystalline precursor phases, which were identified and characterised by X-ray diffraction and scanning electron microscopy. Depending on the initial composition and Ba:Mg and Pb:Mg ratios in the slurries, different precursors and reaction kinetics were observed. This demonstrates the existence of different reaction pathways towards the formation of the investigated dolomite-analogues. Our experimental results provide new insights into the possible mechanisms of formation of dolomite and other double carbonates in nature.

Solid-state modeling of the terahertz spectrum of the high explosive HMX.

PubMed

Allis, Damian G; Prokhorova, Darya A; Korter, Timothy M

2006-02-09

The experimental solid-state terahertz (THz) spectrum (3-120 cm(-1)) of the beta-crystal form of the high explosive octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) has been analyzed using solid-state density functional theory calculations. Various density functionals (both generalized gradient approximation and local density approximation) are compared in terms of their abilities to reproduce the experimentally observed solid-state structure and low-frequency vibrational motions. Good-to-excellent agreement between solid-state theory and experiment can be achieved in the THz region where isolated-molecule calculations fail to reproduce the observed spectral features, demonstrating a clear limitation of using isolated-molecule calculations for the assignment of THz frequency motions in molecular solids. The deficiency of isolated-molecule calculations is traced to modification of the molecular structure in the solid state through crystal packing effects and the formation of weak C-H...O hydrogen bonds.

Optofluidic devices with integrated solid-state nanopores

PubMed Central

Hawkins, Aaron R.; Schmidt, Holger

2016-01-01

This review (with 90 refs.) covers the state of the art in optofluidic devices with integrated solid-state nanopores for use in detection and sensing. Following an introduction into principles of optofluidics and solid-state nanopore technology, we discuss features of solid-state nanopore based assays using optofluidics. This includes the incorporation of solid-state nanopores into optofluidic platforms based on liquid-core anti-resonant reflecting optical waveguides (ARROWs), methods for their fabrication, aspects of single particle detection and particle manipulation. We then describe the new functionalities provided by solid-state nanopores integrated into optofluidic chips, in particular acting as smart gates for correlated electro-optical detection and discrimination of nanoparticles. This enables the identification of viruses and λ-DNA, particle trajectory simulations, enhancing sensitivity by tuning the shape of nanopores. The review concludes with a summary and an outlook. PMID:27046940

26Al- 26Mg dating of asteroidal magmatism in the young Solar System

NASA Astrophysics Data System (ADS)

Schiller, Martin; Baker, Joel A.; Bizzarro, Martin

2010-08-01

We present high-precision Mg isotope data for most classes of basaltic meteorites including eucrites, mesosiderite silicate clasts, angrites and the ungrouped Northwest Africa (NWA) 2976 measured by pseudo-high-resolution multiple-collector inductively coupled plasma mass spectrometry and utilising improved techniques for chemical purification of Mg. With the exception of the angrites Angra dos Reis, Lewis Cliff (LEW) 86010, NWA 1296 and NWA 2999 and the diogenite Bilanga, which have either been shown to have young ages by other dating techniques or have low Al/Mg ratios, all bulk samples of basaltic meteorites have 26Mg excesses ( δ26Mg=+0.0135 to +0.0392‰). The 26Mg excesses cannot be explained by analytical artefacts, cosmogenic effects or heterogeneity of initial 26Al/ 27Al, Al/Mg ratios or Mg isotopes in asteroidal parent bodies as compared to Earth or chondrites. The 26Mg excesses record asteroidal melting and formation of basaltic magmas with super-chondritic Al/Mg and confirm that radioactive decay of short-lived 26Al was the primary heat source that melted planetesimals. Model 26Al- 26Mg ages for magmatism on the eucrite/mesosiderite, angrite and NWA 2976 parent bodies are 2.6-3.2, 3.9-4.1 and 3.5 Myr, respectively, after formation of calcium-aluminium-rich inclusions (CAIs). However, the validity of these model ages depends on whether the elevated Al/Mg ratios of basaltic meteorites result from magma ocean evolution on asteroids through fractional crystallisation or directly during partial melting. Mineral isochrons for the angrites Sahara (Sah) 99555 and D'Orbigny, and NWA 2976, yield ages of 5.06-0.05+0.06Myr and 4.86-0.09+0.10Myr, respectively, after CAI formation. Both isochrons have elevated initial δ26Mg values. Given the brecciated and equilibrated texture of NWA 2976 it is probable that its isochron age and elevated initial δ26Mg(+0.0175±0.0034‰) reflects thermal resetting during an impact event and slow cooling on its parent body. However, in the case of the angrites the marginally elevated initial δ26Mg(+0.0068±0.0058‰) may reflect either δ26Mg ingrowth in a magma ocean prior to eruption and crystallisation or in an older igneous protolith with super-chondritic Al/Mg prior to impact melting and crystallisation of these angrites, or partial internal re-equilibration of Mg isotopes after crystallisation. 26Al- 26Mg model ages and an olivine + pyroxene + whole rock isochron for the angrites Sah 99555 and D'Orbigny are in good agreement with age constraints from 53Mn- 53Cr and 182Hf- 182W short-lived chronometers, suggesting that the 26Al- 26Mg feldspar-controlled isochron ages for these angrites may be compromised by the partial resetting of feldspar Mg isotope systematics. Even when age constraints from the 26Al- 26Mg angrite model ages or the mafic mineral + whole rock isochron are considered, the relative time difference between Sah 99555/D'Orbigny crystallisation and CAI formation cannot be reconciled with Pb-Pb ages for Sah 99555/D'Orbigny and CAIs, which are ca. 1.0 Myr too old (angrites) or too young (CAIs) for reasons that are not clear. This discrepancy might indicate that 26Al was markedly lower (ca. 40%) in the planetesimal- and planet-forming regions of the proto-planetary disc as compared to CAIs, or that CAI Pb-Pb ages may not accurately date CAI formation, which might be better dated by the 182Hf- 182W and 26Al- 26Mg chronometers as 4568.3±0.7 (Burkhardt et al., 2008) and 4568.5±0.3Ma (herein), respectively, when mapped onto an absolute timescale using Pb-Pb ages for angrites.

First principles study on electrochemical and chemical stability of solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries

DOE PAGES

Zhu, Yizhou; He, Xingfeng; Mo, Yifei

2015-12-11

All-solid-state Li-ion batteries based on ceramic solid electrolyte materials are a promising next-generation energy storage technology with high energy density and enhanced cycle life. The poor interfacial conductance is one of the key limitations in enabling all-solid-state Li-ion batteries. However, the origin of this poor conductance has not been understood, and there is limited knowledge about the solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries. In this paper, we performed first principles calculations to evaluate the thermodynamics of the interfaces between solid electrolyte and electrode materials and to identify the chemical and electrochemical stabilities of these interfaces. Our computation results revealmore » that many solid electrolyte–electrode interfaces have limited chemical and electrochemical stability, and that the formation of interphase layers is thermodynamically favorable at these interfaces. These formed interphase layers with different properties significantly affect the electrochemical performance of all-solid-state Li-ion batteries. The mechanisms of applying interfacial coating layers to stabilize the interface and to reduce interfacial resistance are illustrated by our computation. This study demonstrates a computational scheme to evaluate the chemical and electrochemical stability of heterogeneous solid interfaces. Finally, the enhanced understanding of the interfacial phenomena provides the strategies of interface engineering to improve performances of all-solid-state Li-ion batteries.« less

An extrapolation scheme for solid-state NMR chemical shift calculations

NASA Astrophysics Data System (ADS)

Nakajima, Takahito

2017-06-01

Conventional quantum chemical and solid-state physical approaches include several problems to accurately calculate solid-state nuclear magnetic resonance (NMR) properties. We propose a reliable computational scheme for solid-state NMR chemical shifts using an extrapolation scheme that retains the advantages of these approaches but reduces their disadvantages. Our scheme can satisfactorily yield solid-state NMR magnetic shielding constants. The estimated values have only a small dependence on the low-level density functional theory calculation with the extrapolation scheme. Thus, our approach is efficient because the rough calculation can be performed in the extrapolation scheme.

From a long-lived upper-crustal magma chamber to rapid porphyry copper emplacement: Reading the geochemistry of zircon crystals at Bajo de la Alumbrera (NW Argentina)

NASA Astrophysics Data System (ADS)

Buret, Yannick; von Quadt, Albrecht; Heinrich, Christoph; Selby, David; Wälle, Markus; Peytcheva, Irena

2016-09-01

The formation of world class porphyry copper deposits reflect magmatic processes that take place in a deeper and much larger underlying magmatic system, which provides the source of porphyry magmas, as well as metal and sulphur-charged mineralising fluids. Reading the geochemical record of this large magmatic source region, as well as constraining the time-scales for creating a much smaller porphyry copper deposit, are critical in order to fully understand and quantify the processes that lead to metal concentration within these valuable mineral deposits. This study focuses on the Bajo de la Alumbrera porphyry copper deposit in Northwest Argentina. The deposit is centred on a dacitic porphyry intrusive stock that was mineralised by several pulses of porphyry magma emplacement and hydrothermal fluid injections. To constrain the duration of ore formation, we dated zircons from four porphyry intrusions, including pre-, syn- and post-mineralisation porphyries based on intersection relations between successive intrusion and vein generations, using high precision CA-ID-TIMS. Based on the youngest assemblages of zircon grains, which overlap within analytical error, all four intrusions were emplaced within 29 ka, which places an upper limit on the total duration of hydrothermal mineralisation. Re/Os dating of hydrothermal molybdenite fully overlaps with this high-precision age bracket. However, all four porphyries contain zircon antecrysts which record protracted zircon crystallisation during the ∼200 ka preceding the emplacement of the porphyries. Zircon trace element variations, Ti-in-zircon temperatures, and Hf isotopic compositions indicate that the four porphyry magmas record a common geochemical and thermal history, and that the four intrusions were derived from the same upper-crustal magma chamber. Trace element zoning within single zircon crystals confirms a fractional crystallisation trend dominated by titanite and apatite crystallisation. However, zircon cathodoluminescence imaging reveals the presence of intermediate low luminescent (dark) growth zones in many crystals from all intrusions, characterised by anomalously high Th, U and REE concentrations and transient excursions in trace element ratios. A return to the same fractionation trend after this excursion excludes external compositional forcing such as magma mixing. Instead we interpret the ;dark-zones; to record zircon crystallisation during a transient event of rapid growth that resulted from mafic magma injection into the base of the magma chamber, releasing a CO2-rich vapour phase into the dacitic crystal mush. We propose that this vapour phase then migrated upwards to the apical part of the magma chamber from where it was expelled, together with successive batches of magma, to form the porphyry copper deposit within a short time-span of less than a few 10,000 years. The short duration of host rock emplacement, hydrothermal alteration and mineralisation presented in this study provides critical constraints on fluid storage in magma chambers and the genesis of large porphyry copper deposits.

Solid-state rechargeable magnesium battery

DOEpatents

Shao, Yuyan; Liu, Jun; Liu, Tianbiao; Li, Guosheng

2016-09-06

Embodiments of a solid-state electrolyte comprising magnesium borohydride, polyethylene oxide, and optionally a Group IIA or transition metal oxide are disclosed. The solid-state electrolyte may be a thin film comprising a dispersion of magnesium borohydride and magnesium oxide nanoparticles in polyethylene oxide. Rechargeable magnesium batteries including the disclosed solid-state electrolyte may have a coulombic efficiency .gtoreq.95% and exhibit cycling stability for at least 50 cycles.

Solid State Research, 1980:1.

DTIC Science & Technology

1980-02-15

ESD-TR-79-325 H 1 Solid State Research 1980 Prepared under Electronic Systems Division Contract FI%28-80-C-0002 by Lincoln Laboratory MASSkCHIISETTS...it is no longer needed. MASSACHUSETTS IN*STITUTE OF TECHNOLOGY LINCOLN LABORATORY V SOLID STATE RESEARCH QUARTERLY TECHNICAL SUMMARY REPORT I NOVEMBER...January 1990. The topics covered a-e Solid State Device Research , Quantum Electronics, Materials Rese.rch, Microelec- tronics, and Analog Device

Integrated Interface Strategy toward Room Temperature Solid-State Lithium Batteries.

PubMed

Ju, Jiangwei; Wang, Yantao; Chen, Bingbing; Ma, Jun; Dong, Shanmu; Chai, Jingchao; Qu, Hongtao; Cui, Longfei; Wu, Xiuxiu; Cui, Guanglei

2018-04-25

Solid-state lithium batteries have drawn wide attention to address the safety issues of power batteries. However, the development of solid-state lithium batteries is substantially limited by the poor electrochemical performances originating from the rigid interface between solid electrodes and solid-state electrolytes. In this work, a composite of poly(vinyl carbonate) and Li 10 SnP 2 S 12 solid-state electrolyte is fabricated successfully via in situ polymerization to improve the rigid interface issues. The composite electrolyte presents a considerable room temperature conductivity of 0.2 mS cm -1 , an electrochemical window exceeding 4.5 V, and a Li + transport number of 0.6. It is demonstrated that solid-state lithium metal battery of LiFe 0.2 Mn 0.8 PO 4 (LFMP)/composite electrolyte/Li can deliver a high capacity of 130 mA h g -1 with considerable capacity retention of 88% and Coulombic efficiency of exceeding 99% after 140 cycles at the rate of 0.5 C at room temperature. The superior electrochemical performance can be ascribed to the good compatibility of the composite electrolyte with Li metal and the integrated compatible interface between solid electrodes and the composite electrolyte engineered by in situ polymerization, which leads to a significant interfacial impedance decrease from 1292 to 213 Ω cm 2 in solid-state Li-Li symmetrical cells. This work provides vital reference for improving the interface compatibility for room temperature solid-state lithium batteries.

Modified Reference SPS with Solid State Transmitting Antenna

NASA Technical Reports Server (NTRS)

Woodcock, G. R.; Sperber, B. R.

1980-01-01

The development of solid state microwave power amplifiers for a solar power satellite transmitting antenna is discussed. State-of-the-art power-added efficiency, gain, and single device power of various microwave solid state devices are compared. The GaAs field effect transistors and the Si-bipolar transistors appear potentially feasible for solar power satellite use. The integration of solid state devices into antenna array elements is examined and issues concerning antenna integration and consequent satellite configurations are examined.

A solid state video recorder as a direct replacement of a mechanically driven disc recording device in a security system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Terry, P.L.

1989-01-01

Whether upgrading or developing a security system, investing in a solid state video recorder may prove to be quite prudent. Even though the initial cost of a solid state recorder may be more expensive, when comparing it to a disc recorder it is practically maintenance free. Thus, the cost effectiveness of a solid state video recorder over an extended period of time more than justifies the initial expense. This document illustrates the use of a solid state video recorder as a direct replacement. It replaces a mechanically driven disc recorder that existed in a synchronized video recording system. The originalmore » system was called the Universal Video Disc Recorder System. The modified system will now be referred to as the Solid State Video Recording System. 5 figs.« less

Lipid immiscibility and biophysical properties: Molecular order within and among unit cell volumes

USDA-ARS?s Scientific Manuscript database

Saturated and unsaturated fatty acids clearly have a discrete chemical structure in the solid state. In a saturated solution, the solid state and solution state are in chemical equilibrium. The lipid stearic acid packs in unit cell volumes in the liquid state as well as in the solid state. Normal...

Solid-state optical refrigeration to sub-100 Kelvin regime

DOE Office of Scientific and Technical Information (OSTI.GOV)

Melgaard, Seth D.; Albrecht, Alexander R.; Hehlen, Markus P.

We report that since the first demonstration of net cooling twenty years ago, optical refrigeration of solids has progressed to outperform all other solid-state cooling processes. It has become the first and only solid-state refrigerator capable of reaching cryogenic temperatures, and now the first solid-state cooling below 100 K. Such substantial progress required a multi-disciplinary approach of pump laser absorption enhancement, material characterization and purification, and thermal management. Here we present the culmination of two decades of progress, the record cooling to ≈91K from room temperature.

Solid-state optical refrigeration to sub-100 Kelvin regime

DOE PAGES

Melgaard, Seth D.; Albrecht, Alexander R.; Hehlen, Markus P.; ...

2016-02-05

We report that since the first demonstration of net cooling twenty years ago, optical refrigeration of solids has progressed to outperform all other solid-state cooling processes. It has become the first and only solid-state refrigerator capable of reaching cryogenic temperatures, and now the first solid-state cooling below 100 K. Such substantial progress required a multi-disciplinary approach of pump laser absorption enhancement, material characterization and purification, and thermal management. Here we present the culmination of two decades of progress, the record cooling to ≈91K from room temperature.

Solid-state optical refrigeration to sub-100 Kelvin regime

PubMed Central

Melgaard, Seth D.; Albrecht, Alexander R.; Hehlen, Markus P.; Sheik-Bahae, Mansoor

2016-01-01

Since the first demonstration of net cooling twenty years ago, optical refrigeration of solids has progressed to outperform all other solid-state cooling processes. It has become the first and only solid-state refrigerator capable of reaching cryogenic temperatures, and now the first solid-state cooling below 100 K. Such substantial progress required a multi-disciplinary approach of pump laser absorption enhancement, material characterization and purification, and thermal management. Here we present the culmination of two decades of progress, the record cooling to ≈ 91 K from room temperature. PMID:26847703

Comparison of solid-state and submerged-state fermentation for the bioprocessing of switchgrass to ethanol and acetate by Clostridium phytofermentans.

PubMed

Jain, Abhiney; Morlok, Charles K; Henson, J Michael

2013-01-01

The conversion of sustainable energy crops using microbiological fermentation to biofuels and bioproducts typically uses submerged-state processes. Alternatively, solid-state fermentation processes have several advantages when compared to the typical submerged-state processes. This study compares the use of solid-state versus submerged-state fermentation using the mesophilic anaerobic bacterium Clostridium phytofermentans in the conversion of switchgrass to the end products of ethanol, acetate, and hydrogen. A shift in the ratio of metabolic products towards more acetate and hydrogen production than ethanol production was observed when C. phytofermentans was grown under solid-state conditions as compared to submerged-state conditions. Results indicated that the end product concentrations (in millimolar) obtained using solid-state fermentation were higher than using submerged-state fermentation. In contrast, the total fermentation products (in weight of product per weight of carbohydrates consumed) and switchgrass conversion were higher for submerged-state fermentation. The conversion of xylan was greater than glucan conversion under both fermentation conditions. An initial pH of 7 and moisture content of 80 % resulted in maximum end products formation. Scanning electron microscopy study showed the presence of biofilm formed by C. phytofermentans growing on switchgrass under submerged-state fermentation whereas bacterial cells attached to surface and no apparent biofilm was observed when grown under solid-state fermentation. To our knowledge, this is the first study reporting consolidated bioprocessing of a lignocellulosic substrate by a mesophilic anaerobic bacterium under solid-state fermentation conditions.

Superior Blends Solid Polymer Electrolyte with Integrated Hierarchical Architectures for All-Solid-State Lithium-Ion Batteries.

PubMed

Zhang, Dechao; Zhang, Long; Yang, Kun; Wang, Hongqiang; Yu, Chuang; Xu, Di; Xu, Bo; Wang, Li-Min

2017-10-25

Exploration of advanced solid electrolytes with good interfacial stability toward electrodes is a highly relevant research topic for all-solid-state batteries. Here, we report PCL/SN blends integrating with PAN-skeleton as solid polymer electrolyte prepared by a facile method. This polymer electrolyte with hierarchical architectures exhibits high ionic conductivity, large electrochemical windows, high degree flexibility, good flame-retardance ability, and thermal stability (workable at 80 °C). Additionally, it demonstrates superior compatibility and electrochemical stability toward metallic Li as well as LiFePO 4 cathode. The electrolyte/electrode interfaces are very stable even subjected to 4.5 V at charging state for long time. The LiFePO 4 /Li all-solid-state cells based on this electrolyte deliver high capacity, outstanding cycling stability, and superior rate capability better than those based on liquid electrolyte. This solid polymer electrolyte is eligible for next generation high energy density all-solid-state batteries.

The role of cognitive function in the relationship between age and health literacy: a cross-sectional analysis of older adults in Chicago, USA.

PubMed

Kobayashi, Lindsay C; Smith, Samuel G; O'Conor, Rachel; Curtis, Laura M; Park, Denise; von Wagner, Christian; Deary, Ian J; Wolf, Michael S

2015-04-23

To investigate how 3 measures of health literacy correlate with age and the explanatory roles of fluid and crystallised cognitive abilities in these relationships among older adults. Cross-sectional baseline analysis of the 'LitCog' cohort study. 1 academic internal medicine clinic and 5 federally qualified health centres in Chicago, USA. English-speaking adults (n=828) aged 55-74 years, recruited from August 2008 through October 2011. Health literacy was measured by the Test of Functional Health Literacy in Adults (TOFHLA) and the Newest Vital Sign (NVS), both of which assess reading comprehension and numeracy in health contexts, and by the Rapid Estimate of Adult Literacy in Medicine (REALM), which assesses medical vocabulary. Fluid cognitive ability was assessed through the cognitive domains of processing speed, inductive reasoning, and working, prospective and long-term memories, and crystallised cognitive ability through the verbal ability domain. TOFHLA and NVS scores were lower at ages 70-74 years compared with all other age groups (p<0.05 for both tests). The inverse association between age and TOFHLA score was attenuated from β=-0.39 (95% CI -0.55 to -0.22) to β=-0.06 (95% CI -0.20 to 0.08) for ages 70-74 vs 55-59 years when fluid cognitive ability was added to the model (85% attenuation). Similar results were seen with NVS scores (68% attenuation). REALM scores did not differ by age group (p=0.971). Crystallised cognitive ability was stable across age groups, and did not influence the relationships between age and TOFHLA or NVS performance. Health literacy skills show differential patterns of age-related change, which may be explained by cognitive ageing. Researchers should select health literacy tests appropriate for their purposes when assessing the health literacy of older adults. Clinicians should be aware of this issue to ensure that health self-management tasks for older patients have appropriate cognitive and literacy demands. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.

The role of cognitive function in the relationship between age and health literacy: a cross-sectional analysis of older adults in Chicago, USA

PubMed Central

Kobayashi, Lindsay C; Smith, Samuel G; O'Conor, Rachel; Curtis, Laura M; Park, Denise; von Wagner, Christian; Deary, Ian J; Wolf, Michael S

2015-01-01

Objectives To investigate how 3 measures of health literacy correlate with age and the explanatory roles of fluid and crystallised cognitive abilities in these relationships among older adults. Design Cross-sectional baseline analysis of the ‘LitCog’ cohort study. Setting 1 academic internal medicine clinic and 5 federally qualified health centres in Chicago, USA. Participants English-speaking adults (n=828) aged 55–74 years, recruited from August 2008 through October 2011. Outcome measures Health literacy was measured by the Test of Functional Health Literacy in Adults (TOFHLA) and the Newest Vital Sign (NVS), both of which assess reading comprehension and numeracy in health contexts, and by the Rapid Estimate of Adult Literacy in Medicine (REALM), which assesses medical vocabulary. Fluid cognitive ability was assessed through the cognitive domains of processing speed, inductive reasoning, and working, prospective and long-term memories, and crystallised cognitive ability through the verbal ability domain. Results TOFHLA and NVS scores were lower at ages 70–74 years compared with all other age groups (p<0.05 for both tests). The inverse association between age and TOFHLA score was attenuated from β=−0.39 (95% CI −0.55 to −0.22) to β=−0.06 (95% CI −0.20 to 0.08) for ages 70–74 vs 55–59 years when fluid cognitive ability was added to the model (85% attenuation). Similar results were seen with NVS scores (68% attenuation). REALM scores did not differ by age group (p=0.971). Crystallised cognitive ability was stable across age groups, and did not influence the relationships between age and TOFHLA or NVS performance. Conclusions Health literacy skills show differential patterns of age-related change, which may be explained by cognitive ageing. Researchers should select health literacy tests appropriate for their purposes when assessing the health literacy of older adults. Clinicians should be aware of this issue to ensure that health self-management tasks for older patients have appropriate cognitive and literacy demands. PMID:25908675

Synthesis of azines in solid state: reactivity of solid hydrazine with aldehydes and ketones.

PubMed

Lee, Byeongno; Lee, Kyu Hyung; Cho, Jaeheung; Nam, Wonwoo; Hur, Nam Hwi

2011-12-16

Highly conjugated azines were prepared by solid state grinding of solid hydrazine and carbonyl compounds such as aldehydes and ketones, using a mortar and a pestle. Complete conversion to the azine product is generally achieved at room temperature within 24 h, without using solvents or additives. The solid-state reactions afford azines as the sole products with greater than 97% yield, producing only water and carbon dioxide as waste.

40 CFR 256.23 - Requirements for closing or upgrading open dumps.

Code of Federal Regulations, 2010 CFR

2010-07-01

...) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid... classification of existing solid waste disposal facilities according to the criteria. This classification shall... solid waste disposal facility; (2) The availability of State regulatory and enforcement powers; and (3...

40 CFR 256.23 - Requirements for closing or upgrading open dumps.

Code of Federal Regulations, 2011 CFR

2011-07-01

...) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid... classification of existing solid waste disposal facilities according to the criteria. This classification shall... solid waste disposal facility; (2) The availability of State regulatory and enforcement powers; and (3...

Atomistic Simulation of Interfaces in Materials of Solid State Ionics

NASA Astrophysics Data System (ADS)

Ivanov-Schitz, A. K.; Mazo, G. N.

2018-01-01

The possibilities of describing correctly interfaces of different types in solids within a computer experiment using molecular statics simulation, molecular dynamics simulation, and quantum chemical calculations are discussed. Heterophase boundaries of various types, including grain boundaries and solid electrolyte‒solid electrolyte and ionic conductor‒electrode material interfaces, are considered. Specific microstructural features and mechanisms of the ion transport in real heterophase structures (cationic conductor‒metal anode and anionic conductor‒cathode) existing in solid state ionics devices (such as solid-state batteries and fuel cells) are discussed.

Tunable solid state lasers for remote sensing; Proceedings of the Conference, Stanford University, CA, October 1-3, 1984

NASA Technical Reports Server (NTRS)

Byer, R. L. (Editor); Trebino, R. (Editor); Gustafson, E. K. (Editor)

1985-01-01

Papers are presented on solid-state lasers for remote sensing, diode-pumped Nd:YAG lasers, and tunable solid-state-laser systems. Topics discussed include titanium-sapphire tunable laser systems, the performance of slab geometry, and the development of slab lasers. Consideration is given to garnet host solid-state lasers, the growth of lasers and nonlinear materials, and nonlinear frequency conversion and tunable sources.

Nanowire membrane-based nanothermite: towards processable and tunable interfacial diffusion for solid state reactions.

PubMed

Yang, Yong; Wang, Peng-peng; Zhang, Zhi-cheng; Liu, Hui-ling; Zhang, Jingchao; Zhuang, Jing; Wang, Xun

2013-01-01

Interfacial diffusion is of great importance in determining the performance of solid-state reactions. For nanometer sized particles, some solid-state reactions can be triggered accidently by mechanical stress owing to their large surface-to-volume ratio compared with the bulk ones. Therefore, a great challenge is the control of interfacial diffusion for solid state reactions, especially for energetic materials. Here we demonstrate, through the example of nanowire-based thermite membrane, that the thermite solid-state reaction can be easily tuned via the introduction of low-surface-energy coating layer. Moreover, this silicon-coated thermite membrane exhibit controlled wetting behavior ranging from superhydrophilic to superhydrophobic and, simultaneously, to significantly reduce the friction sensitivity of thermite membrane. This effect enables to increase interfacial resistance by increasing the amount of coating material. Indeed, our results described here make it possible to tune the solid-state reactions through the manipulation of interfacial diffusion between the reactants.

Nanowire Membrane-based Nanothermite: towards Processable and Tunable Interfacial Diffusion for Solid State Reactions

NASA Astrophysics Data System (ADS)

Yang, Yong; Wang, Peng-Peng; Zhang, Zhi-Cheng; Liu, Hui-Ling; Zhang, Jingchao; Zhuang, Jing; Wang, Xun

2013-04-01

Interfacial diffusion is of great importance in determining the performance of solid-state reactions. For nanometer sized particles, some solid-state reactions can be triggered accidently by mechanical stress owing to their large surface-to-volume ratio compared with the bulk ones. Therefore, a great challenge is the control of interfacial diffusion for solid state reactions, especially for energetic materials. Here we demonstrate, through the example of nanowire-based thermite membrane, that the thermite solid-state reaction can be easily tuned via the introduction of low-surface-energy coating layer. Moreover, this silicon-coated thermite membrane exhibit controlled wetting behavior ranging from superhydrophilic to superhydrophobic and, simultaneously, to significantly reduce the friction sensitivity of thermite membrane. This effect enables to increase interfacial resistance by increasing the amount of coating material. Indeed, our results described here make it possible to tune the solid-state reactions through the manipulation of interfacial diffusion between the reactants.

76 FR 58496 - Agency Information Collection Activities; Proposed Collection; Comment Request; State Program...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-21

... Activities; Proposed Collection; Comment Request; State Program Adequacy Determination: Municipal Solid Waste... States. Title: State Program Adequacy Determination: Municipal Solid Waste Landfills (MSWLFs) and Non... 4004(a) and Section 1008(a)(3). Section 4005(c) of RCRA, as amended by the Hazardous Solid Waste...

Solid state phase change materials for thermal energy storage in passive solar heated buildings

NASA Astrophysics Data System (ADS)

Benson, D. K.; Christensen, C.

1983-11-01

A set of solid state phase change materials was evaluated for possible use in passive solar thermal energy storage systems. The most promising materials are organic solid solutions of pentaerythritol, pentaglycerine and neopentyl glycol. Solid solution mixtures of these compounds can be tailored so that they exhibit solid-to-solid phase transformations at any desired temperature within the range from less than 25 deg to 188 deg. Thermophysical properties such as thermal conductivity, density and volumetric expansion were measured. Computer simulations were used to predict the performance of various Trombe wall designs incorporating solid state phase change materials. Optimum performance was found to be sensitive to the choice of phase change temperatures and to the thermal conductivity of the phase change material. A molecular mechanism of the solid state phase transition is proposed and supported by infrared spectroscopic evidence.

Solid-State Cloud Radar System (CRS) Upgrade and Deployment

NASA Technical Reports Server (NTRS)

McLinden, Matt; Heymsfield, Gerald; Li, Lihua; Racette, Paul; Coon, Michael; Venkatesh, Vijay

2015-01-01

The recent decade has brought rapid development in solid-state power amplifier (SSPA) technology. This has enabled the use of solid-state precipitation radar in place of high-power and high-voltage systems such as those that use Klystron or Magnetron transmitters. The NASA Goddard Space Flight Center has recently completed a comprehensive redesign of the 94 gigahertz Cloud Radar System (CRS) to incorporate a solid-state transmitter. It is the first cloud radar to achieve sensitivity comparable to that of a high-voltage transmitter using solid-state. The NASA Goddard Space Flight Center's Cloud Radar System (CRS) is a 94 gigahertz Doppler radar that flies on the NASA ER-2 high-altitude aircraft. The upgraded CRS system utilizes a state-of-the-art solid-state 94 gigahertz power amplifier with a peak transmit power of 30 watts. The modernized CRS system is detailed here with data results from its deployment during the 2014 Integrated Precipitation and Hydrology Experiment (IPHEX).

Glass for Solid State Devices

NASA Technical Reports Server (NTRS)

Bailey, R. F.

1982-01-01

Glass film has low intrinsic compressive stress for isolating active layers of magnetic-bubble and other solid-state devices. Solid-state device structure incorporates low-stress glasses as barrier and spacer layers. Glass layers mechanically isolate substrate, conductor, and nickel/iron layers.

Current status of solid-state lithium batteries employing solid redox polymerization cathodes

NASA Astrophysics Data System (ADS)

Visco, S. J.; Doeff, M. M.; Dejonghe, L. C.

1991-03-01

The rapidly growing demand for secondary batteries having high specific energy and power has naturally led to increased efforts in lithium battery technology. Still, the increased safety risks associated with high energy density systems has tempered the enthusiasm of proponents of such systems for use in the consumer marketplace. The inherent advantages of all-solid-state batteries in regards to safety and reliability are strong factors in advocating their introduction to the marketplace. However, the low ionic conductivity of solid electrolytes relative to nonaqueous liquid electrolytes implies low power densities for solid state systems operating at ambient temperatures. Recent advances in polymer electrolytes have led to the introduction of solid electrolytes having conductivities in the range of 10(exp -4)/ohm cm at room temperature; this is still two orders of magnitude lower than liquid electrolytes. Although these improved ambient conductivities put solid state batteries in the realm of practical devices, it is clear that solid state batteries using such polymeric separators will be thin film devices. Fortunately, thin film fabrication techniques are well established in the plastics and paper industry, and present the possibility of continuous web-form manufacturing. This style of battery manufacture should make solid polymer batteries very cost-competitive with conventional secondary cells. In addition, the greater geometric flexibility of thin film solid state cells should provide benefits in terms of the end-use form factor in device design. This work discusses the status of solid redox polymerization cathodes.

Effects of Drying Process on an IgG1 Monoclonal Antibody Using Solid-State Hydrogen Deuterium Exchange with Mass Spectrometric Analysis (ssHDX-MS).

PubMed

Moussa, Ehab M; Wilson, Nathan E; Zhou, Qi Tony; Singh, Satish K; Nema, Sandeep; Topp, Elizabeth M

2018-01-03

Lyophilization and spray drying are widely used to manufacture solid forms of therapeutic proteins. Lyophilization is used to stabilize proteins vulnerable to degradation in solution, whereas spray drying is mainly used to prepare inhalation powders or as an alternative to freezing for storing bulk drug substance. Both processes impose stresses that may adversely affect protein structure, stability and bioactivity. Here, we compared lyophilization with and without controlled ice nucleation, and spray drying for their effects on the solid-state conformation and matrix interactions of a model IgG1 monoclonal antibody (mAb). Solid-state conformation and matrix interactions of the mAb were probed using solid-state hydrogen-deuterium exchange with mass spectrometric analysis (ssHDX-MS), and solid-state Fourier transform infrared (ssFTIR) and solid-state fluorescence spectroscopies. mAb conformation and/or matrix interactions were most perturbed in mannitol-containing samples and the distribution of states was more heterogeneous in sucrose and trehalose samples that were spray dried. The findings demonstrate the sensitivity of ssHDX-MS to changes weakly indicated by spectroscopic methods, and support the broader use of ssHDX-MS to probe formulation and process effects on proteins in solid samples.

Understanding Phase-Change Memory Alloys from a Chemical Perspective

NASA Astrophysics Data System (ADS)

Kolobov, A. V.; Fons, P.; Tominaga, J.

2015-09-01

Phase-change memories (PCM) are associated with reversible ultra-fast low-energy crystal-to-amorphous switching in GeTe-based alloys co-existing with the high stability of the two phases at ambient temperature, a unique property that has been recently explained by the high fragility of the glass-forming liquid phase, where the activation barrier for crystallisation drastically increases as the temperature decreases from the glass-transition to room temperature. At the same time the atomistic dynamics of the phase-change process and the associated changes in the nature of bonding have remained unknown. In this work we demonstrate that key to this behavior is the formation of transient three-center bonds in the excited state that is enabled due to the presence of lone-pair electrons. Our findings additionally reveal previously ignored fundamental similarities between the mechanisms of reversible photoinduced structural changes in chalcogenide glasses and phase-change alloys and offer new insights into the development of efficient PCM materials.

Understanding Phase-Change Memory Alloys from a Chemical Perspective.

PubMed

Kolobov, A V; Fons, P; Tominaga, J

2015-09-01

Phase-change memories (PCM) are associated with reversible ultra-fast low-energy crystal-to-amorphous switching in GeTe-based alloys co-existing with the high stability of the two phases at ambient temperature, a unique property that has been recently explained by the high fragility of the glass-forming liquid phase, where the activation barrier for crystallisation drastically increases as the temperature decreases from the glass-transition to room temperature. At the same time the atomistic dynamics of the phase-change process and the associated changes in the nature of bonding have remained unknown. In this work we demonstrate that key to this behavior is the formation of transient three-center bonds in the excited state that is enabled due to the presence of lone-pair electrons. Our findings additionally reveal previously ignored fundamental similarities between the mechanisms of reversible photoinduced structural changes in chalcogenide glasses and phase-change alloys and offer new insights into the development of efficient PCM materials.

Clathrate structure-type recognition: Application to hydrate nucleation and crystallisation

NASA Astrophysics Data System (ADS)

Lauricella, Marco; Meloni, Simone; Liang, Shuai; English, Niall J.; Kusalik, Peter G.; Ciccotti, Giovanni

2015-06-01

For clathrate-hydrate polymorphic structure-type (sI versus sII), geometric recognition criteria have been developed and validated. These are applied to the study of the rich interplay and development of both sI and sII motifs in a variety of hydrate-nucleation events for methane and H2S hydrate studied by direct and enhanced-sampling molecular dynamics (MD) simulations. In the case of nucleation of methane hydrate from enhanced-sampling simulation, we notice that already at the transition state, ˜80% of the enclathrated CH4 molecules are contained in a well-structured (sII) clathrate-like crystallite. For direct MD simulation of nucleation of H2S hydrate, some sI/sII polymorphic diversity was encountered, and it was found that a realistic dissipation of the nucleation energy (in view of non-equilibrium relaxation to either microcanonical (NVE) or isothermal-isobaric (NPT) distributions) is important to determine the relative propensity to form sI versus sII motifs.

Influence of reaction-induced fracturing on serpentinisation rate

NASA Astrophysics Data System (ADS)

Malvoisin, B.; Brantut, N.; Kaczmarek, M. A.

2017-12-01

The alteration of mantle rocks at mid-ocean ridges (i.e. serpentinisation) can lead to a solid volume increase responsible for stress build-up and cracking during reaction (reaction-induced fracturing). This mechanism has been proposed to play a key role for maintaining fluid pathways during reaction. However, its impact on the reaction rate is not yet quantified. We propose here a micromechanical model to quantify the influence of the crystallisation pressure generated during serpentine precipitation on crack propagation in olivine. This model is then coupled to a simple geometrical model to calculate the generation of reactive surface area during grain splitting, and thus bulk reaction rate. The model is able to reproduce experimental kinetic data as well as the mesh texture observed in natural samples. The model results are compared to olivine grain size distribution in serpentinised peridotites from the Marum ophiolite and the Papuan ultramafic belt (Papuan New Guinea). The observations and the model both indicate a decrease of the mean grain size by one order of magnitude as the reaction progresses from 5 to 40 %. Based on this good agreement, we use our model to predict that cracking reduces the characteristic time of serpentinisation by one order of magnitude, down to values comprised between 10 and 1,000 yr. The peak serpentinisation is also shifted 4 km above the previous predictions due to effective pressure increase with depth.

