Carbonate-coordinated metal complexes precede the formation of liquid amorphous mineral emulsions of divalent metal carbonates†

PubMed Central

Wolf, Stephan E.; Müller, Lars; Barrea, Raul; Kampf, Christopher J.; Leiterer, Jork; Panne, Ulrich; Hoffmann, Thorsten

2011-01-01

During the mineralisation of metal carbonates MCO3 (M = Ca, Sr, Ba, Mn, Cd, Pb) liquid-like amorphous intermediates emerge. These intermediates that form via a liquid/liquid phase separation behave like a classical emulsion and are stabilized electrostatically. The occurrence of these intermediates is attributed to the formation of highly hydrated networks whose stability is mainly based on weak interactions and the variability of the metal-containing pre-critical clusters. Their existence and compositional freedom are evidenced by electrospray ionization mass spectrometry (ESI-MS). Liquid intermediates in non-classical crystallisation pathways seem to be more common than assumed. PMID:21218241

Advancing dynamic and thermodynamic modelling of magma oceans

NASA Astrophysics Data System (ADS)

Bower, Dan; Wolf, Aaron; Sanan, Patrick; Tackley, Paul

2017-04-01

The techniques for modelling low melt-fraction dynamics in planetary interiors are well-established by supplementing the Stokes equations with Darcy's Law. But modelling high-melt fraction phenomena, relevant to the earliest phase of magma ocean cooling, necessitates parameterisations to capture the dynamics of turbulent flow that are otherwise unresolvable in numerical models. Furthermore, it requires knowledge about the material properties of both solid and melt mantle phases, the latter of which are poorly described by typical equations of state. To address these challenges, we present (1) a new interior evolution model that, in a single formulation, captures both solid and melt dynamics and hence charts the complete cooling trajectory of a planetary mantle, and (2) a physical and intuitive extension of a "Hard Sphere" liquid equation of state (EOS) to describe silicate melt properties for the pressure-temperature (P-T) range of Earth's mantle. Together, these two advancements provide a comprehensive and versatile modelling framework for probing the far-reaching consequences of magma ocean cooling and crystallisation for Earth and other rocky planets. The interior evolution model accounts for heat transfer by conduction, convection, latent heat, and gravitational separation. It uses the finite volume method to ensure energy conservation at each time-step and accesses advanced time integration algorithms by interfacing with PETSc. This ensures it accurately and efficiently computes the dynamics throughout the magma ocean, including within the ultra-thin thermal boundary layers (< 2 cm thickness) at the core-mantle boundary and surface. PETSc also enables our code to support a parallel implementation and quad-precision calculations for future modelling capabilities. The thermodynamics of mantle melting are represented using a pseudo-one-component model, which retains the simplicity of a standard one-component model while introducing a finite temperature interval for melting (important for multi-component systems). Our new high P-T liquid EOS accurately captures the energetics and physical properties of the partially molten system whilst retaining the largest number of familiar EOS parameters. We demonstrate the power of our integrated dynamic and EOS model by exploring two crystallisation scenarios for Earth that are dictated by the coincidence of the liquid adiabat and melting curve. Experiments on melting of primitive chondrite composition predict that crystallisation occurs from the "bottom-up", whereas molecular dynamics simulations of MgSiO3 perovskite suggest crystallisation occurs from the "middle-out". In each case, we evaluate the lifetime of the magma ocean using our model and find that in both scenarios, initial cooling is rapid and the rheological transition (boundary between melt- and solid-like behaviour) is reached within a few kyrs. During this stage efficient mixing prevents the establishment of thermal and chemical heterogeneity, so it may be challenging to locate a signature of the earliest phase of magma ocean evolution. At the rheological transition, cooling is governed by gravitational separation and viscous creep, and even in the absence of iron partitioning our models predict long-lasting (> 500 Myr) melt at the base of the mantle.

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.

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.

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.

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.

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.

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.

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.

Structural studies of the crystallisation of microporous materials

NASA Astrophysics Data System (ADS)

Davies, Andrew Treharne

A range of powerful synchrotron radiation characterisation techniques have been used to study fundamental aspects of the fonnation of microporous solids, specifically alumi nosilicates, heteroatom substituted aluminophosphates and titanosilicates. This work has been performed with the aim of investigating in situ the structural changes occurring during crystallisation and post synthetic treatment. In situ EDXRD was used to follow the crystallisation of these materials under a wide range of synthesis conditions using a hydrothermal cell and a solid-state detector array. A quantitative analysis of the crystallisation kinetics was performed for the large pore aluminosilicate, zeolite A, using a simple mathematical model to calculate the activation energy of formation. The results obtained were found to closely agree with both the experimental results and theoretical models of others. A qualitative study of the effect of altering the synthesis conditions was also investigated for this material. Similar kinetic studies were then performed for a range of microporous aluminophosphates and their cobalt substituted derivatives in order to follow the effects of varying synthesis conditions such as the synthesis temperature, organic template type, and cobalt concentration. Distinct trends were noted in the formation times, stability and nature of the resulting crystalline phases as conditions were varied. The relationship between the cobalt and organic template molecules during crystallisation was considered in some detail with reference to other experimental data and theoretical models. The alumi nophosphate studies were subsequently extended to a range of other heteroatom substituted aluminophosphates, using in situ EDXRD, complimented by EXAFS, which allowed investigation of the local environments around the heteroatoms within the microporous structure. EDXRD and EXAFS studies have been performed on the microporous titanosilicate, ETS-10, while the thermal stability of this material has also been investigated in situ using synchrotron X-ray diffraction in conjunction with a high temperature environmental cell.

An Investigation of the Effects of Self-Assembled Monolayers on Protein Crystallisation

PubMed Central

Zhang, Chen-Yan; Shen, He-Fang; Wang, Qian-Jin; Guo, Yun-Zhu; He, Jin; Cao, Hui-Ling; Liu, Yong-Ming; Shang, Peng; Yin, Da-Chuan

2013-01-01

Most protein crystallisation begins from heterogeneous nucleation; in practice, crystallisation typically occurs in the presence of a solid surface in the solution. The solid surface provides a nucleation site such that the energy barrier for nucleation is lower on the surface than in the bulk solution. Different types of solid surfaces exhibit different surface energies, and the nucleation barriers depend on the characteristics of the solid surfaces. Therefore, treatment of the solid surface may alter the surface properties to increase the chance to obtain protein crystals. In this paper, we propose a method to modify the glass cover slip using a self-assembled monolayer (SAM) of functional groups (methyl, sulfydryl and amino), and we investigated the effect of each SAM on protein crystallisation. The results indicated that both crystallisation success rate in a reproducibility study, and crystallisation hits in a crystallisation screening study, were increased using the SAMs, among which, the methyl-modified SAM demonstrated the most significant improvement. These results illustrated that directly modifying the crystallisation plates or glass cover slips to create surfaces that favour heterogeneous nucleation can be potentially useful in practical protein crystallisation, and the utilisation of a SAM containing a functional group can be considered a promising technique for the treatment of the surfaces that will directly contact the crystallisation solution. PMID:23749116

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

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.

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.

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.

Photo-induced optical activity in phase-change memory materials.

PubMed

Borisenko, Konstantin B; Shanmugam, Janaki; Williams, Benjamin A O; Ewart, Paul; Gholipour, Behrad; Hewak, Daniel W; Hussain, Rohanah; Jávorfi, Tamás; Siligardi, Giuliano; Kirkland, Angus I

2015-03-05

We demonstrate that optical activity in amorphous isotropic thin films of pure Ge2Sb2Te5 and N-doped Ge2Sb2Te5N phase-change memory materials can be induced using rapid photo crystallisation with circularly polarised laser light. The new anisotropic phase transition has been confirmed by circular dichroism measurements. This opens up the possibility of controlled induction of optical activity at the nanosecond time scale for exploitation in a new generation of high-density optical memory, fast chiroptical switches and chiral metamaterials.

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…

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.

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.

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.

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).

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

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.

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.

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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.

Zr, Hf, Mo and W-containing oxide phases as pinning additives in Bi-2212 superconductor

NASA Astrophysics Data System (ADS)

Makarova, M. V.; Kazin, P. E.; Tretyakov, Yu. D.; Jansen, M.; Reissner, M.; Steiner, W.

2005-02-01

Phase formation was investigated in Bi-Sr-Ca-Cu-M-O (M = Mo, W) systems at 850-900 °C. It was found that Sr 2CaMO 6 phases were chemically compatible with Bi-2212. The composites Bi-2212-Sr 2CaMO 6 and Bi-2212-SrAO 3 (A = Zr, Hf) were obtained from a sol-gel precursor using crystallisation from the melt. The materials consisted of Bi-2212 matrix and submicron or micron grains of the corresponding dispersed phase. Tc was equal or exceeded that for undoped Bi-2212, reaching Tc = 97 K in the Mo-containing composite. The composites exhibited enhanced pinning in comparison with similar prepared pure Bi-2212, especially at T = 60 K. The best pinning parameters were observed for the Bi-2212-Sr 2CaWO 6 composite.

Numerical Simulations of Melting-Crystallisation Processes at the Boundaries Between Magma Oceans and Solid Mantle

NASA Astrophysics Data System (ADS)

Bolrão, D. P.; Rozel, A.; Morison, A.; Labrosse, S.; Tackley, P. J.

2017-12-01

The idea that the Earth had a global magma ocean, mostly created by impacts, core formation, radiogenic and tidal heating, is well accepted nowadays. When this ocean starts to crystallise, if the melt is denser than the solid, a basal magma ocean is created below the solid part. These two magma oceans influence the dynamics and evolution of solid mantle. Near the boundaries, the vertical flow in the solid part creates a topography. If this topography is destroyed by melting/crystallisation processes in a time scale much shorter than the time needed to adjust the topography by viscous relaxation, then matter can cross the boundary. In this case, the boundary is said to be permeable. On the other hand, if this time is longer, matter cannot cross and the boundary is said impermeable. This permeability is defined by a non-dimensional phase change number, φ, introduced by Deguen, 2013. This φ is the ratio of the two timescales mentioned, and defines a permeable boundary when φ « 1, and an impermeable one when φ » 1. To understand the impact of magma oceans on the dynamics of the solid mantle, we use the convection code StagYY, with a 2D spherical annulus geometry, to compute the convection of the solid part. Our results show different convection behaviours depending on the type of boundary chosen. For the permeable case, we investigate the thermo-compositional evolution of the solid domain, explicitly taking into account the compositional evolution of the magma oceans. Reference: Deguen, R. Thermal convection in a spherical shell with melting/freezing at either or both of its boundaries. Journal of Earth Science, Vol. 24, No. 5, p. 669-682, 2013. doi: 10.1007/s12583-013-0364-8

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.

Building solids inside nano-space: from confined amorphous through confined solvate to confined 'metastable' polymorph.

PubMed

Nartowski, K P; Tedder, J; Braun, D E; Fábián, L; Khimyak, Y Z

2015-10-14

The nanocrystallisation of complex molecules inside mesoporous hosts and control over the resulting structure is a significant challenge. To date the largest organic molecule crystallised inside the nano-pores is a known pharmaceutical intermediate - ROY (259.3 g mol(-1)). In this work we demonstrate smart manipulation of the phase of a larger confined pharmaceutical - indomethacin (IMC, 357.8 g mol(-1)), a substance with known conformational flexibility and complex polymorphic behaviour. We show the detailed structural analysis and the control of solid state transformations of encapsulated molecules inside the pores of mesoscopic cellular foam (MCF, pore size ca. 29 nm) and controlled pore glass (CPG, pore size ca. 55 nm). Starting from confined amorphous IMC we drive crystallisation into a confined methanol solvate, which upon vacuum drying leads to the stabilised rare form V of IMC inside the MCF host. In contrast to the pure form, encapsulated form V does not transform into a more stable polymorph upon heating. The size of the constraining pores and the drug concentration within the pores determine whether the amorphous state of the drug is stabilised or it recrystallises into confined nanocrystals. The work presents, in a critical manner, an application of complementary techniques (DSC, PXRD, solid-state NMR, N2 adsorption) to confirm unambiguously the phase transitions under confinement and offers a comprehensive strategy towards the formation and control of nano-crystalline encapsulated organic solids.

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.

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.

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.

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.

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.

The fractionation of nickel between olivine and augite as a geothermometer

USGS Publications Warehouse

Hakli, T.A.; Wright, T.L.

1967-01-01

The coexisting olivine, clinopyroxene and glass of five samples collected from the Makaopuhi lava lake in Hawaii, at temperatures ranging from 1050 to 1160??C were analysed for nickel with an electron probe microanalyser. The results strongly suggest that the distribution of nickel between these three phase pairs well obeys the thermodynamic partition law, and that under favourable conditions, the distribution coefficients permit the estimation of the crystallisation temperature within an accuracy of 10-20??C. It is concluded that the application of the Makaopuhi data to plutonic and to other volcanic rocks should be carried out with caution because the effect of pressure and the changing composition of the phases upon the numerical values of the distribution coefficients is not known quantitatively. ?? 1967.

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.

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.

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

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

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.

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.

Electrostatic swelling of bicontinuous cubic lipid phases.

PubMed

Tyler, Arwen I I; Barriga, Hanna M G; Parsons, Edward S; McCarthy, Nicola L C; Ces, Oscar; Law, Robert V; Seddon, John M; Brooks, Nicholas J

2015-04-28

Lipid bicontinuous cubic phases have attracted enormous interest as bio-compatible scaffolds for use in a wide range of applications including membrane protein crystallisation, drug delivery and biosensing. One of the major bottlenecks that has hindered exploitation of these structures is an inability to create targeted highly swollen bicontinuous cubic structures with large and tunable pore sizes. In contrast, cubic structures found in vivo have periodicities approaching the micron scale. We have been able to engineer and control highly swollen bicontinuous cubic phases of spacegroup Im3m containing only lipids by (a) increasing the bilayer stiffness by adding cholesterol and (b) inducing electrostatic repulsion across the water channels by addition of anionic lipids to monoolein. By controlling the composition of the ternary mixtures we have been able to achieve lattice parameters up to 470 Å, which is 5 times that observed in pure monoolein and nearly twice the size of any lipidic cubic phase reported previously. These lattice parameters significantly exceed the predicted maximum swelling for bicontinuous cubic lipid structures, which suggest that thermal fluctuations should destroy such phases for lattice parameters larger than 300 Å.

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.

Effect of Slag Impregnation on Macroscopic Deformation of Bauxite-Based Material

NASA Astrophysics Data System (ADS)

Coulon, Antoine; De Bilbao, Emmanuel; Michel, Rudy; Bouchetou, Marie-Laure; Brassamin, Séverine; Gazeau, Camille; Zanghi, Didier; Poirier, Jacques

This work aims at studying the volume change of bauxite corroded by a molten slag. Cylindrical samples were prepared by mixing ground bauxite with slag. Optical measurement at high temperature (1450 °C) of deformation with a high-resolution camera has been developed. Image processing allowed for determining the change in diameter of the sample. We showed that the deformation was induced by the precipitation of new expansive crystallised phases observed by SEM-EDS analyses. Adding pellets of the same slag upon the samples allowed to emphasize the effect of the slag amount on the size change. The change in diameter significantly increased in the impregnated area.

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.

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 .

Apatite-hosted melt inclusions in Damiao massif anorthosite complex, North China

NASA Astrophysics Data System (ADS)

Wang, M.; Veksler, I. V.; Zhang, Z.

2014-12-01

Models for the nelsonite formation are currently highly contentious, with liquid immiscibility and fractional crystallization as frequently proposed formation mechanisms. The nelsonites in the Damiao massif anorthosite complex in the North China Craton and experimental evidence are revisited for the existence of silica-free CaO-FeO-Fe2O3-TiO2-P2O5 immiscible nelsonitic liquids. Our results of differential scanning calorimetry (DSC) demonstrate that nelsonite with the composition of one-third apatite and two-thirds Fe-Ti oxides by weight completely melts well above 1450 ºC, which is in good agreement with numerous experimental studies of the CaO-P2O5-FexO system in connection to metallurgy. Thus, the composition cannot be molten at temperatures relevant for crystallization of the Damiao magma. A review of experimental studies of liquid immiscibility and analyses of natural immiscible glasses show that all the liquids on the Fe- and P-rich side of the miscibility gap have at least 20 wt. % of aluminosilicate components. Main results of this study come from the analyses of apatite-hosted melt inclusions in Damiao nelsonite. The inclusions range from ~3 to 200 μm in diameter. They are ubiquitous and meet all the morphological criteria of primary melt inclusions crystallised into assemblages of daughter minerals. Almost all of them contain vermiculite and chlorite, and some contain biotite, amphibole, phlogopite and Fe-Ti oxides. Out of dozens analysed inclusions, only three have high contents of SiO2 (62.1-73.8 wt. %) and low contents of FeO (0.25-2.35 wt. %). Bulk compositions of other inclusions show large variations in SiO2 (20.79-50.16 wt. %) and FeOt (13.44-32.78 wt. %). With a few exceptions, the inclusions are very low in CaO (0.04-1.51 wt. %, and high in Al2O3 (10-21.17 wt. %). Despite the high Fe content, the compositions differ from those of the typical immiscible Fe-rich melts. It appears that the cumulus apatite crystallised from Fe-rich, hydrated silicate melt. We propose that the inclusions at Damiao record a trend of intercumulus melt evolution, which was strongly affected by separation of a hydrothermal fluid phase and the losses of alkali and Ca silicate components from the melt into the fluid.

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

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.

Nanofluid based on self-nanoencapsulated metal/metal alloys phase change materials with tuneable crystallisation temperature.

PubMed

Navarrete, Nuria; Gimeno-Furio, Alexandra; Mondragon, Rosa; Hernandez, Leonor; Cabedo, Luis; Cordoncillo, Eloisa; Julia, J Enrique

2017-12-14

Nanofluids using nanoencapsulated Phase Change Materials (nePCM) allow increments in both the thermal conductivity and heat capacity of the base fluid. Incremented heat capacity is produced by the melting enthalpy of the nanoparticles core. In this work two important advances in this nanofluid type are proposed and experimentally tested. It is firstly shown that metal and metal alloy nanoparticles can be used as self-encapsulated nePCM using the metal oxide layer that forms naturally in most commercial synthesis processes as encapsulation. In line with this, Sn/SnOx nanoparticles morphology, size and thermal properties were studied by testing the suitability and performance of encapsulation at high temperatures and thermal cycling using a commercial thermal oil (Therminol 66) as the base fluid. Secondly, a mechanism to control the supercooling effect of this nePCM type based on non-eutectic alloys was developed.

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.

Phase transitions in colloidal fluids: Kinetically or thermodynamically controlled?

NASA Astrophysics Data System (ADS)

Duran-Olivencia, Miguel A.; Yatsyshin, Peter; Lutsko, James F.; Kalliadasis, Serafim

2017-11-01

In recent years, a flurry of experimental observations suggests that most phase transitions occur in a multistage manner and via intermediate phases. These precursors to the final phase are commonly understood as the local minima of the free energy of the system. Inherently, the classical paradigm of nucleation has no capacity to describe neither the origin nor the role played by these precursors in the nucleation pathway. Here we present a systematic theoretical framework capable of describing the precursor phases in a self-consistent way. We demonstrate that nucleation precursors can appear even in situations involving a single free-energy barrier. This contradicts previous phenomenological approaches, which always characterise intermediate phases as the minima of a complex free-energy landscape. We show that a kinetically-induced mechanism temporarily stabilises an intermediate phase, which thus is not the result of a local minimum of the free energy but a consequence of the entropic cost of cluster formation. Moreover, the appearance of precursors does not seem to influence the overall nucleation time, which is governed by the free-energy barrier. The mechanism uncovered in this study can be used to explain recently reported experimental findings in crystallisation. European Research Council - Advanced Grant No. 247031; Engineering and Physical Sciences Research Council - Grant Nos. EP/L020564 and EP/L025159.

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.

Formation of the Vysoká-Zlatno Cu-Au skarn-porphyry deposit, Slovakia

NASA Astrophysics Data System (ADS)

Koděra, Peter; Lexa, Jaroslav; Fallick, Anthony E.

2010-12-01

The central zone of the Miocene Štiavnica stratovolcano hosts several occurrences of Cu-Au skarn-porphyry mineralisation, related to granodiorite/quartz-diorite porphyry dyke clusters and stocks. Vysoká-Zlatno is the largest deposit (13.4 Mt at 0.52% Cu), with mineralised Mg-Ca exo- and endoskarns, developed at the prevolcanic basement level. The alteration pattern includes an internal K- and Na-Ca silicate zone, surrounded by phyllic and argillic zones, laterally grading into a propylitic zone. Fluid inclusions in quartz veinlets in the internal zone contain mostly saline brines with 31-70 wt.% NaCl eq. and temperatures of liquid-vapour homogenization (Th) of 186-575°C, indicating fluid heterogenisation. Garnet contains inclusions of variable salinity with 1-31 wt.% NaCl eq. and Th of 320-360°C. Quartz-chalcopyrite veinlets host mostly low-salinity fluid inclusions with 0-3 wt.% NaCl eq. and Th of 323-364°C. Data from sphalerite from the margin of the system indicate mixing with dilute and cooler fluids. The isotopic composition of fluids in equilibrium with K-alteration and most skarn minerals (both prograde and retrograde) indicates predominantly a magmatic origin (δ18Ofluid 2.5-12.3‰) with a minor meteoric component. Corresponding low δDfluid values are probably related to isotopic fractionation during exsolution of the fluid from crystallising magma in an open system. The data suggest the general pattern of a distant source of magmatic fluids that ascended above a zone of hydraulic fracturing below the temperature of ductile-brittle transition. The magma chamber at ˜5-6 km depth exsolved single-phase fluids, whose properties were controlled by changing PT conditions along their fluid paths. During early stages, ascending fluids display liquid-vapour immiscibility, followed by physical separation of both phases. Low-salinity liquid associated with ore veinlets probably represents a single-phase magmatic fluid/magmatic vapour which contracted into liquid upon its ascent.

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.

The origin of secondary heavy rare earth element enrichment in carbonatites: Constraints from the evolution of the Huanglongpu district, China

NASA Astrophysics Data System (ADS)

Smith, M.; Kynicky, J.; Xu, Cheng; Song, Wenlei; Spratt, J.; Jeffries, T.; Brtnicky, M.; Kopriva, A.; Cangelosi, D.

2018-05-01

The silico‑carbonatite dykes of the Huanglongpu area, Lesser Qinling, China, are unusual in that they are quartz-bearing, Mo-mineralised and enriched in the heavy rare earth elements (HREE) relative to typical carbonatites. The textures of REE minerals indicate crystallisation of monazite-(Ce), bastnäsite-(Ce), parisite-(Ce) and aeschynite-(Ce) as magmatic phases. Burbankite was also potentially an early crystallising phase. Monazite-(Ce) was subsequently altered to produce a second generation of apatite, which was in turn replaced and overgrown by britholite-(Ce), accompanied by the formation of allanite-(Ce). Bastnäsite and parisite where replaced by synchysite-(Ce) and röntgenite-(Ce). Aeschynite-(Ce) was altered to uranopyrochlore and then pyrochlore with uraninite inclusions. The mineralogical evolution reflects the evolution from magmatic carbonatite, to more silica-rich conditions during early hydrothermal processes, to fully hydrothermal conditions accompanied by the formation of sulphate minerals. Each alteration stage resulted in the preferential leaching of the LREE and enrichment in the HREE. Mass balance considerations indicate hydrothermal fluids must have contributed HREE to the mineralisation. The evolution of the fluorcarbonate mineral assemblage requires an increase in aCa2+ and aCO32- in the metasomatic fluid (where a is activity), and breakdown of HREE-enriched calcite may have been the HREE source. Leaching in the presence of strong, LREE-selective ligands (Cl-) may account for the depletion in late stage minerals in the LREE, but cannot account for subsequent preferential HREE addition. Fluid inclusion data indicate the presence of sulphate-rich brines during alteration, and hence sulphate complexation may have been important for preferential HREE transport. Alongside HREE-enriched magmatic sources, and enrichment during magmatic processes, late stage alteration with non-LREE-selective ligands may be critical in forming HREE-enriched carbonatites.

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.

Temperature and pressure tuneable swollen bicontinuous cubic phases approaching nature's length scales.

PubMed

Barriga, H M G; Tyler, A I I; McCarthy, N L C; Parsons, E S; Ces, O; Law, R V; Seddon, J M; Brooks, N J

2015-01-21

Bicontinuous cubic structures offer enormous potential in applications ranging from protein crystallisation to drug delivery systems and have been observed in cellular membrane structures. One of the current bottlenecks in understanding and exploiting these structures is that cubic scaffolds produced in vitro are considerably smaller in size than those observed in biological systems, differing by almost an order of magnitude in some cases. We have addressed this technological bottleneck and developed a methodology capable of manufacturing highly swollen bicontinuous cubic membranes with length scales approaching those seen in vivo. Crucially, these cubic systems do not require the presence of proteins. We have generated highly swollen Im3m symmetry bicontinuous cubic phases with lattice parameters of up to 480 Å, composed of ternary mixtures of monoolein, cholesterol and negatively charged lipid (DOPS or DOPG) and we have been able to tune their lattice parameters. The swollen cubic phases are highly sensitive to both temperature and pressure; these structural changes are likely to be controlled by a fine balance between lipid headgroup repulsions and lateral pressure in the hydrocarbon chain region.

Variation of oxygen content in selected potassium fluorido-oxido-tantalate phases

NASA Astrophysics Data System (ADS)

Boča, Miroslav; Moncoĺ, Ján; Netriová, Zuzana; Velič, Dušan; Jerigová, Monika; Nunney, Tim S.; Baily, Christopher J.; Kubíková, Blanka; Šimko, František; Janderka, Pavel

2011-12-01

The compound K 3[TaO 4]•K 3[TaF 4O 2] crystallises in a tetragonal system (space group I-4) with cell parameters a = 6.2220(3) Å and c = 8.7625(34) Å, respectively. The crystal structure consists of two anions, [TaO 4] 3- and [TaF 4O 2] 3- and cations K +. The tantalum atoms lie in special positions and serve as centres of both anions, which are substitution disorders. XPS measurements confirmed the existence of different binding energies corresponding to the different bonds of Ta sbnd O and Ta sbnd F. Oxygen is bound more strongly in [TaF 4O 2] 3-. By combination of single crystal analysis, XRD, SIMS and XPS it was suggested that previously reported cubic phase K 3TaOF 6 is in fact K 3TaO 2F 4 and previously reported tetragonal phase K 3TaO 2F 4 is in fact K 3[TaO 4]•K 3[TaF 4O 2].

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.

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.

PHOTONICS AND NANOTECHNOLOGY Laser nanostructuring of materials surfaces

NASA Astrophysics Data System (ADS)

Zavestovskaya, I. N.

2010-12-01

This paper reviews results of experimental and theoretical studies of surface micro- and nanostructuring of metals and other materials irradiated directly by short and ultrashort laser pulses. Special attention is paid to direct laser action involving melting of the material (with or without ablation), followed by ultrarapid surface solidification, which is an effective approach to producing surface nanostructures. Theoretical analysis of recrystallisation kinetics after irradiation by ultrashort laser pulses makes it possible to determine the volume fraction of crystallised phase and the average size of forming crystalline structures as functions of laser treatment regime and thermodynamic properties of the material. The present results can be used to optimise pulsed laser treatment regime in order to ensure control nanostructuring of metal surfaces.

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.

The influence of phosphorus precursors on the synthesis and bioactivity of SiO2-CaO-P 2O 5 sol-gel glasses and glass-ceramics.

PubMed

Siqueira, Renato Luiz; Zanotto, Edgar Dutra

2013-02-01

Bioactive glasses and glass-ceramics of the SiO(2)-CaO-P(2)O(5) system were synthesised by means of a sol-gel method using different phosphorus precursors according to their respective rates of hydrolysis-triethylphosphate (OP(OC(2)H(5))(3)), phosphoric acid (H(3)PO(4)) and a solution prepared by dissolving phosphorus oxide (P(2)O(5)) in ethanol. The resulting materials were characterised by differential scanning calorimetry and thermogravimetry, X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy and by in vitro bioactivity tests in acellular simulated body fluid. The different precursors significantly affected the main steps of the synthesis, beginning with the time required for gel formation. The most striking influence of these precursors was observed during the thermal treatments at 700-1,200 °C that were used to convert the gels into glasses and glass-ceramics. The samples exhibited very different mineralisation behaviours; especially those prepared using the phosphoric acid, which had a reduced onset temperature of crystallisation and an increased resistance to devitrification. However, all resulting materials were bioactive. The in vitro bioactivity of these materials was strongly affected by the heat treatment temperature. In general, their bioactivity decreased with increasing treatment temperature. For crystallised samples obtained above 900 °C, the bioactivity was favoured by the presence of two crystalline phases: wollastonite (CaSiO(3)) and tricalcium phosphate (α-Ca(3)(PO(4))(2)).

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.

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.

CO2-rich phonolitic melt and carbonatite immiscibility in melt inclusions in nephelinite (Hanang volcano, North Tanzanian Divergence, East African Rift).

NASA Astrophysics Data System (ADS)

Baudouin, C.; Parat, F.

2016-12-01

Hanang is the southern volcano of the East branch of the East African Rift and represents volcanic activity at early stage rifting (0.9 Ma). Lavas are highly alkaline Mg-poor nephelinites (Mg#=24.4-35.2) with cpx, garnet, nepheline, titanite, and apatite and result from fractional crystallisation of primary melilitite magmas (Parat et al. AGU2016). In this study, we investigate glassy melt inclusions at the rim of nepheline phenocrysts to constrain the late stage of nephelinite evolution and the behaviour of volatiles (CO2, H2O, S, F, Cl) during magma storage and ascent. The melt inclusions have a green silicate glass, a microcrystalline carbonate phase and a shrinkage bubble free of gas phase (Raman analyses) suggesting that carbonatite-silicate liquid immiscibility (85:15) occurred during nephelinite differentiation. The silicate glasses have trachytic composition (Na+K/Al=1.6-7.2, SiO2=54-65.5 wt%) with high CO2 (0.43 wt% CO2, SIMS analyses), sulfur (0.21-0.92 wt% S) and halogens (0.28-0.84 wt% Cl; 0.35-2.54 wt% F) content and very low H2O content (<0.1wt%, Raman analyses). The carbonate phase is an anhydrous Ca-Na±S,K- carbonate with 33 wt% CaO, 20 wt% Na2O, 3 wt% K2O, and 3 wt% S. The pre-immiscible silicate liquid (e.g. silicate melt + carbonatite) in equilibrium with nepheline and cpx phenocrysts has CO2-rich phonolitic composition (Na+K/Al=6.2-6.9) with 6 ± 1.5 wt% CO2 at pressure of 700-1100 MPa. The entrapped melt in nepheline corresponds to evolved interstitial silicate melt after crystallisation of cpx (16.7%), nepheline (40%) garnet (6.5%) and apatite (1.7%) from Mg-nephelinite magma. The immiscibility process leading to glassy silicate melt and microcrystalline carbonatitic melt occurred in closed system during rapid ascent at crustal level at 200-230 MPa. The absence of gas phase in shrinkage bubble in melt inclusions suggests CO2-undersaturated conditions during quenching. The absence of carbonatite lavas at Hanang volcano is then explained by open system differentiation with primary melilititic magma replenishment preventing alkaline enrichment and carbonatite-silicate liquid immiscibility at depth as observed for the nephelinite-natrocarbonatite Oldoinyo Lengai volcano in the Natron Basin (150 km north).

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.

Modelling the effect of acoustic waves on the thermodynamics and kinetics of phase transformation in a solution: Including mass transportation

NASA Astrophysics Data System (ADS)

Haqshenas, S. R.; Ford, I. J.; Saffari, N.

2018-01-01

Effects of acoustic waves on a phase transformation in a metastable phase were investigated in our previous work [S. R. Haqshenas, I. J. Ford, and N. Saffari, "Modelling the effect of acoustic waves on nucleation," J. Chem. Phys. 145, 024315 (2016)]. We developed a non-equimolar dividing surface cluster model and employed it to determine the thermodynamics and kinetics of crystallisation induced by an acoustic field in a mass-conserved system. In the present work, we developed a master equation based on a hybrid Szilard-Fokker-Planck model, which accounts for mass transportation due to acoustic waves. This model can determine the kinetics of nucleation and the early stage of growth of clusters including the Ostwald ripening phenomenon. It was solved numerically to calculate the kinetics of an isothermal sonocrystallisation process in a system with mass transportation. The simulation results show that the effect of mass transportation for different excitations depends on the waveform as well as the imposed boundary conditions and tends to be noticeable in the case of shock waves. The derivations are generic and can be used with any acoustic source and waveform.

Modelling the effect of acoustic waves on the thermodynamics and kinetics of phase transformation in a solution: Including mass transportation.

PubMed

Haqshenas, S R; Ford, I J; Saffari, N

2018-01-14

Effects of acoustic waves on a phase transformation in a metastable phase were investigated in our previous work [S. R. Haqshenas, I. J. Ford, and N. Saffari, "Modelling the effect of acoustic waves on nucleation," J. Chem. Phys. 145, 024315 (2016)]. We developed a non-equimolar dividing surface cluster model and employed it to determine the thermodynamics and kinetics of crystallisation induced by an acoustic field in a mass-conserved system. In the present work, we developed a master equation based on a hybrid Szilard-Fokker-Planck model, which accounts for mass transportation due to acoustic waves. This model can determine the kinetics of nucleation and the early stage of growth of clusters including the Ostwald ripening phenomenon. It was solved numerically to calculate the kinetics of an isothermal sonocrystallisation process in a system with mass transportation. The simulation results show that the effect of mass transportation for different excitations depends on the waveform as well as the imposed boundary conditions and tends to be noticeable in the case of shock waves. The derivations are generic and can be used with any acoustic source and waveform.

Degradation studies on highly oriented poly(glycolic acid) fibres with different lamellar structures.

PubMed

de Oca, Horacio Montes; Farrar, David F; Ward, Ian M

2011-04-01

Highly oriented poly(glycolic acid) (PGA) fibres with an initial tensile strength of 1.1 GPa and different lamellar morphologies were prepared and studied during degradation in aqueous media at 37°C. A combination of small- and wide-angle X-ray scattering was used to study the structural changes during degradation and to generate two structural models of highly oriented PGA fibres with different lamellar morphologies. It is shown that as a result of crystallisation during degradation PGA crystals grow preferentially along the (110) and (020) directions of the crystal lattice or perpendicular to the orientation direction of the fibres. (1)H nuclear magnetic resonance measurements revealed three phases within the fibres with different relaxation times: (1) a mobile amorphous phase with a short relaxation time; (2) a semi-rigid phase with an intermediate relaxation time; (3) a rigid crystalline phase with a longer relaxation time. It is shown that the mobile amorphous phase degrades very rapidly and that it plays only a small role in the tensile mechanical behaviour of the fibres during degradation. It is shown that semi-rigid chains connecting crystalline domains are responsible for transferring the stress between crystalline domains and carrying the tensile deformation. It is proposed that once these tie molecules degrade considerably the oriented fibres very rapidly lose their strength retention. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Partitioning of Mg, Ca, and Na between carbonatite melt and hydrous fluid at 0.1-0.2 GPa

NASA Astrophysics Data System (ADS)

Veksler, Ilya V.; Keppler, Hans

Experimental studies of the element distribution between carbonatite melts and hydrous fluids are hampered by the fact that neither the fluid nor the melt can be isochemically quenched in conventional high-pressure vessels. In order to overcome this problem, we used a double-capsule technique to separate immiscible fluid and melt phases during and after the runs. The inner platinum capsules were charged with carbonate mixtures (CaCO3, MgCO3 and Na2CO3) and placed inside the outer capsules charged with distilled water and diamond powder. The latter was used as an inert trap for solids precipitating from the fluid on quenching. Carbonate melt and hydrous fluid equilibrated through a small hole left in the upper end of the inner capsule. The runs were performed in rapid-quench cold-seal pressure vessels at 0.1-0.2 GPa and 700-900°C in the two-phase (fluid+melt) stability region. Both quenched melt and quenched fluid were dissolved in dilute HCl and analysed by inductively coupled plasma atomic emission spectroscopy. The results show that under all conditions investigated, fluid/melt partition coefficients for Ca and Mg are similar and several times smaller than those for Na. At 0.1 GPa and a water/carbonatite ratio of 1 (by weight), the partition coefficients are DNa= 0.35+/- 0.02, DCa=0.09+/-0.02, and DMg=0.13+/- 0.01. Between 700 and 900°C, the effect of temperature on partitioning is negligible. However, DNa increases significantly with decreasing water/carbonatite ratio in the system. Our data show that the release of a hydrous fluid enriched in sodium and simultaneous crystallisation of calcite can transform an alkaline, vapour-saturated carbonatite melt into a body of pure calcite surrounded by zones of sodium metasomatism. Thus, it is quite possible that carbonate magmas with substantial amounts of alkalies were common parental liquids of plutonic carbonatites.

Magmatic Longevity Constrained by ID-TIMS U-Pb Dating of Zircon and Titanite

NASA Astrophysics Data System (ADS)

Szymanowski, D.; Wotzlaw, J. F.; Ellis, B. S.; Bachmann, O.; Von Quadt, A.

2016-12-01

Clues about the timescales and thermal conditions associated with the growth and evacuation of large silicic magma reservoirs are frequently drawn from radiometric dating, diffusion modelling, or thermomechanical modelling. A growing amount of petrological and geochronological evidence, supported by thermal modelling, suggests that many silicic magma reservoirs may exist for some 104-106 years in the form of high-crystallinity mushes at relatively low temperatures ( 700-750°C; [1-3]). Geochronological studies addressing this issue typically utilise the U-Pb system in zircon capable of recording extended periods of crystallisation, particularly in evolved calc-alkaline systems that spend most of their lifetime zircon-saturated. In this study, we integrate U-Pb dating of zircon and titanite to investigate the longevity of the magma reservoir that produced the Kneeling Nun Tuff, a 35 Ma, >900 km3 crystal-rich rhyolitic super-eruption from the Mogollon-Datil volcanic field in New Mexico (USA). High-precision ID-TIMS U-Pb dates of single crystals of both zircon and titanite independently record a continuous crystallisation history over >400,000 years. We combine the dating of both accessory phases with textural, major, trace element and isotopic studies of single crystals, placing tight constraints on the thermal conditions of magma accumulation and storage while recording differentiation and rejuvenation processes within the magma reservoir. The results suggest a protracted `cool' upper-crustal storage of magma prior to the Kneeling Nun Tuff eruption followed by a melting event which reduced the magma crystallinity and conditioned it for eruption. [1] Bachmann & Bergantz (2004), J. Petrol. 45, 1565-1582. [2] Gelman et al. (2013), Geology 41, 759-762. [3] Cooper & Kent (2014), Nature 506, 480-483.

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.

Tautomeric and ionisation forms of dopamine and tyramine in the solid state

NASA Astrophysics Data System (ADS)

Cruickshank, Laura; Kennedy, Alan R.; Shankland, Norman

2013-11-01

Crystallisation of the phenylethylamine neurotransmitter dopamine from basic aqueous solution yielded the 3-phenoxide Zwitterionic tautomer, despite this being a minority form in the solution state. In the crystal structure, dopamine has a dimeric [OCCOH]2 hydrogen bonded catechol motif that expands through Nsbnd H⋯O interactions to give a 2-dimensional sheet of classical hydrogen bonds. These sheets are further interconnected by Nsbnd H⋯π interactions. The structurally related base tyramine crystallises under similar conditions as a hemihydrate with all four possible species of tyramine present (cationic, anionic, Zwitterionic and neutral) in the crystal structure. Single crystal X-ray diffraction studies at 121 and 293 K showed dynamic hydrogen atom disorder for the phenol/phenoxide group, suggesting that the tyramine speciation observed arises from a solid-state process.

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.

Investigations on nonlinear absorption and nonlinear refraction of a new photonic crystal using Z-scan

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

Shetty, T. C. S., E-mail: tcsshetty@gmail.com; Department of Post Graduate Studies in Physics, St Aloysius College; Sandeep, K. M.

A new photonic material, (2E)-1-(3-chlorophenyl)-3-(2,4-dichlorophenyl)prop-2-en-1-one (DCPP) was synthesized and crystallised at room temperature. The functional groups of synthesised material were confirmed using FT-IR. The third order nonlinear optical (NLO) properties were investigated using Z-scan technique with 5 ns Nd:YAG laser pulses operating at a wavelength of 532 nm. Linear absorption spectrum of DCPP crystals shows an optical transmittance window and a lower cutoff wavelength of absorption at 380 nm. The direct transition band gap energy was determined using Tauc’s plot. The melting point and thermal stability of the crystal have been investigated by thermo gravimetric analysis/differential thermal analysis (TGA/DTA). Themore » Thermo gravimetric curve showed absence of any phase transition before melting point.« less

Solid-state polymerisation via [2+2] cycloaddition reaction involving coordination polymers.

PubMed

Medishetty, Raghavender; Park, In-Hyeok; Lee, Shim Sung; Vittal, Jagadese J

2016-03-14

Highly crystalline metal ions containing organic polymers are potentially useful to manipulate the magnetic and optical properties to make advanced multifunctional materials. However, it is challenging to synthesise monocrystalline metal complexes of organic polymers and single-phase hybrid materials made up of both coordination and organic polymers by traditional solution crystallisation. This requires an entirely different approach in the solid-state by thermal or photo polymerisation of the ligands. Among the photochemical methods available, [2+2] cycloaddition reaction has been recently employed to generate cyclobutane based coordination polymers from the metal complexes. Cyclobutane polymers have also been integrated into coordination polymers in this way. Recent advancements in the construction of polymeric chains of cyclobutane rings through photo-dimerisation reaction in the monocrystalline solids containing metal complexes, coordination polymers and metal-organic framework structures are discussed here.

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.

From micron to mountain-scale, using accessory phase petrochronology to quantify the rates of deformation in the Himalaya and beyond

NASA Astrophysics Data System (ADS)

Mottram, C. M.

2016-12-01

Mountains form where the Earth's plates collide; during this upheaval rocks are deformed by massive forces. The rates and timescales over which these deformational processes occur are determined from tiny accessory minerals that record geological time through radioactive decay. However, there remain major unresolved challenges in using chemical and microstructural markers to link the dates yielded from these accessory phases to specific deformation events and discerning the effects of deformation on the isotopic and elemental tracers in these phases. Here, the chemical signatures and deformation textures from micron-scale accessory phases are used to decode the record of mountain belt-scale deformational processes encrypted in the rocks. The Himalayan orogen is used as an ideal natural laboratory to understand the chemical processes that have modified the Earth's crust during orogenesis. Combined laser ablation split-stream U-Th-Pb and REE analysis of deformed monazite and titanite, along with Electron BackScatter Diffraction (EBSD) imaging and Pressure-Temperature (P-T) phase equilibria modelling are used to: (1) link accessory phase `age' to `metamorphic stage'; (2) to quantify the influence of deformation on monazite (re)crystallisation mechanisms and its subsequent effect on the crystallographic structure, ages and trace-element distribution in individual grains; and (3) understand how deformation is accommodated through different chemical and structural processes that operate at varying scales through time. This study highlights the importance of fully integrating the pressure-temperature-time-deformation history of multiple accessory phases to better interpret the deformational history of the cores of evolving mountain belts.

Modification of the solid-state nature of sulfathiazole and sulfathiazole sodium by spray drying.

PubMed

Bianco, Stefano; Caron, Vincent; Tajber, Lidia; Corrigan, Owen I; Nolan, Lorraine; Hu, Yun; Healy, Anne Marie

2012-06-01

Solid-state characterisation of a drug following pharmaceutical processing and upon storage is fundamental to successful dosage form development. The aim of the study was to investigate the effects of using different solvents, feed concentrations and spray drier configuration on the solid-state nature of the highly polymorphic model drug, sulfathiazole (ST) and its sodium salt (STNa). The drugs were spray-dried from ethanol, acetone and mixtures of these organic solvents with water. Additionally, STNa was spray-dried from pure water. The physicochemical properties including the physical stability of the spray-dried powders were compared to the unprocessed materials. Spray drying of ST from either acetonic or ethanolic solutions with the spray drier operating in a closed cycle mode yielded crystalline powders. In contrast, the powders obtained from ethanolic solutions with the spray drier operating in an open cycle mode were amorphous. Amorphous ST crystallised to pure form I at ≤35 % relative humidity (RH) or to polymorphic mixtures at higher RH values. The usual crystal habit of form I is needle-like, but spherical particles of this polymorph were generated by spray drying. STNa solutions resulted in an amorphous material upon processing, regardless of the solvent and the spray drier configuration employed. Moisture induced crystallisation of amorphous STNa to a sesquihydrate, whilst crystallisation upon heating gave rise to a new anhydrous polymorph. This study indicated that control of processing and storage parameters can be exploited to produce drugs with a specific/desired solid-state nature.

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.

Experimental observations on noble metal nanonuggets and Fe-Ti oxides, and the transport of platinum group elements in silicate melts

NASA Astrophysics Data System (ADS)

Anenburg, Michael; Mavrogenes, John A.

2016-11-01

Platinum group element (PGE) nanonuggets are a nuisance in experimental studies designed to measure solubility or partitioning of noble metals in silicate melts. Instead of treating nanonuggets as experimental artifacts, we studied their behaviour motivated by recent discoveries of PGE nanonuggets in a variety of natural settings. We used an experimental setup consisting of AgPd, Pt or AuPd capsules and Fe(-Ti) oxide-saturated hydrous peralkaline silicate melts to maximise nanonugget production. TABS (Te, As, Bi, Sb, Sn) commonly occur in PGM (platinum group minerals), prompting addition of Bi to our experiments to investigate its properties as well. Three-dimensional optical examination by 100× objective and immersion oil reveals variable colour which correlates with nanonugget size and shape due to plasmon resonance effects. We observe two textural types: (1) intermediate-sized nanonuggets dispersed in the glass and adhering to oxides, and (2) abundant fine nanonuggets dispersed in the glass with coarse euhedral crystals in contact with oxides. Slow cooling removes dispersed nanonuggets and greatly coarsens existing oxide-associated metal crystals. Nanonugget-free halos are commonly observed around oxide grains. All metal phases are composed of major (Ag, Pd) and trace (Pt, Ir, Au) capsule material. Our results show reduction processes, imposed by growing oxides, causing local metal saturation in the oxide rich zones with preferential nucleation on smaller oxide grains. The redox gradient then blocks additional metals from diffusing into oxide rich zones, forming halos. As the entire experimental charge is reduced throughout the run, nanonuggets form in the distal glass. Bismuth contents of metal phases do not depend on Bi2O3 amounts dissolved in the melt. Further PGM crystallisation consumes nanonuggets as feedstock. We conclude that the appearance of metallic PGE phases happens in two stages: first as nanonuggets and then as larger PGM. Once formed, nanonuggets cannot be removed by oxidation or dissolution, but only by PGM coarsening. Sulfur-poor PGE ore deposits commonly contain more PGE than permitted by existing estimates of equilibrium solubility in silicate melts. This is commonly explained by initial scavenging of PGE by sulfide liquids followed by S-loss, but evidence for S-loss is not conclusive. We suggest that nanonuggets may be a means to transport PGE from source regions to form ore deposits, followed by direct PGM crystallisation from silicate melt without intermediate concentration by sulfide liquids.

Effects of coformers on phase transformation and release profiles of carbamazepine cocrystals in hydroxypropyl methylcellulose based matrix tablets.

PubMed

Qiu, Shi; Li, Mingzhong

2015-02-01

The aim of this study was to investigate the effects of coformers on phase transformation and release profiles of carbamazepine (CBZ) cocrystals in hydroxypropyl methylcellulose (HPMC) based matrix tablets. It has been found that selection of different coformers of saccharin (SAC) and cinnamic acid (CIN) can affect the stability of CBZ cocrystals in solution, resulting in significant differences in the apparent solubility of CBZ. The dissolution advantage of CBZ-SAC cocrystals can only be shown for a short period during dissolution because of the fast conversion to its dihydrate form (DH). HPMC can partially inhibit the crystallisation of CBZ DH during dissolution of CBZ-SAC cocrystal. However, the increased viscosity of HPMC dissolution medium reduced the dissolution rate of CBZ-SAC cocrystals. Therefore the CBZ-SAC cocrystal formulation did not show any significant advantage in CBZ release rate. In contrast the improved CBZ dissolution rate of CBZ-CIN cocrystal can be realised in both solution and formulation due to its high stability. In conclusion, exploring and understanding the mechanisms of the phase transformation of pharmaceutical cocrystals in aqueous medium for selection of lead cocrystals is the key for success of product development. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

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.

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.

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.

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.

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.

Photo-stability study of a solution-processed small molecule solar cell system: correlation between molecular conformation and degradation

PubMed Central

Newman, Michael J.; Speller, Emily M.; Barbé, Jérémy; Luke, Joel; Li, Meng; Li, Zhe; Wang, Zhao-Kui; Jain, Sagar M.; Kim, Ji-Seon; Lee, Harrison Ka Hin; Tsoi, Wing Chung

2018-01-01

Abstract Solution-processed organic small molecule solar cells (SMSCs) have achieved efficiency over 11%. However, very few studies have focused on their stability under illumination and the origin of the degradation during the so-called burn-in period. Here, we studied the burn-in period of a solution-processed SMSC using benzodithiophene terthiophene rhodamine:[6,6]-phenyl C71 butyric acid methyl ester (BTR:PC71BM) with increasing solvent vapour annealing time applied to the active layer, controlling the crystallisation of the BTR phase. We find that the burn-in behaviour is strongly correlated to the crystallinity of BTR. To look at the possible degradation mechanisms, we studied the fresh and photo-aged blend films with grazing incidence X-ray diffraction, UV–vis absorbance, Raman spectroscopy and photoluminescence (PL) spectroscopy. Although the crystallinity of BTR affects the performance drop during the burn-in period, the degradation is found not to originate from the crystallinity changes of the BTR phase, but correlates with changes in molecular conformation – rotation of the thiophene side chains, as resolved by Raman spectroscopy which could be correlated to slight photobleaching and changes in PL spectra. PMID:29511397

Photo-stability study of a solution-processed small molecule solar cell system: correlation between molecular conformation and degradation.

PubMed

Newman, Michael J; Speller, Emily M; Barbé, Jérémy; Luke, Joel; Li, Meng; Li, Zhe; Wang, Zhao-Kui; Jain, Sagar M; Kim, Ji-Seon; Lee, Harrison Ka Hin; Tsoi, Wing Chung

2018-01-01

Solution-processed organic small molecule solar cells (SMSCs) have achieved efficiency over 11%. However, very few studies have focused on their stability under illumination and the origin of the degradation during the so-called burn-in period. Here, we studied the burn-in period of a solution-processed SMSC using benzodithiophene terthiophene rhodamine:[6,6]-phenyl C 71 butyric acid methyl ester (BTR:PC 71 BM) with increasing solvent vapour annealing time applied to the active layer, controlling the crystallisation of the BTR phase. We find that the burn-in behaviour is strongly correlated to the crystallinity of BTR. To look at the possible degradation mechanisms, we studied the fresh and photo-aged blend films with grazing incidence X-ray diffraction, UV-vis absorbance, Raman spectroscopy and photoluminescence (PL) spectroscopy. Although the crystallinity of BTR affects the performance drop during the burn-in period, the degradation is found not to originate from the crystallinity changes of the BTR phase, but correlates with changes in molecular conformation - rotation of the thiophene side chains, as resolved by Raman spectroscopy which could be correlated to slight photobleaching and changes in PL spectra.

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.

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

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...

Effect of the Hartmann number on phase separation controlled by magnetic field for binary mixture system with large component ratio

NASA Astrophysics Data System (ADS)

Heping, Wang; Xiaoguang, Li; Duyang, Zang; Rui, Hu; Xingguo, Geng

2017-11-01

This paper presents an exploration for phase separation in a magnetic field using a coupled lattice Boltzmann method (LBM) with magnetohydrodynamics (MHD). The left vertical wall was kept at a constant magnetic field. Simulations were conducted by the strong magnetic field to enhance phase separation and increase the size of separated phases. The focus was on the effect of magnetic intensity by defining the Hartmann number (Ha) on the phase separation properties. The numerical investigation was carried out for different governing parameters, namely Ha and the component ratio of the mixed liquid. The effective morphological evolutions of phase separation in different magnetic fields were demonstrated. The patterns showed that the slant elliptical phases were created by increasing Ha, due to the formation and increase of magnetic torque and force. The dataset was rearranged for growth kinetics of magnetic phase separation in a plot by spherically averaged structure factor and the ratio of separated phases and total system. The results indicate that the increase in Ha can increase the average size of separated phases and accelerate the spinodal decomposition and domain growth stages. Specially for the larger component ratio of mixed phases, the separation degree was also significantly improved by increasing magnetic intensity. These numerical results provide guidance for setting the optimum condition for the phase separation induced by magnetic field.