Rapid mixing and short storage timescale in the magma dynamics of a steady-state volcano

NASA Astrophysics Data System (ADS)

Petrone, Chiara Maria; Braschi, Eleonora; Francalanci, Lorella; Casalini, Martina; Tommasini, Simone

2018-06-01

Steady-state volcanic activity implies equilibrium between the rate of magma replenishment and eruption of compositionally homogeneous magmas, lasting for tens to thousands of years in an open conduit system. The Present-day activity of Stromboli volcano (Aeolian Islands, Southern Italy) has long been recognised as typical of a steady-state volcano, with a shallow magmatic reservoir (highly porphyritic or hp-magma) continuously refilled by more mafic magma (with low phenocryst content or lp-magma) at a constant rate and accompanied by mixing, crystallisation and eruption. Our aim is to clarify the timescale and dynamics of the plumbing system at the establishment of the Present-day steady-state activity (<1.2 ka) to pinpoint the onset of the steady-state regime. We investigated the Post-Pizzo (PP) pyroclastic sequence (∼1.7-1.5 ka) and one of the Early Paroxysms (EP) of the Present-day activity, focusing on the clinopyroxene population. Whole rock and clinopyroxene compositional variation among the PP and EP magmas is consistent with the time progression of the Stromboli system towards more mafic and lower 87Sr/86Sr compositions, pointing to the chemical and isotopic signature of the Present-day activity. Clinopyroxenes from both PP and EP record a complex history with compositional zoning that reflects growth in three different melt domains: a high-Mg# proto-lp recharging magma, a low-Mg# proto-hp resident magma, and a transient intermediate-Mg# magma. These are the result of complex turbulent flow fields and mixing regimes produced by repeated injections of the proto-lp magma in the shallow proto-hp magma reservoir. During the PP period the magmatic system was already able to regain the pre-input proto-hp composition, gradually changing toward a less evolved signature after the injection(s) of the more mafic proto-lp magma, owing to efficient (days to a few years) stirring and melt homogenisation (i.e., homogenisation time < residence time). Based upon Fe-Mg diffusion in clinopyroxene the total residence time during PP and EP periods, from the arrival of the mafic magma in the shallow system until the eruption, ranges from 1 to ∼50 years. Longer residence times (up to 150 years) have been recorded in the initial phase of the PP sequence, possibly testifying to the transition from a closed- to the open-conduit, steady-state regime of the Present-day activity. Some clinopyroxenes from the PP recorded the mafic triggering event of the feeding proto-lp magma occurring within few months to a few days before eruption. Remarkably, other clinopyroxene portions crystallised and captured the rapid timescales (a few days) of the on-going mixing and homogenisation process between the proto-lp and the proto-hp magmas leading to the eruption. The modelling of clinopyroxene zoning events at Stromboli provides evidence for growth and storage in three different melt domains, and sets robust constraints on their residence time from lp-magma recharge(s) to eruption, along with the timescales of melt homogenisation and triggering events. The lifetime history captured by Fe-Mg zoning of Stromboli clinopyroxenes suggests that the interplay between rapid mixing and short storage timescales can be a key parameter controlling the dynamics of the plumbing system of steady-state volcanoes.

Rational coating of Li7P3S11 solid electrolyte on MoS2 electrode for all-solid-state lithium ion batteries

NASA Astrophysics Data System (ADS)

Xu, R. C.; Wang, X. L.; Zhang, S. Z.; Xia, Y.; Xia, X. H.; Wu, J. B.; Tu, J. P.

2018-01-01

Large interfacial resistance between electrode and electrolyte limits the development of high-performance all-solid-state batteries. Herein we report a uniform coating of Li7P3S11 solid electrolyte on MoS2 to form a MoS2/Li7P3S11 composite electrode for all-solid-state lithium ion batteries. The as-synthesized Li7P3S11 processes a high ionic of 2.0 mS cm-1 at room temperature. Due to homogeneous union and reduced interfacial resistance, the assembled all-solid-state batteries with the MoS2/Li7P3S11 composite electrode exhibit higher reversible capacity of 547.1 mAh g-1 at 0.1 C and better cycling stability than the counterpart based on untreated MoS2. Our study provides a new reference for design/fabrication of advanced electrode materials for high-performance all-solid-state batteries.

Advanced solid-state NMR spectroscopy of natural organic matter

USDA-ARS?s Scientific Manuscript database

Solid-state NMR is essential for the characterization of natural organic matter (NOM) and is gaining importance in geosciences and environmental sciences. This review is intended to highlight advanced solid-state NMR techniques, especially the systematic approach to NOM characterization, and their ...

Quantitative secondary electron detection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Agrawal, Jyoti; Joy, David C.; Nayak, Subuhadarshi

Quantitative Secondary Electron Detection (QSED) using the array of solid state devices (SSD) based electron-counters enable critical dimension metrology measurements in materials such as semiconductors, nanomaterials, and biological samples (FIG. 3). Methods and devices effect a quantitative detection of secondary electrons with the array of solid state detectors comprising a number of solid state detectors. An array senses the number of secondary electrons with a plurality of solid state detectors, counting the number of secondary electrons with a time to digital converter circuit in counter mode.

Measuring and modelling the structure of chocolate

NASA Astrophysics Data System (ADS)

Le Révérend, Benjamin J. D.; Fryer, Peter J.; Smart, Ian; Bakalis, Serafim

2015-01-01

The cocoa butter present in chocolate exists as six different polymorphs. To achieve the desired crystal form (βV), traditional chocolate manufacturers use relatively slow cooling (<2°C/min). A newer generation of rapid cooling systems has been suggested requiring further understanding of fat crystallisation. To allow better control and understanding of these processes and newer rapid cooling processes, it is necessary to understand both heat transfer and crystallization kinetics. The proposed model aims to predict the temperature in the chocolate products during processing as well as the crystal structure of cocoa butter throughout the process. A set of ordinary differential equations describes the kinetics of fat crystallisation. The parameters were obtained by fitting the model to a set of DSC curves. The heat transfer equations were coupled to the kinetic model and solved using commercially available CFD software. A method using single crystal XRD was developed using a novel subtraction method to quantify the cocoa butter structure in chocolate directly and results were compared to the ones predicted from the model. The model was proven to predict phase change temperature during processing accurately (±1°C). Furthermore, it was possible to correctly predict phase changes and polymorphous transitions. The good agreement between the model and experimental data on the model geometry allows a better design and control of industrial processes.

Lactose behaviour in the presence of lactic acid and calcium.

PubMed

Wijayasinghe, Rangani; Vasiljevic, Todor; Chandrapala, Jayani

2016-08-01

Physical properties of lactose appeared influenced by presence of lactic acid in the system. Some other components such as Ca may further attenuate lactose behaviour and impact its phase transition. A model-based study was thus implemented with varying concentrations of Ca (0·12, 0·072 or 0·035% w/w) and lactic acid (0·05, 0·2, 0·4 or 1% w/w) in establishing the effects of these two main acid whey constituents on lactose phase behaviour. Concentrated solutions (50% w/w) containing lactose, lactic acid and Ca were analysed for thermal behaviour and structural changes by Differential Scanning Colorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FTIR), respectively. Presence of 1% (w/w) lactic acid and 0·12% (w/w) Ca in lactose solution significantly increased the evaporation enthalpy of water, delayed and increased the energy required for lactose crystallisation as compared to pure lactose. FTIR analysis indicated a strong hydration layer surrounding lactose molecules, restricting water mobility and/or inducing structural changes of lactose, hindering its crystallisation. The formation of calcium lactate, which restricts the diffusion of lactose molecules, is also partly responsible. It appears that Ca removal from acid whey may be a necessary step in improving the processability of acid whey.

Tail proteins of phage T5: investigation of the effect of the His6-tag position, from expression to crystallisation.

PubMed

Noirclerc-Savoye, Marjolaine; Flayhan, Ali; Pereira, Cindy; Gallet, Benoit; Gans, Pierre; Ebel, Christine; Breyton, Cécile

2015-05-01

Upon binding to its bacterial host receptor, the tail tip of phage T5 perforates, by an unknown mechanism, the heavily armoured cell wall of the host. This allows the injection of phage DNA into the cytoplasm to hijack the cell machinery and enable the production of new virions. In the perspective of a structural study of the phage tail, we have systematically overproduced eight of the eleven T5 tail proteins, with or without a N- or a C-terminal His6-tag. The widely used Hi6-tag is very convenient to purify recombinant proteins using immobilised-metal affinity chromatography. The presence of a tag however is not always innocuous. We combined automated gene cloning and expression tests to rapidly identify the most promising constructs for proteins of phage T5 tail, and performed biochemical and biophysical characterisation and crystallisation screening on available proteins. Automated small-scale purification was adapted for two highly expressed proteins. We obtained structural information for three of the proteins. We showed that the presence of a His6-tag can have drastic effect on protein expression, solubility, oligomerisation propensity and crystal quality. Copyright © 2015 Elsevier Inc. All rights reserved.

Advax™, a novel microcrystalline polysaccharide particle engineered from delta inulin, provides robust adjuvant potency together with tolerability and safety

PubMed Central

Petrovsky, Nikolai; Cooper, Peter D.

2015-01-01

There is an ongoing need for new adjuvants to facilitate development of vaccines against HIV, tuberculosis, malaria and cancer, amongst many others. Unfortunately, the most potent adjuvants are often associated with toxicity and safety issues. Inulin, a plant-derived polysaccharide, has no immunological activity in its native soluble form but when crystallised into stable microparticles (delta inulin) acquires potent adjuvant activity. Delta inulin has been shown to enhance humoral and cellular immune responses against a broad range of co-administered viral, bacterial, parasitic and toxin antigens. Inulin normally crystallises as large heterogeneous particles with a broad size distribution and variable solubility temperatures. To ensure reproducible delta inulin particles with a consistent size distribution and temperature of solubility, a current Good Manufacturing Practice (cGMP) process was designed to produce Advax™ adjuvant. In its cGMP form, Advax™ adjuvant has proved successful in human trials of vaccines against seasonal and pandemic influenza, hepatitis B and insect sting anaphylaxis, enhancing antibody and T-cell responses while at the same time being safe and well tolerated. Advax™ adjuvant thereby represents a novel human adjuvant with positive effects on both humoral and cellular immunity. This review describes the discovery and development of Advax™ adjuvant and research into its unique mechanism of action. PMID:26407920

Estimation of the growth kinetics for the cooling crystallisation of paracetamol and ethanol solutions

NASA Astrophysics Data System (ADS)

Mitchell, Niall A.; Ó'Ciardhá, Clifford T.; Frawley, Patrick J.

2011-08-01

This work details the estimation of the growth kinetics of paracetamol in ethanol solutions for cooling crystallisation processes, by means of isothermal seeded batch experiments. The growth kinetics of paracetamol crystals were evaluated in isolation, with the growth rate assumed to be size independent. Prior knowledge of the Metastable Zone Width (MSZW) was required, so that supersaturation ratios of 1.7-1.1 could be induced in solution without the occurrence of nucleation. The technique involved the utilisation of two in-situ Process Analytical Techniques (PATs), with a Focused Beam Reflectance Measurement (FBRM ®) utilised to ensure that negligible nucleation occurred and an Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) probe employed for online monitoring of solute concentration. Initial Particle Size Distributions (PSDs) were used in conjunction with desupersaturation profiles to determine the growth rate as a function of temperature and supersaturation. Furthermore, the effects of seed loading and size on the crystal growth rate were investigated. A numerical model, incorporating the population balance equation and the method of moments, was utilised to describe the crystal growth process. Experimental parameters were compared to the model simulation, with the accuracy of the model validated by means of the final product PSDs and solute concentration.

Optimisation of the enamelling of an apatite-mullite glass-ceramic coating on Ti6Al4V.

PubMed

O'Flynn, Kevin P; Stanton, Kenneth T

2011-09-01

Apatite-mullite glass-ceramics (AMGCs) are under investigation as a potential alternative to hydroxyapatite (HA) as a coating for cementless fixation of orthopaedic implants. These materials have tailorable mechanical and chemical properties that make them attractive for use as bioactive coatings. Here, AMGC coatings on Ti(6)Al(4)V were investigated to determine an improved heat treatment regime using a systematic examination of the different inputs: composition of glass, nucleation hold and crystallisation hold. An upper limit to the heat treatment temperature was determined by the α + β --> β of Ti(6)Al(4)V at 970°C. The glass composition was modified to produce different crystallisation temperatures and sintering characteristics. A glass was found that is fully crystalline below 970°C and has good sinterability. The effects of different heat treatment time and temperature combinations on the coating and substrate morphologies were examined and the most suitable combination determined. This sample was further investigated and was found to have qualitatively good adhesion and evidence of an interfacial reaction region between the coating and substrate indicating that a chemical reaction had occurred. Oxygen infiltration into the substrate was quantified and the new route was shown to result in a 63% reduction in penetration depth.

Magnetocaloric effect in amorphous and partially crystallized Fe{sub 40}Ni{sub 38}Mo{sub 4}B{sub 18} alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thanveer, T.; Thomas, S., E-mail: senoythomas@gmail.com; Ramanujan, R. V.

A study of magnetocaloric effect in amorphous and partially crystallized Fe{sub 40}Ni{sub 38}Mo{sub 4}B{sub 18} alloys is reported. Amorphous Fe{sub 40}Ni{sub 38}Mo{sub 4}B{sub 18}, near its magnetic ordering temperature (600 K) showed a magnetic entropy change ΔS{sub M} of 1.1 J/KgK and a relative cooling power of 36 J/Kg in a field change of 10 kOe. Amorphous samples were partially crystallized by annealing at 700 K at different time intervals. Partially crystallized samples showed two distinct magnetic ordering temperature, one corresponding to the precipitated FeNi nanocrystals and the other one corresponding to the boron rich amorphous matrix. Magnetic ordering temperaturemore » of the residual amorphous matrix got shifted to the lower temperatures on increasing the annealing duration. Partially crystallised samples showed a magnetic entropy change of about 0.27 J/kgK near the magnetic ordering temperature of the amorphous matrix (540 K) in a field change of 10 kOe. The decrease in ΔS{sub M} on partial crystallisation is attributed to the biphasic magnetic nature of the sample.« less

40 CFR Table Jj-3 to Subpart Jj of... - State-Specific Volatile Solids (VS) and Nitrogen (N) Excretion Rates for Cattle

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 21 2011-07-01 2011-07-01 false State-Specific Volatile Solids (VS) and Nitrogen (N) Excretion Rates for Cattle JJ Table JJ-3 to Subpart JJ of Part 98 Protection of... Volatile Solids (VS) and Nitrogen (N) Excretion Rates for Cattle State Volatile solids excretion rate (kg...

A survey of current solid state star tracker technology

NASA Astrophysics Data System (ADS)

Armstrong, R. W.; Staley, D. A.

1985-12-01

This paper is a survey of the current state of the art in design of star trackers for spacecraft attitude determination systems. Specific areas discussed are sensor technology, including the current state-of-the-art solid state sensors and techniques of mounting and cooling the sensor, analog image preprocessing electronics performance, and digital processing hardware and software. Three examples of area array solid state star tracker development are presented - ASTROS, developed by the Jet Propulsion Laboratory, the Retroreflector Field Tracker (RFT) by Ball Aerospace, and TRW's MADAN. Finally, a discussion of solid state line arrays explores the possibilities for one-dimensional imagers which offer simplified scan control electronics.

Synthesis of POSS-based ionic conductors with low glass transition temperatures for efficient solid-state dye-sensitized solar cells.

PubMed

Zhang, Wei; Wang, Zhong-Sheng

2014-07-09

Replacing liquid-state electrolytes with solid-state electrolytes has been proven to be an effective way to improve the durability of dye-sensitized solar cells (DSSCs). We report herein the synthesis of amorphous ionic conductors based on polyhedral oligomeric silsesquioxane (POSS) with low glass transition temperatures for solid-state DSSCs. As the ionic conductor is amorphous and in the elastomeric state at the operating temperature of DSSCs, good pore filling in the TiO2 film and good interfacial contact between the solid-state electrolyte and the TiO2 film can be guaranteed. When the POSS-based ionic conductor containing an allyl group is doped with only iodine as the solid-state electrolyte without any other additives, power conversion efficiency of 6.29% has been achieved with good long-term stability under one-sun soaking for 1000 h.

Modeling solid-state transformations occurring in dissolution testing.

PubMed

Laaksonen, Timo; Aaltonen, Jaakko

2013-04-15

Changes in the solid-state form can occur during dissolution testing of drugs. This can often complicate interpretation of results. Additionally, there can be several mechanisms through which such a change proceeds, e.g. solvent-mediated transformation or crystal growth within the drug material itself. Here, a mathematical model was constructed to study the dissolution testing of a material, which undergoes such changes. The model consisted of two processes: the recrystallization of the drug from a supersaturated liquid state caused by the dissolution of the more soluble solid form and the crystal growth of the stable solid form at the surface of the drug formulation. Comparison to experimental data on theophylline dissolution showed that the results obtained with the model matched real solid-state changes and that it was able to distinguish between cases where the transformation was controlled either by solvent-mediated crystallization or solid-state crystal growth. Copyright © 2013 Elsevier B.V. All rights reserved.

40 CFR 256.22 - Recommendations for State regulatory powers.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 25 2014-07-01 2014-07-01 false Recommendations for State regulatory powers. 256.22 Section 256.22 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid Waste...

40 CFR 256.22 - Recommendations for State regulatory powers.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 26 2013-07-01 2013-07-01 false Recommendations for State regulatory powers. 256.22 Section 256.22 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid Waste...

40 CFR 256.21 - Requirements for State regulatory powers.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 26 2013-07-01 2013-07-01 false Requirements for State regulatory powers. 256.21 Section 256.21 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid Waste...

40 CFR 256.21 - Requirements for State regulatory powers.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 26 2012-07-01 2011-07-01 true Requirements for State regulatory powers. 256.21 Section 256.21 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid Waste...

40 CFR 256.20 - Requirements for State legal authority.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 26 2013-07-01 2013-07-01 false Requirements for State legal authority. 256.20 Section 256.20 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid Waste...

40 CFR 256.20 - Requirements for State legal authority.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 26 2012-07-01 2011-07-01 true Requirements for State legal authority. 256.20 Section 256.20 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid Waste...

40 CFR 256.21 - Requirements for State regulatory powers.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 25 2014-07-01 2014-07-01 false Requirements for State regulatory powers. 256.21 Section 256.21 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid Waste...

40 CFR 256.20 - Requirements for State legal authority.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 25 2014-07-01 2014-07-01 false Requirements for State legal authority. 256.20 Section 256.20 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid Waste...

40 CFR 256.22 - Recommendations for State regulatory powers.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 26 2012-07-01 2011-07-01 true Recommendations for State regulatory powers. 256.22 Section 256.22 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid Waste...

40 CFR 256.20 - Requirements for State legal authority.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 25 2011-07-01 2011-07-01 false Requirements for State legal authority. 256.20 Section 256.20 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid Waste...

40 CFR 256.20 - Requirements for State legal authority.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 24 2010-07-01 2010-07-01 false Requirements for State legal authority. 256.20 Section 256.20 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid Waste...

A zwitterionic gel electrolyte for efficient solid-state supercapacitors

PubMed Central

Peng, Xu; Liu, Huili; Yin, Qin; Wu, Junchi; Chen, Pengzuo; Zhang, Guangzhao; Liu, Guangming; Wu, Changzheng; Xie, Yi

2016-01-01

Gel electrolytes have attracted increasing attention for solid-state supercapacitors. An ideal gel electrolyte usually requires a combination of advantages of high ion migration rate, reasonable mechanical strength and robust water retention ability at the solid state for ensuring excellent work durability. Here we report a zwitterionic gel electrolyte that successfully brings the synergic advantages of robust water retention ability and ion migration channels, manifesting in superior electrochemical performance. When applying the zwitterionic gel electrolyte, our graphene-based solid-state supercapacitor reaches a volume capacitance of 300.8 F cm−3 at 0.8 A cm−3 with a rate capacity of only 14.9% capacitance loss as the current density increases from 0.8 to 20 A cm−3, representing the best value among the previously reported graphene-based solid-state supercapacitors, to the best of our knowledge. We anticipate that zwitterionic gel electrolyte may be developed as a gel electrolyte in solid-state supercapacitors. PMID:27225484

Graphene/activated carbon supercapacitors with sulfonated-polyetheretherketone as solid-state electrolyte and multifunctional binder

NASA Astrophysics Data System (ADS)

Chen, Y.-R.; Chiu, K.-F.; Lin, H. C.; Chen, C.-L.; Hsieh, C. Y.; Tsai, C. B.; Chu, B. T. T.

2014-11-01

Sulfonated polyetheretherketone (SPEEK) has been synthesised by sulphonation process and used as the solid-state electrolyte, binder and surfactant for supercapacitors. Reduced graphene dispersed by SPEEK is used as a high-efficiency conducting additive in solid-state supercapacitors. It is found that SPEEK can improve the stability of the reduced graphene dispersion significantly, and therefore, the solid-state supercapacitors show a large decrease in IR drop and charge-transfer resistance (Rct), resulting in a higher rate capability. The solid-state supercapacitors with the activated carbon/reduced graphene/SPEEK/electrode can be operated from 1 to 8 A/g and exhibit capacity retention of 93%. The noteworthy is more than twice higher value for capacity retention by comparison with the solid-state supercapacitors using activated carbon/reduced graphene/PVDF electrode (capacity retention is 36%). The cell of reduced graphene with SPEEK can be cycled over 5000 times at 5 A/g with no capacitance fading.

Cryogenic terahertz spectrum of (+)-methamphetamine hydrochloride and assignment using solid-state density functional theory.

PubMed

Hakey, Patrick M; Allis, Damian G; Ouellette, Wayne; Korter, Timothy M

2009-04-30

The cryogenic terahertz spectrum of (+)-methamphetamine hydrochloride from 10.0 to 100.0 cm(-1) is presented, as is the complete structural analysis and vibrational assignment of the compound using solid-state density functional theory. This cryogenic investigation reveals multiple spectral features that were not previously reported in room-temperature terahertz studies of the title compound. Modeling of the compound employed eight density functionals utilizing both solid-state and isolated-molecule methods. The results clearly indicate the necessity of solid-state simulations for the accurate assignment of solid-state THz spectra. Assignment of the observed spectral features to specific atomic motions is based on the BP density functional, which provided the best-fit solid-state simulation of the experimental spectrum. The seven experimental spectral features are the result of thirteen infrared-active vibrational modes predicted at a BP/DNP level of theory with more than 90% of the total spectral intensity associated with external crystal vibrations.

Nanowire Membrane-based Nanothermite: towards Processable and Tunable Interfacial Diffusion for Solid State Reactions

PubMed Central

Yang, Yong; Wang, Peng-peng; Zhang, Zhi-cheng; Liu, Hui-ling; Zhang, Jingchao; Zhuang, Jing; Wang, Xun

2013-01-01

Interfacial diffusion is of great importance in determining the performance of solid-state reactions. For nanometer sized particles, some solid-state reactions can be triggered accidently by mechanical stress owing to their large surface-to-volume ratio compared with the bulk ones. Therefore, a great challenge is the control of interfacial diffusion for solid state reactions, especially for energetic materials. Here we demonstrate, through the example of nanowire-based thermite membrane, that the thermite solid-state reaction can be easily tuned via the introduction of low-surface-energy coating layer. Moreover, this silicon-coated thermite membrane exhibit controlled wetting behavior ranging from superhydrophilic to superhydrophobic and, simultaneously, to significantly reduce the friction sensitivity of thermite membrane. This effect enables to increase interfacial resistance by increasing the amount of coating material. Indeed, our results described here make it possible to tune the solid-state reactions through the manipulation of interfacial diffusion between the reactants. PMID:23603809

The effect of bonding environment on iron isotope fractionation between minerals at high temperature

NASA Astrophysics Data System (ADS)

Sossi, Paolo A.; O'Neill, Hugh St. C.

2017-01-01

Central to understanding the processes that drive stable isotope fractionation in nature is their quantification under controlled experimental conditions. The polyvalent element iron, given its abundance in terrestrial rocks, exerts controls on the structural and chemical properties of minerals and melts. The iron isotope compositions of typical high temperature minerals are, however, poorly constrained and their dependence on intensive (e.g. fO2) and extensive (e.g. compositional) variables is unknown. In this work, experiments involving a reference phase, 2 M FeCl2·4H2O(l), together with an oxide mix corresponding to the bulk composition of the chosen mineral were performed in a piston cylinder in Ag capsules. The oxide mix crystallised in situ at 1073 K and 1 GPa, in equilibrium with the iron chloride, and was held for 72 h. In order to characterise the effect of co-ordination and oxidation state on the isotope composition independently, exclusively Fe2+ minerals were substituted in: VIII-fold almandine, VI-fold ilmenite, fayalite and IV-fold chromite and hercynite. Δ57FeMin-FeCl2 increases in the order VIII < VI < IV, consistent with a decrease in the mean Fe-O bond length. Magnetite, which has mixed VI- and IV-fold co-ordination, has the heaviest Δ57Fe by virtue of 2/3 of its iron being the smaller, ferric ion. The composition of the VIFe2+-bearing minerals is similar to that of the aqueous FeCl2 fluid. To the degree that this represents the speciation of iron in fluids exsolving from magmas, the fractionation between them should be small, unless the iron is hosted in magnetite. By contrast, predominantly Fe2+-bearing mantle garnets should preserve a much lighter δ57Fe than their lower pressure spinel counterparts, a signature that may be reflected in partial melts from these lithologies. As the Fe-O bond lengths in fayalite and ilmenite are comparable, their isotope compositions overlap, suggesting that high Ti mare basalts acquired their heavy isotopic signature from ilmenite that crystallised late during lunar magma ocean solidification.

Apatite: A New Tool For Understanding The Temporal Variability Of Magmatic Volatile Contents

NASA Astrophysics Data System (ADS)

Stock, M. J.; Humphreys, M.; Smith, V.; Pyle, D. M.; Isaia, R.

2015-12-01

The apatite crystal structure is capable of incorporating H2O, F and Cl, as well as trace CO2 and sulphur. These can be related to parental magma compositions through application of a series of pressure and temperature-dependent exchange reactions (Piccoli and Candela, 1994), permitting apatite crystals to preserve a record of all major volatile species in the melt. Furthermore, due to the general incompatibility of P in other rock-forming minerals, apatite is ubiquitous in igneous systems and often begins crystallising early, such that apatite inclusions within phenocrysts record melt volatile contents throughout magmatic differentiation. In this work, we compare the compositions of apatite inclusions and microphenocrysts with pyroxene-hosted melt inclusions from the Astroni 1 eruption of Campi Flegrei, Italy. These data are coupled with magmatic differentiation models (Gualda et al., 2012), experimental volatile solubility data (Webster et al., 2014) and thermodynamic models of apatite compositional variations (Piccoli and Candela, 1994) to determine a time-series of magmatic volatile evolution in the build-up to eruption. We find that apatite halogen/OH ratios decreased through magmatic differentiation, while melt inclusion F and Cl concentrations increased. Melt inclusion H2O contents are constant at ~2.5 wt%. These data are best explained by volatile-undersaturated differentiation over most of the crystallisation history of the Astroni 1 melt, with melt inclusion H2O contents reset during ascent, due to rapid H diffusion through the phenocryst hosts (Woods et al., 2000). Given the rapid diffusivity of volatiles in apatite (Brenan, 1993), preservation of undersaturated compositions in microphenocrysts suggests that saturation was only achieved a few days to months before eruption and that it may have been the transition into a volatile-saturated state that ultimately triggered eruption. Piccoli and Candela, 1994. Am. J. of Sc., 294, 92-135. Gualda et al., 2012. J. Pet., 53, 875-890. Webster et al., 2014. J. Pet., 55, 2217-2248. Woods et al., 2000. Am. Min., 85, 480-487. Brenan, 1993. Chem. Geol., 110, 195-210.

Maruyamaite, a new K-dominant tourmaline coexisting with diamond -an important accessory mineral in UHP rocks

NASA Astrophysics Data System (ADS)

Stock, M. J.; Humphreys, M.; Smith, V.; Pyle, D. M.; Isaia, R.

2014-12-01

The apatite crystal structure is capable of incorporating H2O, F and Cl, as well as trace CO2 and sulphur. These can be related to parental magma compositions through application of a series of pressure and temperature-dependent exchange reactions (Piccoli and Candela, 1994), permitting apatite crystals to preserve a record of all major volatile species in the melt. Furthermore, due to the general incompatibility of P in other rock-forming minerals, apatite is ubiquitous in igneous systems and often begins crystallising early, such that apatite inclusions within phenocrysts record melt volatile contents throughout magmatic differentiation. In this work, we compare the compositions of apatite inclusions and microphenocrysts with pyroxene-hosted melt inclusions from the Astroni 1 eruption of Campi Flegrei, Italy. These data are coupled with magmatic differentiation models (Gualda et al., 2012), experimental volatile solubility data (Webster et al., 2014) and thermodynamic models of apatite compositional variations (Piccoli and Candela, 1994) to determine a time-series of magmatic volatile evolution in the build-up to eruption. We find that apatite halogen/OH ratios decreased through magmatic differentiation, while melt inclusion F and Cl concentrations increased. Melt inclusion H2O contents are constant at ~2.5 wt%. These data are best explained by volatile-undersaturated differentiation over most of the crystallisation history of the Astroni 1 melt, with melt inclusion H2O contents reset during ascent, due to rapid H diffusion through the phenocryst hosts (Woods et al., 2000). Given the rapid diffusivity of volatiles in apatite (Brenan, 1993), preservation of undersaturated compositions in microphenocrysts suggests that saturation was only achieved a few days to months before eruption and that it may have been the transition into a volatile-saturated state that ultimately triggered eruption. Piccoli and Candela, 1994. Am. J. of Sc., 294, 92-135. Gualda et al., 2012. J. Pet., 53, 875-890. Webster et al., 2014. J. Pet., 55, 2217-2248. Woods et al., 2000. Am. Min., 85, 480-487. Brenan, 1993. Chem. Geol., 110, 195-210.

Amphibole megacrysts as a probe into the deep plumbing system of Merapi volcano, Central Java, Indonesia

NASA Astrophysics Data System (ADS)

Peters, Stefan T. M.; Troll, Valentin R.; Weis, Franz A.; Dallai, Luigi; Chadwick, Jane P.; Schulz, Bernhard

2017-04-01

Amphibole has been discussed to potentially represent an important phase during early chemical evolution of arc magmas, but is not commonly observed in eruptive arc rocks. Here, we present an in-depth study of metastable calcic amphibole megacrysts in basaltic andesites of Merapi volcano, Indonesia. Radiogenic Sr and Nd isotope compositions of the amphibole megacrysts overlap with the host rock range, indicating that they represent antecrysts to the host magmas rather than xenocrysts. Amphibole-based barometry suggests that the megacrysts crystallised at pressures of >500 MPa, i.e., in the mid- to lower crust beneath Merapi. Rare-earth element concentrations, in turn, require the absence of magmatic garnet in the Merapi feeding system and, therefore, place an uppermost limit for the pressure of amphibole crystallisation at ca. 800 MPa. The host magmas of the megacrysts seem to have fractionated significant amounts of amphibole and/or clinopyroxene, because of their low Dy/Yb ratios relative to the estimated compositions of the parent magmas to the megacrysts. The megacrysts' parent magmas at depth may thus have evolved by amphibole fractionation, in line with apparently coupled variations of trace element ratios in the megacrysts, such as e.g., decreasing Zr/Hf with Dy/Yb. Moreover, the Th/U ratios of the amphibole megacrysts decrease with increasing Dy/Yb and are lower than Th/U ratios in the basaltic andesite host rocks. Uranium in the megacrysts' parent magmas, therefore, may have occurred predominantly in the tetravalent state, suggesting that magmatic fO2 in the Merapi plumbing system increased from below the FMQ buffer in the mid-to-lower crust to 0.6-2.2 log units above it in the near surface environment. In addition, some of the amphibole megacrysts experienced dehydrogenation (H2 loss) and/or dehydration (H2O loss), as recorded by their variable H2O contents and D/ H and Fe3+/Fe2+ ratios, and the release of these volatile species into the shallow plumbing system may facilitate Merapi's often erratic eruptive behaviour.

High temperature solid state storage cell

DOEpatents

Rea, Jesse R.; Kallianidis, Milton; Kelsey, G. Stephen

1983-01-01

A completely solid state high temperature storage cell comprised of a solid rechargeable cathode such as TiS.sub.2, a solid electrolyte which remains solid at the high temperature operating conditions of the cell and which exhibits high ionic conductivity at such elevated temperatures such as an electrolyte comprised of lithium iodide, and a solid lithium or other alkali metal alloy anode (such as a lithium-silicon alloy) with 5-50% by weight of said anode being comprised of said solid electrolyte.

Fractional Crystallisation of Archaean Trondhjemite Magma at 12-7 Kbar: Constraints on Rheology of Archaean Continental Crust

NASA Astrophysics Data System (ADS)

Sarkar, Saheli; Saha, Lopamudra; Satyanarayan, Manavalan; Pati, Jayanta

2015-04-01

Fractional Crystallisation of Archaean Trondhjemite Magma at 12-7 Kbar: Constraints on Rheology of Archaean Continental Crust Sarkar, S.1, Saha, L.1, Satyanarayan, M2. and Pati, J.K.3 1. Department of Earth Sciences, Indian Institute of Technology Roorkee, Roorkee-247667, Haridwar, India, 2. HR-ICPMS Lab, Geochemistry Group, CSIR-National Geophysical Research Institute, Hyderabad-50007, India. 3. Department of Earth and Planetary Sciences, Nehru Science Centre, University of Allahabad, Allahabad-211002, India. Tonalite-Trondhjemite-Granodiorite (TTGs) group of rocks, that mostly constitute the Archaean continental crusts, evolved through a time period of ~3.8 Ga-2.7 Ga with major episodes of juvenile magma generations at ~3.6 Ga and ~2.7 Ga. Geochemical signatures, especially HREE depletions of most TTGs conform to formation of this type of magma by partial melting of amphibolites or eclogites at 15-20 kbar pressure. While TTGs (mostly sodic in compositions) dominates the Eoarchaean (~3.8-3.6 Ga) to Mesoarchaean (~3.2-3.0 Ga) domains, granitic rocks (with significantly high potassium contents) became more dominant in the Neoarchaean period. The most commonly accepted model proposed for the formation of the potassic granite in the Neoarchaean time is by partial melting of TTGs along subduction zones. However Archaean granite intrusive into the gabbro-ultramafic complex from Scourie, NW Scotland has been interpreted to have formed by fractional crystallization of hornblende and plagioclase from co-existing trondhjemitic gneiss. In this study we have studied fractional crystallization paths from a Mesoarchaean trondhjemite from the central Bundelkhand craton, India using MELTS algorithm. Fractional crystallization modeling has been performed at pressure ranges of 20 kbar to 7 kbar. Calculations have shown crystallization of garnet-clinopyroxene bearing assemblages with progressive cooling of the magma at 20 kbar. At pressure ranges 19-16 kbar, solid phases fractionating from the magma are mostly clinopyroxene with minor orthopyroxene. Plagioclase crystals appear at pressures ≤ 15 kbar. Plagioclase crystals are mostly albitic in composition (XAb ~0.70-0.75). At each pressure, with progressive cooling and fractionation of solid phases, crystal-melt ratio becomes significantly higher, magma becomes more depleted in Al2O3, MgO, with significant increase in K2O/Na2O ratio and water content. With progressive cooling and fractionation, overall composition of the magma changes from trondhjemitic to granitic, with increase in viscosity from 4.5 poise to 5.5 poise. The study thus reveals that fractional crystallization of trondhemitic magmas at different depths can form more potassic granitic magma with higher viscosity. As Hf isotope signatures from most Archaean TTGs reveal longer crustal residence, it is likely that granitic magmas that became more common in the Neoarchaean period, could also possibly been derived by fractional crystallization from trondhjemitic magmas in Mesoarchaean time. Granitic magmas hence generated have much higher viscosity compared to the parent trondhjemitic magma. Low viscosity of trondhjemitic magmas and low crystal-melt ratios in the initial stages of crystallization (as derived in this study), may be the cause of formation of large bodies of TTGs in Early Archaean period. Close to Neoarchaean period more granitic magmas are observed. In this study it has been observed that crystallization of these magmas lead to high crystal-melt ratios and the magmas have higher viscosity. Such change in composition from Early to Neoarchaean time must have made Archaean crusts stronger and hence more prone to deformation. This observation hence support occurrence of Phanerozoic style signatures from poly-deformed terrains of Neoarchaean time.

40 CFR 256.22 - Recommendations for State regulatory powers.

Code of Federal Regulations, 2010 CFR

2010-07-01

... WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid Waste... prohibit new open dumps and close or upgrade all existing open dumps. (a) Solid waste disposal standards... solid waste disposal facility. These procedures should include identification of future land use or the...

40 CFR 256.22 - Recommendations for State regulatory powers.

Code of Federal Regulations, 2011 CFR

2011-07-01

... WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid Waste... prohibit new open dumps and close or upgrade all existing open dumps. (a) Solid waste disposal standards... solid waste disposal facility. These procedures should include identification of future land use or the...

40 CFR 256.21 - Requirements for State regulatory powers.

Code of Federal Regulations, 2010 CFR

2010-07-01

... WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid Waste... be adequate to enforce solid waste disposal standards which are equivalent to or more stringent than the criteria for classification of solid waste disposal facilities (40 CFR part 257). Such authority...

40 CFR 256.21 - Requirements for State regulatory powers.

Code of Federal Regulations, 2011 CFR

2011-07-01

... WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Solid Waste... be adequate to enforce solid waste disposal standards which are equivalent to or more stringent than the criteria for classification of solid waste disposal facilities (40 CFR part 257). Such authority...

Crystallographic structure refinement with quadrupolar nuclei: a combined solid-state NMR and GIPAW DFT example using MgBr(2).

PubMed

Widdifield, Cory M; Bryce, David L

2009-09-07

Solid-state NMR spectroscopy and GIPAW DFT calculations reveal the pronounced sensitivity of (79/81)Br and (25)Mg quadrupolar coupling constants to subtle aspects of solid state structure which were not previously detected by pXRD methods.

Method and system for making integrated solid-state fire-sets and detonators

DOEpatents

O'Brien, Dennis W.; Druce, Robert L.; Johnson, Gary W.; Vogtlin, George E.; Barbee, Jr., Troy W.; Lee, Ronald S.

1998-01-01

A slapper detonator comprises a solid-state high-voltage capacitor, a low-jitter dielectric breakdown switch and trigger circuitry, a detonator transmission line, an exploding foil bridge, and a flier material. All these components are fabricated in a single solid-state device using thin film deposition techniques.

Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them

DOEpatents

Schwartz, Michael; White, James H.; Sammells, Anthony F.

2005-09-27

This invention relates to gas-impermeable, solid state materials fabricated into membranes for use in catalytic membrane reactors. This invention particularly relates to solid state oxygen anion- and electron-mediating membranes for use in catalytic membrane reactors for promoting partial or full oxidation of different chemical species, for decomposition of oxygen-containing species, and for separation of oxygen from other gases. Solid state materials for use in the membranes of this invention include mixed metal oxide compounds having the brownmillerite crystal structure.

Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them

DOEpatents

Schwartz, Michael; White, James H.; Sammels, Anthony F.

2000-01-01

This invention relates to gas-impermeable, solid state materials fabricated into membranes for use in catalytic membrane reactors. This invention particularly relates to solid state oxygen anion- and electron-mediating membranes for use in catalytic membrane reactors for promoting partial or full oxidation of different chemical species, for decomposition of oxygen-containing species, and for separation of oxygen from other gases. Solid state materials for use in the membranes of this invention include mixed metal oxide compounds having the brownmillerite crystal structure.

What's in a Name Change?

NASA Astrophysics Data System (ADS)

Martin, Joseph D.

2015-03-01

When solid state physics emerged in the 1940s, its name was controversial. By the 1970s, some physicists came to prefer "condensed matter" as a way to identify the discipline of physics examining complex matter. Physicists and historians often gloss this transition as a simple rebranding of a problematically named field, but attention to the motives behind these names reveals telling nuances. "Solid state physics" and "condensed matter physics"—along with "materials science," which also emerged during the Cold War—were named in accordance with ideological commitments about the identity of physics. Historians, therefore, can profitably understand solid state and condensed matter physics as distinct disciplines. Condensed matter, rather than being continuous with solid state physics, should be considered alongside materials science as an outlet for specific frustrations with the way solid state was organized.

Solid-State Powered X-band Accelerator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Othman, Mohamed A.K.; Nann, Emilio A.; Dolgashev, Valery A.

2017-03-06

In this report we disseminate the hot test results of an X-band 100-W solid state amplifier chain for linear accelerator (linac) applications. Solid state power amplifiers have become increasingly attractive solutions for achieving high power in radar and maritime applications. Here the performance of solid state amplifiers when driving an RF cavity is investigated. Commercially available, matched and fully-packaged GaN on SiC HEMTs are utilized, comprising a wideband driver stage and two power stages. The amplifier chain has a high poweradded- efficiency and is able to supply up to ~1.2 MV/m field gradient at 9.2 GHz in a simple testmore » cavity, with a peak power exceeding 100 W. These findings set forth the enabling technology for solid-state powered linacs.« less

Novel Nanostructured Solid Materials for Modulating Oral Drug Delivery from Solid-State Lipid-Based Drug Delivery Systems.

PubMed

Dening, Tahnee J; Rao, Shasha; Thomas, Nicky; Prestidge, Clive A

2016-01-01

Lipid-based drug delivery systems (LBDDS) have gained significant attention in recent times, owing to their ability to overcome the challenges limiting the oral delivery of poorly water-soluble drugs. Despite the successful commercialization of several LBDDS products over the years, a large discrepancy exists between the number of poorly water-soluble drugs displaying suboptimal in vivo performances and the application of LBDDS to mitigate their various delivery challenges. Conventional LBDDS, including lipid solutions and suspensions, emulsions, and self-emulsifying formulations, suffer from various drawbacks limiting their widespread use and commercialization. Accordingly, solid-state LBDDS, fabricated by adsorbing LBDDS onto a chemically inert solid carrier material, have attracted substantial interest as a viable means of stabilizing LBDDS whilst eliminating some of the various limitations. This review describes the impact of solid carrier choice on LBDDS performance and highlights the importance of appropriate solid carrier material selection when designing hybrid solid-state LBDDS. Specifically, emphasis is placed on discussing the ability of the specific solid carrier to modulate drug release, control lipase action and lipid digestion, and enhance biopharmaceutical performance above the original liquid-state LBDDS. To encourage the interested reader to consider their solid carrier choice on a higher level, various novel materials with the potential for future use as solid carriers for LBDDS are described. This review is highly significant in guiding future research directions in the solid-state LBDDS field and fostering the translation of these delivery systems to the pharmaceutical marketplace.

Bioavailability of indomethacin-saccharin cocrystals.

PubMed

Jung, Min-Sook; Kim, Jeong-Soo; Kim, Min-Soo; Alhalaweh, Amjad; Cho, Wonkyung; Hwang, Sung-Joo; Velaga, Sitaram P

2010-11-01

Pharmaceutical cocrystals are new solid forms with physicochemical properties that appear promising for drug product development. However, the in-vivo bioavailability of cocrystals has rarely been addressed. The cocrystal of indomethacin (IND), a Biopharmaceutical Classification System class II drug, with saccharin (SAC) has been shown to have higher solubility than IND at all pH. In this study, we aimed to evaluate the in-vitro dissolution and in-vivo bioavailability of IND-SAC cocrystals in comparison with IND in a physical mixture and the marketed product Indomee. Scale-up of the cocrystals was undertaken using cooling batch crystallisation without seeding. The chemical and physical purity of the up-scaled material was verified using high-performance liquid chromatography, differential scanning calorimetry and powder X-ray diffraction. The IND-SAC cocrystals and IND plus SAC were mixed with lactose and the formulations were placed into gelatin capsules. In-vitro dissolution studies were then performed using the rotating basket dissolution method. The intrinsic dissolution rate of IND and IND-SAC cocrystals was also determined. Finally, a bioavailability study for the formulations was conducted in beagle dogs. The plasma samples were analysed using high-performance liquid chromatography and the pharmacokinetic data were analysed using standard methodologies.   The bulk cocrystals (i.e. scaled-up material) were chemically and physically pure. The in-vitro dissolution rate of the cocrystals was higher than that of IND and similar to that of Indomee at pH 7.4 and pH 1.2. The in-vivo bioavailability of the IND-SAC cocrystals in dogs was significantly higher (ANOVA, P<0.05) than that of IND but not significantly different from Indomee (ANOVA, P>0.05). The study indicates that the improved aqueous solubility of the cocrystals leads to improved bioavailability of IND. Thus, the cocrystals are a viable alternative solid form that can improve the dissolution rate and bioavailability of poorly soluble drugs. © 2010 The Authors. JPP © 2010 Royal Pharmaceutical Society of Great Britain.

Solid-state and solution /sup 13/C NMR in the conformational analysis of methadone-hydrochloride and related narcotic analgesics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sumner, S.C.J.

1986-01-01

Solid state and solution /sup 13/C NMR have been used to study the conformations of the racemic mixtures and single enantiomers of methadone hydrochloride, alpha and beta methadol hydrochloride, and alpha and beta acetylmethadol hydrochloride. The NMR spectra acquired for the compounds as solids, and in polar and nonpolar solvents are compared, in order to determine the conformation of the molecules in solution. To determine the reliability of assigning solution conformations by comparing solution and solid state chemical shift data, three bond coupling constants measured in solution are compared with those calculated from X-ray data. The conformations of the racemicmore » mixture and plus enantiomer of methadone hydrochloride have been shown to be very similar in the solid state, where minor differences in conformation can be seen by comparing NMR spectra obtained for the solids. Also shown is that the molecules of methadone hydrochloride have conformations in polar and in nonpolar solvents which are very similar to the conformation of the molecules in the solid state.« less

Intermediate-depth earthquake generation: what hydrous minerals can tell us

NASA Astrophysics Data System (ADS)

Deseta, N.; Ashwal, L.; Andersen, T. B.

2012-04-01

Subduction zone seismicity has commonly been causally related to the dehydration of minerals within the subducting slab(Hacker et al. 2004, Jung et al. (2004), Dobson et al. 2002, Rondenay et al. 2008). Other models for release of intermediate- and deep earthquakes include spontaneous reaction(s) affecting large rock-bodies along overstepped phase boundaries ( e.g. Green and Houston, 1995) and various shear heating-localization models (e.g. Kelemen and Hirth 2007, John et al. 2009). These concepts are principally reliant on seismic and thermo-petrological modeling; both of which are indirect methods of analysis. Recent discoveries of pseudotachylytes (PST) formed under high pressure conditions (Ivrea-Verbano Zone, Italy, Western Gneiss Region, Norway and Corsica) provide the first tangible opportunity to evaluate these models (Austrheim and Andersen, 2004, Lund and Austrheim, 2003, Obata and Karato, 1995, Jin et al., 1998). This case study focuses on observations based on ultramafic and mafic PST within the Ligurian Ophiolite of the high pressure-low temperature metamorphic (HP-LT) 'Shistes Lustres' complex in Cima di Gratera, Corsica (Andersen et al. 2008). These PST have been preserved in pristine lenses of peridotite and gabbro surrounded by schistose serpentinites. The PST range in thickness from 1mm to 25 cm (Andersen and Austrheim, 2006). Petrography and geochemistry on PST from the peridotite and gabbro samples indicates that total/near-total fusion of the local host rock mineral assemblage occurred; bringing up the temperature of shear zone from 350° C to 1400 - 1700° C; depending on the host rock (Andersen and Austrheim, 2006). The composition of the PST is highly variable, even at the thin section scale and this has been attributed to the coarse-grained nature of the host rock, its small scale inhomogeneity and poor mixing of the fusion melt. Almost all the bulk analyses of the PST are hydrous; the peridotitic PST is always hydrous (H2O content from 3.8 to 14 wt %) but the gabbro is not (H2O content from 0 to 2.6 wt%). The hydrous nature of the PST is due to the preferential melting of hydrous minerals (chlorite and serpentine - peridotite, glaucophane, epidote, Mg-hornblende - gabbro) in the host rock, rather than later hydration associated with exhumation (greenschist facies metamorphism and later alteration). However, in the case of the gabbro, the melt can be hydrous, but is not always. Anhydrous, glassy PST is formed in association with hydrous PST in the gabbro host rock. The gabbroic PST nucleate at the boundary between a coarse-grained pegmatoidal gabbro and a fine-grained gabbro, whereas the exclusively hydrous peridotite-hosted PST only nucleate along pre-existing hydrated fractures. These facts are significant when considering the mechanism of formation of the pseudotachylyte; which is commonly thought to be associated with the preferential melting of hydrous minerals. An anhydrous melt in proximity to other hydrous melts formed contemporaneously must have formed by the same mechanism; one which can exploit more than just one rheological characteristic in the rock vis. hydrous mineralogy AND grain size changes. Furthermore the presence of anhydrous PST suggests that little or no fluid ingress occurred prior to or during PST generation. Hydrous crystallisation products in the gabbro such as glaucophane and edenite indicate that whole-sale melting of the wallrock amphiboles (glaucophane, edenite, actinolite) took place to produce a melt with dissolved H2O, out of which such blue amphiboles were able to crystallise. It is important to note that in order for amphiboles to crystallise out of a melt, H2O is required but necessarily to an under-saturated degree. i.e. it cannot be 'free' water occurring as a separate phase in the melt (Carmen and Gilbert, 1983 and Koons, 1982). It is unlikely therefore that the water in the gabbro-derived fusion melt was the result of solid-state dehydration of the wallrock amphiboles. Microtextural observations of sheared out, kinked, twinned, prolate wallrock grains millimetres from vein boundaries and thermally rounded clasts, similarly deformed, entrained into the melt suggest that the process initiating fusion melting and seismic failure is spatially and temporally related to a high temperature ductile process rather than a brittle one. Together, the microtextural and geochemical observations provide ample support for a ductile thermal run-away process to initiate high pressure PST development and seismic failure and preclude dehydration embrittlement.

Solid State Division annual progress report for period ending December 31, 1975

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilkinson, M.K.; Young, F.W. Jr.

1976-05-01

Research activities are reported in programs on theoretical solid state physics, physical properties of solids, radiation effects in metals, neutron scattering, research materials, and isotope research materials. (JRD)

Tribological properties of surfaces

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1978-01-01

The real area of contact between two solid surfaces is only a small portion of the apparent area. Deformation of these areas can result in solid state contact through surface films. For clean solid to solid contact strong adhesive bonding occurs across the interface. Under these conditions many properties of the solid such as the metallurgical and chemical nature of metals can influence adhesion, friction, and wear behavior. The presence of gases, liquids, and solid films on the surface of solids alter markedly tribological characteristics. These surface films can also considerably change the mechanical effects of solid state contact on bulk material behavior.

Characterization of Pharmaceutical Cocrystals and Salts by Dynamic Nuclear Polarization-Enhanced Solid-State NMR Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Li; Hanrahan, Michael P.; Chakravarty, Paroma

Multicomponent solids such as cocrystals have emerged as a way to control and engineer the stability, solubility and manufacturability of solid active pharmaceutical ingredients (APIs). Cocrystals are typically formed by solution- or solid-phase reactions of APIs with suitable cocrystal coformers, which are often weak acids. One key structural question about a given multicomponent solid is whether it should be classified as a salt, where the basic API is protonated by the acid, or as a cocrystal, where the API and coformer remain neutral and engage in hydrogen bonding interactions. It has previously been demonstrated that solid-state NMR spectroscopy is amore » powerful probe of structure in cocrystals and salts of APIs, however, the poor sensitivity of solid-state NMR spectroscopy usually restricts the types of experiments that can be performed. Here relayed dynamic nuclear polarization (DNP) was applied to reduce solid-state NMR experiments by one to two orders of magnitude for salts and cocrystals of a complex API. The large sensitivity gains from DNP facilitates rapid acquisition of natural isotopic abundance 13C and 15N solid-state NMR spectra. Critically, DNP enables double resonance 1H-15N solid-state NMR experiments such as 2D 1H-15N HETCOR, 1H-15N CP-build up, 15N{1H} J-resolved/attached proton tests, 1H-15N DIPSHIFT and 1H-15N PRESTO. The latter two experiments allow 1H-15N dipolar coupling constants and H-N bond lengths to be accurately measured, providing an unambiguous assignment of nitrogen protonation state and definitive classification of the multi-component solids as cocrystals or salts. In conclusion, these types of measurements should also be extremely useful in the context of polymorph discrimination, NMR crystallography structure determination and for probing hydrogen bonding in a variety of organic materials.« less

Characterization of Pharmaceutical Cocrystals and Salts by Dynamic Nuclear Polarization-Enhanced Solid-State NMR Spectroscopy

DOE PAGES

Zhao, Li; Hanrahan, Michael P.; Chakravarty, Paroma; ...

2018-02-15

Multicomponent solids such as cocrystals have emerged as a way to control and engineer the stability, solubility and manufacturability of solid active pharmaceutical ingredients (APIs). Cocrystals are typically formed by solution- or solid-phase reactions of APIs with suitable cocrystal coformers, which are often weak acids. One key structural question about a given multicomponent solid is whether it should be classified as a salt, where the basic API is protonated by the acid, or as a cocrystal, where the API and coformer remain neutral and engage in hydrogen bonding interactions. It has previously been demonstrated that solid-state NMR spectroscopy is amore » powerful probe of structure in cocrystals and salts of APIs, however, the poor sensitivity of solid-state NMR spectroscopy usually restricts the types of experiments that can be performed. Here relayed dynamic nuclear polarization (DNP) was applied to reduce solid-state NMR experiments by one to two orders of magnitude for salts and cocrystals of a complex API. The large sensitivity gains from DNP facilitates rapid acquisition of natural isotopic abundance 13C and 15N solid-state NMR spectra. Critically, DNP enables double resonance 1H-15N solid-state NMR experiments such as 2D 1H-15N HETCOR, 1H-15N CP-build up, 15N{1H} J-resolved/attached proton tests, 1H-15N DIPSHIFT and 1H-15N PRESTO. The latter two experiments allow 1H-15N dipolar coupling constants and H-N bond lengths to be accurately measured, providing an unambiguous assignment of nitrogen protonation state and definitive classification of the multi-component solids as cocrystals or salts. In conclusion, these types of measurements should also be extremely useful in the context of polymorph discrimination, NMR crystallography structure determination and for probing hydrogen bonding in a variety of organic materials.« less

Application of Solid-State NMR Relaxometry for Characterization and Formulation Optimization of Grinding-Induced Drug Nanoparticle.

PubMed

Ueda, Keisuke; Higashi, Kenjirou; Moribe, Kunikazu

2016-03-07

The formation mechanism of drug nanoparticles was investigated using solid-state nuclear magnetic resonance (NMR) techniques for the efficient discovery of an optimized nanoparticle formulation. The cogrinding of nifedipine (NIF) with polymers, including hydroxypropyl methylcellulose (HPMC) and polyvinylpyrrolidone (PVP), and sodium dodecyl sulfate (SDS) was performed to prepare the NIF nanoparticle formulations. Then, solid-state NMR relaxometry was used for the nanometer-order characterization of NIF in the polymer matrix. Solid-state NMR measurements revealed that the crystal size of NIF was reduced to several tens of nanometers with amorphization of NIF by cogrinding with HPMC and SDS for 100 min. Similarly, the size of the NIF crystal was reduced to less than 90 nm in the 40 min ground mixture of NIF/PVP/SDS. Furthermore, 100 min grinding of NIF/PVP/SDS induced amorphization of almost all the NIF crystals followed by nanosizing. The hydrogen bond between NIF and PVP led to the efficient amorphization of NIF in the NIF/PVP/SDS system compared with NIF/HPMC/SDS system. The efficient nanosizing of the NIF crystal in the solid state, revealed by the solid-state NMR relaxation time measurements, enabled the formation of large amounts of NIF nanoparticles in water followed by the polymer dissolution. In contrast, excess amorphization of the NIF crystals failed to efficiently prepare the NIF nanoparticles. The solid-state characterization of the crystalline NIF revealed good correlation with the NIF nanoparticles formation during aqueous dispersion. Furthermore, the solid-state NMR measurements including relaxometry successfully elucidated the nanometer-order dispersion state of NIF in polymer matrix, leading to the discovery of optimized conditions for the preparation of suitable drug nanoparticles.

Method and system for making integrated solid-state fire-sets and detonators

DOEpatents

O`Brien, D.W.; Druce, R.L.; Johnson, G.W.; Vogtlin, G.E.; Barbee, T.W. Jr.; Lee, R.S.

1998-03-24

A slapper detonator comprises a solid-state high-voltage capacitor, a low-jitter dielectric breakdown switch and trigger circuitry, a detonator transmission line, an exploding foil bridge, and a flier material. All these components are fabricated in a single solid-state device using thin film deposition techniques. 13 figs.

CO2-Doped Diamond: A Potential Solid-State CO2 Laser Material?

NASA Technical Reports Server (NTRS)

Tratt, D.

1994-01-01

This paper describes a novel concept for a solid-state CO subscript 2 laser medium which, by eschewing the gas-phase approach, may offer prospects for a compact, robust 9 - 11 (micro)m coherent source, coupled with the potentially superior frequency stability characteristics afforded by monolithic solid-state construction.

40 CFR 256.02 - Scope of the State solid waste management plan.

Code of Federal Regulations, 2011 CFR

2011-07-01

..., General Requirements, Definitions § 256.02 Scope of the State solid waste management plan. (a)(1) The... 40 Protection of Environment 25 2011-07-01 2011-07-01 false Scope of the State solid waste management plan. 256.02 Section 256.02 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED...

40 CFR 256.02 - Scope of the State solid waste management plan.

Code of Federal Regulations, 2013 CFR

2013-07-01

..., General Requirements, Definitions § 256.02 Scope of the State solid waste management plan. (a)(1) The... 40 Protection of Environment 26 2013-07-01 2013-07-01 false Scope of the State solid waste management plan. 256.02 Section 256.02 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED...

40 CFR 256.02 - Scope of the State solid waste management plan.

Code of Federal Regulations, 2014 CFR

2014-07-01

..., General Requirements, Definitions § 256.02 Scope of the State solid waste management plan. (a)(1) The... 40 Protection of Environment 25 2014-07-01 2014-07-01 false Scope of the State solid waste management plan. 256.02 Section 256.02 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED...

40 CFR 256.02 - Scope of the State solid waste management plan.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., General Requirements, Definitions § 256.02 Scope of the State solid waste management plan. (a)(1) The... 40 Protection of Environment 24 2010-07-01 2010-07-01 false Scope of the State solid waste management plan. 256.02 Section 256.02 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED...

40 CFR 256.02 - Scope of the State solid waste management plan.

Code of Federal Regulations, 2012 CFR

2012-07-01

..., General Requirements, Definitions § 256.02 Scope of the State solid waste management plan. (a)(1) The... 40 Protection of Environment 26 2012-07-01 2011-07-01 true Scope of the State solid waste management plan. 256.02 Section 256.02 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED...

Polyaniline-Modified Oriented Graphene Hydrogel Film as the Free-Standing Electrode for Flexible Solid-State Supercapacitors.

PubMed

Du, Pengcheng; Liu, Huckleberry C; Yi, Chao; Wang, Kai; Gong, Xiong

2015-11-04

In this study, we report polyaniline (PANI)-modified oriented graphene hydrogel (OGH) films as the free-standing electrode for flexible solid-state supercapacitors (SCs). The OGH films are prepared by a facile filtration method using chemically converted graphene sheets and then introduced to PANI on the surface of OGH films by in situ chemical polymerization. The PANI-modified OGH films possess high flexibility, high electrical conductivity, and mechanical robustness. The flexible solid-state SCs based on the PANI-modified OGH films exhibit a specific capacitance of 530 F/g, keeping 80% of its original value up to 10 000 charge-discharge cycles at the current density of 10 A/g. Remarkably, the flexible solid-state SCs maintain ∼100% capacitance retention bent at 180° for 250 cycles. Moreover, the flexible solid-state SCs are further demonstrated to be able to light up a red-light-emitting diode. These results indicate that the flexible solid-state SCs based on PANI-modified OGH films as the free-standing electrode have potential applications as energy-storage devices.

Modular nonvolatile solid state recorder (MONSSTR) update

NASA Astrophysics Data System (ADS)

Klang, Mark R.; Small, Martin B.; Beams, Tom

2001-12-01

Solid state recorders have begun replacing traditional tape recorders in fulfilling the requirement to record images on airborne platforms. With the advances in electro-optical, IR, SAR, Multi and Hyper-spectral sensors and video recording requirements, solid state recorders have become the recorder of choice. Solid state recorders provide the additional storage, higher sustained bandwidth, less power, less weight and smaller footprint to meet the current and future recording requirements. CALCULEX, Inc., manufactures a non-volatile flash memory solid state recorder called the MONSSTR (Modular Non-volatile Solid State Recorder). MONSSTR is being used to record images from many different digital sensors on high performance aircraft such as the RF- 4, F-16 and the Royal Air Force Tornado. MONSSTR, with its internal multiplexer, is also used to record instrumentation data. This includes multiple streams of PCM and multiple channels of 1553 data. Instrumentation data is being recorded by MONSSTR systems in a range of platforms including F-22, F-15, F-16, Comanche Helicopter and US Navy torpedos. MONSSTR can also be used as a cockpit video recorder. This paper will provide an update of the MONSSTR.

KENNEDY SPACE CENTER, FLA. - Workers in KSC's Vertical Processing Facility prepare a solid state recorder for installation in a protective enclosure as part of the prelaunch preparations for STS-82, the second Hubble Space Telescope servicing mission. The digital solid state recorder will replace one of three engineering/science tape recorders on Hubble. The solid state recorder has no moving parts to wear out. It also is more flexible than a reel-to-reel recorder and can store 10 times as much data. Liftoff aboard Discovery is targeted Feb. 11 with a crew of seven.

NASA Image and Video Library

1997-01-16

KENNEDY SPACE CENTER, FLA. - Workers in KSC's Vertical Processing Facility prepare a solid state recorder for installation in a protective enclosure as part of the prelaunch preparations for STS-82, the second Hubble Space Telescope servicing mission. The digital solid state recorder will replace one of three engineering/science tape recorders on Hubble. The solid state recorder has no moving parts to wear out. It also is more flexible than a reel-to-reel recorder and can store 10 times as much data. Liftoff aboard Discovery is targeted Feb. 11 with a crew of seven.

KENNEDY SPACE CENTER, FLA. - Workers in KSC's Vertical Processing Facility install a solid state recorder into a transport assembly in its protective enclosure as part of the prelaunch preparations for STS-82, the second Hubble Space Telescope servicing mission. The digital solid state recorder will replace one of three engineering/science tape recorders on Hubble. The solid state recorder has no moving parts to wear out. It also is more flexible than a reel-to-reel recorder and can store 10 times as much data. Liftoff aboard Discovery is targeted Feb. 11 with a crew of seven.

NASA Image and Video Library

1997-01-16

KENNEDY SPACE CENTER, FLA. - Workers in KSC's Vertical Processing Facility install a solid state recorder into a transport assembly in its protective enclosure as part of the prelaunch preparations for STS-82, the second Hubble Space Telescope servicing mission. The digital solid state recorder will replace one of three engineering/science tape recorders on Hubble. The solid state recorder has no moving parts to wear out. It also is more flexible than a reel-to-reel recorder and can store 10 times as much data. Liftoff aboard Discovery is targeted Feb. 11 with a crew of seven.

Fabrication, testing and simulation of all solid state three dimensional Li-ion batteries

DOE PAGES

Talin, Albert Alec; Ruzmetov, Dmitry; Kolmakov, Andrei; ...

2016-11-10

Realization of safe, long cycle life and simple to package solid-state rechargeable batteries with high energy and power density has been a long-standing goal of the energy storage community. [1,2] Much of the research activity has been focused on developing new solid electrolytes with high Li ionic conductivity. In addition, LiPON, the only solid electrolyte currently used in commercial thin film solid state Li-ion batteris (SSLIBs), has a conductivity of ~10 -6 S/cm, compared to ~0.01 S/cm typically observed for liquid organic electrolytes [3].

Charge transport in strongly coupled quantum dot solids

NASA Astrophysics Data System (ADS)

Kagan, Cherie R.; Murray, Christopher B.

2015-12-01

The emergence of high-mobility, colloidal semiconductor quantum dot (QD) solids has triggered fundamental studies that map the evolution from carrier hopping through localized quantum-confined states to band-like charge transport in delocalized and hybridized states of strongly coupled QD solids, in analogy with the construction of solids from atoms. Increased coupling in QD solids has led to record-breaking performance in QD devices, such as electronic transistors and circuitry, optoelectronic light-emitting diodes, photovoltaic devices and photodetectors, and thermoelectric devices. Here, we review the advances in synthesis, assembly, ligand treatments and doping that have enabled high-mobility QD solids, as well as the experiments and theory that depict band-like transport in the QD solid state. We also present recent QD devices and discuss future prospects for QD materials and device design.

Charge transport in strongly coupled quantum dot solids.

PubMed

Kagan, Cherie R; Murray, Christopher B

2015-12-01

The emergence of high-mobility, colloidal semiconductor quantum dot (QD) solids has triggered fundamental studies that map the evolution from carrier hopping through localized quantum-confined states to band-like charge transport in delocalized and hybridized states of strongly coupled QD solids, in analogy with the construction of solids from atoms. Increased coupling in QD solids has led to record-breaking performance in QD devices, such as electronic transistors and circuitry, optoelectronic light-emitting diodes, photovoltaic devices and photodetectors, and thermoelectric devices. Here, we review the advances in synthesis, assembly, ligand treatments and doping that have enabled high-mobility QD solids, as well as the experiments and theory that depict band-like transport in the QD solid state. We also present recent QD devices and discuss future prospects for QD materials and device design.

Solid state SPS microwave generation and transmission study. Volume 2, phase 2: Appendices

NASA Technical Reports Server (NTRS)

Maynard, O. E.

1980-01-01

The solid state sandwich concept for SPS was further defined. The design effort concentrated on the spacetenna, but did include some system analysis for parametric comparison reasons. Basic solid state microwave devices were defined and modeled. An initial conceptual subsystems and system design was performed as well as sidelobe control and system selection. The selected system concept and parametric solid state microwave power transmission system data were assessed relevant to the SPS concept. Although device efficiency was not a goal, the sensitivities to design of this efficiency were parametrically treated. Sidelobe control consisted of various single step tapers, multistep tapers and Gaussian tapers. A hybrid concept using tubes and solid state was evaluated. Thermal analyses are included with emphasis on sensitivities to waste heat radiator form factor, emissivity, absorptivity, amplifier efficiency, material and junction temperature.

Recent Developments of All-Solid-State Lithium Secondary Batteries with Sulfide Inorganic Electrolytes.

PubMed

Xu, Ruochen; Zhang, Shengzhao; Wang, Xiuli; Xia, Yan; Xia, Xinhui; Wu, Jianbo; Gu, Changdong; Tu, Jiangping

2018-04-20

Due to the increasing demand of security and energy density, all-solid-state lithium ion batteries have become the promising next-generation energy storage devices to replace the traditional liquid batteries with flammable organic electrolytes. In this Minireview, we focus on the recent developments of sulfide inorganic electrolytes for all-solid-state batteries. The challenges of assembling bulk-type all-solid-state batteries for industrialization are discussed, including low ionic conductivity of the present sulfide electrolytes, high interfacial resistance and poor compatibility between electrolytes and electrodes. Many efforts have been focused on the solutions for these issues. Although some progresses have been achieved, it is still far away from practical application. The perspectives for future research on all-solid-state lithium ion batteries are presented. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microfluidic multiplexing of solid-state nanopores

NASA Astrophysics Data System (ADS)

Jain, Tarun; Rasera, Benjamin C.; Guerrero, Ricardo Jose S.; Lim, Jong-Min; Karnik, Rohit

2017-12-01

Although solid-state nanopores enable electronic analysis of many clinically and biologically relevant molecular structures, there are few existing device architectures that enable high-throughput measurement of solid-state nanopores. Herein, we report a method for microfluidic integration of multiple solid-state nanopores at a high density of one nanopore per (35 µm2). By configuring microfluidic devices with microfluidic valves, the nanopores can be rinsed from a single fluid input while retaining compatibility for multichannel electrical measurements. The microfluidic valves serve the dual purpose of fluidic switching and electric switching, enabling serial multiplexing of the eight nanopores with a single pair of electrodes. Furthermore, the device architecture exhibits low noise and is compatible with electroporation-based in situ nanopore fabrication, providing a scalable platform for automated electronic measurement of a large number of integrated solid-state nanopores.

40 CFR 256.63 - Requirements for public participation in the permitting of facilities.

Code of Federal Regulations, 2010 CFR

2010-07-01

... PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE... solid waste disposal facility the State shall hold a public hearing to solicit public reaction and...

3D-Printing Electrolytes for Solid-State Batteries.

PubMed

McOwen, Dennis W; Xu, Shaomao; Gong, Yunhui; Wen, Yang; Godbey, Griffin L; Gritton, Jack E; Hamann, Tanner R; Dai, Jiaqi; Hitz, Gregory T; Hu, Liangbing; Wachsman, Eric D

2018-05-01

Solid-state batteries have many enticing advantages in terms of safety and stability, but the solid electrolytes upon which these batteries are based typically lead to high cell resistance. Both components of the resistance (interfacial, due to poor contact with electrolytes, and bulk, due to a thick electrolyte) are a result of the rudimentary manufacturing capabilities that exist for solid-state electrolytes. In general, solid electrolytes are studied as flat pellets with planar interfaces, which minimizes interfacial contact area. Here, multiple ink formulations are developed that enable 3D printing of unique solid electrolyte microstructures with varying properties. These inks are used to 3D-print a variety of patterns, which are then sintered to reveal thin, nonplanar, intricate architectures composed only of Li 7 La 3 Zr 2 O 12 solid electrolyte. Using these 3D-printing ink formulations to further study and optimize electrolyte structure could lead to solid-state batteries with dramatically lower full cell resistance and higher energy and power density. In addition, the reported ink compositions could be used as a model recipe for other solid electrolyte or ceramic inks, perhaps enabling 3D printing in related fields. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dendritic copper phthalocyanine with aggregation induced blue emission and solid-state fluorescence

NASA Astrophysics Data System (ADS)

Wang, Jiayi; Pan, Lin; Zhou, Xuefei; Jia, Kun; Liu, Xiaobo

2016-09-01

In this work, dendritic copper phthalocyanine (CuPc) showing obvious aggregation induced emission (AIE) and strong solid-state fluorescence was synthesized. It was found that synthesized CuPc can be easily solubilized in polar aprotic solvent, where no fluorescence signal was detected. Interestingly, both the CuPc aggregates in solution and solid-state powder exhibited strong fluorescence emission around 480 nm, which should be attributed to the restriction of intramolecular rotation as rationalized in aggregation induced emission framework. Meanwhile the obvious crystalline enhanced solid-state fluorescent emission is observed for CuPc powder.

Solar Power Satellite (SPS) solid-state antenna power combiner

NASA Technical Reports Server (NTRS)

1980-01-01

A low loss power-combining microstrip antenna suitable for solid state solar power satellite (SPS) application was developed. A unique approach for performing both the combining and radiating function in a single cavity-type circuit was verified, representing substantial refinements over previous demonstration models in terms of detailed geometry to obtain good matching and adequate bandwidth at the design frequency. The combiner circuit was designed, built, and tested and the overall results support the view that the solid state power-combining antenna approach is a viable candidate for a solid state SPS antenna building block.

NASA satellite communications application research. Phase 2: Efficient high power, solid state amplifier for EFH communications

NASA Technical Reports Server (NTRS)

Benet, James

1993-01-01

The final report describes the work performed from 9 Jun. 1992 to 31 Jul. 1993 on the NASA Satellite Communications Application Research (SCAR) Phase 2 program, Efficient High Power, Solid State Amplifier for EHF Communications. The purpose of the program was to demonstrate the feasibility of high-efficiency, high-power, EHF solid state amplifiers that are smaller, lighter, more efficient, and less costly than existing traveling wave tube (TWT) amplifiers by combining the output power from up to several hundred solid state amplifiers using a unique orthomode spatial power combiner (OSPC).

[The design of all solid-state tunable pulsed Ti:sapphire laser system].

PubMed

Chen, Zhe; Ku, Geng; Wan, Junchao; Wang, Wei; Zhou, Chuanqing

2013-05-01

This paper presented a design of broadly all solid-state tunable pulsed Ti:sapphire laser with high power and stable performance. The laser was pumped by custom-made Nd:YAG laser which had water cooling system and amplified by two stage amplifier. The method accomplished tunable output of all solid-state tunable pulsed Ti:sapphire laser by modifying the reflection angle of the back mirror. We investigated the relationship between the power of the pumping laser and the all solid-state tunable pulsed Ti: sapphire laser by changing the power of the pumping source.

A compact 300 kV solid-state high-voltage nanosecond generator for dielectric wall accelerator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Yi; Wang, Wei; Liu, Yi

2015-05-15

Compact solid-state system is the main development trend in pulsed power technologies. A compact solid-state high-voltage nanosecond pulse generator with output voltage of 300 kV amplitude, 10 ns duration (FWHM), and 3 ns rise-time was designed for a dielectric wall accelerator. The generator is stacked by 15 planar-plate Blumlein pulse forming lines (PFL). Each Blumlein PFL consists of two solid-state planar transmission lines, a GaAs photoconductive semiconductor switch, and a laser diode trigger. The key components of the generator and the experimental results are reported in this paper.

Solid State Division progress report for period ending September 30, 1984

DOE Office of Scientific and Technical Information (OSTI.GOV)

Green, P.H.; Watson, D.M.

1985-03-01

During the reporting period, relatively minor changes have occurred in the research areas of interest to the Division. Nearly all the research of the Division can be classified broadly as mission-oriented basic research. Topics covered include: theoretical solid state physics; surface and near-surface properties of solids; defects in solids; transport properties of solids; neutron scattering; and preparation and characterization of research materials. (GHT)

Solid state electrochemical current source

DOEpatents

Potanin, Alexander Arkadyevich; Vedeneev, Nikolai Ivanovich

2002-04-30

A cathode and a solid state electrochemical cell comprising said cathode, a solid anode and solid fluoride ion conducting electrolyte. The cathode comprises a metal oxide and a compound fluoride containing at least two metals with different valences. Representative compound fluorides include solid solutions of bismuth fluoride and potassium fluoride; and lead fluoride and potassium fluoride. Representative metal oxides include copper oxide, lead oxide, manganese oxide, vanadium oxide and silver oxide.

Addressing the Interface Issues in All-Solid-State Bulk-Type Lithium Ion Battery via an All-Composite Approach.

PubMed

Chen, Ru-Jun; Zhang, Yi-Bo; Liu, Ting; Xu, Bing-Qing; Lin, Yuan-Hua; Nan, Ce-Wen; Shen, Yang

2017-03-22

All-solid-state bulk-type lithium ion batteries (LIBs) are considered ultimate solutions to the safety issues associated with conventional LIBs using flammable liquid electrolyte. The development of bulk-type all-solid-state LIBs has been hindered by the low loading of active cathode materials, hence low specific surface capacity, and by the high interface resistance, which results in low rate and cyclic performance. In this contribution, we propose and demonstrate a synergistic all-composite approach to fabricating flexible all-solid-state LIBs. PEO-based composite cathode layers (filled with LiFePO 4 particles) of ∼300 μm in thickness and composite electrolyte layers (filled with Al-LLZTO particles) are stacked layer-by-layer with lithium foils as negative layer and hot-pressed into a monolithic all-solid-state LIB. The flexible LIB delivers a high specific discharge capacity of 155 mAh/g, which corresponds to an ultrahigh surface capacity of 10.8 mAh/cm 2 , exhibits excellent capacity retention up to at least 10 cycles and could work properly under harsh operating conditions such as bending or being sectioned into pieces. The all-composite approach is favorable for improving both mesoscopic and microscopic interfaces inside the all-solid-state LIB and may provide a new toolbox for design and fabrication of all-solid-state LIBs.

40 CFR 256.10 - Requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Identification of Responsibilities... guidelines for identification of regions and agencies for solid waste management (40 CFR part 255), the State...

40 CFR 256.10 - Requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Identification of Responsibilities... guidelines for identification of regions and agencies for solid waste management (40 CFR part 255), the State...

40 CFR 256.10 - Requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Identification of Responsibilities... guidelines for identification of regions and agencies for solid waste management (40 CFR part 255), the State...

40 CFR 256.10 - Requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Identification of Responsibilities... guidelines for identification of regions and agencies for solid waste management (40 CFR part 255), the State...

40 CFR 256.10 - Requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Identification of Responsibilities... guidelines for identification of regions and agencies for solid waste management (40 CFR part 255), the State...

On the Lennard-Jones and Devonshire theory for solid state thermodynamics

NASA Astrophysics Data System (ADS)

Lustig, Rolf

2017-06-01

The Lennard-Jones and Devonshire theory is developed into a self-consistent scheme for essentially complete thermodynamic information. The resulting methodology is compared with molecular simulation of the Lennard-Jones system in the face-centred-cubic solid state over an excessive range of state points. The thermal and caloric equations of state are in almost perfect agreement along the entire fluid-solid coexistence lines over more than six orders of magnitude in pressure. For homogeneous densities greater than twice the solid triple point density, the theory is essentially exact for derivatives of the Helmholtz energy. However, the fluid-solid phase equilibria are in disagreement with simulation. It is shown that the theory is in error by an additive constant to the Helmholtz energy A/(NkBT). Empirical inclusion of the error term makes all fluid-solid equilibria indistinguishable from exact results. Some arguments about the origin of the error are given.

Stabilization of a supersaturated solution of mefenamic acid from a solid dispersion with EUDRAGIT(®) EPO.

PubMed

Kojima, Taro; Higashi, Kenjirou; Suzuki, Toyofumi; Tomono, Kazuo; Moribe, Kunikazu; Yamamoto, Keiji

2012-10-01

The stabilization mechanism of a supersaturated solution of mefenamic acid (MFA) from a solid dispersion with EUDRAGIT(®) EPO (EPO) was investigated. The solid dispersions were prepared by cryogenic grinding method. Powder X-ray diffractometry, in vitro dissolution test, in vivo oral absorption study, infrared spectroscopy, and solid- and solution-state NMR spectroscopies were used to characterize the solid dispersions. Dissolution tests in acetate buffer (pH 5.5) revealed that solid dispersion showed > 200-fold higher concentration of MFA. Supersaturated solution was stable over 1 month and exhibited improved oral bioavailability of MFA in rats, with a 7.8-fold higher area under the plasma concentration-versus-time curve. Solid-state (1)H spin-lattice relaxation time (T(1)) measurement showed that MFA was almost monomolecularly dispersed in the EPO polymer matrix. Intermolecular interaction between MFA and EPO was indicated by solid-state infrared and (13)C-T(1) measurements. Solution-state (1)H-NMR measurement demonstrated that MFA existed in monomolecular state in supersaturated solution. (1)H-T(1) and difference nuclear Overhauser effect measurements indicated that cross relaxation occurred between MFA and EPO due to the small distance between them. The formation and high stability of the supersaturated solution were attributable to the specifically formed intermolecular interactions between MFA and EPO.

Effect of milling conditions on solid-state amorphization of glipizide, and characterization and stability of solid forms.