A novel mechanical model for phase-separation in debris flows

NASA Astrophysics Data System (ADS)

Pudasaini, Shiva P.

2015-04-01

Understanding the physics of phase-separation between solid and fluid phases as a two-phase mass moves down slope is a long-standing challenge. Here, I propose a fundamentally new mechanism, called 'separation-flux', that leads to strong phase-separation in avalanche and debris flows. This new model extends the general two-phase debris flow model (Pudasaini, 2012) to include a separation-flux mechanism. The new flux separation mechanism is capable of describing and controlling the dynamically evolving phase-separation, segregation, and/or levee formation in a real two-phase, geometrically three-dimensional debris flow motion and deposition. These are often observed phenomena in natural debris flows and industrial processes that involve the transportation of particulate solid-fluid mixture material. The novel separation-flux model includes several dominant physical and mechanical aspects that result in strong phase-separation (segregation). These include pressure gradients, volume fractions of solid and fluid phases and their gradients, shear-rates, flow depth, material friction, viscosity, material densities, boundary structures, gravity and topographic constraints, grain shape, size, etc. Due to the inherent separation mechanism, as the mass moves down slope, more and more solid particles are brought to the front, resulting in a solid-rich and mechanically strong frontal surge head followed by a weak tail largely consisting of the viscous fluid. The primary frontal surge head followed by secondary surge is the consequence of the phase-separation. Such typical and dominant phase-separation phenomena are revealed here for the first time in real two-phase debris flow modeling and simulations. However, these phenomena may depend on the bulk material composition and the applied forces. Reference: Pudasaini, Shiva P. (2012): A general two-phase debris flow model. J. Geophys. Res., 117, F03010, doi: 10.1029/2011JF002186.

Multiple fuel supply system for an internal combustion engine

DOEpatents

Crothers, William T.

1977-01-01

A multiple fuel supply or an internal combustion engine wherein phase separation of components is deliberately induced. The resulting separation permits the use of a single fuel tank to supply components of either or both phases to the engine. Specifically, phase separation of a gasoline/methanol blend is induced by the addition of a minor amount of water sufficient to guarantee separation into an upper gasoline phase and a lower methanol/water phase. A single fuel tank holds the two-phase liquid with separate fuel pickups and separate level indicators for each phase. Either gasoline or methanol, or both, can be supplied to the engine as required by predetermined parameters. A fuel supply system for a phase-separated multiple fuel supply contained in a single fuel tank is described.

Phase-separation induced extraordinary toughening of magnetic hydrogels

NASA Astrophysics Data System (ADS)

Tang, Jingda; Li, Chenghai; Li, Haomin; Lv, Zengyao; Sheng, Hao; Lu, Tongqing; Wang, T. J.

2018-05-01

Phase separation markedly influences the physical properties of hydrogels. Here, we find that poly (N, N-dimethylacrylamide) (PDMA) hydrogels suffer from phase separation in aqueous sodium hydroxide solutions when the concentration is higher than 2 M. The polymer volume fraction and mechanical properties show an abrupt change around the transition point. We utilize this phase separation mechanism to synthesize tough magnetic PDMA hydrogels with the in-situ precipitation method. For comparison, we also prepared magnetic poly (2-acrylamido-2-methyl-propane sulfonic acid sodium) (PNaAMPS) magnetic hydrogels, where no phase separation occurs. The phase-separated magnetic PDMA hydrogels exhibit an extraordinarily high toughness of ˜1000 J m-2; while non-phase-separated magnetic PNaAMPS hydrogels only show a toughness of ˜1 J m-2, three orders of magnitude lower than that of PDMA hydrogels. This phase separation mechanism may become a new approach to prepare tough magnetic hydrogels and inspire more applications.

Phase-separated, epitaxial composite cap layers for electronic device applications and method of making the same

DOEpatents

Aytug, Tolga [Knoxville, TN; Paranthaman, Mariappan Parans [Knoxville, TN; Polat, Ozgur [Knoxville, TN

2012-07-17

An electronic component that includes a substrate and a phase-separated layer supported on the substrate and a method of forming the same are disclosed. The phase-separated layer includes a first phase comprising lanthanum manganate (LMO) and a second phase selected from a metal oxide (MO), metal nitride (MN), a metal (Me), and combinations thereof. The phase-separated material can be an epitaxial layer and an upper surface of the phase-separated layer can include interfaces between the first phase and the second phase. The phase-separated layer can be supported on a buffer layer comprising a composition selected from the group consisting of IBAD MgO, LMO/IBAD-MgO, homoepi-IBAD MgO and LMO/homoepi-MgO. The electronic component can also include an electronically active layer supported on the phase-separated layer. The electronically active layer can be a superconducting material, a ferroelectric material, a multiferroic material, a magnetic material, a photovoltaic material, an electrical storage material, and a semiconductor material.

Synthesis, characterisation and thermoelectric properties of the oxytelluride Bi{sub 2}O{sub 2}Te

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

Luu, Son D.N.; Department of Chemistry, University of Reading, Whiteknights, Reading RG6 6AD; Vaqueiro, Paz, E-mail: p.vaqueiro@reading.ac.uk

2015-03-15

Bi{sub 2}O{sub 2}Te was synthesised from a stoichiometric mixture of Bi, Bi{sub 2}O{sub 3} and Te by a solid state reaction. Analysis of powder X-ray diffraction data indicates that this material crystallises in the anti-ThCr{sub 2}Si{sub 2} structure type (space group I4/mmm), with lattice parameters a=3.98025(4) and c=12.70391(16) Å. The electrical and thermal transport properties of Bi{sub 2}O{sub 2}Te were investigated as a function of temperature over the temperature range 300≤T (K)≤665. These measurements indicate that Bi{sub 2}O{sub 2}Te is an n-type semiconductor, with a band gap of 0.23 eV. The thermal conductivity of Bi{sub 2}O{sub 2}Te is remarkably lowmore » for a crystalline material, with a value of only 0.91 W m{sup −1} K{sup −1} at room temperature. - Graphical abstract: Bi{sub 2}O{sub 2}Te, which crystallises in the anti-ThCr{sub 2}Si{sub 2} structure type, is an n-type semiconductor with a remarkably low thermal conductivity. - Highlights: • Bi{sub 2}O{sub 2}Te crystallises in the anti-ThCr{sub 2}Si{sub 2} structure type. • Bi{sub 2}O{sub 2}Te is an n-type semiconductor, with a band gap of 0.23 eV. • The thermal conductivity of Bi{sub 2}O{sub 2}Te approaches values found for amorphous solids. • The thermoelectric figure of merit of undoped Bi{sub 2}O{sub 2}Te reaches 0.13 at 573 K.« less

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.

Crystallisation and crystal forms of carbohydrate derivatives

NASA Astrophysics Data System (ADS)

Lennon, Lorna

This thesis is focused on the synthesis and solid state analysis of carbohydrate derivatives, including many novel compounds. Although the synthetic chemistry surrounding carbohydrates is well established in the literature, the crystal chemistry of carbohydrates is less well studied. Therefore this research aims to improve understanding of the solid state properties of carbohydrate derivatives through gaining more information on their supramolecular bonding. Chapter One focuses on an introduction to the solid state of organic compounds, with a background to crystallisation, including issues that can arise during crystal growth. Chapter Two is based on glucopyranuronate derivatives which are understudied in terms of their solid state forms. This chapter reports on the formation of novel glucuronamides and utilising the functionality of the amide bond for crystallisation. TEMPO oxidation was completed to form glucopyranuronates by oxidation of the primary alcohol groups of glucosides to the carboxylic acid derivatives, to increase functionality for enhanced crystal growth. Chapter Three reports on the synthesis of glucopyranoside derivatives by O-glycosylation reactions and displays crystal structures, including a number of previously unsolved acetate protected and deprotected crystal structures. More complex glycoside derivatives were also researched in an aim to study the resultant supramolecular motifs. Chapter Four contains the synthesis of aryl cellobioside derivatives including the novel crystal structures that were solved for the acetate protected and deprotected compounds. Research was carried out to determine if 1-deoxycellodextrins could act as putative isostructures for cellulose. Our research displays the presence of isostructural references with 1-deoxycellotriose shown to be similar to cellulose III11, 1-deoxycellotetraose correlates with cellulose IV11 and 1-deoxycellopentose shows isostructurality similar to that of cellulose II. Chapter Five contains the full experimental details and spectral characterisation of all novel compounds synthesised in this project and relevant crystallographic information.

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.

Method for separating disparate components in a fluid stream

DOEpatents

Meikrantz, David H.

1990-01-01

The invention provides a method of separating a mixed component waste stream in a centrifugal separator. The mixed component waste stream is introduced into the separator and is centrifugally separated within a spinning rotor. A dual vortex separation occurs due to the phase density differences, with the phases exiting the rotor distinct from one another. In a preferred embodiment, aqueous solutions of organics can be separated with up to 100% efficiency. The relatively more dense water phase is centrifugally separated through a radially outer aperture in the separator, while the relatively less dense organic phase is separated through a radially inner aperture.

Origin of Aphyric Phonolitic Magmas: Natural Evidences and Experimental Constraints

NASA Astrophysics Data System (ADS)

Masotta, M.; Freda, C.; Gaeta, M.

2010-12-01

Large explosive phonolitic eruptions are commonly characterised by aphyric juvenile eruptive products. Taking into account the low density contrast among phonolitic composition and settling phases (i.e., feldspar and leucite), the almost complete lack of crystals in these differentiated compositions rises the question of which process could produce such an efficient crystal-melt separation. Seeking for an answer, we have investigated crystallization in presence of a thermal gradient as a possible mechanism for crystal-melt separation, considering both chemical and physical effects acting on a variably crystallized system. Using a natural tephri-phonolitic composition as starting material (M.te Aguzzo scoria cone, Sabatini Volcanic District, Central Italy), we have reproduced thermal gradient-driven crystallization in order to simulate the crystallization process in a thermally zoned magma chamber. Crystallization degree (paragenesis made of clinopyroxene±feldspars±leucite) as well as melt composition varies along the thermal gradient. In particular, melt composition ranges from the tephri-phonolitic starting composition at the bottom of the charge (hottest and aphyric zone) to phonolitic at the top (cooler and heterogeneously-crystallised zone). Backscattered images of experimental products clearly evidence: i) the aphyric tephri-phonolitic melt region at the bottom of the charge; ii) a drop-shaped crystal clustering in the middle zone; and iii) large aphyric belt and pockets (up to 100 µm wide) of phonolitic melt, with large deformed-shaped sanidine occurring at their margin, at the charge top region. The latter two features, resulting from solid-melt displacements, suggest that the segregation of phonolitic melt can be related to crystal sinking and compaction. On the other hand, the compositional variability of the melt along the thermal gradient is directly related to the crystallization degree, indicating that chemical diffusion and thermal migration have negligible effect at the experimental scale. Experimental results suggest that, in presence of a thermal gradient, a filter-press differentiation mechanism (i.e. sinking+compaction) is able to produce heterogeneous magma differentiation characterised by a wide range of melt compositions (in our case from tephri-phonolitic to phonolitic). Although the limitation due to the vertical shape of the charge and consequent shear effects occurring at the lateral walls (thus limiting the mobility of the crystal clusters), experimental duration of 24 h is enough to allow crystal-melt separation by means of settling and compaction, indicating that timescale for such a process is extremely rapid and effective at experimental conditions. Actually, experimental textures and phase relations are in good agreement with those observed in natural lithic enclaves (from Sabatini Volcanic District) representative of the crystallizing boundary layer of a phonolitic magma chamber. Thus, we speculate that gravitative collapses of a mushy zone from the magma chamber roof of a thermally zoned magma chamber may produce top accumulation of highly differentiated and aphyric melts.

Reaction-mediated entropic effect on phase separation in a binary polymer system

NASA Astrophysics Data System (ADS)

Sun, Shujun; Guo, Miaocai; Yi, Xiaosu; Zhang, Zuoguang

2017-10-01

We present a computer simulation to study the phase separation behavior induced by polymerization in a binary system comprising polymer chains and reactive monomers. We examined the influence of interaction parameter between components and monomer concentration on the reaction-induced phase separation. The simulation results demonstrate that increasing interaction parameter (enthalpic effect) would accelerate phase separation, while entropic effect plays a key role in the process of phase separation. Furthermore, scanning electron microscopy observations illustrate identical morphologies as found in theoretical simulation. This study may enrich our comprehension of phase separation in polymer mixture.

Separation of aqueous two-phase polymer systems in microgravity

NASA Technical Reports Server (NTRS)

Vanalstine, J. M.; Harris, J. M.; Synder, S.; Curreri, P. A.; Bamberger, S. B.; Brooks, D. E.

1984-01-01

Phase separation of polymer systems in microgravity is studied in aircraft flights to prepare shuttle experiments. Short duration (20 sec) experiments demonstrate that phase separation proceeds rapidly in low gravity despite appreciable phase viscosities and low liquid interfacial tensions (i.e., 50 cP, 10 micro N/m). Ostwald ripening does not appear to be a satisfactory model for the phase separation mechanism. Polymer coated surfaces are evaluated as a means to localize phases separated in low gravity. Contact angle measurements demonstrate that covalently coupling dextran or PEG to glass drastically alters the 1-g wall wetting behavior of the phases in dextran-PEG two phase systems.

Film thickness dependence of phase separation and dewetting behaviors in PMMA/SAN blend films.

PubMed

You, Jichun; Liao, Yonggui; Men, Yongfeng; Shi, Tongfei; An, Lijia

2010-09-21

Film thickness dependence of complex behaviors coupled by phase separation and dewetting in blend [poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN)] films on silicon oxide substrate at 175 °C was investigated by grazing incidence ultrasmall-angle X-ray scattering (GIUSAX) and in situ atomic force microscopy (AFM). It was found that the dewetting pathway was under the control of the parameter U(q0)/E, which described the initial amplitude of the surface undulation and original thickness of film, respectively. Furthermore, our results showed that interplay between phase separation and dewetting depended crucially on film thickness. Three mechanisms including dewetting-phase separation/wetting, dewetting/wetting-phase separation, and phase separation/wetting-pseudodewetting were discussed in detail. In conclusion, it is relative rates of phase separation and dewetting that dominate the interplay between them.

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.

MgCu metallic glass

NASA Astrophysics Data System (ADS)

Durandurdu, Murat

2018-03-01

We generate an amorphous MgCu model using the rapid solidification of the melt through a first-principles molecular dynamics approach within a generalised gradient approximation and reveal, for the first time, its structural features and mechanical properties in details. The liquid and glassy MgCu are found to acquire slightly distinct local structures. Yet in both forms of MgCu, most Cu atoms have a tendency to form the ideal and defective icosahedrons while Mg atoms are arranged in complex configurations. The mean coordination number of Cu and Mg at 300 K is 11.31 and 13.73, respectively. The short-range order of MgCu glass is projected to be different than the known crystalline MgCu and Mg2Cu phases. The mechanical properties of MgCu glass and the CsCl-type MgCu crystal are computed and compared. On the basis of the enthalpy analyses, a possible pressure-induced crystallisation of the MgCu glass into a CsCl-type structure is proposed to occur at around 11 GPa.

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.

Age and geochemistry of host rocks of the Cobre Panama porphyry Cu-Au deposit, central Panama: Implications for the Paleogene evolution of the Panamanian magmatic arc

NASA Astrophysics Data System (ADS)

Baker, Michael J.; Hollings, Peter; Thompson, Jennifer A.; Thompson, Jay M.; Burge, Colin

2016-04-01

The Cobre Panama porphyry Cu-Au deposit, located in the Petaquilla district of central Panama, is hosted by a sequence of medium- to high-K calc-alkaline volcanic and sub-volcanic rocks. New crystallisation ages obtained from a granodiorite Petaquilla batholith and associated mineralised diorite to granodiorite porphyry stocks and dikes at Cobre Panama indicate that the batholith was emplaced as a multi-phase intrusion, over a period of 4 million years from 32.20 ± 0.76 Ma to 28.26 ± 0.61 Ma, while the porphyritic rocks were emplaced over a 2 million year period from 28.96 ± 0.62 Ma to 27.48 ± 0.68 Ma. Both the volcanic to sub-volcanic host rocks and intrusive rocks of the Cobre Panama deposit evolved via fractional crystallisation processes, as demonstrated by the major elements (e.g. Al2O3, Fe2O3, TiO2 and MgO) displaying negative trends with increasing SiO2. The Petaquilla intrusive rocks, including the diorite-granodiorite porphyries and granodiorite batholith, are geochemically evolved and appear to have formed from more hydrous magmas than the preceding host volcanic rocks, as evidenced by the presence of hornblende phenocrysts, higher degrees of large-ion lithophile element (LILE) and light rare earth element (LREE) enrichment and heavy rare earth element (HREE) depletion, and higher Sr/Y and La/Yb values. However, the degree of LREE enrichment, HREE depletion and La/Yb values are insufficient for the intrusive rocks to be considered as adakites. Collectively, the volcanic and intrusive rocks have LILE, REE and mobile trace element concentrations similar to enriched Miocene-age Cordilleran arc magmatism found throughout central and western Panama. Both the Petaquilla and Cordilleran arc magmatic suites are geochemically more evolved than the late Cretaceous to Eocene Chagres-Bayano arc magmas from northeastern Panama, as they display higher degrees of LILE and LREE enrichment. The geochemical similarities between the Petaquilla and Cordilleran arc magmas suggest that evolved calc-alkaline arc magmatism may extend to the late Eocene, at least 10 million years earlier than previously estimated. The crystallisation ages for intrusive rocks associated with mineralisation at Cobre Panama imply that the deposit formed in the early Oligocene, between a period of late Cretaceous to Eocene magmatism (ca. 66-42 Ma; Chagres-Bayano arc) and Cordilleran arc magmatism (22-7 Ma). Similarities in the timing of intrusive suite emplacement and the fingerprinting of magmatic fractionation processes between the Cobre Panama porphyry deposit and the Cerro Colorado porphyry deposit in western Panama (ca. 5.3 Ma) suggest that these features provide favourable geodynamic and geochemical prerequisites for the formation of porphyry deposits along the Panamanian magmatic arc during the Cenozoic.

Metal-silicate interaction in quenched shock-induced melt of the Tenham L6-chondrite

NASA Astrophysics Data System (ADS)

Leroux, Hugues; Doukhan, Jean-Claude; Guyot, François

2000-07-01

The metal-silicate microstructures in the shock-induced melt pockets of the Tenham (L6) chondrite have been investigated by analytical transmission electron microscopy. The melt areas, formed under high-pressure, high-temperature dynamic shock conditions, consist of spherical Fe-Ni metal/iron sulfide globules embedded in a silicate glass matrix, showing that the melt was quenched at high cooling rate. The Fe-Ni fraction in the globules is two-phase, composed of a bcc phase (˜5 wt% Ni) and an fcc phase (˜49 wt% Ni), indicating that fractional crystallisation of the metal occurred during the fast cooling. The metal fraction also contains appreciable amounts of non-siderophile elements (mostly Si, Mg and O) suggesting that these elements were trapped in the metal, either as alloying components or as tiny silicate or oxide inclusions. In the iron sulfide fraction, the Na content is high (>3 wt%), suggesting chalcophile behaviour for Na during the shock event. The composition of the silicate glass reflects non-equilibrium melting of several silicate phases (olivine, pyroxene and plagioclase). Moreover, the FeO content is high compared to the FeO contents of the unmelted silicates. Some Fe redistribution took place between metal and silicate liquids during the shock event. The silicate glass also contains tiny iron sulfide precipitates which most probably originated by exsolution during quench, suggesting that the molten silicate retained significant amounts of S, dissolved at high temperature and high pressure. Based on these observations, we suggest that non-equilibrium phenomena may be important in determining the compositions of metal and silicate reservoirs during their differentiation.

Synthesis of a mixed-model stationary phase derived from glutamine for HPLC separation of structurally different biologically active compounds: HILIC and reversed-phase applications.

PubMed

Aral, Tarık; Aral, Hayriye; Ziyadanoğulları, Berrin; Ziyadanoğulları, Recep

2015-01-01

A novel mixed-mode stationary phase was synthesised starting from N-Boc-glutamine, aniline and spherical silica gel (4 µm, 60 Å). The prepared stationary phase was characterized by IR and elemental analysis. The new stationary phase bears an embedded amide group into phenyl ring, highly polar a terminal amide group and non-polar groups (phenyl and alkyl groups). At first, this new mixed-mode stationary phase was used for HILIC separation of four nucleotides and five nucleosides. The effects of different separation conditions, such as pH value, mobile phase and temperature, on the separation process were investigated. The optimum separation for nucleotides was achieved using HILIC isocratic elution with aqueous mobile phase and acetonitrile with 20°C column temperature. Under these conditions, the four nucleotides could be separated and detected at 265 nm within 14 min. Five nucleosides were separated under HILIC isocratic elution with aqueous mobile phase containing pH=3.25 phosphate buffer (10mM) and acetonitrile with 20°C column temperature and detected at 265 nm within 14 min. Chromatographic parameters as retention factor, selectivity, theoretical plate number and peak asymmetry factor were calculated for the effect of temperature and water content in mobile phase on the separation process. The new column was also tested for nucleotides and nucleosides mixture and six analytes were separated in 10min. The chromatographic behaviours of these polar analytes on the new mixed-model stationary phase were compared with those of HILIC columns under similar conditions. Further, phytohormones and phenolic compounds were separated in order to see influence of the new stationary phase in reverse phase conditions. Eleven plant phytohormones were separated within 13 min using RP-HPLC gradient elution with aqueous mobile phase containing pH=2.5 phosphate buffer (10mM) and acetonitrile with 20°C column temperature and detected at 230 or 278 nm. The best separation conditions for seven phenolic compounds was also achieved using reversed-phase HPLC gradient elution with aqueous mobile phase containing pH=2.5 phosphate buffer (10mM) and acetonitrile with 20°C column temperature and seven phenolic compounds could be separated and detected at 230 nm within 16 min. Copyright © 2014 Elsevier B.V. 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

Structural investigations of sol-gel derived silicate gels using Eu 3+ ion-probe luminescence

NASA Astrophysics Data System (ADS)

Secu, C. E.; Predoi, D.; Secu, M.; Cernea, M.; Aldica, G.

2009-09-01

Undoped and Eu 3+-doped CaF 2-SiO 2 gels were prepared by the sol-gel method and their optical properties have been studied. The UV-VIS-NIR absorption and photoluminescence spectra have shown the bands typical for the Eu 3+ ions transitions. When the Eu-doped gel is annealed at temperatures up to 800 °C (i.e. above the CaF 2 crystallisation peak at ˜460 °C) the photoluminescence spectra intensity increase, the 590 nm (5D→7F) and 620 nm (5D→7F) luminescence bands become comparable and a structuring of the 620 nm band is observed. The phonon sidebands peaks associated with the 5F→7D transition of the Eu 3+ ion were observed at around 1000 and 620 cm -1 and have been assigned to the Si-O and Ca-O bonds, respectively. A phonon sideband signal in the range of 300-400 cm -1 was attributed to Ca-F bonds in the precipitated CaF 2 phase. From the optical absorption, photoluminescence and phonon sidebands spectra we have concluded that in the gels annealed at 800 °C, the Eu 3+ ions are incorporated into the silica network and in the precipitated CaF 2 phase.

Phase separation and large deviations of lattice active matter

NASA Astrophysics Data System (ADS)

Whitelam, Stephen; Klymko, Katherine; Mandal, Dibyendu

2018-04-01

Off-lattice active Brownian particles form clusters and undergo phase separation even in the absence of attractions or velocity-alignment mechanisms. Arguments that explain this phenomenon appeal only to the ability of particles to move persistently in a direction that fluctuates, but existing lattice models of hard particles that account for this behavior do not exhibit phase separation. Here we present a lattice model of active matter that exhibits motility-induced phase separation in the absence of velocity alignment. Using direct and rare-event sampling of dynamical trajectories, we show that clustering and phase separation are accompanied by pronounced fluctuations of static and dynamic order parameters. This model provides a complement to off-lattice models for the study of motility-induced phase separation.

Effect of applied strain on phase separation of Fe-28 at.% Cr alloy: 3D phase-field simulation

NASA Astrophysics Data System (ADS)

Zhu, Lihui; Li, Yongsheng; Liu, Chengwei; Chen, Shi; Shi, Shujing; Jin, Shengshun

2018-04-01

A quantitative simulation of the separation of the α‧ phase in Fe-28 at.% Cr alloy under the effects of applied strain is performed by utilizing a three-dimensional phase-field model. The elongation of the Cr-enriched α‧ phase becomes obvious with the influence of applied uniaxial strain for the phase separation transforms from spinodal decomposition of 700 K to nucleation and growth of 773 K. The applied strain shows a significant influence on the early stage phase separation, and the influence is enlarged with the elevated temperature. The steady-state coarsening with the mechanism of spinodal decomposition is substantially affected by the applied strain for low-temperature aging, while the influence is reduced as the temperature increases and as the phase separation mechanism changes to nucleation and growth. The peak value of particle size distribution decreases, and the PSD for 773 K becomes more widely influenced by the applied strain. The simulation results of separation of the Cr-enriched α‧ phase with the applied strain provide a further understanding of the strain effect on the phase separation of Fe-Cr alloys from the metastable region to spinodal regions.

Accessory Mineral Records of Early Earth Crust-Mantle Systematics: an Example From West Greenland

NASA Astrophysics Data System (ADS)

Storey, C. D.; Hawkesworth, C. J.

2008-12-01

Conditions for the formation and the nature of Earth's early crust are enigmatic due to poor preservation. Before c.4 Ga the only archives are detrital minerals eroded from earlier crust, such as the Jack Hills zircons in western Australia, or extinct isotope systematics. Zircons are particularly powerful since they retain precise records of their ages of crystallisation, and the Lu-Hf radiogenic isotope and O stable isotope systematics of the reservoir from which they crystallised. In principle, this allows insight into the nature of the crust, the mantle reservoir from which the melt was extracted and any reworked material incorporated into that melt. We have used in situ methods to measure U-Pb, O and Lu-Hf within single zircon crystals from tonalitic gneisses from West Greenland in the vicinity of the Isua Supracrustal Belt. They have little disturbed ages of c.3.8 Ga, mantle-like O isotope signatures and Lu-Hf isotope signatures that lie on the CHUR evolution line at 3.8 Ga. These samples have previously been subjected to Pb isotope feldspar and 142Nd whole rock analysis and have helped constrain models in which early differentiation of a proto-crust must have occurred. The CHUR-like Lu-Hf signature, along with mantle-like O signature from these zircons suggests juvenile melt production at 3.8 Ga from undifferentiated mantle, yet the other isotope systems preclude this possibility. Alternatively, this is further strong evidence for a heterogeneous mantle in the early Earth. Whilst zircons afford insight into the nature of the early crust and mantle, it is through the Sm-Nd system that the mantle has traditionally been viewed. Titanite often contains several thousand ppm Nd, making it amenable to precise analysis, and is a common accessory phase. It has a reasonably high closure temperature for Pb and O, and it can retain cores with older ages and distinct REE chemistry. It is often the main accessory phase alongside zircon, and it is the main carrier of Nd within the whole rock such that Nd isotope analysis of titanite may be able to see-through later alteration that may have partially reset the whole rock system. We present new in-situ U-Pb, O and Sm-Nd and high-precision U-Pb ID-TIMS and Sm-Nd MC- ICPMS data from individual or fragmented titanite grains. We discuss how these data complement the zircon data and may help to resolve long-standing debates in ancient gneiss terranes, with utility to the nature and formation of crust on the early Earth.

Stability and Oil Migration of Oil-in-Water Emulsions Emulsified by Phase-Separating Biopolymer Mixtures.

PubMed

Yang, Nan; Mao, Peng; Lv, Ruihe; Zhang, Ke; Fang, Yapeng; Nishinari, Katsuyoshi; Phillips, Glyn O

2016-08-01

Oil-in-water (O/W) emulsions with varying concentration of oil phase, medium-chain triglyceride (MCT), were prepared using phase-separating gum arabic (GA)/sugar beet pectin (SBP) mixture as an emulsifier. Stability of the emulsions including emulsion phase separation, droplet size change, and oil migration were investigated by means of visual observation, droplet size analysis, oil partition analysis, backscattering of light, and interfacial tension measurement. It was found that in the emulsions prepared with 4.0% GA/1.0% SBP, when the concentration of MCT was greater than 2.0%, emulsion phase separation was not observed and the emulsions were stable with droplet size unchanged during storage. This result proves the emulsification ability of phase-separating biopolymer mixtures and their potential usage as emulsifiers to prepare O/W emulsion. However, when the concentration of MCT was equal or less than 2.0%, emulsion phase separation occurred after preparation resulting in an upper SBP-rich phase and a lower GA-rich phase. The droplet size increased in the upper phase whereas decreased slightly in the lower phase with time, compared to the freshly prepared emulsions. During storage, the oil droplets exhibited a complex migration process: first moving to the SBP-rich phase, then to the GA-rich phase and finally gathering at the interface between the two phases. The mechanisms of the emulsion stability and oil migration in the phase-separated emulsions were discussed. © 2016 Institute of Food Technologists®

Fluid Phase Separation (FPS) experiment for flight on a space shuttle Get Away Special (GAS) canister

NASA Technical Reports Server (NTRS)

Peters, Bruce; Wingo, Dennis; Bower, Mark; Amborski, Robert; Blount, Laura; Daniel, Alan; Hagood, Bob; Handley, James; Hediger, Donald; Jimmerson, Lisa

1990-01-01

The separation of fluid phases in microgravity environments is of importance to environmental control and life support systems (ECLSS) and materials processing in space. A successful fluid phase separation experiment will demonstrate a proof of concept for the separation technique and add to the knowledge base of material behavior. The phase separation experiment will contain a premixed fluid which will be exposed to a microgravity environment. After the phase separation of the compound has occurred, small samples of each of the species will be taken for analysis on the Earth. By correlating the time of separation and the temperature history of the fluid, it will be possible to characterize the process. The experiment has been integrated into space available on a manifested Get Away Special (GAS) experiment, CONCAP 2, part of the Consortium for Materials Complex Autonomous Payload (CAP) Program, scheduled for STS-42. The design and the production of a fluid phase separation experiment for rapid implementation at low cost is presented.

Rapid Separation of Copper Phase and Iron-Rich Phase From Copper Slag at Low Temperature in a Super-Gravity Field

NASA Astrophysics Data System (ADS)

Lan, Xi; Gao, Jintao; Huang, Zili; Guo, Zhancheng

2018-03-01

A novel approach for quickly separating a metal copper phase and iron-rich phase from copper slag at low temperature is proposed based on a super-gravity method. The morphology and mineral evolution of the copper slag with increasing temperature were studied using in situ high-temperature confocal laser scanning microscopy and ex situ scanning electron microscopy and X-ray diffraction methods. Fe3O4 particles dispersed among the copper slag were transformed into FeO by adding an appropriate amount of carbon as a reducing agent, forming the slag melt with SiO2 at low temperature and assisting separation of the copper phase from the slag. Consequently, in a super-gravity field, the metallic copper and copper matte were concentrated as the copper phase along the super-gravity direction, whereas the iron-rich slag migrated in the opposite direction and was quickly separated from the copper phase. Increasing the gravity coefficient (G) significantly enhanced the separation efficiency. After super-gravity separation at G = 1000 and 1473 K (1200 °C) for 3 minutes, the mass fraction of Cu in the separated copper phase reached 86.11 wt pct, while that in the separated iron-rich phase was reduced to 0.105 wt pct. The recovery ratio of Cu in the copper phase was as high as up to 97.47 pct.

Rapid Separation of Copper Phase and Iron-Rich Phase From Copper Slag at Low Temperature in a Super-Gravity Field

NASA Astrophysics Data System (ADS)

Lan, Xi; Gao, Jintao; Huang, Zili; Guo, Zhancheng

2018-06-01

A novel approach for quickly separating a metal copper phase and iron-rich phase from copper slag at low temperature is proposed based on a super-gravity method. The morphology and mineral evolution of the copper slag with increasing temperature were studied using in situ high-temperature confocal laser scanning microscopy and ex situ scanning electron microscopy and X-ray diffraction methods. Fe3O4 particles dispersed among the copper slag were transformed into FeO by adding an appropriate amount of carbon as a reducing agent, forming the slag melt with SiO2 at low temperature and assisting separation of the copper phase from the slag. Consequently, in a super-gravity field, the metallic copper and copper matte were concentrated as the copper phase along the super-gravity direction, whereas the iron-rich slag migrated in the opposite direction and was quickly separated from the copper phase. Increasing the gravity coefficient (G) significantly enhanced the separation efficiency. After super-gravity separation at G = 1000 and 1473 K (1200 °C) for 3 minutes, the mass fraction of Cu in the separated copper phase reached 86.11 wt pct, while that in the separated iron-rich phase was reduced to 0.105 wt pct. The recovery ratio of Cu in the copper phase was as high as up to 97.47 pct.

Electron irradiation induced phase separation in a sodium borosilicate glass

NASA Astrophysics Data System (ADS)

Sun, K.; Wang, L. M.; Ewing, R. C.; Weber, W. J.

2004-06-01

Electron irradiation induced phase separation in a sodium borosilicate glass was studied in situ by analytical electron microscopy. Distinctly separate phases that are rich in boron and silicon formed at electron doses higher than 4.0 × 10 11 Gy during irradiation. The separated phases are still in amorphous states even at a much high dose (2.1 × 10 12 Gy). It indicates that most silicon atoms remain tetrahedrally coordinated in the glass during the entire irradiation period, except some possible reduction to amorphous silicon. The particulate B-rich phase that formed at high dose was identified as amorphous boron that may contain some oxygen. Both ballistic and ionization processes may contribute to the phase separation.

Spectro-microscopic Characterization of Physical Properties and Phase Separations in Individual Atmospheric Particles

NASA Astrophysics Data System (ADS)

OBrien, R. E.; Wang, B.; Neu, A.; Kelly, S. T.; Lundt, N.; Epstein, S. A.; MacMillan, A.; You, Y.; Laskin, A.; Nizkorodov, S.; Bertram, A. K.; Moffet, R.; Gilles, M.

2013-12-01

The phase state and liquid-liquid phase separations of ambient and laboratory generated aerosol particles were investigated using (1) scanning transmission x-ray microscopy/near-edge x-ray absorption fine structure spectroscopy (STXM/NEXAFS) coupled to a relative humidity (RH) controlled in-situ chamber and (2) environmental scanning electron microscopy (ESEM). The phase states of the particles were determined from measurements of their size and optical density. A comparison is made between the observed phase states of ambient samples and of laboratory generated aerosols to determine how well laboratory samples represent the phase of ambient samples. In addition, liquid-liquid phase separations in laboratory generated particles were investigated. Preliminary results showing that liquid-liquid phase separations occur at RH's between the deliquescence and efflorescence points and that the organic phase surrounds the inorganic phase will be presented. The STXM/NEXAFS technique provides insight into the degree of mixing at the deliquescence point and the degree of phase separation for particles of atmospherically relevant sizes.

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.

Microstructure Evolution and Related Magnetic Properties of Cu-Zr-Al-Gd Phase-Separating Metallic Glasses

NASA Astrophysics Data System (ADS)

Kim, Sang Jun; Kim, Jinwoo; Park, Eun Soo

2018-04-01

We carefully investigated the correlation between microstructures and magnetic properties of Cu-Zr-Al-Gd phase-separating metallic glasses (PSMGs). The saturation magnetizations of the PSMGs were determined by total Gd contents of the alloys, while their coercivity exhibits a large deviation by the occurrence of phase separation due to the boundary pinning effect of hierarchically separated amorphous phases. Especially, the PSMGs containing Gd-rich amorphous nanoparticles show the highest coercivity which can be attributed to the size effect of the ferromagnetic amorphous phase. Furthermore, the selective crystallization of ferromagnetic amorphous phases can affect the magnetization behavior of the PSMGs. Our results could provide a novel strategy for tailoring unique soft magnetic properties of metallic glasses by introducing hierarchically separated amorphous phases and controlling their crystallinity.

Microstructure Evolution and Related Magnetic Properties of Cu-Zr-Al-Gd Phase-Separating Metallic Glasses

NASA Astrophysics Data System (ADS)

Kim, Sang Jun; Kim, Jinwoo; Park, Eun Soo

2018-06-01

We carefully investigated the correlation between microstructures and magnetic properties of Cu-Zr-Al-Gd phase-separating metallic glasses (PSMGs). The saturation magnetizations of the PSMGs were determined by total Gd contents of the alloys, while their coercivity exhibits a large deviation by the occurrence of phase separation due to the boundary pinning effect of hierarchically separated amorphous phases. Especially, the PSMGs containing Gd-rich amorphous nanoparticles show the highest coercivity which can be attributed to the size effect of the ferromagnetic amorphous phase. Furthermore, the selective crystallization of ferromagnetic amorphous phases can affect the magnetization behavior of the PSMGs. Our results could provide a novel strategy for tailoring unique soft magnetic properties of metallic glasses by introducing hierarchically separated amorphous phases and controlling their crystallinity.

Pi-Pi contacts are an overlooked protein feature relevant to phase separation

PubMed Central

Vernon, Robert McCoy; Chong, Paul Andrew; Tsang, Brian; Kim, Tae Hun; Bah, Alaji; Farber, Patrick; Lin, Hong

2018-01-01

Protein phase separation is implicated in formation of membraneless organelles, signaling puncta and the nuclear pore. Multivalent interactions of modular binding domains and their target motifs can drive phase separation. However, forces promoting the more common phase separation of intrinsically disordered regions are less understood, with suggested roles for multivalent cation-pi, pi-pi, and charge interactions and the hydrophobic effect. Known phase-separating proteins are enriched in pi-orbital containing residues and thus we analyzed pi-interactions in folded proteins. We found that pi-pi interactions involving non-aromatic groups are widespread, underestimated by force-fields used in structure calculations and correlated with solvation and lack of regular secondary structure, properties associated with disordered regions. We present a phase separation predictive algorithm based on pi interaction frequency, highlighting proteins involved in biomaterials and RNA processing. PMID:29424691

Superfluid helium 2 liquid-vapor phase separation: Technology assessment

NASA Technical Reports Server (NTRS)

Lee, J. M.

1984-01-01

A literature survey of helium 2 liquid vapor phase separation is presented. Currently, two types of He 2 phase separators are being investigated: porous, sintered metal plugs and the active phase separator. The permeability K(P) shows consistency in porous plug geometric characterization. Both the heat and mass fluxes increase with K(P). Downstream pressure regulation to adjust for varying heat loads and both temperatures is possible. For large dynamic heat loads, the active phase separator shows a maximum heat rejection rate of up to 2 W and bath temperature stability of 0.1 mK. Porous plug phase separation performance should be investigated for application to SIRTF and, in particular, that plugs of from 10 to the minus ninth square centimeters to 10 to the minus eighth square centimeters in conjunction with downstream pressure regulation be studied.

On the phase form of a deformation quantization with separation of variables

NASA Astrophysics Data System (ADS)

Karabegov, Alexander

2016-06-01

Given a star product with separation of variables on a pseudo-Kähler manifold, we obtain a new formal (1, 1)-form from its classifying form and call it the phase form of the star product. The cohomology class of a star product with separation of variables equals the class of its phase form. We show that the phase forms can be arbitrary and they bijectively parametrize the star products with separation of variables. We also describe the action of a change of the formal parameter on a star product with separation of variables, its formal Berezin transform, classifying form, phase form, and canonical trace density.

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).

Direct NMR Monitoring of Phase Separation Behavior of Highly Supersaturated Nifedipine Solution Stabilized with Hypromellose Derivatives.

PubMed

Ueda, Keisuke; Higashi, Kenjirou; Moribe, Kunikazu

2017-07-03

We investigated the phase separation behavior and maintenance mechanism of the supersaturated state of poorly water-soluble nifedipine (NIF) in hypromellose (HPMC) derivative solutions. Highly supersaturated NIF formed NIF-rich nanodroplets through phase separation from aqueous solution containing HPMC derivative. Dissolvable NIF concentration in the bulk water phase was limited by the phase separation of NIF from the aqueous solution. HPMC derivatives stabilized the NIF-rich nanodroplets and maintained the NIF supersaturation with phase-separated NIF for several hours. The size of the NIF-rich phase was different depending on the HPMC derivatives dissolved in aqueous solution, although the droplet size had no correlation with the time for which NIF supersaturation was maintained without NIF crystallization. HPMC acetate and HPMC acetate succinate (HPMC-AS) effectively maintained the NIF supersaturation containing phase-separated NIF compared with HPMC. Furthermore, HPMC-AS stabilized NIF supersaturation more effectively in acidic conditions. Solution 1 H NMR measurements of NIF-supersaturated solution revealed that HPMC derivatives distributed into the NIF-rich phase during the phase separation of NIF from the aqueous solution. The hydrophobicity of HPMC derivative strongly affected its distribution into the NIF-rich phase. Moreover, the distribution of HPMC-AS into the NIF-rich phase was promoted at lower pH due to the lower aqueous solubility of HPMC-AS. The distribution of a large amount of HPMC derivatives into NIF-rich phase induced the strong inhibition of NIF crystallization from the NIF-rich phase. Polymer distribution into the drug-rich phase directly monitored by solution NMR technique can be a useful index for the stabilization efficiency of drug-supersaturated solution containing a drug-rich phase.

Rationalizing the light-induced phase separation of mixed halide organic-inorganic perovskites.

PubMed

Draguta, Sergiu; Sharia, Onise; Yoon, Seog Joon; Brennan, Michael C; Morozov, Yurii V; Manser, Joseph S; Kamat, Prashant V; Schneider, William F; Kuno, Masaru

2017-08-04

Mixed halide hybrid perovskites, CH 3 NH 3 Pb(I 1-x Br x ) 3 , represent good candidates for low-cost, high efficiency photovoltaic, and light-emitting devices. Their band gaps can be tuned from 1.6 to 2.3 eV, by changing the halide anion identity. Unfortunately, mixed halide perovskites undergo phase separation under illumination. This leads to iodide- and bromide-rich domains along with corresponding changes to the material's optical/electrical response. Here, using combined spectroscopic measurements and theoretical modeling, we quantitatively rationalize all microscopic processes that occur during phase separation. Our model suggests that the driving force behind phase separation is the bandgap reduction of iodide-rich phases. It additionally explains observed non-linear intensity dependencies, as well as self-limited growth of iodide-rich domains. Most importantly, our model reveals that mixed halide perovskites can be stabilized against phase separation by deliberately engineering carrier diffusion lengths and injected carrier densities.Mixed halide hybrid perovskites possess tunable band gaps, however, under illumination they undergo phase separation. Using spectroscopic measurements and theoretical modelling, Draguta and Sharia et al. quantitatively rationalize the microscopic processes that occur during phase separation.

A Preliminary Assessment of Phase Separator Ground-Based and Reduced-Gravity Testing for ALS Systems

NASA Technical Reports Server (NTRS)

Hall, Nancy Rabel

2006-01-01

A viewgraph presentation of phase separator ground-based and reduced-gravity testing for Advanced Life Support (ALS) systems is shown. The topics include: 1) Multiphase Flow Technology Program; 2) Types of Separators; 3) MOBI Phase Separators; 4) Experiment set-up; and 5) Preliminary comparison/results.

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.

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.

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.

Pi-Pi contacts are an overlooked protein feature relevant to phase separation.

PubMed

Vernon, Robert McCoy; Chong, Paul Andrew; Tsang, Brian; Kim, Tae Hun; Bah, Alaji; Farber, Patrick; Lin, Hong; Forman-Kay, Julie Deborah

2018-02-09

Protein phase separation is implicated in formation of membraneless organelles, signaling puncta and the nuclear pore. Multivalent interactions of modular binding domains and their target motifs can drive phase separation. However, forces promoting the more common phase separation of intrinsically disordered regions are less understood, with suggested roles for multivalent cation-pi, pi-pi, and charge interactions and the hydrophobic effect. Known phase-separating proteins are enriched in pi-orbital containing residues and thus we analyzed pi-interactions in folded proteins. We found that pi-pi interactions involving non-aromatic groups are widespread, underestimated by force-fields used in structure calculations and correlated with solvation and lack of regular secondary structure, properties associated with disordered regions. We present a phase separation predictive algorithm based on pi interaction frequency, highlighting proteins involved in biomaterials and RNA processing. © 2018, Vernon et al.

Vertical phase separation in bulk heterojunction solar cells formed by in situ polymerization of fulleride

PubMed Central

Zhang, Lipei; Xing, Xing; Zheng, Lingling; Chen, Zhijian; Xiao, Lixin; Qu, Bo; Gong, Qihuang

2014-01-01

Vertical phase separation of the donor and the acceptor in organic bulk heterojunction solar cells is crucial to improve the exciton dissociation and charge transport efficiencies. This is because whilst the exciton diffusion length is limited, the organic film must be thick enough to absorb sufficient light. However, it is still a challenge to control the phase separation of a binary blend in a bulk heterojunction device architecture. Here we report the realization of vertical phase separation induced by in situ photo-polymerization of the acrylate-based fulleride. The power conversion efficiency of the devices with vertical phase separation increased by 20%. By optimising the device architecture, the power conversion efficiency of the single junction device reached 8.47%. We believe that in situ photo-polymerization of acrylate-based fulleride is a universal and controllable way to realise vertical phase separation in organic blends. PMID:24861168

The study of membrane formation via phase inversion method by cloud point and light scattering experiment

NASA Astrophysics Data System (ADS)

Arahman, Nasrul; Maimun, Teuku; Mukramah, Syawaliah

2017-01-01

The composition of polymer solution and the methods of membrane preparation determine the solidification process of membrane. The formation of membrane structure prepared via non-solvent induced phase separation (NIPS) method is mostly determined by phase separation process between polymer, solvent, and non-solvent. This paper discusses the phase separation process of polymer solution containing Polyethersulfone (PES), N-methylpirrolidone (NMP), and surfactant Tetronic 1307 (Tet). Cloud point experiment is conducted to determine the amount of non-solvent needed on induced phase separation. Amount of water required as a non-solvent decreases by the addition of surfactant Tet. Kinetics of phase separation for such system is studied by the light scattering measurement. With the addition of Tet., the delayed phase separation is observed and the structure growth rate decreases. Moreover, the morphology of fabricated membrane from those polymer systems is analyzed by scanning electron microscopy (SEM). The images of both systems show the formation of finger-like macrovoids through the cross-section.

Method and turbine for extracting kinetic energy from a stream of two-phase fluid

NASA Technical Reports Server (NTRS)

Elliott, D. G. (Inventor)

1979-01-01

An axial flow separator turbine is described which includes a number of nozzles for delivering streams of a two-phase fluid along linear paths. A phase separator which responsively separates the vapor and liquid is characterized by concentrically related annuli supported for rotation within the paths. The separator has endless channels for confining the liquid under the influence of centrifugal forces. A vapor turbine fan extracts kinetic energy from the liquid. Angular momentum of both the liquid phase and the vapor phase of the fluid is converted to torque.

Ionic liquid/water mixtures: from hostility to conciliation.

PubMed

Kohno, Yuki; Ohno, Hiroyuki

2012-07-21

Water was originally inimical to ionic liquids (ILs) especially in the analysis of their detailed properties. Various data on the properties of ILs indicate that there are two ways to design functions of ionic liquids. The first is to change the structure of component ions, to provide "task-specific ILs". The second is to mix ILs with other components, such as other ILs, organic solvents or water. Mixing makes it easy to control the properties of the solution. In this strategy, water is now a very important partner. Below, we summarise our recent results on the properties of IL/water mixtures. Stable phase separation is an effective method in some separation processes. Conversely, a dynamic phase change between a homogeneous mixture and separation of phases is important in many fields. Analysis of the relation between phase behaviour and the hydration state of the component ions indicates that the pattern of phase separation is governed by the hydrophilicity of the ions. Sufficiently hydrophilic ions yielded ILs that are miscible with water, and hydrophobic ions gave stable phase separation with water. ILs composed of hydrophobic but hydrated ions undergo a dynamic phase change between a homogeneous mixture and separate phases according to temperature. ILs having more than seven water molecules per ion pair undergo this phase transition. These dynamic phase changes are considered, with some examples, and application is made to the separation of water-soluble proteins.

Formation of magmatic brine lenses via focussed fluid-flow beneath volcanoes

NASA Astrophysics Data System (ADS)

Afanasyev, Andrey; Blundy, Jon; Melnik, Oleg; Sparks, Steve

2018-03-01

Many active or dormant volcanoes show regions of high electrical conductivity at depths of a few kilometres beneath the edifice. We explore the possibility that these regions represent lenses of high-salinity brine separated from a single-phase magmatic fluid containing H2O and NaCl. Since chloride-bearing fluids are highly conductive and have an exceptional capacity to transport metals, these regions can be an indication of an active hydrothermal ore-formation beneath volcanoes. To investigate this possibility we have performed hydrodynamic simulations of magma degassing into permeable rock. In our models the magma source is located at 7 km depth and the fluid salinity approximates that expected for fluids released from typical arc magmas. Our model differs from previous models of a similar process because it is (a) axisymmetric and (b) includes a static high-permeability pathway that links the magma source to the surface. This pathway simulates the presence of a volcanic conduit and/or plexus of feeder dykes that are typical of most volcanic systems. The presence of the conduit leads to a number of important hydrodynamic consequences, not observed in previous models. Importantly, we show that an annular brine lens capped by crystallised halite is likely to form above an actively degassing sub-volcanic magma body and can persist for more than 250 kyr after degassing ceases. Parametric analysis shows that brine lenses are more prevalent when the fluid is released at temperatures above the wet granite solidus, when magmatic fluid salinity is high, and when the high-permeability pathway is narrow. The calculated depth, form and electrical conductivity of our modelled system shares many features with published magnetotelluric images of volcano subsurfaces. The formation and persistence of sub-volcanic brine lenses has implications for geothermal systems and hydrothermal ore formation, although these features are not explored in the presented model.

Separation of multiphosphorylated peptide isomers by hydrophilic interaction chromatography on an aminopropyl phase.

PubMed

Singer, David; Kuhlmann, Julia; Muschket, Matthias; Hoffmann, Ralf

2010-08-01

The separation of isomeric phosphorylated peptides is challenging and often impossible for multiphosphorylated isomers using chromatographic and capillary electrophoretic methods. In this study we investigated the separation of a set of single-, double-, and triple-phosphorylated peptides (corresponding to the human tau protein) by ion-pair reversed-phase chromatography (IP-RPC) and hydrophilic interaction chromatography (HILIC). In HILIC both hydroxyl and aminopropyl stationary phases were tested with aqueous acetonitrile in order to assess their separation efficiency. The hydroxyl phase separated the phosphopeptides very well from the unphosphorylated analogue, while on the aminopropyl phase even isomeric phosphopeptides attained baseline separation. Thus, up to seven phosphorylated versions of a given tau domain were separated. Furthermore, the low concentration of an acidic ammonium formate buffer allowed an online analysis with electrospray ionization tandem mass spectrometry (ESI-MS/MS) to be conducted, enabling peptide sequencing and identification of phosphorylation sites.

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.

Development of a novel amide-silica stationary phase for the reversed-phase HPLC separation of different classes of phytohormones.

PubMed

Aral, Hayriye; Aral, Tarık; Ziyadanoğulları, Berrin; Ziyadanoğulları, Recep

2013-11-15

A novel amide-bonded silica stationary phase was prepared starting from N-Boc-phenylalanine, cyclohexylamine and spherical silica gel (4 µm, 60 Å). The amide ligand was synthesised with high yield. The resulting amide bonded stationary phase was characterised by SEM, IR and elemental analysis. The resulting selector bearing a polar amide group is used for the reversed-phase chromatography separation of different classes of thirteen phytohormones (plant hormones). The chromatographic behaviours of these analytes on the amide-silica stationary phase were compared with those of RP-C18 column under same conditions. The effects of different separation conditions, such as mobile phase, pH value, flow rate and temperature, on the separation and retention behaviours of the 13 phytohormones in this system were studied. The optimum separation was achieved using reversed-phase HPLC gradient elution with an aqueous mobile phase containing pH=6.85 potassium phosphate buffer (20 mM) and acetonitrile with a 22 °C column temperature. Under these experimental conditions, the 12 phytohormones could be separated and detected at 230 or 270 nm within 26 min. Copyright © 2013 Elsevier B.V. All rights reserved.

Phase behaviour of casein micelles and barley beta-glucan polymer molecules in dietary fibre-enriched dairy systems.

PubMed

Repin, Nikolay; Scanlon, Martin G; Fulcher, R Gary

2012-07-01

Enrichment of colloidal dairy systems with dietary fibre frequently causes quality defects because of phase separation. We investigate phase separation in skimmed milk enriched with Glucagel (a commercial product made from barley that is predominantly comprised of the polysaccharide β-glucan). The driving force for phase separation was depletion flocculation of casein micelles in the presence of molecules of the polysaccharide. Depending on the volume fraction of casein micelles and the concentration of Glucagel, the stable system phase separated either as a transient gel or as a sedimented system. The rate at which phase separation progressed also depended on the volume fraction of casein micelles and the concentration of Glucagel. To confirm the role of depletion flocculation in the phase separation process, enzymatic reduction in the molecular weight of β-glucan was shown to limit the range of attraction between micelles and allow the stable phase to exist at a higher β-glucan concentration for any given volume fraction of casein micelles. These phase diagrams will be useful to dairy product manufacturers striving to improve the nutrient profile of their products while avoiding product quality impairment. Copyright © 2012 Elsevier Inc. All rights reserved.

Conserved interdomain linker promotes phase separation of the multivalent adaptor protein Nck

PubMed Central

Banjade, Sudeep; Wu, Qiong; Mittal, Anuradha; Peeples, William B.; Pappu, Rohit V.; Rosen, Michael K.

2015-01-01

The organization of membranes, the cytosol, and the nucleus of eukaryotic cells can be controlled through phase separation of lipids, proteins, and nucleic acids. Collective interactions of multivalent molecules mediated by modular binding domains can induce gelation and phase separation in several cytosolic and membrane-associated systems. The adaptor protein Nck has three SRC-homology 3 (SH3) domains that bind multiple proline-rich segments in the actin regulatory protein neuronal Wiskott-Aldrich syndrome protein (N-WASP) and an SH2 domain that binds to multiple phosphotyrosine sites in the adhesion protein nephrin, leading to phase separation. Here, we show that the 50-residue linker between the first two SH3 domains of Nck enhances phase separation of Nck/N-WASP/nephrin assemblies. Two linear motifs within this element, as well as its overall positively charged character, are important for this effect. The linker increases the driving force for self-assembly of Nck, likely through weak interactions with the second SH3 domain, and this effect appears to promote phase separation. The linker sequence is highly conserved, suggesting that the sequence determinants of the driving forces for phase separation may be generally important to Nck functions. Our studies demonstrate that linker regions between modular domains can contribute to the driving forces for self-assembly and phase separation of multivalent proteins. PMID:26553976

Fluid Phase Separation (FPS) experiment for flight on the shuttle in a Get Away Special (GAS) canister: Design and fabrication

NASA Technical Reports Server (NTRS)

1990-01-01

The separation of fluid phases in microgravity environments is of importance to environmental control and life support systems (ECLSS) and materials processing in space. A successful fluid phase separation experiment will demonstrate a proof of concept for the separation technique and add to the knowledge base of material behavior. The phase separation experiment will contain a premixed fluid that will be exposed to a microgravity environment. After the phase separation of the compound has occurred, small samples of each of the species will be taken for analysis on Earth. By correlating the time of separation and the temperature history of the fluid, it will be possible to characterize the process. The phase separation experiment is totally self-contained, with three levels of containment on all fluids, and provides all necessary electrical power and control. The controller regulates the temperature of the fluid and controls data logging and sampling. An astronaut-activated switch will initiate the experiment and an unmaskable interrupt is provided for shutdown. The experiment has been integrated into space available on a manifested Get Away Special (GAS) experiment, CONCAP 2, part of the Consortium for Materials Complex Autonomous Payload (CAP) Program, scheduled for STS 42 in April 1991. Presented here are the design and the production of a fluid phase separation experiment for rapid implementation at low cost.

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.

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…

Versatile assembly of p-carboxylatocalix[4]arene-O-alkyl ethers

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

Kennedy, Stuart; Teat, Simon J.; Dalgarno, Scott J.

Crystallisation of lower-rim tetra-O-alkylated p-carboxylatocalix[4]arenes from pyridine results in the formation of both bi-layer and pillar type supramolecular motifs. Full alkylation at the calixarene lower rim has significant influence over the supramolecular self-assembly motif, including preclusion of pyridine guest molecules from the calixarene cavity in the solid state.

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…

Modification of linear prepolymers to tailor heterogeneous network formation through photo-initiated Polymerization-Induced Phase Separation

PubMed Central

Szczepanski, Caroline R.; Stansbury, Jeffrey W.

2015-01-01

Polymerization-induced phase separation (PIPS) was studied in ambient photopolymerizations of triethylene glycol dimethacrylate (TEGDMA) modified by poly(methyl methacrylate) (PMMA). The molecular weight of PMMA and the rate of network formation (through incident UV-irradiation) were varied to influence both the promotion of phase separation through increases in overall free energy, as well as the extent to which phase development occurs during polymerization through diffusion prior to network gelation. The overall free energy of the polymerizing system increases with PMMA molecular weight, such that PIPS is promoted thermodynamically at low loading levels (5 wt%) of a higher molecular weight PMMA (120 kDa), while a higher loading level (20 wt%) is needed to induce PIPS with lower PMMA molecular weight (11 kDa), and phase separation was not promoted at any loading level tested of the lowest molecular weight PMMA (1 kDa). Due to these differences in overall free energy, systems modified by PMMA (11 kDa) underwent phase separation via Nucleation and Growth, and systems modified by PMMA (120 kDa), followed the Spinodal Decomposition mechanism. Despite differences in phase structure, all materials form a continuous phase rich in TEGDMA homopolymer. At high irradiation intensity (Io=20mW/cm2), the rate of network formation prohibited significant phase separation, even when thermodynamically preferred. A staged curing approach, which utilizes low intensity irradiation (Io=300µW/cm2) for the first ~50% of reaction to allow phase separation via diffusion, followed by a high intensity flood-cure to achieve a high degree of conversion, was employed to form phase-separated networks with reduced polymerization stress yet equivalent final conversion and modulus. PMID:26190865

Phase separation and second-order phase transition in the phenomenological model for a Coulomb-frustrated two-dimensional system

NASA Astrophysics Data System (ADS)

Mamin, R. F.; Shaposhnikova, T. S.; Kabanov, V. V.

2018-03-01

We have considered the model of the phase transition of the second order for the Coulomb frustrated 2D charged system. The coupling of the order parameter with the charge was considered as the local temperature. We have found that in such a system, an appearance of the phase-separated state is possible. By numerical simulation, we have obtained different types ("stripes," "rings," "snakes") of phase-separated states and determined the parameter ranges for these states. Thus the system undergoes a series of phase transitions when the temperature decreases. First, the system moves from the homogeneous state with a zero order parameter to the phase-separated state with two phases in one of which the order parameter is zero and, in the other, it is nonzero (τ >0 ). Then a first-order transition occurs to another phase-separated state, in which both phases have different and nonzero values of the order parameter (for τ <0 ). Only a further decrease of temperature leads to a transition to a homogeneous ordered state.

Effect of temperature gradient on liquid-liquid phase separation in a polyolefin blend.

PubMed

Jiang, Hua; Dou, Nannan; Fan, Guoqiang; Yang, Zhaohui; Zhang, Xiaohua

2013-09-28

We have investigated experimentally the structure formation processes during phase separation via spinodal decomposition above and below the spinodal line in a binary polymer blend system exposed to in-plane stationary thermal gradients using phase contrast optical microscopy and temperature gradient hot stage. Below the spinodal line there is a coupling of concentration fluctuations and thermal gradient imposed by the temperature gradient hot stage. Also under the thermal gradient annealing phase-separated domains grow faster compared with the system under homogeneous temperature annealing on a zero-gradient or a conventional hot stage. We suggest that the in-plane thermal gradient accelerates phase separation through the enhancement in concentration fluctuations in the early and intermediate stages of spinodal decomposition. In a thermal gradient field, the strength of concentration fluctuation close to the critical point (above the spinodal line) is strong enough to induce phase separation even in one-phase regime of the phase diagram. In the presence of a temperature gradient the equilibrium phase diagrams are no longer valid, and the systems with an upper critical solution temperature can be quenched into phase separation by applying the stationary temperature gradient. The in-plane temperature gradient drives enhanced concentration fluctuations in a binary polymer blend system above and below the spinodal line.

Amide-induced phase separation of hexafluoroisopropanol-water mixtures depending on the hydrophobicity of amides.

PubMed

Takamuku, Toshiyuki; Wada, Hiroshi; Kawatoko, Chiemi; Shimomura, Takuya; Kanzaki, Ryo; Takeuchi, Munetaka

2012-06-21

Amide-induced phase separation of hexafluoro-2-propanol (HFIP)-water mixtures has been investigated to elucidate solvation properties of the mixtures by means of small-angle neutron scattering (SANS), (1)H and (13)C NMR, and molecular dynamics (MD) simulation. The amides included N-methylformamide (NMF), N-methylacetamide (NMA), and N-methylpropionamide (NMP). The phase diagrams of amide-HFIP-water ternary systems at 298 K showed that phase separation occurs in a closed-loop area of compositions as well as an N,N-dimethylformamide (DMF) system previously reported. The phase separation area becomes wider as the hydrophobicity of amides increases in the order of NMF < NMA < DMF < NMP. Thus, the evolution of HFIP clusters around amides due to the hydrophobic interaction gives rise to phase separation of the mixtures. In contrast, the disruption of HFIP clusters causes the recovery of the homogeneity of the ternary systems. The present results showed that HFIP clusters are evolved with increasing amide content to the lower phase separation concentration in the same mechanism among the four amide systems. However, the disruption of HFIP clusters in the NMP and DMF systems with further increasing amide content to the upper phase separation concentration occurs in a different way from those in the NMF and NMA systems.

Phase Separation and Crystallization of Hemoglobin C in Transgenic Mouse and Human Erythrocytes

PubMed Central

Canterino, Joseph E.; Galkin, Oleg; Vekilov, Peter G.; Hirsch, Rhoda Elison

2008-01-01

Individuals expressing hemoglobin C (β6 Glu→Lys) present red blood cells (RBC) with intraerythrocytic crystals that form when hemoglobin (Hb) is oxygenated. Our earlier in vitro liquid-liquid (L-L) phase separation studies demonstrated that liganded HbC exhibits a stronger net intermolecular attraction with a longer range than liganded HbS or HbA, and that L-L phase separation preceded and enhanced crystallization. We now present evidence for the role of phase separation in HbC crystallization in the RBC, and the role of the RBC membrane as a nucleation center. RBC obtained from both human homozygous HbC patients and transgenic mice expressing only human HbC were studied by bright-field and differential interference contrast video-enhanced microscopy. RBC were exposed to hypertonic NaCl solution (1.5–3%) to induce crystallization within an appropriate experimental time frame. L-L phase separation occurred inside the RBC, which in turn enhanced the formation of intraerythrocytic crystals. RBC L-L phase separation and crystallization comply with the thermodynamic and kinetics laws established through in vitro studies of phase transformations. This is the first report, to the best of our knowledge, to capture a temporal view of intraerythrocytic HbC phase separation, crystal formation, and dissolution. PMID:18621841

Phase separations in mixtures of a liquid crystal and a nanocolloidal particle.

PubMed

Matsuyama, Akihiko

2009-11-28

We present a mean field theory to describe phase separations in mixtures of a liquid crystal and a nanocolloidal particle. By taking into account a nematic, a smectic A ordering of the liquid crystal, and a crystalline ordering of the nanoparticle, we calculate the phase diagrams on the temperature-concentration plane. We predict various phase separations, such as a smectic A-crystal phase separation and a smectic A-isotropic-crystal triple point, etc., depending on the interactions between the liquid crystal and the colloidal surface. Inside binodal curves, we find new unstable and metastable regions, which are important in the phase ordering dynamics. We also find a crystalline ordering of the nanoparticles dispersed in a smectic A phase and a nematic phase. The cooperative phenomena between liquid-crystalline ordering and crystalline ordering induce a variety of phase diagrams.

Kinetics of phase separation and coarsening in dilute surfactant pentaethylene glycol monododecyl ether solutions

NASA Astrophysics Data System (ADS)

Tanaka, S.; Kubo, Y.; Yokoyama, Y.; Toda, A.; Taguchi, K.; Kajioka, H.

2011-12-01

We investigated the phase separation phenomena in dilute surfactant pentaethylene glycol monodedecyl ether (C12E5) solutions focusing on the growth law of separated domains. The solutions confined between two glass plates were found to exhibit the phase inversion, characteristic of the viscoelastic phase separation; the majority phase (water-rich phase) nucleated as droplets and the minority phase (micelle-rich phase) formed a network temporarily, then they collapsed into an usual sea-island pattern where minority phase formed islands. We found from the real-space microscopic imaging that the dynamic scaling hypothesis did not hold throughout the coarsening process. The power law growth of the domains with the exponent close to 1/3 was observed even though the coarsening was induced mainly by hydrodynamic flow, which was explained by Darcy's law of laminar flow.

Cell partition in two phase polymer systems

NASA Technical Reports Server (NTRS)

Brooks, D. E.

1979-01-01

Aqueous phase-separated polymer solutions can be used as support media for the partition of biological macromolecules, organelles and cells. Cell separations using the technique have proven to be extremely sensitive to cell surface properties but application of the systems are limited to cells or aggregates which do not significantly while the phases are settling. Partition in zero g in principle removes this limitation but an external driving force must be applied to induce the phases to separate since their density difference disappears. We have recently shown that an applied electric field can supply the necessary driving force. We are proposing to utilize the NASA FES to study field-driven phase separation and cell partition on the ground and in zero g to help define the separation/partition process, with the ultimate goal being to develop partition as a zero g cell separation technique.

Liquid Crystals in Chromatography

NASA Astrophysics Data System (ADS)

Witkiewicz, Zygfryd

The following sections are included: * INTRODUCTION * LIQUID CRYSTALS SUITABLE FOR GAS CHROMATOGRAPHY * Monomeric Liquid Crystal Stationary Phases * Polymeric Liquid Crystal Stationary Phases * Polymeric Liquid Crystal Stationary Phases * Conventional Analytical Columns * Capillary Columns * FACTORS AFFECTING THE CHROMATOGRAPHIC SEPARATIONS ON LIQUID CRYSTAL STATIONARY PHASES * Kind of Mesophase of the Liquid Crystal * Molecular Structure of the Liquid Crystals and of the Chromatographed Substances * Substrate on which the Liquid Crystal is Deposited * ANALYTICAL APPLICATIONS OF LIQUID CRYSTAL STATIONARY PHASES IN GAS CHROMATOGRAPHY * Separation of Isomers of Benzene and Naphthalene Derivatives * Separation of Alkane and Alkene Isomers * Separation of Mixtures of Benzene and Aliphatic Hydrocarbon Derivatives Containing Heteroatoms * Separation of Polynuclear Hydrocarbons * INVESTIGATION OF THE PROPERTIES OF LIQUID CRYSTALS BY GAS CHROMATOGRAPHY * APPLICATION OF LIQUID CRYSTALS IN LIQUID CHROMATOGRAPHY * Column Chromatography * Thin-Layer Chromatography * APPLICATION OF LIQUID CRYSTAL STATIONARY PHASES IN SUPERCRITICAL FLUID CHROMATOGRAPHY * FINAL REMARKS * References

Thermal cycling effects on static and dynamic properties of a phase separated manganite

NASA Astrophysics Data System (ADS)

Sacanell, J.; Sievers, B.; Quintero, M.; Granja, L.; Ghivelder, L.; Parisi, F.

2018-06-01

In this work we address the interplay between two phenomena which are signatures of the out-of-equilibrium state in phase separated manganites: irreversibility against thermal cycling and aging/rejuvenation process. The sample investigated is La0.5Ca0.5MnO3, a prototypical manganite exhibiting phase separation. Two regimes for isothermal relaxation were observed according to the temperature range: for T > 100 K, aging/rejuvenation effects are observed, while for T < 100 K an irreversible aging was found. Our results show that thermal cycles act as a tool to unveil the dynamical behavior of the phase separated state in manganites, revealing the close interplay between static and dynamic properties of phase separated manganites.

Stress-Triggered Phase Separation Is an Adaptive, Evolutionarily Tuned Response

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

Riback, Joshua A.; Katanski, Christopher D.; Kear-Scott, Jamie L.

In eukaryotic cells, diverse stresses trigger coalescence of RNA-binding proteins into stress granules. In vitro, stress-granule-associated proteins can demix to form liquids, hydrogels, and other assemblies lacking fixed stoichiometry. Observing these phenomena has generally required conditions far removed from physiological stresses. We show that poly(A)-binding protein (Pab1 in yeast), a defining marker of stress granules, phase separates and forms hydrogels in vitro upon exposure to physiological stress conditions. Other RNA-binding proteins depend upon low-complexity regions (LCRs) or RNA for phase separation, whereas Pab1’s LCR is not required for demixing, and RNA inhibits it. Based on unique evolutionary patterns, we createmore » LCR mutations, which systematically tune its biophysical properties and Pab1 phase separation in vitro and in vivo. Mutations that impede phase separation reduce organism fitness during prolonged stress. Poly(A)-binding protein thus acts as a physiological stress sensor, exploiting phase separation to precisely mark stress onset, a broadly generalizable mechanism.« less

Method for separating water soluble organics from a process stream by aqueous biphasic extraction

DOEpatents

Chaiko, David J.; Mego, William A.

1999-01-01

A method for separating water-miscible organic species from a process stream by aqueous biphasic extraction is provided. An aqueous biphase system is generated by contacting a process stream comprised of water, salt, and organic species with an aqueous polymer solution. The organic species transfer from the salt-rich phase to the polymer-rich phase, and the phases are separated. Next, the polymer is recovered from the loaded polymer phase by selectively extracting the polymer into an organic phase at an elevated temperature, while the organic species remain in a substantially salt-free aqueous solution. Alternatively, the polymer is recovered from the loaded polymer by a temperature induced phase separation (cloud point extraction), whereby the polymer and the organic species separate into two distinct solutions. The method for separating water-miscible organic species is applicable to the treatment of industrial wastewater streams, including the extraction and recovery of complexed metal ions from salt solutions, organic contaminants from mineral processing streams, and colorants from spent dye baths.

Process for improving soluble coal yield in a coal deashing process

DOEpatents

Rhodes, Donald E.

1980-01-01

Coal liquefaction products are contacted with a deashing solvent and introduced into a first separation zone. The first separation zone is maintained at an elevated temperature and pressure, determined to maximize the recovery of soluble coal products, to cause said coal liquefaction products to separate into a first light phase and a first heavy phase. Under these conditions the heavy phase while still fluid-like in character is substantially non-flowable. Flowability is returned to the fluid-like heavy phase by the introduction of an additional quantity of deashing solvent into the first separation zone at a location below the interface between the first light and heavy phases or into the heavy phase withdrawal conduit during withdrawal of the first heavy phase and prior to any substantial pressure reduction. The first heavy phase then is withdrawn from the first separation zone for additional downstream processing without plugging either the withdrawal conduit or the downstream apparatus. The first light phase comprising the soluble coal products is withdrawn and recovered in an increased yield to provide a more economical coal deashing process.

Understanding the Impact of Water on the Miscibility and Microstructure of Amorphous Solid Dispersions: An AFM-LCR and TEM-EDX Study.

PubMed

Li, Na; Gilpin, Christopher J; Taylor, Lynne S

2017-05-01

Miscibility is critical for amorphous solid dispersions (ASDs). Phase-separated ASDs are more prone to crystallization, and thus can lose their solubility advantage leading to product failure. Additionally, dissolution performance can be diminished as a result of phase separation in the ASD matrix. Water is known to induce phase separation during storage for some ASDs. However, the impact of water introduced during preparation has not been as thoroughly investigated to date. The purpose of this study was to develop a mechanistic understanding of the effect of water on the phase behavior and microstructure of ASDs. Evacetrapib and two polymers were selected as the model system. Atomic force microscopy coupled with Lorentz contact resonance, and transmission electron microscopy with energy dispersive X-ray spectroscopy were employed to evaluate the microstructure and composition of phase-separated ASDs. It was found that phase separation could be induced via two routes: solution-state phase separation during ASD formation caused by water absorption during film formation by a hydrophilic solvent, or solid-phase separation following exposure to high RH during storage. Water contents of as low as 2% in the organic solvent system used to dissolve the drug and polymer were found to result in phase separation in the resultant ASD film. These findings have profound implications on lab-scale ASD preparation and potentially also for industrial production. Additionally, these high-resolution imaging techniques combined with orthogonal analyses are powerful tools to visualize structural changes in ASDs, which in turn will enable better links to be made between ASD structure and performance.

Oriented Nucleation of both Ge-Fresnoite and Benitoite/BaGe4O9 during the Surface Crystallisation of Glass Studied by Electron Backscatter Diffraction

PubMed Central

Wisniewski, Wolfgang; Patschger, Marek; Murdzheva, Steliana; Thieme, Christian; Rüssel, Christian

2016-01-01

Two glasses of the compositions 2 BaO - TiO2 - 2.75 GeO2 and 2 BaO – TiO2 –3.67 GeO2 (also known as BTG55) are annealed at temperatures from 680 to 970 °C to induce surface crystallization. The resulting samples are analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) including electron backscatter diffraction (EBSD). Ge-Fresnoite (Ba2TiGe2O8, BTG) is observed at the immediate surface of all samples and oriented nucleation is proven in both compositions. After a very fast kinetic selection, the crystal growth of BTG into the bulk occurs via highly oriented dendrites where the c-axes are oriented perpendicular to the surface. The growth of this oriented layer is finally blocked by dendritc BTG originating from bulk nucleation. The secondary phases BaTiGe3O9 (benitoite) and BaGe4O9 are also identified near the surface by XRD and localized by EBSD which additionally indicates orientation preferences for these phases. This behaviour is in contrast with previous reports from the Ba2TiSi2O8 as well as the Sr2TiSi2O8 systems. PMID:26853738

The thickness of the crystal mush on the floor of the Bushveld magma chamber

NASA Astrophysics Data System (ADS)

Holness, Marian B.; Cawthorn, R. Grant; Roberts, James

2017-12-01

The thickness of the crystal mush on magma chamber floors can be constrained using the offset between the step-change in the median value of dihedral angles formed at the junctions between two grains of plagioclase and a grain of another phase (typically clinopyroxene, but also orthopyroxene and olivine) and the first appearance or disappearance of the liquidus phase associated with the step-change in median dihedral angle. We determined the mush thickness in the Rustenburg Layered Suite of the Bushveld Complex at clinopyroxene-in (in Lower Main Zone) and magnetite-in (in Upper Zone). We also examined an intermittent appearance of cumulus apatite in Upper Zone, using both the appearance and disappearance of cumulus apatite. In all cases, the mush thickness does not exceed 4 m. These values are consistent with field observations of a mechanically rigid mush at the bases of both magnetitite and chromitite layers overlying anorthosite. Mush thickness of the order of a few metres suggests that neither gravitationally-driven compaction nor compositional convection within the mush layer is likely to have been important processes during solidification: adcumulates in the Bushveld are most likely to have formed at the top of the mush during primary crystallisation. Similarly, it is unlikely either that migration of reactive liquids occurs through large stretches of stratigraphy, or that layering is formed by mechanisms other than primary accumulation.

Morphology and formation mechanism in precipitation of calcite induced by Curvibacter lanceolatus strain HJ-1

NASA Astrophysics Data System (ADS)

Zhang, Chonghong; Li, Fuchun; Lv, Jiejie

2017-11-01

Precipitation of calcium carbobate induced by microbial activities is common occurrence in controlled solution, but the formation mechanism and morphology in precipitation of calcite in solution systems is unclear, and the role of microbes is disputed. Here, culture experiment was performed for 50 days using the Curvibacter lanceolatus strain HJ-1 in a M2 culture medium, and the phase composition and morphology of the precipitates were characterized by the X-ray diffraction (XRD), Fourier transform infrared (FT-IR), and scanning electron microscopy (SEM) techniques. We show that the precipitation processes in our experiment lead to unusual morphologies of crystals corresponding to different growth stages, and the morphologies of the precipitated crystal aggregates ranging from the main rod-, cross-, star-, cauliflower-like morphologies to spherulitic structure. The complex and unusual morphologies of the precipitated calcite by strain HJ-1 may provide a reference point for better understanding the biomineralization mechanism of calcite, moreover, morphological transition of minerals revealed that the multi-ply crystals-aggregation mechanism for calcite growth in crystallisation media.

The isolation, purification and amino-acid sequence of insulin from the teleost fish Cottus scorpius (daddy sculpin).

PubMed

Cutfield, J F; Cutfield, S M; Carne, A; Emdin, S O; Falkmer, S

1986-07-01

Insulin from the principal islets of the teleost fish, Cottus scorpius (daddy sculpin), has been isolated and sequenced. Purification involved acid/alcohol extraction, gel filtration, and reverse-phase high-performance liquid chromatography to yield nearly 1 mg pure insulin/g wet weight islet tissue. Biological potency was estimated as 40% compared to porcine insulin. The sculpin insulin crystallised in the absence of zinc ions although zinc is known to be present in the islets in significant amounts. Two other hormones, glucagon and pancreatic polypeptide, were copurified with the insulin, and an N-terminal sequence for pancreatic polypeptide was determined. The primary structure of sculpin insulin shows a number of sequence changes unique so far amongst teleost fish. These changes occur at A14 (Arg), A15 (Val), and B2 (Asp). The B chain contains 29 amino acids and there is no N-terminal extension as seen with several other fish. Presumably as a result of the amino acid substitutions, sculpin insulin does not readily form crystals containing zinc-insulin hexamers, despite the presence of the coordinating B10 His.

EBSD Imaging of Monazite: a Petrochronological Tool?

NASA Astrophysics Data System (ADS)

Mottram, C. M.; Cottle, J. M.

2014-12-01

Recent advances in in-situ U-Th/Pb monazite petrochronology allow ages obtained from micron-scale portions of texturally-constrained, individual crystals to be placed directly into a quantitative Pressure-Temperature framework. However, there remain major unresolved challenges in linking monazite ages to specific deformation events and discerning the effects of deformation on the isotopic and elemental tracers in these phases. Few studies have quantitatively investigated monazite microstructure, and these studies have largely focused only on crystals produced experimentally (e.g. Reddy et al., 2010). The dispersion in age data commonly yielded from monazite U-Th/Pb datasets suggest that monazite dynamically recrystallises during deformation. It remains unclear how this continual recrystallisation is reflected in the monazite crystal structure, and how this subsequently impacts the ages (or age ranges) yielded from single crystals. Here, combined laser ablation split-stream analysis of deformed monazite, EBSD imaging and Pressure-Temperature (P-T) phase equilibria modelling is used to quantify the influence of deformation on monazite (re)crystallisation mechanisms and its subsequent effect on the crystallographic structure, ages and trace-element distribution in individual grains. These data provide links between ages and specific deformation events, thus helping further our understanding of the role of dynamic recrystallisation in producing age variation within and between crystals in a deformed rock. These data provide a new dimension to the field of petrochronology, demonstrating the importance of fully integrating the Pressure-Temperature-time-deformation history of accessory phases to better interpret the meaningfulness of ages yielded from deformed rocks. Reddy, S. et al., 2010. Mineralogical Magazine 74: 493-506

Continuously phase-modulated standing surface acoustic waves for separation of particles and cells in microfluidic channels containing multiple pressure nodes

NASA Astrophysics Data System (ADS)

Lee, Junseok; Rhyou, Chanryeol; Kang, Byungjun; Lee, Hyungsuk

2017-04-01

This paper describes continuously phase-modulated standing surface acoustic waves (CPM-SSAW) and its application for particle separation in multiple pressure nodes. A linear change of phase in CPM-SSAW applies a force to particles whose magnitude depends on their size and contrast factors. During continuous phase modulation, we demonstrate that particles with a target dimension are translated in the direction of moving pressure nodes, whereas smaller particles show oscillatory movements. The rate of phase modulation is optimized for separation of target particles from the relationship between mean particle velocity and period of oscillation. The developed technique is applied to separate particles of a target dimension from the particle mixture. Furthermore, we also demonstrate human keratinocyte cells can be separated in the cell and bead mixture. The separation technique is incorporated with a microfluidic channel spanning multiple pressure nodes, which is advantageous over separation in a single pressure node in terms of throughput.

Selective Detection of Peptide-Oligonucleotide Heteroconjugates Utilizing Capillary HPLC-ICPMS

NASA Astrophysics Data System (ADS)

Catron, Brittany; Caruso, Joseph A.; Limbach, Patrick A.

2012-06-01

A method for the selective detection and quantification of peptide:oligonucleotide heteroconjugates, such as those generated by protein:nucleic acid cross-links, using capillary reversed-phase high performance liquid chromatography (cap-RPHPLC) coupled with inductively coupled plasma mass spectrometry detection (ICPMS) is described. The selective detection of phosphorus as 31P+, the only natural isotope, in peptide-oligonucleotide heteroconjugates is enabled by the elemental detection capabilities of the ICPMS. Mobile phase conditions that allow separation of heteroconjugates while maintaining ICPMS compatibility were investigated. We found that trifluoroacetic acid (TFA) mobile phases, used in conventional peptide separations, and hexafluoroisopropanol/triethylamine (HFIP/TEA) mobile phases, used in conventional oligonucleotide separations, both are compatible with ICPMS and enable heteroconjugate separation. The TFA-based separations yielded limits of detection (LOD) of ~40 ppb phosphorus, which is nearly seven times lower than the LOD for HFIP/TEA-based separations. Using the TFA mobile phase, 1-2 pmol of a model heteroconjugate were routinely separated and detected by this optimized capLC-ICPMS method.

Images reveal that atmospheric particles can undergo liquid–liquid phase separations

PubMed Central

You, Yuan; Renbaum-Wolff, Lindsay; Carreras-Sospedra, Marc; Hanna, Sarah J.; Hiranuma, Naruki; Kamal, Saeid; Smith, Mackenzie L.; Zhang, Xiaolu; Weber, Rodney J.; Shilling, John E.; Dabdub, Donald; Martin, Scot T.; Bertram, Allan K.

2012-01-01

A large fraction of submicron atmospheric aerosol particles contains both organic material and inorganic salts. As the relative humidity cycles in the atmosphere and the water content of the particles correspondingly changes, these mixed particles can undergo a range of phase transitions, possibly including liquid–liquid phase separation. If liquid–liquid phase separation occurs, the gas-particle partitioning of atmospheric semivolatile organic compounds, the scattering and absorption of solar radiation, and the reactive uptake of gas species on atmospheric particles may be affected, with important implications for climate predictions. The actual occurrence of liquid–liquid phase separation within individual atmospheric particles has been considered uncertain, in large part because of the absence of observations for real-world samples. Here, using optical and fluorescence microscopy, we present images that show the coexistence of two noncrystalline phases for real-world samples collected on multiple days in Atlanta, GA as well as for laboratory-generated samples under simulated atmospheric conditions. These results reveal that atmospheric particles can undergo liquid–liquid phase separations. To explore the implications of these findings, we carried out simulations of the Atlanta urban environment and found that liquid–liquid phase separation can result in increased concentrations of gas-phase NO3 and N2O5 due to decreased particle uptake of N2O5. PMID:22847443

Images reveal that atmospheric particles can undergo liquid-liquid phase separations.

PubMed

You, Yuan; Renbaum-Wolff, Lindsay; Carreras-Sospedra, Marc; Hanna, Sarah J; Hiranuma, Naruki; Kamal, Saeid; Smith, Mackenzie L; Zhang, Xiaolu; Weber, Rodney J; Shilling, John E; Dabdub, Donald; Martin, Scot T; Bertram, Allan K

2012-08-14

A large fraction of submicron atmospheric aerosol particles contains both organic material and inorganic salts. As the relative humidity cycles in the atmosphere and the water content of the particles correspondingly changes, these mixed particles can undergo a range of phase transitions, possibly including liquid-liquid phase separation. If liquid-liquid phase separation occurs, the gas-particle partitioning of atmospheric semivolatile organic compounds, the scattering and absorption of solar radiation, and the reactive uptake of gas species on atmospheric particles may be affected, with important implications for climate predictions. The actual occurrence of liquid-liquid phase separation within individual atmospheric particles has been considered uncertain, in large part because of the absence of observations for real-world samples. Here, using optical and fluorescence microscopy, we present images that show the coexistence of two noncrystalline phases for real-world samples collected on multiple days in Atlanta, GA as well as for laboratory-generated samples under simulated atmospheric conditions. These results reveal that atmospheric particles can undergo liquid-liquid phase separations. To explore the implications of these findings, we carried out simulations of the Atlanta urban environment and found that liquid-liquid phase separation can result in increased concentrations of gas-phase NO(3) and N(2)O(5) due to decreased particle uptake of N(2)O(5).

Self-referenced locking of optical coherence by single-detector electronic-frequency tagging

NASA Astrophysics Data System (ADS)

Shay, T. M.; Benham, Vincent; Spring, Justin; Ward, Benjamin; Ghebremichael, F.; Culpepper, Mark A.; Sanchez, Anthony D.; Baker, J. T.; Pilkington, D.; Berdine, Richard

2006-02-01

We report a novel coherent beam combining technique. This is the first actively phase locked optical fiber array that eliminates the need for a separate reference beam. In addition, only a single photodetector is required. The far-field central spot of the array is imaged onto the photodetector to produce the phase control loop signals. Each leg of the fiber array is phase modulated with a separate RF frequency, thus tagging the optical phase shift for each leg by a separate RF frequency. The optical phase errors for the individual array legs are separated in the electronic domain. In contrast with the previous active phase locking techniques, in our system the reference beam is spatially overlapped with all the RF modulated fiber leg beams onto a single detector. The phase shift between the optical wave in the reference leg and in the RF modulated legs is measured separately in the electronic domain and the phase error signal is feedback to the LiNbO 3 phase modulator for that leg to minimize the phase error for that leg relative to the reference leg. The advantages of this technique are 1) the elimination of the reference beam and beam combination optics and 2) the electronic separation of the phase error signals without any degradation of the phase locking accuracy. We will present the first theoretical model for self-referenced LOCSET and describe experimental results for a 3 x 3 array.

Improved Separations of Proteins and Sugar Derivatives Using the Small-Scale Cross-Axis Coil Planet Centrifuge with Locular Multilayer Coiled Columns.

PubMed

Shinomiya, Kazufusa; Umezawa, Motoki; Seki, Manami; Nitta, Jun; Zaima, Kazumasa; Harikai, Naoki; Ito, Yoichiro

2016-12-01

Countercurrent chromatography (CCC) is liquid-liquid partition chromatography without using a solid support matrix. This technique requires further improvement of partition efficiency and shortening theseparation time. The locular multilayer coils modified with and without mixer glass beads were developed for the separation of proteins and 4-methylumbelliferyl (MU) sugar derivatives using the small-scale cross-axis coil planet centrifuge. Proteins were well separated from each other and the separation was improved at a low flow rate of the mobile phase. On the other hand, 4-MU sugar derivatives were sufficiently resolved with short separation time at a highflow rate of the mobile phase under satisfactory stationary phase retention. Effective separations were achieved using the locular multilayer coil for proteins with aqueous-aqueous polymer phase systems and for 4-MU sugar derivatives with organic-aqueous two-phase solvent systems by inserting a glass bead into each locule.

Enantiomeric separation of type I and type II pyrethroid insecticides with different chiral stationary phases by reversed-phase high-performance liquid chromatography.

PubMed

Zhang, Ping; Yu, Qian; He, Xiulong; Qian, Kun; Xiao, Wei; Xu, Zhifeng; Li, Tian; He, Lin

2018-04-01

The enantiomeric separation of type I (bifenthrin, BF) and type II (lambda-cyhalothrin, LCT) pyrethroid insecticides on Lux Cellulose-1, Lux Cellulose-3, and Chiralpak IC chiral columns was investigated by reversed-phase high-performance liquid chromatography. Methanol/water or acetonitrile/water was used as mobile phase at a flow rate of 0.8 mL/min. The effects of chiral stationary phase, mobile phase composition, column temperature, and thermodynamic parameters on enantiomer separation were carefully studied. Bifenthrin got a partial separation on Lux Cellulose-1 column and baseline separation on Lux Cellulose-3 column, while LCT enantiomers could be completely separated on both Lux Cellulose-1 and Lux Cellulose-3 columns. Chiralpak IC provided no separation ability for both BF and LCT. Retention factor (k) and selectivity factor (α) decreased with the column temperature increasing from 10°C to 40°C for both BF and LCT enantiomers. Thermodynamic parameters including ∆H and ∆S were also calculated, and the maximum R s were not always obtained at lowest temperature. Furthermore, the quantitative analysis methods for BF and LCT enantiomers in soil and water were also established. Such results provide a new approach for pyrethroid separation under reversed-phase condition and contribute to environmental risk assessment of pyrethroids at enantiomer level. © 2017 Wiley Periodicals, Inc.

Separation of Iron Phase and P-Bearing Slag Phase from Gaseous-Reduced, High-Phosphorous Oolitic Iron Ore at 1473 K (1200 °C) by Super Gravity

NASA Astrophysics Data System (ADS)

Gao, Jintao; Zhong, Yiwei; Guo, Lei; Guo, Zhancheng

2016-04-01

In situ observation on the morphology evolution and phosphorous migration of gaseous-reduced, high-phosphorous oolitic iron ore during the melting process was carried out with a high-temperature confocal scanning laser microscope. The results showed that 1473 K (1200 °C) was a critical temperature at which the gangue minerals started to form into the slag phase while the iron grains remained in a solid state; in addition, the phosphorus remained in the slag phase. Since the separation of iron grains and P-bearing slag was not achieved at the low temperature under the conventional conditions, separate experiments of the iron phase and the P-bearing slag phase from gaseous-reduced, high-phosphorous oolitic iron ore at 1473 K (1200 °C) by super gravity were carried out in this study. Based on the iron-slag separation by super gravity, phosphorus was removed effectively from the iron phase at the temperature below the melting point of iron. Iron grains moved along the super-gravity direction, joined, and concentrated as the iron phase on the filter, whereas the slag phase containing apatite crystals broke through the barriers of the iron grains and went through the filter. Consequently, increasing the gravity coefficient was definitely beneficial for the separation of the P-bearing slag phase from the iron phase. With the gravity coefficient of G = 1200, the mass fractions of separated slag and iron phases were close to their respective theoretical values, and the mass fraction of MFe in the separated iron phase was up to 98.09 wt pct and that of P was decreased to 0.083 wt pct. The recovery of MFe in the iron phase and that of P in the slag phase were up to 99.19 and 95.83 pct, respectively.

Formation of porous crystals via viscoelastic phase separation

NASA Astrophysics Data System (ADS)

Tsurusawa, Hideyo; Russo, John; Leocmach, Mathieu; Tanaka, Hajime

2017-10-01

Viscoelastic phase separation of colloidal suspensions can be interrupted to form gels either by glass transition or by crystallization. With a new confocal microscopy protocol, we follow the entire kinetics of phase separation, from homogeneous phase to different arrested states. For the first time in experiments, our results unveil a novel crystallization pathway to sponge-like porous crystal structures. In the early stages, we show that nucleation requires a structural reorganization of the liquid phase, called stress-driven ageing. Once nucleation starts, we observe that crystallization follows three different routes: direct crystallization of the liquid phase, the Bergeron process, and Ostwald ripening. Nucleation starts inside the reorganized network, but crystals grow past it by direct condensation of the gas phase on their surface, driving liquid evaporation, and producing a network structure different from the original phase separation pattern. We argue that similar crystal-gel states can be formed in monatomic and molecular systems if the liquid phase is slow enough to induce viscoelastic phase separation, but fast enough to prevent immediate vitrification. This provides a novel pathway to form nanoporous crystals of metals and semiconductors without dealloying, which may be important for catalytic, optical, sensing, and filtration applications.

Phase separation of self-propelled ballistic particles

NASA Astrophysics Data System (ADS)

Bruss, Isaac R.; Glotzer, Sharon C.

2018-04-01

Self-propelled particles phase-separate into coexisting dense and dilute regions above a critical density. The statistical nature of their stochastic motion lends itself to various theories that predict the onset of phase separation. However, these theories are ill-equipped to describe such behavior when noise becomes negligible. To overcome this limitation, we present a predictive model that relies on two density-dependent timescales: τF, the mean time particles spend between collisions; and τC, the mean lifetime of a collision. We show that only when τF<τC do collisions last long enough to develop a growing cluster and initiate phase separation. Using both analytical calculations and active particle simulations, we measure these timescales and determine the critical density for phase separation in both two and three dimensions.

Suppression of turbulent energy cascade due to phase separation in homogenous binary mixture fluid

NASA Astrophysics Data System (ADS)

Takagi, Youhei; Okamoto, Sachiya

2015-11-01

When a multi-component fluid mixture becomes themophysically unstable state by quenching from well-melting condition, phase separation due to spinodal decomposition occurs, and a self-organized structure is formed. During phase separation, free energy is consumed for the structure formation. In our previous report, the phase separation in homogenous turbulence was numerically simulated and the coarsening process of phase separation was discussed. In this study, we extended our numerical model to a high Schmidt number fluid corresponding to actual polymer solution. The governing equations were continuity, Navier-Stokes, and Chan-Hiliard equations as same as our previous report. The flow filed was an isotropic homogenous turbulence, and the dimensionless parameters in the Chan-Hilliard equation were estimated based on the thermophysical condition of binary mixture. From the numerical results, it was found that turbulent energy cascade was drastically suppressed in the inertial subrange by phase separation for the high Schmidt number flow. By using the identification of turbulent and phase separation structure, we discussed the relation between total energy balance and the structures formation processes. This study is financially supported by the Grand-in-Aid for Young Scientists (B) (No. T26820045) from the Ministry of Education, Cul-ture, Sports, Science and Technology of Japan.

Temperature-Induced Phase Separation in Molecular Assembly of Nanotubes Comprising Amphiphilic Polypeptide with Poly( N-Ethyl Glycine) in Water by a Hydrophilic-Region Driven Type Mechanism.

PubMed

Hattori, Tetsuya; Itagaki, Toru; Uji, Hirotaka; Kimura, Shunsaku

2018-06-20

Two kinds of amphiphilic polypeptides having different types of hydrophilic polypeptoids, poly(sarcosine)-b-(L-Leu-Aib)6 (ML12) and poly(N-ethyl glycine)-b-(L-Leu-Aib)6 (EL12), were self-assembled via two paths to phase-separated nanotubes. One path was via sticking ML12 nanotubes with EL12 nanotubes, and the other was a preparation from a mixture of ML12 and EL12 in solution. In either case, nanotubes showed temperature-induced phase separation along the long axis, which was observed by two methods of labeling one phase with gold nanoparticles and fluorescence resonance energy transfer between the components. The phase-separation was ascribed to aggregation of poly(N-ethyl glycine) blocks over the cloud point temperature. The addition of 5% trifluoroethanol was needed for the phase separation, because the tight association of the helices in the hydrophobic region should be loosened to allow lateral diffusion of the components to be separated. The phase-separation in molecular assemblies in water based on the hydrophilic-region driven type mechanism therefore requires sophisticated balances of association forces exerting among the hydrophilic and hydrophobic regions of the amphiphilic polypeptoids.

Impinging jet separators for liquid metal magnetohydrodynamic power cycles

NASA Technical Reports Server (NTRS)

Bogdanoff, D. W.

1973-01-01

In many liquid metal MHD power, cycles, it is necessary to separate the phases of a high-speed liquid-gas flow. The usual method is to impinge the jet at a glancing angle against a solid surface. These surface separators achieve good separation of the two phases at a cost of a large velocity loss due to friction at the separator surface. This report deals with attempts to greatly reduce the friction loss by impinging two jets against each other. In the crude impinging jet separators tested to date, friction losses were greatly reduced, but the separation of the two phases was found to be much poorer than that achievable with surface separators. Analyses are presented which show many lines of attack (mainly changes in separator geometry) which should yield much better separation for impinging jet separators).

Observations of liquid-liquid phase separation in several types of secondary organic materials free of inorganic salts

NASA Astrophysics Data System (ADS)

Song, M.; Liu, P.; Martin, S. T.; Bertram, A. K.; Ham, S.

2016-12-01

Particles consisting of secondary organic materials (SOMs) are ubiquitous in the atmosphere. In order to predict the role of these particles in climate, visibility, and atmospheric chemistry, knowledge of the phase states of the particles is required. However, the phase states of the SOMs are still poorly understood. Herein we focused on liquid-liquid phase separation in different types of SOM particles free of inorganic salts produced by the ozonolysis of β-caryophyllene, ozonolysis of limonene, photo-oxidation of isoprene, and photo-oxidation of toluene. Liquid-liquid phase separation was investigated using optical microscopy and SOM particle mass concentrations ranging from 15 µg·m-3 to 7000 µg·m-3. During humidity cycles, liquid-liquid phase separation was observed in β-caryophyllene-derived SOM and limonene-derived SOM particles while no liquid-liquid phase separation was observed in isoprene-derived SOM and toluene-derived SOM particles. Results from the studies will be presented.

Cell Partition in Two Polymer Aqueous Phases

NASA Technical Reports Server (NTRS)

Brooks, D. E.

1985-01-01

In a reduced gravity environment the two polymer phases will not separate via density driven settling in an acceptably short length of time. It is to be expected that a certain amount of phase separation will take place, however, driven by the reduction in free energy gained when the interfacial area is reduced. This stage of separation process will therefore depend directly on the magnitude of the interfacial tension between the phases. In order to induce complete phase separation in a short time, electric field-induced separation which occurs because the droplets of one phase in the other have high electrophoretic mobilities which increase with droplet size was investigated. These mobilities are significant only in the presence of certain salts, particularly phosphates. The presence of such salts, in turn has a strong effect on the cell partition behavior in dextran-poly (ethylene glycol) (PEG) systems. The addition of the salts necessary to produce phase drop mobilities has a large effect on the interfacial tensions in the systems.

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.

Binary Colloidal Alloy Test-5: Phase Separation

NASA Technical Reports Server (NTRS)

Lynch, Matthew; Weitz, David A.; Lu, Peter J.

2008-01-01

The Binary Colloidal Alloy Test - 5: Phase Separation (BCAT-5-PhaseSep) experiment will photograph initially randomized colloidal samples onboard the ISS to determine their resulting structure over time. This allows the scientists to capture the kinetics (evolution) of their samples, as well as the final equilibrium state of each sample. BCAT-5-PhaseSep studies collapse (phase separation rates that impact product shelf-life); in microgravity the physics of collapse is not masked by being reduced to a simple top and bottom phase as it is on Earth.

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

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.

Gas-Liquid Flows and Phase Separation

NASA Technical Reports Server (NTRS)

McQuillen, John

2004-01-01

Common issues for space system designers include:Ability to Verify Performance in Normal Gravity prior to Deployment; System Stability; Phase Accumulation & Shedding; Phase Separation; Flow Distribution through Tees & Manifolds Boiling Crisis; Heat Transfer Coefficient; and Pressure Drop.The report concludes:Guidance similar to "A design that operates in a single phase is less complex than a design that has two-phase flow" is not always true considering the amount of effort spent on pressurizing, subcooling and phase separators to ensure single phase operation. While there is still much to learn about two-phase flow in reduced gravity, we have a good start. Focus now needs to be directed more towards system level problems .

Distinction of synthetic dl-α-tocopherol from natural vitamin E (d-α-tocopherol) by reversed-phase liquid chromatography. Enhanced selectivity of a polymeric C18 stationary phase at low temperature and/or at high pressure.

PubMed

Yui, Yuko; Miyazaki, Shota; Ma, Yan; Ohira, Masayoshi; Fiehn, Oliver; Ikegami, Tohru; McCalley, David V; Tanaka, Nobuo

2016-06-10

Separation of diastereomers of dl-α-tocopherol was studied by reversed-phase liquid chromatography using three types of stationary phases, polymeric ODS, polymeric C30, and monomeric ODS. Polymeric ODS stationary phase (Inertsil ODS-P, 3mmID, 20cm) was effective for the separation of the isomers created by the presence of three chiral centers on the alkyl chain of synthetic dl-α-tocopherol. Considerable improvement of the separation of isomers was observed on ODS-P phase at high pressure and at low temperature. Complete separation of four pairs of diastereomers was achieved at 12.0°C, 536bar, while three peaks were observed when the separation was carried out either at 12.0°C at low pressure or at 20°C at 488bar. Higher temperature (30.0°C) with the ODS-P phase resulted in only partial separation of the diastereomers even at high pressure. Only slight resolution was observed for the mixture of diastereomers with the C30 stationary phase (Inertsil C30) at 12.0°C and 441bar, although the stationary phase afforded greater resolution for β- and γ-tocopherol than ODS-P. A monomeric C18 stationary phase did not show any separation at 12.0°C and 463bar. The results suggest that the binding site of the polymeric ODS-P phase is selective for flexible alkyl chains that provided the longest retention for the natural form, (R,R,R) form, and the enantiomer, (S,S,S) form, of dl-α-tocopherol. Copyright © 2016. Published by Elsevier B.V.

Integral equation theory study on the phase separation in star polymer nanocomposite melts.

PubMed

Zhao, Lei; Li, Yi-Gui; Zhong, Chongli

2007-10-21

The polymer reference interaction site model theory is used to investigate phase separation in star polymer nanocomposite melts. Two kinds of spinodal curves were obtained: classic fluid phase boundary for relatively low nanoparticle-monomer attraction strength and network phase boundary for relatively high nanoparticle-monomer attraction strength. The network phase boundaries are much more sensitive with nanoparticle-monomer attraction strength than the fluid phase boundaries. The interference among the arm number, arm length, and nanoparticle-monomer attraction strength was systematically investigated. When the arm lengths are short, the network phase boundary shows a marked shift toward less miscibility with increasing arm number. When the arm lengths are long enough, the network phase boundaries show opposite trends. There exists a crossover arm number value for star polymer nanocomposite melts, below which the network phase separation is consistent with that of chain polymer nanocomposite melts. However, the network phase separation shows qualitatively different behaviors when the arm number is larger than this value.

Liquid-liquid phase separation of freely falling undercooled ternary Fe-Cu-Sn alloy

NASA Astrophysics Data System (ADS)

Wang, W. L.; Wu, Y. H.; Li, L. H.; Zhai, W.; Zhang, X. M.; Wei, B.

2015-11-01

The active modulation and control of the liquid phase separation for high-temperature metallic systems are still challenging the development of advanced immiscible alloys. Here we present an attempt to manipulate the dynamic process of liquid-liquid phase separation for ternary Fe47.5Cu47.5Sn5 alloy. It was firstly dispersed into numerous droplets with 66 ~ 810 μm diameters and then highly undercooled and rapidly solidified under the containerless microgravity condition inside drop tube. 3-D phase field simulation was performed to explore the kinetic evolution of liquid phase separation. Through regulating the combined effects of undercooling level, phase separation time and Marangoni migration, three types of separation patterns were yielded: monotectic cell, core shell and dispersive structures. The two-layer core-shell morphology proved to be the most stable separation configuration owing to its lowest chemical potential. Whereas the monotectic cell and dispersive microstructures were both thermodynamically metastable transition states because of their highly active energy. The Sn solute partition profiles of Fe-rich core and Cu-rich shell in core-shell structures varied only slightly with cooling rate.

Extent and mechanism of phase separation during the extrusion of calcium phosphate pastes.

PubMed

O'Neill, Rory; McCarthy, Helen O; Cunningham, Eoin; Montufar, Edgar; Ginebra, Maria-Pau; Wilson, D Ian; Lennon, Alex; Dunne, Nicholas

2016-02-01

The aim of this study was to increase understanding of the mechanism and dominant drivers influencing phase separation during ram extrusion of calcium phosphate (CaP) paste for orthopaedic applications. The liquid content of extrudate was determined, and the flow of liquid and powder phases within the syringe barrel during extrusion were observed, subject to various extrusion parameters. Increasing the initial liquid-to-powder mass ratio, LPR, (0.4-0.45), plunger rate (5-20 mm/min), and tapering the barrel exit (45°-90°) significantly reduced the extent of phase separation. Phase separation values ranged from (6.22 ± 0.69 to 18.94 ± 0.69 %). However altering needle geometry had no significant effect on phase separation. From powder tracing and liquid content determination, static zones of powder and a non-uniform liquid distribution was observed within the barrel. Measurements of extrudate and paste LPR within the barrel indicated that extrudate LPR remained constant during extrusion, while LPR of paste within the barrel decreased steadily. These observations indicate the mechanism of phase separation was located within the syringe barrel. Therefore phase separation can be attributed to either; (1) the liquid being forced downstream by an increase in pore pressure as a result of powder consolidation due to the pressure exerted by the plunger or (2) the liquid being drawn from paste within the barrel, due to suction, driven by dilation of the solids matrix at the barrel exit. Differentiating between these two mechanisms is difficult; however results obtained suggest that suction is the dominant phase separation mechanism occurring during extrusion of CaP paste.

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.

Comparing the selectivity and chiral separation of d- and l- fluorenylmethyloxycarbonyl chloride protected amino acids in analytical high performance liquid chromatography and supercritical fluid chromatography; evaluating throughput, economic and environmental impact.