PubMed

Xu, Kailin; Xiong, Xinnuo; Zhai, Yuanming; Wang, Lili; Li, Shanshan; Yan, Jin; Wu, Di; Ma, Xiaoli; Li, Hui

2016-09-10

In this study, the amorphization of glipizide was systematically investigated through high-energy ball milling at different temperatures. The results of solid-state amorphization through milling indicated that glipizide underwent direct crystal-to-glass transformation at 15 and 25°C and crystal-to-glass-to-crystal conversion at 35°C; hence, milling time and temperature had significant effects on the amorphization of glipizide, which should be effectively controlled to obtain totally amorphous glipizide. Solid forms of glipizide were detailedly characterized through analyses of X-ray powder diffraction, morphology, thermal curves, vibrational spectra, and solid-state nuclear magnetic resonance. The physical stability of solid forms was investigated under different levels of relative humidity (RH) at 25°C. Forms I and III are kinetically stable and do not form any new solid-state forms at various RH levels. By contrast, Form II is kinetically unstable, undergoing direct glass-to-crystal transformation when RH levels higher than 32.8%. Therefore, stability investigation indicated that Form II should be stored under relatively dry conditions to prevent rapid crystallization. High temperatures can also induce the solid-state transformation of Form II; the conversion rate increased with increasing temperature. Copyright © 2016 Elsevier B.V. All rights reserved.

Solid State Inflation Balloon Active Deorbiter: Scalable Low-Cost Deorbit System for Small Satellites

NASA Technical Reports Server (NTRS)

Huang, Adam

2016-01-01

The goal of the Solid State Inflation Balloon Active Deorbiter project is to develop and demonstrate a scalable, simple, reliable, and low-cost active deorbiting system capable of controlling the downrange point of impact for the full-range of small satellites from 1 kg to 180 kg. The key enabling technology being developed is the Solid State Gas Generator (SSGG) chip, generating pure nitrogen gas from sodium azide (NaN3) micro-crystals. Coupled with a metalized nonelastic drag balloon, the complete Solid State Inflation Balloon (SSIB) system is capable of repeated inflation/deflation cycles. The SSGG minimizes size, weight, electrical power, and cost when compared to the current state of the art.

Real-Time Time-Frequency Two-Dimensional Imaging of Ultrafast Transient Signals in Solid-State Organic Materials

PubMed Central

Takeda, Jun; Ishida, Akihiro; Makishima, Yoshinori; Katayama, Ikufumi

2010-01-01

In this review, we demonstrate a real-time time-frequency two-dimensional (2D) pump-probe imaging spectroscopy implemented on a single shot basis applicable to excited-state dynamics in solid-state organic and biological materials. Using this technique, we could successfully map ultrafast time-frequency 2D transient absorption signals of β-carotene in solid films with wide temporal and spectral ranges having very short accumulation time of 20 ms per unit frame. The results obtained indicate the high potential of this technique as a powerful and unique spectroscopic tool to observe ultrafast excited-state dynamics of organic and biological materials in solid-state, which undergo rapid photodegradation. PMID:22399879

Study of the extra-ionic electron distributions in semi-metallic structures by nuclear quadrupole resonance techniques

NASA Technical Reports Server (NTRS)

Murty, A. N.

1976-01-01

A straightforward self-consistent method was developed to estimate solid state electrostatic potentials, fields and field gradients in ionic solids. The method is a direct practical application of basic electrostatics to solid state and also helps in the understanding of the principles of crystal structure. The necessary mathematical equations, derived from first principles, were presented and the systematic computational procedure developed to arrive at the solid state electrostatic field gradients values was given.

The Iron-Iron Carbide Phase Diagram: A Practical Guide to Some Descriptive Solid State Chemistry.

ERIC Educational Resources Information Center

Long, Gary J.; Leighly, H. P., Jr.

1982-01-01

Discusses the solid state chemistry of iron and steel in terms of the iron-iron carbide phase diagram. Suggests that this is an excellent way of introducing the phase diagram (equilibrium diagram) to undergraduate students while at the same time introducing the descriptive solid state chemistry of iron and steel. (Author/JN)

Method of forming emitters for a back-contact solar cell

DOEpatents

Li, Bo; Cousins, Peter J.; Smith, David D.

2015-09-29

Methods of forming emitters for back-contact solar cells are described. In one embodiment, a method includes forming a first solid-state dopant source above a substrate. The first solid-state dopant source includes a plurality of regions separated by gaps. Regions of a second solid-state dopant source are formed above the substrate by printing.

Method of forming emitters for a back-contact solar cell

DOEpatents

Li, Bo; Cousins, Peter J; Smith, David D

2014-12-16

Methods of forming emitters for back-contact solar cells are described. In one embodiment, a method includes forming a first solid-state dopant source above a substrate. The first solid-state dopant source includes a plurality of regions separated by gaps. Regions of a second solid-state dopant source are formed above the substrate by printing.

Method or forming emitters for a back-contact solar cell

DOEpatents

Li, Bo; Cousins, Peter J.; Smith, David D.

2014-08-12

Methods of forming emitters for back-contact solar cells are described. In one embodiment, a method includes forming a first solid-state dopant source above a substrate. The first solid-state dopant source includes a plurality of regions separated by gaps. Regions of a second solid-state dopant source are formed above the substrate by printing.

Supercooling ability is surprisingly invariable in eggs of the land snail Cantareus aspersus.

PubMed

Ansart, Armelle; Madec, Luc; Vernon, Philippe

2007-02-01

From an ontogenetic point of view, invertebrate eggs are generally the most freezing intolerant stage of a species. Development state, water content and acclimation may affect their supercooling ability. In this study, we measured fresh mass, water content and temperature of crystallisation (T(c)) of eggs of the edible land snail Cantareus aspersus, depending on its form ("aspersa"vs. "maxima"), incubation temperature (20, 12 and 7 degrees C) and physiological age (as part of the complete development). We also tested their tolerance to freezing. Despite a high number of individual observations (n=759) and significant differences of fresh mass and water content between both subspecies, no effect of origin, incubation temperature or development state has been found in this study. T(c) remained constant whatever the condition, with an overall mean of -5.40+/-0.24 degrees C (mean+/-SD). We suggest that fresh mass is important, a high water content and a constantly wet surface confer to land snail eggs a poor ability to supercool. Moreover, the presence of ice nucleating agents at the egg surface (microorganisms present in the soil, calcium carbonate crystals of the egg shell) might induce freezing. Thus, considering the present results, to delay hatching by cryopreservation of eggs does not seem possible.

The Global Fund and the re-configuration and re-emergence of 'civil society': widening or closing the democratic deficit?

PubMed

Kapilashrami, Anuj; O'Brien, Oonagh

2012-01-01

The past decade has witnessed a tremendous growth in the scale and policy influence of civil society in global health governance. The AIDS 'industry' in particular opens up spaces for active mobilisation and participation of non-state actors, which further crystallise with an ever-increasing dominance of global health initiatives. While country evaluations of global initiatives call for a greater participation of 'civil society', the evidence base examining the organisation, nature and operation of 'civil society' and its claims to legitimacy is very thin. Drawing on the case of one of the most visible players in the global response to HIV epidemic, the Global Fund to Fight AIDS, Tuberculosis and Malaria, this article seeks to highlight the complex micropolitics of its interactions with civil society. It examines the nature of civil society actors involved in the Fund projects and the processes through which they gain credibility. We argue that the imposition of global structures and principles facilitates a reconfiguration of actors around newer forms of expertise and power centres. In this context, the notion of 'civil society' underplays differences and power dynamics between various institutions and conceals the agency of outsiders under the guise of autonomy of the state and people.

Deformation-related microstructures in magmatic zircon and implications for diffusion

NASA Astrophysics Data System (ADS)

Reddy, Steven Michael; Timms, Nicholas E.; Hamilton, Patrick Joseph; Smyth, Helen R.

2009-02-01

An undeformed glomeroporphyritic andesite from the Sunda Arc of Java, Indonesia, contains zoned plagioclase and amphibole glomerocrysts in a fine-grained groundmass and records a complex history of adcumulate formation and subsequent magmatic disaggregation. A suite of xenocrystic zircon records Proterozoic and Archaean dates whilst a discrete population of zoned, euhedral, igneous zircon yields a SHRIMP U-Pb crystallisation age of 9.3 ± 0.2 Ma. Quantitative microstructural analysis of zircon by electron backscatter diffraction (EBSD) shows no deformation in the inherited xenocrysts, but intragrain orientation variations of up to 30° in 80% of the young zircon population. These variations are typically accommodated by both progressive crystallographic bending and discrete low angle boundaries that overprint compositional growth zoning. Dispersion of crystallographic orientations are dominantly by rotation about an axis parallel to the zircon c-axis [001], which is coincident with the dominant orientation of misorientation axes of adjacent analysis points in EBSD maps. Less common <100> misorientation axes account for minor components of crystallographic dispersion. These observations are consistent with zircon deformation by dislocation creep and the formation of tilt and twist boundaries associated with the operation of <001>{100} and <100>{010} slip systems. The restriction of deformation microstructures to large glomerocrysts and the young magmatic zircon population, and the absence of deformation within the host igneous rock and inherited zircon grains, indicate that zircon deformation took place within a low-melt fraction (<5% melt), mid-lower crustal cumulate prior to fragmentation during magmatic disaggregation and entrainment of xenocrystic zircons during magmatic decompression. Tectonic stresses within the compressional Sunda Arc at the time of magmatism are considered to be the probable driver for low-strain deformation of the cumulate in the late stages of initial crystallisation. These results provide the first evidence of crystal plastic dislocation creep in zircon associated with magmatic crystallisation and indicate that the development of crystal-plastic microstructures in zircon is not restricted to high-strain rocks. Such microstructures have previously been shown to enhance bulk diffusion of trace elements (U, Th and REE) in zircon. The development of deformation microstructures, and therefore multiple diffusion pathways in zircon in the magmatic environment, has significant implications for the interpretation of geochemical data from igneous zircon and the trace element budgets of melts due to the potential enhancement of bulk diffusion and dissolution rates.

U-Pb thermochronology of rutile from Alpine Corsica: constraints on the thermal evolution of the European margin during Jurassic continental breakup

NASA Astrophysics Data System (ADS)

Ewing, T. A.; Beltrando, M.; Müntener, O.

2017-12-01

U-Pb thermochronology of rutile can provide valuable temporal constraints on the exhumation history of the lower crust, given its moderate closure temperature and the occurrence of rutile in appropriate lithologies. We present an example from Alpine Corsica, in which we investigate the thermal evolution of the distal European margin during Jurassic continental rifting that culminated in the opening of the Alpine Tethys ocean. The Belli Piani unit of the Santa Lucia nappe (Corsica) experienced minimal Alpine overprint and bears a striking resemblance to the renowned Ivrea Zone lower crustal section (Italy). At its base, a 2-4 km thick gabbroic complex contains slivers of granulite facies metapelites that represent Permian lower crust. Zr-in-rutile temperatures and U-Pb ages were determined for rutile from three metapelitic slivers from throughout the Mafic Complex. High Zr-in-rutile temperatures of 850-950 °C corroborate textural evidence for rutile formation during Permian granulite facies metamorphism. Lower Zr-in-rutile temperatures of 750-800 °C in a few grains are partly associated with elongate strings of rutile within quartz ribbons, which record recrystallisation of some rutile during high-temperature shearing. Zr thermometry documents that both crystallisation and re-crystallisation of rutile occurred above the closure temperature of Pb in rutile, such that the U-Pb system can be expected to record cooling ages uncomplicated by re-crystallisation. Our new high-precision single-spot LA-ICPMS U-Pb dates are highly consistent between and within samples. The three samples gave ages from 160 ± 1 Ma to 161 ± 2 Ma, with no other age populations detected. The new data indicate that the Santa Lucia lower crust last cooled through 550-650 °C at 160 Ma, coeval with the first formation of oceanic crust in the Tethys. The new data are compared to previous depth profiling rutile U-Pb data for the Belli Piani unit1, and exploited to cast light on the tectonothermal evolution of the Santa Lucia lower crust in the Jurassic. The new data integrated with published data from the Ivrea zone allow comparison of the thermal evolution of the opposing European (Santa Lucia) and Adriatic (Ivrea) continental margins created by rifting associated with the opening of the Tethys. 1Seymour NM et al., 2016, Tectonics 35, 2439-2466

Anatomy of a frozen axial melt lens from a fast-spreading paleo-ridge (Wadi Gideah, Oman ophiolite)

NASA Astrophysics Data System (ADS)

Müller, T.; Koepke, J.; Garbe-Schönberg, C.-D.; Dietrich, M.; Bauer, U.; Wolff, P. E.

2017-02-01

At fast-spreading mid-ocean ridges, axial melt lenses (AMLs) sandwiched between the sheeted dyke section and the uppermost gabbros are assumed to be the major magma source of crust formation. Here, we present our results from a field study based on a single outcrop of a frozen AML in the Samail ophiolite in the Sultanate of Oman which presents a whole suite of different lithologies and complex cutting relationships: varitextured gabbro with relics of primitive poikilitic clinopyroxene is intruded by massive quartz diorites and tonalites bearing relics of assimilated sheeted dykes, which in turn are cut by trondhjemite dykes. The whole is cut by basaltic dykes with chilled margins. The geochemical evolutionary trend of the varitextured gabbros, including some of the quartz diorites and tonalites, can be best modelled by fractional crystallisation of an experimental MORB parental melt composition containing 0.4 to 0.8 wt.% H2O. Patchy varitextured gabbros containing domains of primitive poikilitic clinopyroxene and evolved granular networks represent the record of in situ crystallisation. Some quartz diorites, often with xenoliths of sheeted dykes and exceptionally high Al2O3 contents, show a bulk trace element pattern more in accord with melts generated by experimental partial melting of dyke material. Highly evolved, crosscutting trondhjemite dykes show characteristic trace element patterns implying a formation by partial melting of sheeted dykes under lower water activity which is indicated by relatively low Al2O3 contents. The late basaltic dykes with chilled margins crosscutting all other lithologies show a relatively depleted geochemical character with pronounced negative Nb-Ta anomalies implying a genetic relationship to the second phase of magmatic Oman paleo-ridge activity (V2). The field relationships in combination with the petrological/geochemical trends reveal multiple sequences of MORB-type magma cooling (resulting in fractional crystallisation) and re-heating (producing partial melting) during the formation of this special horizon; these are best explained by alternating cycles of vertical AML migration. Since the investigated outcrop shows many characteristic lithological and petrographic features that are well-known from the uppermost gabbros drilled at Site 1256 by the Integrated Ocean Drilling Program (IODP) in the equatorial Eastern Pacific, our results based on 3-D observation in the field help to elucidate the geological observations obtained from the 1-D drill core.

Petrological constraints on the high-Mg basalts from Capo Marargiu (Sardinia, Italy): Evidence of cryptic amphibole fractionation in polybaric environments

NASA Astrophysics Data System (ADS)

Tecchiato, Vanni; Gaeta, Mario; Mollo, Silvio; Scarlato, Piergiorgio; Bachmann, Olivier; Perinelli, Cristina

2018-01-01

This study deals with the textural and compositional characteristics of the calc-alkaline stratigraphic sequence from Capo Marargiu Volcanic District (CMVD; Sardinia island, Italy). The area is dominated by basaltic to intermediate hypabyssal (dikes and sills) and volcanic rocks (lava flows and pyroclastic deposits) emplaced during the Oligo-Miocene orogenic magmatism of Sardinia. Interestingly, a basaltic andesitic dome hosts dark-grey, crystal-rich enclaves containing up 50% of millimetre- to centimetre-sized clinopyroxene and amphibole crystals. This mineral assemblage is in equilibrium with a high-Mg basalt recognised as the parental magma of the entire stratigraphic succession at CMVD. Analogously, centimetre-sized clots of medium- and coarse-grained amphibole + plagioclase crystals are entrapped in andesitic dikes that ultimately intrude the stratigraphic sequence. Amphibole-plagioclase cosaturation occurs at equilibrium with a differentiated basaltic andesite. Major and trace element modelling indicates that the evolutionary path of magma is controlled by a two-step process driven by early olivine + clinopyroxene and late amphibole + plagioclase fractionation. In this context, enclaves represent parts of a cumulate horizon segregated at the early stage of differentiation of the precursory high-Mg basalt. This is denoted by i) resorption effects and sharp transitions between Mg-rich and Mg-poor clinopyroxenes, indicative of pervasive dissolution phenomena followed by crystal re-equilibration and overgrowth, and ii) reaction minerals found in amphibole coronas formed at the interface with more differentiated melts infiltrating within the cumulate horizon, and carrying the crystal-rich material with them upon eruption. Coherently, the mineral chemistry and phase relations of enclaves indicate crystallisation in a high-temperature, high-pressure environment under water-rich conditions. On the other hand, the upward migration and subsequent fractionation of the residual basaltic andesite in a shallower, colder, and hydrous region of the CMVD plumbing system lead to the formation of the amphibole-plagioclase crystal clots finally entrained by the andesitic dikes. Indeed, phenocrysts from these more evolved products record the final crystallisation path of magma during ascent towards the surface. Magma decompression and volatile loss cause the formation of amphibole reaction coronas and the crystallisation of a more sodic plagioclase in equilibrium with basaltic andesitic to andesitic melts. The bulk-rock geochemical signature of these products testifies to open-system, polybaric magma dynamics, accounting for variable degrees of crustal assimilation of the Hercynian basement of Sardinia.

A 125Te and 23Na NMR investigation of the structure and crystallisation of sodium tellurite glasses.

PubMed

Holland, D; Bailey, J; Ward, G; Turner, B; Tierney, P; Dupree, R

2005-01-01

125Te static nuclear magnetic resonance (NMR) and 23Na and 125Te magic angle spinning (MAS) NMR have been used, in conjunction with X-ray diffraction, to examine the structure and crystallisation behaviour of glasses of composition xNa2O.(1-x)TeO2 (0.075 x 0.4). The MAS NMR 23Na spectra from the glasses are broad and featureless but shift by approximately +5 ppm with increased x, i.e. as the system becomes more ionic. The static 125Te NMR spectra show an increase in axial symmetry with increasing x, indicating a shift from predominantly [TeO4] to [TeO3] structural units. The 23Na and 125Te spectra from the crystallised samples have been fitted to obtain information on the sites in the metastable crystal phases, which are the first to form on heating and which are therefore more closely related to the glass structure than thermodynamically stable crystal phases. New sodium tellurite phases are reported, including a sodium stabilised, face centred cubic phase related to delta-TeO2; a metastable form of Na2Te4O9 containing 3 sodium and 4 tellurium sites; and a metastable form of Na2Te2O5 containing 2 sodium sites. There is evidence of oxidation of TeIV to TeVI occurring in glasses with high values of x and, at x=0.40 and 0.50 (outside the glass forming range), some sodium metatellurate (Na2TeO4) is formed at the same time as sodium metatellurite (Na2TeO3). The 125Te shift is very sensitive to environment within the sodium tellurite system, covering more than 320 ppm, with anisotropies varying from 640 to 1540 ppm. The lack of features in the 125Te spectra of the glass phases, combined with the large shift range and high but variable anisotropy, means than it is not possible to obtain a unique fit to any presumed species present. Furthermore, the chemical shift anisotropy parameters for three of the four Te sites in the Na2Te4O9 phase are found to lie outside the range used for previous simulations of glass spectra.

Solid-State NMR Investigation of Drug-Excipient Interactions and Phase Behavior in Indomethacin-Eudragit E Amorphous Solid Dispersions.

PubMed

Lubach, Joseph W; Hau, Jonathan

2018-02-20

To investigate the nature of drug-excipient interactions between indomethacin (IMC) and methacrylate copolymer Eudragit® E (EE) in the amorphous state, and evaluate the effects on formulation and stability of these amorphous systems. Amorphous solid dispersions containing IMC and EE were spray dried with drug loadings from 20% to 90%. PXRD was used to confirm the amorphous nature of the dispersions, and DSC was used to measure glass transition temperatures (T g ). 13 C and 15 N solid-state NMR was utilized to investigate changes in local structure and protonation state, while 1 H T 1 and T 1ρ relaxation measurements were used to probe miscibility and phase behavior of the dispersions. T g values for IMC-EE solid dispersions showed significant positive deviations from predicted values in the drug loading range of 40-90%, indicating a relatively strong drug-excipient interaction. 15 N solid-state NMR exhibited a change in protonation state of the EE basic amine, with two distinct populations for the EE amine at -360.7 ppm (unprotonated) and -344.4 ppm (protonated). Additionally, 1 H relaxation measurements showed phase separation at high drug load, indicating an amorphous ionic complex and free IMC-rich phase. PXRD data showed all ASDs up to 90% drug load remained physically stable after 2 years. 15 N solid-state NMR experiments show a change in protonation state of EE, indicating that an ionic complex indeed forms between IMC and EE in amorphous solid dispersions. Phase behavior was determined to exhibit nanoscale phase separation at high drug load between the amorphous ionic complex and excess free IMC.

Electrode property of single-walled carbon nanotubes in all-solid-state lithium ion battery using polymer electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sakamoto, Y.; Ishii, Y.; Kawasaki, S., E-mail: kawasaki.shinji@nitech.ac.jp

2016-07-06

Electrode properties of single-walled carbon nanotubes (SWCNTs) in an all-solid-state lithium ion battery were investigated using poly-ethylene oxide (PEO) solid electrolyte. Charge-discharge curves of SWCNTs in the solid electrolyte cell were successfully observed. It was found that PEO electrolyte decomposes on the surface of SWCNTs.

Solid state SPS microwave generation and transmission study. Volume 1: Phase 2

NASA Technical Reports Server (NTRS)

Maynard, O. E.

1980-01-01

The solid state sandwich concept for Solar Power Station (SPS) was investigated. The design effort concentrated on the spacetenna, but did include some system analysis for parametric comparison reasons. The study specifically included definition and math modeling of basic solid state microwave devices, an initial conceptual subsystems and system design, sidelobe control and system selection, an assessment of selected system concept and parametric solid state microwave power transmission system data relevant to the SPS concept. Although device efficiency was not a goal, the sensitivities to design of this efficiency were parametrically treated. Sidelobe control consisted of various single step tapers, multistep tapers, and Gaussian tapers. A preliminary assessment of a hybrid concept using tubes and solid state is also included. There is a considerable amount of thermal analysis provided with emphasis on sensitivities to waste heat radiator form factor, emissivity, absorptivity, amplifier efficiency, material and junction temperature.

Solid state laser technology - A NASA perspective

NASA Technical Reports Server (NTRS)

Allario, F.

1985-01-01

NASA's program for developing solid-state laser technology and applying it to the Space Shuttle and Space Platform is discussed. Solid-state lasers are required to fulfill the Earth Observation System's requirements. The role of the Office of Aeronautics and Space Technology in developing a NASA tunable solid-state laser program is described. The major goals of the program involve developing a solid-state pump laser in the green, using AlGaAs array technology, pumping a Nd:YAG/SLAB crystal or glass, and fabricating a lidar system, with either a CO2 laser at 10.6 microns or a Nd:YAG laser at 1.06 microns, to measure tropospheric winds to an accuracy of + or - 1 m/s and a vertical resolution of 1 km. The procedures to be followed in order to visualize this technology plan include: (1) material development and characterization, (2) laser development, and (3) implementation of the lasers.

Tunable solid-state laser technology for applications to scientific and technological experiments from space

NASA Technical Reports Server (NTRS)

Allario, F.; Taylor, L. V.

1986-01-01

Current plans for the Earth Observing System (EOS) include development of a lidar facility to conduct scientific experiments from a polar orbiting platforms. A recommended set of experiments were scoped, which includes techniques of atmospheric backscatter (Lidar), Differential Absorption Lidar (DIAL), altimetry, and retroranging. Preliminary assessments of the resources (power, weight, volume) required by the Eos Lidar Facility were conducted. A research program in tunable solid state laser technology was developed, which includes laser materials development, modeling and experiments on the physics of solid state laser materials, and development of solid state laser transmitters with a strong focus on Eos scientific investigations. Some of the system studies that were conducted which highlight the payoff of solid state laser technology for the Eos scientific investigations will be discussed. Additionally, a summary of some promising research results which have recently emerged from the research program will be presented.

Solid-state Bonding of Superplastic Aluminum Alloy 7475 Sheet

NASA Technical Reports Server (NTRS)

Byun, T. D. S.; Vastava, R. B.

1985-01-01

Experimental works were carried out to study the feasibility of solid state bonding of superplastic aluminum 7475 sheet. Amount of deformation, bonding time, surface cleaning method and intermediate layer were the process parameters investigated. Other parameters, held constant by the superplastic forming condition which is required to obtain a concurrent solid state bonding, are bonding temperature, bonding pressure and atmosphere. Bond integrity was evaluated through metallographic examination, X-ray line scan analysis, SEM fractographic analysis and lap shear tests. The early results of the development program indicated that sound solid state bonding was accomplished for this high strength 7475 alloy with significant amounts of deformation. A thin intermediate layer of the soft 5052 aluminum alloy aided in achieving a solid state bonding by reducing the required amount of plastic deformation at the interface. Bond strength was substantially increased by a post bond heat treatment.

Bioethanol production: an integrated process of low substrate loading hydrolysis-high sugars liquid fermentation and solid state fermentation of enzymatic hydrolysis residue.

PubMed

Chu, Qiulu; Li, Xin; Ma, Bin; Xu, Yong; Ouyang, Jia; Zhu, Junjun; Yu, Shiyuan; Yong, Qiang

2012-11-01

An integrated process of enzymatic hydrolysis and fermentation was investigated for high ethanol production. The combination of enzymatic hydrolysis at low substrate loading, liquid fermentation of high sugars concentration and solid state fermentation of enzymatic hydrolysis residue was beneficial for conversion of steam explosion pretreated corn stover to ethanol. The results suggested that low substrate loading hydrolysis caused a high enzymatic hydrolysis yield; the liquid fermentation of about 200g/L glucose by Saccharomyces cerevisiae provided a high ethanol concentration which could significantly decrease cost of the subsequent ethanol distillation. A solid state fermentation of enzymatic hydrolysis residue was combined, which was available to enhance ethanol production and cellulose-to-ethanol conversion. The results of solid state fermentation demonstrated that the solid state fermentation process accompanied by simultaneous saccharification and fermentation. Copyright © 2012 Elsevier Ltd. All rights reserved.

Solid-state diffusion in amorphous zirconolite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, C.; Dove, M. T.; Trachenko, K.

2014-11-14

We discuss how structural disorder and amorphization affect solid-state diffusion, and consider zirconolite as a currently important case study. By performing extensive molecular dynamics simulations, we disentangle the effects of amorphization and density, and show that a profound increase of solid-state diffusion takes place as a result of amorphization. Importantly, this can take place at the same density as in the crystal, representing an interesting general insight regarding solid-state diffusion. We find that decreasing the density in the amorphous system increases pre-factors of diffusion constants, but does not change the activation energy in the density range considered. We also findmore » that atomic species in zirconolite are affected differently by amorphization and density change. Our microscopic insights are relevant for understanding how solid-state diffusion changes due to disorder and for building predictive models of operation of materials to be used to encapsulate nuclear waste.« less

Nanoscale solid-state cooling: a review.

PubMed

Ziabari, Amirkoushyar; Zebarjadi, Mona; Vashaee, Daryoosh; Shakouri, Ali

2016-09-01

The recent developments in nanoscale solid-state cooling are reviewed. This includes both theoretical and experimental studies of different physical concepts, as well as nanostructured material design and device configurations. We primarily focus on thermoelectric, thermionic and thermo-magnetic coolers. Particular emphasis is given to the concepts based on metal-semiconductor superlattices, graded materials, non-equilibrium thermoelectric devices, Thomson coolers, and photon assisted Peltier coolers as promising methods for efficient solid-state cooling. Thermomagnetic effects such as magneto-Peltier and Nernst-Ettingshausen cooling are briefly described and recent advances and future trends in these areas are reviewed. The ongoing progress in solid-state cooling concepts such as spin-calorimetrics, electrocalorics, non-equilibrium/nonlinear Peltier devices, superconducting junctions and two-dimensional materials are also elucidated and practical achievements are reviewed. We explain the thermoreflectance thermal imaging microscopy and the transient Harman method as two unique techniques developed for characterization of thermoelectric microrefrigerators. The future prospects for solid-state cooling are briefly summarized.

Efficient Storing Energy Harvested by Triboelectric Nanogenerators Using a Safe and Durable All-Solid-State Sodium-Ion Battery.

PubMed

Hou, Huidan; Xu, Qingkai; Pang, Yaokun; Li, Lei; Wang, Jiulin; Zhang, Chi; Sun, Chunwen

2017-08-01

Storing energy harvested by triboelectric nanogenerators (TENGs) from ambient mechanical motion is still a great challenge for achieving low-cost and environmental benign power sources. Here, an all-solid-state Na-ion battery with safe and durable performance used for efficient storing pulsed energy harvested by the TENG is demonstrated. The solid-state sodium-ion batteries are charged by galvanostatic mode and pulse mode with the TENG, respectively. The all-solid-state sodium-ion battery displays excellent cyclic performance up to 1000 cycles with a capacity retention of about 85% even at a high charge and discharge current density of 48 mA g -1 . When charged by the TENG, an energy conversion efficiency of 62.3% is demonstrated. The integration of TENGs with the safe and durable all-solid-state sodium-ion batteries is potential for providing more stable power output for self-powered systems.

Complete tomography of a high-fidelity solid-state entangled spin-photon qubit pair.

PubMed

De Greve, Kristiaan; McMahon, Peter L; Yu, Leo; Pelc, Jason S; Jones, Cody; Natarajan, Chandra M; Kim, Na Young; Abe, Eisuke; Maier, Sebastian; Schneider, Christian; Kamp, Martin; Höfling, Sven; Hadfield, Robert H; Forchel, Alfred; Fejer, M M; Yamamoto, Yoshihisa

2013-01-01

Entanglement between stationary quantum memories and photonic qubits is crucial for future quantum communication networks. Although high-fidelity spin-photon entanglement was demonstrated in well-isolated atomic and ionic systems, in the solid-state, where massively parallel, scalable networks are most realistically conceivable, entanglement fidelities are typically limited due to intrinsic environmental interactions. Distilling high-fidelity entangled pairs from lower-fidelity precursors can act as a remedy, but the required overhead scales unfavourably with the initial entanglement fidelity. With spin-photon entanglement as a crucial building block for entangling quantum network nodes, obtaining high-fidelity entangled pairs becomes imperative for practical realization of such networks. Here we report the first results of complete state tomography of a solid-state spin-photon-polarization-entangled qubit pair, using a single electron-charged indium arsenide quantum dot. We demonstrate record-high fidelity in the solid-state of well over 90%, and the first (99.9%-confidence) achievement of a fidelity that will unambiguously allow for entanglement distribution in solid-state quantum repeater networks.

Electrochemical properties of all solid state Li/S battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Ji-Hyun; Park, Jin-Woo; Wang, Qing

All-solid-state lithium/sulfur (Li/S) battery is prepared using siloxane cross-linked network solid electrolyte at room temperature. The solid electrolytes show high ionic conductivity and good electrochemical stability with lithium and sulfur. In the first discharge curve, all-solid-state Li/S battery shows three plateau potential regions of 2.4 V, 2.12 V and 2.00 V, respectively. The battery shows the first discharge capacity of 1044 mAh g{sup −1}-sulfur at room temperature. This first discharge capacity rapidly decreases in 4th cycle and remains at 512 mAh g{sup −1}-sulfur after 10 cycles.

Solid-state supercapacitors with ionic liquid gel polymer electrolyte based on poly (3, 4-ethylenedioxythiophene), carbon nanotubes, and metal oxides nanocomposites for electrical energy storage

NASA Astrophysics Data System (ADS)

Obeidat, Amr M.

Clean and renewable energy systems have emerged as an important area of research having diverse and significant new applications. These systems utilize different energy storage methods such as the batteries and supercapacitors. Supercapacitors are electrochemical energy storage devices that are designed to bridge the gap between batteries and conventional capacitors. Supercapacitors which store electrical energy by electrical double layer capacitance are based on large surface area structured carbons. The materials systems in which the Faradaic reversible redox reactions store electrical energy are the transition metal oxides and electronically conducting polymers. Among the different types of conducting polymers, poly (3, 4- ethylenedioxythiophene) (PEDOT) is extensively investigated owing to its chemical and mechanical stability. Due to instability of aqueous electrolytes at high voltages and toxicity of organic electrolytes, potential of supercapacitors has not been fully exploited. A novel aspect of this work is in utilizing the ionic liquid gel polymer electrolyte to design solid-state supercapacitors for energy storage. Various electrochemical systems were investigated including graphene, PEDOT, PEDOT-carbon nanotubes, PEDOT-manganese oxide, and PEDOT-iron oxide nanocomposites. The electrochemical performance of solid-state supercapacitor devices was evaluated based on cyclic voltammetry (CV), charge-discharge (CD), prolonged cyclic tests, and electrochemical impedance spectroscopy (EIS) techniques. Raman spectroscopy technique was also utilized to analyze the bonding structure of the electrode materials. The graphene solid-state supercapacitor system displayed areal capacitance density of 141.83 mF cm-2 based on high potential window up to 4V. The PEDOT solid-state supercapacitor system was synthesized in acetonitrile and aqueous mediums achieving areal capacitance density of 219.17 mF cm-2. The hybrid structure of solid-state supercapacitors was also studied in solid-state design based on PEDOT and graphene electrodes that produced areal capacitance density of 198.26 mF cm-2. Symmetrical PEDOT-manganese oxide nanocomposites were synthesized by co-deposition and dip-coating techniques to fabricate solid-state supercapacitor systems achieving areal capacitance density of 122.08 mF cm-2 credited to the PEDOT-MnO2 supercapacitor that was synthesized by dipping the PEDOT electrode in pure KMnO4 solution. The electrochemical performance of PEDOT-carbon nanotube solid-state supercapacitors was also investigated in both acetonitrile and aqueous medium showing good dispersion characteristics with optimum CNT content of 1 mg. The PEDOT-CNT solid-state supercapacitor system synthesized in acetonitrile displayed areal capacitance density of 297.43 mF cm-2. PEDOT-Fe2O3 nanocomposites were synthesized by single-step co-deposition techniques, and these were used to fabricate solid-state supercapacitors achieving areal capacitance density of 96.89 mF cm-2. Furthermore, some of these thin flexible solid-state supercapacitors were integrated with solar cells for direct storage of solar electricity, which proved to be promising as autonomous power source for flexible and wearable electronics. This dissertation describes the electrode synthesis, design and properties of solid-state supercapacitors, and their electrochemical performance in the storage of electrical energy.

NiF2/NaF:CaF2/Ca Solid-State High-Temperature Battery Cells

NASA Technical Reports Server (NTRS)

West, William; Whitacre, Jay; DelCastillo, Linda

2009-01-01

Experiments and theoretical study have demonstrated the promise of all-solid-state, high-temperature electrochemical battery cells based on NiF2 as the active cathode material, CaF2 doped with NaF as the electrolyte material, and Ca as the active anode material. These and other all-solid-state cells have been investigated in a continuing effort to develop batteries for instruments that must operate in environments much hotter than can be withstood by ordinary commercially available batteries. Batteries of this type are needed for exploration of Venus (where the mean surface temperature is about 450 C), and could be used on Earth for such applications as measuring physical and chemical conditions in geothermal wells and oil wells. All-solid-state high-temperature power cells are sought as alternatives to other high-temperature power cells based, variously, on molten anodes and cathodes or molten eutectic salt electrolytes. Among the all-solid-state predecessors of the present NiF2/NaF:CaF2/Ca cells are those described in "Solid-State High-Temperature Power Cells" (NPO-44396), NASA Tech Briefs, Vol. 32, No. 5 (May 2008), page 40. In those cells, the active cathode material is FeS2, the electrolyte material is a crystalline solid solution of equimolar amounts of Li3PO4 and LiSiO4, and the active anode material is Li contained within an alloy that remains solid in the intended high operational temperature range.

Combining optical trapping in a microfluidic channel with simultaneous micro-Raman spectroscopy and motion detection

NASA Astrophysics Data System (ADS)

Lawton, Penelope F.; Saunter, Christopher D.; Girkin, John M.

2014-03-01

Since their invention by Ashkin optical tweezers have demonstrated their ability and versatility as a non-invasive tool for micromanipulation. One of the most useful additions to the basic optical tweezers system is micro-Raman spectroscopy, which permits highly sensitive analysis of single cells or particles. We report on the development of a dual laser system combining two spatial light modulators to holographically manipulate multiple traps (at 1064nm) whilst undertaking Raman spectroscopy using a 532nm laser. We can thus simultaneously trap multiple particles and record their Raman spectra, without perturbing the trapping system. The dual beam system is built around micro-fluidic channels where crystallisation of calcium carbonate occurs on polymethylmethacrylate (PMMA) beads. The setup is designed to simulate at a microscopic level the reactions that occur on items in a dishwasher, where permanent filming of calcium carbonate on drinking glasses is a problem. Our system allows us to monitor crystal growth on trapped particles in which the Raman spectrum and changes in movement of the bead are recorded. Due to the expected low level of crystallisation on the bead surfaces this allows us to obtain results quickly and with high sensitivity. The long term goal is to study the development of filming on samples in-situ with the microfl.uidic system acting as a model dishwasher.

Effect of quality and origin of technical sucrose solutions on the inclusion of colourants into the sugar crystal matrix.

PubMed

Schlumbach, Karl; Scharfe, Maria; Flöter, Eckhard

2018-06-01

Due to the liberalisation of the European sugar market the pressure to improve factory utilisation is growing. Currently, beet and cane as sucrose sources are produced in isolation, according to geography. Co-production of sugar from beet and cane origin in one stream is a promising option. However, the knowledge base for production sugar is practically non-existent. This paper is part of our contribution to this field and specifically addresses effects of raw material quality. This framework formulated for the colouring of sugars crystallised from mixed syrups is also valid for different raw material qualities: raw cane sugars: colour values 1221 to 2505 IU, dextran levels 50 to 1200 mg kg -1 ; beet syrups: 1509 to 2058 IU. Co-crystallisation is the main colour incorporation mechanism. Colour due to liquid inclusion increases strongly at cane inclusion levels in excess of 60%. The prediction of final sugar colour based on characteristics of pure mixture constituents is verified and indicates significant differences to current recommendations. A first comprehensive description of the colour values in sugars produced from mixed cane and beet syrups is presented. Prediction of colour values from data on sugar colour of single sources marks a major contribution to future applications of co-production. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

A low viscosity, low boiling point, clean solvent system for the rapid crystallisation of highly specular perovskite films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Noel, Nakita K.; Habisreutinger, Severin N.; Wenger, Bernard

2017-01-01

Perovskite-based photovoltaics have, in recent years, become poised to revolutionise the solar industry. While there have been many approaches taken to the deposition of this material, one-step spin-coating remains the simplest and most widely used method in research laboratories. Although spin-coating is not recognised as the ideal manufacturing methodology, it represents a starting point from which more scalable deposition methods, such as slot-dye coating or ink-jet printing can be developed. Here, we introduce a new, low-boiling point, low viscosity solvent system that enables rapid, room temperature crystallisation of methylammonium lead triiodide perovskite films, without the use of strongly coordinating aproticmore » solvents. Through the use of this solvent, we produce dense, pinhole free films with uniform coverage, high specularity, and enhanced optoelectronic properties. We fabricate devices and achieve stabilised power conversion efficiencies of over 18% for films which have been annealed at 100 degrees C, and over 17% for films which have been dried under vacuum and have undergone no thermal processing. This deposition technique allows uniform coating on substrate areas of up to 125 cm2, showing tremendous promise for the fabrication of large area, high efficiency, solution processed devices, and represents a critical step towards industrial upscaling and large area printing of perovskite solar cells.« less

40 CFR 256.42 - Recommendations for assuring facility development.

Code of Federal Regulations, 2010 CFR

2010-07-01

... development. 256.42 Section 256.42 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Facility... unrestricted movement of solid and hazardous waste across State and local boundaries. ...