PubMed

Vera, C M; Shock, D; Dennis, G R; Farrell, W; Shalliker, R A

2017-04-14

The chiral separation of d- and l- FMOC amino acids was undertaken using the Lux Cellulose-1 polysaccharide based chiral column in HPLC (normal phase and reverse phase) and SFC conditions. This was done to compare the relative selectivity and separation between the three separation modes and to evaluate the potential benefits of SFC separations with regards to resolution, throughput, economic and environmental impact. It was established that the separation of d- and l- FMOC amino acids in SFC displayed behaviours that were similar to both normal phase and reversed phase, rather than distinctly one or the other. Additionally, although reversed phase conditions yielded significantly higher resolution values between enantiomers across the range of amino acids studied, improvements in selectivity in SFC via the introduction of higher concentrations of formic acid in the mobile phase allowed for better resolution per unit of time. Moreover since the SFC mobile phase is composed mostly of recyclable CO 2 , there is a reduction in organic solvent consumption, which minimises the economic and environmental costs. Copyright © 2017. Published by Elsevier B.V.

Nanoscopy of Phase Separation in InxGa1-xN Alloys.

PubMed

Abate, Yohannes; Seidlitz, Daniel; Fali, Alireza; Gamage, Sampath; Babicheva, Viktoriia; Yakovlev, Vladislav S; Stockman, Mark I; Collazo, Ramon; Alden, Dorian; Dietz, Nikolaus

2016-09-07

Phase separations in ternary/multinary semiconductor alloys is a major challenge that limits optical and electronic internal device efficiency. We have found ubiquitous local phase separation in In1-xGaxN alloys that persists to nanoscale spatial extent by employing high-resolution nanoimaging technique. We lithographically patterned InN/sapphire substrates with nanolayers of In1-xGaxN down to few atomic layers thick that enabled us to calibrate the near-field infrared response of the semiconductor nanolayers as a function of composition and thickness. We also developed an advanced theoretical approach that considers the full geometry of the probe tip and all the sample and substrate layers. Combining experiment and theory, we identified and quantified phase separation in epitaxially grown individual nanoalloys. We found that the scale of the phase separation varies widely from particle to particle ranging from all Ga- to all In-rich regions and covering everything in between. We have found that between 20 and 25% of particles show some level of Ga-rich phase separation over the entire sample region, which is in qualitative agreement with the known phase diagram of In1-xGaxN system.

Low density microcellular foams

DOEpatents

Aubert, J.H.; Clough, R.L.; Curro, J.G.; Quintana, C.A.; Russick, E.M.; Shaw, M.T.

1985-10-02

Low density, microporous polymer foams are provided by a process which comprises forming a solution of polymer and a suitable solvent followed by rapid cooling of the solution to form a phase-separated system and freeze the phase-separated system. The phase-separated system comprises a polymer phase and a solvent phase, each of which is substantially continuous within the other. The morphology of the polymer phase prior to and subsequent to freezing determine the morphology of the resultant foam. Both isotropic and anisotropic foams can be produced. If isotropic foams are produced, the polymer and solvent are tailored such that the solution spontaneously phase-separates prior to the point at which any component freezes. The morphology of the resultant polymer phase determines the morphology of the reusltant foam and the morphology of the polymer phase is retained by cooling the system at a rate sufficient to freeze one or both components of the system before a change in morphology can occur. Anisotropic foams are produced by forming a solution of polymer and solvent that will not phase separate prior to freezing of one or both components of the solution. In such a process, the solvent typically freezes before phase separation occurs. The morphology of the resultant frozen two-phase system determines the morphology of the resultant foam. The process involves subjecting the solution to essentially one-dimensional cooling. Foams having a density of less than 0.1 g/cc and a uniform cell size of less than 10 ..mu..m and a volume such that the foams have a length greater than 1 cm are provided.

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.

Origin of Reversible Photoinduced Phase Separation in Hybrid Perovskites.

PubMed

Bischak, Connor G; Hetherington, Craig L; Wu, Hao; Aloni, Shaul; Ogletree, D Frank; Limmer, David T; Ginsberg, Naomi S

2017-02-08

The distinct physical properties of hybrid organic-inorganic materials can lead to unexpected nonequilibrium phenomena that are difficult to characterize due to the broad range of length and time scales involved. For instance, mixed halide hybrid perovskites are promising materials for optoelectronics, yet bulk measurements suggest the halides reversibly phase separate upon photoexcitation. By combining nanoscale imaging and multiscale modeling, we find that the nature of halide demixing in these materials is distinct from macroscopic phase separation. We propose that the localized strain induced by a single photoexcited charge interacting with the soft, ionic lattice is sufficient to promote halide phase separation and nucleate a light-stabilized, low-bandgap, ∼8 nm iodide-rich cluster. The limited extent of this polaron is essential to promote demixing because by contrast bulk strain would simply be relaxed. Photoinduced phase separation is therefore a consequence of the unique electromechanical properties of this hybrid class of materials. Exploiting photoinduced phase separation and other nonequilibrium phenomena in hybrid materials more generally could expand applications in sensing, switching, memory, and energy storage.

Solar fuels generator

DOEpatents

Lewis, Nathan S.; Spurgeon, Joshua M.

2016-10-25

The solar fuels generator includes an ionically conductive separator between a gaseous first phase and a second phase. A photoanode uses one or more components of the first phase to generate cations during operation of the solar fuels generator. A cation conduit is positioned provides a pathway along which the cations travel from the photoanode to the separator. The separator conducts the cations. A second solid cation conduit conducts the cations from the separator to a photocathode.

Separation by solvent extraction

DOEpatents

Holt, Jr., Charles H.

1976-04-06

17. A process for separating fission product values from uranium and plutonium values contained in an aqueous solution, comprising adding an oxidizing agent to said solution to secure uranium and plutonium in their hexavalent state; contacting said aqueous solution with a substantially water-immiscible organic solvent while agitating and maintaining the temperature at from -1.degree. to -2.degree. C. until the major part of the water present is frozen; continuously separating a solid ice phase as it is formed; separating a remaining aqueous liquid phase containing fission product values and a solvent phase containing plutonium and uranium values from each other; melting at least the last obtained part of said ice phase and adding it to said separated liquid phase; and treating the resulting liquid with a new supply of solvent whereby it is practically depleted of uranium and plutonium.

Ordering-separation phase transitions in a Co3V alloy

NASA Astrophysics Data System (ADS)

Ustinovshchikov, Yu. I.

2017-01-01

The microstructure of the Co3V alloy formed by heat treatment at various temperatures is studied by transmission electron microscopy. Two ordering-separation phase transitions are revealed at temperatures of 400-450 and 800°C. At the high-temperature phase separation, the microstructure consists of bcc vanadium particles and an fcc solid solution; at the low-temperature phase separation, the microstructure is cellular. In the ordering range, the microstructure consists of chemical compound Co3V particles chaotically arranged in the solid solution. The structure of the Co3V alloy is shown not to correspond to the structures indicated in the Co-V phase diagram at any temperatures.

Formation of ion clusters in the phase separated structures of neutral-charged polymer blends

NASA Astrophysics Data System (ADS)

Kwon, Ha-Kyung; Olvera de La Cruz, Monica

2015-03-01

Polyelectrolyte blends, consisting of at least one charged species, are promising candidate materials for fuel cell membranes, for their mechanical stability and high selectivity for proton conduction. The phase behavior of the blends is important to understand, as this can significantly affect the performance of the device. The phase behavior is controlled by χN, the Flory-Huggins parameter multiplied by the number of mers, as well as the electrostatic interactions between the charged backbone and the counterions. It has recently been shown that local ionic correlations, incorporated via liquid state (LS) theory, enhance phase separation of the blend, even in the absence of polymer interactions. In this study, we show phase diagrams of neutral-charged polymer blends including ionic correlations via LS theory. In addition to enhanced phase separation at low χN, the blends show liquid-liquid phase separation at high electrostatic interaction strengths. Above the critical strength, the charged polymer phase separates into ion-rich and ion-poor regions, resulting in the formation of ion clusters within the charged polymer phase. This can be shown by the appearance of multiple spinodal and critical points, indicating the coexistence of several charge separated phases. This work was performed under the following financial assistance award 70NANB14H012 from U.S. Department of Commerce, National Institute of Standards and Technology as part of the Center for Hierarchical Materials Design (CHiMaD).

Phase Separation in Solutions of Monoclonal Antibodies

NASA Astrophysics Data System (ADS)

Benedek, George; Wang, Ying; Lomakin, Aleksey; Latypov, Ramil

2012-02-01

We report the observation of liquid-liquid phase separation (LLPS) in a solution of humanized monoclonal antibodies, IgG2, and the effects of human serum albumin, a major blood protein, on this phase separation. We find a significant reduction of phase separation temperature in the presence of albumin, and a preferential partitioning of the albumin into the antibody-rich phase. We provide a general thermodynamic analysis of the antibody-albumin mixture phase diagram and relate its features to the magnitude of the effective inter-protein interactions. Our analysis suggests that additives (HSA in this report), which have moderate attraction with antibody molecules, may be used to forestall undesirable protein condensation in antibody solutions. Our findings are relevant to understanding the stability of pharmaceutical solutions of antibodies and the mechanisms of cryoglobulinemia.

Lo/Ld phase coexistence modulation induced by GM1.

PubMed

Puff, Nicolas; Watanabe, Chiho; Seigneuret, Michel; Angelova, Miglena I; Staneva, Galya

2014-08-01

Lipid rafts are assumed to undergo biologically important size-modulations from nanorafts to microrafts. Due to the complexity of cellular membranes, model systems become important tools, especially for the investigation of the factors affecting "raft-like" Lo domain size and the search for Lo nanodomains as precursors in Lo microdomain formation. Because lipid compositional change is the primary mechanism by which a cell can alter membrane phase behavior, we studied the effect of the ganglioside GM1 concentration on the Lo/Ld lateral phase separation in PC/SM/Chol/GM1 bilayers. GM1 above 1mol % abolishes the formation of the micrometer-scale Lo domains observed in GUVs. However, the apparently homogeneous phase observed in optical microscopy corresponds in fact, within a certain temperature range, to a Lo/Ld lateral phase separation taking place below the optical resolution. This nanoscale phase separation is revealed by fluorescence spectroscopy, including C12NBD-PC self-quenching and Laurdan GP measurements, and is supported by Gaussian spectral decomposition analysis. The temperature of formation of nanoscale Lo phase domains over an Ld phase is determined, and is shifted to higher values when the GM1 content increases. A "morphological" phase diagram could be made, and it displays three regions corresponding respectively to Lo/Ld micrometric phase separation, Lo/Ld nanometric phase separation, and a homogeneous Ld phase. We therefore show that a lipid only-based mechanism is able to control the existence and the sizes of phase-separated membrane domains. GM1 could act on the line tension, "arresting" domain growth and thereby stabilizing Lo nanodomains. Copyright © 2014 Elsevier B.V. All rights reserved.

Study Of Phase Separation In Glass

NASA Technical Reports Server (NTRS)

Neilson, George F.; Weinberg, Michael C.; Smith, Gary L.

1989-01-01

Report describes an experimental study of effect of hydroxide content on phase separation in soda/silica glasses. Ordinary and gel glasses melted at 1,565 degree C, and melts stirred periodically. "Wet" glasses produced by passing bubbles of N2 saturated with water through melts; "dry" glasses prepared in similar manner, except N2 dried before passage through melts. Analyses of compositions of glasses performed by atomic-absorption and index-of-refraction measurements. Authors conclude hydroxide speeds up phase separation, regardless of method (gel or ordinary) by which glass prepared. Eventually helps material scientists to find ways to control morphology of phase separation.

Improved Separations of Proteins and Sugar Derivatives Using the Small-Scale Cross-Axis Coil Planet Centrifuge with Locular Multilayer Coiled Columns

PubMed Central

Shinomiya, Kazufusa; Umezawa, Motoki; Seki, Manami; Nitta, Jun; Zaima, Kazumasa; Harikai, Naoki; Ito, Yoichiro

2016-01-01

1) Background Countercurrent chromatography (CCC) is liquid-liquid partition chromatography without using a solid support matrix. This technique requires further improvement of partition efficiency and shortening theseparation time. 2) Methods The locular multilayer coils modified with and without mixer glass beads were developed for the separation of proteins and 4-methylumbelliferyl (MU) sugar derivatives using the small-scale cross-axis coil planet centrifuge. 3) Results Proteins were well separated from each other and the separation was improved at a low flow rate of the mobile phase. On the other hand, 4-MU sugar derivatives were sufficiently resolved with short separation time at a highflow rate of the mobile phase under satisfactory stationary phase retention. 4) Conclusion Effective separations were achieved using the locular multilayer coil for proteins with aqueous-aqueous polymer phase systems and for 4-MU sugar derivatives with organic-aqueous two-phase solvent systems by inserting a glass bead into each locule. PMID:27891507

The Role of RNA in Biological Phase Separations.

PubMed

Fay, Marta M; Anderson, Paul J

2018-05-10

Phase transitions that alter the physical state of ribonucleoprotein particles contribute to the spacial and temporal organization of the densely packed intracellular environment. This allows cells to organize biologically coupled processes as well as respond to environmental stimuli. RNA plays a key role in phase separation events that modulate various aspects of RNA metabolism. Here, we review the role that RNA plays in ribonucleoprotein phase separations. Copyright © 2018 Elsevier Ltd. All rights reserved.

Phase behavior of casein micelles/exocellular polysaccharide mixtures: Experiment and theory

NASA Astrophysics Data System (ADS)

Tuinier, R.; de Kruif, C. G.

1999-05-01

Dispersions of casein micelles and an exocellular polysaccharide (EPS), obtained from Lactococcus lactis subsp. cremoris NIZO B40 EPS, show a phase separation. The phase separation is of the colloidal gas-liquid type. We have determined a phase diagram that describes the separation of skim milk with EPS into a casein-micelle rich phase and an EPS rich phase. We compare the phase diagram with those calculated from theories developed by Vrij, and by Lekkerkerker and co-workers, showing that the experimental phase boundary can be predicted quite well. From dynamic light scattering measurements of the self-diffusion of the casein micelles in the presence of EPS the spinodal could be located and it corresponds with the experimental phase boundary.

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 Physical Model for Three-Phase Compaction in Silicic Magma Reservoirs

NASA Astrophysics Data System (ADS)

Huber, Christian; Parmigiani, Andrea

2018-04-01

We develop a model for phase separation in magma reservoirs containing a mixture of silicate melt, crystals, and fluids (exsolved volatiles). The interplay between the three phases controls the dynamics of phase separation and consequently the chemical and physical evolution of magma reservoirs. The model we propose is based on the two-phase damage theory approach of Bercovici et al. (2001, https://doi.org/10.1029/2000JB900430) and Bercovici and Ricard (2003, https://doi.org/10.1046/j.1365-246X.2003.01854.x) because it offers the leverage of considering interface (in the macroscopic limit) between phases that can deform depending on the mechanical work and phase changes taking place locally in the magma. Damage models also offer the advantage that pressure is defined uniquely to each phase and does not need to be equal among phases, which will enable us to consider, in future studies, the large capillary pressure at which fluids are mobilized in mature, crystal-rich, magma bodies. In this first analysis of three-phase compaction, we solve the three-phase compaction equations numerically for a simple 1-D problem where we focus on the effect of fluids on the efficiency of melt-crystal separation considering the competition between viscous and buoyancy stresses only. We contrast three sets of simulations to explore the behavior of three-phase compaction, a melt-crystal reference compaction scenario (two-phase compaction), a three-phase scenario without phase changes, and finally a three-phase scenario with a parameterized second boiling (crystallization-induced exsolution). The simulations show a dramatic difference between two-phase (melt crystals) and three-phase (melt-crystals-exsolved volatiles) compaction-driven phase separation. We find that the presence of a lighter, significantly less viscous fluid hinders melt-crystal separation.

Phenomenological model and phase behavior of saturated and unsaturated lipids and cholesterol.

PubMed

Putzel, G Garbès; Schick, M

2008-11-15

We present a phenomenological theory for the phase behavior of ternary mixtures of cholesterol and saturated and unsaturated lipids, one that describes both liquid and gel phases. It leads to the following description of the mechanism of the phase behavior: In a binary system of the lipids, phase separation occurs when the saturated chains are well ordered, as in the gel phase, simply due to packing effects. In the liquid phase, the saturated ones are not sufficiently well ordered for separation to occur. The addition of cholesterol, however, increases the saturated lipid order to the point that phase separation is once again favorable. Our theory addresses this last mechanism-the means by which cholesterol-mediated ordering of membrane lipids leads to liquid-liquid immiscibility. It produces, for the system above the main chain transition of the saturated lipid, phase diagrams in which there can be liquid-liquid phase separation in the ternary system but not in any of the binary ones, while below that temperature it yields the more common phase diagram in which a gel phase, rich in saturated lipid, appears in addition to the two liquid phases.

Separation of gas from liquid in a two-phase flow system

NASA Technical Reports Server (NTRS)

Hayes, L. G.; Elliott, D. G.

1973-01-01

Separation system causes jets which leave two-phase nozzles to impinge on each other, so that liquid from jets tends to coalesce in center of combined jet streams while gas phase is forced to outer periphery. Thus, because liquid coalescence is achieved without resort to separation with solid surfaces, cycle efficiency is improved.

Microscopic origin of the magnetoelectronic phase separation in Sr-doped LaCoO3

NASA Astrophysics Data System (ADS)

Németh, Zoltán; Szabó, András; Knížek, Karel; Sikora, Marcin; Chernikov, Roman; Sas, Norbert; Bogdán, Csilla; Nagy, Dénes Lajos; Vankó, György

2013-07-01

The nanoscopic magnetoelectronic phase separation in doped La1-xSrxCoO3 perovskites was studied with local probes. The phase separation is directly observed by Mössbauer spectroscopy in the studied doping range of 0.05 ≤ x ≤ 0.25 both at room temperature and in the low-temperature magnetic phase. Extended with current synchrotron-based x-ray spectroscopies, these data help to characterize the volume as well as the local electric and magnetic properties of the distinct phases. A simple model based on a random distribution of the doping Sr ions describes well both the evolution of the separated phases and the variation of the Co spin state. The experiments suggest that Sr doping initiates small droplets and a high degree of doping-driven cobalt spin-state transition, while the Sr-free second phase vanishes rapidly with increasing Sr content.

Cell separations and the demixing of aqueous two phase polymer solutions in microgravity

NASA Technical Reports Server (NTRS)

Brooks, Donald E.; Bamberger, Stephan; Harris, J. M.; Van Alstine, James M.

1991-01-01

Partition in phase separated aqueous polymer solutions is a cell separation procedure thought to be adversely influenced by gravity. In preparation for performing cell partitioning experiments in space, and to provide general information concerning the demixing of immiscible liquids in low gravity, a series of phase separated aqueous polymer solutions have been flown on two shuttle flights. Fluorocarbon oil and water emulsions were also flown on the second flight. The aqueous polymer emulsions, which in one g demix largely by sedimentation and convection due to the density differences between the phases, demixed more slowly than on the ground and the final disposition of the phases was determined by the wetting of the container wall by the phases. The demixing behavior and kinetics were influenced by the phase volume ratio, physical properties of the systems and chamber wall interaction. The average domain size increased linearly with time as the systems demixed.

Rationalizing the light-induced phase separation of mixed halide organic–inorganic perovskites

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

Draguta, Sergiu; Sharia, Onise; Yoon, Seog Joon

Mixed halide hybrid perovskites, CH 3NH 3Pb(I 1-xBrx) 3' represent good candidates for lowcost, high efficiency photovoltaic, and light-emitting devices. Their band gaps can be tuned from 1.6 to 2.3 eV, by changing the halide anion identity. Unfortunately, mixed halide perovskites undergo phase separation under illumination. This leads to iodide- and bromide-rich domains along with corresponding changes to the material’s optical/electrical response. Here, using combined spectroscopic measurements and theoretical modeling, we quantitatively rationalize all microscopic processes that occur during phase separation. Our model suggests that the driving force behind phase separation is the bandgap reduction of iodiderich phases. It additionallymore » explains observed non-linear intensity dependencies, as well as self-limited growth of iodide-rich domains. Most importantly, our model reveals that mixed halide perovskites can be stabilized against phase separation by deliberately engineering carrier diffusion lengths and injected carrier densities.« less

Rationalizing the light-induced phase separation of mixed halide organic–inorganic perovskites

DOE PAGES

Draguta, Sergiu; Sharia, Onise; Yoon, Seog Joon; ...

2017-08-04

Mixed halide hybrid perovskites, CH 3NH 3Pb(I 1-xBrx) 3' represent good candidates for lowcost, high efficiency photovoltaic, and light-emitting devices. Their band gaps can be tuned from 1.6 to 2.3 eV, by changing the halide anion identity. Unfortunately, mixed halide perovskites undergo phase separation under illumination. This leads to iodide- and bromide-rich domains along with corresponding changes to the material’s optical/electrical response. Here, using combined spectroscopic measurements and theoretical modeling, we quantitatively rationalize all microscopic processes that occur during phase separation. Our model suggests that the driving force behind phase separation is the bandgap reduction of iodiderich phases. It additionallymore » explains observed non-linear intensity dependencies, as well as self-limited growth of iodide-rich domains. Most importantly, our model reveals that mixed halide perovskites can be stabilized against phase separation by deliberately engineering carrier diffusion lengths and injected carrier densities.« less

Visualization of entry flow separation for oscillating flow in tubes

NASA Technical Reports Server (NTRS)

Qiu, Songgang; Simon, Terence W.

1992-01-01

Neutrally buoyant helium-filled soap bubbles with laser illumination are used to document entry flow separation for oscillating flow in tubes. For a symmetric entry case, the size of the separation zone appears to mildly depend on Reynolds number in the acceleration phase, but is roughly Reynolds number independent in the deceleration phase. For the asymmetric entry case, the separation zone was larger and appeared to grow somewhat during the deceleration phase. The separation zones for both entry geometry cases remain relatively small throughout the cycle. This is different from what would be observed in all-laminar, oscillator flows and is probably due to the high turbulence of the flow, particularly during the deceleration phase of the cycle.

[Influence of mobile phase composition on chiral separation of organic selenium racemates].

PubMed

Han, Xiao-qian; Qi, Bang-feng; Dun, Hui-juan; Zhu, Xin-yi; Na, Peng-jun; Jiang, Sheng-xiang; Chen, Li-ren

2002-05-01

The chiral separation of some chiral compounds with similar structure on the cellulose tris (3,5-dimethylphenylcarbamate) chiral stationary phase prepared by us was obtained. Ternary mobile phases influencing chiral recognition were investigated. A mode of interaction between the structural character of samples and chiral stationary phase is discussed. The results indicated that the retention and chiral separation of the analytes had a bigger change with minute addition of alcohols or acetonitrile as modifier in n-hexane/2-propanol (80/20, volume ratio) binary mobile phase.

Role of lipid phase separations and membrane hydration in phospholipid vesicle fusion.

PubMed

Hoekstra, D

1982-06-08

The relationship between lipid phase separation and fusion of small unilamellar phosphatidylserine-containing vesicles was investigated. The kinetics of phase separation were monitored by following the increase of self-quenching of the fluorescent phospholipid analogue N-(7-nitro-2,1,3-benzoxadiazol-4-yl)phosphatidylethanolamine, which occurs when the local concentration of the probe increases upon Ca2+-induced phase separation in phosphatidylserine (PS) bilayers [Hoekstra, D. (1982) Biochemistry 21, 1055-1061]. Fusion was determined by using the resonance energy transfer fusion assay [Struck, D. K., Hoekstra, D., & Pagano, R. E. (1981) Biochemistry 20, 4093-4099], which monitors the mixing of fluorescent lipid donor and acceptor molecules, resulting in an increase in energy transfer efficiency. The results show that in the presence of Ca2+, fusion proceeds much more rapidly (t 1/2 less than 5 s) than the process of phase separation (T 1/2 congruent to 1 min). Mg2+ also induced fusion, albeit at higher concentrations than Ca2+. Mg2+-induced phase separation were not detected, however. Subthreshold concentrations of Ca2+ (0.5 mM) or Mg2+ (2 mM) induced extensive fusion of PS-containing vesicles in poly(ethylene glycol) containing media. This effect did not appear to be a poly(ethylene glycol)-facilitated enhancement of cation binding to the bilayer, and consequently Ca2+-induced phase separation was not observed. The results suggest that macroscopic phase separation may facilitate but does not induced the fusion process and is therefore, not directly involved in the actual fusion mechanism. The fusion experiments performed in the presence of poly(ethylene glycol) suggest that the degree of bilayer dehydration and the creation of "point defects" in the bilayer without rigorous structural rearrangements in the membrane are dominant factors in the initial fusion events.

Supercritical fluid chromatographic resolution of water soluble isomeric carboxyl/amine terminated peptides facilitated via mobile phase water and ion pair formation.

PubMed

Patel, M A; Riley, F; Ashraf-Khorassani, M; Taylor, L T

2012-04-13

Both analytical scale and preparative scale packed column supercritical fluid chromatography (SFC) have found widespread applicability for chiral separations of multiple polar pharmaceutical candidates. However, SFC is rapidly becoming an achiral technique. More specifically, ion pair SFC is finding greater utility for separation of ionic analytes such as amine salts and organic sulfonates. The key to this success is, in part, the incorporation of additives such as trifluoroacetic acid and ammonium acetate into the mobile phase in association with a wide variety of both bonded silica stationary phases and high purity bare silica. Ion pairing SFC coupled with evaporative light scattering detection and mass spectrometric detection is presented here for the separation of water soluble, uncapped, isomeric peptide pairs that differ in amino acid arrangement. The separation is best achieved on either diol-bonded silica or bare silica with 1-5% (w/w) water as a significant ingredient in the mobile phase. Nitrogenous stationary phases such as 2-ethylpyridine, which had been very successful for the separation of capped peptides failed to yield the desired separation regardless of the mobile phase composition. A HILIC type retention mechanism is postulated for the separation of both isomeric uncapped peptide pairs. Copyright © 2012 Elsevier B.V. All rights reserved.

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

Low density microcellular foams

DOEpatents

Aubert, James H.; Clough, Roger L.; Curro, John G.; Quintana, Carlos A.; Russick, Edward M.; Shaw, Montgomery T.

1987-01-01

Low density, microporous polymer foams are provided by a process which comprises forming a solution of polymer and a suitable solvent followed by rapid cooling of the solution to form a phase-separated system and freeze the phase-separated system. The phase-separated system comprises a polymer phase and a solvent phase, each of which is substantially continuous within the other. The morphology of the polymer phase prior to and subsequent to freezing determine the morphology of the resultant foam. Both isotropic and anisotropic foams can be produced. If isotropic foams are produced, the polymer and solvent are tailored such that the solution spontaneously phase-separates prior to the point at which any component freezes. The morphology of the resultant polymer phase determines the morphology of the resultant foam and the morphology of the polymer phase is retained by cooling the system at a rate sufficient to freeze one or both components of the system before a change in morphology can occur. Anisotropic foams are produced by forming a solution of polymer and solvent that will not phase separate prior to freezing of one or both components of the solution. In such a process, the solvent typically freezes before phase separation occurs. The morphology of the resultant frozen two-phase system determines the morphology of the resultant foam. The process involves subjecting the solution to essentially one-dimensional cooling. Means for subjecting such a solvent to one-dimensional cooling are also provided. Foams having a density of less than 0.1 g/cc and a uniform cell size of less than 10 .mu.m and a volume such that the foams have a length greater than 1 cm are provided.

A fracture mechanics study of the phase separating planar electrodes: Phase field modeling and analytical results

NASA Astrophysics Data System (ADS)

Haftbaradaran, H.; Maddahian, A.; Mossaiby, F.

2017-05-01

It is well known that phase separation could severely intensify mechanical degradation and expedite capacity fading in lithium-ion battery electrodes during electrochemical cycling. Experiments have frequently revealed that such degradation effects could be substantially mitigated via reducing the electrode feature size to the nanoscale. The purpose of this work is to present a fracture mechanics study of the phase separating planar electrodes. To this end, a phase field model is utilized to predict how phase separation affects evolution of the solute distribution and stress profile in a planar electrode. Behavior of the preexisting flaws in the electrode in response to the diffusion induced stresses is then examined via computing the time dependent stress intensity factor arising at the tip of flaws during both the insertion and extraction half-cycles. Further, adopting a sharp-interphase approximation of the system, a critical electrode thickness is derived below which the phase separating electrode becomes flaw tolerant. Numerical results of the phase field model are also compared against analytical predictions of the sharp-interphase model. The results are further discussed with reference to the available experiments in the literature. Finally, some of the limitations of the model are cautioned.

Elongated phase separation domains in spin-cast polymer blend thin films characterized using a panoramic image.

PubMed

Zhang, Hong; Okamura, Yosuke

2018-02-14

Polymer thin films with micro/nano-structures can be prepared by a solvent evaporation induced phase separation process via spin-casting a polymer blend, where the elongated phase separation domains are always inevitable. The striation defect, as a thickness nonunifomity in spin-cast films, is generally coexistent with the elongated domains. Herein, the morphologies of polymer blend thin films are recorded from the spin-cast center to the edge in a panoramic view. The elongated domains are inclined to appear at the ridge regions of striations with increasing radial distance and align radially, exhibiting a coupling between the phase separation morphology and the striation defect that may exist. We demonstrate that the formation of elongated domains is not attributed to shape deformation, but is accomplished in situ. A possible model to describe the initiation and evolution of the polymer blend phase separation morphology during spin-casting is proposed.

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

Baldini, Maria; Muramatsu, Takaki; Sherafati, Mohammad

Phase separation is a crucial ingredient of the physics of manganites; however, the role of mixed phases in the development of the colossal magnetoresistance (CMR) phenomenon still needs to be clarified. In this paper, we report the realization of CMR in a single-valent LaMnO 3 manganite. We found that the insulator-to-metal transition at 32 GPa is well described using the percolation theory. Pressure induces phase separation, and the CMR takes place at the percolation threshold. A large memory effect is observed together with the CMR, suggesting the presence of magnetic clusters. The phase separation scenario is well reproduced, solving amore » model Hamiltonian. Finally, our results demonstrate in a clean way that phase separation is at the origin of CMR in LaMnO 3.« less

Solvent annealing induced phase separation and dewetting in PMMA∕SAN blend film: film thickness and solvent dependence.

PubMed

You, Jichun; Zhang, Shuangshuang; Huang, Gang; Shi, Tongfei; Li, Yongjin

2013-06-28

The competition between "dewetting" and "phase separation" behaviors in polymer blend films attracts significant attention in the last decade. The simultaneous phase separation and dewetting in PMMA∕SAN [poly(methyl methacrylate) and poly(styrene-ran-acrylonitrile)] blend ultrathin films upon solvent annealing have been observed for the first time in our previous work. In this work, film thickness and annealing solvent dependence of phase behaviors in this system has been investigated using atomic force microscopy and grazing incidence small-angle X-ray scattering (GISAXS). On one hand, both vertical phase separation and dewetting take place upon selective solvent vapor annealing, leading to the formation of droplet∕mimic-film structures with various sizes (depending on original film thickness). On the other hand, the whole blend film dewets the substrate and produces dispersed droplets on the silicon oxide upon common solvent annealing. GISAXS results demonstrate the phase separation in the big dewetted droplets resulted from the thicker film (39.8 nm). In contrast, no period structure is detected in small droplets from the thinner film (5.1 nm and 9.7 nm). This investigation indicates that dewetting and phase separation in PMMA∕SAN blend film upon solvent annealing depend crucially on the film thickness and the atmosphere during annealing.

Gas-Liquid Processing in Microchannels

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

TeGrotenhuis, Ward E.; Stenkamp, Victoria S.; Twitchell, Alvin

Processing gases and liquids together in microchannels having at least one dimension <1 mm has unique advantages for rapid heat and mass transfer. One approach for managing the two phases is to use porous structures as wicks within microchannels to segregate the liquid phase from the gas phase. Gas-liquid processing is accomplished by providing a gas flow path and inducing flow of the liquid phase through or along the wick under an induced pressure gradient. A variety of unit operations are enabled, including phase separation, partial condensation, absorption, desorption, and distillation. Results are reported of an investigation of microchannel phasemore » separation in a transparent, single-channel device. Next, heat exchange is integrated with the microchannel wick approach to create a partial condenser that also separates the condensate. Finally, the scale-up to a multi-channel phase separator is described.« less

Phase separation in solutions of monoclonal antibodies and the effect of human serum albumin

PubMed Central

Wang, Ying; Lomakin, Aleksey; Latypov, Ramil F.; Benedek, George B.

2011-01-01

We report the observation of liquid-liquid phase separation in a solution of human monoclonal antibody, IgG2, and the effects of human serum albumin, a major blood protein, on this phase separation. We find a significant reduction of phase separation temperature in the presence of albumin, and a preferential partitioning of the albumin into the antibody-rich phase. We provide a general thermodynamic analysis of the antibody-albumin mixture phase diagram and relate its features to the magnitude of the effective interprotein interactions. Our analysis suggests that additives (HSA in this report), which have moderate attraction with antibody molecules, may be used to forestall undesirable proetin condensation in antibody solutions. Our findings are relevant to understanding the stability of pharmaceutical solutions of antibodies and the mechanisms of cryoglobulinemia. PMID:21921237

Exploring the dynamics of phase separation in colloid-polymer mixtures with long range attraction.

PubMed

Sabin, Juan; Bailey, Arthur E; Frisken, Barbara J

2016-06-28

We have studied the kinetics of phase separation and gel formation in a low-dispersity colloid - non-adsorbing polymer system with long range attraction using small-angle light scattering. This system exhibits two-phase and three-phase coexistence of gas, liquid and crystal phases when the strength of attraction is between 2 and 4kBT and gel phases when the strength of attraction is increased. For those samples that undergo macroscopic phase separation, whether to gas-crystal, gas-liquid or gas-liquid-crystal coexistence, we observe dynamic scaling of the structure factor and growth of a characteristic length scale that behaves as expected for phase separation in fluids. In samples that gel, the power law associated with the growth of the dominant length scale is not equal to 1/3, but appears to depend mainly on the strength of attraction, decreasing from 1/3 for samples near the coexistence region to 1/27 at 8kBT, over a wide range of colloid and polymer concentrations.

Critical review: Injectability of calcium phosphate pastes and cements.

PubMed

O'Neill, R; McCarthy, H O; Montufar, E B; Ginebra, M-P; Wilson, D I; Lennon, A; Dunne, N

2017-03-01

Calcium phosphate cements (CPC) have seen clinical success in many dental and orthopaedic applications in recent years. The properties of CPC essential for clinical success are reviewed in this article, which includes properties of the set cement (e.g. bioresorbability, biocompatibility, porosity and mechanical properties) and unset cement (e.g. setting time, cohesion, flow properties and ease of delivery to the surgical site). Emphasis is on the delivery of calcium phosphate (CaP) pastes and CPC, in particular the occurrence of separation of the liquid and solid components of the pastes and cements during injection; and established methods to reduce this phase separation. In addition a review of phase separation mechanisms observed during the extrusion of other biphasic paste systems and the theoretical models used to describe these mechanisms are discussed. Occurrence of phase separation of calcium phosphate pastes and cements during injection limits their full exploitation as a bone substitute in minimally invasive surgical applications. Due to lack of theoretical understanding of the phase separation mechanism(s), optimisation of an injectable CPC that satisfies clinical requirements has proven difficult. However, phase separation of pastes during delivery has been the focus across several research fields. Therefore in addition to a review of methods to reduce phase separation of CPC and the associated constraints, a review of phase separation mechanisms observed during extrusion of other pastes and the theoretical models used to describe these mechanisms is presented. It is anticipated this review will benefit future attempts to develop injectable calcium phosphate based systems. Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.

Hydrogen isotope systematics of phase separation in submarine hydrothermal systems: Experimental calibration and theoretical models

USGS Publications Warehouse

Berndt, M.E.; Seal, R.R.; Shanks, Wayne C.; Seyfried, W.E.

1996-01-01

Hydrogen isotope fractionation factors were measured for coexisting brines and vapors formed by phase separation of NaCl/H2O fluids at temperatures ranging from 399-450??C and pressures from 277-397 bars. It was found that brines are depleted in D compared to coexisting vapors at all conditions studied. The magnitude of hydrogen isotope fractionation is dependent on the relative amounts of Cl in the two phases and can be empirically correlated to pressure using the following relationship: 1000 ln ??(vap-brine) = 2.54(??0.83) + 2.87(??0.69) x log (??P), where ??(vap-brine) is the fractionation factor and ??P is a pressure term representing distance from the critical curve in the NaCl/H2O system. The effect of phase separation on hydrogen isotope distribution in subseafloor hydrothermal systems depends on a number of factors, including whether phase separation is induced by heating at depth or by decompression of hydrothermal fluids ascending to the seafloor. Phase separation in most subseafloor systems appears to be a simple process driven by heating of seawater to conditions within the two-phase region, followed by segregation and entrainment of brine or vapor into a seawater dominated system. Resulting vent fluids exhibit large ranges in Cl concentration with no measurable effect on ??D. Possible exceptions to this include hydrothermal fluids venting at Axial and 9??N on the East Pacific Rise. High ??D values of low Cl fluids venting at Axial are consistent with phase separation taking place at relatively shallow levels in the oceanic crust while negative ??D values in some low Cl fluids venting at 9??N suggest involvement of a magmatic fluid component or phase separation of D-depleted brines derived during previous hydrothermal activity.

Vapor-liquid phase separator studies

NASA Technical Reports Server (NTRS)

Yuan, S. W. K.; Lee, J. M.; Kim, Y. I.; Hepler, W. A.; Frederking, T. H. K.

1983-01-01

Porous plugs serve as both entropy rejection devices and phase separation components separating the vapor phase on the downstream side from liquid Helium 2 upstream. The liquid upstream is the cryo-reservoir fluid needed for equipment cooling by means of Helium 2, i.e Helium-4 below its lambda temperature in near-saturated states. The topics outlined are characteristic lengths, transport equations and plug results.

Coil planet centrifugation as a means for small particle separation

NASA Technical Reports Server (NTRS)

Herrmann, F. T.

1983-01-01

The coil planet centrifuge uses a centrifugal force field to provide separation of particles based on differences in sedimentation rates by flow through a rotating coiled tube. Three main separations are considered: (1) single phase fresh sheep and human erythrocytes, (2) single phase fixed heep and human erythrocytes, and (3) electrophoretically enhanced single phase fresh sheep and human erythrocytes.

Reversed phase liquid chromatography with UV absorbance and flame ionization detection using a water mobile phase and a cyano propyl stationary phase Analysis of alcohols and chlorinated hydrocarbons.

PubMed

Quigley, W W; Ecker, S T; Vahey, P G; Synovec, R E

1999-10-01

The development of liquid chromatography with a commercially available cyano propyl stationary phase and a 100% water mobile phase is reported. Separations were performed at ambient temperature, simplifying instrumental requirements. Excellent separation efficiency using a water mobile phase was achieved, for example N=18 800, or 75 200 m(-1), was obtained for resorcinol, at a retention factor of k'=4.88 (retention time of 9.55 min at 1 ml min(-1) for a 25 cmx4.6 mm i.d. column, packed with 5 mum diameter particles with the cyano propyl stationary phase). A separation via reversed phase liquid chromatography (RP-LC) with a 100% water mobile phase of six phenols and related compounds was compared to a separation of the same compounds by traditional RP-LC, using octadecylsilane (ODS), i.e. C18, bound to silica and an aqueous mobile phase modified with acetonitrile. Nearly identical analysis time was achieved for the separation of six phenols and related compounds using the cyano propyl stationary phase with a 100% water mobile phase, as compared to traditional RP-LC requiring a relatively large fraction of organic solvent modifier in the mobile phase (25% acetonitrile:75% water). Additional understanding of the retention mechanism with the 100% water mobile phase was obtained by relating measured retention factors of aliphatic alcohols, phenols and related compounds, and chlorinated hydrocarbons to their octanol:water partition coefficients. The retention mechanism is found to be consistent with a RP-LC mechanism coupled with an additional retention effect due to residual hydroxyl groups on the cyano propyl stationary phase. Advantages due to a 100% water mobile phase for the chemical analysis of alcohol mixtures and chlorinated hydrocarbons are reported. By placing an absorbance detector in-series and preceding a novel drop interface to a flame ionization detector (FID), selective detection of a separated mixture of phenols and related compounds and aliphatic alcohols is achieved. The compound class of aliphatic alcohols is selectively and sensitively detected by the drop interface/FID, and the phenols and related compounds are selectively and sensitively detected by absorbance detection at 200 nm. The separation and detection of chlorinated hydrocarbons in a water sample matrix further illustrated the advantages of this methodology. The sensitivity and selectivity of the FID signal for the chlorinated hydrocarbons are significantly better than absorbance detection, even at 200 nm. This methodology is well suited to continuous and automated monitoring of water samples. The applicability of samples initially in an organic solvent matrix is explored, since an organic sample matrix may effect retention and efficiency. Separations in acetonitrile and isopropyl alcohol sample matrices compared well to separations with a water sample matrix.

Purification of biomaterials by phase partitioning

NASA Technical Reports Server (NTRS)

Harris, J. M.

1984-01-01

A technique which is particularly suited to microgravity environments and which is potentially more powerful than electrophoresis is phase partitioning. Phase partitioning is purification by partitioning between the two immiscible aqueous layers formed by solution of the polymers poly(ethylene glycol) and dextran in water. This technique proved to be very useful for separations in one-g but is limited for cells because the cells are more dense than the phase solutions thus tend to sediment to the bottom of the container before reaching equilibrium with the preferred phase. There are three phases to work in this area: synthesis of new polymers for affinity phase partitioning; development of automated apparatus for ground-based separations; and design of apparatus for performing simple phase partitioning space experiments, including examination of mechanisms for separating phases in the absence of gravity.

Continuum theory of phase separation kinetics for active Brownian particles.

PubMed

Stenhammar, Joakim; Tiribocchi, Adriano; Allen, Rosalind J; Marenduzzo, Davide; Cates, Michael E

2013-10-04

Active Brownian particles (ABPs), when subject to purely repulsive interactions, are known to undergo activity-induced phase separation broadly resembling an equilibrium (attraction-induced) gas-liquid coexistence. Here we present an accurate continuum theory for the dynamics of phase-separating ABPs, derived by direct coarse graining, capturing leading-order density gradient terms alongside an effective bulk free energy. Such gradient terms do not obey detailed balance; yet we find coarsening dynamics closely resembling that of equilibrium phase separation. Our continuum theory is numerically compared to large-scale direct simulations of ABPs and accurately accounts for domain growth kinetics, domain topologies, and coexistence densities.

Green chiral HPLC enantiomeric separations using high temperature liquid chromatography and subcritical water on Chiralcel OD and Chiralpak AD.

PubMed

Droux, Serge; Félix, Guy

2011-01-01

We report here the application of subcritical water in chiral separations on two popular polysaccharide chiral stationary phases (CSPs): Chiralpak AD and Chiralcel OD. The behavior of these two CSPs was studied under reversed phase conditions at room temperature to discover the maximum percentage of water in the mobile phase, which provided the separation of enantiomers of flavanone and benzoin, respectively, in a reasonable time (i.e., less than 1 h). Then, the stability of Chiralpak AD and Chiralcel OD versus temperature was investigated and discussed. Chiralcel OD separation of flavanone racemate was obtained at 120 °C with water and 2-propanol (80/20) as the mobile phase, while benzoin racemate was separated in pure water at 160 °C. Separations of several racemates were also presented, and advantages and limitations of the technique were discussed. Copyright © 2011 Wiley Periodicals, Inc.

Optimization of the high-performance liquid chromatographic separation of a complex mixture containing urinary steroids, boldenone and bolasterone: application to urine samples.

PubMed

Gonzalo-Lumbreras, R; Izquierdo-Hornillos, R

2000-05-26

An HPLC separation of a complex mixture containing 13 urinary anabolics and corticoids, and boldenone and bolasterone (synthetic anabolics) has been carried out. The applied optimization method involved the use of binary, ternary and quaternary mobile phases containing acetonitrile, methanol or tetrahydrofuran as organic modifiers. The effect of different reversed-phase packings and temperature on the separation was studied. The optimum separation was achieved by using a water-acetonitrile (60:40, v/v) mobile phase in reversed-phase HPLC at 30 degrees C, allowing the separation of all the analytes in about 24 min. Calibration graphs were obtained using bolasterone or methyltestosterone as internal standards. Detection limits were in the range 0.012-0.107 microg ml(-1). The optimized separation was applied to the analysis, after liquid-liquid extraction, of human urine samples spiked with steroids.

Phase separation in the t-J model. [in theory of high-temperature superconductors

NASA Technical Reports Server (NTRS)

Emery, V. J.; Lin, H. Q.; Kivelson, S. A.

1990-01-01

A detailed understanding of the motion of 'holes' in an antiferromagnet is of fundamental importance for the theory of high-temperature superconductors. It is shown here that, for the t-J model, dilute holes in an antiferromagnet are unstable against phase separation into a hole-rich and a no-hole phase. When the spin-exchange interaction J exceeds a critical value Jc, the hole-rich phase has no electrons. It is proposed that, for J slightly less than Jc, the hole-rich phase is a low-density superfluid of electron pairs. Phase separation in related models is briefly discussed.

Separation of O/X Polarization Modes on Oblique Ionospheric Soundings

NASA Astrophysics Data System (ADS)

Harris, T. J.; Cervera, M. A.; Pederick, L. H.; Quinn, A. D.

2017-12-01

The oblique-incidence sounder (OIS) is a well-established instrument for determining the state of the ionosphere, with several advantages over vertical-incidence sounders (VIS). However, the processing and interpretation of OIS ionograms is more complicated than that of VIS ionograms. Due to the Earth's magnetic field, the ionosphere is birefringent at radio frequencies and a VIS or OIS will typically see two distinct ionospheric returns, known as the O and X modes. The separation of these two modes on a VIS, using a polarimetric receive antenna, is a well-established technique. However, this process is more complicated on an OIS due to a variable separation in the phase difference between the two modes, as measured between the two arms of a polarimetric antenna. Using a polarimetric antenna that can be rotated and tilted, we show that this variation in phase separation within an ionogram is caused by the variation in incidence angle, with some configurations leading to greater variation in phase separation. We then develop an algorithm for separating O and X modes in oblique ionograms that can account for the variation in phase separation, and we demonstrate successful separation even in relatively difficult cases. The variation in phase separation can also be exploited to estimate the incident elevation, a technique which may be useful for other applications of HF radio.

Centrifugal partition chromatography in a biorefinery context: Separation of monosaccharides from hydrolysed sugar beet pulp.

PubMed

Ward, David P; Cárdenas-Fernández, Max; Hewitson, Peter; Ignatova, Svetlana; Lye, Gary J

2015-09-11

A critical step in the bioprocessing of sustainable biomass feedstocks, such as sugar beet pulp (SBP), is the isolation of the component sugars from the hydrolysed polysaccharides. This facilitates their subsequent conversion into higher value chemicals and pharmaceutical intermediates. Separation methodologies such as centrifugal partition chromatography (CPC) offer an alternative to traditional resin-based chromatographic techniques for multicomponent sugar separations. Highly polar two-phase systems containing ethanol and aqueous ammonium sulphate are examined here for the separation of monosaccharides present in hydrolysed SBP pectin: l-rhamnose, l-arabinose, d-galactose and d-galacturonic acid. Dimethyl sulfoxide (DMSO) was selected as an effective phase system modifier improving monosaccharide separation. The best phase system identified was ethanol:DMSO:aqueous ammonium sulphate (300gL(-1)) (0.8:0.1:1.8, v:v:v) which enabled separation of the SBP monosaccharides by CPC (200mL column) in ascending mode (upper phase as mobile phase) with a mobile phase flow rate of 8mLmin(-1). A mixture containing all four monosaccharides (1.08g total sugars) in the proportions found in hydrolysed SBP was separated into three main fractions; a pure l-rhamnose fraction (>90%), a mixed l-arabinose/d-galactose fraction and a pure d-galacturonic acid fraction (>90%). The separation took less than 2h demonstrating that CPC is a promising technique for the separation of these sugars with potential for application within an integrated, whole crop biorefinery. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Development of the Two Phase Flow Separator Experiment for a Reduced Gravity Aircraft Flight

NASA Technical Reports Server (NTRS)

Golliher, Eric; Gotti, Daniel; Owens, Jay; Gilkey, Kelly; Pham, Nang; Stehno, Philip

2016-01-01

The recent hardware development and testing of a reduced gravity aircraft flight experiment has provided valuable insights for the future design of the Two Phase Flow Separator Experiment (TPFSE). The TPFSE is scheduled to fly within the Fluids Integration Rack (FIR) aboard the International Space Station (ISS) in 2020. The TPFSE studies the operational limits of gas and liquid separation of passive cyclonic separators. A passive cyclonic separator utilizes only the inertia of the incoming flow to accomplish the liquid-gas separation. Efficient phase separation is critical for environmental control and life support systems, such as recovery of clean water from bioreactors, for long duration human spaceflight missions. The final low gravity aircraft flight took place in December 2015 aboard NASA's C9 airplane.

Renormalization-group study of superfluidity and phase separation of helium mixtures immersed in a nonrandom aerogel

NASA Astrophysics Data System (ADS)

Lopatnikova, Anna; Nihat Berker, A.

1997-02-01

Superfluidity and phase separation in 3-4He mixtures immersed in a jungle-gym (nonrandom) aerogel are studied by renormalization-group theory. Phase diagrams are calculated for a variety of aerogel concentrations. Superfluidity at very low 4He concentrations and a depressed tricritical temperature are found at the onset of superfluidity. A superfluid-superfluid phase separation, terminating at an isolated critical point, is found entirely within the superfluid phase. These phenomena and trends with respect to aerogel concentration are explained by the connectivity and tenuousness of a jungle-gym aerogel.

Fabrication of PVDF-based blend membrane with a thin hydrophilic deposition layer and a network structure supporting layer via the thermally induced phase separation followed by non-solvent induced phase separation process

NASA Astrophysics Data System (ADS)

Wu, Zhiguo; Cui, Zhenyu; Li, Tianyu; Qin, Shuhao; He, Benqiao; Han, Na; Li, Jianxin

2017-10-01

A simple strategy of thermally induced phase separation followed by non-solvent induced phase separation (TIPS-NIPS) is reported to fabricate poly (vinylidene fluoride) (PVDF)-based blend membrane. The dissolved poly (styrene-co-maleic anhydride) (SMA) in diluent prevents the crystallization of PVDF during the cooling process and deposites on the established PVDF matrix in the later extraction. Compared with traditional coating technique, this one-step TIPS-NIPS method can not only fabricate a supporting layer with an interconnected network structure even via solid-liquid phase separation of TIPS, but also form a uniform SMA skin layer approximately as thin as 200 nm via surface deposition of NIPS. Besides the better hydrophilicity, what's interesting is that the BSA rejection ratio increases from 48% to 94% with the increase of SMA, which indicates that the separation performance has improved. This strategy can be conveniently extended to the creation of firmly thin layer, surface functionalization and structure controllability of the membrane.

Poly(1-allylimidazole)-grafted silica, a new specific stationary phase for reversed-phase and anion-exchange liquid chromatography.

PubMed

Sun, Min; Qiu, Hongdeng; Wang, Licheng; Liu, Xia; Jiang, Shengxiang

2009-05-01

A new specific stationary phase based on poly(1-allylimidazole)-grafted silica has been synthesized and characterized, by infrared spectra, elemental analysis, thermogravimetric analysis and X-ray photoelectron spectroscopy. The results of test showed that poly(1-allylimidazole) can effectively mask the residual silanol groups and reduce the adverse effect of residual silanol. Using this stationary phase, phenol compounds, aniline compounds, and polycyclic aromatic hydrocarbons were successfully separated with symmetric peak shapes in the reversed-phase chromatography. Inorganic anions (IO(3)(-), BrO(3)(-), Br(-), NO(3)(-), I(-), SCN(-)) were also separated completely in the anion-exchange chromatography using sodium chloride solution as the mobile phase. The effects of pH and the concentration of eluent on the separation of inorganic anions were studied. The separation mechanism appears to involve the mixed interactions of hydrogen bonding, hydrophobic, pi-pi, electrostatic, and anion-exchange interactions.

Preparation and evaluation of a silica-based 1-alkyl-3-(propyl-3-sulfonate) imidazolium zwitterionic stationary phase for high-performance liquid chromatography.