Cellulose nanofibril/reduced graphene oxide/carbon nanotube hybrid aerogels for highly flexible and all-solid-state supercapacitors

Treesearch

Qifeng Zheng; Zhiyong Cai; Zhenqiang Ma; Shaoqin Gong

2015-01-01

A novel type of highly flexible and all-solid-state supercapacitor that uses cellulose nanofibril (CNF)/reduced graphene oxide (RGO)/carbon nanotube (CNT) hybrid aerogels as electrodes and H2SO4 poly (vinyl alcohol) PVA gel as the electrolyte was developed and is reported here. These flexible solid-state supercapacitors...

Solid state fermentation of carinata (Brassica carinata) meal using various fungal strains to produce a protein-rich product for feed application

USDA-ARS?s Scientific Manuscript database

In this study, the efficacy of several fungal strains to reduce GLS (GLS) content and enhance protein content during solid state fermentation (SSF) of carinata meal was evaluated. Solid state fermentation of hexane extracted (HE) and cold pressed (CP) carinata meals were performed at 50% moisture co...

Solid state protein monolayers: Morphological, conformational, and functional properties

NASA Astrophysics Data System (ADS)

Pompa, P. P.; Biasco, A.; Frascerra, V.; Calabi, F.; Cingolani, R.; Rinaldi, R.; Verbeet, M. Ph.; de Waal, E.; Canters, G. W.

2004-12-01

We have studied the morphological, conformational, and electron-transfer (ET) function of the metalloprotein azurin in the solid state, by a combination of physical investigation methods, namely atomic force microscopy, intrinsic fluorescence spectroscopy, and scanning tunneling microscopy. We demonstrate that a "solid state protein film" maintains its nativelike conformation and ET function, even after removal of the aqueous solvent.

Solid State Physics in the People's Republic of China. A Trip Report of the American Solid State Physics Delegation.

ERIC Educational Resources Information Center

Fitzgerald, Anne; Slichter, Charles P.

This is the fifth chapter of a six chapter report which discusses Chinese research and education in solid state physics, and their relations to technology and the other sciences. This specific chapter concerns the communication of information in the scientific community and the transfer of information to students and practical users…

The solid state detector technology for picosecond laser ranging

NASA Technical Reports Server (NTRS)

Prochazka, Ivan

1993-01-01

We developed an all solid state laser ranging detector technology, which makes the goal of millimeter accuracy achievable. Our design and construction philosophy is to combine the techniques of single photon ranging, ultrashort laser pulses, and fast fixed threshold discrimination while avoiding any analog signal processing within the laser ranging chain. The all solid state laser ranging detector package consists of the START detector and the STOP solid state photon counting module. Both the detectors are working in an optically triggered avalanche switching regime. The optical signal is triggering an avalanche current buildup which results in the generation of a uniform, fast risetime output pulse.

Molecularly Engineered Azobenzene Derivatives for High Energy Density Solid-State Solar Thermal Fuels.

PubMed

Cho, Eugene N; Zhitomirsky, David; Han, Grace G D; Liu, Yun; Grossman, Jeffrey C

2017-03-15

Solar thermal fuels (STFs) harvest and store solar energy in a closed cycle system through conformational change of molecules and can release the energy in the form of heat on demand. With the aim of developing tunable and optimized STFs for solid-state applications, we designed three azobenzene derivatives functionalized with bulky aromatic groups (phenyl, biphenyl, and tert-butyl phenyl groups). In contrast to pristine azobenzene, which crystallizes and makes nonuniform films, the bulky azobenzene derivatives formed uniform amorphous films that can be charged and discharged with light and heat for many cycles. Thermal stability of the films, a critical metric for thermally triggerable STFs, was greatly increased by the bulky functionalization (up to 180 °C), and we were able to achieve record high energy density of 135 J/g for solid-state STFs, over a 30% improvement compared to previous solid-state reports. Furthermore, the chargeability in the solid state was improved, up to 80% charged from 40% charged in previous solid-state reports. Our results point toward molecular engineering as an effective method to increase energy storage in STFs, improve chargeability, and improve the thermal stability of the thin film.

A Unique Hybrid Quasi-Solid-State Electrolyte for Li-O2 Batteries with Improved Cycle Life and Safety.

PubMed

Yi, Jin; Zhou, Haoshen

2016-09-08

In the context of the development of electric vehicle to solve the contemporary energy and environmental issues, the possibility of pushing future application of Li-O2 batteries as a power source for electric vehicles is particularly attractive. However, safety concerns, mainly derived from the use of flammable organic liquid electrolytes, become a major bottleneck for the strategically crucial applications of Li-O2 batteries. To overcome this issue, rechargeable solid-state Li-O2 batteries with enhanced safety is regarded as an appealing candidate. In this study, a hybrid quasi-solid-state electrolyte combing a polymer electrolyte with a ceramic electrolyte is first designed and explored for Li-O2 batteries. The proposed rechargeable solid-state Li-O2 battery delivers improved cycle life (>100 cycles) and safety. The feasibility study demonstrates that the hybrid quasi-solid-state electrolytes could be employed as a promising alternative strategy for the development of rechargeable Li-O2 batteries, hence encouraging more efforts devoted to explore other hybrid solid-state electrolytes for Li-O2 batteries upon future application. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Golden Age of Radio: Solid State's Debt to the Rad Lab

NASA Astrophysics Data System (ADS)

Martin, Joseph D.

2011-03-01

While MIT's Radiation Laboratory is rightly celebrated for its contributions to World War II radar research, its legacy extended beyond the war. The Rad Lab provided a model for interdisciplinary collaboration that continued to influence research at MIT in the post-war decades. The Rad Lab's institutional legacy--MIT's interdepartmental laboratories--drove the Institute's postwar research agenda. This talk examines how solid state physics research at MIT was shaped by a laboratory structure that encouraged cross-disciplinary collaboration. As the sub-discipline of solid state physics emerged through the late-1940s and 1950s, MIT was unique among universities in its laboratory structure, made possible by a large degree of government and military funding. Nonetheless, the manner in which MIT research groups from physics, chemistry, engineering, and metallurgy interfaced through the medium of solid state physics exemplified how the discipline of solid state physics came to be structured in the rest of the country. Through examining the Rad Lab's institutional legacy, I argue that World War II radar research, by establishing precedent for a particular mode of interdisciplinary collaboration, shaped the future structure of solid state research in the United States. Research supported by a grant-in-aid from the Friends of the Center for the History of Physics, American Institute of Physics.

Enhancing the resolution of 1H and 13C solid-state NMR spectra by reduction of anisotropic bulk magnetic susceptibility broadening.

PubMed

Hanrahan, Michael P; Venkatesh, Amrit; Carnahan, Scott L; Calahan, Julie L; Lubach, Joseph W; Munson, Eric J; Rossini, Aaron J

2017-10-25

We demonstrate that natural isotopic abundance 2D heteronuclear correlation (HETCOR) solid-state NMR spectra can be used to significantly reduce or eliminate the broadening of 1 H and 13 C solid-state NMR spectra of organic solids due to anisotropic bulk magnetic susceptibility (ABMS). ABMS often manifests in solids with aromatic groups, such as active pharmaceutical ingredients (APIs), and inhomogeneously broadens the NMR peaks of all nuclei in the sample. Inhomogeneous peaks with full widths at half maximum (FWHM) of ∼1 ppm typically result from ABMS broadening and the low spectral resolution impedes the analysis of solid-state NMR spectra. ABMS broadening of solid-state NMR spectra has previously been eliminated using 2D multiple-quantum correlation experiments, or by performing NMR experiments on diluted materials or single crystals. However, these experiments are often infeasible due to their poor sensitivity and/or provide limited gains in resolution. 2D 1 H- 13 C HETCOR experiments have previously been applied to reduce susceptibility broadening in paramagnetic solids and we show that this strategy can significantly reduce ABMS broadening in diamagnetic organic solids. Comparisons of 1D solid-state NMR spectra and 1 H and 13 C solid-state NMR spectra obtained from 2D 1 H- 13 C HETCOR NMR spectra show that the HETCOR spectrum directly increases resolution by a factor of 1.5 to 8. The direct gain in resolution is determined by the ratio of the inhomogeneous 13 C/ 1 H linewidth to the homogeneous 1 H linewidth, with the former depending on the magnitude of the ABMS broadening and the strength of the applied field and the latter on the efficiency of homonuclear decoupling. The direct gains in resolution obtained using the 2D HETCOR experiments are better than that obtained by dilution. For solids with long proton longitudinal relaxation times, dynamic nuclear polarization (DNP) was applied to enhance sensitivity and enable the acquisition of 2D 1 H- 13 C HETCOR NMR spectra. 2D 1 H- 13 C HETCOR experiments were applied to resolve and partially assign the NMR signals of the form I and form II polymorphs of aspirin in a sample containing both forms. These findings have important implications for ultra-high field NMR experiments, optimization of decoupling schemes and assessment of the fundamental limits on the resolution of solid-state NMR spectra.

Rapid Thermal Annealing of Cathode-Garnet Interface toward High-Temperature Solid State Batteries.

PubMed

Liu, Boyang; Fu, Kun; Gong, Yunhui; Yang, Chunpeng; Yao, Yonggang; Wang, Yanbin; Wang, Chengwei; Kuang, Yudi; Pastel, Glenn; Xie, Hua; Wachsman, Eric D; Hu, Liangbing

2017-08-09

High-temperature batteries require the battery components to be thermally stable and function properly at high temperatures. Conventional batteries have high-temperature safety issues such as thermal runaway, which are mainly attributed to the properties of liquid organic electrolytes such as low boiling points and high flammability. In this work, we demonstrate a truly all-solid-state high-temperature battery using a thermally stable garnet solid-state electrolyte, a lithium metal anode, and a V 2 O 5 cathode, which can operate well at 100 °C. To address the high interfacial resistance between the solid electrolyte and cathode, a rapid thermal annealing method was developed to melt the cathode and form a continuous contact. The resulting interfacial resistance of the solid electrolyte and V 2 O 5 cathode was significantly decreased from 2.5 × 10 4 to 71 Ω·cm 2 at room temperature and from 170 to 31 Ω·cm 2 at 100 °C. Additionally, the diffusion resistance in the V 2 O 5 cathode significantly decreased as well. The demonstrated high-temperature solid-state full cell has an interfacial resistance of 45 Ω·cm 2 and 97% Coulombic efficiency cycling at 100 °C. This work provides a strategy to develop high-temperature all-solid-state batteries using garnet solid electrolytes and successfully addresses the high contact resistance between the V 2 O 5 cathode and garnet solid electrolyte without compromising battery safety or performance.

All-solid-state lithium-ion and lithium metal batteries - paving the way to large-scale production

NASA Astrophysics Data System (ADS)

Schnell, Joscha; Günther, Till; Knoche, Thomas; Vieider, Christoph; Köhler, Larissa; Just, Alexander; Keller, Marlou; Passerini, Stefano; Reinhart, Gunther

2018-04-01

Challenges and requirements for the large-scale production of all-solid-state lithium-ion and lithium metal batteries are herein evaluated via workshops with experts from renowned research institutes, material suppliers, and automotive manufacturers. Aiming to bridge the gap between materials research and industrial mass production, possible solutions for the production chains of sulfide and oxide based all-solid-state batteries from electrode fabrication to cell assembly and quality control are presented. Based on these findings, a detailed comparison of the production processes for a sulfide based all-solid-state battery with conventional lithium-ion cell production is given, showing that processes for composite electrode fabrication can be adapted with some effort, while the fabrication of the solid electrolyte separator layer and the integration of a lithium metal anode will require completely new processes. This work identifies the major steps towards mass production of all-solid-state batteries, giving insight into promising manufacturing technologies and helping stakeholders, such as machine engineering, cell producers, and original equipment manufacturers, to plan the next steps towards safer batteries with increased storage capacity.

Real-time monitoring of ischemia inside stomach.

PubMed

Tahirbegi, Islam Bogachan; Mir, Mònica; Samitier, Josep

2013-02-15

The low pH in the gastric juice of the stomach makes it difficult to fabricate stable and functional all-solid-state pH ISE sensors to sense ischemia, mainly because of anion interference and adhesion problem between the ISE membrane and the electrode surface. In this work, the adhesion of ISE membrane on solid surface at low pH was improved by modifying the surface with a conductive substrate containing hydrophilic and hydrophobic groups. This creates a stable and robust candidate for low pH applications. Moreover, anion interference problem at low pH was solved by integration of all-solid-state ISE and internal reference electrodes on an array. So, the same tendencies of anion interferences for all-solid-state ISE and all-solid-state reference electrodes cancel each other in differential potentiometric detection. The developed sensor presents a novel all-solid-state potentiometric, miniaturized and mass producible pH ISE sensor for detecting ischemia on the stomach tissue on an array designed for endoscopic applications. Copyright © 2012 Elsevier B.V. All rights reserved.

Fundamental characteristics of degradation-recoverable solid-state DFB polymer laser.

PubMed

Yoshioka, Hiroaki; Yang, Yu; Watanabe, Hirofumi; Oki, Yuji

2012-02-13

A novel solid-state dye laser with degradation recovery was proposed and demonstrated. Polydimethylsiloxane was used as a nanoporous solid matrix to enable the internal circulation of dye molecules in the solid state. An internal circulation model for the dye molecules was also proposed and verified numerically by assuming molecular mobility and using a proposed diffusion equation. The durability of the laser was increased 20.5-fold compared with that of a conventional polymethylmethacrylate laser. This novel laser solves the low-durability problem of dye-doped polymer lasers.

Studying Dynamics by Magic-Angle Spinning Solid-State NMR Spectroscopy: Principles and Applications to Biomolecules

PubMed Central

Schanda, Paul; Ernst, Matthias

2016-01-01

Magic-angle spinning solid-state NMR spectroscopy is an important technique to study molecular structure, dynamics and interactions, and is rapidly gaining importance in biomolecular sciences. Here we provide an overview of experimental approaches to study molecular dynamics by MAS solid-state NMR, with an emphasis on the underlying theoretical concepts and differences of MAS solid-state NMR compared to solution-state NMR. The theoretical foundations of nuclear spin relaxation are revisited, focusing on the particularities of spin relaxation in solid samples under magic-angle spinning. We discuss the range of validity of Redfield theory, as well as the inherent multi-exponential behavior of relaxation in solids. Experimental challenges for measuring relaxation parameters in MAS solid-state NMR and a few recently proposed relaxation approaches are discussed, which provide information about time scales and amplitudes of motions ranging from picoseconds to milliseconds. We also discuss the theoretical basis and experimental measurements of anisotropic interactions (chemical-shift anisotropies, dipolar and quadrupolar couplings), which give direct information about the amplitude of motions. The potential of combining relaxation data with such measurements of dynamically-averaged anisotropic interactions is discussed. Although the focus of this review is on the theoretical foundations of dynamics studies rather than their application, we close by discussing a small number of recent dynamics studies, where the dynamic properties of proteins in crystals are compared to those in solution. PMID:27110043

Solid State Ionics: from Michael Faraday to green energy-the European dimension.

PubMed

Funke, Klaus

2013-08-01

Solid State Ionics has its roots essentially in Europe. First foundations were laid by Michael Faraday who discovered the solid electrolytes Ag 2 S and PbF 2 and coined terms such as cation and anion , electrode and electrolyte . In the 19th and early 20th centuries, the main lines of development toward Solid State Ionics, pursued in Europe, concerned the linear laws of transport, structural analysis, disorder and entropy and the electrochemical storage and conversion of energy. Fundamental contributions were then made by Walther Nernst, who derived the Nernst equation and detected ionic conduction in heterovalently doped zirconia, which he utilized in his Nernst lamp. Another big step forward was the discovery of the extraordinary properties of alpha silver iodide in 1914. In the late 1920s and early 1930s, the concept of point defects was established by Yakov Il'ich Frenkel, Walter Schottky and Carl Wagner, including the development of point-defect thermodynamics by Schottky and Wagner. In terms of point defects, ionic (and electronic) transport in ionic crystals became easy to visualize. In an 'evolving scheme of materials science', point disorder precedes structural disorder, as displayed by the AgI-type solid electrolytes (and other ionic crystals), by ion-conducting glasses, polymer electrolytes and nano-composites. During the last few decades, much progress has been made in finding and investigating novel solid electrolytes and in using them for the preservation of our environment, in particular in advanced solid state battery systems, fuel cells and sensors. Since 1972, international conferences have been held in the field of Solid State Ionics, and the International Society for Solid State Ionics was founded at one of them, held at Garmisch-Partenkirchen, Germany, in 1987.

Solid State Ionics: from Michael Faraday to green energy—the European dimension

PubMed Central

Funke, Klaus

2013-01-01

Solid State Ionics has its roots essentially in Europe. First foundations were laid by Michael Faraday who discovered the solid electrolytes Ag2S and PbF2 and coined terms such as cation and anion, electrode and electrolyte. In the 19th and early 20th centuries, the main lines of development toward Solid State Ionics, pursued in Europe, concerned the linear laws of transport, structural analysis, disorder and entropy and the electrochemical storage and conversion of energy. Fundamental contributions were then made by Walther Nernst, who derived the Nernst equation and detected ionic conduction in heterovalently doped zirconia, which he utilized in his Nernst lamp. Another big step forward was the discovery of the extraordinary properties of alpha silver iodide in 1914. In the late 1920s and early 1930s, the concept of point defects was established by Yakov Il'ich Frenkel, Walter Schottky and Carl Wagner, including the development of point-defect thermodynamics by Schottky and Wagner. In terms of point defects, ionic (and electronic) transport in ionic crystals became easy to visualize. In an ‘evolving scheme of materials science’, point disorder precedes structural disorder, as displayed by the AgI-type solid electrolytes (and other ionic crystals), by ion-conducting glasses, polymer electrolytes and nano-composites. During the last few decades, much progress has been made in finding and investigating novel solid electrolytes and in using them for the preservation of our environment, in particular in advanced solid state battery systems, fuel cells and sensors. Since 1972, international conferences have been held in the field of Solid State Ionics, and the International Society for Solid State Ionics was founded at one of them, held at Garmisch-Partenkirchen, Germany, in 1987. PMID:27877585

Real time neutron diffraction and NMR of the Empress II glass-ceramic system.

PubMed

O'Donnell, M D; Hill, R G; Karpukhina, N; Law, R V

2011-10-01

This study reports real time neutron diffraction on the Empress II glass-ceramic system. The commercial glass-ceramics was characterized by real time neutron diffraction, ³¹P and ²⁹Si solid-state MAS-NMR, DSC and XRD. On heating, the as-received glass ceramic contained lithium disilicate (Li₂Si₂O₅), which melted with increasing temperature. This was revealed by neutron diffraction which showed the Bragg peaks for this phase had disappeared by 958°C in agreement with thermal analysis. On cooling lithium metasilicate (Li₂SiO₃) started to form at around 916°C and a minor phase of cristobalite at around 852°C. The unit cell volume of both Li-silicate phases increased linearly with temperature at a rate of +17×10⁻³ ų.°C⁻¹. Room temperature powder X-ray diffraction (XRD) of the material after cooling confirms presence of the lithium metasilicate and cristobalite as the main phases and shows, in addition, small amount of lithium disilicate and orthophosphate. ³¹P MAS-NMR reveals presence of the lithiorthophosphate (Li₃PO₄) before and after heat treatment. The melting of lithium disilicate on heating and crystallisation of lithium metasilicate on cooling agree with endothermic and exotermic features respectively observed by DSC. ²⁹Si MAS-NMR shows presence of lithium disilicate phase in the as-received glass-ceramic, though not in the major proportion, and lithium metasilicate in the material after heat treatment. Both phases have significantly long T₁ relaxation time, especially the lithium metasilicate, therefore, a quantitative analysis of the ²⁹Si MAS-NMR spectra was not attempted. Significance. The findings of the present work demonstrate importance of the commercially designed processing parameters in order to preserve desired characteristics of the material. Processing the Empress II at a rate slower than recommended 60°C min⁻¹ or long isothermal hold at the maximal processing temperature 920°C can cause crystallization of lithium metasilicate and cristobalite instead of lithium disilicate as major phase. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

A numerical study of thermal conditions in the THM growth of HgTe

NASA Astrophysics Data System (ADS)

Martínez-Tomás, M. C.; Muñoz-Sanjosé, V.; Reig, C.

2002-09-01

A numerical simulation of the travelling heater method (THM) process in the growth of HgTe is carried out. The whole system (furnace, ampoule and charge) is taken into account in the frame of a quasi-steady-state model. The mass conservation condition for the solute in the liquid zone permits the determination of the rate of advance of the crystallisation isotherm as a function of the heater position. We claim to study the evolution of different magnitudes along the growth process, searching for the physical reasons which could be at the origin of defects in the form of thin layers observed in some growing experiences. To solve the governing equations of fluid flow, heat transfer and mass transport we have made use of a commercial code which can run in a PC. The simulation is made by using a three-level strategy, which allows the reduction of the computational effort. In the first level, heat transport is assumed to be by conduction, convection and radiation between the furnace and the ampoule, and by conduction through the ampoule wall, coating, solid and liquid zones. The temperature calculated at this level in the air/ampoule boundary is used as boundary condition for the second and third level. In these two levels the ampoule and its content are studied in detail. Convection in the liquid zone is considered at the second level and thermosolutal convection is finally included at the third level. The analysis of the incoming/outcoming heat flux per second through the ampoule for the whole system shows that the lower part of the ampoule exhibits some ineffectiveness for the heat evacuation at certain positions of the growth run, depending on thermal properties of the whole system and the particular material to be grown. As a consequence, the growth rate suffers a significant variation just for these positions of the heater. From these considerations a plausible interpretation has been proposed to understand the apparition of solvent inclusions in the form of thin layers when a material as HgTe is grown by the THM method.

Modeling of Shock Waves with Multiple Phase Transitions in Condensed Materials

NASA Astrophysics Data System (ADS)

Missonnier, Marc; Heuzé, Olivier

2006-07-01

When a shock wave crosses a solid material and subjects it to solid-solid or solid-liquid phase transition, related phenomena occur: shock splitting, and the corresponding released shock wave after reflection. Modelling of these phenomena raises physical and numerical issues. After shock loading, such materials can reach different kinds of states: single-phase states, binary-phase states, and triple points. The thermodynamic path can be studied and easily understood in the (V,E) or (V,S) planes. In the case of 3 phase tin (β,γ, and liquid) submitted to shock waves, seven states can occur: β,γ, liquid, β-γ, β-liquid, γ-liquid, and β-γ-liquid. After studying the thermodynamic properties with a complete 3-phase Equation of State, we show the existence of these seven states with a hydrodynamic simulation.

Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pearse, Alexander J.; Schmitt, Thomas E.; Fuller, Elliot J.

Several active areas of research in novel energy storage technologies, including three-dimensional solid state batteries and passivation coatings for reactive battery electrode components, require conformal solid state electrolytes. We describe an atomic layer deposition (ALD) process for a member of the lithium phosphorus oxynitride (LiPON) family, which is employed as a thin film lithium-conducting solid electrolyte. The reaction between lithium tert-butoxide (LiO tBu) and diethyl phosphoramidate (DEPA) produces conformal, ionically conductive thin films with a stoichiometry close to Li 2PO 2N between 250 and 300°C. The P/N ratio of the films is always 1, indicative of a particular polymorph ofmore » LiPON which closely resembles a polyphosphazene. Films grown at 300°C have an ionic conductivity of (6.51 ± 0.36)×10 -7 S/cm at 35°C, and are functionally electrochemically stable in the window from 0 to 5.3V vs. Li/Li +. We demonstrate the viability of the ALD-grown electrolyte by integrating it into full solid state batteries, including thin film devices using LiCoO 2 as the cathode and Si as the anode operating at up to 1 mA/cm 2. The high quality of the ALD growth process allows pinhole-free deposition even on rough crystalline surfaces, and we demonstrate the fabrication and operation of thin film batteries with the thinnest (<40nm) solid state electrolytes yet reported. Finally, we show an additional application of the moderate-temperature ALD process by demonstrating a flexible solid state battery fabricated on a polymer substrate.« less

Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte

DOE PAGES

Pearse, Alexander J.; Schmitt, Thomas E.; Fuller, Elliot J.; ...

2017-04-10

Several active areas of research in novel energy storage technologies, including three-dimensional solid state batteries and passivation coatings for reactive battery electrode components, require conformal solid state electrolytes. We describe an atomic layer deposition (ALD) process for a member of the lithium phosphorus oxynitride (LiPON) family, which is employed as a thin film lithium-conducting solid electrolyte. The reaction between lithium tert-butoxide (LiO tBu) and diethyl phosphoramidate (DEPA) produces conformal, ionically conductive thin films with a stoichiometry close to Li 2PO 2N between 250 and 300°C. The P/N ratio of the films is always 1, indicative of a particular polymorph ofmore » LiPON which closely resembles a polyphosphazene. Films grown at 300°C have an ionic conductivity of (6.51 ± 0.36)×10 -7 S/cm at 35°C, and are functionally electrochemically stable in the window from 0 to 5.3V vs. Li/Li +. We demonstrate the viability of the ALD-grown electrolyte by integrating it into full solid state batteries, including thin film devices using LiCoO 2 as the cathode and Si as the anode operating at up to 1 mA/cm 2. The high quality of the ALD growth process allows pinhole-free deposition even on rough crystalline surfaces, and we demonstrate the fabrication and operation of thin film batteries with the thinnest (<40nm) solid state electrolytes yet reported. Finally, we show an additional application of the moderate-temperature ALD process by demonstrating a flexible solid state battery fabricated on a polymer substrate.« less

From dense monomer salt crystals to CO2 selective microporous polyimides via solid-state polymerization.

PubMed

Unterlass, Miriam M; Emmerling, Franziska; Antonietti, Markus; Weber, Jens

2014-01-14

Fully aromatic polyimides are synthesized via solid-state polymerization of the corresponding monomer salts. The crystal structure of salts shows strong hydrogen bonding of the reactive groups and thereby paves the way for solid-state transformations. The polycondensation yields copies of the initial salt crystallite habits, accompanied by the development of a porosity especially suited for CO2.

Universal features of the equation of state of solids

NASA Technical Reports Server (NTRS)

Vinet, Pascal; Rose, James H.; Ferrante, John; Smith, John R.

1989-01-01

A study of the energetics of solids leads to the conclusion that the equation of state for all classes of solids in compression can be expressed in terms of a universal function. The form of this universal function is determined by scaling experimental compression data for measured isotherms of a wide variety of solids. The equation of state is thus known (in the absence of phase transitions), if zero-pressure volume and isothermal compression and its pressure derivative are known. The discovery described in this paper has two immediate consequences: first, despite the well known differences in the microscopic energetics of the various classes of solids, there is a single equation of state for all classes in compression; and second, a new method is provided for analyzing measured isotherms and extrapolating high-pressure data from low-pressure (e.g. acoustic) data.

Charge and discharge characteristics of lithium-ion graphite electrodes in solid-state cells

NASA Astrophysics Data System (ADS)

Lemont, S.; Billaud, D.

Lithium ions have been electrochemically intercalated into graphite in solid-state cells operating with solid polymer electrolytes based on poly(ethylene oxide) (PEO) complexed with lithium perchlorate (LiClO 4). The working composite electrode is composed of active-divided natural graphite associated with P(EO) 8-LiClO 4 acting as a binder and a Li + ionic conductor. Intercalation and de-intercalation of Li + were performed using galvanostatic or voltammetry techniques. The curves obtained in our solid-state cells were compared with those performed in liquid ethylene carbonate-LiClO 4 electrolyte. It is shown that in solid-state cells, side reactions occur both in the reduction and in the oxidation processes which leads to some uncertainty in the determination of the maximum reversible capacity of the graphite material.

Solid state fermentation (SSF): diversity of applications to valorize waste and biomass.

PubMed

Lizardi-Jiménez, M A; Hernández-Martínez, R

2017-05-01

Solid state fermentation is currently used in a range of applications including classical applications, such as enzyme or antibiotic production, recently developed products, such as bioactive compounds and organic acids, new trends regarding bioethanol and biodiesel as sources of alternative energy, and biosurfactant molecules with environmental purposes of valorising unexploited biomass. This work summarizes the diversity of applications of solid state fermentation to valorize biomass regarding alternative energy and environmental purposes. The success of applying solid state fermentation to a specific process is affected by the nature of specific microorganisms and substrates. An exhaustive number of microorganisms able to grow in a solid matrix are presented, including fungus such as Aspergillus or Penicillum for antibiotics, Rhizopus for bioactive compounds, Mortierella for biodiesel to bacteria, Bacillus for biosurfactant production, or yeast for bioethanol.

Fluorine-doped antiperovskite electrolyte for all-solid-state Lithium-ion batteries

DOE PAGES

Li, Yutao; Zhou, Weidong; Xin, Sen; ...

2016-06-30

A fluorine-doped antiperovskite Li-ion conducto Li 2(OH)X (X=Cl, Br) is shown to be a promising candidat for a solid electrolyte in an all-solid-state Li-ion rechargeabl battery. Substitution of F¯ for OH¯ transforms orthorhombi Li 2OHCl to a room-temperature cubic phase, which show electrochemical stability to 9 V versus Li +/Li and two orders o magnitude higher Li-ion conductivity than that of orthorhombi Li 2OHCl. As a result, an all-solid-state Li/LiFePO 4 with F-dope Li 2OHCl as the solid electrolyte showed good cyclability an a high coulombic efficiency over 40 charge/discharge cycles

Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Yunfeng; Cai, Weiwei; Rohan, Rupesh; Pan, Meize; Liu, Yuan; Liu, Xupo; Li, Cuicui; Sun, Yubao; Cheng, Hansong

2016-02-01

The ionic conductivity decay problem of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) when increase the lithium salt of the SPEs up to high concentration is here functionally overcome by the incorporation of a charge delocalized sp3 boron based single ion conducting polymer electrolyte (SIPE) with poly(ethylene oxide) to fabricate solid-state sp3 boron based SIPE membranes (S-BSMs). By characterizations, particularly differential scanning calorimeter (DSC) and ionic conductivity studies, the fabricated S-BSMs showed decreased melting points and increased ionic conductivity as steadily increase the content of sp3 boron based SIPE, which significantly improved the low temperature performance of the all-solid-state lithium batteries. The fabricated Li | S-BSMs | LiFePO4 cells exhibit highly electrochemical stability and excellent cycling at temperature below melting point of PEO, which has never been reported so far for SIPEs based all-solid-state lithium batteries.

Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface.

PubMed

Yu, Chuang; Ganapathy, Swapna; Eck, Ernst R H van; Wang, Heng; Basak, Shibabrata; Li, Zhaolong; Wagemaker, Marnix

2017-10-20

Solid-state batteries potentially offer increased lithium-ion battery energy density and safety as required for large-scale production of electrical vehicles. One of the key challenges toward high-performance solid-state batteries is the large impedance posed by the electrode-electrolyte interface. However, direct assessment of the lithium-ion transport across realistic electrode-electrolyte interfaces is tedious. Here we report two-dimensional lithium-ion exchange NMR accessing the spontaneous lithium-ion transport, providing insight on the influence of electrode preparation and battery cycling on the lithium-ion transport over the interface between an argyrodite solid-electrolyte and a sulfide electrode. Interfacial conductivity is shown to depend strongly on the preparation method and demonstrated to drop dramatically after a few electrochemical (dis)charge cycles due to both losses in interfacial contact and increased diffusional barriers. The reported exchange NMR facilitates non-invasive and selective measurement of lithium-ion interfacial transport, providing insight that can guide the electrolyte-electrode interface design for future all-solid-state batteries.

Materials research for passive solar systems: Solid-state phase-change materials

NASA Astrophysics Data System (ADS)

Benson, D. K.; Webb, J. D.; Burrows, R. W.; McFadden, J. D. O.; Christensen, C.

1985-03-01

A set of solid-state phase-change materials is being evaluated for possible use in passive solar thermal energy storage systems. The most promising materials are organic solid solutions of pentaerythritol (C5H12O4), pentaglycerinve (C5H12O3), and neopentyl glycol (C5H12O2). Solid solution mixtures of these compounds can be tailored so that they exhibit solid-to-solid phase transformations at any desired temperature between 25 C and 188 C, and have latent heats of transformation etween 20 and 70 cal/g. Transformation temperatures, specific heats, and latent heats of transformation have been measured for a number of these materials. Limited cyclic experiments suggest that the solid solutions are stable. These phase-change materials exhibit large amounts of undercooling; however, the addition of certain nucleating agents as particulate dispersions in the solid phase-change material greatly reduces this effect. Computer simulations suggest that the use of an optimized solid-state phase-change material in a Trombe wall could provide better performance than a concrete Trombe wall four times thicker and nine times heavier.

Method and apparatus for semi-solid material processing

DOEpatents

Han, Qingyou [Knoxville, TN; Jian, Xiaogang [Knoxville, TN; Xu, Hanbing [Knoxville, TN; Meek, Thomas T [Knoxville, TN

2009-02-24

A method of forming a material includes the steps of: vibrating a molten material at an ultrasonic frequency while cooling the material to a semi-solid state to form non-dendritic grains therein; forming the semi-solid material into a desired shape; and cooling the material to a solid state. The method makes semi-solid castings directly from molten materials (usually a metal), produces grain size usually in the range of smaller than 50 .mu.m, and can be easily retrofitted into existing conventional forming machine.

Method and apparatus for semi-solid material processing

DOEpatents

Han, Qingyou [Knoxville, TN; Jian, Xiaogang [Knoxville, TN; Xu, Hanbing [Knoxville, TN; Meek, Thomas T [Knoxville, TN

2009-11-24

A method of forming a material includes the steps of: vibrating a molten material at an ultrasonic frequency while cooling the material to a semi-solid state to form non-dendritic grains therein; forming the semi-solid material into a desired shape; and cooling the material to a solid state. The method makes semi-solid castings directly from molten materials (usually a metal), produces grain size usually in the range of smaller than 50 .mu.m, and can be easily retrofitted into existing conventional forming maching.

Method and apparatus for semi-solid material processing

DOEpatents

Han, Qingyou [Knoxville, TN; Jian, Xiaogang [Knoxville, TN; Xu, Hanbing [Knoxville, TN; Meek, Thomas T [Knoxville, TN

2007-05-15

A method of forming a material includes the steps of: vibrating a molten material at an ultrasonic frequency while cooling the material to a semi-solid state to form non-dendritic grains therein; forming the semi-solid material into a desired shape; and cooling the material to a solid state. The method makes semi-solid castings directly from molten materials (usually a metal), produces grain size usually in the range of smaller than 50 .mu.m, and can be easily retrofitted into existing conventional forming machine.

Solid-solution thermodynamics in Al-Li alloys

NASA Astrophysics Data System (ADS)

Alekseev, A. A.; Lukina, E. A.

2016-05-01

The relative equilibrium concentrations of lithium atoms distributed over different electron-structural states has been estimated. The possibility of the existence of various nonequilibrium electron-structural states of Li atoms in the solid solution in Al has been substantiated thermodynamically. Upon the decomposition of the supersaturated solid solution, the supersaturation on three electron-structural states of Li atoms that arises upon the quenching of the alloy can lead to the formation of lithium-containing phases in which the lithium atoms enter in one electron-structural state.

Magnetic coupling between liquid 3He and a solid state substrate: a new approach

NASA Astrophysics Data System (ADS)

Klochkov, Alexander V.; Naletov, Vladimir V.; Tayurskii, Dmitrii A.; Tagirov, Murat S.; Suzuki, Haruhiko

2000-07-01

We suggest a new approach for solving the long-standing problem of a magnetic coupling between liquid 3He and a solid state substrate at temperatures above the Fermi temperature. The approach is based on our previous careful investigations of the physical state of a solid substrate by means of several experimental methods (EPR, NMR, conductometry, and magnetization measurements). The developed approach allows, first, to get more detailed information about the magnetic coupling phenomenon by varying the repetition time in pulse NMR investigations of liquid 3He in contact with the solid state substrate and, second, to compare the obtained dependences and the data of NMR-cryoporometry and AFM-microscopy.

Solid-state NMR studies of form I of atorvastatin calcium.

PubMed

Wang, Wei David; Gao, Xudong; Strohmeier, Mark; Wang, Wei; Bai, Shi; Dybowski, Cecil

2012-03-22

Solid-state (13)C, (19)F, and (15)N magic angle spinning NMR studies of Form I of atorvastatin calcium are reported, including chemical shift tensors of all resolvable carbon sites and fluorine sites. The complete (13)C and (19)F chemical shift assignments are given based on an extensive analysis of (13)C-(1)H HETCOR and (13)C-(19)F HETCOR results. The solid-state NMR data indicate that the asymmetric unit of this material contains two atorvastatin molecules. A possible structure of Form I of atorvastatin calcium (ATC-I), derived from solid-state NMR data and density functional theory calculations of various structures, is proposed for this important active pharmaceutical ingredient (API).

Solid-state chemistry and particle engineering with supercritical fluids in pharmaceutics.

PubMed

Pasquali, Irene; Bettini, Ruggero; Giordano, Ferdinando

2006-03-01

The present commentary aims to review the modern and innovative strategies in particle engineering by the supercritical fluid technologies and it is principally concerned with the aspects of solid-state chemistry. Supercritical fluids based processes for particle production have been proved suitable for controlling solid-state, morphology and particle size of pharmaceuticals, in some cases on an industrial scale. Supercritical fluids should be considered in a prominent position in the development processes of drug products for the 21st century. In this respect, this innovative technology will help in meeting the more and more stringent requirements of regulatory authorities in terms of solid-state characterisation and purity, and environmental acceptability.

Solid state electrolyte composites based on complex hydrides and metal doped fullerenes/fulleranes for batteries and electrochemical applications

DOEpatents

Zidan, Ragaiy; Teprovich, Jr., Joseph A.; Colon-Mercado, Hector R.; Greenway, Scott D.

2018-05-01

A LiBH₄--C₆₀ nanocomposite that displays fast lithium ionic conduction in the solid state is provided. The material is a homogenous nanocomposite that contains both LiBH₄ and a hydrogenated fullerene species. In the presence of C₆₀, the lithium ion mobility of LiBH₄ is significantly enhanced in the as prepared state when compared to pure LiBH₄. After the material is annealed the lithium ion mobility is further enhanced. Constant current cycling demonstrated that the material is stable in the presence of metallic lithium electrodes. The material can serve as a solid state electrolyte in a solid-state lithium ion battery.

Solid-State Division progress report for period ending March 31, 1983

DOE Office of Scientific and Technical Information (OSTI.GOV)

Green, P.H.; Watson, D.M.

1983-09-01

Progress and activities are reported on: theoretical solid-state physics (surfaces; electronic, vibrational, and magnetic properties; particle-solid interactions; laser annealing), surface and near-surface properties of solids (surface, plasma-material interactions, ion implantation and ion-beam mixing, pulsed-laser and thermal processing), defects in solids (radiation effects, fracture, impurities and defects, semiconductor physics and photovoltaic conversion), transport properties of solids (fast-ion conductors, superconductivity, mass and charge transport in materials), neutron scattering (small-angle scattering, lattice dynamics, magnetic properties, structure and instrumentation), and preparation and characterization of research materials (growth and preparative methods, nuclear waste forms, special materials). (DLC)

Investigation of Rhodopsin Dynamics in its Signaling State by Solid-State Deuterium NMR Spectroscopy

PubMed Central

Struts, Andrey V.; Chawla, Udeep; Perera, Suchithranga M.D.C.; Brown, Michael F.