PubMed

Qiu, Hongdeng; Jiang, Qiong; Wei, Zheng; Wang, Xusheng; Liu, Xia; Jiang, Shengxiang

2007-09-07

A new zwitterionic stationary phase based on silica bonded with 1-alkyl-3-(propyl-3-sulfonate) imidazolium was synthesized and characterized in this paper. The materials have been confirmed and evaluated by elemental analysis, thermogravimetric analysis and X-ray photoelectron spectroscopy. Potassium and calcium were separated simultaneously with several common inorganic anions including an iodate, chloride, bromide, nitrate and iodide on the phase. The effects of the concentration, organic solvent and pH of the eluent on the separation of anions were studied. Operated in the anion-exchange mode, this new stationary phase shows considerable promise for the separation of anions. Bases, vitamins and three imidazolium ionic liquids with different alkyl chains are also separated successfully on this column. The stationary phase has multiple retention mechanisms, such as anion-exchange, electrostatic attraction and repulsion interactions, and hydrophobic interaction between the zwitterionic stationary phase and specimens.

Molar mass fractionation in aqueous two-phase polymer solutions of dextran and poly(ethylene glycol).

PubMed

Zhao, Ziliang; Li, Qi; Ji, Xiangling; Dimova, Rumiana; Lipowsky, Reinhard; Liu, Yonggang

2016-06-24

Dextran and poly(ethylene glycol) (PEG) in phase separated aqueous two-phase systems (ATPSs) of these two polymers, with a broad molar mass distribution for dextran and a narrow molar mass distribution for PEG, were separated and quantified by gel permeation chromatography (GPC). Tie lines constructed by GPC method are in excellent agreement with those established by the previously reported approach based on density measurements of the phases. The fractionation of dextran during phase separation of ATPS leads to the redistribution of dextran of different chain lengths between the two phases. The degree of fractionation for dextran decays exponentially as a function of chain length. The average separation parameters, for both dextran and PEG, show a crossover from mean field behavior to Ising model behavior, as the critical point is approached. Copyright © 2016 Elsevier B.V. All rights reserved.

Space cryogenics components based on the thermomechanical effect - Vapor-liquid phase separation

NASA Technical Reports Server (NTRS)

Yuan, S. W. K.; Frederking, T. H. K.

1989-01-01

Applications of the thermomechanical effect has been qualified including incorporation in large-scale space systems in the area of vapor-liquid phase separation (VLPS). The theory of the porous-plug phase separator is developed for the limit of a high thermal impedance of the solid-state grains. Extensions of the theory of nonlinear turbulent flow are presented based on experimental results.

Plume dynamics beneath the African plate inferred from the geochemistry of the Tertiary basalts of southern Ethiopia

NASA Astrophysics Data System (ADS)

George, R. M.; Rogers, N. W.

2002-09-01

Southern Ethiopian flood basalts erupted in two episodes: the pre-rift Amaro and Gamo transitional tholeiites (45-35 million years) followed by the syn-extensional Getra-Kele alkali basalts (19-11 million years). These two volcanic episodes are distinct in both trace element and isotope ratios (Zr/Nb ratios in Amaro/Gamo lavas fall between 7 and 14, and 3-4.7 in the Getra-Kele lavas whereas 206Pb/204Pb ratios fall between 18-19 and 18.9-20, respectively). The distinctive chemistries of the two eruptive phases record the tapping of two distinct source regions: a mantle plume source for the Amaro/Gamo phase and an enriched continental mantle lithosphere source for the Getra-Kele phase. Isotope and trace element variations within the Amaro/Gamo lavas reflect polybaric fractional crystallisation initiated at high pressures accompanied by limited crustal contamination. We show that clinopyroxene removal at high (0.5 GPa) crustal pressures provides an explanation for the common occurrence of transitional tholeiites in Ethiopia relative to other, typically tholeiitic flood basalt provinces. The mantle plume signature inferred from the most primitive Amaro basalts is isotopically distinct from that contributing to melt generation in central Ethiopian and Afar. This, combined with Early Tertiary plate reconstructions and similarities with Kenyan basalts farther south, lends credence to derivation of these melts from the Kenyan plume rather than the Afar mantle plume. The break in magmatism between 35 and 19 Ma is consistent with the northward movement away from the Kenya plume predicted from plate tectonic reconstructions. In this model the Getra-Kele magmatism is a response to heating of carbonatitically metasomatised lithosphere by the Afar mantle plume beneath southern Ethiopia at this time.

Temperature-responsive chromatography for the separation of biomolecules.

PubMed

Kanazawa, Hideko; Okano, Teruo

2011-12-09

Temperature-responsive chromatography for the separation of biomolecules utilizing poly(N-isopropylacrylamide) (PNIPAAm) and its copolymer-modified stationary phase is performed with an aqueous mobile phase without using organic solvent. The surface properties and function of the stationary phase are controlled by external temperature changes without changing the mobile-phase composition. This analytical system is based on nonspecific adsorption by the reversible transition of a hydrophilic-hydrophobic PNIPAAm-grafted surface. The driving force for retention is hydrophobic interaction between the solute molecules and the hydrophobized polymer chains on the stationary phase surface. The separation of the biomolecules, such as nucleotides and proteins was achieved by a dual temperature- and pH-responsive chromatography system. The electrostatic and hydrophobic interactions could be modulated simultaneously with the temperature in an aqueous mobile phase, thus the separation system would have potential applications in the separation of biomolecules. Additionally, chromatographic matrices prepared by a surface-initiated atom transfer radical polymerization (ATRP) exhibit a strong interaction with analytes, because the polymerization procedure forms a densely packed polymer, called a polymer brush, on the surfaces. The copolymer brush grafted surfaces prepared by ATRP was an effective tool for separating basic biomolecules by modulating the electrostatic and hydrophobic interactions. Applications of thermally responsive columns for the separations of biomolecules are reviewed here. Copyright © 2011 Elsevier B.V. All rights reserved.

High-performance liquid-chromatographic separation of subcomponents of antimycin-A

USGS Publications Warehouse

Abidi, S.L.

1988-01-01

Using a reversed-phase high-performance liquid chromatographic (HPLC) technique, a mixture of antimycins A was separated into eight hitherto unreported subcomponents, Ala, Alb, A2a, A2b, A3a, A3b, A4a, and A4b. Although a base-line resolution of the known four major antimycins Al, A2, A3, and A4 was readily achieved with mobile phases containing acetate buffers, the separation of the new antibiotic subcomponents was highly sensitive to variation in mobile phase conditions. The type and composition of organic modifiers, the nature of buffer salts, and the concentration of added electrolytes had profound effects on capacity factors, separation factors, and peak resolution values. Of the numerous chromatographic systems examined, a mobile phase consisting of methanol-water (70:30) and 0.005 M tetrabutylammonium phosphate at pH 3.0 yielded the most satisfactory results for the separation of the subcomponents. Reversed-phase gradient HPLC separation of the dansylated or methylated antibiotic compounds produced superior chromatographic characteristics and the presence of added electrolytes was not a critical factor for achieving separation. Differences in the chromatographic outcome between homologous and structural isomers were interpretated based on a differential solvophobic interaction rationale. Preparative reversed-phase HPLC under optimal conditions enabled isolation of pure samples of the methylated antimycin subcomponents for use in structural studies.

Texas A&M vortex type phase separator

NASA Astrophysics Data System (ADS)

Best, Frederick

2000-01-01

Phase separation is required for regenerative biological and chemical process systems as well as thermal transport and rejection systems. Liquid and gas management requirements for future spacecraft will demand small, passive systems able to operate over wide ranges of inlet qualities. Conservation and recycling of air and water is a necessary part of the construction and operation of the International Space Station as well as future long duration space missions. Space systems are sensitive to volume, mass, and power. Therefore, it is necessary to develop a method to recycle wastewater with minimal power consumption. Regenerative life support systems currently being investigated require phase separation to separate the liquid from the gas produced. The microgravity phase separator designed and fabricated at Texas A&M University relies on centripetal driven buoyancy forces to form a gas-liquid vortex within a fixed, right-circular cylinder. Two-phase flow is injected tangentially along the inner wall of this cylinder producing a radial acceleration gradient. The gradient produced from the intrinsic momentum of the injected mixture results in a rotating flow that drives the buoyancy process by the production of a hydrostatic pressure gradient. Texas A&M has flown several KC-135 flights with separator. These flights have included scaling studies, stability and transient investigations, and tests for inventory instrumentation. Among the hardware tested have been passive devices for separating mixed vapor/liquid streams into single-phase streams of vapor only and liquid only. .

Limitation of predictive 2-D liquid chromatography in reducing the database search space in shotgun proteomics: in silico studies.

PubMed

Moskovets, Eugene; Goloborodko, Anton A; Gorshkov, Alexander V; Gorshkov, Mikhail V

2012-07-01

A two-dimensional (2-D) liquid chromatography (LC) separation of complex peptide mixtures that combines a normal phase utilizing hydrophilic interactions and a reversed phase offers reportedly the highest level of 2-D LC orthogonality by providing an even spread of peptides across multiple LC fractions. Matching experimental peptide retention times to those predicted by empirical models describing chromatographic separation in each LC dimension leads to a significant reduction in a database search space. In this work, we calculated the retention times of tryptic peptides separated in the C18 reversed phase at different separation conditions (pH 2 and pH 10) and in TSK gel Amide-80 normal phase. We show that retention times calculated for different 2-D LC separation schemes utilizing these phases start to correlate once the mass range of peptides under analysis becomes progressively narrow. This effect is explained by high degree of correlation between retention coefficients in the considered phases. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Process boundaries of irreversible scCO2 -assisted phase separation in biphasic whole-cell biocatalysis.

PubMed

Brandenbusch, Christoph; Glonke, Sebastian; Collins, Jonathan; Hoffrogge, Raimund; Grunwald, Klaudia; Bühler, Bruno; Schmid, Andreas; Sadowski, Gabriele

2015-11-01

The formation of stable emulsions in biphasic biotransformations catalyzed by microbial cells turned out to be a major hurdle for industrial implementation. Recently, a cost-effective and efficient downstream processing approach, using supercritical carbon dioxide (scCO2 ) for both irreversible emulsion destabilization (enabling complete phase separation within minutes of emulsion treatment) and product purification via extraction has been proposed by Brandenbusch et al. (2010). One of the key factors for a further development and scale-up of the approach is the understanding of the mechanism underlying scCO2 -assisted phase separation. A systematic approach was applied within this work to investigate the various factors influencing phase separation during scCO2 treatment (that is pressure, exposure of the cells to CO2 , and changes of cell surface properties). It was shown that cell toxification and cell disrupture are not responsible for emulsion destabilization. Proteins from the aqueous phase partially adsorb to cells present at the aqueous-organic interface, causing hydrophobic cell surface characteristics, and thus contribute to emulsion stabilization. By investigating the change in cell-surface hydrophobicity of these cells during CO2 treatment, it was found that a combination of catastrophic phase inversion and desorption of proteins from the cell surface is responsible for irreversible scCO2 mediated phase separation. These findings are essential for the definition of process windows for scCO2 -assisted phase separation in biphasic whole-cell biocatalysis. © 2015 Wiley Periodicals, Inc.

Effects of temperature and solvent condition on phase separation induced molecular fractionation of gum arabic/hyaluronan aqueous mixtures.

PubMed

Hu, Bing; Han, Lingyu; Gao, Zhiming; Zhang, Ke; Al-Assaf, Saphwan; Nishinari, Katsuyoshi; Phillips, Glyn O; Yang, Jixin; Fang, Yapeng

2018-05-14

Effects of temperature and solvent condition on phase separation-induced molecular fractionation of gum arabic/hyaluronan (GA/HA) mixed solutions were investigated. Two gum arabic samples (EM10 and STD) with different molecular weights and polydispersity indices were used. Phase diagrams, including cloud and binodal curves, were established by visual observation and GPC-RI methods. The molecular parameters of control and fractionated GA, from upper and bottom phases, were measured by GPC-MALLS. Fractionation of GA increased the content of arabinogalactan-protein complex (AGP) from ca. 11% to 18% in STD/HA system and 28% to 55% in EM10/HA system. The phase separation-induced molecular fractionation was further studied as a function of temperature and solvent condition (varying ionic strength and ethanol content). Increasing salt concentration (from 0.5 to 5 mol/L) greatly reduced the extent of phase separation-induced fractionation. This effect may be ascribed to changes in the degree of ionization and shielding of the acid groups. Increasing temperature (from 4 °C to 80 °C) also exerted a significant influence on phase separation-induced fractionation. The best temperature for GA/HA mixture system was 40 °C while higher temperature negatively affected the fractionation due to denaturation and possibly degradation in mixed solutions. Increasing the ethanol content up to 30% showed almost no effect on the phase separation induced fractionation. Copyright © 2018 Elsevier B.V. All rights reserved.

Effect of Coriolis force on counter-current chromatographic separation by centrifugal partition chromatography.

PubMed

Ikehata, Jun-Ichi; Shinomiya, Kazufusa; Kobayashi, Koji; Ohshima, Hisashi; Kitanaka, Susumu; Ito, Yoichiro

2004-02-06

The effect of Coriolis force on the counter-current chromatographic separation was studied using centrifugal partition chromatography (CPC) with four different two-phase solvent systems including n-hexane-acetonitrile (ACN); tert-butyl methyl ether (MtBE)-aqueous 0.1% trifluoroacetic acid (TFA) (1:1); MtBE-ACN-aqueous 0.1% TFA (2:2:3); and 12.5% (w/w) polyethylene glycol (PEG) 1000-12.5% (w/w) dibasic potassium phosphate. Each separation was performed by eluting either the upper phase in the ascending mode or the lower phase in the descending mode, each in clockwise (CW) and counterclockwise column rotation. Better partition efficiencies were attained by the CW rotation in both mobile phases in all the two-phase solvent systems examined. The mathematical analysis also revealed the Coriolis force works favorably under the CW column rotation for both mobile phases. The overall results demonstrated that the Coriolis force produces substantial effects on CPC separation in both organic-aqueous and aqueous-aqueous two-phase systems.

Creating Drug Solubilization Compartments via Phase Separation in Multicomponent Buccal Patches Prepared by Direct Hot Melt Extrusion-Injection Molding.

PubMed

Alhijjaj, Muqdad; Bouman, Jacob; Wellner, Nikolaus; Belton, Peter; Qi, Sheng

2015-12-07

Creating in situ phase separation in solid dispersion based formulations to allow enhanced functionality of the dosage form, such as improving dissolution of poorly soluble model drug as well as being mucoadhesive, can significantly maximize the in vitro and in vivo performance of the dosage form. This formulation strategy can benefit a wide range of solid dosage forms for oral and alternative routes of delivery. This study using buccal patches as an example created separated phases in situ of the buccal patches by selecting the excipients with different miscibility with each other and the model drug. The quaternary dispersion based buccal patches containing PEG, PEO, Tween 80, and felodipine were prepared by direct hot melt extrusion-injection molding (HME-IM). The partial miscibility between Tween 80 and semicrystalline PEG-PEO led to the phase separation after extrusion. The Tween phases acted as drug solubilization compartments, and the PEG-PEO phase had the primary function of providing mucoadhesion and carrier controlled dissolution. As felodipine was preferably solubilized in the amorphous regions of PEG-PEO, the high crystallinity of PEG-PEO resulted in an overall low drug solubilizing capacity. Tween 80 was added to improve the solubilization capacity of the system as the model drug showed good solubility in Tween. Increasing the drug loading led to the supersaturation of drug in Tween compartments and crystalline drug dispersed in PEG-PEO phases. The spatial distribution of these phase-separated compartments was mapped using X-ray micro-CT, which revealed that the domain size and heterogeneity of the phase separation increased with increasing the drug loading. The outcome of this study provides new insights into the applicability of in situ formed phase separation as a formulation strategy for the delivery of poorly soluble drugs and demonstrated the basic principle of excipient selection for such technology.

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.

Manufacture, characterisation and properties of novel fluorcanasite glass-ceramics.

PubMed

Pollington, Sarah; van Noort, Richard

2012-11-01

The aim of this study was to investigate the manufacture and characterisation of different compositions of fluorcanasite glass-ceramics with reduced fluorine content and to assess their mechanical and physical properties. Three compositional variations (S80, S81 and S82) of a fluorcanasite glass were investigated. Differential thermal analysis (DTA) and X-ray diffraction (XRD) identified crystallisation temperatures and phases. X-ray fluorescence (XRF) determined the element composition in the glass-ceramics. Different heat treatments [2 h nucleation and either 2 or 4 h crystallisation] were used for the glasses. Scanning electron microscopy (SEM) examined the microstructure of the cerammed glass. The chemical solubility, biaxial flexural strength, fracture toughness, hardness and brittleness index of S81 and S82 fluorcanasite were investigated with lithium disilicate (e.max CAD, Ivoclar Vivadent) as a commercial comparison. Statistical analysis was performed using one-way ANOVA with Tukey's multiple comparison tests (P<0.05). Weibull analysis was employed to examine the reliability of the strength data. All compositions successfully produced glasses. XRD analysis confirmed fluorcanasite formation with the S81 and S82 compositions, with the S82 (2+2h) showing the most prominent crystal structure. The chemical solubility of the glass-ceramics was significantly different, varying from 2565 ± 507 μg/cm(2) for the S81 (2+2 h) to 722 ± 177 μg/cm(2) for the S82 (2+2 h) to 37.4 ± 25.2 μg/cm(2) for the lithium disilicate. BFS values were highest for the S82 (2+2 h) composition (250 ± 26 MPa) and lithium disilicate (266 ± 37 MPa) glass-ceramics. The fracture toughness was higher for the S82 compositions, with the S82 (2+2h) attaining the highest value of 4.2 ± 0.3 MPa m(1/2)(P=0.01). The S82 (2+2 h) fluorcanasite glass-ceramic had the lowest brittleness index. The S82 (2+2 h) fluorcanasite glass-ceramic has acceptable chemical solubility, high biaxial flexural strength, fracture toughness and hardness. A novel glass-ceramic has been developed with potential as a restorative material. The S82 (2+2 h) has mechanical and physical properties that would allow the glass-ceramic to be used as a machinable core material for veneered resin-bonded ceramic restorations. Copyright © 2012 Elsevier Ltd. All rights reserved.

Timing magma migration through the Icelandic Crust: from the Moho to the surface

NASA Astrophysics Data System (ADS)

Mutch, E. J. F.; Maclennan, J.; Edmonds, M.

2017-12-01

The rate of magma transfer throughout the crust, particularly the amount of time it takes for melt to travel from the upper mantle to the surface, is largely unknown. Only one previous study has investigated the timescales of transport of crystals that were in equilibrium with mantle melts [1]. Despite estimating timescales on the order of months to years, the depths from which these crystals were entrained is poorly constrained. Borgarhraun is an exceptionally well-characterised picrite lava flow in the Theistareykir Volcanic System of Northern Iceland. The crystal-cargo of this lava includes macrocrysts of olivine (Fo86-90), plagioclase (An84-90), clinopyroxene and spinel with much rarer wehrlitic nodules. Crystallisation has been estimated to have taken place in deep sub-Moho magma chambers ( 24 km). Melt inclusions in primitive olivine macrocrysts (Fo88-90) are the result of mixing a suite of geochemically distinct mantle melts that were CO2 undersaturated [2-3]. Zoning in the macrocrysts holds a record of concurrent crystallisation and mixing of these variable mantle melts, as well as ascent through the crust prior to eruption [4]. We have conducted a multi-phase, multi-element approach by applying finite-element diffusion models to wehrlite olivines and plagioclase macrocrysts to constrain the timescales of crystal residence and magma ascent prior to eruption. Model results suggest that at 1250 °C the timescale of final ascent was on the order of 20-50 days, whilst longer-term crystal residence times can exceed 700 years. This analysis shows that magma can ascend from the base of the crust to the surface in under a couple of months, suggesting picrites such as Borgarhraun are the result of high speed conduits to sub-Moho magma chambers. These rapid ascent timescales have important implications for the physical modelling of primitive magmas as well as for understanding the architecture of magma-plumbing systems in the temporal domain. References [1] Ruprecht, P., & Plank, T. (2013). Nature, 500(7460), 68-72. [2] Maclennan et al. (2003) Geochemistry, Geophysics, Geosystems, 4(11). [3] Hauri, E. et al. In AGU Spring Meeting Abstracts (Vol. 1, p. 03). [4] Winpenny & Maclennan (2011). Journal of Petrology, 52(9), 1791-1812.

Percolation of isotopically heterogeneous interstitial melts in the crystal mush of the Rum layered intrusion, NW Scotland

NASA Astrophysics Data System (ADS)

O'Driscoll, B.; Hepworth, L. N.; Daly, J. S.; Gertisser, R.; Emeleus, C. H.

2017-12-01

The cumulate stratigraphy of layered intrusions offers a means of interrogating the replenishment and solidification histories of mafic magma chambers. Cumulates comprise cumulus minerals, which accumulate to form a silicate framework, and intercumulus minerals, which represent melt crystallised within the crystal mush. This fundamental textural distinction lies at the heart of cumulus theory and underpins some of the classic models of crystal-liquid differentiation that are based on layered intrusions. In order to shed further light on the importance of postcumulus processes in layered intrusions, and to demonstrate that crystal mushes may behave as open-systems during the crystallisation of cumulates, we investigated mineral-scale textural and geochemical heterogeneity in Unit 10 of the 60 Ma Rum layered intrusion. Numerous ( 1 mm thick) Cr-spinel seams occur throughout the 65 m Unit 10 peridotite stratigraphy. Unusually, intercumulus plagioclase and clinopyroxene crystals in the peridotite several centimetres above and below these seams exhibit complex optical and major element zoning. Sampling of individual intra-crystal zones in these phases was carried out using a New Wave Micromill, for analysis of their 87Sr/86Sr compositions to be measured on unspiked samples by TIMS. Both minerals reveal intra-crystalline isotopic heterogeneity. The maximum range (with 2σ uncertainties) of 87Sr/86Sr in the Unit 10 plagioclase is 0.704026±17-0.704591±8 and in clinopyroxene is 0.703533±23-0.704517±17. Within a single, oscillatory-zoned plagioclase, three discrete zones yield 87Sr/86Sr values of 0.704337±20, 0.704095±20 and 0.704052±11. A complex patchily-zoned clinopyroxene yields a 87Sr/86Sr range of 0.703533±23-0.703894±23. The new data demonstrate that multiple generations of isotopically distinct melts percolated through the Unit 10 crystal mush, suggesting solidification from cumulates that underwent repeated cycles of resorption and recrystallisation at the postcumulus stage. The cumulate products of layered intrusions may therefore form from magma addition within the crystal mush, and such a process might be especially relevant for precious metal enrichment, given the association between isotopic disequilibrium and the locations of Cr-spinel seams observed here.

Chemical evolution of Himalayan leucogranites based on an O, U-Pb and Hf study of zircon

NASA Astrophysics Data System (ADS)

Hopkinson, Thomas N.; Warren, Clare J.; Harris, Nigel B. W.; Hammond, Samantha J.; Parrish, Randall R.

2015-04-01

Crustal melting is a characteristic process at convergent plate margins, where crustal rocks are heated and deformed. Miocene leucogranite sheets and plutons are found intruded into the high-grade metasedimentary core (the Greater Himalayan Sequence, GHS) across the Himalayan orogen. Previously-published Himalayan whole-rock data suggest that these leucogranites formed from a purely meta-sedimentary source, isotopically similar to those into which they now intrude. Bulk rock analyses carry inherent uncertainties, however: they may hide contributions from different contributing sources, and post-crystallization processes such as fluid interaction may significantly alter the original chemistry. In contrast, zircon is more able to retain precise information of the contributing sources of the melt from which it crystallises whilst its resistant nature is impervious to post-magmatic processes. This multi-isotope study of Oligocene-Miocene leucogranite zircons from the Bhutan Himalaya, seeks to differentiate between various geochemical processes that contribute to granite formation. Hf and O isotopes are used to detect discrete changes in melt source while U-Pb isotopes provide the timing of zircon crystallisation. Our data show that zircon rims of Himalayan age yield Hf-O signatures that lie within the previously reported whole-rock GHS field, confirming the absence of a discernible mantle contribution to the leucogranite source. Importantly, we document a decrease in the minimum ɛHf values during Himalayan orogenesis through time, correlating to a change in Hf model age from 1.4 Ga to 2.4 Ga. Nd model ages for the older Lesser Himalayan metasediments (LHS) that underthrust the GHS are significantly older than those for the GHS (2.4-2.9 Ga compared with 1.4-2.2 Ga), and as such even minor contributions of LHS material incorporated into a melt would significantly increase the resulting Hf model age. Hence our leucogranite data suggest either a change of source within the GHS over time, or an increasing contribution from older Lesser Himalayan (LHS) material in the melt. This is the first time that an evolutionary trend in the chemistry of Himalayan crustal melts has been recognized. Thus these new data show that, at least in the Himalaya, accessory phase geochemistry can provide more detailed insight into tectonic processes than bulk rock geochemistry.

Multi-mode application of graphene quantum dots bonded silica stationary phase for high performance liquid chromatography.

PubMed

Wu, Qi; Sun, Yaming; Zhang, Xiaoli; Zhang, Xia; Dong, Shuqing; Qiu, Hongdeng; Wang, Litao; Zhao, Liang

2017-04-07

Graphene quantum dots (GQDs), which possess hydrophobic, hydrophilic, π-π stacking and hydrogen bonding properties, have great prospect in HPLC. In this study, a novel GQDs bonded silica stationary phase was prepared and applied in multiple separation modes including normal phase, reversed phase and hydrophilic chromatography mode. Alkaloids, nucleosides and nucleobases were chosen as test compounds to evaluate the separation performance of this column in hydrophilic chromatographic mode. The tested polar compounds achieved baseline separation and the resolutions reached 2.32, 4.62, 7.79, 1.68 for thymidine, uridine, adenosine, cytidine and guanosine. This new column showed satisfactory chromatographic performance for anilines, phenols and polycyclic aromatic hydrocarbons in normal and reversed phase mode. Five anilines were completely separated within 10min under the condition of mobile phase containing only 10% methanol. The effect of water content, buffer concentration and pH on chromatographic separation was further investigated, founding that this new stationary phase showed a complex retention mechanism of partitioning, adsorption and electrostatic interaction in hydrophilic chromatography mode, and the multiple retention interactions such as π-π stacking and π-π electron-donor-acceptor interaction played an important role during the separation process. This GQDs bonded column, which allows us to adjust appropriate chromatography mode according to the properties of analytes, has possibility in actual application after further research. Copyright © 2017 Elsevier B.V. All rights reserved.

Reversed-phase thin-layer chromatography of homologs of Antimycin-A and related derivatives

USGS Publications Warehouse

Abidi, Sharon L.

1989-01-01

Using a reversed-phase high-performance liquid chromatographic (HPLC) technique, a mixture of antimycins A was separated into eight hitherto unreported subcomponents, Ala, Alb, A2a, A2b, A3a, A3b, A4a, and A4b. Although a base-line resolution of the known four major antimycins Al, A2, A3, and A4 was readily achieved with mobile phases containing acetate buffers, the separation of the new antibiotic subcomponents was highly sensitive to variation in mobile phase conditions. The type and composition of organic modifiers, the nature of buffer salts, and the concentration of added electrolytes had profound effects on capacity factors, separation factors, and peak resolution values. Of the numerous chromatographic systems examined, a mobile phase consisting of methanol-water (70:30) and 0.005 M tetrabutylammonium phosphate at pH 3.0 yielded the most satisfactory results for the separation of the subcomponents. Reversed-phase gradient HPLC separation of the dansylated or methylated antibiotic compounds produced superior chromatographic characteristics and the presence of added electrolytes was not a critical factor for achieving separation. Differences in the chromatographic outcome between homologous and structural isomers were interpretated based on a differential solvophobic interaction rationale. Preparative reversed-phase HPLC under optimal conditions enabled isolation of pure samples of the methylated antimycin subcomponents for use in structural studies.

Re-entrant phase behavior for systems with competition between phase separation and self-assembly

NASA Astrophysics Data System (ADS)

Reinhardt, Aleks; Williamson, Alexander J.; Doye, Jonathan P. K.; Carrete, Jesús; Varela, Luis M.; Louis, Ard A.

2011-03-01

In patchy particle systems where there is a competition between the self-assembly of finite clusters and liquid-vapor phase separation, re-entrant phase behavior can be observed, with the system passing from a monomeric vapor phase to a region of liquid-vapor phase coexistence and then to a vapor phase of clusters as the temperature is decreased at constant density. Here, we present a classical statistical mechanical approach to the determination of the complete phase diagram of such a system. We model the system as a van der Waals fluid, but one where the monomers can assemble into monodisperse clusters that have no attractive interactions with any of the other species. The resulting phase diagrams show a clear region of re-entrance. However, for the most physically reasonable parameter values of the model, this behavior is restricted to a certain range of density, with phase separation still persisting at high densities.

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.

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.

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

Phase separation of bio-oil produced by co-pyrolysis of corn cobs and polypropylene

NASA Astrophysics Data System (ADS)

Supramono, D.; Julianto; Haqqyana; Setiadi, H.; Nasikin, M.

2017-11-01

In co-pyrolysis of biomass-plastics, bio-oil produced contains both oxygenated and non-oxygenated compounds. High oxygen composition is responsible for instability and low heating value of bio-oil and high acid content for corrosiveness. Aims of the present work are to evaluate possibilities of achieving phase separation between oxygenated and non-oxygenated compounds in bio-oil using a proposed stirred tank reactor and to achieve synergistic effects on bio-oil yield and non-oxygenated compound layer yield. Separation of bio-oil into two layers, i.e. that containing oxygenated compounds (polar phase) and non-oxygenated compounds (non-polar phase) is important to obtain pure non-polar phase ready for the next processing of hydrogenation and used directly as bio-fuel. There has been no research work on co-pyrolysis of biomass-plastic considering possibility of phase separation of bio-oil. The present work is proposing a stirred tank reactor for co-pyrolysis with nitrogen injection, which is capable of tailoring co-pyrolysis conditions leading to low viscosity and viscosity asymmetry, which induce phase separation between polar phase and non-polar phase. The proposed reactor is capable of generating synergistic effect on bio-oil and non-polar yields as the composition of PP in feed is more than 25% weight in which non-polar layers contain only alkanes, alkenes, cycloalkanes and cycloalkenes.

Polymerization- and Solvent-Induced Phase Separation in Hydrophilic-rich Dentin Adhesive Mimic

PubMed Central

Abedin, Farhana; Ye, Qiang; Good, Holly J; Parthasarathy, Ranganathan; Spencer, Paulette

2014-01-01

Current dental resin undergoes phase separation into hydrophobic-rich and hydrophilic-rich phases during infiltration of the over-wet demineralized collagen matrix. Such phase separation undermines the integrity and durability of the bond at the composite/tooth interface. This study marks the first time that the polymerization kinetics of model hydrophilic-rich phase of dental adhesive has been determined. Samples were prepared by adding varying water content to neat resins made from 95 and 99wt% hydroxyethylmethacrylate (HEMA) and 5 and 1wt% (2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl1]-propane (BisGMA) prior to light curing. Viscosity of the formulations decreased with increased water content. The photo-polymerization kinetics study was carried out by time-resolved FTIR spectrum collector. All of the samples exhibited two-stage polymerization behavior which has not been reported previously for dental resin formulation. The lowest secondary rate maxima were observed for water content of 10-30%wt. Differential scanning calorimetry (DSC) showed two glass transition temperatures for the hydrophilic-rich phase of dental adhesive. The DSC results indicate that the heterogeneity within the final polymer structure decreased with increased water content. The results suggest a reaction mechanism involving both polymerization-induced phase separation (PIPs) and solvent-induced phase separation (SIPs) for the model hydrophilic-rich phase of dental resin. PMID:24631658

Laser-induced phase separation of silicon carbide

PubMed Central

Choi, Insung; Jeong, Hu Young; Shin, Hyeyoung; Kang, Gyeongwon; Byun, Myunghwan; Kim, Hyungjun; Chitu, Adrian M.; Im, James S.; Ruoff, Rodney S.; Choi, Sung-Yool; Lee, Keon Jae

2016-01-01

Understanding the phase separation mechanism of solid-state binary compounds induced by laser–material interaction is a challenge because of the complexity of the compound materials and short processing times. Here we present xenon chloride excimer laser-induced melt-mediated phase separation and surface reconstruction of single-crystal silicon carbide and study this process by high-resolution transmission electron microscopy and a time-resolved reflectance method. A single-pulse laser irradiation triggers melting of the silicon carbide surface, resulting in a phase separation into a disordered carbon layer with partially graphitic domains (∼2.5 nm) and polycrystalline silicon (∼5 nm). Additional pulse irradiations cause sublimation of only the separated silicon element and subsequent transformation of the disordered carbon layer into multilayer graphene. The results demonstrate viability of synthesizing ultra-thin nanomaterials by the decomposition of a binary system. PMID:27901015

Sequence control of phase separation and dewetting in PS/PVME blend thin films by changing molecular weight of PS.

PubMed

Xia, Tian; Qin, Yaping; Huang, Yajiang; Huang, Ting; Xu, Jianhui; Li, Youbing

2016-11-28

The morphology evolution mechanism of polystyrene (PS)/poly (vinyl methyl ether) (PVME) blend thin films with different PS molecular weights (M w ) was studied. It was found that the morphology evolution was closely related to the molecular weight asymmetry between PS and PVME. In the film where M w (PS) ≈ M w (PVME), dewetting happened at the interface between the bottom layer and substrate after SD phase separation. While in the film where M w (PS) > M w (PVME), dewetting happened at the interface between the middle PS/PVME blend layer and bottom PVME layer near the substrate prior to phase separation. The different sequences of phase separation and dewetting and different interface for dewetting occurrence were studied by regarding the competitive effects of viscoelasticity contrast between polymer components and preferential wetting between PVME and the substrate. The viscoelastic nature of the PS component played a crucial role in the sequence of phase separation and dewetting.

Tube radial distribution phenomenon with a two-phase separation solution of a fluorocarbon and hydrocarbon organic solvent mixture in a capillary tube and metal compounds separation.

PubMed

Kitaguchi, Koichi; Hanamura, Naoya; Murata, Masaharu; Hashimoto, Masahiko; Tsukagoshi, Kazuhiko

2014-01-01

A fluorocarbon and hydrocarbon organic solvent mixture is known as a temperature-induced phase-separation solution. When a mixed solution of tetradecafluorohexane as a fluorocarbon organic solvent and hexane as a hydrocarbon organic solvent (e.g., 71:29 volume ratio) was delivered in a capillary tube that was controlled at 10°C, the tube radial distribution phenomenon (TRDP) of the solvents was clearly observed through fluorescence images of the dye, perylene, dissolved in the mixed solution. The homogeneous mixed solution (single phase) changed to a heterogeneous solution (two phases) with inner tetradecafluorohexane and outer hexane phases in the tube under laminar flow conditions, generating the dynamic liquid-liquid interface. We also tried to apply TRDP to a separation technique for metal compounds. A model analyte mixture, copper(II) and hematin, was separated through the capillary tube, and detected with a chemiluminescence detector in this order within 4 min.

Formation and Maturation of Phase Separated Liquid Droplets by RNA Binding Proteins

PubMed Central

Lin, Yuan; Protter, David S. W.; Rosen, Michael K.; Parker, Roy

2015-01-01

Eukaryotic cells possess numerous dynamic membrane-less organelles, RNP granules, enriched in RNA and RNA binding proteins containing disordered regions. We demonstrate that the disordered regions of key RNP granule components, and the full-length granule protein hnRNPA1, can phase separate in vitro, producing dynamic liquid droplets. Phase separation is promoted by low salt concentrations or RNA. Over time, the droplets mature to more stable states, as assessed by slowed fluorescence recovery after photobleaching and resistance to salt. Maturation often coincides with formation of fibrous structures. Different disordered domains can co-assemble into phase-separated droplets. These biophysical properties demonstrate a plausible mechanism by which interactions between disordered regions, coupled with RNA binding, could contribute to RNP granule assembly in vivo through promoting phase separation. Progression from dynamic liquids to stable fibers may be regulated to produce cellular structures with diverse physiochemical properties and functions. Misregulation could contribute to diseases involving aberrant RNA granules. PMID:26412307

Dynamics of polymerization induced phase separation in reactive polymer blends

NASA Astrophysics Data System (ADS)

Lee, Jaehyung

Mechanisms and dynamics of phase decomposition following polymerization induced phase separation (PIPS) of reactive polymer blends have been investigated experimentally and theoretically. The phenomenon of PIPS is a non-equilibrium and non-linear dynamic process. The mechanism of PIPS has been thought to be a nucleation and growth (NG) type originally, however, newer results indicate spinodal decomposition (SD). In PIPS, the coexistence curve generally passes through the reaction temperature at off-critical compositions, thus phase separation has to be initiated first in the metastable region where nucleation occurs. When the system farther drifts from the metastable to unstable region, the NG structure transforms to the SD bicontinuous morphology. The crossover behavior of PIPS may be called nucleation initiated spinodal decomposition (NISD). The formation of newer domains between the existing ones is responsible for the early stage of PIPS. Since PIPS is non- equilibrium kinetic process, it would not be surprising to discern either or both structures. The phase separation dynamics of DGEBA/CTBN mixtures having various kinds of curing agents from low reactivity to high reactivity and various amount of curing agents were examined at various reaction temperatures. The phase separation behavior was monitored by a quantity of scattered light intensity experimentally and by a quantity of collective structure factor numerically. Prior to the study of phase separation dynamics, a preliminary investigation on the isothermal cure behavior of the mixtures were executed in order to determine reaction kinetics parameters. The cure behavior followed the overall second order reaction kinetics. Next, based on the knowledge obtained from the phase separation dynamics study of DGEBA/CTBN mixtures, the phase separation dynamics of various composition of DGEBA/R45EPI mixtures having MDA as a curing agent were investigated. The phase separation behavior was quite dependent upon the composition variation. R45EPI itself can react with itself or with DGEBA without curing, therefore three-component system was considered in this mixture. For the numerical studies of this three- component mixture, a system that is composed of a reactive component-1 that is miscible with its growing molecules and another reactive component-2 that is not miscible with its growing molecules was considered with crosslinking reaction kinetics of the each component.

Direct visualization of phase separation between superconducting and nematic domains in Co-doped CaFe2As2 close to a first-order phase transition

NASA Astrophysics Data System (ADS)

Fente, Antón; Correa-Orellana, Alexandre; Böhmer, Anna E.; Kreyssig, Andreas; Ran, S.; Bud'ko, Sergey L.; Canfield, Paul C.; Mompean, Federico J.; García-Hernández, Mar; Munuera, Carmen; Guillamón, Isabel; Suderow, Hermann

2018-01-01

We show that biaxial strain induces alternating tetragonal superconducting and orthorhombic nematic domains in Co-substituted CaFe2As2 . We use atomic force, magnetic force, and scanning tunneling microscopy to identify the domains and characterize their properties, finding in particular that tetragonal superconducting domains are very elongated, more than several tens of micrometers long and about 30 nm wide; have the same Tc as unstrained samples; and hold vortices in a magnetic field. Thus, biaxial strain produces a phase-separated state, where each phase is equivalent to what is found on either side of the first-order phase transition between antiferromagnetic orthorhombic and superconducting tetragonal phases found in unstrained samples when changing Co concentration. Having such alternating superconducting domains separated by normal conducting domains with sizes of the order of the coherence length opens opportunities to build Josephson junction networks or vortex pinning arrays and suggests that first-order quantum phase transitions lead to nanometric-size phase separation under the influence of strain.

Direct visualization of phase separation between superconducting and nematic domains in Co-doped CaFe 2 As 2 close to a first-order phase transition

DOE PAGES

Fente, Antón; Correa-Orellana, Alexandre; Böhmer, Anna E.; ...

2018-01-09

We show that biaxial strain induces alternating tetragonal superconducting and orthorhombic nematic domains in Co substituted CaFe 2As 2. We use Atomic Force, Magnetic Force and Scanning Tunneling Microscopy (AFM, MFM and STM) to identify the domains and characterize their properties, nding in particular that tetragonal superconducting domains are very elongated, more than several tens of μm long and about 30 nm wide, have the same Tc than unstrained samples and hold vortices in a magnetic eld. Thus, biaxial strain produces a phase separated state, where each phase is equivalent to what is found at either side of the rstmore » order phase transition between antiferromagnetic orthorhombic and superconducting tetragonal phases found in unstrained samples when changing Co concentration. Having such alternating superconducting domains separated by normal conducting domains with sizes of order of the coherence length opens opportunities to build Josephson junction networks or vortex pinning arrays and suggests that first order quantum phase transitions lead to nanometric size phase separation under the influence of strain.« less

Investigation of foam flotation and phase partitioning techniques

NASA Technical Reports Server (NTRS)

Currin, B. L.

1985-01-01

The present status of foam flotation as a separation process is evaluated and limitations for cells and proteins are determined. Possible applications of foam flotation to separations in microgravity are discussed. Application of the fluid mechanical aspects of foam separation techniques is made to phase partitioning in order to investigate the viscous drag forces that may effect the partitioning of cells in a two phase poly(ethylene glycol) and dextran system.

Ternary Phase-Separation Investigation of Sol-Gel Derived Silica from Ethyl Silicate 40

PubMed Central

Wang, Shengnan; Wang, David K.; Smart, Simon; Diniz da Costa, João C.

2015-01-01

A ternary phase-separation investigation of the ethyl silicate 40 (ES40) sol-gel process was conducted using ethanol and water as the solvent and hydrolysing agent, respectively. This oligomeric silica precursor underwent various degrees of phase separation behaviour in solution during the sol-gel reactions as a function of temperature and H2O/Si ratios. The solution composition within the immiscible region of the ES40 phase-separated system shows that the hydrolysis and condensation reactions decreased with decreasing reaction temperature. A mesoporous structure was obtained at low temperature due to weak drying forces from slow solvent evaporation on one hand and formation of unreacted ES40 cages in the other, which reduced network shrinkage and produced larger pores. This was attributed to the concentration of the reactive sites around the phase-separated interface, which enhanced the condensation and crosslinking. Contrary to dense silica structures obtained from sol-gel reactions in the miscible region, higher microporosity was produced via a phase-separated sol-gel system by using high H2O/Si ratios. This tailoring process facilitated further condensation reactions and crosslinking of silica chains, which coupled with stiffening of the network, made it more resistant to compression and densification. PMID:26411484

Spatial patterning of P granules by RNA-induced phase separation of the intrinsically-disordered protein MEG-3

PubMed Central

Smith, Jarrett; Calidas, Deepika; Schmidt, Helen; Lu, Tu; Rasoloson, Dominique; Seydoux, Geraldine

2016-01-01

RNA granules are non-membrane bound cellular compartments that contain RNA and RNA binding proteins. The molecular mechanisms that regulate the spatial distribution of RNA granules in cells are poorly understood. During polarization of the C. elegans zygote, germline RNA granules, called P granules, assemble preferentially in the posterior cytoplasm. We present evidence that P granule asymmetry depends on RNA-induced phase separation of the granule scaffold MEG-3. MEG-3 is an intrinsically disordered protein that binds and phase separates with RNA in vitro. In vivo, MEG-3 forms a posterior-rich concentration gradient that is anti-correlated with a gradient in the RNA-binding protein MEX-5. MEX-5 is necessary and sufficient to suppress MEG-3 granule formation in vivo, and suppresses RNA-induced MEG-3 phase separation in vitro. Our findings suggest that MEX-5 interferes with MEG-3’s access to RNA, thus locally suppressing MEG-3 phase separation to drive P granule asymmetry. Regulated access to RNA, combined with RNA-induced phase separation of key scaffolding proteins, may be a general mechanism for controlling the formation of RNA granules in space and time. DOI: http://dx.doi.org/10.7554/eLife.21337.001 PMID:27914198

Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars

DOEpatents

Black, S.K.; Hames, B.R.; Myers, M.D.

1998-03-24

A method is described for separating lignocellulosic material into (a) lignin, (b) cellulose, and (c) hemicellulose and dissolved sugars. Wood or herbaceous biomass is digested at elevated temperature in a single-phase mixture of alcohol, water and a water-immiscible organic solvent (e.g., a ketone). After digestion, the amount of water or organic solvent is adjusted so that there is phase separation. The lignin is present in the organic solvent, the cellulose is present in a solid pulp phase, and the aqueous phase includes hemicellulose and any dissolved sugars.

Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars

DOEpatents

Black, Stuart K.; Hames, Bonnie R.; Myers, Michele D.

1998-01-01

A method for separating lignocellulosic material into (a) lignin, (b) cellulose, and (c) hemicellulose and dissolved sugars. Wood or herbaceous biomass is digested at elevated temperature in a single-phase mixture of alcohol, water and a water-immiscible organic solvent (e.g., a ketone). After digestion, the amount of water or organic solvent is adjusted so that there is phase separation. The lignin is present in the organic solvent, the cellulose is present in a solid pulp phase, and the aqueous phase includes hemicellulose and any dissolved sugars.

Separation of piracetam derivatives on polysaccharide-based chiral stationary phases.

PubMed

Kažoka, H; Koliškina, O; Veinberg, G; Vorona, M

2013-03-15

High-performance liquid chromatography was used for the enantiomeric separation of two chiral piracetam derivatives. The suitability of six commercially available polysaccharide-based chiral stationary phases (CSPs) under normal phase mode for direct enantioseparation has been investigated. The influence of the CSPs as well the nature and content of an alcoholic modifier in the mobile phase on separation and elution order was studied. It was established that CSP Lux Amylose-2 shows high chiral recognition ability towards 4-phenylsubstituted piracetam derivatives. Copyright © 2013 Elsevier B.V. All rights reserved.

Origin of colossal magnetoresistance in LaMnO 3 manganite

DOE PAGES

Baldini, Maria; Muramatsu, Takaki; Sherafati, Mohammad; ...

2015-08-13

Phase separation is a crucial ingredient of the physics of manganites; however, the role of mixed phases in the development of the colossal magnetoresistance (CMR) phenomenon still needs to be clarified. In this paper, we report the realization of CMR in a single-valent LaMnO 3 manganite. We found that the insulator-to-metal transition at 32 GPa is well described using the percolation theory. Pressure induces phase separation, and the CMR takes place at the percolation threshold. A large memory effect is observed together with the CMR, suggesting the presence of magnetic clusters. The phase separation scenario is well reproduced, solving amore » model Hamiltonian. Finally, our results demonstrate in a clean way that phase separation is at the origin of CMR in LaMnO 3.« less

Synthesis and structural characterisation of Pd(II) and Pt(II) complexes with a flexible, ferrocene-based P,S-donor amidophosphine ligand.

PubMed

Tauchman, Jiří; Císařová, Ivana; Stěpnička, Petr

2014-01-28

1'-Diphenylphosphino-1-{[(2-(methylthio)ethyl)amino]carbonyl}ferrocene (1), accessible via amidation of 1'-(diphenylphosphino)ferrocene-1-carboxylic acid (Hdpf) with 2-(methylthio)ethylamine, reacts with [PdCl2(cod)] (cod = cycloocta-1,5-diene) at a 1 : 1 metal-to-ligand ratio to give trans-[PdCl2(1-κ(2)P,S)] (trans-2) as the sole product. A similar reaction with [PtCl2(cod)] affords a mixture of cis- and trans-[PtCl2(1-κ(2)P,S)] (cis- and trans-3), which can be separated by fractional crystallisation. Complexation reactions performed with 2 equiv. of the ligand are less selective, yielding mixtures of the expected bis-phosphine complexes (i.e., trans-[PdCl2(1-κP)2], or a mixture of cis- and trans-[PtCl2(-κP)2]) with the respective monophosphine complexes. The structures of 1, trans-2, cis-3 and trans-3 determined by X-ray diffraction demonstrate the ability of the title ligand to act as a flexible cis- or trans-P,S-chelate donor (the ligand bite angles are 174.03(2)/173.05(2)° for trans-2/3 and 92.86(2)° for cis-3).

Cyclohexylamine additives for enhanced peptide separations in reversed phase liquid chromatography.

PubMed

Cole, S R; Dorsey, J G

1997-01-01

While the choice of stationary phase, organic modifier, and gradient strength can have significant effects on biomolecule separations, mobile phase additives can also have a significant effect on the chromatographic selectivity, recovery, efficiency and resolution. Given the importance of stationary phase coverage, the beneficial, silanol-masking properties of amines, and the potential for selectivity modification through ion-pair interactions, cyclohexylamine was examined as a mobile phase additive and compared with triethylamine and trifluoroacetic acid. Greatly improved separation was possible when cyclohexylamine was used as compared with phosphate buffer, and cyclohexylamine did not require purification before use, while triethylamine required distillation before 'clean' chromatograms were obtained.

Renormalization-Group Theory Study of Superfluidity and Phase Separation of Helium Mixtures Immersed in Jungle-Gym Aerogel

NASA Astrophysics Data System (ADS)

Lopatnikova, Anna; Berker, A. Nihat

1997-03-01

Superfluidity and phase separation in ^3He-^4He mixtures immersed in jungle-gym (non-random) aerogel are studied by renormalization-group theory.(Phys. Rev. B, in press (1996)) Phase diagrams are calculated for a variety of aerogel concentrations. Superfluidity at very low ^4He concentrations and a depressed tricritical temperature are found at the onset of superfluidity. A superfluid-superfluid phase separation, terminating at an isolated critical point, is found entirely within the superfluid phase. These phenomena, and trends with respect to aerogel concentration, are explained by the connectivity and tenuousness of jungle-gym aerogel.

Renormalization-group study of superfluidity and phase separation of helium mixtures immersed in a nonrandom aerogel

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

Lopatnikova, A.; Berker, A.N.

1997-02-01

Superfluidity and phase separation in {sup 3}He-{sup 4}He mixtures immersed in a jungle-gym (nonrandom) aerogel are studied by renormalization-group theory. Phase diagrams are calculated for a variety of aerogel concentrations. Superfluidity at very low {sup 4}He concentrations and a depressed tricritical temperature are found at the onset of superfluidity. A superfluid-superfluid phase separation, terminating at an isolated critical point, is found entirely within the superfluid phase. These phenomena and trends with respect to aerogel concentration are explained by the connectivity and tenuousness of a jungle-gym aerogel. {copyright} {ital 1997} {ital The American Physical Society}

Phase separation and the formation of cellular bodies

NASA Astrophysics Data System (ADS)

Xu, Bin; Broedersz, Chase P.; Meir, Yigal; Wingreen, Ned S.

Cellular bodies in eukaryotic cells spontaneously assemble to form cellular compartments. Among other functions, these bodies carry out essential biochemical reactions. Cellular bodies form micron-sized structures, which, unlike canonical cell organelles, are not surrounded by membranes. A recent in vitro experiment has shown that phase separation of polymers in solution can explain the formation of cellular bodies. We constructed a lattice-polymer model to capture the essential mechanism leading to this phase separation. We used both analytical and numerical tools to predict the phase diagram of a system of two interacting polymers, including the concentration of each polymer type in the condensed and dilute phase.

Influence of particle size and shell thickness of core-shell packing materials on optimum experimental conditions in preparative chromatography.

PubMed

Horváth, Krisztián; Felinger, Attila

2015-08-14

The applicability of core-shell phases in preparative separations was studied by a modeling approach. The preparative separations were optimized for two compounds having bi-Langmuir isotherms. The differential mass balance equation of chromatography was solved by the Rouchon algorithm. The results show that as the size of the core increases, larger particles can be used in separations, resulting in higher applicable flow rates, shorter cycle times. Due to the decreasing volume of porous layer, the loadability of the column dropped significantly. As a result, the productivity and economy of the separation decreases. It is shown that if it is possible to optimize the size of stationary phase particles for the given separation task, the use of core-shell phases are not beneficial. The use of core-shell phases proved to be advantageous when the goal is to build preparative column for general purposes (e.g. for purification of different products) in small scale separations. Copyright © 2015 Elsevier B.V. All rights reserved.