2017-01-01

Site-directed deuterium NMR spectroscopy is a valuable tool to study the structural dynamics of biomolecules in cases where solution NMR is inapplicable. Solid-state 2H NMR spectral studies of aligned membrane samples of rhodopsin with selectively labeled retinal provide information on structural changes of the chromophore in different protein states. In addition, solid-state 2H NMR relaxation time measurements allow one to study the dynamics of the ligand during the transition from the inactive to the active state. Here we describe the methodological aspects of solid-state 2H NMR spectroscopy for functional studies of rhodopsin, with an emphasis on the dynamics of the retinal cofactor. We provide complete protocols for the preparation of NMR samples of rhodopsin with 11-cis-retinal selectively deuterated at the methyl groups in aligned membranes. In addition, we review optimized conditions for trapping the rhodopsin photointermediates; and lastly we address the challenging problem of trapping the signaling state of rhodopsin in aligned membrane films. PMID:25697522

Applications of solid-state NMR to membrane proteins.

PubMed

Ladizhansky, Vladimir

2017-11-01

Membrane proteins mediate flow of molecules, signals, and energy between cells and intracellular compartments. Understanding membrane protein function requires a detailed understanding of the structural and dynamic properties involved. Lipid bilayers provide a native-like environment for structure-function investigations of membrane proteins. In this review we give a general discourse on the recent progress in the field of solid-state NMR of membrane proteins. Solid-state NMR is a variation of NMR spectroscopy that is applicable to molecular systems with restricted mobility, such as high molecular weight proteins and protein complexes, supramolecular assemblies, or membrane proteins in a phospholipid environment. We highlight recent advances in applications of solid-state NMR to membrane proteins, specifically focusing on the recent developments in the field of Dynamic Nuclear Polarization, proton detection, and solid-state NMR applications in situ (in cell membranes). This article is part of a Special Issue entitled: Biophysics in Canada, edited by Lewis Kay, John Baenziger, Albert Berghuis and Peter Tieleman. Copyright © 2017 Elsevier B.V. All rights reserved.

By-products from the biodiesel chain as a substrate to citric acid production by solid-state fermentation.

PubMed

Schneider, Manuella; Zimmer, Gabriela F; Cremonese, Ezequiel B; de C de S Schneider, Rosana; Corbellini, Valeriano A

2014-07-01

In this study, we propose the use of tung cake for the production of organic acids, with an emphasis on citric acid by solid-state fermentation. We evaluated the conditions of production and the by-products from the biodiesel chain as raw materials involved in this bioprocess. First, we standardized the conditions of solid-state fermentation in tung cake with and without residual fat and with different concentrations of glycerine using the fungus Aspergillus niger The solid-state fermentation process was monitored for 7 days considering the biomass growth and pH level. Citric acid production was determined by high-performance liquid chromatography. Fungal development was better in the crude tung cake, consisting of 20% glycerine. The highest citric acid yield was 350 g kg(-1) of biomass. Therefore, the solid-state fermentation of the tung cake with glycerine led to citric acid production using the Aspergillus niger fungus. © The Author(s) 2014.

Correlation of Solid State and Solution Coordination Numbers with Infrared Spectroscopy in Five-, Six-, and Eight-Coordinate Transition Metal Complexes of DOTAM.

PubMed

Nagata, Maika K C T; Brauchle, Paul S; Wang, Sen; Briggs, Sarah K; Hong, Young Soo; Laorenza, Daniel W; Lee, Andrea G; Westmoreland, T David

2016-08-16

Three new DOTAM (1,4,7,10-tetrakis(acetamido)-1,4,7,10-tetraazacyclododecane) complexes have been synthesized and characterized by X-ray crystallography: [Co(DOTAM)]Cl 2 •3H 2 O, [Ni(DOTAM)]Cl 2 •4H 2 O, and [Cu(DOTAM)](ClO 4 ) 2 •H 2 O. Solid state and solution IR spectroscopic features for a series of [M(DOTAM)] 2+ complexes (M=Mn, Co, Cu, Ni, Ca, Zn) correlate with solid state and solution coordination numbers. [Co(DOTAM)] 2+ , [Ni(DOTAM)] 2+ , and [Zn(DOTAM)] 2+ are demonstrated to be six-coordinate in both the solid state and in solution, while [Mn(DOTAM)] 2+ and [Ca(DOTAM)] 2+ are eight-coordinate in the solid state and remain so in solution. [Cu(DOTAM)] 2+ , which is five-coordinate by X-ray crystallography, is shown to increase its coordination number in solution to six-coordinate.

Highly Efficient Plastic Crystal Ionic Conductors for Solid-state Dye-sensitized Solar Cells

PubMed Central

Hwang, Daesub; Kim, Dong Young; Jo, Seong Mu; Armel, Vanessa; MacFarlane, Douglas R.; Kim, Dongho; Jang, Sung-Yeon

2013-01-01

We have developed highly efficient, ambient temperature, solid-state ionic conductors (SSICs) for dye-sensitized solar cells (DSSCs) by doping a molecular plastic crystal, succinonitrile (SN), with trialkyl-substituted imidazolium iodide salts. High performance SSICs with enhanced ionic conductivity (2–4 mScm−1) were obtained. High performance solid-state DSSCs with power conversion efficiency of 7.8% were fabricated using our SSICs combined with unique hierarchically nanostructured TiO2 sphere (TiO2-SP) photoelectrodes; these electrodes have significant macroporosity, which assists penetration of the solid electrolyte into the electrode. The performance of our solid-state DSSCs is, to the best of our knowledge, the highest reported thus far for cells using plastic crystal-based SSICs, and is comparable to that of the state-of-the-art DSSCs which use ionic liquid type electrolytes. This report provides a logical strategy for the development of efficient plastic crystal-based SSICs for DSSCs and other electrochemical devices. PMID:24343425

Carbon dot/polyvinylpyrrolidone hybrid nanofibers with efficient solid-state photoluminescence constructed using an electrospinning technique

NASA Astrophysics Data System (ADS)

Zhai, Yue; Bai, Xue; Cui, Haining; Zhu, Jinyang; Liu, Wei; Zhang, Tianxiang; Dong, Biao; Pan, Gencai; Xu, Lin; Zhang, Shuang; Song, Hongwei

2018-01-01

Carbon dots (CDs) are the promising candidates for application in optoelectronic and biological areas due to their excellent photostability, unique photoluminescence, good biocompatibility, low toxicity and chemical inertness. However, the self-quenching of photoluminescence as they are dried into the solid state dramatically limits their further application. Therefore, realizing efficient photoluminescence and large-scale production of CDs in the solid state is an urgent challenge. Herein, solid-state hybrid nanofibers based on CDs and polyvinylpyrrolidone (PVP) are constructed through an electrospinning process. The resulting solid-state hybrid PVP/CD nanofibers present much enhanced photoluminescence performance compared to the corresponding pristine colloidal CDs due to the decrease in non-radiative recombination of electron-holes. Owing to the suppressed self-quenching of CDs, the photoluminescence quantum yield is considerably improved from 42.9% of pristine CDs to 83.5% of nanofibers under the excitation wavelength of 360 nm. This has great application potential in optical or optoelectronic devices.

Production and Characterization of Lipases by Two New Isolates of Aspergillus through Solid-State and Submerged Fermentation

PubMed Central

Colla, Luciane Maria; Ficanha, Aline M. M.; Rizzardi, Juliana; Bertolin, Telma Elita; Reinehr, Christian Oliveira; Costa, Jorge Alberto Vieira

2015-01-01

Due to the numerous applications of lipases in industry, there is a need to study their characteristics, because lipases obtained from different sources may present different properties. The aim of this work was to accomplish the partial characterization of lipases obtained through submerged fermentation and solid-state fermentation by two species of Aspergillus. Fungal strains were isolated from a diesel-contaminated soil and selected as good lipases producers. Lipases obtained through submerged fermentation presented optimal activities at 37°C and pH 7.2 and those obtained through solid-state fermentation at 35°C and pH 6.0. The enzymes produced by submerged fermentation were more temperature-stable than those obtained by solid-state fermentation, presenting 72% of residual activity after one hour of exposition at 90°C. Lipases obtained through submerged fermentation had 80% of stability in acidic pH and those obtained through solid-state fermentation had stability greater than 60% in alkaline pH. PMID:26180809

Impact of operating conditions on performance of a novel gas double-dynamic solid-state fermentation bioreactor (GDSFB).

PubMed

Chen, Hongzhang; Li, Yanjun; Xu, Fujian

2013-11-01

A self-designed novel solid-state fermentation (SSF) bioreactor named "gas double-dynamic solid-state fermentation bioreactor (GDSFB)" showed great success in processes for the production of several valuable products. For the present study, a simple GDSFB (2 L in volume) was designed to investigate the impact of exhaust time on SSF performance. Both air pressure and vent aperture significantly influenced the exhaust time. The production of cellulase by Penicillium decumbens JUA10 was studied in this bioreactor. When the vent aperture was maintained at 0.2 cm, the highest FPA activity of 17.2 IU/g dry solid-state medium was obtained at an air pressure of 0.2 MPa (gauge pressure). When the air pressure was maintained at 0.2 MPa, a vent aperture of 0.3 cm gave the highest FPA activity of 18.0 IU/g dry solid-state medium. Further analysis revealed that the exhaust time was a crucial indicator of good performance in GDSFB.

Sintered Cathodes for All-Solid-State Structural Lithium-Ion Batteries

NASA Technical Reports Server (NTRS)

Huddleston, William; Dynys, Frederick; Sehirlioglu, Alp

2017-01-01

All-solid-state structural lithium ion batteries serve as both structural load-bearing components and as electrical energy storage devices to achieve system level weight savings in aerospace and other transportation applications. This multifunctional design goal is critical for the realization of next generation hybrid or all-electric propulsion systems. Additionally, transitioning to solid state technology improves upon battery safety from previous volatile architectures. This research established baseline solid state processing conditions and performance benchmarks for intercalation-type layered oxide materials for multifunctional application. Under consideration were lithium cobalt oxide and lithium nickel manganese cobalt oxide. Pertinent characteristics such as electrical conductivity, strength, chemical stability, and microstructure were characterized for future application in all-solid-state structural battery cathodes. The study includes characterization by XRD, ICP, SEM, ring-on-ring mechanical testing, and electrical impedance spectroscopy to elucidate optimal processing parameters, material characteristics, and multifunctional performance benchmarks. These findings provide initial conditions for implementing existing cathode materials in load bearing applications.

Intermediate couplings: NMR at the solids-liquids interface

NASA Astrophysics Data System (ADS)

Spence, Megan

2006-03-01

Anisotropic interactions like dipolar couplings and chemical shift anisotropy have long offered solid-state NMR spectroscopists valuable structural information. Recently, solution-state NMR structural studies have begun to exploit residual dipolar couplings of biological molecules in weakly anisotropic solutions. These residual couplings are about 0.1% of the coupling magnitudes observed in the solid state, allowing simple, high-resolution NMR spectra to be retained. In this work, we examine the membrane-associated opioid, leucine enkephalin (lenk), in which the ordering is ten times larger than that for residual dipolar coupling experiments, requiring a combination of solution-state and solid-state NMR techniques. We adapted conventional solid-state NMR techniques like adiabatic cross- polarization and REDOR for use with such a system, and measured small amide bond dipolar couplings in order to determine the orientation of the amide bonds (and therefore the peptide) with respect to the membrane surface. However, the couplings measured indicate large structural rearrangements on the surface and contradict the published structures obtained by NOESY constraints, a reminder that such methods are of limited use in the presence of large-scale dynamics.

Spin Crossover in Solid and Liquid (Mg,Fe)O at Extreme Conditions

NASA Astrophysics Data System (ADS)

Stixrude, L. P.; Holmstrom, E.

2016-12-01

Ferropericlase, (Mg,Fe)O, is a major constituent of the Earth's lowermantle (24-136 GPa). Understanding the properties of this component is importantnot only in the solid state, but also in the molten state, as theplanet almost certainly hosted an extensive magma ocean initiallyWith increasing pressure, the Fe ions in the material begin to collapse from a magnetic to a nonmagnetic spin state. This crossover affects thermodynamic, transport, and electrical properties.Using first-principles molecular dynamics simulations,thermodynamic integration, and adiabatic switching, we present a phasediagram of the spin crossover In both solid and liquid, we find a broad pressure range of coexisting magnetic and non-magnetic ions due to the favorable enthalpy of mixing of the two. In the solid increasingtemperature favors the high spin state, while in the liquid the oppositeoccurs, due to the higher electronic entropy of the low spin state. Becausethe physics of the crossover differ in solid and liquid, melting produces a large change in spin state that may affect the buoyancy of crystals freezing from the magma ocean in the earliest Earth.

A "special perspectives" issue: Recent achievements and new directions in biomolecular solid state NMR

NASA Astrophysics Data System (ADS)

Tycko, Robert

2015-04-01

Twenty years ago, applications of solid state nuclear magnetic resonance (NMR) methods to real problems involving biological systems or biological materials were few and far between. Starting in the 1980s, a small number of research groups had begun to explore the possibility of obtaining structural and dynamical information about peptides, proteins, and other biopolymers from solid state NMR spectra. Progress was initially slow due to the relatively primitive state of solid state NMR probes, spectrometers, sample preparation methods, and pulse sequence techniques, coupled with the small number of people contributing to this research area. By the early 1990s, with the advent of new ideas about pulse sequence techniques such as dipolar recoupling, improvements in techniques for orienting membrane proteins and in technology for magic-angle spinning (MAS), improvements in the capabilities of commercial NMR spectrometers, and general developments in multidimensional spectroscopy, it began to appear that biomolecular solid state NMR might have a viable future. It was not until 1993 that the annual number of publications in this area crept above twenty.

Solid state fermentation for extracellular polysaccharide production by Lactobacillus confusus with coconut water and sugar cane juice as renewable wastes.

PubMed

Seesuriyachan, Phisit; Techapun, Charin; Shinkawa, Hidenori; Sasaki, Ken

2010-01-01

Extracellular polysaccharide (EPS) production by Lactobacillus confusus in liquid and solid state fermentation was carried out using coconut water and sugarcane juice as renewable wastes. High concentrations of EPS of 62 (sugarcane juice) and 18 g/l of coconut water were produced in solid state fermentation when nitrogen sources were reduced 5-fold from the original medium.

Energy-saving approaches to solid state street lighting

NASA Astrophysics Data System (ADS)

Vitta, Pranciškus; Stanikūnas, Rytis; Tuzikas, Arūnas; Reklaitis, Ignas; Stonkus, Andrius; Petrulis, Andrius; Vaitkevičius, Henrikas; Žukauskas, Artūras

2011-10-01

We consider the energy-saving potential of solid-state street lighting due to improved visual performance, weather sensitive luminance control and tracking of pedestrians and vehicles. A psychophysical experiment on the measurement of reaction time with a decision making task was performed under mesopic levels of illumination provided by a highpressure sodium (HPS) lamp and different solid-state light sources, such as daylight and warm-white phosphor converted light-emitting diodes (LEDs) and red-green-blue LED clusters. The results of the experiment imply that photopic luminances of road surface provided by solid-state light sources with an optimized spectral power distribution might be up to twice as low as those provided by the HPS lamp. Dynamical correction of road luminance against road surface conditions typical of Lithuanian climate was estimated to save about 20% of energy in comparison with constant-level illumination. The estimated energy savings due to the tracking of pedestrians and vehicles amount at least 25% with the cumulative effect of intelligent control of at least 40%. A solid-state street lighting system with intelligent control was demonstrated using a 300 m long test ground consisting of 10 solid-state street luminaires, a meteorological station and microwave motion sensor network operated via power line communication.

The C2H2-type transcription factor, FlbC, is involved in the transcriptional regulation of Aspergillus oryzae glucoamylase and protease genes specifically expressed in solid-state culture.

PubMed

Tanaka, Mizuki; Yoshimura, Midori; Ogawa, Masahiro; Koyama, Yasuji; Shintani, Takahiro; Gomi, Katsuya

2016-07-01

Aspergillus oryzae produces a large amount of secreted proteins in solid-state culture, and some proteins such as glucoamylase (GlaB) and acid protease (PepA) are specifically produced in solid-state culture, but rarely in submerged culture. From the disruption mutant library of A. oryzae transcriptional regulators, we successfully identified a disruption mutant showing an extremely low production level of GlaB but a normal level of α-amylase production. This strain was a disruption mutant of the C2H2-type transcription factor, FlbC, which is reported to be involved in the regulation of conidiospore development. Disruption mutants of other upstream regulators comprising a conidiation regulatory network had no apparent effect on GlaB production in solid-state culture. In addition to GlaB, the production of acid protease in solid-state culture was also markedly decreased by flbC disruption. Northern blot analyses revealed that transcripts of glaB and pepA were significantly decreased in the flbC disruption strain. These results suggested that FlbC is involved in the transcriptional regulation of genes specifically expressed under solid-state cultivation conditions, possibly independent of the conidiation regulatory network.

All-solid-state reduced graphene oxide supercapacitor with large volumetric capacitance and ultralong stability prepared by electrophoretic deposition method.

PubMed

Wang, Mei; Duong, Le Dai; Mai, Nguyen Thi; Kim, Sanghoon; Kim, Youngjun; Seo, Heewon; Kim, Ye Chan; Jang, Woojin; Lee, Youngkwan; Suhr, Jonghwan; Nam, Jae-Do

2015-01-21

Portable energy storage devices have gained special attention due to the growing demand for portable electronics. Herein, an all-solid-state supercapacitor is successfully fabricated based on a poly(vinyl alcohol)-H3PO4 (PVA-H3PO4) polymer electrolyte and a reduced graphene oxide (RGO) membrane electrode prepared by electrophoretic deposition (EPD). The RGO electrode fabricated by EPD contains an in-plane layer-by-layer alignment and a moderate porosity that accommodate the electrolyte ions. The all-solid-state RGO supercapacitor is thoroughly tested to give high specific volumetric capacitance (108 F cm(-3)) and excellent energy and power densities (7.5 Wh cm(-3) and 2.9 W cm(-3), respectively). In addition, the all-solid-state RGO supercapacitor exhibits an ultralong lifetime for as long as 180 days (335 000 cycles), which is an ultrahigh cycling capability for a solid-state supercapacitor. The RGO is also tested for being used as a transparent supercapacitor electrode demonstrating its possible use in various transparent optoelectronic devices. Due to the facile scale-up capability of the EPD process and RGO dispersion, the developed all-solid-state supercapacitor is highly applicable to large-area portable energy storage devices.

State humanitarian verticalism versus universal health coverage: a century of French international health assistance revisited.

PubMed

Atlani-Duault, Laëtitia; Dozon, Jean-Pierre; Wilson, Andrew; Delfraissy, Jean-François; Moatti, Jean-Paul

2016-05-28

The French contribution to global public health over the past two centuries has been marked by a fundamental tension between two approaches: State-provided universal free health care and what we propose to call State humanitarian verticalism. Both approaches have historical roots in French colonialism and have led to successes and failures that continue until the present day. In this paper, the second in The Lancet's Series on France, we look at how this tension has evolved. During the French colonial period (1890s to 1950s), the Indigenous Medical Assistance structure was supposed to bring metropolitan France's model of universal and free public health care to the colonies, and French State imperial humanitarianism crystallised in vertical programmes inspired by Louis Pasteur, while vying with early private humanitarian activism in health represented by Albert Schweitzer. From decolonisation to the end of the Cold War (1960-99), French assistance to newly independent states was affected by sans frontièrisme, Health for All, and the AIDS pandemic. Since 2000, France has had an active role in development of global health initiatives and favoured multilateral action for health assistance. Today, with adoption of the 2030 Sustainable Development Goals and the challenges of non-communicable diseases, economic inequality, and climate change, French international health assistance needs new direction. In the context of current debate over global health as a universal goal, understanding and acknowledging France's history could help strengthen advocacy in favour of universal health coverage and contribute to advancing global equity through income redistribution, from healthy populations to people who are sick and from wealthy individuals to those who are poor. Copyright © 2016 Elsevier Ltd. All rights reserved.

A Good Name and Great Riches: Rebranding Solid State Physics for the National Laboratories

NASA Astrophysics Data System (ADS)

Martin, Joseph

2012-03-01

In 1943 Oliver Buckley, lamenting the inadequacy of term ``physics'' to evoke what physicists did, quoted the proverb, ``A good name is rather to be chosen than great riches.'' Some forty years later, solid state physicists confronted similar discontent with their name, precipitating the rise of the appellation ``condensed matter physics.'' Ostensibly a rebranding of a well-established field, the change signaled deeper conceptual and institutional realignment. Whereas ``solid state'' emerged in the 1940s in the service of institutional aims, ``condensed matter'' more accurately captured a distinct set of theoretical and experimental approaches. Reimagining the field around core conceptual approaches set condensed matter apart from the inchoate field of materials science, which subsumed a growing proportion of solid state funding and personnel through the 1980s. Federally funded research installations were the source of ``great riches'' for scientific research. The DOE National Laboratory System and the DARPA network of Interdisciplinary Laboratories, given their responsiveness to shifts in national funding priorities, provide a sensitive historical instrument through which to trace the transition from solid state to condensed matter. The reorganization of solid state in response to the evolution of national priorities and funding practices precipitated a sharpening of the field's intellectual mission. At the same time, it reflected the difficulties solid state faced articulating its intellectual--as opposed to technological--merit. The proverb continues, `` and loving favor rather than silver and gold.'' The adoption of a name that emphasized intellectual cohesion and associated social esteem exposed the growing tension between technology-oriented national funding goals for materials research and condensed matter physics' ascendant intellectual identity.

40 CFR 256.11 - Recommendations.

Code of Federal Regulations, 2014 CFR

2014-07-01

... authorized State hazardous waste management program under subtitle C of the Act. (e) The State plan should... Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Identification of Responsibilities...

40 CFR 256.11 - Recommendations.

Code of Federal Regulations, 2012 CFR

2012-07-01

... authorized State hazardous waste management program under subtitle C of the Act. (e) The State plan should... Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Identification of Responsibilities...

Density functional theory in the solid state

PubMed Central

Hasnip, Philip J.; Refson, Keith; Probert, Matt I. J.; Yates, Jonathan R.; Clark, Stewart J.; Pickard, Chris J.

2014-01-01

Density functional theory (DFT) has been used in many fields of the physical sciences, but none so successfully as in the solid state. From its origins in condensed matter physics, it has expanded into materials science, high-pressure physics and mineralogy, solid-state chemistry and more, powering entire computational subdisciplines. Modern DFT simulation codes can calculate a vast range of structural, chemical, optical, spectroscopic, elastic, vibrational and thermodynamic phenomena. The ability to predict structure–property relationships has revolutionized experimental fields, such as vibrational and solid-state NMR spectroscopy, where it is the primary method to analyse and interpret experimental spectra. In semiconductor physics, great progress has been made in the electronic structure of bulk and defect states despite the severe challenges presented by the description of excited states. Studies are no longer restricted to known crystallographic structures. DFT is increasingly used as an exploratory tool for materials discovery and computational experiments, culminating in ex nihilo crystal structure prediction, which addresses the long-standing difficult problem of how to predict crystal structure polymorphs from nothing but a specified chemical composition. We present an overview of the capabilities of solid-state DFT simulations in all of these topics, illustrated with recent examples using the CASTEP computer program. PMID:24516184

An Investigation into the Polymorphism and Crystallization of Levetiracetam and the Stability of its Solid Form.

PubMed

Xu, Kailin; Xiong, Xinnuo; Guo, Liuqi; Wang, Lili; Li, Shanshan; Tang, Peixiao; Yan, Jin; Wu, Di; Li, Hui

2015-12-01

Levetiracetam (LEV) crystals were prepared using different solvents at different temperatures. The LEV crystals were systematically characterized by X-ray powder diffraction (XRPD) and morphological analysis. The results indicated that many kinds of crystal habits exist in a solid form of LEV. To investigate the effects of LEV concentration, crystallization temperature, and crystallization type on crystallization and solid phase transformation of LEV, multiple methods were performed for LEV aqueous solution to determine if a new solid form exists in solid-state LEV. However, XRPD data demonstrate that the LEV solid forms possess same spatial arrangements that are similar to the original solid form. This result indicates that the LEV concentration, crystallization temperature, and crystallization type in aqueous solution have no influence on the crystallization and solid phase transformation of LEV. Moreover, crystallization by sublimation, melt cooling, and quench cooling, as well as mechanical effect, did not result in the formation of new LEV solid state. During melt cooling, the transformation of solid form LEV is a direct process from melting amorphous phase to the original LEV crystal phase, and the conversion rate is very quick. In addition, stability investigation manifested that LEV solid state is very stable under various conditions. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

All-solid state lithium carbon monofluoride batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, Chengdu; Rangasamy, Ezhiylmurugan

A solid state lithium carbon monofluoride battery includes an anode comprising Li, a solid electrolyte, and a cathode including CF.sub.x and LPS. The cathode can also include a carbon compound. The solid electrolyte can include LPS. The LPS can include .beta.-Li.sub.3PS.sub.4. The cathode LPS can include .beta.-Li.sub.3PS.sub.4. A method of making a battery is also disclosed.

Proteomic analysis of extracellular proteins from Aspergillus oryzae grown under submerged and solid-state culture conditions.

PubMed

Oda, Ken; Kakizono, Dararat; Yamada, Osamu; Iefuji, Haruyuki; Akita, Osamu; Iwashita, Kazuhiro

2006-05-01

Filamentous fungi are widely used for the production of homologous and heterologous proteins. Recently, there has been increasing interest in Aspergillus oryzae because of its ability to produce heterologous proteins in solid-state culture. To provide an overview of protein secretion by A. oryzae in solid-state culture, we carried out a comparative proteome analysis of extracellular proteins in solid-state and submerged (liquid) cultures. Extracellular proteins prepared from both cultures sequentially from 0 to 40 h were subjected to two-dimensional electrophoresis, and protein spots at 40 h were identified by peptide mass fingerprinting using matrix-assisted laser desorption ionization-time-of-flight mass spectrometry. We also attempted to identify cell wall-bound proteins of the submerged culture. We analyzed 85 spots from the solid-state culture and 110 spots from the submerged culture. We identified a total of 29 proteins, which were classified into 4 groups. Group 1 consisted of extracellular proteins specifically produced in the solid-state growth condition, such as glucoamylase B and alanyl dipeptidyl peptidase. Group 2 consisted of extracellular proteins specifically produced in the submerged condition, such as glucoamylase A (GlaA) and xylanase G2 (XynG2). Group 3 consisted of proteins produced in both conditions, such as xylanase G1. Group 4 consisted of proteins that were secreted to the medium in the solid-state growth condition but trapped in the cell wall in the submerged condition, such as alpha-amylase (TAA) and beta-glucosidase (Bgl). A Northern analysis of seven genes from the four groups suggested that the secretion of TAA and Bgl was regulated by trapping these proteins in the cell wall in submerged culture and that secretion of GlaA and XynG2 was regulated at the posttranscriptional level in the solid-state culture.

Proteomic Analysis of Extracellular Proteins from Aspergillus oryzae Grown under Submerged and Solid-State Culture Conditions

PubMed Central

Oda, Ken; Kakizono, Dararat; Yamada, Osamu; Iefuji, Haruyuki; Akita, Osamu; Iwashita, Kazuhiro

2006-01-01

Filamentous fungi are widely used for the production of homologous and heterologous proteins. Recently, there has been increasing interest in Aspergillus oryzae because of its ability to produce heterologous proteins in solid-state culture. To provide an overview of protein secretion by A. oryzae in solid-state culture, we carried out a comparative proteome analysis of extracellular proteins in solid-state and submerged (liquid) cultures. Extracellular proteins prepared from both cultures sequentially from 0 to 40 h were subjected to two-dimensional electrophoresis, and protein spots at 40 h were identified by peptide mass fingerprinting using matrix-assisted laser desorption ionization-time-of-flight mass spectrometry. We also attempted to identify cell wall-bound proteins of the submerged culture. We analyzed 85 spots from the solid-state culture and 110 spots from the submerged culture. We identified a total of 29 proteins, which were classified into 4 groups. Group 1 consisted of extracellular proteins specifically produced in the solid-state growth condition, such as glucoamylase B and alanyl dipeptidyl peptidase. Group 2 consisted of extracellular proteins specifically produced in the submerged condition, such as glucoamylase A (GlaA) and xylanase G2 (XynG2). Group 3 consisted of proteins produced in both conditions, such as xylanase G1. Group 4 consisted of proteins that were secreted to the medium in the solid-state growth condition but trapped in the cell wall in the submerged condition, such as α-amylase (TAA) and β-glucosidase (Bgl). A Northern analysis of seven genes from the four groups suggested that the secretion of TAA and Bgl was regulated by trapping these proteins in the cell wall in submerged culture and that secretion of GlaA and XynG2 was regulated at the posttranscriptional level in the solid-state culture. PMID:16672490

Detection of low-level PTFE contamination: An application of solid-state NMR to structure elucidation in the pharmaceutical industry.

PubMed

Pham, Tran N; Day, Caroline J; Edwards, Andrew J; Wood, Helen R; Lynch, Ian R; Watson, Simon A; Bretonnet, Anne-Sophie Z; Vogt, Frederick G

2011-01-25

We report a novel use of solid-state ¹⁹F nuclear magnetic resonance to detect and quantify polytetrafluoroethylene contamination from laboratory equipment, which due to low quantity (up to 1% w/w) and insolubility remained undetected by standard analytical techniques. Solid-state ¹⁹F NMR is shown to be highly sensitive to such fluoropolymers (detection limit 0.02% w/w), and is demonstrated as a useful analytical tool for structure elucidation of unknown solid materials. Copyright © 2010 Elsevier B.V. All rights reserved.

High-Resolution Solid-State NMR Spectroscopy: Characterization of Polymorphism in Cimetidine, a Pharmaceutical Compound

ERIC Educational Resources Information Center

Pacilio, Julia E.; Tokarski, John T.; Quiñones, Rosalynn; Iuliucci, Robbie J.

2014-01-01

High-resolution solid-state NMR (SSNMR) spectroscopy has many advantages as a tool to characterize solid-phase material that finds applications in polymer chemistry, nanotechnology, materials science, biomolecular structure determination, and others, including the pharmaceutical industry. The technology associated with achieving high resolution…

40 CFR 256.01 - Purpose and scope of the guidelines.

Code of Federal Regulations, 2010 CFR

2010-07-01

... WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Purpose... guidelines is to assist in the development and implementation of State solid waste management plans, in accordance with section 4002(b) of the Solid Waste Disposal Act, as amended by the Resource Conservation and...

[Analyze on volatile compounds of Antrodia camphorata using HS-SPME-GC-MS].

PubMed

He, Zhe; Lu, Zhen-Ming; Xu, Hong-Yu; Shi, Jing-Song; Xu, Zheng-Hong

2011-11-01

To analyze the volatile compounds of Antrodia camphorata in solid-state and submerged cultures. A headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry(GC-MS) were used to evaluate the profile of the volatile compounds. 49 volatile compounds were identified in A. camphorata mycelia in submerged culture, while 43 volatile compounds were identified in mycelia in solid-state culture. 1-octen-3-ol, 3-octanone, 1-octen-3-ylacetate, acetic acid octyl ester and ethanol were the main volatile compounds in A. camphorata mycelia in submerged culture, while 1-octen-3-ol, 3-octanone, 3-methyl-butyraldenhyde, gamma-podecalactone and methyl 2-furozte were the most potent key volatile compounds in mycelia in solid-state culture. The volatile compounds in the mycelia of A. camphorata in solid-state and submerged cultures are similar but their relative contents are different.

Methods of amorphization and investigation of the amorphous state.

PubMed

Einfal, Tomaž; Planinšek, Odon; Hrovat, Klemen

2013-09-01

The amorphous form of pharmaceutical materials represents the most energetic solid state of a material. It provides advantages in terms of dissolution rate and bioavailability. This review presents the methods of solid- -state amorphization described in literature (supercooling of liquids, milling, lyophilization, spray drying, dehydration of crystalline hydrates), with the emphasis on milling. Furthermore, we describe how amorphous state of pharmaceuticals differ depending on the method of preparation and how these differences can be screened by a variety of spectroscopic (X-ray powder diffraction, solid state nuclear magnetic resonance, atomic pairwise distribution, infrared spectroscopy, terahertz spectroscopy) and calorimetry methods.

'All-solid-state' electrochemistry of a protein-confined polymer electrolyte film

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parthasarathy, Meera; Pillai, Vijayamohanan K.; Mulla, Imtiaz S.

2007-12-07

Interfacial redox behavior of a heme protein (hemoglobin) confined in a solid polymer electrolyte membrane, Nafion (a perfluoro sulfonic acid ionomer) is investigated using a unique 'all-solid-state' electrochemical methodology. The supple phase-separated structure of the polymer electrolyte membrane, with hydrophilic pools containing solvated protons and water molecules, is found to preserve the incorporated protein in its active form even in the solid-state, using UV-visible, Fluorescence (of Tryptophan and Tyrosine residues) and DRIFT (diffuse reflectance infrared Fourier transform) spectroscopy. More specifically, solid-state cyclic voltammetry and electrochemical impedance of the protein-incorporated polymer films reveal that the Fe{sup 2+}-form of the entrapped proteinmore » is found to bind molecular oxygen more strongly than the native protein. In the 'all-solid-state' methodology, as there is no need to dip the protein-modified electrode in a liquid electrolyte (like the conventional electrochemical methods), it offers an easier means to study a number of proteins in a variety of polymer matrices (even biomimetic assemblies). In addition, the results of the present investigation could find interesting application in a variety of research disciplines, in addition to its fundamental scientific interest, including protein biotechnology, pharmaceutical and biomimetic chemistry.« less

Exploiting the Synergy of Powder X-ray Diffraction and Solid-State NMR Spectroscopy in Structure Determination of Organic Molecular Solids

PubMed Central

2013-01-01

We report a strategy for structure determination of organic materials in which complete solid-state nuclear magnetic resonance (NMR) spectral data is utilized within the context of structure determination from powder X-ray diffraction (XRD) data. Following determination of the crystal structure from powder XRD data, first-principles density functional theory-based techniques within the GIPAW approach are exploited to calculate the solid-state NMR data for the structure, followed by careful scrutiny of the agreement with experimental solid-state NMR data. The successful application of this approach is demonstrated by structure determination of the 1:1 cocrystal of indomethacin and nicotinamide. The 1H and 13C chemical shifts calculated for the crystal structure determined from the powder XRD data are in excellent agreement with those measured experimentally, notably including the two-dimensional correlation of 1H and 13C chemical shifts for directly bonded 13C–1H moieties. The key feature of this combined approach is that the quality of the structure determined is assessed both against experimental powder XRD data and against experimental solid-state NMR data, thus providing a very robust validation of the veracity of the structure. PMID:24386493

Exploiting the Synergy of Powder X-ray Diffraction and Solid-State NMR Spectroscopy in Structure Determination of Organic Molecular Solids.

PubMed

Dudenko, Dmytro V; Williams, P Andrew; Hughes, Colan E; Antzutkin, Oleg N; Velaga, Sitaram P; Brown, Steven P; Harris, Kenneth D M

2013-06-13

We report a strategy for structure determination of organic materials in which complete solid-state nuclear magnetic resonance (NMR) spectral data is utilized within the context of structure determination from powder X-ray diffraction (XRD) data. Following determination of the crystal structure from powder XRD data, first-principles density functional theory-based techniques within the GIPAW approach are exploited to calculate the solid-state NMR data for the structure, followed by careful scrutiny of the agreement with experimental solid-state NMR data. The successful application of this approach is demonstrated by structure determination of the 1:1 cocrystal of indomethacin and nicotinamide. The 1 H and 13 C chemical shifts calculated for the crystal structure determined from the powder XRD data are in excellent agreement with those measured experimentally, notably including the two-dimensional correlation of 1 H and 13 C chemical shifts for directly bonded 13 C- 1 H moieties. The key feature of this combined approach is that the quality of the structure determined is assessed both against experimental powder XRD data and against experimental solid-state NMR data, thus providing a very robust validation of the veracity of the structure.

Measuring Long-Range 13C– 13C Correlations on a Surface under Natural Abundance Using Dynamic Nuclear Polarization-Enhanced Solid-State Nuclear Magnetic Resonance [Measuring Long Range 13C– 13C Correlations on Surface under Natural Abundance Using DNP-enhanced Solid-state NMR

DOE PAGES

Kobayashi, Takeshi; Slowing, Igor I.; Pruski, Marek

2017-10-13

Here, we report that spatial (<1 nm) proximity between different molecules in solid bulk materials and, for the first time, different moieties on the surface of a catalyst, can be established without isotope enrichment by means of homonuclear CHHC solid-state nuclear magnetic resonance experiment. This 13C– 13C correlation measurement, which hitherto was not possible for natural-abundance solids, was enabled by the use of dynamic nuclear polarization. Importantly, it allows the study of long-range correlations in a variety of materials with high resolution.

Measuring Long-Range 13C– 13C Correlations on a Surface under Natural Abundance Using Dynamic Nuclear Polarization-Enhanced Solid-State Nuclear Magnetic Resonance [Measuring Long Range 13C– 13C Correlations on Surface under Natural Abundance Using DNP-enhanced Solid-state NMR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kobayashi, Takeshi; Slowing, Igor I.; Pruski, Marek

Here, we report that spatial (<1 nm) proximity between different molecules in solid bulk materials and, for the first time, different moieties on the surface of a catalyst, can be established without isotope enrichment by means of homonuclear CHHC solid-state nuclear magnetic resonance experiment. This 13C– 13C correlation measurement, which hitherto was not possible for natural-abundance solids, was enabled by the use of dynamic nuclear polarization. Importantly, it allows the study of long-range correlations in a variety of materials with high resolution.

Identical Collision Terms/Solutions of Kinetic Eqn. and Explanation of Damping of Waves in Plasmas and Solids Known by Different Names

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, S. K.

2010-11-23

In this paper we show that identical collision terms are known by different names in gaseous plasmas and solids. Method used by plasma physicists and the one used by solid state physicists to solve Kinetic equation are also exactly same but they are also known by different names. In fact the physical explanation of damping of plasma Waves given by plasma physicists is quite similar to that given by solid state physicists to explain the absorption of acoustic waves in solids.

500(deg)C electronics for harsh environments

NASA Technical Reports Server (NTRS)

Sadwick, Laurence P.; Hwu, R. Jennifer; Chern, J. H. Howard; Lin, Ching-Hsu; Castillo, Linda Del; Johnson, Travis

2005-01-01

Solid state vacuum devices (SSVDs) are a relatively new class of electronic devices. Innosys is a leading producer of high frequency SSVDs for a number of applications, including RF communications. SSVDs combine features inherent to both solid state and vacuum transistors. Electron transport can be by solid state or vacuum or both. The focus of this talk is on thermionic SSVDs, in which the primary vacuum transport is by thermionically liberated electron emission.

CP/MAS /sup 13/C NMR spectroscopic study of chlorophyll a in the solid state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, C.E.; Spencer, R.B.; Burger, V.T.

1983-09-01

Solid-state cross-polarization, magic-angle sample spinning carbon-13 nuclear magnetic resonance spectra have been recorded on chlorophyll a- water aggregates, methyl pyrochlorophyllide a and methyl pyropheophorbide a (derivatives that lack a phytyl chain). Spectra have also been collected under a decoupling regime in which resonances of certain hydrogen-bearing carbon atoms are suppressed. These observations are used to assign the solid state spectra.