Development of Electrospun Nanomaterials and their Applications in Separation Science

NASA Astrophysics Data System (ADS)

Newsome, Toni Elwell

In separations, efficiency is inversely related to the diameter of the sorbent particles of the stationary phase. Thus, materials research in separation science has primarily been directed towards reducing the diameter of the sorbent particle used in the stationary phase. In this dissertation, innovative methods designed for the fabrication and application of electrospun sorbent nanomaterials for separation science are described. Electrospinning is a facile, cost-effective technique that relies on repulsive electrostatic forces to produce nanofibers from a viscoelastic solution. Here, electrospinning is used to generate polymer, carbon, and silica-based nanofibers which are employed as sorbent nanomaterials in extractions and separations. Electrospun carbon nanofibers have proven to be ideal extractive phases for solid-phase microextraction (SPME) when coupled to gas chromatography (GC) for headspace sampling of volatile analytes. Herein, these carbon nanofibers were employed in the direct extraction of nonvolatile analytes and coupled to liquid chromatography (LC) for the first time. The high surface area of the coatings led to enhanced extraction efficiencies; they offered a 3-33 fold increase in efficiency relative to a commercial SPME phase. Carbon nanofibers proved to be stable when immersed in liquids common to LC demonstrating the enhanced stability of these coatings in SPME coupled to LC relative to conventional SPME fibers. The enhanced chemical and mechanical stability of the carbon SPME coatings considerably expanded the range of compounds applicable to SPME and extended the lifetimes of the fibers. Electrospun nanofibers have also proven to be ideal stationary phases in ultra-thin layer chromatography (UTLC). Nanofibers provide faster separations and enhanced separation efficiencies compared to commercial particle-based stationary phases in a relatively short distance. Here, the electrospun-UTLC technology was extended for the first time to nanofibers composed of silica, the most commonly used surface for TLC. An electrospinning method was optimized to produce silica-based nanofibers with the smallest diameter possible (300-380 nm) while maintaining homogenous nanofiber morphology. Highly efficient separations were performed in 15 mm with observed plate heights as low as 8.6 mum. Silica-based nanofibers proved to be chemically stable with a wide variety of TLC reagents demonstrating the enhanced compatibility of these phases with common TLC methods relative to polymer and carbon nanofiber UTLC plates. The extension of electrospun UTLC to silica-based nanofibers vastly expanded the range of analytes and TLC methods which can be used with this technology. The main disadvantage of conventional TLC development methods is that the mobile phase velocity decreases with increasing separation distance. Here, the chromatographic performance of electrospun polymer stationary phases was further improved by using a forced-flow mobile phase in planar electrochromatography (PEC) in which mobile phase velocity does not diminish with increasing distance. Separations were performed on polymer nanofiber UTLC plates in 1-2 min. Compared to UTLC, PEC offered unique selectivity, decreased analysis times (> 4 times faster), and enhanced efficiency (2-3 times lower plate height). In addition, two-dimensional (2D) separations of a complex analyte mixture using UTLC followed by PEC required only 11 min and exhibited a significant increase in separation number (70-77).

Effects of Swirler Shape on Two-Phase Swirling Flow in a Steam Separator

NASA Astrophysics Data System (ADS)

Kataoka, Hironobu; Shinkai, Yusuke; Tomiyama, Akio

Experiments on two-phase swirling flow in a separator are carried out using several swirlers having different vane angles, different hub diameters and different number of vanes to seek a way for improving steam separators of uprated boiling water reactors. Ratios of the separated liquid flow rate to the total liquid flow rate, flow patterns, liquid film thicknesses and pressure drops are measured to examine the effects of swirler shape on air-water two-phase swirling annular flows in a one-fifth scale model of the separator. As a result, the following conclusions are obtained for the tested swirlers: (1) swirler shape scarcely affects the pressure drop in the barrel of the separator, (2) decreasing the vane angle is an effective way for reducing the pressure drop in the diffuser of the separator, and (3) the film thickness at the inlet of the pick-off-ring of the separator is not sensitive to swirler shape, which explains the reason why the separator performance does not depend on swirler shape.

Recovery of cesium

DOEpatents

Izatt, Reed M.; Christensen, James J.; Hawkins, Richard T.

1984-01-01

A process of recovering cesium ions from mixtures of ions containing them and other ions, e.g., a solution of nuclear waste materials, which comprises establishing a separate source phase containing such a mixture of ions, establishing a separate recipient phase, establishing a liquid membrane phase in interfacial contact with said source and recipient phases, said membrane phase containing a ligand, preferably a selected calixarene as depicted in the drawing, maintaining said interfacial contact for a period of time long enough to transport by said ligand a substantial portion of the cesium ion from the source phase to the recipient phase, and recovering the cesium ion from the recipient phase. The separation of the source and recipient phases may be by the membrane phase only, e.g., where these aqueous phases are emulsified as dispersed phases in a continuous membrane phase, or may include a physical barrier as well, e.g., an open-top outer container with an inner open-ended container of smaller cross-section mounted in the outer container with its open bottom end spaced from and above the closed bottom of the outer container so that the membrane phase may fill the outer container to a level above the bottom of the inner container and have floating on its upper surface a source phase and a recipient phase separated by the wall of the inner container as a physical barrier. A preferred solvent for the ligand is a mixture of methylene chloride and carbon tetrachloride.

Phase Separation of Superconducting Phases in the Penson-Kolb-Hubbard Model

NASA Astrophysics Data System (ADS)

Jerzy Kapcia, Konrad; Czart, Wojciech Robert; Ptok, Andrzej

2016-04-01

In this paper, we determine the phase diagrams (for T = 0 as well as T > 0) of the Penson-Kolb-Hubbard model for two dimensional square lattice within Hartree-Fock mean-field theory focusing on an investigation of superconducting phases and on a possibility of the occurrence of the phase separation. We obtain that the phase separation, which is a state of coexistence of two different superconducting phases (with s- and η-wave symmetries), occurs in definite ranges of the electron concentration. In addition, increasing temperature can change the symmetry of the superconducting order parameter (from η-wave into s-wave). The system considered exhibits also an interesting multicritical behaviour including bicritical points. The relevance of the results to experiments for real materials is also discussed.

Chromatographic Separations Using Solid-Phase Extraction Cartridges: Separation of Wine Phenolics

NASA Astrophysics Data System (ADS)

Brenneman, Charles A.; Ebeler, Susan E.

1999-12-01

We describe a simple laboratory experiment that demonstrates the principles of chromatographic separation using solid-phase extraction columns and red wine. By adjusting pH and mobile phase composition, the wine is separated into three fractions of differing polarity. The content of each fraction can be monitored by UV-vis spectroscopy. When the experiment is combined with experiments involving HPLC or GC separations, students gain a greater appreciation for and understanding of the highly automated instrumental systems currently available. In addition, they learn about the chemistry of polyphenolic compounds, which are present in many foods and beverages and which are receiving much attention for their potentially beneficial health effects.

Photocatalytic performance of freestanding tetragonal zirconia nanotubes formed in H2O2/NH4F/ethylene glycol electrolyte by anodisation of zirconium

NASA Astrophysics Data System (ADS)

Rozana, Monna; Izza Soaid, Nurul; Kian, Tan Wai; Kawamura, Go; Matsuda, Atsunori; Lockman, Zainovia

2017-04-01

ZrO2 nanotubes (ZrNTs) were produced by anodisation of zirconium foil in H2O2/NH4F/ethylene glycol electrolyte. The as-anodised foils were then soaked in the anodising electrolyte for 12 h. Soaking weakens the adherence of the anodic layer from the substrate resulting in freestanding ZrNTs (FS-ZrNTs). Moreover, the presence of H2O2 in the electrolyte also aids in weakening the adhesion of the film from the foil, as foil anodised in electrolyte without H2O2 has good film adherence. The as-anodised FS-ZrNTs film was amorphous and crystallised to predominantly tetragonal phase upon annealing at >300 °C. Annealing must, however, be done at <500 °C to avoid monoclinic ZrO2 formation and nanotubes disintegration. FS-ZrNTs annealed at 450 °C exhibited the highest photocatalytic ability to degrade methyl orange (MO), whereby 82% MO degradation was observed after 5 h, whereas FS-ZrNTs with a mixture of monoclinic and tetragonal degraded 70% of MO after 5 h.

A new class of Cu/ZnO catalysts derived from zincian georgeite precursors prepared by co-precipitation† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc04130b Click here for additional data file.

PubMed Central

Smith, Paul J.; Kondrat, Simon A.; Chater, Philip A.; Yeo, Benjamin R.; Shaw, Greg M.; Lu, Li; Bartley, Jonathan K.; Taylor, Stuart H.; Spencer, Michael S.; Kiely, Christopher J.; Kelly, Gordon J.; Park, Colin W.

2017-01-01

Zincian georgeite, an amorphous copper–zinc hydroxycarbonate, has been prepared by co-precipitation using acetate salts and ammonium carbonate. Incorporation of zinc into the georgeite phase and mild ageing conditions inhibits crystallisation into zincian malachite or aurichalcite. This zincian georgeite precursor was used to prepare a Cu/ZnO catalyst, which exhibits a superior performance to a zincian malachite derived catalyst for methanol synthesis and the low temperature water–gas shift (LTS) reaction. Furthermore, the enhanced LTS activity and stability in comparison to that of a commercial Cu/ZnO/Al2O3 catalyst, indicates that the addition of alumina as a stabiliser may not be required for the zincian georgeite derived Cu/ZnO catalyst. The enhanced performance is partly attributed to the exclusion of alkali metals from the synthesis procedure, which are known to act as catalyst poisons. The effect of residual sodium on the microstructural properties of the catalyst precursor was investigated further from preparations using sodium carbonate. PMID:28451351

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.

Growth and luminescent properties of Lu2SiO5 and Lu2SiO5:Ce single crystalline films

NASA Astrophysics Data System (ADS)

Zorenko, Yu; Nikl, M.; Gorbenko, V.; Mares, J. A.; Savchyn, V.; Voznyak, T.; Solsky, I.; Grynyov, B.; Sidletskiy, O.; Kurtsev, D.; Beitlerova, A.; Kucerkova, R.

2010-11-01

Single crystalline films (SCF) of Lu2SiO5 (LSO) and Lu2SiO5:Ce (LSO:Ce) silicates with thickness of 2.5-21 μm were crystallised by liquid phase epitaxy method onto undoped LSO substrates from melt-solution based on PbO-B2O3 flux. The luminescence and scintillation properties of LSO and LSO:Ce SCFs were compared with the properties of a reference LSO:Ce and LYSO:Ce crystals. The light yield (LY) of LSO and LSO:Ce SCF reaches up 30 % and 145 %, respectively, of that of a reference LSO:Ce crystal under excitation by α-particles of 241Am source (5.5 MeV). We found that the luminescence spectrum of LSO:Ce SCF is red-shifted with respect to the spectrum of a reference LSO:Ce crystal. Differences in luminescence properties of LSO:Ce SCF and single crystal are explained by the different distribution of Ce3+ over the Lu1 and Lu2 positions of LSO host and are also due to Pb2+ contamination in the former.

Mineralisation of reconstituted collagen using polyvinylphosphonic acid/polyacrylic acid templating matrix protein analogues in the presence of calcium, phosphate and hydroxyl ions

PubMed Central

Kim, Young Kyung; Gu, Li-sha; Bryan, Thomas E.; Kim, Jong Ryul; Chen, Liang; Liu, Yan; Yoon, James C.; Breschi, Lorenzo; Pashley, David H.; Tay, Franklin R.

2010-01-01

The complex morphologies of mineralised collagen fibrils are regulated through interactions between the collagen matrix and non-collagenous extracellular proteins. In the present study, polyvinylphosphonic acid, a biomimetic analogue of matrix phosphoproteins, was synthesised and confirmed with FTIR and NMR. Biomimetic mineralisation of reconstituted collagen fibrils devoid of natural non-collagenous proteins was demonstrated with TEM using a Portland cement-containing resin composite and a phosphate-containing fluid in the presence of polyacrylic acid as sequestration, and polyvinylphosphonic acid as templating matrix protein analogues. In the presence of these dual biomimetic analogues in the mineralisation medium, intrafibrillar and extrafibrillar mineralisation via bottom-up nanoparticle assembly based on the nonclassical crystallisation pathway could be identified. Conversely, only large mineral spheres with no preferred association with collagen fibrils were observed in the absence of biomimetic analogues in the medium. Mineral phases were evident within the collagen fibrils as early as 4 hours after the initially-formed amorphous calcium phosphate nanoprecursors were transformed into apatite nanocrystals. Selected area electron diffraction patterns of highly mineralised collagen fibrils were nearly identical to those of natural bone, with apatite crystallites preferentially aligned along the collagen fibril axes. PMID:20621767

Multiple melt bodies fed the AD 2011 eruption of Puyehue-Cordón Caulle, Chile.

PubMed

Alloway, B V; Pearce, N J G; Villarosa, G; Outes, V; Moreno, P I

2015-12-02

Within the volcanological community there is a growing awareness that many large- to small-scale, point-source eruptive events can be fed by multiple melt bodies rather than from a single magma reservoir. In this study, glass shard major- and trace-element compositions were determined from tephra systematically sampled from the outset of the Puyehue-Cordón Caulle (PCC) eruption (~1 km(3)) in southern Chile which commenced on June 4(th), 2011. Three distinct but cogenetic magma bodies were simultaneously tapped during the paroxysmal phase of this eruption. These are readily identified by clear compositional gaps in CaO, and by Sr/Zr and Sr/Y ratios, resulting from dominantly plagioclase extraction at slightly different pressures, with incompatible elements controlled by zircon crystallisation. Our results clearly demonstrate the utility of glass shard major- and trace-element data in defining the contribution of multiple magma bodies to an explosive eruption. The complex spatial association of the PCC fissure zone with the Liquiñe-Ofqui Fault zone was likely an influential factor that impeded the ascent of the parent magma and allowed the formation of discrete melt bodies within the sub-volcanic system that continued to independently fractionate.

To adopt is to adapt: the process of implementing the ICF with an acute stroke multidisciplinary team in England.

PubMed

Tempest, Stephanie; Harries, Priscilla; Kilbride, Cherry; De Souza, Lorraine

2012-01-01

The success of the International Classification of Functioning, Disability and Health (ICF) depends on its uptake in clinical practice. This project aimed to explore ways the ICF could be used with an acute stroke multidisciplinary team and identify key learning from the implementation process. Using an action research approach, iterative cycles of observe, plan, act and evaluate were used within three phases: exploratory; innovatory and reflective. Thematic analysis was undertaken, using a model of immersion and crystallisation, on data collected via interview and focus groups, e-mail communications, minutes from relevant meetings, field notes and a reflective diary. Two overall themes were determined from the data analysis which enabled implementation. There is a need to: (1) adopt the ICF in ways that meet local service needs; and (2) adapt the ICF language and format. The empirical findings demonstrate how to make the ICF classification a clinical reality. First, we need to adopt the ICF as a vehicle to implement local service priorities e.g. to structure a multidisciplinary team report, thus enabling ownership of the implementation process. Second, we need to adapt the ICF terminology and format to make it acceptable for use by clinicians.

Community solar salt production in Goa, India

PubMed Central

2012-01-01

Traditional salt farming in Goa, India has been practised for the past 1,500 years by a few communities. Goa’s riverine estuaries, easy access to sea water and favourable climatic conditions makes salt production attractive during summer. Salt produced through this natural evaporation process also played an important role in the economy of Goa even during the Portuguese rule as salt was the chief export commodity. In the past there were 36 villages involved in salt production, which is now reduced to 9. Low income, lack of skilled labour, competition from industrially produced salt, losses incurred on the yearly damage of embankments are the major reasons responsible for the reduction in the number of salt pans. Salt pans (Mithagar or Mithache agor) form a part of the reclaimed waterlogged khazan lands, which are also utilised for aquaculture, pisciculture and agriculture. Salt pans in Goa experience three phases namely, the ceased phase during monsoon period of June to October, preparatory phase from December to January, and salt harvesting phase, from February to June. After the monsoons, the salt pans are prepared manually for salt production. During high tide, an influx of sea water occurs, which enters the reservoir pans through sluice gates. The sea water after 1–2 days on attaining a salinity of approximately 5ºBé, is released into the evaporator pans and kept till it attains a salinity of 23 - 25ºBé. The brine is then released to crystallizer pans, where the salt crystallises out 25 - 27ºBé and is then harvested. Salt pans form a unique ecosystem where succession of different organisms with varying environmental conditions occurs. Organisms ranging from bacteria, archaea to fungi, algae, etc., are known to colonise salt pans and may influence the quality of salt produced. The aim of this review is to describe salt farming in Goa’s history, importance of salt production as a community activity, traditional method of salt production and the biota associated with salt pans. PMID:23198813

Community solar salt production in Goa, India.

PubMed

Mani, Kabilan; Salgaonkar, Bhakti B; Das, Deepthi; Bragança, Judith M

2012-12-01

Traditional salt farming in Goa, India has been practised for the past 1,500 years by a few communities. Goa's riverine estuaries, easy access to sea water and favourable climatic conditions makes salt production attractive during summer. Salt produced through this natural evaporation process also played an important role in the economy of Goa even during the Portuguese rule as salt was the chief export commodity. In the past there were 36 villages involved in salt production, which is now reduced to 9. Low income, lack of skilled labour, competition from industrially produced salt, losses incurred on the yearly damage of embankments are the major reasons responsible for the reduction in the number of salt pans.Salt pans (Mithagar or Mithache agor) form a part of the reclaimed waterlogged khazan lands, which are also utilised for aquaculture, pisciculture and agriculture. Salt pans in Goa experience three phases namely, the ceased phase during monsoon period of June to October, preparatory phase from December to January, and salt harvesting phase, from February to June. After the monsoons, the salt pans are prepared manually for salt production. During high tide, an influx of sea water occurs, which enters the reservoir pans through sluice gates. The sea water after 1-2 days on attaining a salinity of approximately 5ºBé, is released into the evaporator pans and kept till it attains a salinity of 23 - 25ºBé. The brine is then released to crystallizer pans, where the salt crystallises out 25 - 27ºBé and is then harvested.Salt pans form a unique ecosystem where succession of different organisms with varying environmental conditions occurs. Organisms ranging from bacteria, archaea to fungi, algae, etc., are known to colonise salt pans and may influence the quality of salt produced.The aim of this review is to describe salt farming in Goa's history, importance of salt production as a community activity, traditional method of salt production and the biota associated with salt pans.

Adhesive phase separation at the dentin interface under wet bonding conditions.

PubMed

Spencer, Paulette; Wang, Yong

2002-12-05

Under in vivo conditions, there is little control over the amount of water left on the tooth and, thus, there is the danger of leaving the dentin surface so wet that the bonding resin undergoes physical separation into hydrophobic and hydrophilic-rich phases. The purpose of this study was to investigate phase separation in 2,2-bis[4(2-hydroxy-3-methacryloyloxy-propyloxy)-phenyl] propane (BisGMA)-based adhesive using molecular microanalysis and to examine the effect of phase separation on the structural characteristics of the hybrid layer. Model BisGMA/HEMA (hydroxyethl methacrylate) mixtures with/without ethanol and commercial BisGMA-based adhesive (Single Bond) were combined with water at concentrations from 0 to 50 vol%. Macrophase separation in the BisGMA/HEMA/water mixtures was detected using cloud point measurements. In parallel with these measurements, the BisGMA/HEMA and adhesive/water mixtures were cast as films and polymerized. Molecular structure was recorded from the distinct features in the phase-separated adhesive using confocal Raman microspectroscopy (CRM). Human dentin specimens treated with Single Bond were analyzed with scanning electron microscopy (SEM) and CRM mapping across the dentin/adhesive interface. The model BisGMA/HEMA mixtures with ethanol and the commercial BisGMA-based adhesive experienced phase separation at approximately 25 vol% water. Raman spectra collected from the phase-separated adhesive indicated that the composition of the particles and surrounding matrix material was primarily BisGMA and HEMA, respectively. Based on SEM analysis, there was substantial porosity at the adhesive interface with dentin. Micro-Raman spectral analysis of the dentin/adhesive interface indicates that the contribution from the BisGMA component decreases by nearly 50% within the first micrometer. The morphologic results in corroboration with the spectroscopic data suggest that as a result of adhesive phase separation the hybrid layer is not an impervious 3-dimensional collagen/polymer network but a porous web characterized by hydrophobic BisGMA-rich particles distributed in a hydrophilic HEMA-rich matrix. Copyright 2002 Wiley Periodicals, Inc.

Phase-Separated Polyaniline/Graphene Composite Electrodes for High-Rate Electrochemical Supercapacitors.

PubMed

Wu, Jifeng; Zhang, Qin'e; Zhou, An'an; Huang, Zhifeng; Bai, Hua; Li, Lei

2016-12-01

Polyaniline/graphene hydrogel composites with a macroscopically phase-separated structure are prepared. The composites show high specific capacitance and excellent rate performance. Further investigation demonstrates that polyaniline inside the graphene hydrogel has low rate performance, thus a phase-separated structure, in which polyaniline is mainly outside the graphene hydrogel matrix, can enhance the rate performance of the composites. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Device for two-dimensional gas-phase separation and characterization of ion mixtures

DOEpatents

Tang, Keqi [Richland, WA; Shvartsburg, Alexandre A [Richland, WA; Smith, Richard D [Richland, WA

2006-12-12

The present invention relates to a device for separation and characterization of gas-phase ions. The device incorporates an ion source, a field asymmetric waveform ion mobility spectrometry (FAIMS) analyzer, an ion mobility spectrometry (IMS) drift tube, and an ion detector. In one aspect of the invention, FAIMS operating voltages are electrically floated on top of the IMS drift voltage. In the other aspect, the FAIMS/IMS interface is implemented employing an electrodynamic ion funnel, including in particular an hourglass ion funnel. The present invention improves the efficiency (peak capacity) and sensitivity of gas-phase separations; the online FAIMS/IMS coupling creates a fundamentally novel two-dimensional gas-phase separation technology with high peak capacity, specificity, and exceptional throughput.

Steric Pressure among Membrane-Bound Polymers Opposes Lipid Phase Separation.

PubMed

Imam, Zachary I; Kenyon, Laura E; Carrillo, Adelita; Espinoza, Isai; Nagib, Fatema; Stachowiak, Jeanne C

2016-04-19

Lipid rafts are thought to be key organizers of membrane-protein complexes in cells. Many proteins that interact with rafts have bulky polymeric components such as intrinsically disordered protein domains and polysaccharide chains. Therefore, understanding the interaction between membrane domains and membrane-bound polymers provides insights into the roles rafts play in cells. Multiple studies have demonstrated that high concentrations of membrane-bound polymeric domains create significant lateral steric pressure at membrane surfaces. Furthermore, our recent work has shown that lateral steric pressure at membrane surfaces opposes the assembly of membrane domains. Building on these findings, here we report that membrane-bound polymers are potent suppressors of membrane phase separation, which can destabilize lipid domains with substantially greater efficiency than globular domains such as membrane-bound proteins. Specifically, we created giant vesicles with a ternary lipid composition, which separated into coexisting liquid ordered and disordered phases. Lipids with saturated tails and poly(ethylene glycol) (PEG) chains conjugated to their head groups were included at increasing molar concentrations. When these lipids were sparse on the membrane surface they partitioned to the liquid ordered phase. However, as they became more concentrated, the fraction of GUVs that were phase-separated decreased dramatically, ultimately yielding a population of homogeneous membrane vesicles. Experiments and physical modeling using compositions of increasing PEG molecular weight and lipid miscibility phase transition temperature demonstrate that longer polymers are the most efficient suppressors of membrane phase separation when the energetic barrier to lipid mixing is low. In contrast, as the miscibility transition temperature increases, longer polymers are more readily driven out of domains by the increased steric pressure. Therefore, the concentration of shorter polymers required to suppress phase separation decreases relative to longer polymers. Collectively, our results demonstrate that crowded, membrane-bound polymers are highly efficient suppressors of phase separation and suggest that the ability of lipid domains to resist steric pressure depends on both their lipid composition and the size and concentration of the membrane-bound polymers they incorporate.

An atom probe perspective on phase separation and precipitation in duplex stainless steels

NASA Astrophysics Data System (ADS)

Guo, Wei; Garfinkel, David A.; Tucker, Julie D.; Haley, Daniel; Young, George A.; Poplawsky, Jonathan D.

2016-06-01

Three-dimensional chemical imaging of Fe-Cr alloys showing Fe-rich (α)/Cr-rich (α‧) phase separation is reported using atom probe tomography techniques. The extent of phase separation, i.e., amplitude and wavelength, has been quantitatively assessed using the Langer-Bar-on-Miller, proximity histogram, and autocorrelation function methods for two separate Fe-Cr alloys, designated 2101 and 2205. Although the 2101 alloy possesses a larger wavelength and amplitude after annealing at 427 °C for 100-10 000 h, it exhibits a lower hardness than the 2205 alloy. In addition to this phase separation, ultra-fine Ni-Mn-Si-Cu-rich G-phase precipitates form at the α/α‧ interfaces in both alloys. For the 2101 alloy, Cu clusters act to form a nucleus, around which a Ni-Mn-Si shell develops during the precipitation process. For the 2205 alloy, the Ni and Cu atoms enrich simultaneously and no core-shell chemical distribution was found. This segregation phenomenon may arise from the exact Ni/Cu ratio inside the ferrite. After annealing for 10 000 h, the number density of the G-phase within the 2205 alloy was found to be roughly one order of magnitude higher than in the 2101 alloy. The G-phase precipitates have an additional deleterious effect on the thermal embrittlement, as evaluated by the Ashby-Orowan equation, which explains the discrepancy between the hardness and the rate of phase separation with respect to annealing time (Gladman T 1999 Mater. Sci. Tech. Ser. 15 30-36). ).

An atom probe perspective on phase separation and precipitation in duplex stainless steels

DOE PAGES

Garfinkel, David A.; Tucker, Julie D.; Haley, Daniel A.; ...

2016-05-16

Here, three-dimensional chemical imaging of Fe–Cr alloys showing Fe-rich (α)/Cr-rich (α') phase separation is reported using atom probe tomography techniques. The extent of phase separation, i.e., amplitude and wavelength, has been quantitatively assessed using the Langer-Bar-on-Miller, proximity histogram, and autocorrelation function methods for two separate Fe–Cr alloys, designated 2101 and 2205. Although the 2101 alloy possesses a larger wavelength and amplitude after annealing at 427 °C for 100–10 000 h, it exhibits a lower hardness than the 2205 alloy. In addition to this phase separation, ultra-fine Ni–Mn–Si–Cu-rich G-phase precipitates form at the α/α' interfaces in both alloys. For the 2101more » alloy, Cu clusters act to form a nucleus, around which a Ni–Mn–Si shell develops during the precipitation process. For the 2205 alloy, the Ni and Cu atoms enrich simultaneously and no core–shell chemical distribution was found. This segregation phenomenon may arise from the exact Ni/Cu ratio inside the ferrite. After annealing for 10 000 h, the number density of the G-phase within the 2205 alloy was found to be roughly one order of magnitude higher than in the 2101 alloy. The G-phase precipitates have an additional deleterious effect on the thermal embrittlement, as evaluated by the Ashby–Orowan equation, which explains the discrepancy between the hardness and the rate of phase separation with respect to annealing time (Gladman T 1999 Mater. Sci. Tech. Ser. 15 30–36).« less

Hierarchical multiscale hyperporous block copolymer membranes via tunable dual-phase separation

PubMed Central

Yoo, Seungmin; Kim, Jung-Hwan; Shin, Myoungsoo; Park, Hyungmin; Kim, Jeong-Hoon; Lee, Sang-Young; Park, Soojin

2015-01-01

The rational design and realization of revolutionary porous structures have been long-standing challenges in membrane science. We demonstrate a new class of amphiphilic polystyrene-block-poly(4-vinylpyridine) block copolymer (BCP)–based porous membranes featuring hierarchical multiscale hyperporous structures. The introduction of surface energy–modifying agents and the control of major phase separation parameters (such as nonsolvent polarity and solvent drying time) enable tunable dual-phase separation of BCPs, eventually leading to macro/nanoscale porous structures and chemical functionalities far beyond those accessible with conventional approaches. Application of this BCP membrane to a lithium-ion battery separator affords exceptional improvement in electrochemical performance. The dual-phase separation–driven macro/nanopore construction strategy, owing to its simplicity and tunability, is expected to be readily applicable to a rich variety of membrane fields including molecular separation, water purification, and energy-related devices. PMID:26601212

Detailed monitoring of two biogas plants and mechanical solid-liquid separation of fermentation residues.

PubMed

Bauer, Alexander; Mayr, Herwig; Hopfner-Sixt, Katharina; Amon, Thomas

2009-06-01

The Austrian "green electricity act" (Okostromgesetz) has led to an increase in biogas power plant size and consequently to an increased use of biomass. A biogas power plant with a generating capacity of 500 kW(el) consumes up to 38,000 kg of biomass per day. 260 ha of cropland is required to produce this mass. The high water content of biomass necessitates a high transport volume for energy crops and fermentation residues. The transport and application of fermentation residues to farmland is the last step in this logistic chain. The use of fermentation residues as fertilizer closes the nutrient cycle and is a central element in the efficient use of biomass for power production. Treatment of fermentation residues by separation into liquid and solid phases may be a solution to the transport problem. This paper presents detailed results from the monitoring of two biogas plants and from the analysis of the separation of fermentation residues. Furthermore, two different separator technologies for the separation of fermentation residues of biogas plants were analyzed. The examined biogas plants correspond to the current technological state of the art and have designs developed specifically for the utilization of energy crops. The hydraulic retention time ranged between 45.0 and 83.7 days. The specific methane yields were 0.40-0.43 m(3)N CH(4) per kg VS. The volume loads ranged between 3.69 and 4.00 kg VS/m(3). The degree of degradation was between 77.3% and 82.14%. The screw extractor separator was better suited for biogas slurry separation than the rotary screen separator. The screw extractor separator exhibited a high throughput and good separation efficiency. The efficiency of slurry separation depended on the dry matter content of the fermentation residue. The higher the dry matter content, the higher the proportion of solid phase after separation. In this project, we found that the fermentation residues could be divided into 79.2% fluid phase with a dry matter content of 4.5% and 20.8% solid phase with a dry matter content of 19.3%. Dry matter, volatile solids and carbon, raw ash and phosphate--in relation to the mass--accumulated strongly in the solid phase. Nitrogen and ammonia nitrogen were slightly enriched in the solid phase. Only the potassium content decreased slightly in the solid phase.

Microfluidic Droplet Dehydration for Concentrating Processes in Biomolecules

NASA Astrophysics Data System (ADS)

Anna, Shelley

2014-03-01

Droplets in microfluidic devices have proven useful as picoliter reactors for biochemical processing operations such as polymerase chain reaction, protein crystallization, and the study of enzyme kinetics. Although droplets are typically considered to be self-contained, constant volume reactors, there can be significant transport between the dispersed and continuous phases depending on solubility and other factors. In the present talk, we show that water droplets trapped within a microfluidic device for tens of hours slowly dehydrate, concentrating the contents encapsulated within. We use this slow dehydration along with control of the initial droplet composition to influence gellation, crystallization, and phase separation processes. By examining these concentrating processes in many trapped drops at once we gain insight into the stochastic nature of the events. In one example, we show that dehydration rate impacts the probability of forming a specific crystal habit in a crystallizing amino acid. In another example, we phase separate a common aqueous two-phase system within droplets and use the ensuing two phases to separate DNA from an initial mixture. We further influence wetting conditions between the two aqueous polymer phases and the continuous oil, promoting complete de-wetting and physical separation of the polymer phases. Thus, controlled dehydration of droplets allows for concentration, separation, and purification of important biomolecules on a chip.

A new approach to network heterogeneity: Polymerization Induced Phase Separation in photo-initiated, free-radical methacrylic systems

PubMed Central

Szczepanski, Caroline R.; Pfeifer, Carmem S.; Stansbury, Jeffrey W.

2012-01-01

Non-reactive, thermoplastic prepolymers (poly- methyl, ethyl and butyl methacrylate) were added to a model homopolymer matrix composed of triethylene glycol dimethacrylate (TEGDMA) to form heterogeneous networks via polymerization induced phase separation (PIPS). PIPS creates networks with distinct phase structure that can partially compensate for volumetric shrinkage during polymerization through localized internal volume expansion. This investigation utilizes purely photo-initiated, free-radical systems, broadening the scope of applications for PIPS since these processing conditions have not been studied previously. The introduction of prepolymer into TEGDMA monomer resulted in stable, homogeneous monomer formulations, most of which underwent PIPS upon photo-irradiation, creating heterogeneous networks. During polymerization the presence of prepolymer enhanced autoacceleration, allowing for a more extensive ambient cure of the material. Phase separation, as characterized by dynamic changes in sample turbidity, was monitored simultaneously with monomer conversion and either preceded or was coincident with network gelation. Dynamic mechanical analysis shows a broadening of the tan delta peak and secondary peak formation, characteristic of phase-separated materials, indicating one phase rich in prepolymer and another depleted form upon phase separation. In certain cases, PIPS leads to an enhanced physical reduction of volumetric shrinkage, which is attractive for many applications including dental composite materials. PMID:23109733

Linear solvation energy relationships in normal phase chromatography based on gradient separations.

PubMed

Wu, Di; Lucy, Charles A

2017-09-22

Coupling the modified Soczewiñski model and one gradient run, a gradient method was developed to build a linear solvation energy relationship (LSER) for normal phase chromatography. The gradient method was tested on dinitroanilinopropyl (DNAP) and silica columns with hexane/dichloromethane (DCM) mobile phases. LSER models built based on the gradient separation agree with those derived from a series of isocratic separations. Both models have similar LSER coefficients and comparable goodness of fit, but the LSER model based on gradient separation required fewer trial and error experiments. Copyright © 2017 Elsevier B.V. All rights reserved.

Development of a passive phase separator for space and earth applications

PubMed Central

Wu, Xiongjun; Loraine, Greg; Hsiao, Chao-Tsung; Chahine, Georges L.

2018-01-01

The limited amount of liquids and gases that can be carried to space makes it imperative to recycle and reuse these fluids for extended human operations. During recycling processes gas and liquid phases are often intermixed. In the absence of gravity, separating gases from liquids is challenging due to the absence of buoyancy. This paper describes development of a passive phase separator that is capable of efficiently and reliably separating gas–liquid mixtures of both high and low void fractions in a wide range of flow rates that is applicable to for both space and earth applications. PMID:29628785

Effect of pressure on the selectivity of polymeric C18 and C30 stationary phases in reversed-phase liquid chromatography. Increased separation of isomeric fatty acid methyl esters, triacylglycerols, and tocopherols at high pressure.

PubMed

Okusa, Kensuke; Iwasaki, Yuki; Kuroda, Ikuma; Miwa, Shohei; Ohira, Masayoshi; Nagai, Toshiharu; Mizobe, Hoyo; Gotoh, Naohiro; Ikegami, Tohru; McCalley, David V; Tanaka, Nobuo

2014-04-25

A high-density, polymeric C18 stationary phase (Inertsil ODS-P) or a polymeric C30 phase (Inertsil C30) provided improved resolution of the isomeric fatty acids (FAs), FA methyl esters (FAMEs), triacylglycerols (TAGs), and tocopherols with an increase in pressure of 20-70MPa in reversed-phase HPLC. With respect to isomeric C18 FAMEs with one cis-double bond, ODS-P phase was effective for recognizing the position of a double bond among petroselinic (methyl 6Z-octadecenoate), oleic (methyl 9Z-octadecenoate), and cis-vaccenic (methyl 11Z-octadecenoate), especially at high pressure, but the differentiation between oleic and cis-vaccenic was not achieved by C30 phase regardless of the pressure. A monomeric C18 phase (InertSustain C18) was not effective for recognizing the position of the double bond in monounsaturated FAME, while the separation of cis- and trans-isomers was achieved by any of the stationary phases. The ODS-P and C30 phases provided increased separation for TAGs and β- and γ-tocopherols at high pressure. The transfer of FA, FAME, or TAG molecules from the mobile phase to the ODS-P stationary phase was accompanied by large volume reduction (-30∼-90mL/mol) resulting in a large increase in retention (up to 100% for an increase of 50MPa) and improved isomer separation at high pressure. For some isomer pairs, the ODS-P and C30 provided the opposite elution order, and in each case higher pressure improved the separation. The two stationary phases showed selectivity for the isomers having rigid structures, but only the ODS-P was effective for differentiating the position of a double bond in monounsaturated FAMEs. The results indicate that the improved isomer separation was provided by the increased dispersion interactions between the solute and the binding site of the stationary phase at high pressure. Copyright © 2014 Elsevier B.V. All rights reserved.

Interactions between coherent twin boundaries and phase transition of iron under dynamic loading and unloading

NASA Astrophysics Data System (ADS)

Wang, Kun; Chen, Jun; Zhang, Xueyang; Zhu, Wenjun

2017-09-01

Phase transitions and deformation twins are constantly reported in many BCC metals under high pressure, whose interactions are of fundamental importance to understand the strengthening mechanism of these metals under extreme conditions. However, the interactions between twins and phase transition in BCC metals remain largely unexplored. In this work, interactions between coherent twin boundaries and α ↔ ɛ phase transition of iron are investigated using both non-equilibrium molecular dynamics simulations and the nudged elastic band method. Mechanisms of both twin-assisted phase transition and reverse phase transition are studied, and orientation relationships between BCC and HCP phases are found to be ⟨"separators="|11 1 ¯ ⟩ B C C||⟨"separators="|1 ¯2 1 ¯ 0 ⟩ H C P and ⟨"separators="|1 1 ¯ 0 ⟩ B C C||⟨"separators="|0001 ⟩ H C P for both cases. The twin boundary corresponds to {"separators="|10 1 ¯ 0 } H C P after the phase transition. It is amazing that the reverse transition seems to be able to "memorize" and recover the initial BCC twins. The memory would be partly lost when plastic slips take place in the HCP phase before the reverse transition. In the recovered initial BCC twins, three major twin spacings are observed, which are well explained in terms of energy barriers of transition from the HCP phase to the BCC twin. Besides, the variant selection rule of the twin assisted phase transition is also discussed. The results of present work could be expected to give some clues for producing ultra-fine grain structures in materials exhibiting martensitic phase transition.

Charge pattern matching as a ‘fuzzy’ mode of molecular recognition for the functional phase separations of intrinsically disordered proteins

NASA Astrophysics Data System (ADS)

Lin, Yi-Hsuan; Brady, Jacob P.; Forman-Kay, Julie D.; Chan, Hue Sun

2017-11-01

Biologically functional liquid-liquid phase separation of intrinsically disordered proteins (IDPs) is driven by interactions encoded by their amino acid sequences. Little is currently known about the molecular recognition mechanisms for distributing different IDP sequences into various cellular membraneless compartments. Pertinent physics was addressed recently by applying random-phase-approximation (RPA) polymer theory to electrostatics, which is a major energetic component governing IDP phase properties. RPA accounts for charge patterns and thus has advantages over Flory-Huggins (FH) and Overbeek-Voorn mean-field theories. To make progress toward deciphering the phase behaviors of multiple IDP sequences, the RPA formulation for one IDP species plus solvent is hereby extended to treat polyampholyte solutions containing two IDP species plus solvent. The new formulation generally allows for binary coexistence of two phases, each containing a different set of volume fractions ({φ }1,{φ }2) for the two different IDP sequences. The asymmetry between the two predicted coexisting phases with regard to their {φ }1/{φ }2 ratios for the two sequences increases with increasing mismatch between their charge patterns. This finding points to a multivalent, stochastic, ‘fuzzy’ mode of molecular recognition that helps populate various IDP sequences differentially into separate phase compartments. An intuitive illustration of this trend is provided by FH models, whereby a hypothetical case of ternary coexistence is also explored. Augmentations of the present RPA theory with a relative permittivity {ɛ }{{r}}(φ ) that depends on IDP volume fraction φ ={φ }1+{φ }2 lead to higher propensities to phase separate, in line with the case with one IDP species we studied previously. Notably, the cooperative, phase-separation-enhancing effects predicted by the prescriptions for {ɛ }{{r}}(φ ) we deem physically plausible are much more prominent than that entailed by common effective medium approximations based on Maxwell Garnett and Bruggeman mixing formulas. Ramifications of our findings on further theoretical development for IDP phase separation are discussed.

Combined heat and mass transfer device for improving separation process

DOEpatents

Tran, Thanh Nhon

1999-01-01

A two-phase small channel heat exchange matrix simultaneously provides for heat transfer and mass transfer between the liquid and vapor phases of a multi-component mixture at a single, predetermined location within a separation column, significantly improving the thermodynamic efficiency of the separation process. The small channel heat exchange matrix is composed of a series of channels having a hydraulic diameter no greater than 5.0 millimeters for conducting a two-phase coolant. In operation, the matrix provides the liquid-vapor contacting surfaces within the separation column, such that heat and mass are transferred simultaneously between the liquid and vapor phases. The two-phase coolant allows for a uniform heat transfer coefficient to be maintained along the length of the channels and across the surface of the matrix. Preferably, a perforated, concave sheet connects each channel to an adjacent channel to facilitate the flow of the liquid and vapor phases within the column and to increase the liquid-vapor contacting surface area.

Combined heat and mass transfer device for improving separation process

DOEpatents

Tran, T.N.

1999-08-24

A two-phase small channel heat exchange matrix simultaneously provides for heat transfer and mass transfer between the liquid and vapor phases of a multi-component mixture at a single, predetermined location within a separation column, significantly improving the thermodynamic efficiency of the separation process. The small channel heat exchange matrix is composed of a series of channels having a hydraulic diameter no greater than 5.0 millimeters for conducting a two-phase coolant. In operation, the matrix provides the liquid-vapor contacting surfaces within the separation column, such that heat and mass are transferred simultaneously between the liquid and vapor phases. The two-phase coolant allows for a uniform heat transfer coefficient to be maintained along the length of the channels and across the surface of the matrix. Preferably, a perforated, concave sheet connects each channel to an adjacent channel to facilitate the flow of the liquid and vapor phases within the column and to increase the liquid-vapor contacting surface area. 12 figs.

Molecular beam epitaxy growth and magnetic properties of Cr-Co-Ga Heusler alloy films

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

Feng, Wuwei, E-mail: wfeng@cugb.edu.cn; Wang, Weihua; Zhao, Chenglong

2015-11-15

We have re-investigated growth and magnetic properties of Cr{sub 2}CoGa films using molecular beam epitaxy technique. Phase separation and precipitate formation were observed experimentally again in agreement with observation of multiple phases separation in sputtered Cr{sub 2}CoGa films by M. Meinert et al. However, significant phase separation could be suppressed by proper control of growth conditions. We showed that Cr{sub 2}CoGa Heusler phase, rather than Co{sub 2}CrGa phase, constitutes the majority of the sample grown on GaAs(001) at 450 {sup o}C. The measured small spin moment of Cr{sub 2}CoGa is in agreement with predicted HM-FCF nature; however, its Curie temperaturemore » is not as high as expected from the theoretical prediction probably due to the off-stoichiometry of Cr{sub 2}CoGa and the existence of the disorders and phase separation.« less

The effect of protein on phase separation in giant unilamellar lipid vesicles.

NASA Astrophysics Data System (ADS)

Hutchison, J. B.; Weis, R. M.; Dinsmore, A. D.

2009-03-01

We explore the coarsening and out of plane curvature (budding) of domains in lipid bilayer vesicles composed of DOPC (unsaturated), PSM (saturated), and cholesterol. Green fluorescent protein (GFP) was added to the membrane in controlled amounts by binding to the Ni-chelating lipid, Ni-DOGS. Vesicles with diameters between 10 and 50 microns were prepared via a standard electroformation procedure. As a sample is lowered through temperature Tmix, a previously homogeneous vesicle phase separates into two fluid phases with distinct compositions. Phase-separated domains have a line tension (energy/length) at the boundary with the major phase which competes with bending energy and lateral tension to determine the overall configuration of the vesicle. Domain budding and coarsening were observed and recorded using both bright field and fluorescence microscopy during temperature scans and with varying concentrations of GFP. The addition of a model protein into our system allows for a broader understanding of the effect of protein, which are ubiquitous in cell membranes, on phase separation, budding, and coarsening.

Equilibrium polymerization models of re-entrant self-assembly

NASA Astrophysics Data System (ADS)

Dudowicz, Jacek; Douglas, Jack F.; Freed, Karl F.

2009-04-01

As is well known, liquid-liquid phase separation can occur either upon heating or cooling, corresponding to lower and upper critical solution phase boundaries, respectively. Likewise, self-assembly transitions from a monomeric state to an organized polymeric state can proceed either upon increasing or decreasing temperature, and the concentration dependent ordering temperature is correspondingly called the "floor" or "ceiling" temperature. Motivated by the fact that some phase separating systems exhibit closed loop phase boundaries with two critical points, the present paper analyzes self-assembly analogs of re-entrant phase separation, i.e., re-entrant self-assembly. In particular, re-entrant self-assembly transitions are demonstrated to arise in thermally activated equilibrium self-assembling systems, when thermal activation is more favorable than chain propagation, and in equilibrium self-assembly near an adsorbing boundary where strong competition exists between adsorption and self-assembly. Apparently, the competition between interactions or equilibria generally underlies re-entrant behavior in both liquid-liquid phase separation and self-assembly transitions.

Phase separation of electrons strongly coupled with phonons in cuprates and manganites

NASA Astrophysics Data System (ADS)

Alexandrov, Sasha

2009-03-01

Recent advanced Monte Carlo simulations have not found superconductivity and phase separation in the Hubbard model with on-site repulsive electron-electron correlations. I argue that microscopic phase separations in cuprate superconductors and colossal magnetoresistance (CMR) manganites originate from a strong electron-phonon interaction (EPI) combined with unavoidable disorder. Attractive electron correlations, caused by an almost unretarded EPI, are sufficient to overcome the direct inter-site Coulomb repulsion in these charge-transfer Mott-Hubbard insulators, so that low energy physics is that of small polarons and small bipolarons. They form clusters localized by disorder below the mobility edge, but propagate as the Bloch states above the mobility edge. I identify the Froehlich EPI as the most essential for pairing and phase separation in superconducting layered cuprates. The pairing of oxygen holes into heavy bipolarons in the paramagnetic phase (current-carrier density collapse (CCDC)) explains also CMR and high and low-resistance phase coexistence near the ferromagnetic transition of doped manganites.

A Laterally-Mobile Mixed Polymer/Polyelectrolyte Brush Undergoes a Macroscopic Phase Separation

NASA Astrophysics Data System (ADS)

Lee, Hoyoung; Park, Hae-Woong; Tsouris, Vasilios; Choi, Je; Mustafa, Rafid; Lim, Yunho; Meron, Mati; Lin, Binhua; Won, You-Yeon

2013-03-01

We studied mixed PEO and PDMAEMA brushes. The question we attempted to answer was: When the chain grafting points are laterally mobile, how will this lateral mobility influence the structure and phase behavior of the mixed brush? Two different model mixed PEO/PDMAEMA brush systems were prepared: a mobile mixed brush by spreading a mixture of two diblock copolymers, PEO-PnBA and PDMAEMA-PnBA, onto the air-water interface, and an inseparable mixed brush using a PEO-PnBA-PDMAEMA triblock copolymer having respective brush molecular weights matched to those of the diblock copolymers. These two systems were investigated by surface pressure-area isotherm, X-ray reflectivity and AFM imaging measurements. The results suggest that the mobile mixed brush undergoes a lateral macroscopic phase separation at high chain grafting densities, whereas the inseparable system is only microscopically phase separated under comparable brush density conditions. We also conducted an SCF analysis of the phase behavior of the mixed brush system. This analysis further supported the experimental findings. The macroscopic phase separation observed in the mobile system is in contrast to the microphase separation behavior commonly observed in two-dimensional laterally-mobile small molecule mixtures.

Thermal vacancies and phase separation in bcc mixtures of helium-3 and helium-4

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

Fraass, Benedick Andrew

1980-01-01

Thermal vacancy concentrations in crystals of 3He- 4He mixtures have been determined. A new x-ray diffractometer-position sensitive detector system is used to make measurements of the absolute lattice parameter of the helium crystals with an accuracy of 300 ppM, and measurements of changes in lattice parameters to better than 60 ppM. The phase separation of the concentrated 3He- 4He mixtures has been studied in detail with the x-ray measurements. Vacancy concentrations in crystals with 99%, 51%, 28%, 12%, and 0% 3He have been determined. Phase separation has been studied in mixed crystals with concentrations of 51%, 28%, and 12% 3Hemore » and melting pressures between 3.0 and 6.1 MPa. The phase separation temperatures determined in this work are in general agreement with previous work. The pressure dependence of T c, the phase separation temperature for a 50% mixture, is found to be linear: dT c/dP = -34 mdeg/MPa. The x-ray measurements are used to make several comments on the low temperature phase diagram of the helium mixtures.« less

Hybrid films with phase-separated domains: A new class of functional materials

NASA Astrophysics Data System (ADS)

Kang, Minjee; Leal, Cecilia

The cell membrane is highly compartmentalized over micro-and nano scale. The compartmentalized domains play an important role in regulating the diffusion and distribution of species within and across the membrane. In this work, we introduced nanoscale heterogeneities into lipid films for the purpose of developing nature-mimicking phase-separated materials. The mixtures of phospholipids and amphiphilic block copolymers self-assemble into supported 1D multi-bilayers. We observed that in each lamella, mixtures of lipid and polymer phase-separate into domains that differ in their composition akin to sub-phases in cholesterol-containing lipid bilayers. Interestingly, we found evidence that like-domains are in registry across multilayers, making phase separation three-dimensional. To exploit such distinctive domain structure for surface-mediated drug delivery, we incorporated pharmaceutical molecules into the films. The drug release study revealed that the presence of domains in hybrid films modifies the diffusion pathways of drugs that become confined within phase-separated domains. A comprehensive domain structure coupled with drug diffusion pathways in films will be presented, offering new perspectives in designing a thin-film matrix system for controlled drug delivery. This work was supported by the National Science Foundation under Grant No. DMR-1554435.

Gradient enhanced-fluidity liquid hydrophilic interaction chromatography of ribonucleic acid nucleosides and nucleotides: A "green" technique.

PubMed

Beilke, Michael C; Beres, Martin J; Olesik, Susan V

2016-03-04

A "green" hydrophilic interaction liquid chromatography (HILIC) technique for separating the components of mixtures with a broad range of polarities is illustrated using enhanced-fluidity liquid mobile phases. Enhanced-fluidity liquid chromatography (EFLC) involves the addition of liquid CO2 to conventional liquid mobile phases. Decreased mobile phase viscosity and increased analyte diffusivity results when a liquefied gas is dissolved in common liquid mobile phases. The impact of CO2 addition to a methanol:water (MeOH:H2O) mobile phase was studied to optimize HILIC gradient conditions. For the first time a fast separation of 16 ribonucleic acid (RNA) nucleosides/nucleotides was achieved (16min) with greater than 1.3 resolution for all analyte pairs. By using a gradient, the analysis time was reduced by over 100% compared to similar separations conducted under isocratic conditions. The optimal separation using MeOH:H2O:CO2 mobile phases was compared to MeOH:H2O and acetonitrile:water (ACN:H2O) mobile phases. Based on chromatographic performance parameters (efficiency, resolution and speed of analysis) and an assessment of the environmental impact of the mobile phase mixtures, MeOH:H2O:CO2 mixtures are preferred over ACN:H2O or MeOH:H2O mobile phases for the separation of mixtures of RNA nucleosides and nucleotides. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of atomic disorder on the magnetic phase separation.

PubMed

Groshev, A G; Arzhnikov, A K

2018-05-10

The effect of disorder on the magnetic phase separation between the antiferromagnetic and incommensurate helical [Formula: see text] and [Formula: see text] phases is investigated. The study is based on the quasi-two-dimensional single-band Hubbard model in the presence of atomic disorder (the [Formula: see text] Anderson-Hubbard model). A model of binary alloy disorder is considered, in which the disorder is determined by the difference in energy between the host and impurity atomic levels at a fixed impurity concentration. The problem is solved within the theory of functional integration in static approximation. Magnetic phase diagrams are obtained as functions of the temperature, the number of electrons and impurity concentration with allowance for phase separation. It is shown that for the model parameters chosen, the disorder caused by impurities whose atomic-level energy is greater than that of the host atomic levels, leads to qualitative changes in the phase diagram of the impurity-free system. In the opposite case, only quantitative changes occur. The peculiarities of the effect of disorder on the phase separation regions of the quasi-two-dimensional Hubbard model are discussed.

Effect of atomic disorder on the magnetic phase separation

NASA Astrophysics Data System (ADS)

Groshev, A. G.; Arzhnikov, A. K.

2018-05-01

The effect of disorder on the magnetic phase separation between the antiferromagnetic and incommensurate helical and phases is investigated. The study is based on the quasi-two-dimensional single-band Hubbard model in the presence of atomic disorder (the Anderson–Hubbard model). A model of binary alloy disorder is considered, in which the disorder is determined by the difference in energy between the host and impurity atomic levels at a fixed impurity concentration. The problem is solved within the theory of functional integration in static approximation. Magnetic phase diagrams are obtained as functions of the temperature, the number of electrons and impurity concentration with allowance for phase separation. It is shown that for the model parameters chosen, the disorder caused by impurities whose atomic-level energy is greater than that of the host atomic levels, leads to qualitative changes in the phase diagram of the impurity-free system. In the opposite case, only quantitative changes occur. The peculiarities of the effect of disorder on the phase separation regions of the quasi-two-dimensional Hubbard model are discussed.

Therapeutic Antibody Engineering To Improve Viscosity and Phase Separation Guided by Crystal Structure.