Cross-polarization/magic-angle sample-spinning /sup 13/C NMR spectroscopic study of chlorophyll a in the solid state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, C.E.; Spencer, R.B.; Burger, V.T.

1984-01-01

Solid-state cross-polarization/magic-angle sample-spinning /sup 13/C NMR spectra have been recorded on chlorophyll a-water aggregates, methyl pyrochlorophyllide a, and methyl pyropheophorbide a. Spectra have also been collected under a decoupling regime in which resonances of certain hydrogen-bearing carbon atoms are suppressed. These observations are used to assign the solid-state spectra. 18 references, 2 figures, 1 table.

Solid state switch

DOEpatents

Merritt, Bernard T.; Dreifuerst, Gary R.

1994-01-01

A solid state switch, with reverse conducting thyristors, is designed to operate at 20 kV hold-off voltage, 1500 A peak, 1.0 .mu.s pulsewidth, and 4500 pps, to replace thyratrons. The solid state switch is more reliable, more economical, and more easily repaired. The switch includes a stack of circuit card assemblies, a magnetic assist and a trigger chassis. Each circuit card assembly contains a reverse conducting thyristor, a resistor capacitor network, and triggering circuitry.

Solid-state resistor for pulsed power machines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoltzfus, Brian; Savage, Mark E.; Hutsel, Brian Thomas

2016-12-06

A flexible solid-state resistor comprises a string of ceramic resistors that can be used to charge the capacitors of a linear transformer driver (LTD) used in a pulsed power machine. The solid-state resistor is able to absorb the energy of a switch prefire, thereby limiting LTD cavity damage, yet has a sufficiently low RC charge time to allow the capacitor to be recharged without disrupting the operation of the pulsed power machine.

Solid-state X-band Combiner Study

NASA Technical Reports Server (NTRS)

Pitzalis, O., Jr.; Russell, K. J.

1979-01-01

The feasibility of developing solid-state amplifiers at 4 and 10 GHz for application in spacecraft altimeters was studied. Bipolar-transistor, field-effect-transistor, and Impatt-diode amplifier designs based on 1980 solid-state technology are investigated. Several output power levels of the pulsed, low-duty-factor amplifiers are considered at each frequency. Proposed transistor and diode amplifier designs are illustrated in block diagrams. Projections of size, weight, and primary power requirements are given for each design.

Solid-State Electrolyte Anchored with a Carboxylated Azo Compound for All-Solid-State Lithium Batteries.

PubMed

Luo, Chao; Ji, Xiao; Chen, Ji; Gaskell, Karen J; He, Xinzi; Liang, Yujia; Jiang, Jianjun; Wang, Chunsheng

2018-05-23

Organic electrode materials are promising for green and sustainable lithium-ion batteries. However, the high solubility of organic materials in the liquid electrolyte results in the shuttle reaction and fast capacity decay. Herein, azo compounds are firstly applied in all-solid-state lithium batteries (ASSLB) to suppress the dissolution challenge. Due to the high compatibility of azobenzene (AB) based compounds to Li 3 PS 4 (LPS) solid electrolyte, the LPS solid electrolyte is used to prevent the dissolution and shuttle reaction of AB. To maintain the low interface resistance during the large volume change upon cycling, a carboxylate group is added into AB to provide 4-(phenylazo) benzoic acid lithium salt (PBALS), which could bond with LPS solid electrolyte via the ionic bonding between oxygen in PBALS and lithium ion in LPS. The ionic bonding between the active material and solid electrolyte stabilizes the contact interface and enables the stable cycle life of PBALS in ASSLB. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Femtosecond solid-state laser based on a few-layered black phosphorus saturable absorber.

PubMed

Su, Xiancui; Wang, Yiran; Zhang, Baitao; Zhao, Ruwei; Yang, Kejian; He, Jingliang; Hu, Qiangqiang; Jia, Zhitai; Tao, Xutang

2016-05-01

In this Letter, a high-quality, few-layered black phosphorus (BP) saturable absorber (SA) was fabricated successfully, and a femtosecond solid-state laser modulated by BP-SA was experimentally demonstrated for the first time, to the best of our knowledge. Pulses as short as 272 fs were achieved with an average output power of 0.82 W, corresponding to the pulse energy of 6.48 nJ and peak power of 23.8 MW. So far, these represent the shortest pulse duration and highest output power ever obtained with a BP-based mode-locked solid-state laser. The results indicate the promising potential of few-layered BP-SA for applications in solid-state femtosecond mode-locked lasers.

Analysis of S-band solid-state transmitters for the solar power satellite

NASA Technical Reports Server (NTRS)

Belohoubek, E. F.; Ettenberg, M.; Huang, H. C.; Nowogrodzki, M.; Sechi, F. N.

1979-01-01

The possibility of replacing the Reference System antenna in which thermionic devices are used for the dc-to-microwave conversion, with solid-state elements was explored. System, device, and antenna module tradeoff investigations strongly point toward the desirability of changing the transmitter concept to a distributed array of relatively low power elements, deriving their dc power directly from the solar cell array and whose microwave power outputs are combined in space. The approach eliminates the thermal, weight, and dc-voltage distribution problems of a system in which high power tubes are simply replaced with clusters of solid state amplifiers. The proposed approach retains the important advantages of a solid state system: greatly enhanced reliability and graceful degradation of the system.

Preliminary Analysis of a Fully Solid State Magnetocaloric Refrigeration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abdelaziz, Omar

Magnetocaloric refrigeration is an alternative refrigeration technology with significant potential energy savings compared to conventional vapor compression refrigeration technology. Most of the reported active magnetic regenerator (AMR) systems that operate based on the magnetocaloric effect use heat transfer fluid to exchange heat, which results in complicated mechanical subsystems and components such as rotating valves and hydraulic pumps. In this paper, we propose an alternative mechanism for heat transfer between the AMR and the heat source/sink. High-conductivity moving rods/sheets (e.g. copper, brass, iron, graphite, aluminum or composite structures from these) are utilized instead of heat transfer fluid significantly enhancing the heatmore » transfer rate hence cooling/heating capacity. A one-dimensional model is developed to study the solid state AMR. In this model, the heat exchange between the solid-solid interfaces is modeled via a contact conductance, which depends on the interface apparent pressure, material hardness, thermal conductivity, surface roughness, surface slope between the interfaces, and material filled in the gap between the interfaces. Due to the tremendous impact of the heat exchange on the AMR cycle performance, a sensitivity analysis is conducted employing a response surface method, in which the apparent pressure, effective surface roughness and grease thermal conductivity are the uncertainty factors. COP and refrigeration capacity are presented as the response in the sensitivity analysis to reveal the important factors influencing the fully solid state AMR and optimize the solid state AMR efficiency. The performances of fully solid state AMR and traditional AMR are also compared and discussed in present work. The results of this study will provide general guidelines for designing high performance solid state AMR systems.« less

Mathematical modeling of ethanol production in solid-state fermentation based on solid medium' dry weight variation.

PubMed

Mazaheri, Davood; Shojaosadati, Seyed Abbas; Zamir, Seyed Morteza; Mousavi, Seyyed Mohammad

2018-04-21

In this work, mathematical modeling of ethanol production in solid-state fermentation (SSF) has been done based on the variation in the dry weight of solid medium. This method was previously used for mathematical modeling of enzyme production; however, the model should be modified to predict the production of a volatile compound like ethanol. The experimental results of bioethanol production from the mixture of carob pods and wheat bran by Zymomonas mobilis in SSF were used for the model validation. Exponential and logistic kinetic models were used for modeling the growth of microorganism. In both cases, the model predictions matched well with the experimental results during the exponential growth phase, indicating the good ability of solid medium weight variation method for modeling a volatile product formation in solid-state fermentation. In addition, using logistic model, better predictions were obtained.

Review on solid electrolytes for all-solid-state lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zheng, Feng; Kotobuki, Masashi; Song, Shufeng; Lai, Man On; Lu, Li

2018-06-01

All-solid-state (ASS) lithium-ion battery has attracted great attention due to its high safety and increased energy density. One of key components in the ASS battery (ASSB) is solid electrolyte that determines performance of the ASSB. Many types of solid electrolytes have been investigated in great detail in the past years, including NASICON-type, garnet-type, perovskite-type, LISICON-type, LiPON-type, Li3N-type, sulfide-type, argyrodite-type, anti-perovskite-type and many more. This paper aims to provide comprehensive reviews on some typical types of key solid electrolytes and some ASSBs, and on gaps that should be resolved.

The Tompkins County Solid Waste Annual Fee: Background and overview

DOE Office of Scientific and Technical Information (OSTI.GOV)

Penniman, P.W.

1995-05-01

This report outlines the development by Tompkins County of a new revenue source for solid waste programs -- The Solid Waste Annual Fee. Over the past two decades in New York State, regulatory demands and the decline in available landfill space have combined to cause a rapid escalation in the cost of solid waste disposal. While the New York State Department of Environmental Conservation (NYSDEC) has implemented tighter regulations for the siting of solid waste landfills, they have also mandated the permitting or closure of all existing landfills in the state. The result is that all communities have been requiredmore » to invest millions of dollars in landfill siting, closure and solid waste processing facilities. In addition, programs for reducing and recycling solid wastes have been mandated to reduce the outflow to landfills. Until recent years, solid waste services in most New York counties have been funded almost entirely through a collection of property taxes. During the past six years, fiscal stress has stimulated a movement toward funding solid waste programs by other means. Alternatives to the property tax include: (1) special assessment taxes or fees; (2) user charges (including tipping fees); and (3) intergovernment grants.« less

Room-Temperature Performance of Poly(Ethylene Ether Carbonate)-Based Solid Polymer Electrolytes for All-Solid-State Lithium Batteries.

PubMed

Jung, Yun-Chae; Park, Myung-Soo; Kim, Duck-Hyun; Ue, Makoto; Eftekhari, Ali; Kim, Dong-Won

2017-12-13

Amorphous poly(ethylene ether carbonate) (PEEC), which is a copolymer of ethylene oxide and ethylene carbonate, was synthesized by ring-opening polymerization of ethylene carbonate. This route overcame the common issue of low conductivity of poly(ethylene oxide)(PEO)-based solid polymer electrolytes at low temperatures, and thus the solid polymer electrolyte could be successfully employed at the room temperature. Introducing the ethylene carbonate units into PEEC improved the ionic conductivity, electrochemical stability and lithium transference number compared with PEO. A cross-linked solid polymer electrolyte was synthesized by photo cross-linking reaction using PEEC and tetraethyleneglycol diacrylate as a cross-linking agent, in the form of a flexible thin film. The solid-state Li/LiNi 0.6 Co 0.2 Mn 0.2 O 2 cell assembled with solid polymer electrolyte based on cross-linked PEEC delivered a high initial discharge capacity of 141.4 mAh g -1 and exhibited good capacity retention at room temperature. These results demonstrate the feasibility of using this solid polymer electrolyte in all-solid-state lithium batteries that can operate at ambient temperatures.

A self-forming composite electrolyte for solid-state sodium battery with ultra-long cycle life

DOE PAGES

Zhang, Zhizhen; Yang, Xiao -Qing; Zhang, Qinghua; ...

2016-10-31

Replacing organic liquid electrolyte with inorganic solid electrolytes (SE) can potentially address the inherent safety problems in conventional rechargeable batteries. Furthermore, all-solid-state batteries have been plagues by the relatively low ionic conductivity of solid electrolytes and large charge-transfer resistance resulted from solid-solid interfaces between electrode materials and solid electrolytes. Here we report a new design strategy for improving the ionic conductivity of solid electrolyte by self-forming a composite material. An optimized Na + ion conducting composite electrolyte derived from the NASICON structure was successfully synthesized, yielding ultra-high ionic conductivity of 3.4 mS cm –1 at 25°C and 14 ms cmmore » –1 at 80°C.« less

Solid State Division progress report for period ending March 31, 1992

DOE Office of Scientific and Technical Information (OSTI.GOV)

Green, P.H.; Hinton, L.W.

1992-09-01

During this period, the division conducted a broad, interdisciplinary materials research program with emphasis on theoretical solid state physics, superconductivity, neutron scattering, synthesis and characterization of materials, ion beam and laser processing, and the structure of solids and surfaces. The High Flux Isotope Reactor was returned to full operation.

76 FR 53897 - EPA Seeking Input Materials Measurement; Municipal Solid Waste (MSW), Recycling, and Source...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-08-30

... stakeholder input regarding the efficacy and scope of the MSW Characterization Report called ``Municipal Solid Waste in the United States'' as part of a broader discussion about sustainable materials management... efficacy and scope of the MSW Characterization Report called ``Municipal Solid Waste in the United States...

Effect of Solid-State Power-Converter Harmonics on Electric-Power-Supply Systems

DOT National Transportation Integrated Search

1973-03-01

The United States utility industry has not set suitable standards, other than TIF (Telephone Interference Factor), for controlling the design of solid-state wayside and on-board power-conversion equipment, to limit the harmonic currents and voltages ...

High capacity and stable all-solid-state Li ion battery using SnO2-embedded nanoporous carbon.

PubMed

Notohara, Hiroo; Urita, Koki; Yamamura, Hideyuki; Moriguchi, Isamu

2018-06-08

Extensive research efforts are devoted to development of high performance all-solid-state lithium ion batteries owing to their potential in not only improving safety but also achieving high stability and high capacity. However, conventional approaches based on a fabrication of highly dense electrode and solid electrolyte layers and their close contact interface is not always applicable to high capacity alloy- and/or conversion-based active materials such as SnO 2 accompanied with large volume change in charging-discharging. The present work demonstrates that SnO 2 -embedded nanoporous carbons without solid electrolyte inside the nanopores are a promising candidate for high capacity and stable anode material of all-solid-state battery, in which the volume change reactions are restricted in the nanopores to keep the constant electrode volume. A prototype all-solid-state full cell consisting of the SnO 2 -based anode and a LiNi 1/3 Co 1 / 3 Mn 1/3 O 2 -based cathode shows a good performance of 2040 Wh/kg at 268.6 W/kg based on the anode material weight.

Polycarbonate-based polyurethane as a polymer electrolyte matrix for all-solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Bao, Junjie; Shi, Gaojian; Tao, Can; Wang, Chao; Zhu, Chen; Cheng, Liang; Qian, Gang; Chen, Chunhua

2018-06-01

Four kinds of polycarbonate-based polyurethane with 8-14 wt% hard segments content are synthesized via reactions of polycarbonatediol, hexamethylene diisocyanate and diethylene glycol. The mechanical strength of the polyurethanes increase with the increase of hard segments content. Solid polymer electrolytes composed of the polycarbonate-based polyurethanes and LiTFSI exhibits fascinating characteristics for all-solid-state lithium batteries with a high ionic conductivity of 1.12 × 10-4 S cm-1 at 80 °C, an electrochemical stability window up to 4.5 V (vs. Li+/Li), excellent mechanical strength and superior interfacial stability against lithium metal. The all-solid-state batteries using LiFePO4 cathode can deliver high discharge capacities (161, 158, 134 and 93 mAh g-1 at varied rates of 0.2, 0.5, 1 and 2 C) at 80 °C and excellent cycling performance (with 91% capacity retention after 600 cycles at 1 C). All the results indicate that such a polyurethane-based solid polymer electrolyte can be a promising candidate for all-solid-state lithium batteries.

The recycling of chromitites in ophiolites from southwestern North America

NASA Astrophysics Data System (ADS)

González-Jiménez, José M.; Camprubí, Antoni; Colás, Vanessa; Griffin, William L.; Proenza, Joaquín A.; O'Reilly, Suzanne Y.; Centeno-García, Elena; García-Casco, Antonio; Belousova, Elena; Talavera, Cristina; Farré-de-Pablo, Júlia; Satsukawa, Takako

2017-12-01

Podiform chromitites occur in mantle peridotites of the Late Triassic Puerto Nuevo Ophiolite, Baja California Sur State, Mexico. These are high-Cr chromitites [Cr# (Cr/Cr + Al atomic ratio = 0.61-0.69)] that contain a range of minor- and trace-elements and show whole-rock enrichment in IPGE (Os, Ir, Ru). That are similar to those of high-Cr ophiolitic chromitites crystallised from melts similar to high-Mg island-arc tholeiites (IAT) and boninites in supra-subduction-zone mantle wedges. Crystallisation of these chromitites from S-undersaturated melts is consistent with the presence of abundant inclusions of platinum-group minerals (PGM) such as laurite (RuS2)-erlichmanite (OsS2), osmium and irarsite (IrAsS) in chromite, that yield TMA ≈ TRD model ages peaking at 325 Ma. Thirty-three xenocrystic zircons recovered from mineral concentrates of these chromitites yield ages (2263 ± 44 Ma to 278 ± 4 Ma) and Hf-O compositions [ɛHf(t) = - 18.7 to + 9.1 and 18O values < 12.4‰] that broadly match those of zircons reported in nearby exposed crustal blocks of southwestern North America. We interpret these chromitite zircons as remnants of partly digested continental crust or continent-derived sediments on oceanic crust delivered into the mantle via subduction. They were captured by the parental melts of the chromitites when the latter formed in a supra-subduction zone mantle wedge polluted with crustal material. In addition, the Puerto Nuevo chromites have clinopyroxene lamellae with preferred crystallographic orientation, which we interpret as evidence that chromitites have experienced high-temperature and ultra high-pressure conditions (< 12 GPa and 1600 °C). We propose a tectonic scenario that involves the formation of chromitite in the supra-subduction zone mantle wedge underlying the Vizcaino intra-oceanic arc ca. 250 Ma ago, deep-mantle recycling, and subsequent diapiric exhumation in the intra-oceanic basin (the San Hipólito marginal sea) generated during an extensional stage of the Vizcaino intra-oceanic arc ca. 221 Ma ago. The TRD ages at 325 Ma record a partial melting event in the mantle prior to the construction of the Vizcaino intra-oceanic arc, which is probably related to the Permian continental subduction, dated at 311 Ma.

Fabrication of ultrathin solid electrolyte membranes of β-Li 3PS 4 nanoflakes by evaporation-induced self-assembly for all-solid-state batteries

DOE PAGES

Wang, Hui; Hood, Zachary D.; Xia, Younan; ...

2016-04-25

All-solid-state lithium batteries are attractive candidates for next-generation energy storage devices because of their anticipated high energy density and intrinsic safety. Owing to their excellent ionic conductivity and stability with metallic lithium anodes, nanostructured lithium thiophosphate solid electrolytes such as β-Li 3PS 4 have found use in the fabrication of all-solid lithium batteries for large-scale energy storage systems. However, current methods for preparing air-sensitive solid electrolyte membranes of lithium thiophosphates can only generate thick membranes that compromise the battery's gravimetric/volumetric energy density and thus its rate performance. To overcome this limitation, the solid electrolyte's thickness needs to be effectively decreasedmore » to achieve ideal energy density and enhanced rate performance. In this paper, we show that the evaporation-induced self-assembly (EISA) technique produces ultrathin membranes of a lithium thiophosphate solid electrolyte with controllable thicknesses between 8 and 50 μm while maintaining the high ionic conductivity of β-Li 3PS 4 and stability with metallic lithium anodes up to 5 V. Finally, it is clearly demonstrated that this facile EISA approach allows for the preparation of ultrathin lithium thiophosphate solid electrolyte membranes for all-solid-state batteries.« less

Growth behavior of LiMn{sub 2}O{sub 4} particles formed by solid-state reactions in air and water vapor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kozawa, Takahiro, E-mail: t-kozawa@jwri.osaka-u.ac.jp; Yanagisawa, Kazumichi; Murakami, Takeshi

Morphology control of particles formed during conventional solid-state reactions without any additives is a challenging task. Here, we propose a new strategy to control the morphology of LiMn{sub 2}O{sub 4} particles based on water vapor-induced growth of particles during solid-state reactions. We have investigated the synthesis and microstructural evolution of LiMn{sub 2}O{sub 4} particles in air and water vapor atmospheres as model reactions; LiMn{sub 2}O{sub 4} is used as a low-cost cathode material for lithium-ion batteries. By using spherical MnCO{sub 3} precursor impregnated with LiOH, LiMn{sub 2}O{sub 4} spheres with a hollow structure were obtained in air, while angulated particlesmore » with micrometer sizes were formed in water vapor. The pore structure of the particles synthesized in water vapor was found to be affected at temperatures below 700 °C. We also show that the solid-state reaction in water vapor is a simple and valuable method for the large-scale production of particles, where the shape, size, and microstructure can be controlled. - Graphical abstract: This study has demonstrated a new strategy towards achieving morphology control without the use of additives during conventional solid-state reactions by exploiting water vapor-induced particle growth. - Highlights: • A new strategy to control the morphology of LiMn{sub 2}O{sub 4} particles is proposed. • Water vapor-induced particle growth is exploited in solid-state reactions. • The microstructural evolution of LiMn{sub 2}O{sub 4} particles is investigated. • The shape, size and microstructure can be controlled by solid-state reactions.« less

Solid State Division progress report, September 30, 1981

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1982-04-01

Progress made during the 19 months from March 1, 1980, through September 30, 1981, is reported in the following areas: theoretical solid state physics (surfaces, electronic and magnetic properties, particle-solid interactions, and laser annealing); surface and near-surface properties of solids (plasma materials interactions, ion-solid interactions, pulsed laser annealing, and semiconductor physics and photovoltaic conversion); defects in solids (radiation effects, fracture, and defects and impurities in insulating crystals); transport properties of solids (fast-ion conductors, superconductivity, and physical properties of insulating materials); neutron scattering (small-angle scattering, lattice dynamics, and magnetic properties); crystal growth and characterization (nuclear waste forms, ferroelectric mateirals, high-temperature materials,more » and special materials); and isotope research materials. Publications and papers are listed. (WHK)« less

Solid state NMR: The essential technology for helical membrane protein structural characterization

PubMed Central

Cross, Timothy A.; Ekanayake, Vindana; Paulino, Joana; Wright, Anna

2014-01-01

NMR spectroscopy of helical membrane proteins has been very challenging on multiple fronts. The expression and purification of these proteins while maintaining functionality has consumed countless graduate student hours. Sample preparations have depended on whether solution or solid-state NMR spectroscopy was to be performed – neither have been easy. In recent years it has become increasingly apparent that membrane mimic environments influence the structural result. Indeed, in these recent years we have rediscovered that Nobel laureate, Christian Anfinsen, did not say that protein structure was exclusively dictated by the amino acid sequence, but rather by the sequence in a given environment (Anfinsen, 1973) [106]. The environment matters, molecular interactions with the membrane environment are significant and many examples of distorted, non-native membrane protein structures have recently been documented in the literature. However, solid-state NMR structures of helical membrane proteins in proteoliposomes and bilayers are proving to be native structures that permit a high resolution characterization of their functional states. Indeed, solid-state NMR is uniquely able to characterize helical membrane protein structures in lipid environments without detergents. Recent progress in expression, purification, reconstitution, sample preparation and in the solid-state NMR spectroscopy of both oriented samples and magic angle spinning samples has demonstrated that helical membrane protein structures can be achieved in a timely fashion. Indeed, this is a spectacular opportunity for the NMR community to have a major impact on biomedical research through the solid-state NMR spectroscopy of these proteins. PMID:24412099

Solid state NMR: The essential technology for helical membrane protein structural characterization

NASA Astrophysics Data System (ADS)

Cross, Timothy A.; Ekanayake, Vindana; Paulino, Joana; Wright, Anna

2014-02-01

NMR spectroscopy of helical membrane proteins has been very challenging on multiple fronts. The expression and purification of these proteins while maintaining functionality has consumed countless graduate student hours. Sample preparations have depended on whether solution or solid-state NMR spectroscopy was to be performed - neither have been easy. In recent years it has become increasingly apparent that membrane mimic environments influence the structural result. Indeed, in these recent years we have rediscovered that Nobel laureate, Christian Anfinsen, did not say that protein structure was exclusively dictated by the amino acid sequence, but rather by the sequence in a given environment (Anfinsen, 1973) [106]. The environment matters, molecular interactions with the membrane environment are significant and many examples of distorted, non-native membrane protein structures have recently been documented in the literature. However, solid-state NMR structures of helical membrane proteins in proteoliposomes and bilayers are proving to be native structures that permit a high resolution characterization of their functional states. Indeed, solid-state NMR is uniquely able to characterize helical membrane protein structures in lipid environments without detergents. Recent progress in expression, purification, reconstitution, sample preparation and in the solid-state NMR spectroscopy of both oriented samples and magic angle spinning samples has demonstrated that helical membrane protein structures can be achieved in a timely fashion. Indeed, this is a spectacular opportunity for the NMR community to have a major impact on biomedical research through the solid-state NMR spectroscopy of these proteins.

Nuclear conversion theory: molecular hydrogen in non-magnetic insulators

NASA Astrophysics Data System (ADS)

Ilisca, Ernest; Ghiglieno, Filippo

2016-09-01

The hydrogen conversion patterns on non-magnetic solids sensitively depend upon the degree of singlet/triplet mixing in the intermediates of the catalytic reaction. Three main `symmetry-breaking' interactions are brought together. In a typical channel, the electron spin-orbit (SO) couplings introduce some magnetic excitations in the non-magnetic solid ground state. The electron spin is exchanged with a molecular one by the electric molecule-solid electron repulsion, mixing the bonding and antibonding states and affecting the molecule rotation. Finally, the magnetic hyperfine contact transfers the electron spin angular momentum to the nuclei. Two families of channels are considered and a simple criterion based on the SO coupling strength is proposed to select the most efficient one. The denoted `electronic' conversion path involves an emission of excitons that propagate and disintegrate in the bulk. In the other denoted `nuclear', the excited electron states are transients of a loop, and the electron system returns to its fundamental ground state. The described model enlarges previous studies by extending the electron basis to charge-transfer states and `continui' of band states, and focuses on the broadening of the antibonding molecular excited state by the solid conduction band that provides efficient tunnelling paths for the hydrogen conversion. After working out the general conversion algebra, the conversion rates of hydrogen on insulating and semiconductor solids are related to a few molecule-solid parameters (gap width, ionization and affinity potentials) and compared with experimental measures.

Nuclear conversion theory: molecular hydrogen in non-magnetic insulators

PubMed Central

Ghiglieno, Filippo

2016-01-01

The hydrogen conversion patterns on non-magnetic solids sensitively depend upon the degree of singlet/triplet mixing in the intermediates of the catalytic reaction. Three main ‘symmetry-breaking’ interactions are brought together. In a typical channel, the electron spin–orbit (SO) couplings introduce some magnetic excitations in the non-magnetic solid ground state. The electron spin is exchanged with a molecular one by the electric molecule–solid electron repulsion, mixing the bonding and antibonding states and affecting the molecule rotation. Finally, the magnetic hyperfine contact transfers the electron spin angular momentum to the nuclei. Two families of channels are considered and a simple criterion based on the SO coupling strength is proposed to select the most efficient one. The denoted ‘electronic’ conversion path involves an emission of excitons that propagate and disintegrate in the bulk. In the other denoted ‘nuclear’, the excited electron states are transients of a loop, and the electron system returns to its fundamental ground state. The described model enlarges previous studies by extending the electron basis to charge-transfer states and ‘continui’ of band states, and focuses on the broadening of the antibonding molecular excited state by the solid conduction band that provides efficient tunnelling paths for the hydrogen conversion. After working out the general conversion algebra, the conversion rates of hydrogen on insulating and semiconductor solids are related to a few molecule–solid parameters (gap width, ionization and affinity potentials) and compared with experimental measures. PMID:27703681

All-Solid-State Sodium-Selective Electrode with a Solid Contact of Chitosan/Prussian Blue Nanocomposite

PubMed Central

Ghosh, Tanushree; Rieger, Jana

2017-01-01

Conventional ion-selective electrodes with a liquid junction have the disadvantage of potential drift. All-solid-state ion-selective electrodes with solid contact in between the metal electrode and the ion-selective membrane offer high capacitance or conductance to enhance potential stability. Solution-casted chitosan/Prussian blue nanocomposite (ChPBN) was employed as the solid contact layer for an all-solid-state sodium ion-selective electrode in a potentiometric sodium ion sensor. Morphological and chemical analyses confirmed that the ChPBN is a macroporous network of chitosan that contains abundant Prussian blue nanoparticles. Situated between a screen-printed carbon electrode and a sodium-ionophore-filled polyvinylchloride ion-selective membrane, the ChPBN layer exhibited high redox capacitance and fast charge transfer capability, which significantly enhanced the performance of the sodium ion-selective electrode. A good Nernstian response with a slope of 52.4 mV/decade in the linear range from 10−4–1 M of NaCl was observed. The stability of the electrical potential of the new solid contact was tested by chronopotentiometry, and the capacitance of the electrode was 154 ± 4 µF. The response stability in terms of potential drift was excellent (1.3 µV/h) for 20 h of continuous measurement. The ChPBN proved to be an efficient solid contact to enhance the potential stability of the all-solid-state ion-selective electrode. PMID:29099804

Solid-State Nanopore.

PubMed

Yuan, Zhishan; Wang, Chengyong; Yi, Xin; Ni, Zhonghua; Chen, Yunfei; Li, Tie

2018-02-20

Solid-state nanopore has captured the attention of many researchers due to its characteristic of nanoscale. Now, different fabrication methods have been reported, which can be summarized into two broad categories: "top-down" etching technology and "bottom-up" shrinkage technology. Ion track etching method, mask etching method chemical solution etching method, and high-energy particle etching and shrinkage method are exhibited in this report. Besides, we also discussed applications of solid-state nanopore fabrication technology in DNA sequencing, protein detection, and energy conversion.

Grating enhanced solid-state laser amplifiers

DOEpatents

Erlandson, Alvin C.; Britten, Jerald A.

2010-11-09

A novel method and apparatus for suppressing ASE and parasitic oscillation modes in a high average power laser is introduced. Such an invention, as disclosed herein, uses diffraction gratings to increase gain, stored energy density, and pumping efficiency of solid-state laser gain media, such as, but not limited to rods, disks and slabs. By coupling predetermined gratings to solid-state gain media, such as crystal or ceramic laser gain media, ASE and parasitic oscillation modes can be effectively suppressed.

Solid-State Nanopore

NASA Astrophysics Data System (ADS)

Yuan, Zhishan; Wang, Chengyong; Yi, Xin; Ni, Zhonghua; Chen, Yunfei; Li, Tie

2018-02-01

Solid-state nanopore has captured the attention of many researchers due to its characteristic of nanoscale. Now, different fabrication methods have been reported, which can be summarized into two broad categories: "top-down" etching technology and "bottom-up" shrinkage technology. Ion track etching method, mask etching method chemical solution etching method, and high-energy particle etching and shrinkage method are exhibited in this report. Besides, we also discussed applications of solid-state nanopore fabrication technology in DNA sequencing, protein detection, and energy conversion.

Automated Visibility & Cloud Cover Measurements with a Solid State Imaging System

DTIC Science & Technology

1989-03-01

GL-TR-89-0061 SIO Ref. 89-7 MPL-U-26/89 AUTOMATED VISIBILITY & CLOUD COVER MEASUREMENTS WITH A SOLID-STATE IMAGING SYSTEM C) to N4 R. W. Johnson W. S...include Security Classification) Automated Visibility & Cloud Measurements With A Solid State Imaging System 12. PERSONAL AUTHOR(S) Richard W. Johnson...based imaging systems , their ics and control algorithms, thus they ar.L discussed sepa- initial deployment and the preliminary application of rately

Face-to-Face Packing of 2,3,9,10-Tetrasubstituted Pentacene Derivatives Revealed through a Solid State [4 + 4] Thermal Cycloaddition and Molecular Dynamic Simulation.

PubMed

Pal, Bikash; Lin, Bo-Chao; Dela Cerna, Mark Vincent Carreon; Hsu, Chao-Ping; Lin, Chih-Hsiu

2016-08-05

2,3,9,10-Substituted pentacene tetraesters and pentacene diester-dinitriles were synthesized. These pentacene derivatives underwent an unusual solid state [4 + 4] thermal dimerization with good efficiency and complete stereoselectivity. This observation indicates this series of pentacene derivatives adopt π-π stacking geometry with large mutual overlap in solid state. This notion was confirmed by molecualr dynamic simulation.

Solid-state lithium battery

DOEpatents

Ihlefeld, Jon; Clem, Paul G; Edney, Cynthia; Ingersoll, David; Nagasubramanian, Ganesan; Fenton, Kyle Ross

2014-11-04

The present invention is directed to a higher power, thin film lithium-ion electrolyte on a metallic substrate, enabling mass-produced solid-state lithium batteries. High-temperature thermodynamic equilibrium processing enables co-firing of oxides and base metals, providing a means to integrate the crystalline, lithium-stable, fast lithium-ion conductor lanthanum lithium tantalate (La.sub.1/3-xLi.sub.3xTaO.sub.3) directly with a thin metal foil current collector appropriate for a lithium-free solid-state battery.

Solid state switch

DOEpatents

Merritt, B.T.; Dreifuerst, G.R.

1994-07-19

A solid state switch, with reverse conducting thyristors, is designed to operate at 20 kV hold-off voltage, 1,500 A peak, 1.0 [mu]s pulsewidth, and 4,500 pps, to replace thyratrons. The solid state switch is more reliable, more economical, and more easily repaired. The switch includes a stack of circuit card assemblies, a magnetic assist and a trigger chassis. Each circuit card assembly contains a reverse conducting thyristor, a resistor capacitor network, and triggering circuitry. 6 figs.

Atomic layer deposition of lithium phosphates as solid-state electrolytes for all-solid-state microbatteries

NASA Astrophysics Data System (ADS)

Wang, Biqiong; Liu, Jian; Sun, Qian; Li, Ruying; Sham, Tsun-Kong; Sun, Xueliang

2014-12-01

Atomic layer deposition (ALD) has been shown as a powerful technique to build three-dimensional (3D) all-solid-state microbattery, because of its unique advantages in fabricating uniform and pinhole-free thin films in 3D structures. The development of solid-state electrolyte by ALD is a crucial step to achieve the fabrication of 3D all-solid-state microbattery by ALD. In this work, lithium phosphate solid-state electrolytes were grown by ALD at four different temperatures (250, 275, 300, and 325 °C) using two precursors (lithium tert-butoxide and trimethylphosphate). A linear dependence of film thickness on ALD cycle number was observed and uniform growth was achieved at all four temperatures. The growth rate was 0.57, 0.66, 0.69, and 0.72 Å/cycle at deposition temperatures of 250, 275, 300, and 325 °C, respectively. Furthermore, x-ray photoelectron spectroscopy confirmed the compositions and chemical structures of lithium phosphates deposited by ALD. Moreover, the lithium phosphate thin films deposited at 300 °C presented the highest ionic conductivity of 1.73 × 10-8 S cm-1 at 323 K with ˜0.51 eV activation energy based on the electrochemical impedance spectroscopy. The ionic conductivity was calculated to be 3.3 × 10-8 S cm-1 at 26 °C (299 K).

Advanced solid-state NMR spectroscopy of natural organic matter.

PubMed

Mao, Jingdong; Cao, Xiaoyan; Olk, Dan C; Chu, Wenying; Schmidt-Rohr, Klaus

2017-05-01

Solid-state NMR is essential for the characterization of natural organic matter (NOM) and is gaining importance in geosciences and environmental sciences. This review is intended to highlight advanced solid-state NMR techniques, especially a systematic approach to NOM characterization, and their applications to the study of NOM. We discuss some basics of how to acquire high-quality and quantitative solid-state 13 C NMR spectra, and address some common technical mistakes that lead to unreliable spectra of NOM. The identification of specific functional groups in NOM, primarily based on 13 C spectral-editing techniques, is described and the theoretical background of some recently-developed spectral-editing techniques is provided. Applications of solid-state NMR to investigating nitrogen (N) in NOM are described, focusing on limitations of the widely used 15 N CP/MAS experiment and the potential of improved advanced NMR techniques for characterizing N forms in NOM. Then techniques used for identifying proximities, heterogeneities and domains are reviewed, and some examples provided. In addition, NMR techniques for studying segmental dynamics in NOM are reviewed. We also briefly discuss applications of solid-state NMR to NOM from various sources, including soil organic matter, aquatic organic matter, organic matter in atmospheric particulate matter, carbonaceous meteoritic organic matter, and fossil fuels. Finally, examples of NMR-based structural models and an outlook are provided. Copyright © 2016 Elsevier B.V. All rights reserved.

31P Solid-state NMR based monitoring of permeation of cell penetrating peptides into skin

PubMed Central

Desai, Pinaki R.; Cormier, Ashley R.; Shah, Punit P.; Patlolla, Ram R.; Paravastu, Anant K.; Singh, Mandip

2013-01-01

The main objective of the current study was to investigate penetration of cell penetrating peptides (CPPs: TAT, R8, R11 and YKA) through skin intercellular lipids using 31P magic angle spinning (MAS) solid-state NMR. In vitro skin permeation studies were performed on rat skin, sections (0–60, 61–120 and 121–180 µm) were collected and analyzed for 31P NMR signal. The concentration dependent shift of 0, 25, 50, 100 and 200 mg/ml of TAT on skin layers, diffusion of TAT, R8, R11 and YKA in the skin and time dependent permeation of R11 was measured on various skin sections using 31P solid-state NMR. Further, CPPs and CPP-tagged fluorescent dye encapsulate liposomes (FLip) in skin layers were tagged using confocal microscopy. The change in 31P NMR chemical shift was found to depend monotonically on the amount of CPP applied on skin, with saturation behavior above 100 mg/ml CPP concentration. R11 and TAT caused more shift in solid-state NMR peaks compared to other peptides. Furthermore, NMR spectra showed R11 penetration up to 180 µm within 30 min. The results of the solid-state NMR study were in agreement with confocal microscopy studies. Thus, 31P solid-state NMR can be used to track CPP penetration into different skin layers. PMID:23702274

Realization of reliable solid-state quantum memory for photonic polarization qubit.

PubMed

Zhou, Zong-Quan; Lin, Wei-Bin; Yang, Ming; Li, Chuan-Feng; Guo, Guang-Can

2012-05-11

Faithfully storing an unknown quantum light state is essential to advanced quantum communication and distributed quantum computation applications. The required quantum memory must have high fidelity to improve the performance of a quantum network. Here we report the reversible transfer of photonic polarization states into collective atomic excitation in a compact solid-state device. The quantum memory is based on an atomic frequency comb (AFC) in rare-earth ion-doped crystals. We obtain up to 0.999 process fidelity for the storage and retrieval process of single-photon-level coherent pulse. This reliable quantum memory is a crucial step toward quantum networks based on solid-state devices.

Even-odd alternation of near-infrared spectra of alkane-α,ω-diols in their solid states

NASA Astrophysics Data System (ADS)

Toyama, Yuta; Murakami, Kohei; Yoshimura, Norio; Takayanagi, Masao

2018-05-01

Even-odd alternation of the melting points of α,ω-disubstituted linear alkanes such as alkane-α,ω-diols, alkane-α,ω-dinitriles and α,ω-diaminoalkanes is well known. Melting points for compounds with an even number of carbons in their alkyl chains are systematically higher than those for compounds with an odd number of carbons. In order to clarify the origin of this alternation, near-infrared absorption spectra of linear alkane-α,ω-diols with 3 to 9 carbon atoms in their alkyl chains were measured in the liquid and solid states. The band due to the first overtone of the Osbnd H stretching mode was investigated. The temperature-dependent spectra of all alkane-α,ω-diols in their liquid states were found to be similar; no even-odd alternation was observed. In the solid state, however, spectra of alkane-α,ω-diols with even and odd numbers of carbon atoms differed greatly. Spectra of alkane-α,ω-diols with an odd number of carbon atoms in their solid states were similar to those in the liquid states, although the variation of spectra observed upon lowering the temperature of liquid seemed to continue when the liquids were frozen. In contrast, spectra of alkane-α,ω-diols with an even number of carbon atoms in their liquid and solid states were found to be quite different. New bands appeared upon freezing. The observed even-odd alternation of the spectra observed for alkane-α,ω-diols in their solid states is presumably caused by their even-odd alternation of crystal structures.

Single Protein Structural Analysis with a Solid-state Nanopore Sensor

NASA Astrophysics Data System (ADS)

Li, Jiali; Golovchenko, Jene; McNabb, David

2005-03-01

We report on the use of solid-state nanopore sensors to detect single polypeptides. These solid-state nanopores are fabricated in thin membranes of silicon nitride by ion beam sculpting...[1]. When an electrically biased nanopore is exposed to denatured proteins in ionic solution, discrete transient electronic signals: current blockages are observed. We demonstrate examples of such transient electronic signals for Bovine Serum Albumin (BSA) and human placental laminin M proteins in Guanidine hydrochloride solution, which suggest that these polypeptides are individually translocating through the nanopore during the detecting process. The amplitude of the current blockages is proportional to the bias voltage. No transient current blockages are observed when proteins are not present in the solution. To probe protein-folding state, pH and temperature dependence experiments are performed. The results demonstrate a solid-state nanopore sensor can be used to detect and analyze single polypeptide chains. Similarities and differences with signals obtained from double stranded DNA in a solid-state nanopore and single stranded DNA in a biological nanopore are discussed. [.1] Li, J., D. Stein, C. McMullan, D. Branton, M.J. Aziz, and J.A. Golovchenko, Ion-beam sculpting at nanometre length scales. Nature, 2001. 412(12 July): p. 166-169.

In Situ Atomic-Scale Observation of Electrochemical Delithiation Induced Structure Evolution of LiCoO2 Cathode in a Working All-Solid-State Battery.

PubMed

Gong, Yue; Zhang, Jienan; Jiang, Liwei; Shi, Jin-An; Zhang, Qinghua; Yang, Zhenzhong; Zou, Dongli; Wang, Jiangyong; Yu, Xiqian; Xiao, Ruijuan; Hu, Yong-Sheng; Gu, Lin; Li, Hong; Chen, Liquan

2017-03-29

We report a method for in situ atomic-scale observation of electrochemical delithiation in a working all-solid-state battery using a state-of-the-art chip based in situ transmission electron microscopy (TEM) holder and focused ion beam milling to prepare an all-solid-state lithium-ion battery sample. A battery consisting of LiCoO 2 cathode, LLZO solid state electrolyte and gold anode was constructed, delithiated and observed in an aberration corrected scanning transmission electron microscope at atomic scale. We found that the pristine single crystal LiCoO 2 became nanosized polycrystal connected by coherent twin boundaries and antiphase domain boundaries after high voltage delithiation. This is different from liquid electrolyte batteries, where a series of phase transitions take place at LiCoO 2 cathode during delithiation. Both grain boundaries become more energy favorable along with extraction of lithium ions through theoretical calculation. We also proposed a lithium migration pathway before and after polycrystallization. This new methodology could stimulate atomic scale in situ scanning/TEM studies of battery materials and provide important mechanistic insight for designing better all-solid-state battery.

Synthetic routes to a nanoscale inorganic cluster [Ga{sub 13}(μ{sub 3}-OH){sub 6}(μ{sub 2}-OH){sub 18}(H{sub 2}O)](NO{sub 3}){sub 15} evaluated by solid-state {sup 71}Ga NMR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hammann, Blake A.; Marsh, David A.; Ma, Zayd L.

Solid-state {sup 71}Ga NMR was used to characterize a series of [Ga{sub 13}(μ{sub 3}-OH){sub 6}(μ{sub 2}-OH){sub 18}(H{sub 2}O)](NO{sub 3}){sub 15} “Ga{sub 13}” molecular clusters synthesized by multiple methods. These molecular clusters are precursors to thin film electronics and may be employed in energy applications. The synthetic routes provide varying levels of impurities in the solid phase, and these impurities often elude traditional characterization techniques such as powder X-ray diffraction and Raman spectroscopy. Solid-state NMR can provide a window into the gallium species even in amorphous phases. This information is vital in order to prevent the impurities from causing defect sitesmore » in the corresponding thin films upon gelation and condensation (polymerization) of the Ga{sub 13} clusters. This work demonstrates the resolving power of solid-state NMR to evaluate structure and synthetic quality in the solid state, and the application of high-field NMR to study quadrupolar species, such as {sup 71}Ga. - Graphical abstract: The various synthetic routes and {sup 71}Ga solid-state NMR spectra of the nanoscale inorganic cluster [Ga{sub 13}(μ{sub 3}-OH){sub 6}(μ{sub 2}-OH){sub 18}(H{sub 2}O)](NO{sub 3}){sub 15}. - Highlights: • Solid-state {sup 71}Ga NMR of hydroxo-aquo metal clusters and the impurities present. • High-field NMR capability allows for quadrupolar species, such as {sup 71}Ga, to be routinely studied. • Efficient and environmentally friendly synthetic routes have been developed to prepare hydroxo-aquo metal clusters.« less

The use of inverse phase gas chromatography to study the change of surface energy of amorphous lactose as a function of relative humidity and the processes of collapse and crystallisation.

PubMed

Newell, H E; Buckton, G; Butler, D A; Thielmann, F; Williams, D R

2001-04-17

The purpose of this study was to assess the effect of relative humidity (RH) on the surface energy of amorphous lactose. Two samples of amorphous lactose were investigated; a spray dried 100% amorphous material and a ball milled sample of crystalline lactose. The milled sample had less than 1% amorphous content by mass, but on investigation at 0% RH, yielded surface energies comparable to those obtained from the 100% amorphous material, indicating that the surface was amorphous. The effect of increasing humidity was to reduce the dispersive surface energy of the two samples from 36.0 +/- 0.14 and 41.6 +/- 1.4 mJ m(-2) at 0% RH for the spray dried and milled samples respectively, to a value comparable to that obtained for the crystalline alpha-lactose monohydrate of 31.3 +/- 0.41 mJ m(-2). The change in surface energy due to water sorption was only reversible up to 20% RH; after exposure to higher RH values subsequent drying did not result in a return to the original surface energy of the amorphous form. This shows that the surface is reorganising as the glass transition temperature (Tg) is reduced, even though the sample has not collapsed or crystallised. It was possible to follow the collapse behaviour in the column with ease, using a number of different methods.

Orthopyroxene oikocrysts in the MG1 chromitite layer of the Bushveld Complex: implications for cumulate formation and recrystallisation

NASA Astrophysics Data System (ADS)

Kaufmann, Felix E. D.; Vukmanovic, Zoja; Holness, Marian B.; Hecht, Lutz

2018-02-01

Two typical mineral textures of the MG 1 chromitite of the Bushveld Complex, South Africa, were observed; one characterised by abundant orthopyroxene oikocrysts, and the other by coarse-grained granular chromitite with only minor amounts of interstitial material. Oikocrysts form elongate clusters of several crystals aligned parallel to the layering, and typically have subhedral, almost chromite-free, core zones containing remnants of olivine. The core zones are surrounded by poikilitic aureoles overgrowing euhedral to subhedral chromite chadacrysts. Chromite grains show no preferred crystal orientation, whereas orthopyroxene grains forming clusters commonly share the same crystallographic orientation. Oikocryst core zones have lower Mg# and higher concentrations of incompatible trace elements compared to their poikilitic aureoles. Core zones are relatively enriched in REE compared to a postulated parental magma (B1) and did not crystallise in equilibrium with the surrounding minerals, whereas the composition of the poikilitic orthopyroxene is consistent with growth from the B1 magma. These observations cannot be explained by the classic cumulus and post-cumulus models of oikocryst formation. Instead, we suggest that the oikocryst core zones in the MG1 chromitite layer formed by peritectic replacement of olivine primocrysts by reaction with an upwards-percolating melt enriched in incompatible trace elements. Poikilitic overgrowth on oikocryst core zones occurred in equilibrium with a basaltic melt of B1 composition near the magma-crystal mush interface. Finally, adcumulus crystallisation followed by grain growth resulted in the surrounding granular chromitite.

Occupational risk and the development of premalignant skin lesions among paraquat manufacturers.

PubMed

Wang, J D; Li, W E; Hu, F C; Hu, K H

1987-03-01

The objective of this study was to determine the prevalence rate and possible aetiological factors of premalignant skin lesions observed among paraquat manufacturers. A total of 228 workers in 28 factories were interviewed and independently examined by a dermatologist during site inspection in 1985. Information concerning past working experience, current toxic exposures, other risk factors of hyperpigmented macules and keratosis, and the past and present manufacturing processes of each factory was collected. Sixty nine cases of hyperpigmented macules and 17 of hyperkeratosis were found. Typical macules were irregular in shape, pin head size, hyperpigmented, with or without hyperkeratosis, and usually distributed symmetrically over the forearms, hands, neck, and upper chest, where exposure to sunlight was maximal. Six patients with hyperkeratotic lesions subsequently had biopsies performed and two showed Bowenoid changes. Eighty per cent (28 cases) and 67% (38 cases) of workers developed hyperpigmented macules if they had ever been engaged in bipyridine centrifugation and crystallisation, respectively; there were three workers 3% with such lesions among those who performed packaging or administrative jobs, or both. There was a significant trend (p less than 0.0001) for workers to develop hyperpigmented macules and hyperkeratosis the longer they had been exposed to centrifugation or crystallisation, or both, independent of age and the duration of exposure to sunlight. Evidence is presented to suggest that sunlight is a necessary cofactor and that the aetiological agent was produced during high temperature sodium process of bipyridine synthesis, and possibly bipyridine isomer(s).

Synthesis optimisation and characterisation of the organic-inorganic layered materials ZnS(m-xylylenediamine){sub 1/2} and ZnS(p-xylylenediamine){sub 1/2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luberda-Durnaś, K.; Guillén, A. González; Łasocha, W., E-mail: lasocha@chemia.uj.edu.pl

2016-06-15

Hybrid organic-inorganic layered materials of the type ZnS(amine){sub 1/2}, where amine=m-xylylenediamine (MXDA) or p-xylylenediamine (PXDA), were synthesised using a simple solvothermal method. Since the samples crystallised in the form of very fine powder, X-ray powder diffraction techniques were used for structural characterisation. The crystal structure studies, involving direct methods, show that both compounds crystallised in the orthorhombic crystal system, but in different space groups: ZnS(MXDA){sub 1/2} in non-centrosymmetric Ccm2{sub 1}, ZnS(PXDA){sub 1/2} in centrosymmetric Pcab. The obtained materials are built according to similar orders: semiconducting monolayers with the formula ZnS, parallel to the (010) plane, are separated by diamines. Themore » organic and inorganic fragments are connected by covalent bonds between metal atoms of the layers and nitrogen atoms of the amino groups. The optical properties of the hybrid materials differ from those of their bulk counterpart. In both compounds a blue-shift of about 0.8 or 0.9 eV was observed with reference to the bulk phase of ZnS. - Highlights: • New hybrid compounds: ZnS(MXDA){sub 1/2} and ZnS(PXDA){sub 1/2} were obtained. • Hybrids were studied using XRD, TG/DSC, XRK, SEM, UV–vis spectroscopy. • Structures of both materials were solved by powder diffraction methods.« less

Diode pumped solid-state laser oscillators for spectroscopic applications

NASA Technical Reports Server (NTRS)

Byer, R. L.; Basu, S.; Fan, T. Y.; Kozlovsky, W. J.; Nabors, C. D.; Nilsson, A.; Huber, G.

1987-01-01

The rapid improvement in diode laser pump sources has led to the recent progress in diode laser pumped solid state lasers. To date, electrical efficiencies of greater than 10 percent were demonstrated. As diode laser costs decrease with increased production volume, diode laser and diode laser array pumped solid state lasers will replace the traditional flashlamp pumped Nd:YAG laser sources. The use of laser diode array pumping of slab geometry lasers will allow efficient, high peak and average power solid state laser sources to be developed. Perhaps the greatest impact of diode laser pumped solid state lasers will be in spectroscopic applications of miniature, monolithic devices. Single-stripe diode-pumped operation of a continuous-wave 946 nm Nd:YAG laser with less than 10 m/w threshold was demonstrated. A slope efficiency of 16 percent near threshold was shown with a projected slope efficiency well above a threshold of 34 percent based on results under Rhodamine 6G dye-laser pumping. Nonlinear crystals for second-harmonic generation of this source were evaluated. The KNbO3 and periodically poled LiNbO3 appear to be the most promising.

A new solid-state, frequency-doubled neodymium-YAG photocoagulation system.

PubMed

Jalkh, A E; Pflibsen, K; Pomerantzeff, O; Trempe, C L; Schepens, C L

1988-06-01

We have developed a solid-state laser system that produces a continuous green monochromatic laser beam of 532 nm by doubling the frequency of a neodymium-YAG laser wavelength of 1064 nm with a potassium-titamyl-phosphate crystal. Photocoagulation burns of equal size and intensity were placed in two rabbit eyes with the solid-state laser system and the regular green argon laser system, respectively, using the same slit-lamp mode of delivery. Histologic findings of lesion sections revealed no important differences between the two systems. In theory, the longer wavelength of the solid-state laser offers the advantages of less scattering in ocular media, higher absorption by oxyhemoglobin, and less absorption by macular xanthophyll than the 514-nm wavelength of the regular green argon laser. The solid-state laser has impressive technical advantages: it contains no argon-ion gas tube that wears out and is expensive to replace; it is much more power efficient, and thus considerably smaller and compact; it is sturdier and easily movable; it does not require external cooling; it uses a 220-V monophasic alternating current; and it requires little maintenance.

Solid state ionics: a Japan perspective

NASA Astrophysics Data System (ADS)

Yamamoto, Osamu

2017-12-01

The 70-year history of scientific endeavor of solid state ionics research in Japan is reviewed to show the contribution of Japanese scientists to the basic science of solid state ionics and its applications. The term 'solid state ionics' was defined by Takehiko Takahashi of Nagoya University, Japan: it refers to ions in solids, especially solids that exhibit high ionic conductivity at a fairly low temperature below their melting points. During the last few decades of exploration, many ion conducting solids have been discovered in Japan such as the copper-ion conductor Rb4Cu16I7Cl13, proton conductor SrCe1-xYxO3, oxide-ion conductor La0.9Sr0.9Ga0.9Mg0.1O3, and lithium-ion conductor Li10GeP2S12. Rb4Cu16I7Cl13 has a conductivity of 0.33 S cm-1 at 25 °C, which is the highest of all room temperature ion conductive solid electrolytes reported to date, and Li10GeP2S12 has a conductivity of 0.012 S cm-1 at 25 °C, which is the highest among lithium-ion conductors reported to date. Research on high-temperature proton conducting ceramics began in Japan. The history, the discovery of novel ionic conductors and the story behind them are summarized along with basic science and technology.

Facilitated ion transport in all-solid-state flexible supercapacitors.

PubMed

Choi, Bong Gill; Hong, Jinkee; Hong, Won Hi; Hammond, Paula T; Park, HoSeok

2011-09-27

The realization of highly flexible and all-solid-state energy-storage devices strongly depends on both the electrical properties and mechanical integrity of the constitutive materials and the controlled assembly of electrode and solid electrolyte. Herein we report the preparation of all-solid-state flexible supercapacitors (SCs) through the easy assembly of functionalized reduced graphene oxide (f-RGO) thin films (as electrode) and solvent-cast Nafion electrolyte membranes (as electrolyte and separator). In particular, the f-RGO-based SCs (f-RGO-SCs) showed a 2-fold higher specific capacitance (118.5 F/g at 1 A/g) and rate capability (90% retention at 30 A/g) compared to those of all-solid-state graphene SCs (62.3 F/g at 1A/g and 48% retention at 30 A/g). As proven by the 4-fold faster relaxation of the f-RGO-SCs than that of the RGO-SCs and more capacitive behavior of the former at the low-frequency region, these results were attributed to the facilitated ionic transport at the electrical double layer by means of the interfacial engineering of RGO by Nafion. Moreover, the superiority of all-solid-state flexible f-RGO-SCs was demonstrated by the good performance durability under the 1000 cycles of charging and discharging due to the mechanical integrity as a consequence of the interconnected networking structures. Therefore, this research provides new insight into the rational design and fabrication of all-solid-state flexible energy-storage devices as well as the fundamental understanding of ion and charge transport at the interface. © 2011 American Chemical Society

40 CFR 256.05 - Annual work program.

Code of Federal Regulations, 2012 CFR

2012-07-01

....05 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Purpose, General Requirements... implementation of the State plan. ...

Driver circuit for solid state light sources

DOEpatents

Palmer, Fred; Denvir, Kerry; Allen, Steven

2016-02-16

A driver circuit for a light source including one or more solid state light sources, a luminaire including the same, and a method of so driving the solid state light sources are provided. The driver circuit includes a rectifier circuit that receives an alternating current (AC) input voltage and provides a rectified AC voltage. The driver circuit also includes a switching converter circuit coupled to the light source. The switching converter circuit provides a direct current (DC) output to the light source in response to the rectified AC voltage. The driver circuit also includes a mixing circuit, coupled to the light source, to switch current through at least one solid state light source of the light source in response to each of a plurality of consecutive half-waves of the rectified AC voltage.

Carbazole-based BODIPYs with ethynyl substituents at the boron center: solid-state excimer fluorescence in the VIS/NIR region.

PubMed

Maeda, Chihiro; Nagahata, Keiji; Ema, Tadashi

2017-09-26

Carbazole-based BODIPYs 1-6 with several different substituents at the boron atom site were synthesized. These dyes fluoresced in the solid state, and 3a with phenylethynyl groups exhibited a red-shifted and broad fluorescence spectrum, which suggested an excimer emission. Its derivatives 3b-n were synthesized, and the relationship between the solid-state emission and crystal packing was investigated. The X-ray crystal structures revealed cofacial dimers that might form excimers. From the structural optimization results, we found that the introduction of mesityl groups hindered intermolecular access and led to reduced interactions between the dimers. In addition, the red-shifted excimer fluorescence suppressed self-absorption, and dyes with ethynyl groups showed solid-state fluorescence in the vis/NIR region.

Impact of solid state fermentation on nutritional, physical and flavor properties of wheat bran.

PubMed

Zhao, Hui-Min; Guo, Xiao-Na; Zhu, Ke-Xue

2017-02-15

To improve the nutritional, physical and flavor properties of wheat bran, yeast and lactic acid bacteria (LAB) were used for fermenting wheat bran in solid state. Appearance properties, nutritional properties, microstructure, hydration properties and flavor of raw bran and fermented bran were evaluated. After treatments, water extractable arabinoxylans were 3-4 times higher than in raw bran. Total dietary fiber and soluble dietary fiber increased after solid state fermentation. Over 20% of phytic acid was degraded. Microstructure changes and protein degradation were observed in fermented brans. Water holding capacity and water retention capacity of fermented brans were improved. Results suggest that solid state fermentation is an effective way to improve the properties of wheat brans. Copyright © 2016 Elsevier Ltd. All rights reserved.

Quasi-Solid-State Single-Atom Transistors.

PubMed

Xie, Fangqing; Peukert, Andreas; Bender, Thorsten; Obermair, Christian; Wertz, Florian; Schmieder, Philipp; Schimmel, Thomas

2018-06-21

The single-atom transistor represents a quantum electronic device at room temperature, allowing the switching of an electric current by the controlled and reversible relocation of one single atom within a metallic quantum point contact. So far, the device operates by applying a small voltage to a control electrode or "gate" within the aqueous electrolyte. Here, the operation of the atomic device in the quasi-solid state is demonstrated. Gelation of pyrogenic silica transforms the electrolyte into the quasi-solid state, exhibiting the cohesive properties of a solid and the diffusive properties of a liquid, preventing the leakage problem and avoiding the handling of a liquid system. The electrolyte is characterized by cyclic voltammetry, conductivity measurements, and rotation viscometry. Thus, a first demonstration of the single-atom transistor operating in the quasi-solid-state is given. The silver single-atom and atomic-scale transistors in the quasi-solid-state allow bistable switching between zero and quantized conductance levels, which are integer multiples of the conductance quantum G 0  = 2e 2 /h. Source-drain currents ranging from 1 to 8 µA are applied in these experiments. Any obvious influence of the gelation of the aqueous electrolyte on the electron transport within the quantum point contact is not observed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical structures of swine-manure chars produced under different carbonization conditions investigated by advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy

USDA-ARS?s Scientific Manuscript database

Two types of swine manure chars, hydrothermally-produced hydrochar and slow-pyrolysis pyrochar, and their raw swine manure solid were characterized using advanced 13C solid-state nuclear magnetic resonance (NMR) spectroscopy. Compared with the parent raw swine manure, both hydrochars and pyrochar di...

75 FR 82269 - Approval and Promulgation of State Plans for Designated Facilities and Pollutants; State of...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-12-30

... solid waste (MSW). DATES: This direct final rule is effective February 28, 2011 without further notice... requires EPA to conduct a 5-year review of the solid waste incinerator new source performance standards........... Okahumpka. Pasco County Solid Waste Hudson. Hillsborough County Resource Recovery Tampa. McKay Bay Refuse-to...

Titration of a Solid Acid Monitored by X-Ray Diffraction

ERIC Educational Resources Information Center

Dungey, Keenan E.; Epstein, Paul

2007-01-01

An experiment is described to introduce students to an important class of solid-state reactions while reinforcing concepts of titration by using a pH meter and a powder X-ray diffractometer. The experiment was successful in teaching students the abstract concepts of solid-state structure and diffraction by applying the diffraction concepts learned…

Structure and function of nucleotide sugar transporters: Current progress.

PubMed

Hadley, Barbara; Maggioni, Andrea; Ashikov, Angel; Day, Christopher J; Haselhorst, Thomas; Tiralongo, Joe

2014-06-01

The proteomes of eukaryotes, bacteria and archaea are highly diverse due, in part, to the complex post-translational modification of protein glycosylation. The diversity of glycosylation in eukaryotes is reliant on nucleotide sugar transporters to translocate specific nucleotide sugars that are synthesised in the cytosol and nucleus, into the endoplasmic reticulum and Golgi apparatus where glycosylation reactions occur. Thirty years of research utilising multidisciplinary approaches has contributed to our current understanding of NST function and structure. In this review, the structure and function, with reference to various disease states, of several NSTs including the UDP-galactose, UDP-N-acetylglucosamine, UDP-N-acetylgalactosamine, GDP-fucose, UDP-N-acetylglucosamine/UDP-glucose/GDP-mannose and CMP-sialic acid transporters will be described. Little is known regarding the exact structure of NSTs due to difficulties associated with crystallising membrane proteins. To date, no three-dimensional structure of any NST has been elucidated. What is known is based on computer predictions, mutagenesis experiments, epitope-tagging studies, in-vitro assays and phylogenetic analysis. In this regard the best-characterised NST to date is the CMP-sialic acid transporter (CST). Therefore in this review we will provide the current state-of-play with respect to the structure-function relationship of the (CST). In particular we have summarised work performed by a number groups detailing the affect of various mutations on CST transport activity, efficiency, and substrate specificity.

Solid-State NMR Studies Reveal Native-like β-Sheet Structures in Transthyretin Amyloid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, Kwang Hun; Dasari, Anvesh K. R.; Hung, Ivan

Structural characterization of amyloid rich in cross-β structures is crucial for unraveling the molecular basis of protein misfolding and amyloid formation associated with a wide range of human disorders. Elucidation of the β-sheet structure in noncrystalline amyloid has, however, remained an enormous challenge. Here we report structural analyses of the β-sheet structure in a full-length transthyretin amyloid using solid-state NMR spectroscopy. Magic-angle-spinning (MAS) solid-state NMR was employed to investigate native-like β-sheet structures in the amyloid state using selective labeling schemes for more efficient solid-state NMR studies. Analyses of extensive long-range 13 C- 13 C correlation MAS spectra obtained with selectivelymore » 13 CO- and 13 Cα-labeled TTR reveal that the two main β-structures in the native state, the CBEF and DAGH β-sheets, remain intact after amyloid formation. The tertiary structural information would be of great use for examining the quaternary structure of TTR amyloid.« less

Solid-State NMR Studies Reveal Native-like β-Sheet Structures in Transthyretin Amyloid

DOE PAGES

Lim, Kwang Hun; Dasari, Anvesh K. R.; Hung, Ivan; ...

2016-09-02

Structural characterization of amyloid rich in cross-β structures is crucial for unraveling the molecular basis of protein misfolding and amyloid formation associated with a wide range of human disorders. Elucidation of the β-sheet structure in noncrystalline amyloid has, however, remained an enormous challenge. Here we report structural analyses of the β-sheet structure in a full-length transthyretin amyloid using solid-state NMR spectroscopy. Magic-angle-spinning (MAS) solid-state NMR was employed to investigate native-like β-sheet structures in the amyloid state using selective labeling schemes for more efficient solid-state NMR studies. Analyses of extensive long-range 13 C- 13 C correlation MAS spectra obtained with selectivelymore » 13 CO- and 13 Cα-labeled TTR reveal that the two main β-structures in the native state, the CBEF and DAGH β-sheets, remain intact after amyloid formation. The tertiary structural information would be of great use for examining the quaternary structure of TTR amyloid.« less

Crystallisation ages in coeval silicic magma bodies: 238U-230Th disequilibrium evidence from the Rotoiti and earthquake flat eruption deposits, Taupo volcanic zone, New Zealand

USGS Publications Warehouse

Charlier, B.L.A.; Peate, D.W.; Wilson, C.J.N.; Lowenstern, J. B.; Storey, M.; Brown, S.J.A.

2003-01-01

The timescales over which moderate to large bodies of silicic magma are generated and stored are addressed here by studies of two geographically adjacent, successive eruption deposits in the Taupo Volcanic Zone, New Zealand. The earlier, caldera-forming Rotoiti eruption (>100 km3 magma) at Okataina volcano was followed, within months at most, by the Earthquake Flat eruption (??? 10 km3 magma) from nearby Kapenga volcano; both generated nonwelded ignimbrite and coeval widespread fall deposits. The Rotoiti and Earthquake Flat deposits are both crystal-rich high-silica rhyolites, with sparse glass-bearing granitoid fragments also occurring in Rotoiti lag breccias generated during caldera collapse. Here we report 238U-230Th disequilibrium data on whole rocks and mineral separates from representative Rotoiti and Earthquake Flat pumices and the co-eruptive Rotoiti granitoid fragments using TIMS and in situ zircon analyses by SIMS. Multiple-grain zircon-controlled crystallisation ages measured by TIMS from the Rotoiti pumice range from 69??3 ka ( 350 ka, with a pronounced peak at 70-90 ka. The weighted mean of isochrons is 83??14 ka, in accord with the TIMS data. One glass-bearing Rotoiti granitoid clast yielded an age of 57??8 ka by TIMS (controlled by Th-rich phases that, however, are not apparently present in the juvenile pumices). Another glass-bearing Rotoiti granitoid yielded SIMS zircon model ages peaking at 60-90 ka, having a similar age distribution to the pumice. Age data from pumices are consistent with a published 64??4 ka eruptive age (now modified to 62??2 ka), but chemical and/or mineralogical data imply that the granitoid lithics are not largely crystalline Rotoiti rhyolite, but instead represent contemporaneous partly molten intrusions reflecting different sources in their chemistries and mineralogies. Similarly, although the Earthquake Flat eruption immediately followed (and probably was triggered by) the Rotoiti event, age data from juvenile material are significantly different. A multiple-grain zircon-controlled crystallisation age measured by TIMS from a representative pumice is 173??5 ka, while SIMS model ages range from 70-26+34 ka to >350 ka, with a peak at 105 ka. These age data coupled with previously published geochemical and isotopic data show that the Rotoiti and Earthquake Flat deposits were erupted from independent, unconnected magma bodies. Published by Elsevier Science B.V.

Behaviour of Ni-PGE-Au-Cu in mafic-ultramafic volcanic suites of the 2.7 Ga Kambalda Sequence, Kalgoorlie Terrane, Yilgarn Craton

NASA Astrophysics Data System (ADS)

Said, Nuru; Kerrich, Robert; Maier, W. D.; McCuaig, Campbell

2011-05-01

The 2.7 Ga Kambalda Sequence comprises a mafic to ultramafic dominated volcanic rock sequence of the Kalgoorlie Terrane, Yilgarn Craton, Western Australia. The Sequence is divided into Lower and Upper Units separated by the Kambalda Komatiite Formation. Five basalt suites of the Lower Unit are tholeiitic where MgO spans 5-10 wt.% MgO, with minor assimilation-fractional crystallization (AFC), whereas six volcanic suites identified in the Upper Unit are tholeiitic to komatiitic-basalts with MgO 24-5 wt.% having generally greater degrees of AFC. Upper suites plot at Al 2O 3/TiO 2 (17-26) close to the primitive mantle ratio of 21, and Pt + Pd (19-31 ppb), whereas the PGE-depleted Lower basalts plot at generally lower Al 2O 3/TiO 2 (<16) and Pt + Pd (<10 ppb). Most suites have an average Pt/Pd ratio of 1.11, despite large variations in MgO contents, broadly consistent with the Pt/Pd ratio in the primitive mantle. On primitive mantle-normalised PGE plots, Upper suites generally display less fractionated patterns of the IPGE (Os, Ir, Ru and Rh) from the PPGE (Pt and Pd) relative to the Lower basalts. Most suites exhibit patterns with positive slopes reflecting relative enrichment of Pd, Pt, Au and Cu relative to Ni and IPGE. In suites of both Units, the concentrations of Ir and Ru fall with decreasing MgO contents, indicating their broadly compatible behaviour during magmatic evolution that involved AFC. Platinum and Pd behave as incompatible elements in the high-MgO suites, whereas Pt and Pd behave compatibly during crystallisation of the Lower basalt magmas, an interpretation consistent with progressively higher Cu/Pt and Cu/Pd ratios at decreasing MgO contents, and with falling Pt/Ti, collectively due to sulphur saturation induced by AFC as recorded in an antivariance of Pd/Ir with Nb/Th, a monitor of AFC. Collectively, the data suggest that several of the Lower Basalt suites crystallised under sulphide-saturated conditions, whereas most of the Upper Basalt Sequences remained sulphur undersaturated during magmatic evolution. Alteration, and fractional crystallisation of silicate and oxide phases, can be ruled out as factors governing PGE distribution in these mafic-ultramafic suites. Instead, the data suggest that discrete PGE-bearing phase (s) fractionated from the magmas. Such phases could be platinum group minerals (PGM; e.g., laurite) and/or alloys, or discrete PGE-rich nuggets or sulphides.

The Petrogenesis of the Unit 7/8 and 11/12 Chrome-spinel Seams of the Rum Eastern Layered Intrusion (NW Scotland) Re-evaluated

NASA Astrophysics Data System (ADS)

O'Driscoll, B.; Daly, J. S.; Emeleus, C. H.; Donaldson, C. H.

2007-12-01

Laterally extensive (~2 mm thick) chrome-spinel seams in the Rum Layered Suite, NW Scotland, occur at the junctions of several of the coupled peridotite-troctolite macro-rhythmic units that make up the bulk of the eastern part of the intrusion. A detailed petrographic study of the rocks immediately above and below two of these seams suggests that existing models for seam formation involving early crystallisation and gravitational settling of chrome-spinel crystals from a newly emplaced body of picritic magma may be flawed. Instead, the textural relationships between minerals suggest that olivine crystallisation in the peridotite above each of the seams occurred before that of most of the chrome-spinel. Reaction textures between olivine and chrome-spinel crystals are commonly observed, with plagioclase usually occurring as thin rims between both olivine and chrome-spinel where both are in close proximity. The textural evidence suggests a significant degree of olivine crystal-shape change; it seems that many of the olivine crystals immediately above the main seams may initially have had much more complex (harrisitic) crystal shapes before modification to simpler morphologies in a crystal mush. Plagioclase occurs in the peridotite as large oikocrysts up to several cm in size. Additionally, the chrome-spinel seams occur only in those units that display extensive evidence of syn-magmatic deformation of unconsolidated cumulate in the underlying troctolite, and the seams themselves often exhibit small-scale load structures. A model suggesting in-situ crystallisation of the chrome-spinel seams is proposed, whereby mixing of an evolved interstitial liquid with a primitive picritic melt occurred approximately at the crystal mush-magma interface. The former was released from the unconsolidated troctolite mush as a response to re-mobilization and chaotic slumping, possibly triggered by emplacement of some of the hot picrite into the crystal mush pile. Significant undercooling in the picrite due to emplacement-related cooling had already produced a crystal framework comprising complex skeletal olivine crystal morphologies with very fast growth rates. It is envisaged that the significantly modified olivine textures in the peridotite immediately above both seams can be attributed to upward- moving porosity waves of the same 'mixed' interstitial melt that precipitated the chrome-spinel seams. In addition to formation of the seams at the main unit junctions, 'necklace' or 'chain-like' distributions of chrome-spinel crystals around olivine crystals in the peridotite, as well as the large plagioclase oikocrysts, argue for the presence of a mobile interstitial melt with a protracted cooling history.

40 CFR 256.05 - Annual work program.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 256.05 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Purpose, General Requirements... implementation of the State plan. ...

40 CFR 256.05 - Annual work program.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 256.05 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE MANAGEMENT PLANS Purpose, General Requirements... implementation of the State plan. ...

Production of microbial biosurfactants by solid-state cultivation.

PubMed

Krieger, Nadia; Camilios Neto, Doumit; Mitchell, David Alexander

2010-01-01

In recent years biosurfactants have attracted attention because of their low toxicity, biodegradability and ecological acceptability. However, their use is currently extremely limited due to their high cost in relation to that of chemical surfactants. Solid-state cultivation represents an alternative technology for biosurfactant production that can bring two important advantages: firstly, it allows the use of inexpensive substrates and, secondly, it avoids the problem of foaming that complicates submerged cultivation processes for biosurfactant production. In this chapter we show that, despite its potential, to date relatively little attention has been given to solid-state cultivation for biosurfactant production. We also note that this cultivation technique brings its own challenges, such as the selection of a bioreactor type that will allow adequate heat removal, of substrates with appropriate physico-chemical properties and of methods for monitoring of the cultivation process and recovering the biosurfactants from the fermented solid. With suitable efforts in research, solid-state cultivation can be used for large-scale production of biosurfactants.

Solid-waste contract-negotiation handbook

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

The Environmental Protection Agency has estimated that the United States generated 164 million tons of municipal solid waste in 1986, and that the amount is increasing at a rate of more than 1 percent annually. Landfills are reaching capacity and closing. The cost of disposing of waste is growing and local officials are concerned about how they will meet the challenge of managing solid waste. This handbook is designed to help local officials develop contracts with private companies and other governmental units that will protect the interests of the citizens in their communities. This handbook is based on information andmore » analysis derived from a questionnaire survey of 160 local governments located in EPA Region X, plus selected other states; review and analysis of sample provisions from actual solid waste contracts and agreements; follow-up interviews with solid waste managers in several of the states and with responding local governments; and a review of the literature as well as state federal statutes and regulations.« less

Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries.

PubMed

Hayashi, Akitoshi; Noi, Kousuke; Sakuda, Atsushi; Tatsumisago, Masahiro

2012-05-22

Innovative rechargeable batteries that can effectively store renewable energy, such as solar and wind power, urgently need to be developed to reduce greenhouse gas emissions. All-solid-state batteries with inorganic solid electrolytes and electrodes are promising power sources for a wide range of applications because of their safety, long-cycle lives and versatile geometries. Rechargeable sodium batteries are more suitable than lithium-ion batteries, because they use abundant and ubiquitous sodium sources. Solid electrolytes are critical for realizing all-solid-state sodium batteries. Here we show that stabilization of a high-temperature phase by crystallization from the glassy state dramatically enhances the Na(+) ion conductivity. An ambient temperature conductivity of over 10(-4) S cm(-1) was obtained in a glass-ceramic electrolyte, in which a cubic Na(3)PS(4) crystal with superionic conductivity was first realized. All-solid-state sodium batteries, with a powder-compressed Na(3)PS(4) electrolyte, functioned as a rechargeable battery at room temperature.

One-step synthesis of solid state luminescent carbon-based silica nanohybrids for imaging of latent fingerprints

NASA Astrophysics Data System (ADS)

Li, Feng; Li, Hongren; Cui, Tianfang

2017-11-01

Fluorescent carbon-based nanomaterials(CNs) with tunable visible emission are biocompatible, environment friendly and most suitable for various biomedical applications. Despite the successes in preparing strongly fluorescent CNs, preserving the luminescence in solid materials is still challenging because of the serious emission quenching of CNs in solid state materials. In this work, fluorescent carbon and silica nanohybrids (SiCNHs) were synthesized via a simple one-step hydrothermal approach by carbonizing sodium citrate and (3-aminopropyl)triethoxysilane(APTES), and hydrolysis of tetraethyl orthosilicate(TEOS). The resultant SiCNs were characterized through X-ray diffraction (XRD), transmission electron microscopy (TEM), FT-IR, X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectroscopy. The SiCNs exhibited strong fluorescence in both aqueous and solid states. The luminescent solid state SiCNs power were successfully used as a fluorescent labeling material for enhanced imaging of latent fingerprints(LFPs) on single background colour and multi-coloured surfaces substrates in forensic science for individual identification.

Model of Laser-Induced Temperature Changes in Solid-State Optical Refrigerators

DTIC Science & Technology

2010-01-01

Model of laser-induced temperature changes in solid-state optical refrigerators W. M. Patterson,1,a M. Sheik- Bahae ,1 R. I . Epstein,2 and M. P...Applications of Laser Cooling of Sol- ids, edited by R. I . Epstein and M. Sheik- Bahae Wiley, Weinheim, 2009. 2W. Koechner, Solid-State Laser...2004. 19D. V. Seletskiy, S. D. Melgaard, S. Bigotta, A. Di Lieto, M. Tonelli, R. I . Epstein, and M. Sheik- Bahae , in Conference on Lasers and Electro

Microporous Ni₁₁(HPO₃)₈(OH)₆ nanocrystals for high-performance flexible asymmetric all solid-state supercapacitors.

PubMed

Gao, Yanping; Zhao, Junhong; Run, Zhen; Zhang, Guangqin; Pang, Huan

2014-12-07

Microporous nickel phosphite [Ni11(HPO3)8(OH)6] nanocrystals were prepared using a hydrothermal method, and were successfully applied as a positive electrode in a flexible all solid-state asymmetric supercapacitor. Because of the specific micro/nanostructure, the flexible solid-state asymmetric supercapacitor can achieve a maximum energy density of 0.45 mW h cm(-3), which is higher than most reported supercapacitors. More importantly, the device performance remains efficient for 10,000 cycles.

Ultracold Fermions in the P-Orbital Band of an Optical Lattice

DTIC Science & Technology

2015-07-27

introduces (1) a new degree of freedom due to orbital degeneracy and (2) a tunneling anisotropy which depends on the orientation of the orbital wavefunction...demonstrated this new technique with a diode -pumped solid-state laser operating at 1342 nm that could be frequency doubled to provide 671 nm light for laser...Figure 3: Self-injection locked, diode -pumped solid-state laser for laser cooling of Li atoms. The solid-state Nd:YVO4 laser at the top consists of a