PubMed

Chow, Chi-Kin; Allan, Barrett W; Chai, Qing; Atwell, Shane; Lu, Jirong

2016-03-07

Antibodies at high concentrations often reveal unanticipated biophysical properties suboptimal for therapeutic development. The purpose of this work was to explore the use of point mutations based on crystal structure information to improve antibody physical properties such as viscosity and phase separation (LLPS) at high concentrations. An IgG4 monoclonal antibody (Mab4) that exhibited high viscosity and phase separation at high concentration was used as a model system. Guided by the crystal structure, four CDR point mutants were made to evaluate the role of hydrophobic and charge interactions on solution behavior. Surprisingly and unpredictably, two of the charge mutants, R33G and N35E, showed a reduction in viscosity and a lower propensity to form LLPS at high concentration compared to the wild-type (WT), while a third charge mutant S28K showed an increased propensity to form LLPS compared to the WT. A fourth mutant, F102H, had reduced hydrophobicity, but unchanged viscosity and phase separation behavior. We further evaluated the correlation of various biophysical measurements including second virial coefficient (A2), interaction parameter (kD), weight-average molecular weight (WAMW), and hydrodynamic diameters (DH), at relatively low protein concentration (4 to 15 mg/mL) to physical properties, such as viscosity and liquid-liquid phase separation (LLPS), at high concentration. Surprisingly, kD measured using dynamic light scattering (DLS) at low antibody concentration correlated better with viscosity and phase separation than did A2 for Mab4. Our results suggest that the high viscosity and phase separation observed at high concentration for Mab4 are mainly driven by charge and not hydrophobicity.

A new submarine oil-water separation system

NASA Astrophysics Data System (ADS)

Cai, Wen-Bin; Liu, Bo-Hong

2017-12-01

In order to solve the oil field losses of environmental problems and economic benefit caused by the separation of lifting production liquid to offshore platforms in the current offshore oil production, from the most basic separation principle, a new oil-water separation system has been processed of adsorption and desorption on related materials, achieving high efficiency and separation of oil and water phases. And the submarine oil-water separation device has been designed. The main structure of the device consists of gas-solid phase separation device, period separating device and adsorption device that completed high efficiency separation of oil, gas and water under the adsorption and desorption principle, and the processing capacity of the device is calculated.

Method for separating mono- and di-octylphenyl phosphoric acid esters

DOEpatents

Arnold, Jr., Wesley D.

1977-01-01

A method for separating mono-octylphenyl phosphoric acid ester and di-octylphenyl phosphoric acid ester from a mixture thereof comprises reacting the ester mixture with a source of lithium or sodium ions to form a mixture of the phosphate salts; contacting the salt mixture with an organic solvent which causes the dioctylphenyl phosphate salt to be dissolved in the organic solvent phase and the mono-octylphenyl phosphate salt to exist in a solid phase; separating the phases; recovering the phosphate salts from their respective phases; and acidifying the recovered salts to form the original phosphoric acid esters.

Two-phase turbine engines. [using gas-liquid mixture accelerated in nozzles

NASA Technical Reports Server (NTRS)

Elliott, D. G.; Hays, L. G.

1976-01-01

A description is given of a two-phase turbine which utilizes a uniform mixture of gas and liquid accelerated in nozzles of the types reported by Elliott and Weinberg (1968). The mixture acts directly on an axial flow or tangential impulse turbine or is separated into gas and liquid streams which operate separately on a gas turbine and a hydraulic turbine. The basic two-phase cycles are examined, taking into account working fluids, aspects of nozzle expansion, details of turbine cycle operation, and the effect of mixture ratio variation. Attention is also given to two-phase nozzle efficiency, two-phase turbine operating characteristics and efficiencies, separator turbines, and impulse turbine experiments.

Prediction of Phase Separation of Immiscible Ga-Tl Alloys

NASA Astrophysics Data System (ADS)

Kim, Yunkyum; Kim, Han Gyeol; Kang, Youn-Bae; Kaptay, George; Lee, Joonho

2017-06-01

Phase separation temperature of Ga-Tl liquid alloys was investigated using the constrained drop method. With this method, density and surface tension were investigated together. Despite strong repulsive interactions, molar volume showed ideal mixing behavior, whereas surface tension of the alloy was close to that of pure Tl due to preferential adsorption of Tl. Phase separation temperatures and surface tension values obtained with this method were close to the theoretically calculated values using three different thermodynamic models.

Phase separation of in situ forming poly (lactide-co-glycolide acid) implants investigated using a hydrogel-based subcutaneous tissue surrogate and UV-vis imaging.

PubMed

Sun, Yu; Jensen, Henrik; Petersen, Nickolaj J; Larsen, Susan W; Østergaard, Jesper

2017-10-25

Phase separation of in situ forming poly (lactide-co-glycolide acid) (PLGA) implants with agarose hydrogels as the provider of nonsolvent (water) mimicking subcutaneous tissue was investigated using a novel UV-vis imaging-based analytical platform. In situ forming implants of PLGA-1-methyl-2-pyrrolidinone and PLGA-triacetin representing fast and slow phase separating systems, respectively, were evaluated using this platform. Upon contact with the agarose hydrogel, the phase separation of the systems was followed by the study of changes in light transmission and absorbance as a function of time and position. For the PLGA-1-methyl-2-pyrrolidinone system, the rate of spatial phase separation was determined and found to decrease with increasing the PLGA concentration from 20% to 40% (w/w). Hydrogels with different agarose concentrations (1% and 10% (w/v)) were prepared for providing the nonsolvent, water, to the in situ forming PLGA implants simulating the injection site environment. The resulting implant morphology depended on the stiffness of hydrogel matrix, indicating that the matrix in which implants are formed is of importance. Overall, the work showed that the UV-vis imaging-based platform with an agarose hydrogel mimicking the subcutaneous tissue holds potential in providing bio-relevant and mechanistic information on the phase separation processes of in situ forming implants. Copyright © 2017 Elsevier B.V. All rights reserved.

The chiral separation of triazole pesticides enantiomers by amylose-tris (3,5-dimethylphenylcarbamate) chiral stationary phase.

PubMed

Wang, Peng; Liu, Donghui; Jiang, Shuren; Xu, Yangguang; Zhou, Zhiqiang

2008-10-01

The amylose-tris(3,5-dimethylphenylcarbamate) chiral stationary phase was synthesized and used to separate the enantiomers of triazole pesticides by high-performance liquid chromatography. The mobile phase was n-hexane-isopropanol applying a flow rate of 1.0 mL/min. Six triazole pesticides were enantioselectively separated. Myclobutanil, paclobutrazol, tebuconazole, and uniconazole obtained complete separation with the resolution factors of 5.73, 2.99, 1.72, and 2.07, respectively, and imazalil and diniconazole obtained partial separation with the resolution factors of 0.79 and 0.77 under the optimized conditions. The effect of the content of isopropanol as well as column temperature on the separation was investigated. A circular dichroism detector was used to identify the enantiomers and determine the elution orders. The results showed the low temperature was good for the chiral separation except for diniconazole. The thermodynamic parameters calculated based on linear Van't Hoff plots showed the chiral separations were controlled by enthalpy.

Analyses of procyanidins in foods using Diol phase HPLC

USDA-ARS?s Scientific Manuscript database

Separation of procyanidins using silica-based HPLC suffered from poor resolution for higher oligomers and low sensitivity due to the fluorescence quenching effects of methylene chloride in the mobile phase. Optimization of a published Diol-phase HPLC method resulted in near baseline separation for p...

Identifying Effective Design Approaches to Allocate Genotypes in Two-Phase Designs: A Case Study in Pelargonium zonale.

PubMed

Molenaar, Heike; Boehm, Robert; Piepho, Hans-Peter

2017-01-01

Robust phenotypic data allow adequate statistical analysis and are crucial for any breeding purpose. Such data is obtained from experiments laid out to best control local variation. Additionally, experiments frequently involve two phases, each contributing environmental sources of variation. For example, in a former experiment we conducted to evaluate production related traits in Pelargonium zonale , there were two consecutive phases, each performed in a different greenhouse. Phase one involved the propagation of the breeding strains to obtain the stem cutting count, and phase two involved the assessment of root formation. The evaluation of the former study raised questions regarding options for improving the experimental layout: (i) Is there a disadvantage to using exactly the same design in both phases? (ii) Instead of generating a separate layout for each phase, can the design be optimized across both phases, such that the mean variance of a pair-wise treatment difference (MVD) can be decreased? To answer these questions, alternative approaches were explored to generate two-phase designs either in phase-wise order (Option 1) or across phases (Option 2). In Option 1 we considered the scenarios (i) using in both phases the same experimental design and (ii) randomizing each phase separately. In Option 2, we considered the scenarios (iii) generating a single design with eight replicates and splitting these among the two phases, (iv) separating the block structure across phases by dummy coding, and (v) design generation with optimal alignment of block units in the two phases. In both options, we considered the same or different block structures in each phase. The designs were evaluated by the MVD obtained by the intra-block analysis and the joint inter-block-intra-block analysis. The smallest MVD was most frequently obtained for designs generated across phases rather than for each phase separately, in particular when both phases of the design were separated with a single pseudo-level. The joint optimization ensured that treatment concurrences were equally balanced across pairs, one of the prerequisites for an efficient design. The proposed alternative approaches can be implemented with any model-based design packages with facilities to formulate linear models for treatment and block structures.

Dynamics of coarsening in multicomponent lipid vesicles with non-uniform mechanical properties

NASA Astrophysics Data System (ADS)

Funkhouser, Chloe M.; Solis, Francisco J.; Thornton, K.

2014-04-01

Multicomponent lipid vesicles are commonly used as a model system for the complex plasma membrane. One phenomenon that is studied using such model systems is phase separation. Vesicles composed of simple lipid mixtures can phase-separate into liquid-ordered and liquid-disordered phases, and since these phases can have different mechanical properties, this separation can lead to changes in the shape of the vesicle. In this work, we investigate the dynamics of phase separation in multicomponent lipid vesicles, using a model that couples composition to mechanical properties such as bending rigidity and spontaneous curvature. The model allows the vesicle surface to deform while conserving surface area and composition. For vesicles initialized as spheres, we study the effects of phase fraction and spontaneous curvature. We additionally initialize two systems with elongated, spheroidal shapes. Dynamic behavior is contrasted in systems where only one phase has a spontaneous curvature similar to the overall vesicle surface curvature and systems where the spontaneous curvatures of both phases are similar to the overall curvature. The bending energy contribution is typically found to slow the dynamics by stabilizing configurations with multiple domains. Such multiple-domain configurations are found more often in vesicles with spheroidal shapes than in nearly spherical vesicles.

FUS Phase Separation Is Modulated by a Molecular Chaperone and Methylation of Arginine Cation-π Interactions.

PubMed

Qamar, Seema; Wang, GuoZhen; Randle, Suzanne J; Ruggeri, Francesco Simone; Varela, Juan A; Lin, Julie Qiaojin; Phillips, Emma C; Miyashita, Akinori; Williams, Declan; Ströhl, Florian; Meadows, William; Ferry, Rodylyn; Dardov, Victoria J; Tartaglia, Gian G; Farrer, Lindsay A; Kaminski Schierle, Gabriele S; Kaminski, Clemens F; Holt, Christine E; Fraser, Paul E; Schmitt-Ulms, Gerold; Klenerman, David; Knowles, Tuomas; Vendruscolo, Michele; St George-Hyslop, Peter

2018-04-19

Reversible phase separation underpins the role of FUS in ribonucleoprotein granules and other membrane-free organelles and is, in part, driven by the intrinsically disordered low-complexity (LC) domain of FUS. Here, we report that cooperative cation-π interactions between tyrosines in the LC domain and arginines in structured C-terminal domains also contribute to phase separation. These interactions are modulated by post-translational arginine methylation, wherein arginine hypomethylation strongly promotes phase separation and gelation. Indeed, significant hypomethylation, which occurs in FUS-associated frontotemporal lobar degeneration (FTLD), induces FUS condensation into stable intermolecular β-sheet-rich hydrogels that disrupt RNP granule function and impair new protein synthesis in neuron terminals. We show that transportin acts as a physiological molecular chaperone of FUS in neuron terminals, reducing phase separation and gelation of methylated and hypomethylated FUS and rescuing protein synthesis. These results demonstrate how FUS condensation is physiologically regulated and how perturbations in these mechanisms can lead to disease. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.

Separation of polyethylene glycols and amino-terminated polyethylene glycols by high-performance liquid chromatography under near critical conditions.

PubMed

Wei, Y-Z; Zhuo, R-X; Jiang, X-L

2016-05-20

The separation and characterization of polyethylene glycols (PEGs) and amino-substituted derivatives on common silica-based reversed-phase packing columns using isocratic elution is described. This separation is achieved by liquid chromatography under the near critical conditions (LCCC), based on the number of amino functional end groups without obvious effect of molar mass for PEGs. The mobile phase is acetonitrile in water with an optimal ammonium acetate buffer. The separation mechanism of PEG and amino-substituted PEG under the near LCCC on silica-based packing columns is confirmed to be ion-exchange interaction. Under the LCCC of PEG backbone, with fine tune of buffer concentration, the retention factor ratios for benzylamine and phenol in buffered mobile phases, α(benzylamine/phenol)-values, were used to assess the ion-exchange capacity on silica-based reversed-phase packing columns. To the best of our knowledge, this is the first report on separation of amino-functional PEGs independent of the molar mass by isocratic elution using common C18 or phenyl reversed-phase packing columns. Copyright © 2016 Elsevier B.V. All rights reserved.

Effects of ammonium sulfate and sodium chloride concentration on PEG/protein liquid-liquid phase separation.

PubMed

Dumetz, André C; Lewus, Rachael A; Lenhoff, Abraham M; Kaler, Eric W

2008-09-16

When added to protein solutions, poly(ethylene glycol) (PEG) creates an effective attraction between protein molecules due to depletion forces. This effect has been widely used to crystallize proteins, and PEG is among the most successful crystallization agents in current use. However, PEG is almost always used in combination with a salt at either low or relatively high concentrations. Here the effects of sodium chloride and ammonium sulfate concentration on PEG 8000/ovalbumin liquid-liquid (L-L) phase separation are investigated. At low salt the L-L phase separation occurs at decreasing protein concentration with increasing salt concentration, presumably due to repulsive electrostatic interactions between proteins. At high salt concentration, the behavior depends on the nature of the salt. Sodium chloride has little effect on the L-L phase separation, but ammonium sulfate decreases the protein concentration at which the L-L phase separation occurs. This trend is attributed to the effects of critical fluctuations on depletion forces. The implications of these results for designing solution conditions optimal for protein crystallization are discussed.

Numerical analysis of wet separation of particles by density differences

NASA Astrophysics Data System (ADS)

Markauskas, D.; Kruggel-Emden, H.

2017-07-01

Wet particle separation is widely used in mineral processing and plastic recycling to separate mixtures of particulate materials into further usable fractions due to density differences. This work presents efforts aiming to numerically analyze the wet separation of particles with different densities. In the current study the discrete element method (DEM) is used for the solid phase while the smoothed particle hydrodynamics (SPH) is used for modeling of the liquid phase. The two phases are coupled by the use of a volume averaging technique. In the current study, simulations of spherical particle separation were performed. In these simulations, a set of generated particles with two different densities is dropped into a rectangular container filled with liquid. The results of simulations with two different mixtures of particles demonstrated how separation depends on the densities of particles.

Green chromatography separation of analytes of greatly differing properties using a polyethylene glycol stationary phase and a low-toxic water-based mobile phase.

PubMed

Šatínský, Dalibor; Brabcová, Ivana; Maroušková, Alena; Chocholouš, Petr; Solich, Petr

2013-07-01

A simple, rapid, and environmentally friendly HPLC method was developed and validated for the separation of four compounds (4-aminophenol, caffeine, paracetamol, and propyphenazone) with different chemical properties. A "green" mobile phase, employing water as the major eluent, was proposed and applied to the separation of analytes with different polarity on polyethylene glycol (PEG) stationary phase. The chromatography separation of all compounds and internal standard benzoic acid was performed using isocratic elution with a low-toxicity mobile phase consisting of 0.04% (v/v) triethylamine and water. HPLC separation was carried out using a PEG reversed-phase stationary phase Supelco Discovery HS PEG column (15 × 4 mm; particle size 3 μm) at a temperature of 30 °C and flow rate at 1.0 mL min(-1). The UV detector was set at 210 nm. In this study, a PEG stationary phase was shown to be suitable for the efficient isocratic separation of compounds that differ widely in hydrophobicity and acid-base properties, particularly 4-aminophenol (log P, 0.30), caffeine (log P, -0.25), and propyphenazone (log P, 2.27). A polar PEG stationary phase provided specific selectivity which allowed traditional chromatographic problems related to the separation of analytes with different polarities to be solved. The retention properties of the group of structurally similar substances (aromatic amines, phenolic compounds, and xanthine derivatives) were tested with different mobile phases. The proposed green chromatography method was successfully applied to the analysis of active substances and one degradation impurity (4-aminophenol) in commercial preparation. Under the optimum chromatographic conditions, standard calibration was carried out with good linearity correlation coefficients for all compounds in the range (0.99914-0.99997, n = 6) between the peak areas and concentration of compounds. Recovery of the sample preparation was in the range 100 ± 5% for all compounds. The intraday method precision was determined as RSD, and the values were lower than 1.00%.

Supramolecular separation mechanism of pentafluorophenyl column using ibuprofen and omeprazole as markers: LC-MS and simulation study.

PubMed

Hussain, Afzal; AlAjmi, Mohamed F; Ali, Imran

2018-06-01

The pentafluorophenyl (PFP) column is emerging as a new advancement in separation science to analyze a wide range of analytes and, thus, its separation mechanism at supramolecular level is significant. We developed a mechanism for the separation of ibuprofen and omeprazole using different combinations (ranging from 50:50 to 60:40) of water-acetonitrile containing 0.1% formic acid as the mobile phase. The column used was Waters Acquity UPLC HSS PFP (75 × 2.1 mm, 1.8 μm). The reverse order of elution was observed in different combinations of the mobile phases. The docking study indicated hydrogen bonding between ibuprofen and PFP stationary phase (binding energy was -11.30 kJ/mol). Separation at PFP stationary phase is controlled by hydrogen bonding along with π-π interactions. This stationary phase may be used to analyze both aromatic and aliphatic analytes. The developed mechanism will be useful to separate various analytes by considering the possible interactions, leading to saving of energy, time and money. In addition, this work will be highly useful in preparative chromatography where separation is the major problem at a large scale. Moreover, the developed LC-MS-QTOF method may be used to analyze ibuprofen and omeprazole in an unknown sample owing to the low value of detection limits. Copyright © 2018 John Wiley & Sons, Ltd.

Electrospun Polymer Blend Nanofibers for Tunable Drug Delivery: The Role of Transformative Phase Separation on Controlling the Release Rate.

PubMed

Tipduangta, Pratchaya; Belton, Peter; Fábián, László; Wang, Li Ying; Tang, Huiru; Eddleston, Mark; Qi, Sheng

2016-01-04

Electrospun fibrous materials have a wide range of biomedical applications, many of them involving the use of polymers as matrices for incorporation of therapeutic agents. The use of polymer blends improves the tuneability of the physicochemical and mechanical properties of the drug loaded fibers. This also benefits the development of controlled drug release formulations, for which the release rate can be modified by altering the ratio of the polymers in the blend. However, to realize these benefits, a clear understanding of the phase behavior of the processed polymer blend is essential. This study reports an in depth investigation of the impact of the electrospinning process on the phase separation of a model partially miscible polymer blend, PVP K90 and HPMCAS, in comparison to other conventional solvent evaporation based processes including film casting and spin coating. The nanoscale stretching and ultrafast solvent removal of electrospinning lead to an enhanced apparent miscibility between the polymers, with the same blends showing micronscale phase separation when processed using film casting and spin coating. Nanoscale phase separation in electrospun blend fibers was confirmed in the dry state. Rapid, layered, macroscale phase separation of the two polymers occurred during the wetting of the fibers. This led to a biphasic drug release profile from the fibers, with a burst release from PVP-rich phases and a slower, more continuous release from HPMCAS-rich phases. It was noted that the model drug, paracetamol, had more favorable partitioning into the PVP-rich phase, which is likely to be a result of greater hydrogen bonding between PVP and paracetamol. This led to higher drug contents in the PVP-rich phases than the HPMCAS-rich phases. By alternating the proportions of the PVP and HPMCAS, the drug release rate can be modulated.

TES buffer-induced phase separation of aqueous solutions of several water-miscible organic solvents at 298.15 K: phase diagrams and molecular dynamic simulations.

PubMed

Taha, Mohamed; Lee, Ming-Jer

2013-06-28

Water and the organic solvents tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, 1-propanol, 2-propanol, tert-butanol, acetonitrile, or acetone are completely miscible in all proportions at room temperature. Here, we present new buffering-out phase separation systems that the above mentioned organic aqueous solutions can be induced to form two liquid phases in the presence of a biological buffer 2-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]ethanesulfonic acid (TES). The lower liquid phase is rich in water and buffer, and the upper phase is organic rich. This observation has both practical and mechanistic interests. The phase diagrams of these systems were constructed by experimental measurements at ambient conditions. Molecular dynamic (MD) simulations were performed for TES + water + THF system to understand the interactions between TES, water, and organic solvent at molecular level. Several composition-sets for this system, beyond and inside the liquid-liquid phase-splitting region, have been simulated. Interestingly, the MD simulation for compositions inside the phase separation region showed that THF molecules are forced out from the water network to start forming a new liquid phase. The hydrogen-bonds, hydrogen-bonds lifetimes, hydrogen-bond energies, radial distribution functions, coordination numbers, the electrostatic interactions, and the van der Waals interactions between the different pairs have been calculated. Additionally, MD simulations for TES + water + tert-butanol∕acetonitrile∕acetone phase separation systems were simulated. The results from MD simulations provide an explanation for the buffering-out phenomena observed in [TES + water + organic solvent] systems by a mechanism controlled by the competitive interactions of the buffer and the organic solvent with water. The molecular mechanism reported here is helpful for designing new benign separation materials.

Advances in organic polymer-based monolithic column technology for high-resolution liquid chromatography-mass spectrometry profiling of antibodies, intact proteins, oligonucleotides, and peptides.

PubMed

Eeltink, Sebastiaan; Wouters, Sam; Dores-Sousa, José Luís; Svec, Frantisek

2017-05-19

This review focuses on the preparation of organic polymer-based monolithic stationary phases and their application in the separation of biomolecules, including antibodies, intact proteins and protein isoforms, oligonucleotides, and protein digests. Column and material properties, and the optimization of the macropore structure towards kinetic performance are also discussed. State-of-the-art liquid chromatography-mass spectrometry biomolecule separations are reviewed and practical aspects such as ion-pairing agent selection and carryover are presented. Finally, advances in comprehensive two-dimensional LC separations using monolithic columns, in particular ion-exchange×reversed-phase and reversed-phase×reversed-phase LC separations conducted at high and low pH, are shown. Copyright © 2017 Elsevier B.V. All rights reserved.

Recent progress of chiral stationary phases for separation of enantiomers in gas chromatography.

PubMed

Xie, Sheng-Ming; Yuan, Li-Ming

2017-01-01

Chromatography techniques based on chiral stationary phases are widely used for the separation of enantiomers. In particular, gas chromatography has developed rapidly in recent years due to its merits such as fast analysis speed, lower consumption of stationary phases and analytes, higher column efficiency, making it a better choice for chiral separation in diverse industries. This article summarizes recent progress of novel chiral stationary phases based on cyclofructan derivatives and chiral porous materials including chiral metal-organic frameworks, chiral porous organic frameworks, chiral inorganic mesoporous materials, and chiral porous organic cages in gas chromatography, covering original research papers published since 2010. The chiral recognition properties and mechanisms of separation toward enantiomers are also introduced. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanocomposites for ultra high density information storage, devices including the same, and methods of making the same

DOEpatents

Goyal, Amit; Shin, Junsoo

2014-04-01

A nanocomposite article that includes a single-crystal or single-crystal-like substrate and heteroepitaxial, phase-separated layer supported by a surface of the substrate and a method of making the same are described. The heteroepitaxial layer can include a continuous, non-magnetic, crystalline, matrix phase, and an ordered, magnetic magnetic phase disposed within the matrix phase. The ordered magnetic phase can include a plurality of self-assembled crystalline nanostructures of a magnetic material. The phase-separated layer and the single crystal substrate can be separated by a buffer layer. An electronic storage device that includes a read-write head and a nanocomposite article with a data storage density of 0.75 Tb/in.sup.2 is also described.

Stability of Mixed Preparations Consisting of Commercial Moisturizing Creams with an Ointment Base Investigated by Magnetic Resonance Imaging.

PubMed

Onuki, Yoshinori; Funatani, Chiaki; Yamamoto, Yoshihisa; Fukami, Toshiro; Koide, Tatsuo; Hayashi, Yoshihiro; Takayama, Kozo

2017-01-01

A moisturizing cream mixed with a steroid ointment is frequently prescribed to patients suffering from atopic dermatitis. However, there is a concern that the mixing operation causes destabilization. The present study was performed to investigate the stability of such preparations closely using magnetic resonance imaging (MRI). As sample preparations, five commercial moisturizing creams that are popular in Japan were mixed with an ointment base, a white petrolatum, at a volume ratio of 1 : 1. The mixed preparations were stored at 60°C to accelerate the destabilization processes. Subsequently, the phase separations induced by the storage test were monitored using MRI. Using advanced MR technologies including spin-spin relaxation time (T 2 ) mapping and MR spectroscopy, we successfully characterized the phase-separation behavior of the test samples. For most samples, phase separations developed by the bleeding of liquid oil components. From a sample consisting of an oil-in-water-type cream, Urepearl Cream 10%, a distinct phase-separation mode was observed, which was initiated by the aqueous component separating from the bottom part of the sample. The resultant phase separation was the most distinct among the test samples. To investigate the phase separation quantitatively and objectively, we conducted a histogram analysis on the acquired T 2 maps. The water-in-oil type creams were found to be much more stable after mixing with ointment base than those of oil-in-water type creams. This finding strongly supported the validity of the mixing operation traditionally conducted in pharmacies.

Heterogeneous ice nucleation on phase-separated organic-sulfate particles: effect of liquid vs. glassy coatings

NASA Astrophysics Data System (ADS)

Schill, G. P.; Tolbert, M. A.

2013-05-01

Atmospheric ice nucleation on aerosol particles relevant to cirrus clouds remains one of the least understood processes in the atmosphere. Upper tropospheric aerosols as well as sub-visible cirrus residues are known to be enhanced in both sulfates and organics. The hygroscopic phase transitions of organic-sulfate particles can have an impact on both the cirrus cloud formation mechanism and resulting cloud microphysical properties. In addition to deliquescence and efflorescence, organic-sulfate particles are known to undergo another phase transition known as liquid-liquid phase separation. The ice nucleation properties of particles that have undergone liquid-liquid phase separation are unknown. Here, Raman microscopy coupled with an environmental cell was used to study the low temperature deliquescence, efflorescence, and liquid-liquid phase separation behavior of 2 : 1 mixtures of organic polyols (1,2,6-hexanetriol and 1 : 1 1,2,6-hexanetriol + 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol) and ammonium sulfate from 240-265 K. Further, the ice nucleation efficiency of these organic-sulfate systems after liquid-liquid phase separation and efflorescence was investigated from 210-235 K. Raman mapping and volume-geometry analysis indicate that these particles contain solid ammonium sulfate cores fully engulfed in organic shells. For the ice nucleation experiments, we find that if the organic coatings are liquid, water vapor diffuses through the shell and ice nucleates on the ammonium sulfate core. In this case, the coatings minimally affect the ice nucleation efficiency of ammonium sulfate. In contrast, if the coatings become semi-solid or glassy, ice instead nucleates on the organic shell. Consistent with recent findings that glasses can be efficient ice nuclei, the phase-separated particles are nearly as efficient at ice nucleation as pure crystalline ammonium sulfate.

Heterogeneous ice nucleation on phase-separated organic-sulfate particles: effect of liquid vs. glassy coatings

NASA Astrophysics Data System (ADS)

Schill, G. P.; Tolbert, M. A.

2012-12-01

Atmospheric ice nucleation on aerosol particles relevant to cirrus clouds remains one of the least understood processes in the atmosphere. Upper tropospheric aerosols as well as sub-visible cirrus residues are known to be enhanced in both sulfates and organics. The hygroscopic phase transitions of organic-sulfate particles can have an impact on both the cirrus cloud formation mechanism and resulting cloud microphysical properties. In addition to deliquescence and efflorescence, organic-sulfate particles are known to undergo another phase transition known as liquid-liquid phase separation. The ice nucleation properties of particles that have undergone liquid-liquid phase separation are unknown. Here, Raman microscopy coupled with an environmental cell was used to study the low temperature deliquescence, efflorescence, and liquid-liquid phase separation behavior of 2:1 mixtures of organic polyols (1,2,6-hexanetriol, and 1:1 1,2,6-hexanetriol +2,2,6,6-tetrakis(hydroxymethyl)cycohexanol) and ammonium sulfate from 240-265 K. Further, the ice nucleation efficiency of these organic-sulfate systems after liquid-liquid phase separation and efflorescence was investigated from 210-235 K. Raman mapping and volume-geometry analysis indicates that these particles contain solid ammonium sulfate cores fully engulfed in organic shells. For the ice nucleation experiments, we find that if the organic coatings are liquid, water vapor diffuses through the shell and ice nucleates on the ammonium sulfate core. In this case, the coatings minimally affect the ice nucleation efficiency of ammonium sulfate. In contrast, if the coatings become semi-solid or glassy, ice instead nucleates on the organic shell. Consistent with recent findings that glasses can be efficient ice nuclei, the phase separated particles are nearly as efficient at ice nucleation as pure crystalline ammonium sulfate.

The antagonistic role of chaotropic hexafluorophosphate anions and imidazolium cations composing ionic liquids applied as phase additives in the separation of tri-cyclic antidepressants.

PubMed

Caban, Magda; Stepnowski, Piotr

2017-05-15

The main advantage of alkylimidazolium cation-based ionic liquids (ILs) as phase additives in RP-HPLC is believed to be the suppression of deleterious residual free silanols in chemically modified silica stationary phases. However, up to now, the influence of ILs was usually evaluated having in mind a particular IL salt as one compound, not as a specific mixture of cations and anions. This in fact led to some misinterpretation of observed results, very often related to the suppression effect, while in fact caused by the nature of IL anions, which contribute to the elevated chaotropicity of the separation phases. In the present study, we have attempted to consider the effect gained due to the presence of both ionic liquid entities in the mobile phase used for the separation of basic compounds. Tri-cyclic antidepressants (TCAs) were taken as representative analytes. The effect of ILs on the chromatographic separation of TCAs was investigated in comparison to common mobile phase additives and by the presentation of retention factors, tailing factors and theoretical plates. In addition, an overloading study was performed for the IL-based phases for the first time. In general, it was found that the effect of chaotropic hexafluorophosphate anions in ILs is much stronger and opposite to that caused by imidazolium cations. The overloading study gives interesting information on how imidazolium cations affect the separation of cationic analytes. Finally, the usefulness of imidazolium-based ILs as mobile phase modifiers in the RP-HPLC separation of basic compounds was discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Experimental Investigation and Thermodynamic Assessment of Phase Equilibria in the PLLA/Dioxane/Water Ternary System for Applications in the Biomedical Field.

PubMed

Ruggiero, Flavia; Netti, Paolo Antonio; Torino, Enza

2015-12-01

Fundamental understanding of thermodynamic of phase separation plays a key role in tuning the desired features of biomedical devices. In particular, phase separation of ternary solution is of remarkable interest in processes to obtain biodegradable and biocompatible architectures applied as artificial devices to repair, replace, or support damaged tissues or organs. In these perspectives, thermally induced phase separation (TIPS) is the most widely used technique to obtained porous morphologies and, in addition, among different ternary systems, polylactic acid (PLLA)/dioxane/water has given promising results and has been largely studied. However, to increase the control of TIPS-based processes and architectures, an investigation of the basic energetic phenomena occurring during phase separation is still required. Here we propose an experimental investigation of the selected ternary system by using isothermal titration calorimetric approach at different solvent/antisolvent ratio and a thermodynamic explanation related to the polymer-solvents interactions in terms of energetic contribution to the phase separation process. Furthermore, relevant information about the phase diagrams and interaction parameters of the studied systems are furnished in terms of liquid-liquid miscibility gap. Indeed, polymer-solvents interactions are responsible for the mechanism of the phase separation process and, therefore, of the final features of the morphologies; the knowledge of such data is fundamental to control processes for the production of membranes, scaffolds and several nanostructures. The behavior of the polymer at different solvent/nonsolvent ratios is discussed in terms of solvation mechanism and a preliminary contribution to the understanding of the role of the hydrogen bonding in the interface phenomena is also reported. It is the first time that thermodynamic data of a ternary system are collected by mean of nano-isothermal titration calorimetry (nano-ITC). Supporting Information is available.

Separation as an Important Risk Factor for Suicide: A Systematic Review

ERIC Educational Resources Information Center

Ide, Naoko; Wyder, Marianne; Kolves, Kairi; De Leo, Diego

2010-01-01

Examining how different phases of relationship separation effects the development of suicidal behaviors has been largely ignored in suicide studies. The few studies conducted suggest that individuals experiencing the acute phase of marital/de facto separation may be at greater risk of suicide compared with those experiencing long-term separation…

URANIUM SEPARATION PROCESS

DOEpatents

McVey, W.H.; Reas, W.H.

1959-03-10

The separation of uranium from an aqueous solution containing a water soluble uranyl salt is described. The process involves adding an alkali thiocyanate to the aqueous solution, contacting the resulting solution with methyl isobutyl ketons and separating the resulting aqueous and organic phase. The uranium is extracted in the organic phase as UO/sub 2/(SCN)/sub/.

Combination of Complex-Based and Magnitude-Based Multiecho Water-Fat Separation for Accurate Quantification of Fat-Fraction

PubMed Central

Yu, Huanzhou; Shimakawa, Ann; Hines, Catherine D. G.; McKenzie, Charles A.; Hamilton, Gavin; Sirlin, Claude B.; Brittain, Jean H.; Reeder, Scott B.

2011-01-01

Multipoint water–fat separation techniques rely on different water–fat phase shifts generated at multiple echo times to decompose water and fat. Therefore, these methods require complex source images and allow unambiguous separation of water and fat signals. However, complex-based water–fat separation methods are sensitive to phase errors in the source images, which may lead to clinically important errors. An alternative approach to quantify fat is through “magnitude-based” methods that acquire multiecho magnitude images. Magnitude-based methods are insensitive to phase errors, but cannot estimate fat-fraction greater than 50%. In this work, we introduce a water–fat separation approach that combines the strengths of both complex and magnitude reconstruction algorithms. A magnitude-based reconstruction is applied after complex-based water–fat separation to removes the effect of phase errors. The results from the two reconstructions are then combined. We demonstrate that using this hybrid method, 0–100% fat-fraction can be estimated with improved accuracy at low fat-fractions. PMID:21695724

Morphological Simulation of Phase Separation Coupled Oscillation Shear and Varying Temperature Fields

NASA Astrophysics Data System (ADS)

Wang, Heping; Li, Xiaoguang; Lin, Kejun; Geng, Xingguo

2018-05-01

This paper explores the effect of the shear frequency and Prandtl number ( Pr) on the procedure and pattern formation of phase separation in symmetric and asymmetric systems. For the symmetric system, the periodic shear significantly prolongs the spinodal decomposition stage and enlarges the separated domain in domain growth stage. By adjusting the Pr and shear frequency, the number and orientation of separated steady layer structures can be controlled during domain stretch stage. The numerical results indicate that the increase in Pr and decrease in the shear frequency can significantly increase in the layer number of the lamellar structure, which relates to the decrease in domain size. Furthermore, the lamellar orientation parallel to the shear direction is altered into that perpendicular to the shear direction by further increasing the shear frequency, and also similar results for larger systems. For asymmetric system, the quantitative analysis shows that the decrease in the shear frequency enlarges the size of separated minority phases. These numerical results provide guidance for setting the optimum condition for the phase separation under periodic shear and slow cooling.

The Two-Phase Flow Separator Experiment Breadboard Model: Reduced Gravity Aircraft Results

NASA Technical Reports Server (NTRS)

Rame, E; Sharp, L. M.; Chahine, G.; Kamotani, Y.; Gotti, D.; Owens, J.; Gilkey, K.; Pham, N.

2015-01-01

Life support systems in space depend on the ability to effectively separate gas from liquid. Passive cyclonic phase separators use the centripetal acceleration of a rotating gas-liquid mixture to carry out phase separation. The gas migrates to the center, while gas-free liquid may be withdrawn from one of the end plates. We have designed, constructed and tested a breadboard that accommodates the test sections of two independent principal investigators and satisfies their respective requirements, including flow rates, pressure and video diagnostics. The breadboard was flown in the NASA low-gravity airplane in order to test the system performance and design under reduced gravity conditions.

A two-dimensional phase separation on the spherical surface of the metallic glass Au55Pb22.5Sb22.5

NASA Technical Reports Server (NTRS)

Lee, M. C.; Johnson, W. L.

1982-01-01

Recent experiments indicate that a phase separation in a spherical sample of the metallic glass Au55Pb22.5Sb22.5 occurs near the surface of the sphere. This strongly suggests either a contribution of surface-free energy to the decomposition process or a possible influence of near surface impurities absorbed during synthesis of the sphere. The surface phase separation has been studied as a function of cooling rate of the sphere. At high cooling rates (small sphere sizes), the surface separation disappears altogether suggesting that the surface of the parent liquid droplet is initially homogeneous.

3D CFD simulation of Multi-phase flow separators

NASA Astrophysics Data System (ADS)

Zhu, Zhiying

2017-10-01

During the exploitation of natural gas, some water and sands are contained. It will be better to separate water and sands from natural gas to insure favourable transportation and storage. In this study, we use CFD to analyse the effect of multi-phase flow separator, whose detailed geometrical parameters are designed in advanced. VOF model and DPM are used here. From the results of CFD, we can draw a conclusion that separated effect of multi-phase flow achieves better results. No solid and water is carried out from gas outlet. CFD simulation provides an economical and efficient approach to shed more light on details of the flow behaviour.

Polymer Dispersed Liquid Crystal Displays

NASA Astrophysics Data System (ADS)

Doane, J. William

The following sections are included: * INTRODUCTION AND HISTORICAL DEVELOPMENT * PDLC MATERIALS PREPARATION * Polymerization induced phase separation (PIPS) * Thermally induced phase separation (TIPS) * Solvent induced phase separation (SIPS) * Encapsulation (NCAP) * RESPONSE VOLTAGE * Dielectric and resistive effects * Radial configuration * Bipolar configuration * Other director configurations * RESPONSE TIME * DISPLAY CONTRAST * Light scattering and index matching * Incorporation of dyes * Contrast measurements * PDLC DISPLAY DEVICES AND INNOVATIONS * Reflective direct view displays * Large-scale, flexible displays * Switchable windows * Projection displays * High definition spatial light modulator * Haze-free PDLC shutters: wide angle view displays * ENVIRONMENTAL STABILITY * ACKNOWLEDGEMENTS * REFERENCES

Separation of VX, RVX and GB Enantiomers Using Liquid ChromatographyTime-of-Flight Mass Spectrometry

DTIC Science & Technology

2016-02-01

Torrance, CA). The mobile phase consisted of n - hexane (A) and isopropyl alcohol (B), and sample volume was 10 µL. Separation was achieved using...level for preparative separation. All reagents and solvents were high-performance LC grade. Hexane and isopropyl alcohol were purchased from Fisher...1 column and normal-phase LC were used with a mobile phase of 96/4 (v/v %) hexane /isopropyl alcohol at a flow rate of 0.6 mL/min. The enantiomers

Gas-liquid chromatography with a volatile "stationary" liquid phase.

PubMed

Wells, P S; Zhou, S; Parcher, J F

2002-05-01

A unique type of gas-liquid chromatography is described in which both mobile and "stationary" phases are composed of synthetic mixtures of helium and carbon dioxide. At temperatures below the critical point of the binary mixture and pressures above the vapor pressure of pure liquid carbon dioxide, helium and carbon dioxide can form two immiscible phases over extended composition ranges. A binary vapor phase enriched in helium can act as the mobile phase for chromatographic separations, whereas a CO2-rich liquid in equilibrium with the vapor phase, but condensed on the column wall, can act as a pseudostationary phase. Several examples of chromatographic separations obtained in "empty" capillary columns with no ordinary stationary liquid phase illustrate the range of conditions that produce such separations. In addition, several experiments are reported that confirm the proposed two-phase hypothesis. The possible consequences of the observed chromatographic phenomenon in the field of supercritical fluid chromatography with helium headspace carbon dioxide are discussed.

CEC with new monolithic stationary phase based on a fluorinated monomer, trifluoroethyl methacrylate.

PubMed

Yurtsever, Arda; Saraçoğlu, Berna; Tuncel, Ali

2009-02-01

A new, fluorinated monolithic stationary phase for CEC was first synthesized by a single-stage, thermally initiated copolymerization of a fluorinated monomer, 2,2,2-trifluoroethyl methacrylate (TFEM) and ethylene dimethacrylate (EDMA) in the presence of a porogen mixture. In this preparation, 2-acrylamido-2-methyl-1-propanesulfonic acid was used as the charge-bearing monomer. The porogen mixture was prepared by mixing isoamylalcohol and 1,4-butanediol. A clear increase in the electroosmotic mobility was observed with increasing pH. The electroosmotic mobility decreased with increasing ACN concentration. Poly(TFEM-co-EDMA) monolith prepared under optimized polymerization conditions was successfully used in the separation of alkylbenzenes and phenols by CEC. The best chromatographic separation for alkylbenzenes was performed with lower ACN concentrations (i.e. 60% v/v) with respect to the common acrylic-based CEC monoliths. The theoretical plate numbers up to 220 000 plates/m were achieved in the reversed phase separation of phenols. Poly(TFEM-co-EDMA) monolith also allowed the simultaneous separation of aniline and benzoic acid derivatives by a single run and by using a lower ACN concentration in the mobile phase with respect to the similar electrochromatographic separations. A stable retention behaviour in reversed phase separation of alkylbenzenes was obtained with the poly(TFEM-co-EDMA) monolith.

A nitromethane-based HPLC system alternative to acetonitrile for carotenoid analysis of fruit and vegetables.

PubMed

Sandmann, Gerhard

2010-01-01

Acetonitrile-based HPLC systems are the most commonly used for carotenoid analysis from different plant tissues. Because of the acetonitrile shortage, an HPLC system for the separation of carotenoids on C(18) reversed-phase columns was developed in which an acetonitrile-alcohol-based mobile phase was replaced by nitromethane. This solvent comes closest to acetonitrile with respect to its elutrophic property. Our criterion was to obtain similar separation and retention times for a range of differently structured carotenoids. This was achieved by further increase in the lipophilicity with ethylacetate. For all the carotenoids which we tested, we found co-elution only of β-cryptoxanthin and lycopene. By addition of 1% of water, separation of this pair of carotenoids was also achieved. The final recommended mobile phase consisted of nitromethane : 2-propanol : ethyl acetate : water (79 : 10 : 10 : 1, by volume). On Nucleosil C(18) columns and related ones like Hypersil C(18), we obtained separation of carotenes, hydroxyl, epoxy and keto derivatives, which resembles the excellent separation properties of acetonitrile-based mobile phases on C(18) reversed phase columns. We successfully applied the newly developed HPLC system to the separation of carotenoids from different vegetables and fruit. Copyright © 2010 John Wiley & Sons, Ltd.

Synthesis of a stationary phase based on silica modified with branched octadecyl groups by Michael addition and photoinduced thiol-yne click chemistry for the separation of basic compounds.

PubMed

Huang, Guang; Ou, Junjie; Wang, Hongwei; Ji, Yongsheng; Wan, Hao; Zhang, Zhang; Peng, Xiaojun; Zou, Hanfa

2016-04-01

A novel silica-based stationary phase with branched octadecyl groups was prepared by the sequential employment of the Michael addition reaction and photoinduced thiol-yne click chemistry with 3-aminopropyl-functionalized silica microspheres as the initial material. The resulting stationary phase denoted as SiO2 -N(C18)4 was characterized by elemental analysis, FTIR spectroscopy and Raman spectroscopy, demonstrating the existence of branched octadecyl groups in silica microspheres. The separations of benzene homologous compounds, acid compounds and amine analogues were conducted, demonstrating mixed-mode separation mechanism on SiO2 -N(C18)4 . Baseline separation of basic drugs mixture was acquired with the mobile phase of acetonitrile/H2 O (5%, v/v). SiO2 -N(C18)4 was further applied to separate Corydalis yanhusuo Wang water extracts, and more baseline separation peaks were obtained for SiO2 -N(C18)4 than those on Atlantis dC18 column. It can be expected that this new silica-based stationary phase will exhibit great potential in the analysis of basic compounds. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

Separation of phenolic acids from sugarcane rind by online solid-phase extraction with high-speed counter-current chromatography.

PubMed

Geng, Ping; Fang, Yingtong; Xie, Ronglong; Hu, Weilun; Xi, Xingjun; Chu, Qiao; Dong, Genlai; Shaheen, Nusrat; Wei, Yun

2017-02-01

Sugarcane rind contains some functional phenolic acids. The separation of these compounds from sugarcane rind is able to realize the integrated utilization of the crop and reduce environment pollution. In this paper, a novel protocol based on interfacing online solid-phase extraction with high-speed counter-current chromatography (HSCCC) was established, aiming at improving and simplifying the process of phenolic acids separation from sugarcane rind. The conditions of online solid-phase extraction with HSCCC involving solvent system, flow rate of mobile phase as well as saturated extent of absorption of solid-phase extraction were optimized to improve extraction efficiency and reduce separation time. The separation of phenolic acids was performed with a two-phase solvent system composed of butanol/acetic acid/water at a volume ratio of 4:1:5, and the developed online solid-phase extraction with HSCCC method was validated and successfully applied for sugarcane rind, and three phenolic acids including 6.73 mg of gallic acid, 10.85 mg of p-coumaric acid, and 2.78 mg of ferulic acid with purities of 60.2, 95.4, and 84%, respectively, were obtained from 150 mg sugarcane rind crude extracts. In addition, the three different elution methods of phenolic acids purification including HSCCC, elution-extrusion counter-current chromatography and back-extrusion counter-current chromatography were compared. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water outlet control mechanism for fuel cell system operation in variable gravity environments

NASA Technical Reports Server (NTRS)

Vasquez, Arturo (Inventor); McCurdy, Kerri L. (Inventor); Bradley, Karla F. (Inventor)

2007-01-01

A self-regulated water separator provides centrifugal separation of fuel cell product water from oxidant gas. The system uses the flow energy of the fuel cell's two-phase water and oxidant flow stream and a regulated ejector or other reactant circulation pump providing the two-phase fluid flow. The system further uses a means of controlling the water outlet flow rate away from the water separator that uses both the ejector's or reactant pump's supply pressure and a compressibility sensor to provide overall control of separated water flow either back to the separator or away from the separator.

Lower critical solution temperature (LCST) phase separation of glycol ethers for forward osmotic control.

PubMed

Nakayama, Daichi; Mok, Yeongbong; Noh, Minwoo; Park, Jeongseon; Kang, Sunyoung; Lee, Yan

2014-03-21

Lower critical solution temperature (LCST) phase transition of glycol ether (GE)-water mixtures induces an abrupt change in osmotic pressure driven by a mild temperature change. The temperature-controlled osmotic change was applied for the forward osmosis (FO) desalination. Among three GEs evaluated, di(ethylene glycol) n-hexyl ether (DEH) was selected as a potential FO draw solute. A DEH-water mixture with a high osmotic pressure could draw fresh water from a high-salt feed solution such as seawater through a semipermeable membrane at around 10 °C. The water-drawn DEH-water mixture was phase-separated into a water-rich phase and a DEH-rich phase at around 30 °C. The water-rich phase with a much reduced osmotic pressure released water into a low-salt solution, and the DEH-rich phase was recovered into the initial DEH-water mixture. The phase separation behaviour, the residual GE concentration in the water-rich phase, the osmotic pressure of the DEH-water mixture, and the osmotic flux between the DEH-water mixture and salt solutions were carefully analysed for FO desalination. The liquid-liquid phase separation of the GE-water mixture driven by the mild temperature change between 10 °C and 30 °C is very attractive for the development of an ideal draw solute for future practical FO desalination.

Investigation of phase separated polyimide blend films containing boron nitride using FTIR imaging

NASA Astrophysics Data System (ADS)

Chae, Boknam; Hong, Deok Gi; Jung, Young Mee; Won, Jong Chan; Lee, Seung Woo

2018-04-01

Immiscible aromatic polyimide (PI) blend films and a PI blend film incorporated with thermally conductive boron nitride (BN) were prepared, and their phase separation behaviors were examined by optical microscopy and FTIR imaging. The 2,2‧-bis(trifluoromethyl)benzidine (TFMB)-containing and 4,4‧-thiodianiline (TDA)-containing aromatic PI blend films and a PI blend/BN composite film show two clearly separated regions; one region is the TFMB-rich phase, and the other region is the TDA-rich phase. The introduction of BN induces morphological changes in the immiscible aromatic PI blend film without altering the composition of either domain. In particular, the BN is selectively incorporated into the TDA-rich phase in this study.

STS-42 Phase Partitioning Experiment (PPE) closeup taken onboard OV-103

NASA Technical Reports Server (NTRS)

1992-01-01

STS-42 Phase Partitioning Experiment (PPE), an International Microgravity Laboratory 1 (IML-1) experiment, is documented in a closeup taken onboard Discovery, Orbiter Vehicle (OV) 103. Phase partitioning is a very effective technique used by biochemists and cell biologists to obtain fairly pure cells. Cells are separated and collected in a mixture of two immiscible liquids (fluids that tend not to mix) by their surface characteristics. In the PPE, investigators feel they will be able to separate closely related cells because cell density and convection flows are not factors in the phase partitioning process in space. They also hope to study other factors that influence the process. Phase partitioning is used to separate biological materials such as bone marrow cells for cancer treatment.

Thermodynamics and structural transition of binary atomic Bose-Fermi mixtures in box or harmonic potentials: A path-integral study

NASA Astrophysics Data System (ADS)

Kim, Tom; Chien, Chih-Chun

2018-03-01

Experimental realizations of a variety of atomic binary Bose-Fermi mixtures have brought opportunities for studying composite quantum systems with different spin statistics. The binary atomic mixtures can exhibit a structural transition from a mixture into phase separation as the boson-fermion interaction increases. By using a path-integral formalism to evaluate the grand partition function and the thermodynamic grand potential, we obtain the effective potential of binary Bose-Fermi mixtures. Thermodynamic quantities in a broad range of temperatures and interactions are also derived. The structural transition can be identified as a loop of the effective potential curve, and the volume fraction of phase separation can be determined by the lever rule. For 6Li-7Li and 6Li-41K mixtures, we present the phase diagrams of the mixtures in a box potential at zero and finite temperatures. Due to the flexible densities of atomic gases, the construction of phase separation is more complicated when compared to conventional liquid or solid mixtures where the individual densities are fixed. For harmonically trapped mixtures, we use the local density approximation to map out the finite-temperature density profiles and present typical trap structures, including the mixture, partially separated phases, and fully separated phases.

Laser-induced separation of hydrogen isotopes in the liquid phase

DOEpatents

Freund, Samuel M.; Maier, II, William B.; Beattie, Willard H.; Holland, Redus F.

1980-01-01

Hydrogen isotope separation is achieved by either (a) dissolving a hydrogen-bearing feedstock compound in a liquid solvent, or (b) liquefying a hydrogen-bearing feedstock compound, the liquid phase thus resulting being kept at a temperature at which spectral features of the feedstock relating to a particular hydrogen isotope are resolved, i.e., a clear-cut isotope shift is delineated, irradiating the liquid phase with monochromatic radiation of a wavelength which at least preferentially excites those molecules of the feedstock containing a first hydrogen isotope, inducing photochemical reaction in the excited molecules, and separating the reaction product containing the first isotope from the liquid phase.

Phase segregation due to simultaneous migration and coalescence

NASA Technical Reports Server (NTRS)

Davis, Robert H.

1994-01-01

The primary objective of the research is to perform ground-based analysis and experiments on the interaction and coalescence of drops (or bubbles) leading to macroscopic phase separation. Migration of the drops occurs as a result of the individual and collective action of gravity and thermocapillary effects. Larger drops migrate faster than smaller ones, leading to the possibility of collisions and coalescence. Coalescence increases the rate of macroscopic phase separation, since the result is larger drops with higher migration rates. It is hoped that the understanding gained will lead to the design of microgravity experiments to further elucidate the mechanisms governing coalescence and phase separation.

Water Capture Device Signal Integration Board

NASA Technical Reports Server (NTRS)

Chamberlin, Kathryn J.; Hartnett, Andrew J.

2018-01-01

I am a junior in electrical engineering at Arizona State University, and this is my second internship at Johnson Space Center. I am an intern in the Command and Data Handling Branch of Avionics Division (EV2), my previous internship was also in EV2. During my previous internship I was assigned to the Water Capture Device payload, where I designed a prototype circuit board for the electronics system of the payload. For this internship, I have come back to the Water Capture Device project to further the work on the electronics design I completed previously. The Water Capture Device is an experimental payload to test the functionality of two different phase separators aboard the International Space Station (ISS). A phase separator sits downstream of a condensing heat exchanger (CHX) and separates the water from the air particles for environmental control on the ISS. With changing CHX technology, new phase separators are required. The goal of the project is to develop a test bed for the two phase separators to determine the best solution.

Synthesis and evaluation of a maltose-bonded silica gel stationary phase for hydrophilic interaction chromatography and its application in Ginkgo Biloba extract separation in two-dimensional systems.

PubMed

Sheng, Qianying; Yang, Kaiya; Ke, Yanxiong; Liang, Xinmiao; Lan, Minbo

2016-09-01

Maltose covalently bonded to silica was prepared by using carbonyl diimidazole as a cross-linker and employed as a stationary phase for hydrophilic interaction liquid chromatography. The column efficiency and the effect of water content, buffer concentration, and pH value influenced on retention were investigated. The separation or enrichment selectivity was also studied with nucleosides, saccharides, amino acids, peptides, and glycopeptides. The results indicated that the stationary phase processed good separation efficiency and separation selectivity in hydrophilic interaction liquid chromatography mode. Moreover, a two-dimensional hydrophilic interaction liquid chromatography× reversed-phase liquid chromatography method with high orthogonality was developed to analyze the Ginkgo Biloba extract fractions. The development of this two-dimensional chromatographic system would be an effective tool for the separation of complex samples of different polarities and contents. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Integration of carboxyl modified magnetic particles and aqueous two-phase extraction for selective separation of proteins.

PubMed

Gai, Qingqing; Qu, Feng; Zhang, Tao; Zhang, Yukui

2011-07-15

Both of the magnetic particle adsorption and aqueous two-phase extraction (ATPE) were simple, fast and low-cost method for protein separation. Selective proteins adsorption by carboxyl modified magnetic particles was investigated according to protein isoelectric point, solution pH and ionic strength. Aqueous two-phase system of PEG/sulphate exhibited selective separation and extraction for proteins before and after magnetic adsorption. The two combination ways, magnetic adsorption followed by ATPE and ATPE followed by magnetic adsorption, for the separation of proteins mixture of lysozyme, bovine serum albumin, trypsin, cytochrome C and myloglobin were discussed and compared. The way of magnetic adsorption followed by ATPE was also applied to human serum separation. Copyright © 2011 Elsevier B.V. All rights reserved.

Triton X-114 based cloud point extraction: a thermoreversible approach for separation/concentration and dispersion of nanomaterials in the aqueous phase.

PubMed

Liu, Jing-fu; Liu, Rui; Yin, Yong-guang; Jiang, Gui-bin

2009-03-28

Capable of preserving the sizes and shapes of nanomaterials during the phase transferring, Triton X-114 based cloud point extraction provides a general, simple, and cost-effective route for reversible concentration/separation or dispersion of various nanomaterials in the aqueous phase.

SEPARATION OF SOME RARE EARTHS BY REVERSED-PHASE PARTITION CHROMATOGRAPHY. Report No. 129/V; Rozdzielenie Niektorych Ziem Rzadkich za Pomoca Chromatografii Podzialowej z Odwroconymi Fazami

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

Siekierski, S.; Fidelis, I.

1960-01-01

The reversed phase partition chromatography was applied to the separation of small amounts of some rare earths. As a stationary phase TBP was used. and the elution was carried out with concentrated HNO/sub 3/. (auth)

Effects of the dynamic modification of stationary phases by sorbates in gas chromatography: The possibility of separating enantiomers in achiral systems

NASA Astrophysics Data System (ADS)

Zenkevich, I. G.; Pavlovskii, A. A.

2016-10-01

It is shown that the gas chromatographic separation of enantiomers on columns with achiral nonpolar stationary phases is principally possible as a result of the dynamic modification of stationary phases by sorbates under analysis. It is found that a number of key characteristic features is intrinsic to such separation: it can be only partial, it does not occur for all chromatographic columns, and it is observed only for some compounds and only within narrow ranges of quantities of sorbates that are close to the limits of mass overload of chromatographic systems. These characteristic features are illustrated by the examples of separating (1 R,5 R)-(+)- and (1 S,5 S)-(-)-α-pinenes on a WCOT column with an RTX-5 phase. The main characteristic feature of the separation of enantiomers as a result of the dynamic modification of stationary phases is the nonconformity of peaks in chromatograms with two individual enantiomers, compared to other ways and means for their separation; the first eluting peak belongs to the enantiomer that predominates in a mixture irrespective of its configuration, while the second peak corresponds to the racemic mixture of enantiomers; i.e., the ratio of peak areas in chromatograms does not correspond to the actual ratio of enantiomers in samples under analysis and is strongly distorted as a result of their incomplete separation. It is concluded that the separation of racemic mixtures in achiral systems is fundamentally impossible under any conditions, and this is one of the key criteria of the validity of the considered concept as a whole.

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.

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.

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

Phase separation and crystallization process of amorphous Fe{sub 78}B{sub 12}Si{sub 9}Ni{sub 1} alloy

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

Mukhgalin, V. V.; Lad’yanov, V. I.

2015-08-17

The influence of the melt heat treatment on the structure and crystallization process of the rapidly quenched amorphous Fe{sub 78}B{sub 12}Si{sub 9}Ni{sub 1} alloys have been investigated by means of x-ray diffraction, DSC and TEM. Amorphous phase separation has been observed in the alloys quenched after the preliminary high temperature heat treatment of the liquid alloy (heating above 1400°C). Comparative analysis of the pair distribution functions demonstrates that this phase separation accompanied by a changes in the local atomic arrangement. It has been found that crystallization process at heating is strongly dependent on the initial amorphous phase structure - homogeneousmore » or phase separated. In the last case crystallization goes through the formation of a new metastable hexagonal phase [a=12.2849(9) Ǻ, c=7.6657(8) Ǻ]. At the same time the activation energy for crystallization (Ea) reduces from 555 to 475 kJ mole{sup −1}.« less

Origin of Reversible Photoinduced Phase Separation in Hybrid Perovskites

NASA Astrophysics Data System (ADS)

Bischak, Connor G.; Hetherington, Craig L.; Wu, Hao; Aloni, Shaul; Ogletree, D. Frank; Limmer, David T.; Ginsberg, Naomi S.

2017-02-01

Nonequilibrium processes occurring in functional materials can significantly impact device efficiencies and are often difficult to characterize due to the broad range of length and time scales involved. In particular, mixed halide hybrid perovskites are promising for optoelectronics, yet the halides reversibly phase separate when photo-excited, significantly altering device performance. By combining nanoscale imaging and multiscale modeling, we elucidate the mechanism underlying this phenomenon, demonstrating that local strain induced by photo-generated polarons promotes halide phase separation and leads to nucleation of light-stabilized iodide-rich clusters. This effect relies on the unique electromechanical properties of hybrid materials, characteristic of neither their organic nor inorganic constituents alone. Exploiting photo-induced phase separation and other nonequilibrium phenomena in hybrid materials, generally, could enable new opportunities for expanding the functional applications in sensing, photoswitching, optical memory, and energy storage.

Antibody enhancement of free-flow electrophoresis

NASA Technical Reports Server (NTRS)

Cohly, H. H. P.; Morrison, Dennis R.; Atassi, M. Zouhair

1988-01-01

Specific T cell clones and antibodies (ABs) were developed to study the efficiency of purifying closely associated T cells using Continuous Flow Electrophoresis System. Enhanced separation is accomplished by tagging cells first with ABs directed against the antigenic determinants on the cell surface and then with ABs against the Fc portion of the first AB. This second AB protrudes sufficiently beyond the cell membrane and glycocalyx to become the major overall cell surface potential determinant and thus causes a reduction of electrophoretic mobility. This project was divided into three phases. Phase one included development of specific T cell clones and separation of these specific clones. Phase two extends these principles to the separation of T cells from spleen cells and immunized lymph node cells. Phase three applies this double antibody technique to the separation of T cytotoxic cells from bone marrow.

Movie of phase separation during physics of colloids in space experiment

NASA Technical Reports Server (NTRS)

2002-01-01

Still photographs taken over 16 hours on Nov. 13, 2001, on the International Space Station have been condensed into a few seconds to show the de-mixing -- or phase separation -- process studied by the Experiment on Physics of Colloids in Space. Commanded from the ground, dozens of similar tests have been conducted since the experiment arrived on ISS in 2000. The sample is a mix of polymethylmethacrylate (PMMA or acrylic) colloids, polystyrene polymers and solvents. The circular area in the video is 2 cm (0.8 in.) in diameter. The phase separation process occurs spontaneously after the sample is mechanically mixed. The evolving lighter regions are rich in colloid and have the structure of a liquid. The dark regions are poor in colloids and have the structure of a gas. This behavior carnot be observed on Earth because gravity causes the particles to fall out of solution faster than the phase separation can occur. While similar to a gas-liquid phase transition, the growth rate observed in this test is different from any atomic gas-liquid or liquid-liquid phase transition ever measured experimentally. Ultimately, the sample separates into colloid-poor and colloid-rich areas, just as oil and vinegar separate. The fundamental science of de-mixing in this colloid-polymer sample is the same found in the annealing of metal alloys and plastic polymer blends. Improving the understanding of this process may lead to improving processing of these materials on Earth.

Phase separation during the Experiment on Physics of Colloids in Space

NASA Technical Reports Server (NTRS)

2003-01-01

Still photographs taken over 16 hours on Nov. 13, 2001, on the International Space Station have been condensed into a few seconds to show the de-mixing -- or phase separation -- process studied by the Experiment on Physics of Colloids in Space. Commanded from the ground, dozens of similar tests have been conducted since the experiment arrived on ISS in 2000. The sample is a mix of polymethylmethacrylate (PMMA or acrylic) colloids, polystyrene polymers and solvents. The circular area is 2 cm (0.8 in.) in diameter. The phase separation process occurs spontaneously after the sample is mechanically mixed. The evolving lighter regions are rich in colloid and have the structure of a liquid. The dark regions are poor in colloids and have the structure of a gas. This behavior carnot be observed on Earth because gravity causes the particles to fall out of solution faster than the phase separation can occur. While similar to a gas-liquid phase transition, the growth rate observed in this test is different from any atomic gas-liquid or liquid-liquid phase transition ever measured experimentally. Ultimately, the sample separates into colloid-poor and colloid-rich areas, just as oil and vinegar separate. The fundamental science of de-mixing in this colloid-polymer sample is the same found in the annealing of metal alloys and plastic polymer blends. Improving the understanding of this process may lead to improving processing of these materials on Earth.

Comparison of analytical protein separation characteristics for three amine-based capillary-channeled polymer (C-CP) stationary phases.

PubMed

Jiang, Liuwei; Marcus, R Kenneth

2016-02-01

Capillary-channeled polymer (C-CP) fiber stationary phases are finding utility in the realms of protein analytics as well as downstream processing. We have recently described the modification of poly(ethylene terephthalate) (PET) C-CP fibers to affect amine-rich phases for the weak anion-exchange (WAX) separation of proteins. Polyethylenimine (PEI) is covalently coupled to the PET surface, with subsequent cross-linking imparted by treatment with 1,4-butanediol diglycidyl ether (BUDGE). These modifications yield vastly improved dynamic binding capacities over the unmodified fibers. We have also previously employed native (unmodified) nylon 6 C-CP fibers as weak anion/cation-exchange (mixed-mode) and hydrophobic interaction chromatography (HIC) phases for protein separations. Polyamide, nylon 6, consists of amide groups along the polymer backbone, with primary amines and carboxylic acid end groups. The analytical separation characteristics of these three amine-based C-CP fiber phases are compared here. Each of the C-CP fiber columns in this study was shown to be able to separate a bovine serum albumin/hemoglobin/lysozyme mixture at high mobile phase linear velocity (∼70 mm s(-1)) but with different elution characteristics. These differences reflect the types of protein-surface interactions that are occurring, based on the active group composition of the fiber surfaces. This study provides important fundamental understanding for the development of surface-modified C-CP fiber columns for protein separation.

Shuttle unified navigation filter, revision 1

NASA Technical Reports Server (NTRS)

Muller, E. S., Jr.

1973-01-01

Equations designed to meet the navigation requirements of the separate shuttle mission phases are presented in a series of reports entitled, Space Shuttle GN and C Equation Document. The development of these equations is based on performance studies carried out for each particular mission phase. Although navigation equations have been documented separately for each mission phase, a single unified navigation filter design is embodied in these separate designs. The purpose of this document is to present the shuttle navigation equations in a form in which they would most likely be coded-as the single unified navigation filter used in each mission phase. This document will then serve as a single general reference for the navigation equations replacing each of the individual mission phase navigation documents (which may still be used as a description of a particular navigation phase).

Modeling phase separation in mixtures of intrinsically-disordered proteins

NASA Astrophysics Data System (ADS)

Gu, Chad; Zilman, Anton

Phase separation in a pure or mixed solution of intrinsically-disordered proteins (IDPs) and its role in various biological processes has generated interest from the theoretical biophysics community. Phase separation of IDPs has been implicated in the formation of membrane-less organelles such as nucleoli, as well as in a mechanism of selectivity in transport through the nuclear pore complex. Based on a lattice model of polymers, we study the phase diagram of IDPs in a mixture and describe the selective exclusion of soluble proteins from the dense-phase IDP aggregates. The model captures the essential behaviour of phase separation by a minimal set of coarse-grained parameters, corresponding to the average monomer-monomer and monomer-protein attraction strength, as well as the protein-to-monomer size ratio. Contrary to the intuition that strong monomer-monomer interaction increases exclusion of soluble proteins from the dense IDP aggregates, our model predicts that the concentration of soluble proteins in the aggregate phase as a function of monomer-monomer attraction is non-monotonic. We corroborate the predictions of the lattice model using Langevin dynamics simulations of grafted polymers in planar and cylindrical geometries, mimicking various in-vivo and in-vitro conditions.

An easy-to-use calculating machine to simulate steady state and non-steady-state preparative separations by multiple dual mode counter-current chromatography with semi-continuous loading of feed mixtures.

PubMed

Kostanyan, Artak E; Shishilov, Oleg N

2018-06-01

Multiple dual mode counter-current chromatography (MDM CCC) separation processes with semi-continuous large sample loading consist of a succession of two counter-current steps: with "x" phase (first step) and "y" phase (second step) flow periods. A feed mixture dissolved in the "x" phase is continuously loaded into a CCC machine at the beginning of the first step of each cycle over a constant time with the volumetric rate equal to the flow rate of the pure "x" phase. An easy-to-use calculating machine is developed to simulate the chromatograms and the amounts of solutes eluted with the phases at each cycle for steady-state (the duration of the flow periods of the phases is kept constant for all the cycles) and non-steady-state (with variable duration of alternating phase elution steps) separations. Using the calculating machine, the separation of mixtures containing up to five components can be simulated and designed. Examples of the application of the calculating machine for the simulation of MDM CCC processes are discussed. Copyright © 2018 Elsevier B.V. All rights reserved.

Use of Solid Phase Extraction in the Biochemistry Laboratory to Separate Different Lipids

ERIC Educational Resources Information Center

Flurkey, William H.

2005-01-01

Solid-phase extraction (SPE) was used to demonstrate how various lipids and lipid classes could be separated in a biochemistry laboratory setting. Three different SPE methods were chosen on their ability to separate a lipid mixture, consisting of a combination of a either a fatty acid, a triacylglycerol, a mono- or diacylglycerol, phospholipid,…

The ADvanced SEParation (ADSEP)

NASA Technical Reports Server (NTRS)

1998-01-01

The ADvanced SEParation (ADSEP) commercial payload is making use of major advances in separation technology: The Phase Partitioning Experiment (PPE); the Micorencapsulation experiment; and the Hemoglobin Separation Experiment (HSE). Using ADSEP, commercial researchers will attempt to determine the partition coefficients for model particles in a two-phase system. With this information, researchers can develop a higher resolution, more effective cell isolation procedure that can be used for many different types of research and for improved health care. The advanced separation technology is already being made available for use in ground-based laboratories.

Chromatographic behavior of small organic compounds in low-temperature high-performance liquid chromatography using liquid carbon dioxide as the mobile phase.

PubMed

Motono, Tomohiro; Nagai, Takashi; Kitagawa, Shinya; Ohtani, Hajime

2015-07-01

Low-temperature high-performance liquid chromatography, in which a loop injector, column, and detection cell were refrigerated at -35ºC, using liquid carbon dioxide as the mobile phase was developed. Small organic compounds (polyaromatic hydrocarbons, alkylbenzenes, and quinones) were separated by low-temperature high-performance liquid chromatography at temperatures from -35 to -5ºC. The combination of liquid carbon dioxide mobile phase with an octadecyl-silica (C18 ) column provided reversed phase mode separation, and a bare silica-gel column resulted in normal phase mode separation. In both the cases, nonlinear behavior at approximately -15ºC was found in the relationship between the temperature and the retention factors of the analytes (van't Hoff plots). In contrast to general trends in high-performance liquid chromatography, the decrease in temperature enhanced the separation efficiency of both the columns. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamical mean-field theory and weakly non-linear analysis for the phase separation of active Brownian particles

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

Speck, Thomas; Menzel, Andreas M.; Bialké, Julian

2015-06-14

Recently, we have derived an effective Cahn-Hilliard equation for the phase separation dynamics of active Brownian particles by performing a weakly non-linear analysis of the effective hydrodynamic equations for density and polarization [Speck et al., Phys. Rev. Lett. 112, 218304 (2014)]. Here, we develop and explore this strategy in more detail and show explicitly how to get to such a large-scale, mean-field description starting from the microscopic dynamics. The effective free energy emerging from this approach has the form of a conventional Ginzburg-Landau function. On the coarsest scale, our results thus agree with the mapping of active phase separation ontomore » that of passive fluids with attractive interactions through a global effective free energy (motility-induced phase transition). Particular attention is paid to the square-gradient term necessary for the phase separation kinetics. We finally discuss results from numerical simulations corroborating the analytical results.« less

Evaluation of comprehensive multidimensional separations using reversed-phase, reversed-phase liquid chromatography/mass spectrometry for shotgun proteomics.

PubMed

Nakamura, Tatsuji; Kuromitsu, Junro; Oda, Yoshiya

2008-03-01

Two-dimensional liquid-chromatographic (LC) separation followed by mass spectrometric (MS) analysis was examined for the identification of peptides in complex mixtures as an alternative to widely used two-dimensional gel electrophoresis followed by MS analysis for use in proteomics. The present method involves the off-line coupling of a narrow-bore, polymer-based, reversed-phase column using an acetonitrile gradient in an alkaline mobile phase in the first dimension with octadecylsilanized silica (ODS)-based nano-LC/MS in the second dimension. After the first separation, successive fractions were acidified and dried off-line, then loaded on the second dimension column. Both columns separate peptides according to hydrophobicity under different pH conditions, but more peptides were identified than with the conventional technique for shotgun proteomics, that is, the combination of a strong cation exchange column with an ODS column, and the system was robust because no salts were included in the mobile phases. The suitability of the method for proteomics measurements was evaluated.

Demulsification of water/oil/solid emulsions by hollow-fiber membranes

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

Tirmizi, N.P.; Raghuraman, B.; Wiencek, J.

1996-05-01

The demulsification techniques investigated use preferential surface wetting to allow separation of oil and water phases in ultrafiltration and microfiltration membranes. A hydrophobic membrane allows the permeation of an oil phase at almost zero pressure and retains the water phase, even though the molecular weight of the water molecule (18) is much smaller than that of the oil molecule (198 for tetradecane, used in this study). Hydrophobic membranes having pore sizes from 0.02 to 0.2 {micro}m were tested for demulsification of water-in-oil emulsions and water/oil/solid mixtures. The dispersed (aqueous)-phase drop sizes ranged from 1 to 5 {micro}m. High separation rates,more » as well as good permeate quality, were obtained with microfiltration membranes. Water content of permeating oil was 32--830 ppm depending on operating conditions and interfacial properties. For emulsions with high surfactant content, simultaneous operation of a hydrophobic and hydrophilic membrane, or simultaneous membrane separation with electric demulsification was more efficient in obtaining complete phase separation.« less

Segregation in like-charged polyelectrolyte-surfactant mixtures can be precisely tuned via manipulation of the surfactant mass ratio.

PubMed

Wills, Peter W; Lopez, Sonia G; Burr, Jocelyn; Taboada, Pablo; Yeates, Stephen G

2013-04-09

In this study, we consider segregative phase separation in aqueous mixtures of quaternary ammonium surfactants didecyldimethylammonium chloride (DDQ) and alkyl (C12, 70%; C14 30%) dimethyl benzyl ammonium chloride (BAC) upon the addition of poly(diallyldimethylammonium) chloride (pDADMAC) as a function of both concentration and molecular weight. The nature of the surfactant type is dominant in determining the concentration at which separation into an upper essentially surfactant-rich phase and lower polyelectrolyte-rich phase is observed. However, for high-molecular-weight pDADMAC there is a clear indication of an additional depletion flocculation effect. When the BAC/DDQ ratio is tuned, the segregative phase separation point can be precisely controlled. We propose a phase separation mechanism for like-charged quaternary ammonium polyelectrolyte/surfactant/water mixtures induced by a reduction in the ionic atmosphere around the surfactant headgroup and possible ion pair formation. An additional polyelectrolyte-induced depletion flocculation effect was also observed.

Iptycene-based stationary phase with three-dimensional aromatic structure for highly selective separation of H-bonding analytes and aromatic isomers.

PubMed

Yang, Xiaohong; Han, Ying; Qi, Meiling; Chen, Chuanfeng

2016-05-06

Unique structures and molecular recognition ability endow iptycene derivatives with great potential as stationary phases in chromatography, which, however, has not been explored yet. Herein, we report the first example of utilizing a pentiptycene quinone (PQ) for gas chromatographic (GC) separations. Remarkably, the statically coated capillary column with the stationary phase achieved extremely high column efficiency of 4800 plates/m. It exhibited preferential retention and high resolving capability for H-bonding and aromatic analytes and positional isomers, showing advantages over the ordinary polysiloxane phase. Moreover, the fabricated iptycene column showed excellent separation repeatability with RSD values of 0.02-0.06% for intra-day, 0.20-0.35% for inter-day and 3.1-5.5% for between-column, respectively. In conclusion, iptycene derivatives as a new class of stationary phases show promising future for their use in GC separations. Copyright © 2016 Elsevier B.V. All rights reserved.

De-vitrification of nanoscale phase-separated amorphous thin films in the immiscible copper-niobium system

NASA Astrophysics Data System (ADS)

Puthucode, A.; Devaraj, A.; Nag, S.; Bose, S.; Ayyub, P.; Kaufman, M. J.; Banerjee, R.

2014-05-01

Copper and niobium are mutually immiscible in the solid state and exhibit a large positive enthalpy of mixing in the liquid state. Using vapour quenching via magnetron co-sputter deposition, far-from equilibrium amorphous Cu-Nb films have been deposited which exhibit a nanoscale phase separation. Annealing these amorphous films at low temperatures (~200 °C) initiates crystallization via the nucleation and growth of primary nanocrystals of a face-centred cubic Cu-rich phase separated by the amorphous matrix. Interestingly, subsequent annealing at a higher temperature (>300 °C) leads to the polymorphic nucleation and growth of large spherulitic grains of a body-centred cubic Nb-rich phase within the retained amorphous matrix of the partially crystallized film. This sequential two-stage crystallization process has been investigated in detail by combining transmission electron microscopy [TEM] (including high-resolution TEM) and atom probe tomography studies. These results provide new insights into the crystallization behaviour of such unusual far-from equilibrium phase-separated metallic glasses in immiscible systems.

Fuel

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

Simon, D.L.

1977-07-19

A process is described for making a fuel by combining turpentine, alcohol and blending agent and reducing the temperature of a batch to form two separate phases of differing densities, both of which are separately useable as fuels for internal combustion engines. The proportions of combustion favor the denser phase. However, under certain conditions, the less dense phase may be desired. Either phase may also be combined with gasoline to enhance the performance of the gasoline.

Discussion of Priorities

NASA Technical Reports Server (NTRS)

2003-01-01

The Microgravity Science Division identifies four priority ratings for microgravity research and technology issues: 1) Critical; 2) Severely Limiting; 3) Enhancements; 4) Communication. Reduced gravity instabilities are critical, while severely limiting issues include phase separation, phase change, and flow through components. Enhancements are listed for passive phase separation and phase change. This viewgraph presentation also classifies microgravity issues as spaceflight, ground-based, or other for the time periods 2003-2008, 2009-2015, and beyond.

Design of Phosphonium-Type Zwitterion as an Additive to Improve Saturated Water Content of Phase-Separated Ionic Liquid from Aqueous Phase toward Reversible Extraction of Proteins

PubMed Central

Ito, Yoritsugu; Kohno, Yuki; Nakamura, Nobuhumi; Ohno, Hiroyuki

2013-01-01

We designed phosphonium-type zwitterion (ZI) to control the saturated water content of separated ionic liquid (IL) phase in the hydrophobic IL/water biphasic systems. The saturated water content of separated IL phase, 1-butyl-3-methyimidazolium bis(trifluoromethanesulfonyl)imide, was considerably improved from 0.4 wt% to 62.8 wt% by adding N,N,N-tripentyl-4-sulfonyl-1-butanephosphonium-type ZI (P555C4S). In addition, the maximum water content decreased from 62.8 wt% to 34.1 wt% by increasing KH2PO4/K2HPO4 salt content in upper aqueous phosphate buffer phase. Horse heart cytochrome c (cyt.c) was dissolved selectively in IL phase by improving the water content of IL phase, and spectroscopic analysis revealed that the dissolved cyt.c retained its higher ordered structure. Furthermore, cyt. c dissolved in IL phase was re-extracted again from IL phase to aqueous phase by increasing the concentration of inorganic salts of the buffer solution. PMID:24013379

Synthetic oligonucleotide separations by mixed-mode reversed-phase/weak anion-exchange liquid chromatography.

PubMed

Zimmermann, Aleksandra; Greco, Roberto; Walker, Isabel; Horak, Jeannie; Cavazzini, Alberto; Lämmerhofer, Michael

2014-08-08

Synthetic oligonucleotides gain increasing importance in new therapeutic concepts and as probes in biological sciences. If pharmaceutical-grade purities are required, chromatographic purification using ion-pair reversed-phase chromatography is commonly carried out. However, separation selectivity for structurally closely related impurities is often insufficient, especially at high sample loads. In this study, a "mixed-mode" reversed-phase/weak anion exchanger stationary phase has been investigated as an alternative tool for chromatographic separation of synthetic oligonucleotides with minor sequence variations. The employed mixed-mode phase shows great flexibility in method development. It has been run in various gradient elution modes, viz. one, two or three parameter (mixed) gradients (altering buffer pH, buffer concentration, and organic modifier) to find optimal elution conditions and gain further insight into retention mechanisms. Compared to ion-pair reversed-phase and mere anion-exchange separation, enhanced selectivities were observed with the mixed-mode phase for 20-23 nucleotide (nt) long oligonucleotides with similar sequences. Oligonucleotides differing by 1, 2 or 3 nucleotides in length could be readily resolved and separation factors for single nucleotide replacements declined in the order Cytosine (C)/Guanine (G)>Adenine (A)/Guanine∼Guanine/Thymine (T)>Adenine/Cytosine∼Cytosine/Thymine>Adenine/Thymine. Selectivities were larger when the modification was at the 3' terminal-end, declined when it was in the middle of the sequence and was smallest when it was located at the 5' terminus. Due to the lower surface area of the 200Å pore size mixed-mode stationary phase compared to the corresponding 100Å material, lower retention times with equal selectivities under milder elution conditions were achievable. Considering high sample loading capacities of the mixed-mode anion-exchanger phase, it should have great potential for chromatographic oligonucleotide separation and purification. Copyright © 2014 Elsevier B.V. All rights reserved.

Spatially modulated structural colour in bird feathers.

PubMed

Parnell, Andrew J; Washington, Adam L; Mykhaylyk, Oleksandr O; Hill, Christopher J; Bianco, Antonino; Burg, Stephanie L; Dennison, Andrew J C; Snape, Mary; Cadby, Ashley J; Smith, Andrew; Prevost, Sylvain; Whittaker, David M; Jones, Richard A L; Fairclough, J Patrick A; Parker, Andrew R

2015-12-21

Eurasian Jay (Garrulus glandarius) feathers display periodic variations in the reflected colour from white through light blue, dark blue and black. We find the structures responsible for the colour are continuous in their size and spatially controlled by the degree of spinodal phase separation in the corresponding region of the feather barb. Blue structures have a well-defined broadband ultra-violet (UV) to blue wavelength distribution; the corresponding nanostructure has characteristic spinodal morphology with a lengthscale of order 150 nm. White regions have a larger 200 nm nanostructure, consistent with a spinodal process that has coarsened further, yielding broader wavelength white reflectance. Our analysis shows that nanostructure in single bird feather barbs can be varied continuously by controlling the time the keratin network is allowed to phase separate before mobility in the system is arrested. Dynamic scaling analysis of the single barb scattering data implies that the phase separation arrest mechanism is rapid and also distinct from the spinodal phase separation mechanism i.e. it is not gelation or intermolecular re-association. Any growing lengthscale using this spinodal phase separation approach must first traverse the UV and blue wavelength regions, growing the structure by coarsening, resulting in a broad distribution of domain sizes.

Sodium triflate decreases interaggregate repulsion and induces phase separation in cationic micelles.

PubMed

Lima, Filipe S; Cuccovia, Iolanda M; Buchner, Richard; Antunes, Filipe E; Lindman, Björn; Miguel, Maria G; Horinek, Dominik; Chaimovich, Hernan

2015-03-10

Dodecyltrimethylammonium triflate (DTATf) micelles possess lower degree of counterion dissociation (α), lower hydration, and higher packing of monomers than other micelles of similar structure. Addition of sodium triflate ([NaTf] > 0.05 M) to DTATf solutions promotes phase separation. This phenomenon is commonly observed in oppositely charged surfactant mixtures, but it is rare for ionic surfactants and relatively simple counterions. While the properties of DTATf have already been reported, the driving forces for the observed phase separation with added salt remain unclear. Thus, we propose an interpretation for the observed phase separation in cationic surfactant solutions. Addition of up to 0.03 M NaTf to micellar DTATf solutions led to a limited increase of the aggregation number, to interface dehydration, and to a progressive decrease in α. The viscosity of DTATf solutions of higher concentration ([DTATf] ≥ 0.06 M) reached a maximum with increasing [NaTf], though the aggregation number slightly increased, and no shape change occurred. We hypothesize that this maximum results from a decrease in interaggregate repulsion, as a consequence of increased ion binding. This reduction in micellar repulsion without simultaneous infinite micellar growth is, probably, the major driving force for phase separation at higher [NaTf].

Hybrid and Mixed Matrix Membranes for Separations from Fermentations

PubMed Central

Davey, Christopher John; Leak, David; Patterson, Darrell Alec

2016-01-01

Fermentations provide an alternative to fossil fuels for accessing a number of biofuel and chemical products from a variety of renewable and waste substrates. The recovery of these dilute fermentation products from the broth, however, can be incredibly energy intensive as a distillation process is generally involved and creates a barrier to commercialization. Membrane processes can provide a low energy aid/alternative for recovering these dilute fermentation products and reduce production costs. For these types of separations many current polymeric and inorganic membranes suffer from poor selectivity and high cost respectively. This paper reviews work in the production of novel mixed-matrix membranes (MMMs) for fermentative separations and those applicable to these separations. These membranes combine a trade-off of low-cost and processability of polymer membranes with the high selectivity of inorganic membranes. Work within the fields of nanofiltration, reverse osmosis and pervaporation has been discussed. The review shows that MMMs are currently providing some of the most high-performing membranes for these separations, with three areas for improvement identified: Further characterization and optimization of inorganic phase(s), Greater understanding of the compatibility between the polymer and inorganic phase(s), Improved methods for homogeneously dispersing the inorganic phase. PMID:26938567

Spatially modulated structural colour in bird feathers

PubMed Central

Parnell, Andrew J.; Washington, Adam L.; Mykhaylyk, Oleksandr O.; Hill, Christopher J.; Bianco, Antonino; Burg, Stephanie L.; Dennison, Andrew J. C.; Snape, Mary; Cadby, Ashley J.; Smith, Andrew; Prevost, Sylvain; Whittaker, David M.; Jones, Richard A. L.; Fairclough, J. Patrick. A.; Parker, Andrew R.

2015-01-01

Eurasian Jay (Garrulus glandarius) feathers display periodic variations in the reflected colour from white through light blue, dark blue and black. We find the structures responsible for the colour are continuous in their size and spatially controlled by the degree of spinodal phase separation in the corresponding region of the feather barb. Blue structures have a well-defined broadband ultra-violet (UV) to blue wavelength distribution; the corresponding nanostructure has characteristic spinodal morphology with a lengthscale of order 150 nm. White regions have a larger 200 nm nanostructure, consistent with a spinodal process that has coarsened further, yielding broader wavelength white reflectance. Our analysis shows that nanostructure in single bird feather barbs can be varied continuously by controlling the time the keratin network is allowed to phase separate before mobility in the system is arrested. Dynamic scaling analysis of the single barb scattering data implies that the phase separation arrest mechanism is rapid and also distinct from the spinodal phase separation mechanism i.e. it is not gelation or intermolecular re-association. Any growing lengthscale using this spinodal phase separation approach must first traverse the UV and blue wavelength regions, growing the structure by coarsening, resulting in a broad distribution of domain sizes. PMID:26686280

On the effect of basic and acidic additives on the separation of the enantiomers of some basic drugs with polysaccharide-based chiral selectors and polar organic mobile phases.

PubMed

Mosiashvili, L; Chankvetadze, L; Farkas, T; Chankvetadze, B

2013-11-22

This article reports the systematic study of the effect of basic and acidic additives on HPLC separation of enantiomers of some basic chiral drugs on polysaccharide-based chiral columns under polar organic mobile-phase conditions. In contrary to generally accepted opinion that the basic additives improve the separation of enantiomers of basic compounds, the multiple scenarios were observed including the increase, decrease, disappearance and appearance of separation, as well as the reversal of the enantiomer elution order of studied basic compounds induced by the acidic additives. These effects were observed on most of the studied 6 chiral columns in 2-propanol and acetonitrile as mobile phases and diethylamine as a basic additive. As acidic additives formic acid was used systematically and acetic acid and trifluoroacetic acid were applied for comparative purposes. This study illustrates that the minor acidic additives to the mobile phase can be used as for the adjustment of separation selectivity and the enantiomer elution order of basic compounds, as well as for study of chiral recognition mechanisms with polysaccharide-based chiral stationary phases. Copyright © 2013 Elsevier B.V. All rights reserved.

Intrinsic crystal phase separation in the antiferromagnetic superconductor Rb(y)Fe(2-x)Se2: a diffraction study.

PubMed

Yu Pomjakushin, V; Krzton-Maziopa, A; Pomjakushina, E V; Conder, K; Chernyshov, D; Svitlyk, V; Bosak, A

2012-10-31

The crystal and magnetic structures of the superconducting iron-based chalcogenides Rb(y)Fe(2-x)Se(2) have been studied by means of single-crystal synchrotron x-ray and high-resolution neutron powder diffraction in the temperature range 2-570 K. The ground state of the crystal is an intrinsically phase-separated state with two distinct-by-symmetry phases. The main phase has the iron vacancy ordered √5 × √5 superstructure (I4/m space group) with AFM ordered Fe spins. The minority phase does not have √5 × √5-type of ordering and has a smaller in-plane lattice constant a and larger tetragonal c-axis and can be well described by assuming the parent average vacancy disordered structure (I4/mmm space group) with the refined stoichiometry Rb(0.60(5))(Fe(1.10(5))Se)(2). The minority phase amounts to 8-10% mass fraction. The unit cell volume of the minority phase is 3.2% smaller than the one of the main phase at T = 2 K and has quite different temperature dependence. The minority phase merges with the main vacancy ordered phase on heating above the phase separation temperature T(P) = 475 K. The spatial dimensions of the phase domains strongly increase above T(P) from 1000 to >2500 Å due to the integration of the regions of the main phase that were separated by the second phase at low temperatures. Additional annealing of the crystals at a temperature T = 488 K, close to T(P), for a long time drastically reduces the amount of the minority phase.

Multiple dual mode counter-current chromatography with variable duration of alternating phase elution steps.

PubMed

Kostanyan, Artak E; Erastov, Andrey A; Shishilov, Oleg N

2014-06-20

The multiple dual mode (MDM) counter-current chromatography separation processes consist of a succession of two isocratic counter-current steps and are characterized by the shuttle (forward and back) transport of the sample in chromatographic columns. In this paper, the improved MDM method based on variable duration of alternating phase elution steps has been developed and validated. The MDM separation processes with variable duration of phase elution steps are analyzed. Basing on the cell model, analytical solutions are developed for impulse and non-impulse sample loading at the beginning of the column. Using the analytical solutions, a calculation program is presented to facilitate the simulation of MDM with variable duration of phase elution steps, which can be used to select optimal process conditions for the separation of a given feed mixture. Two options of the MDM separation are analyzed: 1 - with one-step solute elution: the separation is conducted so, that the sample is transferred forward and back with upper and lower phases inside the column until the desired separation of the components is reached, and then each individual component elutes entirely within one step; 2 - with multi-step solute elution, when the fractions of individual components are collected in over several steps. It is demonstrated that proper selection of the duration of individual cycles (phase flow times) can greatly increase the separation efficiency of CCC columns. Experiments were carried out using model mixtures of compounds from the GUESSmix with solvent systems hexane/ethyl acetate/methanol/water. The experimental results are compared to the predictions of the theory. A good agreement between theory and experiment has been demonstrated. Copyright © 2014 Elsevier B.V. All rights reserved.

Utilization of deep eutectic solvents as novel mobile phase additives for improving the separation of bioactive quaternary alkaloids.

PubMed

Tan, Ting; Zhang, Mingliang; Wan, Yiqun; Qiu, Hongdeng

2016-01-01

Deep eutectic solvents (DESs) were used as novel mobile phase additives to improve chromatographic separation of four quaternary alkaloids including coptisine chloride, sanguinarine, berberine chloride and chelerythrine on a C18 column. DESs as a new class of ionic liquids are renewably sourced, environmentally benign, low cost and easy to prepare. Seven DESs were obtained by mixing different hydrogen acceptors and hydrogen-bond donors. The effects of organic solvents, the concentration of DESs, the types of DESs and the pH values of the buffer solution on the separation of the analytes were investigated. The composition of acetonitrile and 1.0% deep eutectic solvents aqueous solution (pH 3.3, adjusted with hydrochloric acid) in a 32:68 (v/v) ratio was used as optimized mobile phase, with which four quaternary alkaloids were well separated. When a small amount of DESs was added in the mobile phase for the separation of alkaloids on the C18 column, noticeable improvements were distinctly observed such as decreasing peak tailing and improving resolution. The separation mechanism mediated by DESs as mobile phase additives can be attributed to combined effect of both hydrogen acceptors and hydrogen-bond donors. For example, choline chloride can effectively cover the residual silanols on silica surface and ethylene glycol can reduce the retention time of analytes. The proposed method has been applied to determine BerbC in Lanqin Chinese herbal oral solution and BerbC tablet. Utilization of DESs in mobile phase can efficiently improve separation and selectivity of analytes from complex samples. Copyright © 2015 Elsevier B.V. All rights reserved.

A green separation strategy for neodymium (III) from cobalt (II) and nickel (II) using an ionic liquid-based aqueous two-phase system.

PubMed

Chen, Yuehua; Wang, Huiyong; Pei, Yuanchao; Wang, Jianji

2018-05-15

It is significant to develop sustainable strategies for the selective separation of rare earth from transition metals from fundamental and practical viewpoint. In this work, an environmentally friendly solvent extraction approach has been developed to selectively separate neodymium (III) from cobalt (II) and nickel (II) by using an ionic liquid-based aqueous two phase system (IL-ATPS). For this purpose, a hydrophilic ionic liquid (IL) tetrabutylphosphonate nitrate ([P 4444 ][NO 3 ]) was prepared and used for the formation of an ATPS with NaNO 3 . Binodal curves of the ATPSs have been determined for the design of extraction process. The extraction parameters such as contact time, aqueous phase pH, content of phase-formation components of NaNO 3 and the ionic liquid have been investigated systematically. It is shown that under optimal conditions, the extraction efficiency of neodymium (III) is as high as 99.7%, and neodymium (III) can be selectively separated from cobalt (II) and nickel (II) with a separation factor of 10 3 . After extraction, neodymium (III) can be stripped from the IL-rich phase by using dilute aqueous sodium oxalate, and the ILs can be quantitatively recovered and reused in the next extraction process. Since [P 4444 ][NO 3 ] works as one of the components of the ATPS and the extractant for the neodymium, no organic diluent, extra etractant and fluorinated ILs are used in the separation process. Thus, the strategy described here shows potential in green separation of neodymium from cobalt and nickel by using simple IL-based aqueous two-phase system. Copyright © 2018 Elsevier B.V. All rights reserved.

Copolymer-grafted silica phase from a cation-anion monomer pair for enhanced separation in reversed-phase liquid chromatography.

PubMed

Mallik, Abul K; Qiu, Hongdeng; Takafuji, Makoto; Ihara, Hirotaka

2014-05-01

This work reports a new imidazolium and L-alanine derived copolymer-grafted silica stationary phase for ready separation of complex isomers using high-performance liquid chromatography (HPLC). For this purpose, 1-allyl-3-octadecylimidazolium bromide ([AyImC18]Br) and N-acryloyl-L-alanine sodium salt ([AAL]Na) ionic liquids (IL) monomers were synthesized. Subsequently, the bromide counteranion was exchanged with the 2-(acrylamido)propanoate organic counteranion by reacting the [AyImC18]Br with excess [AAL]Na in water. The obtained IL cation-anion monomer pair was then copolymerized on mercaptopropyl-modified silica (Sil-MPS) via a surface-initiated radical chain-transfer reaction. The selective retention behaviors of polycyclic aromatic hydrocarbons (PAHs), including some positional isomers, steroids, and nucleobases were investigated using the newly obtained Sil-poly(ImC18-AAL), and octadecyl silylated silica (ODS) was used as the reference column. Interesting results were obtained for the separation of PAHs, steroids, and nucleobases with the new organic phase. The results showed that the Sil-poly(ImC18-AAL) presented multiple noncovalent interactions, including hydrophobic, π-π, carbonyl-π, and ion-dipole interactions for the separation of PAHs and dipolar compounds. Only pure water was sufficient as the mobile phase for the separation of the nucleobases. Ten nucleosides and bases were separated, using only water as the mobile phase, within a very short time using the Sil-poly(ImC18-AAL), which is otherwise difficult to achieve using conventional hydrophobic columns such as ODS. The combination of electrostatic and hydrophobic interactions are important for the effective separation of such basic compounds without the use of any organic additive as the eluent on the Sil-poly(ImC18-AAL) column.

Cleaning and dewatering fine coal

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

Yoon, Roe-Hoan; Eraydin, Mert K.; Freeland, Chad

Fine coal is cleaned of its mineral matter impurities and dewatered by mixing the aqueous slurry containing both with a hydrophobic liquid, subjecting the mixture to a phase separation. The resulting hydrophobic liquid phase contains coal particles free of surface moisture and droplets of water stabilized by coal particles, while the aqueous phase contains the mineral matter. By separating the entrained water droplets from the coal particles mechanically, a clean coal product of substantially reduced mineral matter and moisture contents is obtained. The spent hydrophobic liquid is separated from the clean coal product and recycled. The process can also bemore » used to separate one type of hydrophilic particles from another by selectively hydrophobizing one.« less

Specific features of the cathodoluminescence spectra of AlInGaN QWs, caused by the influence of phase separation and internal electric fields

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

Kuznetsova, Ya. V., E-mail: yana@mail.ioffe.ru; Jmerik, V. N.; Nechaev, D. V.

2016-07-15

The specific features of the cathodoluminescence (CL) spectra in AlInGaN heterostructures, caused by the influence of phase separation and internal electric fields, observed at varied CL excitation density, are studied. It is shown that the evolution of the CL spectrum and the variation in the spectral position of emission lines of nanoscale layers with current density in the primary electron beam makes it possible to identify the occurrence of phase separation in the layer and, in the absence of this separation, to estimate the electric-field strength in the active region of the structure.

Evaluation of Inorganic/Organic Separators

NASA Technical Reports Server (NTRS)

Donnel, C. P., III

1976-01-01

Thirty-six (36) experimental 40AH sealed silver-zinc cells were constructed during phase I of this two (2) phase program. These cells were divided into six (6) groups of six (6) cells each. Each group of six (6) cells was evenly divided into two batches of three (3) cells each. Groups 1 through 4 each featured a different inorganic filler material in the slurry used to coat the separator substrate. Groups 5 and 6 featured an alternate method of separator bag construction. With the exception of the various separator materials, the parts and processes used to produce these thirty-six (36) cells were the same as those used to make the HR40-7 cell. The two (2) batches of cells in each cell group differed only in the lots of solutions and other separator slurry components used. Each cell was given two formation charge/discharge cycles prior to being shipped to NASA Lewis Research Center. Phase II of the program consisted of constructing another thirty-six (36) 40AH experimental cells in six (6) groups of six (6) cells each. Each group was distinguished by the type of precoated separator material used to fabricate separator bags. A new method of separator bag construction was used in this phase of the program. These cells were given two (2) formation cycles and shipped to NASA Lewis Research Center.

Identifying Effective Design Approaches to Allocate Genotypes in Two-Phase Designs: A Case Study in Pelargonium zonale

PubMed Central

Molenaar, Heike; Boehm, Robert; Piepho, Hans-Peter

2018-01-01

Robust phenotypic data allow adequate statistical analysis and are crucial for any breeding purpose. Such data is obtained from experiments laid out to best control local variation. Additionally, experiments frequently involve two phases, each contributing environmental sources of variation. For example, in a former experiment we conducted to evaluate production related traits in Pelargonium zonale, there were two consecutive phases, each performed in a different greenhouse. Phase one involved the propagation of the breeding strains to obtain the stem cutting count, and phase two involved the assessment of root formation. The evaluation of the former study raised questions regarding options for improving the experimental layout: (i) Is there a disadvantage to using exactly the same design in both phases? (ii) Instead of generating a separate layout for each phase, can the design be optimized across both phases, such that the mean variance of a pair-wise treatment difference (MVD) can be decreased? To answer these questions, alternative approaches were explored to generate two-phase designs either in phase-wise order (Option 1) or across phases (Option 2). In Option 1 we considered the scenarios (i) using in both phases the same experimental design and (ii) randomizing each phase separately. In Option 2, we considered the scenarios (iii) generating a single design with eight replicates and splitting these among the two phases, (iv) separating the block structure across phases by dummy coding, and (v) design generation with optimal alignment of block units in the two phases. In both options, we considered the same or different block structures in each phase. The designs were evaluated by the MVD obtained by the intra-block analysis and the joint inter-block–intra-block analysis. The smallest MVD was most frequently obtained for designs generated across phases rather than for each phase separately, in particular when both phases of the design were separated with a single pseudo-level. The joint optimization ensured that treatment concurrences were equally balanced across pairs, one of the prerequisites for an efficient design. The proposed alternative approaches can be implemented with any model-based design packages with facilities to formulate linear models for treatment and block structures. PMID:29354145

A comparison of the transport properties of lithium-stuffed garnets and the conventional phases Li 3Ln3Te 2O 12

NASA Astrophysics Data System (ADS)

Cussen, Edmund J.; Yip, Thomas W. S.; O'Neill, Gemma; O'Callaghan, Michael P.

2011-02-01

The structures of new phases Li 6CaLa 2Sb 2O 12 and Li 6.4Ca 1.4La 2Sb 2O 12 have been characterised using neutron powder diffraction. Rietveld analyses show that both compounds crystallise in the space group la3¯ d and contain the lithium cations in a complex arrangement with occupational disorder across oxide tetrahedra and distorted oxide octahedra, with considerable positional disorder in the latter. Variable temperature neutron diffraction experiments on Li 6.4Ca 1.4La 2Sb 2O 12 show the structure is largely invariant with only a small variation in the lithium distribution as a function of temperature. Impedance spectroscopy measurements show that the total conductivity of Li 6CaLa 2Sb 2O 12 is several orders of magnitude smaller than related lithium-stuffed garnets with σ=10 -7 S cm -1 at 95 °C and an activation energy of 0.82(3) eV. The transport properties of the conventional garnets Li 3Gd 3Te 2O 12, Li 3Tb 3Te 2O 12, Li 3Er 3Te 2O 12 and Li 3Lu 3Te 2O 12 have been evaluated and consistently show much lower values of conductivity, σ≤4.4×10 -6 S cm -1 at 285 °C and activation energies in the range 0.77(4)≤ Ea/eV≤1.21(3).

Simulations of irradiated-enhanced segregation and phase separation in Fe-Cu-Mn alloys

NASA Astrophysics Data System (ADS)

Li, Boyan; Hu, Shenyang; Li, Chengliang; Li, Qiulin; Chen, Jun; Shu, Guogang; Henager, Chuck, Jr.; Weng, Yuqing; Xu, Ben; Liu, Wei

2017-09-01

For reactor pressure vessel steels, the addition of Cu, Mn, and Ni has a positive effect on their mechanical, corrosion and radiation resistance properties. However, experiments show that radiation-enhanced segregation and/or phase separation is one of the important material property degradation processes. In this work, we develop a model integrating rate theory and phase-field approaches to investigate the effect of irradiation on solute segregation and phase separation. The rate theory is used to describe the accumulation and clustering of radiation defects, while the phase-field approach describes the effect of radiation defects on phase stability and microstructure evolution. The Fe-Cu-Mn ternary alloy is taken as a model system. The free energies used in the phase-field model are from CALPHAD. Spatial dependent radiation damage from atomistic simulations is introduced into the simulation cell for a given radiation dose rate. The radiation effect on segregation and phase separation is taken into account through the defect concentration dependence of solute mobility. Using the model, the effect of temperature and radiation rates on Cu and Mn segregation and Cu-rich phase nucleation were systematically investigated. The segregation and nucleation mechanisms were analyzed. The simulations demonstrate that the nucleus of Cu precipitates has a core-shell composition profile, i.e. Cu-rich at the center and Mn-rich at the interface, in good agreement with theoretical calculations as well as experimental observations.

Nano-phase separation and structural ordering in silica-rich mixed network former glasses.

PubMed

Liu, Hao; Youngman, Randall E; Kapoor, Saurabh; Jensen, Lars R; Smedskjaer, Morten M; Yue, Yuanzheng

2018-06-13

We investigate the structure, phase separation, glass transition, and crystallization in a mixed network former glass series, i.e., B2O3-Al2O3-SiO2-P2O5 glasses with varying SiO2/B2O3 molar ratio. All the studied glasses exhibit two separate glassy phases: droplet phase (G1) with the size of 50-100 nm and matrix phase (G2), corresponding to a lower calorimetric glass transition temperature (Tg1) and a higher one (Tg2), respectively. Both Tg values decrease linearly with the substitution of B2O3 for SiO2, but the magnitude of the decrease is larger for Tg1. Based on nuclear magnetic resonance and Raman spectroscopy results, we infer that the G1 phase is rich in boroxol rings, while the G2 phase mainly involves the B-O-Si network. Both phases contain BPO4- and AlPO4-like units. Ordered domains occur in G2 upon isothermal and dynamic heating, driven by the structural heterogeneity in the as-prepared glasses. The structural ordering lowers the activation energy of crystal growth, thus promoting partial crystallization of G2. These findings are useful for understanding glass formation and phase separation in mixed network former oxide systems, and for tailoring their properties.

URANIUM DECONTAMINATION WITH RESPECT TO ZIRCONIUM

DOEpatents

Vogler, S.; Beederman, M.

1961-05-01

A process is given for separating uranium values from a nitric acid aqueous solution containing uranyl values, zirconium values and tetravalent plutonium values. The process comprises contacting said solution with a substantially water-immiscible liquid organic solvent containing alkyl phosphate, separating an organic extract phase containing the uranium, zirconium, and tetravalent plutonium values from an aqueous raffinate, contacting said organic extract phase with an aqueous solution 2M to 7M in nitric acid and also containing an oxalate ion-containing substance, and separating a uranium- containing organic raffinate from aqueous zirconium- and plutonium-containing extract phase.